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  • Chemistry  (42,157)
  • 2020-2024  (45)
  • 1995-1999  (38,453)
  • 1945-1949  (3,659)
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  • 1
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Mineralogy includes thirteen chapters that discuss the methodology of specific mineralogical methods, the composition of minerals from different igneous rocks, and the composition of minerals from different sedimentary rocks.It contains detailed mineralogical studies from Africa, Asia, and Europe. Chapters present different scientific mineralogical methods and detailed descriptions of minerals from different magmatic and sedimentary rocks.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNV Chemistry of minerals, crystals and gems
    Language: English
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  • 2
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Benzimidazole is a comprehensive survey of the known and new methods of benzimidazole synthesis, the spectral and theoretical aspects of existing benzimidazole derivatives, and the anticancer properties of a new class of benzimidazole derivatives. This book examines aspects and newer mechanisms of benzimidazoles containing heterocyclic moiety. Chapters report on anticancer properties of benzimidazole derivatives, novel methods of synthesis of benzimidazoles, versatile nature of the benzimidazoles, spectral and theoretical studies of benzimidazole derivatives, and medicinal importance and pharmacological aspects of benzimidazole derivatives.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry
    Language: English
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  • 3
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Green Chemistry - New Perspectives is at the frontiers of this continuously evolving interdisciplinary science, and publishes research that attempts to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The book covers all aspects of green chemistry, including chemical synthesis, nano synthesis, eco-friendly processes, biomass, extraction techniques, environmental remediation, and energy, making it a unique reference resource. This will continue to encourage scientists around the world to develop novel synthetic methods or improve the existing ones to circumvent some of the problems and favours all aspects of green chemistry. This book is intended for academia, professionals, scientists, as well as graduate and undergraduate students without any geographical limitations.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry
    Language: English
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  • 4
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    EDP SCIENCES
    Publication Date: 2024-04-05
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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  • 5
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    EDP SCIENCES
    Publication Date: 2024-04-05
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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  • 6
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: This book consists of several selected chapters on important subjects in modern high-performance liquid chromatography (HPLC) and ultra-performance liquid chromatography (UPLC). The content addresses aspects related to both improvements in the mainstream HPLC/UPLC technology and utilization, as well as developments of exploratory new materials and equipment. The book presents useful details about the presented subjects as well as describes new applications and/or relevant case studies for each subject. It is addressed to a large audience of analytical chemists involved in separation science. Each chapter is authored by scientists with considerable field and academic experience.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNF Analytical chemistry
    Language: English
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  • 7
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    EDP SCIENCES
    Publication Date: 2024-04-07
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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  • 8
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Recent Advances in Chemical Kinetics provides a comprehensive overview of several types of chemical reactions. It includes six chapters that discuss solvent catalysis, customized flow reactors, p-conjugation in kinetics, kinetics of autoxidation, molecular chameleon for cations and anions, and internal clocks of atoms.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry
    Language: English
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  • 9
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    Taylor & Francis | CRC Press
    Publication Date: 2024-03-31
    Description: Hydroxyapatite coatings are of great importance in the biological and biomedical coatings fields, especially in the current era of nanotechnology and bioapplications. With a bonelike structure that promotes osseointegration, hydroxyapatite coating can be applied to otherwise bioinactive implants to make their surface bioactive, thus achieving faster healing and recovery. In addition to applications in orthopedic and dental implants, this coating can also be used in drug delivery. Hydroxyapatite Coatings for Biomedical Applications explores developments in the processing and property characterization and applications of hydroxyapatite to provide timely information for active researchers and newcomers alike. In eight carefully reviewed chapters, hydroxyapatite experts from the United States, Japan, Singapore, and China present the latest on topics ranging from deposition processes to biomedical applications in implants and drug delivery. This book discusses: Magnetron sputtering and electrochemical deposition The modification of hydroxyapatite properties by sol–gel deposition to incorporate other elements found in natural bones, such as zinc, magnesium, and fluorine The use of pure hydroxyapatite in drug delivery applications The growth or self-assembly of hydroxyapatite on shape memory alloy Hydroxyapatite composite coatings—with carbon nanotubes, titanium dioxide (TiO2), and others—on the titanium alloy Offering valuable insights and a wealth of data, including numerous tables and figures, this is a rich source of information for research on hydroxyapatite coatings. Each chapter also covers material that provides an accessible stepping stone for those who are new to the field.
    Keywords: Pre-clinical medicine: basic sciences ; Chemistry ; Materials science ; thema EDItEUR::M Medicine and Nursing::MF Pre-clinical medicine: basic sciences ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TG Mechanical engineering and materials::TGM Materials science
    Language: English
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  • 10
    Publication Date: 2024-04-05
    Description: Chemiebezogene Kompetenzen werden bereits im Sachunterricht der Grundschule entwickelt und sollen im Chemieunterricht der Sekundarstufe I aufgegriffen und weiterentwickelt werden. Ziel dieser Studie war es, die chemiebezogenen Kompetenzen der Schülerinnen und Schüler in der Übergangsphase zwischen Sachunterricht und Chemieunterricht zu analysieren. In einer Ergänzungsstudie wurden zusätzlich sowohl die Auswirkungen der Schulschließungen aufgrund der SARS-CoV-II Pandemie auf die Kompetenzen der Schülerinnen und Schüler als auch der Einfluss einer veränderten Testadministration untersucht. Insgesamt wurden die Kompetenzen von 2262 Lernenden der Jahrgangsstufen 5 bis 9 zu drei Messzeitpunkten analysiert. Die Ergebnisse zeigen, dass die chemiebezogenen Kompetenzen sowohl zum Ende der Grundschulzeit als auch zu Beginn des Chemieunterrichts über alle Kompetenzbereiche hinweg sehr heterogen ausfallen. Dennoch sind sie zu Beginn des Chemieunterrichts in einigen Kompetenzbereichen höher ausgeprägt als zum Ende der Grundschulzeit. Nach den pandemiebedingten Schulschließungen waren die Kompetenzen ähnlich ausgeprägt wie in den gleichen Jahrgangsstufen vor den Schulschließungen. Eine während der Schulschließungen notwendige Bearbeitung der Testhefte von zu Hause aus führte vor allem bei den jüngeren Schülerinnen und Schülern zu besseren Testergebnissen als die Bearbeitung in der Schule. Um die Entwicklung chemiebezogener Kompetenzen in der Übergangsphase zu optimieren, sollte der Erwerb dieser Kompetenzen bereits im Sachunterricht einheitlicher gestaltet werden.
    Keywords: Science ; Chemistry ; Education ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::J Society and Social Sciences::JN Education
    Language: German
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  • 11
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Redox reactions are involved in biochemistry, energy, corrosion, and much more. In both biology and electrochemistry, the redox reaction is complex and varied. For example, redox shuttles in supercapacitors show aspects of molecular electrochemistry applied to electrode porosity. In pseudocapacitors, the formalism associated with their electrochemical response requires investigation and formalism. Similarly, the simple definition of redox potential opens fundamental questions about its measurement in solutions without supporting salts. This book illustrates the variety of redox reactions in its examination of the importance of redox molecules in the development of new electrical energy storage devices.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry::PNRH Electrochemistry and magnetochemistry
    Language: English
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  • 12
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    Logos Verlag Berlin | Logos Verlag Berlin
    Publication Date: 2024-04-05
    Description: In 2005, the hybrid model was published by Prof. H.-D. Alber and Prof. P. Zhu as an alternative to the Allen-Cahn model for the description of phase field transformations. With low interfacial energy, it is more efficient, since the resolution of the diffuse interface is numerically broader for the same solution accuracy and allows coarser meshing. The solutions of both models are associated with energy minimisation and in this work the error terms introduced in the earlier publications are discussed and documented using one and two dimensional numerical simulations. In the last part of this book, phase field problems, initially not coupled with material equations, are combined with linear elasticity and, after simple introductory examples, a growing martensitic inclusion is simulated and compared with literature data. In addition to the confirmed numerical advantage, another phenomenon not previously described in the literature is found: with the hybrid model, in contrast to the examples calculated with the Allen-Cahn model, an inclusion driven mainly by curvature energy does not disappear completely. The opposite problem prevents inclusions from growing from very small initial configurations, but this fact can be remedied by a very finely chosen diffuse interface width and by analysing and adjusting the terms that generate the modelling errors. The last example shows that the hybrid model can be used with numerical advantages despite the above mentioned peculiarities.
    Keywords: Science ; Chemistry ; Mathematics ; Science ; Physics ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PB Mathematics ; thema EDItEUR::P Mathematics and Science::PH Physics
    Language: English
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  • 13
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: We are living in a critical time, both for humanity and the planet, which has led us to look for more sustainable formulas to interact with the environment. One of the important changes in the design and operation of chemical processes is the search for environmentally friendly technologies. Supercritical carbon dioxide has been revealed as a promising environmentally friendly solvent that is energy efficient, selective and capable of reducing waste, making it a promising alternative to conventional organic solvents. However, reliable and versatile mathematical models of phase equilibrium thermodynamics are needed for the use of supercritical carbon dioxide in process design and viability studies. This book reviews experimental procedures for obtaining high-pressure phase equilibria data and describes the phase diagrams of binary mixtures and some thermodynamic models capable of determining the conditions of phase equilibria at high pressures. These concepts are applied to the components of the transesterification reaction of rac-2-pentanol with a vinyl ester, which is important in the pharmaceutical industry because (S)-2-pentanol can be obtained as a reaction product. This product is a key intermediate in the synthesis of drugs against Alzheimer’s disease.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry
    Language: English
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  • 14
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    MDPI - Multidisciplinary Digital Publishing Institute
    Publication Date: 2024-04-05
    Description: Nanofibers, particularly those of a carbonaceous content, have received increased interest in the past two decades due to their outstanding physico-chemical characteristics and their possibility to form and contribute towards a plethora of potentially advantageous materials for consumer, industrial and medical applications. Despite this, and together with the numerous research studies and published articles that have sought to investigate these aspects, the potential impact of CNTs is still not understood. Whether or not nanofibers may be able to provide a sophisticated alternative to conventional materials is still debatable, whilst their effects upon both environmental and human health are highly equivocal. How nanofibers are conceived can determine how they may interact with different environments, such as the human body. Understanding each key step of the synthesis and production of nanofibers to their use within potential applications is therefore essential in gaining an insight into how they may be perceived by any biological system and environment. Thus, obtaining such information will enable all scientific communities to begin to realize the potential advantages posed by nanofibers. The aim of this Special Issue therefore, was to provide a collective overview of nanofibers; ‘from synthesis to application’. The Issue particularly focuses upon carbon-based nanofibers, but also highlights alternative nanofiber types. Emphasis is given holistically, with articles discussing the production routes of nanofibers, their plight during their life-cycle (origin to applied form and effects over time), as well as how nanofibers could either incite conflict, or provide aid to human and environmental health.
    Keywords: QD1-999 ; Toxicology ; Chemistry ; Biology ; Material Science ; Nanofibers ; Nanotechnology ; thema EDItEUR::P Mathematics and Science::PN Chemistry
    Language: English
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  • 15
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: In recent decades, artificial porous structures have attracted increasing enthusiasm from researchers inspired by the fascinating molecular pores in nature and their unique biological functions. Although substantial achievements in porous materials have been realized, the construction of topologically designed pores is still challenging. Recently, the emergence of covalent organic frameworks (COFs), which are constructed based on organic and polymer chemistry, has made it possible to design artificial pores with controlled pore size, topology and interface properties. COFs are crystalline porous materials constructed by the precise reticulation of organic building blocks via dynamic covalent bonds. Distinct from non-covalent interactions which tend to produce isostructures, covalent bonds enable accurate pore design owing to their predetermined reaction pathways. In addition, the appropriate polycondensation of organic building units enables the formation of extended two-dimensional (2D) and three-dimensional (3D) polymer architectures with periodically ordered skeletons and well-defined pores. With their large surface area, tailorable structures, and tunable chemistry, COFs are regarded as potentially superior candidates for various applications including catalysis, energy storage and conversion, mass transport and biotechnology. This book examines the historic achievement of COFs, providing clear and comprehensive guidance for researchers on their structural design, synthetic protocols and functional exploration.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry
    Language: English
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  • 16
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Fluoride covers a continuum of topics that are frequently studied in the broad area of fluoride (F) research. It provides an overview of the primary sources of environmental fluoride in typical high-fluoride environments and demonstrates the transitions and transformations that emerge and culminate in hydro-geochemical interactions that result in fluoride-fouling of large portions of the world’s water and agricultural resources. This way, the book pinpoints the connection between F enrichment of water sources and the prevalence of endemic fluorosis in certain areas of the world. In order to contribute to a better understanding of the global fluoride problem, new fluoride detection and quantification technologies are proposed with an in-depth analysis of emerging trends in the use of portable user-friendly devices in point-of-use measurements of water fluoride. This has been presented against the backdrop of a robust overview of traditional fluoride quantification methodologies that are still in wide application among the scientific communities. In addressing fluoride toxicities, which are not limited to dental and skeletal dilapidations, the authors have explored the role of natural antioxidants in ameliorating physiological fluoride-induced noxious effects in mammalian systems. Nonetheless, since community dependence on high-fluoride water due to a lack of alternative clean water sources remains to be the principal pathway of human fluoride over-exposure, a review chapter on F mitigation techniques applied all over the world is incorporated aiming at providing a succinct overview of water defluoridation techniques and strategies being used to combat the impacts of human F overexposure around the globe. Since every cloud has a silvery lining, the possibility of using ammonium fluorides as a novel reagent in mineral processing has been considered convenient industrial fluorinating agents, which present the possibility of complete regeneration that is not afforded by the reagents presently used in decomposing silicon component of the ores.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNK Inorganic chemistry
    Language: English
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  • 17
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: This book discusses the chemistry and applications of pyridine derivatives. The library of pyridine derivatives is growing steadily with numerous synthetic analogues already described and the identification of new, naturally occurring pyridine-based compounds. The book includes ten chapters organized into two parts. The first part focuses on the numerous types of reactions that arise from pyridine derivatives. The second part examines the pharmaceutical applications of pyridine derivatives as well as their usefulness as sensors for metal cations and extracting agents for platinum group metals.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry
    Language: English
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  • 18
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: The book discusses multiple issues associated with modern dosimetry in physics and treatment planning and how investigators from diverse world centers and institutions approach problem-solving in these important areas. It examines topics including pretreatment validation and factors affecting reference dosimetry. It also addresses unique issues affecting pediatric populations as well as the modern role of thermoluminescence validation. Several chapters discuss intensity modulation, including defining modern problems associated with both treatment planning and the definition of tumor and normal tissue contours. Furthermore, the book examines the role of imaging as both a vehicle to define tumor targets and normal tissue as well as a tool for dose validation.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry::PNRL Nuclear chemistry, photochemistry and radiation
    Language: English
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  • 19
    Publication Date: 2024-04-05
    Description: Das selbstgesteuerte Experimentieren ist laut den nationalen Bildungsstandards sowie den Lehrplänen im Fach Chemie ein wichtiger Bestandteil der naturwissenschaftlichen Schulbildung. Offene Experimentierformen sind jedoch wenig etabliert. Um das selbstgesteuerte Experimentieren in die Unterrichtspraxis zu implementieren, wurde im Rahmen dieses Forschungsprojekts eine eintägige Lehrkräftefortbildung zur Konzeption von selbstgesteuerten Experimenten im Chemieunterricht durchgeführt. Dazu wurde ein literaturbasiertes Strukturierungskonzept entwickelt, mit dem die Lehrkräfte kochbuchartige Schulversuche zu selbstgesteuerten und kompetenzorientierten Experimenten mit beliebigen Öffnungsgraden modifizieren können. Begleitend zur Fortbildung wurde im Prä-Post-Follow-Up-Design das fachdidaktische Wissen der Teilnehmenden hinsichtlich der Planung von selbstgesteuerten Experimenten empirisch überprüft. Zur Erfassung dieses Konstrukts wurde ein neues Messinstrument literaturbasiert entwickelt und die Güte des Messinstruments evaluiert. Die Auswertungen zeigen, dass die Fortbildung hinsichtlich des fachdidaktischen Wissens der Lehrkräfte kurz- sowie langfristig lernförderlich ist und die Fortbildung von den Teilnehmenden positiv bewertet wird. Die Reliabilitätsanalyse sowie die Validierungsstudie zeigen, dass der Test sowohl reliabel als auch valide ist. In Folgestudien könnte die langfristige Verhaltensänderung der Lehrkräfte bezüglich der Implementierung des selbstgesteuerten Experimentierens in den Unterricht untersucht werden.
    Keywords: Science ; Chemistry ; Science ; Education ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PD Science: general issues ; thema EDItEUR::J Society and Social Sciences::JN Education
    Language: German
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  • 20
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: The book comprises 14 chapters covering all the issues related to water desalination. These chapters emphasize the relationship between problems encountered with the use of feed water, the processes developed to address them, the operation of the required plants and solutions actually implemented. This compendium will assist designers, engineers and investigators to select the process and plant configuration that are most appropriate for the particular feed water to be used, for the geographic region considered, as well as for the characteristics required of the treated water produced. This survey offers a comprehensive, hierarchical and logical assessment of the entire desalination industry. It starts with the worldwide scarcity of water and energy, continues with the thermal - and membrane-based processes and, finally, presents the design and operation of large and small desalination plants. As such, it covers all the scientific, technological and economical aspects of this critical industry, not disregarding its environmental and social points of view. One of InTech's books has received widespread praise across a number of key publications. Desalination, Trends and Technologies (Ed. Schorr, M. 2011) has been reviewed in Corrosion Engineering, Science & Technology – the official magazine for the Institute of Materials, Minerals & Mining, and Taylor & Francis's Desalination Publications. Praised for its “multi-faceted content [which] contributes to enrich it,” and described as “an essential companion...[that] enables the reader to gain a deeper understanding of the desalination industry,” this book is testament to the quality improvements we have been striving towards over the last twelve months.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNF Analytical chemistry
    Language: English
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  • 21
    Publication Date: 2024-04-05
    Description: The Global Methane Initiative (GMI) is a voluntary international partnership that promotes methane recovery and reuse activities in developing and transition economies. The U.S. Department of State requested an evaluation of the activities and outcomes supported in whole or in part by its contributions to GMI to gauge its value added to the program.
    Keywords: Physics ; Environmental Science ; Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TQ Environmental science, engineering and technology ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RB Earth sciences::RBP Meteorology and climatology
    Language: English
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  • 22
    Publication Date: 2024-04-04
    Description: This volume, occasioned by the centenary of the Fritz Haber Institute, formerly the Institute for Physical Chemistry and Electrochemistry, covers the institute's scientific and institutional history from its founding until the present. The institute was among the earliest established by the Kaiser Wilhelm Society, and its inauguration was one of the first steps in the development of Berlin-Dahlem into a center for scientific research. Its establishment was made possible by an endowment from Leopold Koppel, granted on the condition that Fritz Haber, well-known for his discovery of a method to synthesize ammonia from its elements, be made its director. The history of the institute has largely paralleled that of 20th-century Germany. It undertook controversial weapons research during World War I, followed by a "Golden Era" during the 1920s, in spite of financial hardships.
    Keywords: Chemistry ; Chemistry ; Fritz Haber Institute ; thema EDItEUR::P Mathematics and Science::PD Science: general issues::PDX History of science
    Language: English
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  • 23
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Progress in agricultural, biomedical and industrial applications' is a compilation of recent advances and developments in gas chromatography and its applications. The chapters cover various aspects of applications ranging from basic biological, biomedical applications to industrial applications. Book chapters analyze new developments in chromatographic columns, microextraction techniques, derivatisation techniques and pyrolysis techniques. The book also includes several aspects of basic chromatography techniques and is suitable for both young and advanced chromatographers. It includes some new developments in chromatography such as multidimensional chromatography, inverse chromatography and some discussions on two-dimensional chromatography. The topics covered include analysis of volatiles, toxicants, indoor air, petroleum hydrocarbons, organometallic compounds and natural products. The chapters were written by experts from various fields and clearly assisted by simple diagrams and tables. This book is highly recommended for chemists as well as non-chemists working in gas chromatography.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNF Analytical chemistry
    Language: English
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  • 24
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: This book discusses electrocatalysis and electrocatalysts for energy, water electrolysis, water treatment, CO2 conversion, and green chemistry. It reviews various electrocatalysts and their properties and electrochemical performances. The first section of the book covers topics in direct alcohol fuel cells including Pt-based electrocatalysts as non-carbon electrode support materials and the development of electrocatalysts for direct methanol fuel cells. The second section of the book covers various topics in electrocatalysis and electrocatalysts for a cleaner environment, including electrocatalysts for the conversion of CO2 to valuable products and SYNGAS, electrocatalysts for water electrolysis, and much more.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry::PNRH Electrochemistry and magnetochemistry
    Language: English
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  • 25
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    transcript Verlag | transcript Verlag
    Publication Date: 2024-04-04
    Description: Die Chemie büßt zugunsten physikalischer und lebenswissenschaftlicher Konzeptionen zunehmend an Deutungsmacht über die molekulare Welt ein. Sandra Lang untersucht, inwiefern die Ausdifferenzierung der chemischen Wissenschaften mit sich ebenfalls ausdifferenzierenden Zugriffen auf das Molekulare zusammenhängt. Anhand der vier exemplarischen Grenzfelder Materialwissenschaften, Biomedizin, Pharmazie und Quantenchemie und deren Narrative zur molekularen Eigenschaft der Chiralität veranschaulicht sie die transformative Phase der Chemie angesichts sich wandelnder Innovationsdispositive.
    Keywords: Chemie ; Chiralität ; Molekülkonzept ; Naturwissenschaften ; Grenzarbeit ; Interdisziplinarität ; Hybridität ; Wissenschaft ; Technik ; Wissenschaftssoziologie ; Techniksoziologie ; Wissenssoziologie ; Wissenschaftsgeschichte ; Soziologie ; Chemistry ; Chirality ; Molecule Concept ; Natural Sciences ; Border Work ; Interdisciplinarity ; Hybridity ; Science ; Technology ; Sociology of Science ; Sociology of Technology ; Sociology of Knowledge ; History of Science ; Sociology ; thema EDItEUR::P Mathematics and Science::PD Science: general issues::PDR Impact of science and technology on society ; thema EDItEUR::J Society and Social Sciences::JH Sociology and anthropology::JHB Sociology
    Language: German
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  • 26
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Surfactants are ubiquitous and have applications in diverse areas, including food, cosmetics, detergents, lubricants, enhanced oil recovery (EOR), and targeted drug delivery systems. Their wide diversity of applications owes to their unique structure, namely, a hydrophilic and a hydrophobic group present in the same molecule. Although most surfactants used industrially are synthetic, there is a growing need for natural surfactants, as the latter is obtainable from renewable sources and are less toxic and highly biodegradable in contrast to their synthetic counterparts. This book is a compilation of interesting articles by various experts that cover various applications of both synthetic and natural surfactants.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry::PNRC Colloid chemistry
    Language: English
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  • 27
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: The chemical sensor plays an essential role in the fields of environmental conservation and monitoring, disaster and disease prevention, and industrial analysis. A typical chemical sensor is a device that transforms chemical information in a selective and reversible way, ranging from the concentration of a specific sample component to total composition analysis, into an analytically useful signal. Much research work has been performed to achieve a chemical sensor with such excellent qualities as quick response, low cost, small size, superior sensitivity, good reversibility and selectivity, and excellent detection limit. This book introduces the latest advances on chemical sensors. It consists of 15 chapters composed by the researchers active in the field of chemical sensors, and is divided into 5 sections according to the classification following the principles of signal transducer. This collection of up-to-date information and the latest research progress on chemical sensor will provide valuable references and learning materials for all those working in the field of chemical sensors.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNF Analytical chemistry
    Language: English
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    EDP SCIENCES
    Publication Date: 2024-04-05
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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    Publication Date: 2024-04-05
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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    De Gruyter | De Gruyter
    Publication Date: 2024-04-11
    Description: Presents technologies and key concepts to produce suitable smart materials and intelligent structures for sensing, information and communication technology, biomedical applications (drug delivery, hyperthermia therapy), self-healing, flexible memories and construction technologies. Novel developments of environmental friendly, cost-effective and scalable production processes are discussed by experts in the field.
    Keywords: Science ; Chemistry ; Industrial & Technical ; Technology & Engineering ; Textiles & Polymers ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TD Industrial chemistry and manufacturing technologies::TDC Industrial chemistry and chemical engineering ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TG Mechanical engineering and materials::TGM Materials science
    Language: English
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Distillation is an important separation technique that has been used for many centuries to exploit the volatility differences between components in a mixture. The distillation process has many variations and applications. This book includes two sections on desalination and reactive distillation. It discusses desalination in the processes of solar and membrane distillation, with a focus on the reduction of energy costs to obtain potable water. It also discusses reactive distillation, which can be used in some cases to reduce the power duty in the separation process by using the reaction heat directly in the separation. The book includes cases of mathematical modeling, simulation, and optimization of the distillation process.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNF Analytical chemistry
    Language: English
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    Logos Verlag Berlin | Logos Verlag Berlin
    Publication Date: 2024-04-05
    Description: Konsumgüter werden beispielsweise mit Slogans wie "Gut in Bio. Schlecht in Chemie." beworben. Dabei wird intendiert, sich gezielt von "Chemie" abzugrenzen und sich das positive Bild von "Natur" zu Nutze zu machen. Dies prägt die öffentliche Meinung und trägt zu einer antagonistisch-wertenden Sicht von "Chemie" und "Natur" bei. Dass Chemie als Naturwissenschaft der Beschreibung der Natur dient, um deren Stoffe und Stoffumwandlungen zu erklären, ist dem Laien selten bewusst. Chemie findet überall statt, insbesondere in der Natur! Genau an diesem Punkt setzt das Unterrichtskonzept "Chemie Pur - Unterrichten in der Naturglqq an. Ziel ist es, im Freiland, mit direkt vor Ort gewonnenen Naturstoffen, Umweltprozesse experimentell zu erarbeiten. Die projektbegleitende Evaluationsstudie stellte sich der Forschungsfrage, wie sich das Unterrichtskonzept auf das Fach- und Sachinteresse, auf die Naturverbundenheit sowie auf die Einstellung zu Chemie und Natur von Schülerinnen und Schülern der Sekundarstufe II auswirkt. Die Auswertung der Fragebogenergebnisse mit latenten Veränderungsmodellen haben gezeigt, dass die Intervention im Freiland das inhaltsbezogene Sachinteresse steigert und die Einstellung zu Chemie und Natur positiv beeinflusst sowie ein erhöhten Fachwissenszuwachs ermöglicht. Die gewonnenen Erkenntnisse können die Grundlage für die Entwicklung und Evaluation von good-practice-Ansätzen naturwissenschaftlicher Lernsituationen bilden. Das Unterrichtskonzept Chemie Pur leistet zudem einen Beitrag im Bereich Outdoor Education, um den Antagonismus von Chemie und Natur zu verringern.
    Keywords: Science ; Chemistry ; Science ; Education ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PD Science: general issues ; thema EDItEUR::J Society and Social Sciences::JN Education
    Language: German
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    De Gruyter | De Gruyter
    Publication Date: 2024-04-05
    Description: Comprise definition of 1500 terms. Innovation from A to Z presents a glossary, including: Terms, older terms whose meanings have changed, acronyms, synonyms, famous names, selected abbreviations, and cross-references. A highly interdisciplinary approach incorporating strategy and entrepreneurship with technology and engineering sciences, economics, marketing, organizational behavior and theory. Ideal for engineers, managers, sales people and economists. Innovation Technology from A to Z Glossary of terms, including acronyms, synonyms, abbreviations, cross-references 1500 terms supplemented by figures and tables that clearly demonstrate the state-of-the-art in Innovation Technology
    Keywords: Science ; Chemistry ; Technology & Engineering ; Agriculture ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TV Agriculture and farming
    Language: English
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    EDP SCIENCES
    Publication Date: 2024-04-08
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Cyclodextrins (CDs) have attracted great interest from the research community as well as industries in an array of sectors because of their unique structural features. This book provides a comprehensive overview of CDs, beginning with their historical background. Chapters address such topics as the structure and physiochemical properties of CDs, advancements in the field, and potential applications of these materials in fields such as drug delivery and sensing. This book reveals new frontiers in the CD world and is a useful resource for organic, analytical, and supramolecular chemists as well as scientists engaged in biological and material sciences.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: English
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: The book presents a comprehensive overview of sorption, which is a multi-parametric separation process. It is extensively used in the removal of various pollutants from the tertiary stage of wastewater treatment, from leachates, etc. It discusses fundamental points of the technique as well as kinetic theories and isotherms. It also examines the synthesis and characterizations of all studied adsorbent materials to find their paths of sorption. Finally, it highlights the importance of having a cost-estimation plan for the synthesis of sorbent materials as well as predictions for their reusability.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry::PNRX Surface chemistry and adsorption
    Language: English
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    EDP SCIENCES
    Publication Date: 2024-04-05
    Description: Chemistry;Materials science
    Keywords: Chemistry ; Materials science ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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    The MIT Press | The MIT Press
    Publication Date: 2024-03-27
    Description: The original 1818 text of Mary Shelley's classic novel, with annotations and essays highlighting its scientific, ethical, and cautionary aspects. Mary Shelley's Frankenstein has endured in the popular imagination for two hundred years. Begun as a ghost story by an intellectually and socially precocious eighteen-year-old author during a cold and rainy summer on the shores of Lake Geneva, the dramatic tale of Victor Frankenstein and his stitched-together creature can be read as the ultimate parable of scientific hubris. Victor, “the modern Prometheus,” tried to do what he perhaps should have left to Nature: create life. Although the novel is most often discussed in literary-historical terms—as a seminal example of romanticism or as a groundbreaking early work of science fiction—Mary Shelley was keenly aware of contemporary scientific developments and incorporated them into her story. In our era of synthetic biology, artificial intelligence, robotics, and climate engineering, this edition of Frankenstein will resonate forcefully for readers with a background or interest in science and engineering, and anyone intrigued by the fundamental questions of creativity and responsibility. This edition of Frankenstein pairs the original 1818 version of the manuscript—meticulously line-edited and amended by Charles E. Robinson, one of the world's preeminent authorities on the text—with annotations and essays by leading scholars exploring the social and ethical aspects of scientific creativity raised by this remarkable story. The result is a unique and accessible edition of one of the most thought-provoking and influential novels ever written. Essays by Elizabeth Bear, Cory Doctorow, Heather E. Douglas, Josephine Johnston, Kate MacCord, Jane Maienschein, Anne K. Mellor, Alfred Nordmann
    Keywords: science fiction ; gothic ; horror ; European ; British ; literature ; fiction ; cautionary tale ; STEM ; science ; bioethics ; classic ; bicentennial ; Josephine Johnston ; Cory Doctorow ; Jane Maienschein ; Kate MacCord ; Alfred Nordmann ; Elizabeth Bear ; Anne K. Mellor ; Heather E. Douglas ; Frankenstein ; Creature ; Monster ; Mary Shelley ; Makers ; women in science ; science and anti-science ; values in science ; responsible innovation ; Industrial Revolution ; Mary Wollstonecraft ; William Godwin ; Percy Bysshe Shelley ; Galvanism ; Mount Tambora ; Myths ; Two Cultures ; epistolary novel ; Victor Frankenstein ; Geneva ; Prometheus ; Arctic ; Lord Byron ; John Polidori ; ghost stories ; Revisions ; Electricity ; Lightning ; Vitalism ; Chemistry ; Extinction ; Magnetism ; Moral responsibility ; Legal responsibility ; Social responsibility ; Consequences ; Obligations ; Ethics ; Maker Culture ; DIY ; Technology Adjacent Possible ; Facebook ; Surveillance ; Aristotle ; Fetal development ; Epigenesis ; Embryo ; Person ; Technoscience ; Alchemy ; uncanny valley ; animation ; complexity ; Morality ; Monstrosity ; Christianity ; Otherness ; Gender ; Nature ; Domestic Affections ; Women ; Sexuality ; Technical Sweetness ; Los Alamos ; Trinity Test ; Scientific Responsibility ; Nuclear Weapons ; adjacent possible ; synthetic biology ; robotics ; thema EDItEUR::F Fiction and Related items::FB Fiction: general and literary::FBC Classic fiction: general and literary ; thema EDItEUR::F Fiction and Related items::FL Science fiction::FLC Classic science fiction
    Language: English
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    Coimbra University Press
    Publication Date: 2022-01-31
    Description: This work brings together various contributions from experts in very diverse areas of knowledge, to discuss the theme ‘Light’ from various points of view. The subjects gathered in this work come from the areas of Physics, Philosophy, Transcendence, Chemistry, Optics, Literature, History of Sciences, History, Geography, International Relations, Biology, Psychology, Art, Cinema and Photography, Medicine and Museology. The texts partially reflect the contents presented at the interdisciplinary colloquium ‘Visões da Luz’ held in October 2015, on the occasion of the International Year of Light 2015, under the aegis of III-UC and open to academia and society, to teachers of the Basic and Secondary Education.
    Keywords: Geography ; Chemistry ; Literature ; Geology ; Light ; Optics ; Biology ; History ; Physics
    Language: Portuguese
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Carotenoids are natural and versatile secondary metabolites, most of them showing colours that vary from yellow to red. They are widespread among living beings where they are involved in many biological roles reporting beneficial actions. To date, more than 750 carotenoids have been described in nature. Humans cannot synthesize carotenoids de novo, thus they are mainly obtained through diet. In fact, carotenoids are consistently found in tissues or biological fluids where they play a beneficial decreasing the risk of developing some diseases.During the last half-century, significant advances in carotenoids research have been made. This book highlights new perspectives and applications of carotenoids including characterization and isolation of new compounds (including rare carotenoids), their production at a mid-large scale (involving new innovative approaches), and uses of carotenoids in different biotechnological fields like food science, biomedicine, and cosmetics.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry
    Language: English
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    EDP SCIENCES
    Publication Date: 2024-04-05
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Infrared Spectroscopy - Perspectives and Applications is a compendium of contributions from experts in the field of infrared (IR) spectroscopy. This assembly of investigations and reviews provides a comprehensive overview of the fundamentals as well as the groundbreaking applications in the field. Chapters discuss IR spectroscopy applications in the food and biomedicine sectors and for measuring transport through polymer membranes, characterizing lignocellulosic biomasses, detecting adulterants, and characterizing enamel surface advancements. This book is an invaluable resource and reference for students, researchers, and other interested readers.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNF Analytical chemistry::PNFS Spectrum analysis, spectrochemistry, mass spectrometry
    Language: English
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    Logos Verlag Berlin | Logos Verlag Berlin
    Publication Date: 2024-04-05
    Description: When auralizing moving sound sources in Virtual Reality (VR) environments, the two main input parameters are the location and radiated signal of the source. An array measurement-based model is developed to characterize moving sound sources regarding the two parameters in this thesis. This model utilizes beamforming, i.e. delay and sum beamforming (DSB) and compressive beamforming (CB) to obtain the locations and signals of moving sound sources. A spiral and a pseudorandom microphone array are designed for DSB and CB, respectively, to yield good localization ability and meet the requirement of CB. The de-Dopplerization technique is incorporated in the time-domain DSB to address moving source problems. Time-domain transfer functions (TDTFs) are calculated in terms of the spatial locations within the steering window of the moving source. TDTFs then form the sensing matrix of CB, thus allowing CB to solve moving source problem. DSB and CB are further extended to localize moving sound sources, and the reconstructed signals from the beamforming outputs are investigated to obtain the source signals. Moreover, localization and signal reconstruction are evaluated through varying parameters in the beamforming procedures, i.e. steering position, steering window length and source speed for a moving periodic signal using DSB, and regularization parameter, signal to noise ratio (SNR), steering window length, source speed, array to source motion trajectory and mismatch for a moving engine signal using CB. The parameter studies show guidelines of parameter selection based on the given situations in this thesis for modeling moving source using beamforming. Both algorithms are able to reconstruct the moving signals in the given scenarios. Although CB outperforms DSB in terms of signal reconstruction under particular conditions, the localization abilities of the two algorithms are quite similar. The practicability of the model has been applied on pass-by measurements of a moving loudspeaker using the designed arrays, and the results can match the conclusions drawn above from simulations. Finally, a framework on how to apply the model for moving source auralization is proposed.
    Keywords: Science ; Chemistry ; Technology & Engineering ; Construction ; Technology & Engineering ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TN Civil engineering, surveying and building::TNK Building construction and materials ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TB Technology: general issues
    Language: English
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  • 44
    Publication Date: 2024-04-05
    Description: Neuere Erkenntnisse zum Umsatzverhalten an Dieseloxidationskatalysatoren (DOCs) zeigen, dass das Umsatzverhalten von Schadstoffen vom Oxidationsgrad der verwendeten Edelmetallkatalysatoren abhängen kann. Dabei wird deutlich, dass sich der Oxidationsgrad bei typischen Abgaszusammensetzungen langsam und reversibel mit der Katalysatortemperatur ändert. Das kann bei periodischen Katalysatortemperaturänderungen zu einem ausgeprägten Hystereseverhalten führen. Bisherige Ergebnisse liegen insbesondere zum Verhalten der NO-Oxidation an Platin-Katalysatoren vor. Ziel der vorliegenden Arbeit ist es daher, die Untersuchungen auf seriennahe Pd- und PtPd-Mischkatalysatoren sowie auf andere abgastypische Schadstoffe, wie CO und Kohlenwasserstoffe, zu erweitern und dabei auch den Einfluss der Katalysatoralterung zu erfassen. Es wurde ein globalkinetisches Modell entwickelt und an die experimentellen Befunde angepasst. Dabei zeigte sich, dass es in der Regel möglich ist, das Umsatzverhalten bei reinen Pt- und Pd-Katalysatoren mit diesem örtlich eindimensionalen, makrokinetischen Zweiphasenmodell zutreffend zu beschreiben, wohingegen das Verhalten auf Pt/Pd-Mischkatalysatoren weniger gut simuliert werden kann. Dies ist vermutlich auf die heterogene Struktur der Pt/Pd-legierten Partikel zurückzuführen.
    Keywords: Science ; Chemistry ; Technology & Engineering ; Chemical & Biochemical ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TD Industrial chemistry and manufacturing technologies::TDC Industrial chemistry and chemical engineering
    Language: German
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  • 45
    Publication Date: 2023-03-08
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in LeClerc, H., Tompsett, G., Paulsen, A., McKenna, A., Niles, S., Reddy, C., Nelson, R., Cheng, F., Teixeira, A., & Timko, M. Hydroxyapatite catalyzed hydrothermal liquefaction transforms food waste from an environmental liability to renewable fuel. IScience, 25(9), (2022): 104916, https://doi.org/10.1016/j.isci.2022.104916.
    Description: Food waste is an abundant and inexpensive resource for the production of renewable fuels. Biocrude yields obtained from hydrothermal liquefaction (HTL) of food waste can be boosted using hydroxyapatite (HAP) as an inexpensive and abundant catalyst. Combining HAP with an inexpensive homogeneous base increased biocrude yield from 14 ± 1 to 37 ± 3%, resulting in the recovery of 49 ± 2% of the energy contained in the food waste feed. Detailed product analysis revealed the importance of fatty-acid oligomerization during biocrude formation, highlighting the role of acid-base catalysts in promoting condensation reactions. Economic and environmental analysis found that the new technology has the potential to reduce US greenhouse gas emissions by 2.6% while producing renewable diesel with a minimum fuel selling price of $1.06/GGE. HAP can play a role in transforming food waste from a liability to a renewable fuel.
    Description: This work was funded by the DOE Bioenergy Technology Office (DE-EE0008513), a DOE DBIR (DE-SC0015784) and the MassCEC. The authors thank WenWen Yao, Department of Environmental Science at WPI, for TOC analysis, Mainstream Engineering for heating value characterization of the oil and solid samples, Wei Fan for assistance in obtaining SEM images and, Julia Martin and Ronald Grimm for their assistance in collecting XPS data, and Jeffrey R. Page for his assistance with oil upgrading and analysis. HOL was partially funded for this work by NSF Graduate Research Fellowship award number 2038257. A portion of this work was performed at the National High Magnetic Field Laboratory Ion Cyclotron Resonance user facility, which is supported by the NSF Division of Materials Research and Division of Chemistry through DMR 16-44779 and the State of Florida.
    Keywords: Chemistry ; Chemical engineering ; Catalysis
    Repository Name: Woods Hole Open Access Server
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    ISSN: 1432-0975
    Keywords: Key words Otolith ; Chemistry ; ICP-MS ; Stock discrimination ; Epinephelus striatus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract  We examined the utility of otolith minor and trace element chemistry, assayed with inductively coupled plasma mass spectrometry (ICP-MS), as a means of delineating population structure in the Nassau grouper (Epinephelus striatus). We characterized the elemental composition of otoliths collected in 1993 from three locations in Exuma Sound, Bahamas and from Glover Reef, Belize in 1995. A single location in Exuma Sound was sampled in 1994 to test temporal variability in otolith composition. Five elements (Ca, Zn, Sr, Ba and Pb) were routinely detected, at levels significantly above background, by solution-based ICP-MS. Results from analysis of variance of elemental data, expressed as a ratio to Ca, indicated that there were no significant differences among the Exuma locations for any element, but significant variability was found between Glover Reef and the pooled Exuma localities for Zn/Ca, Sr/Ca and Ba/Ca ratios. Significant inter-annual differences at one Exuma Sound location was restricted to Ba/Ca ratios. Discriminant function analysis correctly classified 86% and 95% of the Belize and pooled Exuma sites, respectively. Otoliths from Belize were characterized by low Zn/Ca and high Ba/Ca and Pb/Ca ratios compared to otoliths from fish collected in Exuma Sound. Although differences in Ba levels may be related to upwelling at Glover Reef, more data are needed to definitely link otolith composition with regional differences in water chemistry.
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  • 47
    Electronic Resource
    Electronic Resource
    Springer
    Astrophysics and space science 224 (1995), S. 81-84 
    ISSN: 1572-946X
    Keywords: Chemistry ; Depletions ; Shocks ; IRAS 05338-0624 ; NGC 1333 IRAS 4
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract High resolution interferometer and single-dish observations of young, deeply embedded stellar systems reveal a complex chemistry in the circumstellar environments of low to intermediate mass stars. Depletions of gas-phase molecules, grain mantle evaporation, and shock interactions actively drive chemical processes in different regions around young stars. We present results for two systems, IRAS 05338-0624 and NGC 1333 IRAS 4, to illustrate the behavior found and to examine the physical processes at work.
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  • 48
    Electronic Resource
    Electronic Resource
    Springer
    Astrophysics and space science 233 (1995), S. 125-137 
    ISSN: 1572-946X
    Keywords: Interstellar Medium ; Dark Clouds ; Chemistry ; Bistability ; C-shock Waves
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Shock waves perturb the chemical state of the interstellar gas. We consider the effects of C-shocks on the composition of molecular clouds, for a range of values of the pre-shock gas density and magnetic induction. The time required to re-establish equilibrium in the post-shock gas depends on the initial conditions and can become very large. The significance of the two known chemical phases of dark clouds and of bistability is considered in this context.
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  • 49
    Electronic Resource
    Electronic Resource
    Springer
    Astrophysics and space science 233 (1995), S. 161-164 
    ISSN: 1572-946X
    Keywords: Stars ; Chemistry ; Diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We have assessed the role of diffusion in determining chemical abundances in molecular interface regions. Chemical models have been developed which include the appropriate diffusion terms and that are appropriate to a narrow diffusion region (∼0.01pc) that may exist at the interface between a dark core and a hot, shocked T-Tauri wind. We have assumed pressure balance throughout and have calculated the chemical abundances as functions of time and position through the interface. The results show that significant enhancements of detectable molecules/transitions are expected (e.g. CO J=6→5, OH and CH). Using a realistic value of the diffusion coefficient a diffusive region of dimension 0.01pc may be established within about 104 years. In general it seems likely that diffusion processes are highly significant on these and smaller lengthscales.
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  • 50
    Electronic Resource
    Electronic Resource
    Springer
    Boundary layer meteorology 85 (1997), S. 197-222 
    ISSN: 1573-1472
    Keywords: Turbulence ; Chemistry ; Closure ; Convective boundary layer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract We study the interactions of chemistry and turbulent mixing of tracersin the convective boundary layer with a second-order closure model,including higher order chemistry terms. In order to limit the number of predictive equations we prescribe the profiles for ¯w¯Θ, ¯w¯θ ¯θ and the lengthscale l. However, for model validation we treat temperature and humidity asinert tracers, and compare the results with profiles observed during theAir Mass Transformation Experiment, and with similarity expressions for thesurface layer. We find good agreement of the mean profiles, but the (co-)variances are slightly underpredicted. Furthermore, the model usesdiagnostic equations expressing third moments of concentration in terms ofsecond moments and their vertical derivatives. They are compared withlarge-eddy model results, showing good agreement and, therefore, thesimplifications are justified. The model is applied to the transport of two gases subject to one bimolecular reaction. The importance of concentration correlations on themean transformation rate is studied. For two gases diffusing in oppositedirections we find for moderate and fast chemistry a 50% and90% decreased transformation rate due to the negatively correlatedconcentrations. These values are similar to large-eddy results of Schumannand Sykes et al. For two bottom-up tracers we find that the covariance ofboth reactive species is either positive or negative, increasing or reducingthe effective transformation rate depending on the Damköhler number (the ratio of the turbulent and the chemistry timescale). A significantdirect influence of chemistry on the flux divergence is found in bothcases. According to the model the effective transport to mid-levels of theboundary layer is increased when two reactive tracers diffuse in oppositedirections, and decreased in the case of two bottom-up tracers.
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  • 51
    Electronic Resource
    Electronic Resource
    Springer
    Journal of science education and technology 5 (1996), S. 193-201 
    ISSN: 1573-1839
    Keywords: Chemistry ; chemistry education ; multiple intelligences ; imagery ; visual-spatial thinking
    Source: Springer Online Journal Archives 1860-2000
    Topics: Natural Sciences in General , Technology
    Notes: Abstract Chemistry has evolved from a science dominated by mathematics into a science highly dependent on spatial-visual intelligence. Yet the chemical content of introductory courses remains taught essentially the same as 40–50 years ago. Chemistry, today, is recognized by chemists as the molecular science. Yet, school chemistry is alienated from that perception. Thanks to the computer, young people are more comfortable with visual imaging than their instructors were at the same age. Thus the time is rife to reinvigorate chemistry education by means of the visual-spatial approach, an approach wholly in conformance with the way modern chemistry is thought about and practiced.
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  • 52
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2147-2156 
    ISSN: 1434-1948
    Keywords: Tetrapodal pentadentate ligand ; Ligand periphery ; Polydentate amine complex ; Nickel ; Podand ; Schiff base ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tetrapodal pentaamine ligand 2,6-bis(1′,3′-diamino-2′-methylprop-2′-yl)pyridine (1), which contains four equivalent primary amino groups, can be derivatised partly or completely by Schiff base condensation with suitable carbonyl compounds. The new ligands thus obtained are mononucleating, as shown by the X-ray crystal structures of their respective nickel(II) complexes. Reaction of 1 with 1 equiv. of salicylaldehyde and subsequent reduction allows the selective modification of one of the four sidearms. The resulting ligand 2 is hexadentate and uninegative in its nickel(II) complex {[(2)Ni]PF6} (3) with both the secondary amine and the phenoxide functionalities coordinated to the metal centre. The unreduced Schiff base form of the ligand, 4, does not form a complex with nickel(II) as readily, and only a small quantity of the mixed salt {[(4)Ni][(1)Ni(H2O)](Br)2(PF6)} (5)has been obtained. While the overall coordination of 4 resembles that of 2, there is considerably more strain in the appended chelate ring, due to the presence of the C=N double bond. Modification of one arm in 1 can also be achieved by condensation with 1 equiv. of acetylacetone, to give the new ligand 6 which, likewise, is hexadentate in its NiII complex {[(6)Ni](PF6)2} (7). In this case, however, the N/O-functional sidearm is not deprotonated. Rather, it is coordinated as the keto-imine tautomer, making 7 a rare example of a metal complex containing this structural fragment. Two-fold functionalisation of 1 is observed upon reaction with acetone, regardless of whether the ketone is present in stoichiometric amounts or in excess, to give the pentadentate ligand 8with two diagonally juxtaposed isopropylidene-imine units. The complex isolated with this ligand {[(8)Ni](PF6)2} (9) contains pentacoordinate NiII, the sixth coordination site being blocked by the rigidly positioned isopropylidene groups. When reacted with 4 equiv. of trans-cinnamaldehyde, all the primary amino groups in 1 condense to give the four-fold Schiff base 10, which acts as a pentadentate podand towards nickel(II). In this complex, {[(10)Ni(OH2)]Br2} (11), an aqua ligand completes the coordination octahedron. All ligands are stable towards hydrolysis when coordinated to the metal, despite the presence of alkyl-imine groups in some cases.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2157-2166 
    ISSN: 1434-1948
    Keywords: Septadentate N5S2-ligand ; Dinuclear complexes ; Nickel ; Reactivity ; Redox chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coordination chemistry of a series of dinickel complexes of the new septadentate amine-thiolate ligand N,N′-bis[2-thio-3-aminomethyl-5-tert-butylbenzyl]diethylenetriamine, H29, has been investigated in the context of ligand binding and oxidation state changes. The complexes [Ni2(9)(L)][ClO4]2 (10), [Ni2(9)(Cl)][Cl] (11), [Ni2(9)(L)][BPh4]2 (12), and [Ni2(9)(NCS)][OH·OH2] (13) have central N2Ni(μ-SR)2NiN′3L cores [L = labile solvent molecule (10, 12), Cl- (11), and NCS- (13)] composed of dithiolate bridged planar NiN2S2 and six-coordinate NiN′3S2L units. This is demonstrated for 11 and 13 by crystal structure determinations and for 10 and 12 by UV/Vis spectroscopy and room temperature magnetic susceptibility measurements. Complexes 10, 11, or 12 readily add other co-ligands at the NiN′3S2L fragment by substitution of the solvent molecule L (10, 12) or the chloride substituent (11). The overall structure of the parent complexes is not affected by the substitution reactions. An electrochemical study has shown that complex 10 undergoes two successive one-electron oxidations at +0.88 and +0.41 V vs SCE. The oxidized species are not thermally stable, but electronic absorption spectra and EPR spectra are indicative of the presence of NiIII species.
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  • 54
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2167-2172 
    ISSN: 1434-1948
    Keywords: Macrocyclic compounds ; Amine-Thiolate Donors ; Polynuclear Complexes ; Nickel ; Condensation reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel route to macrocyclic amine-thiophenolate ligands is described. The new, air-stable thiophenolate precursor 1,2-bis(4-tert-butyl-2,6-diformyl-phenylsulfanyl)ethane (4) is readily condensed with two equivalents of 1,2-ethanediamine or 1,3-propanediamine under medium to high dilution conditions to give 2 × 4 condensation products. The smaller 1 × 2 macrocyclic compounds are not produced under these conditions. Subsequent reduction with NaBH4 (reduction of imine groups) and Na/NH3 (reductive cleavage of aryl-alkylsulfides) provides the 36- and 40-membered amine-thiophenolate ligands H46a and H46b. The macrocyclic compounds are versatile ligands for the preparation of polynuclear transition metal complexes. With divalent nickel H46a forms the di- and tetranuclear complexes [Ni2(6a)] (7) and [Ni4(6a)][ClO4]4 (8). Reaction of 8 with four equivalents of NH4SCN yields the novel isothiocyanate complex [Ni4II(6a)(NCS)4]·10MeCN (9). The structure consists of well-separated molecules of the tetranuclear complex [NiII4(6a)(NCS)4] (Ci symmetry). Two symmetry-related binuclear [N2Ni(μ2-SR)2NiN4] fragments composed of thiolate-bridged distorted planar {N2S2Ni}- and distorted cis-octahedral {(SCN)2N2S2Ni} units reside within the cavity of the macrocycle. The intramolecular distance between the two binuclear units is 6.144(1) Å.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2173-2185 
    ISSN: 1434-1948
    Keywords: EPR spectroscopy ; Metallocenylboranes ; Organovanadium radicals ; Redox chemistry (CV) ; X-ray diffraction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The paramagnetic complexes di(mesityl)([5]trovacenyl)borane (5·), (mesityl)di([5]trovacenyl)borane (6··), and tri([5]trovacenyl)borane (7···) were prepared from [5]trovacenyllithium, (η5-C7H7)V(η5-C5H4Li), and (Mes)2BF, (Mes)BF2, and BF3, respectively. The propeller-shaped species 5·, 6··, and 7··· were subjected to X-ray diffraction with the aim of possibly correlating the twist angles with intramolecular intermetallic communication. Cyclic voltammetry points to successive vanadium-centered oxidation processes and boron-centered reduction, a small redox splitting δE1/2[(2+/+), (+/0)] being observed for 6··. According to EPR spectroscopy, performed in fluid solution, the exchange interaction J in the diradical 6·· approaches the fast-exchange region and is attenuated significantly by quaternization at boron in [6··-nBu]-. Although EPR spectroscopy of the triradical 7··· also indicates an extensive exchange interaction, the exchange parameters, derived from spectral simulation, follow the gradation J(7···) ≈ 1/3 J(6··). The magnetic susceptibility of 6·· and 7··· follows the same trend. As expected, compound 7··· exhibits spin frustration because it contains three antiferromagnetically coupled S = 1/2 systems that are arranged in an equilateral triangle.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2187-2199 
    ISSN: 1434-1948
    Keywords: Ansa compounds ; Cp-derived chelate ligands ; Neopentane chemistry ; Spiro compounds ; Tripodal ligands ; Cyclopentadienyl compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The neopentane-derived functionalized oxetane O(CH2)2C(CH3)(CH2OMs), 1, reacts with indenyllithium (LiInd) or fluorenyllithium (LiFlu) to produce the derivatives O(CH2)2C(CH3)(CH2R) (R = indenyl, fluorenyl), 2. The oxetane ring of 2 undergoes nucleophilic ring-opening by reaction with LiPR′2 to give the chiral chelate ligands (HOCH2)(CH3)C(CH2R)(CH2PR′2) (R = indenyl, fluorenyl), 5. Nucleophilic ring-opening by LiInd or LiFlu is possible too, resulting in the functionalized ansa-Cp ligands (HOCH2)(CH3)C(CH2R)(CH2R′) (R, R′ = indenyl, fluorenyl), 12. Electrophilic ring-opening of 2 with HBr to give (HOCH2)(CH3)C(CH2R)(CH2Br) (R = indenyl, fluorenyl), 3, is also possible. The alcohol function of 3 may be activated directly, whereas activation of this group in 5 is only possible after BH3 protection of the phosphane function. The mesylates (MsOCH2)(CH3)C(CH2R)(CH2Br) (R = indenyl, fluorenyl), 4, undergo, under basic conditions, spiro cyclization to produce spirocyclobutane derivatives 9 with the α-carbons of the five-membered cycles acting as the spiro centres. Substitution of the mesylate group of 4 by PR2 nucleophiles is therefore not possible. Ansa-Cp derivative (MsOCH2)(CH3)C(CH2Ind)(CH2Flu), 12c also reacts with LiPPh2 with spiro cyclization to produce 9d, instead of giving the substitution product. Tripodal ligands (CH3)C(CH2R)(CHPPh2)2 (R = indenyl, fluorenyl), 11, are accessible by the reaction of (MsOCH2)(CH3)C(CH2PPh2)2 with LiInd or LiFlu. All compounds are fully characterized by the usual spectroscopic and analytical techniques including single-crystal X-ray analyses in several cases.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2201-2207 
    ISSN: 1434-1948
    Keywords: Carboxylate syn-anti ; N-centered tripodal ligand ; Manganese ; Imidazole ; Helicoïdal inorganic chiral chain ; Magnetism ; π-π interaction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of an infinite inorganic chain consisting of MnII and an N-centered tripodal ligand N,N-(2-pyridylmethyl)[(1-methylimidazol-2-yl)-methyl]glycinate is presented. It exhibits a chiral helical structure with a pitch of two monomeric units (each monomeric unit containing one Mn atom). Each manganese is connected to its neighbor through a carboxylate bridge in a syn-anti geometry. Around each manganese center, two carboxylates bind in a cis geometry. This peculiar bridging geometry (syn-anticis) provides a broken-line chain, running in a zig-zag manner along the b axis of the P21 space group. The magnetic properties have been investigated. They show a pseudo-2D magnetic structure, with one major pathway along the chain and an inter-chain minor one. The intrachain coupling is a weak antiferromagnetic interaction (J/k = -0.25). This low value is entirely consistent with the geometry of the bridge. The interchain coupling is a weaker antiferromagnetic coupling (J′/k = -0.11) and could be mediated through π-π interactions between pyridine and imidazole from two adjacent helixes.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2221-2231 
    ISSN: 1434-1948
    Keywords: Calixarenes ; Inclusion compounds ; Imido Complexes ; Molybdenum ; Tungsten ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Syntheses, spectroscopic properties, molecular structures, and bonding of novel calix[4]arene imido compounds are described. Treatment of M(NtBu)2(NHtBu)2Ia (M = Mo), Ib (M = W) or M(NMes)2Cl2(dme) IIa (M = Mo), IIb (M = W) (Mes = 2,4,6-Me3-C6H2) with p-tBu-calix[4]arene LH4 affords calix[4]arene metal complexes LM(NR) 1a, b (M = Mo, W; R = tBu) and 2a, b (M = Mo, W; R = Mes). Analytical and spectroscopic data are consistent with monomeric structures for 1 and 2, retaining a local C4v symmetry for the calix[4]arene metal fragment. These complexes are well-suited to bind small molecules like acetonitrile, tBu-isonitrile, or water within their macrocyclic pockets. The spectroscopic data of some inclusion compounds and the crystal structures of LMo(NtBu)(NCMe) 1a(NCMe), LW(NtBu)(OH2) 1b(OH2), LW(NtBu)(CNtBu) 1b(CNt Bu), LMo(NMes)(NCMe) 2a(NCMe), and LW(NMes)(NCMe) 2b(NCMe) are reported. All complexes contain a group VI metal imido [M=NR] moiety mounted on the phenoxide rim of the calix[4]arene ligand as well as an incorporated guest molecule within the cavity. Some insights into the structures of complexes of the type L′W(NR′) (L′ = p-H-calix[4]arene; R′ = H, Me) and into bonding in these compounds are provided by density functional theory, applying the B-P86 density functional and an all SVP basis set within the RI-J-DFT approximation. At least one π bond is of importance for calix[4]arene-metal bonding in these compounds. The metal-imido bond can be described as a triple bond. A geometrically optimized minimum structure of L′W(NMe) 4 shows a calix[4]arene ligand only slightly distorted from a local C4v symmetry and an almost linear tungsten-imido moiety.
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  • 59
    ISSN: 1434-1948
    Keywords: Arsonium salts ; Superacidic systems ; Structure elicidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of trimethylarsane in the superacidic systems hydrogen/fluoride antimony pentafluoride and hydrogen fluoride/arsenic pentafluoride leads to trimethylarsonium fluorometallates. These salts are stable up to 60 °C and 5 °C, respectively. Structures were successfully elucidated in the cases of trimethylarsonium undecafluorodiarsenate and trimethylarsonium hexafluoroantimonate. (CH3)3AsH+As2F11- crystallizes in the monoclinic space group P21/n with four formula units per unit cell with the dimensions a = 7.362(1), b = 12.589(1), c = 13.598(1) Å and β = 95.37(1)°. (CH3)3AsH+SbF6- crystallizes in the monoclinic space group P21/m with four formula units per unit cell with the dimensions a = 8.313(1), b = 8.855(1), c = 13.285(1) Å and β = 94.358(1)°.
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    ISSN: 1434-1948
    Keywords: Molybdenum ; μ-Oxo ; Conformational equilibrium ; X-ray diffraction ; NMR spectroscopy ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new thiocyanatomolybdenum(VI) dioxo-μ-oxo complex dimer bearing a 4,4′-di-tert-butyl-2,2′-bipyridine ligand (2) is shown to exist in the crystal cell unit as a meso (Mo-O-Mo angle of 180°) and d,l, pair (Mo-O-Mo angle of 155.7°). These conformers are in equilibrium in solution and have been observed clearly by 1H NMR spectroscopy.
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  • 61
    ISSN: 1434-1948
    Keywords: Macrocycles ; Lithium ; Fluorescence ; Cryptands ; Coordination ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three aza-cages with the anthracene-containing photoactive groups L1, L2, and L3 have been synthesized. All compounds are able to selectively encapsulate a lithium ion and solid complexes have been isolated. The formation equilibria have been investigated by UV/Vis and 1H, 13C and 7Li NMR spectroscopic techniques. The fluorescence emission of both free ligands and lithium complexes have been investigated. Results indicate that the CHEF (chelation enhancement of the fluorescence) effect obtained by lithium coordination exits although lower than that occurring upon full protonation.
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  • 62
    ISSN: 1434-1948
    Keywords: Copper ; Trinuclear complexes ; Formamidines ; Magnetism ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three new copper(II) linear trinuclear compounds are reported, all of which were synthesized in-situ, with the general formula [Cu3(L)4](CF3SO3)2(Y)x, where L is the dehydronated ligand: N,N′-bis(pyridine-2-yl)formamidine (abbreviated as Hpdf), N,N′-bis(pyrimidine-2-yl)formamidine (abbreviated as Hpmf) and N,N′-bis(5-methylpyridine-2-yl)formamidine (abbreviated as Hmpdf), Y = EtOH or H2O and x = 0.5-1.5. The compounds were characterized by X-ray diffraction, IR, LF, and EPR spectroscopy and by magnetic susceptibility down to 4 K. The structure of the compound [Cu3(pmf)4](CF3SO3)2(H2O)1/2 was determined by X-ray crystallography; it was found to crystallise in the triclinic space group P-1 with a = 8.529(5), b = 15.760(5), c = 19.639(5) Å, α = 101.793(5), β = 101.263(5), γ = 102.389(5)°, Z = 2. The structure [Cu-Cu-Cu angle 174.96(11)°] consists of four nearly flat molecules of the ligand, which contribute to the propeller-type structure around the Cu-Cu-Cu axis. A strong antiferromagnetic interaction between the CuII ions is observed with calculated J values, based on the Hamiltonian H = -2J(S1·S2 + S2·S3) - 2J′·S1·S3, of -174(1) cm-1, -120(1) cm-1, and -167(1) cm-1 for the compounds studied with L = pdf, pmf, and mpdf, respectively. These values are in agreement with an S = 1/2 ground state below temperatures of 120-160 K.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2277-2281 
    ISSN: 1434-1948
    Keywords: Boron ; Iron ; Nickel ; Carbyne complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The μ3-boryloxycarbyne complexes [{Fe(CO)3}3{μ3-COBCl{NtBu(SiMe3)}}2] (1) and [{(η5-C5H5)Ni}3{μ3-COBX(NR2)}μ3-CO] (2a: NR2 = NtBu(SiMe3), × = Cl; 2b: NR2 = N(SiMe3)2, × = Cl; 2c: NR2 = NMe2, × = BNMe2Cl) were obtained by reaction of the anionic complexes K2[{Fe(CO)3}3{μ3-CO}2] and K[{(η5-C5H5)Ni(CO)] with the corresponding chloroboranes Cl2BNR2 {NR2 = NtBu(SiMe3), N(SiMe3)2}, or 1,2-dichlorodiboranes(4) B2(NMe2)2Cl2, respectively. The products are formed by a nucleophilic attack of the CO oxygen atom at the boron centres with subsequent salt elimination. All compounds were characterized by IR and multinuclear NMR spectroscopy, and the structures of 1 and 2c in the solid state were determined by single-crystal X-ray diffraction studies.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1271-1279 
    ISSN: 1434-1948
    Keywords: Chirality ; Dinuclear complexes ; Rhodium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dinuclear and polynuclear metal complexes with octahedral centers coordinated to di- or polydentate ligands are often obtained as complicated mixtures of various stereoisomers. Stereospecific synthesis of such species is therefore of high current interest. Chiral derivatives of pyridine can be used for this purpose. Dinuclear μ-chloro-bridged RhIII complexes with two didentate, cyclometalated thienylpyridine-type ligands at each metal center are formed stereoselectively when pinene groups are fused to the pyridine rings. The two octahedral RhIII centers have homochiral configurations, ΔΔ and ΛΛ. The heterochiral diastereomer ΔΛ is not observed. With (8R,10R)-2-(2′-thienyl)-4,5-pinenopyridine [Hth4,5-(R,R)ppy] the ΔΔ to ΛΛ ratio is 9:1 when the separation eluent contains NaCl. Modeling the ΛΛ and the ΔΛ isomers of the dinuclear species shows crowding of the pinene groups in both cases; however, the strain can be released by relatively small distortions only in the case of the ΛΛ isomer. NO3- cleaves the dichloro bridge, yielding the mononuclear species Δ[Rh(L2)2(NO3)] (2) in a completely stereoselective manner when NaCl is replaced by KNO3 in the eluent mixture. The molecular structure has been determined by X-ray structure analysis for both the ΔΔ and the mononuclear complex Δ[Rh(L2)2(NO3)] (2) in order to confirm the configuration at the metal center. 1H-NMR, 13C-NMR and CD spectra were measured and the latter shows that the CD activity is solely due to the chirality at the metal center.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1281-1289 
    ISSN: 1434-1948
    Keywords: Phosphaalkynes ; Dimerization mechanism ; Diphosphacyclobutenes ; Density functional theory ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dimerization of phosphaalkynes (R-C≡P, R = H, Me, tBu) without and with the presence of transition metal fragments, including CpCo (Cp = cyclopentadienyl) and COT-Ti (COT = cyclooctatetraene), has been probed using density functional theory calculations (B3LYP with different basis sets). MP2 and CCSD(T) calculations were also performed for the [H2C2P2] systems. In an attempt to address the exciting controversy and uncertainty about phosphaalkyne dimerization, a number of dimer formation mechanisms proposed in the literature have been examined. Some new and plausible intermediates have also been identified.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1315-1324 
    ISSN: 1434-1948
    Keywords: Ab initio calculations ; EHMO ; Vinylidene complexes ; Cobalt ; Rhodium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transformation of acetylene into vinylidene, as promoted by the metal fragment [(pp3)Co]+ [pp3 = P(CH2CH2PPh2)3], is unimolecular and features the hydride-acetylide species as an intermediate. The paper describes a detailed ab initio study of the reaction, in particular with regard to the step involving 1,3-H shift. The best computational results are obtained by mimicking the pp3 ligand with actual ethylenic chains rather than with single PH3 molecules. The keypoints along the two-step reaction path (π-acetylene, hydride-acetylide, and vinylidene complexes, as well as intermediate transition states) have been optimized for CoI and RhI derivatives at the MP2 level. For the fragment [(pp3)Co]+, the barrier associated with transformation of the hydride-acetylide intermediate to vinylidene (20.6 kcal/mol) is easier to surmount compared to that for reversion to the reactants (28.6 kcal/mol). The situation is reversed for the analogous RhI system, with the initial π-acetylene adduct being slightly more stable. Although higher in energy, the hydride-acetylide species is the experimentally detected product of the reaction of acetylene with the fragment [(pp3)Rh]+. The salient chemical aspects of the 1,3-H shift are discussed in terms of perturbation theory arguments. Parallel EHMO calculations, which have provided a relatively good consistency with the ab initio results, allow the proposal of an orbital rationale for the mode of migration of the hydride ligand along the substantially linear Co-Cα-Cβ grouping.
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1335-1342 
    ISSN: 1434-1948
    Keywords: Photolysis ; Alkynes ; Matrix isolation ; DFT ; Oxygenations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photolytically-induced reactions of chromyl chloride with acetylene and but-2-yne (dimethylacetylene) in low-temperature argon matrices yield end-on ketene and dimethylketene complexes of O=CrCl2, respectively. The product formation probably results from an electrophilic attack of a Cr=O linkage on the C≡C triple bonds, leading to radical-like transition states or intermediates, which subsequently rearrange through 1,2-H or 1,2-methyl shifts. Consequently, allene is attacked at its central carbon and the allyl radical thus generated undergoes subsequent ring-closure to give a cyclopropanone complex of O=CrCl2.
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  • 68
    ISSN: 1434-1948
    Keywords: Copper chelates ; EPR spectroscopy ; Electronic structure ; Schiff base ligands ; Structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of tetrahedrally distorted copper(II) complexes with thiolate and imine coordination were synthesized. Schiff bases derived from 4-benzoyl-3-methyl-1-phenyl-2-pyrazoline-5-thione and various diamines were used as tetradentate ligands to obtain tetrahedrally distorted metal chelates with [CuN2S2] complex units. Crystal structures of the complexes 1, 2, 5 and 6 and of ligand H25 have been determined by means of single-crystal X-ray structure analysis. The structure data show a strong influence of the diamine building blocks on the tetrahedral distortion of the copper(II) complexes. Results of Extended Hückel LCAO calculations correlate strongly with structural, electrochemical, UV/Vis- and EPR-spectroscopic features obtained experimentally. The calculations confirm for the whole complex series a strong delocalization of the frontier orbitals. The highest fully occupied molecular orbital shows a weak contribution, resulting from thiolate donor atoms, whereas the antibonding singly occupied molecular orbitals (SOMOs) are distributed between the copper(II) centre (ca. 35-40%) and the N2S2 donor set. The SOMO energy significantly lowers with increasing tetrahedral distortion of the coordination sphere. The influence of the tetrahedral distortion of copper(II) complexes on redox potentials, UV/Vis and EPR spectra is discussed.
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  • 69
    ISSN: 1434-1948
    Keywords: Half-sandwich complexes ; Molybdenum ; Optically active complexes ; Rhenium ; Tungsten ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of (η5-PinCp*)Re(CO)3 [PinCp* = tetramethyl(pinanyl)cyclopentadienyl] is described. Successive substitution of two CO ligands by NO+ and PPh3 generates a 1:1 diastereomeric mixture of chiral-at-metal [(SRe)/(RRe)-(PinCp*)Re(CO)(NO)(PPh3)]BF4. The diastereomers are converted with sodium methoxide into the derivative “esters” (SRe)/(RRe)-(PinCp*)Re(COOCH3)(NO)(PPh3), and then with (+)-(R)-(1-naphthylethyl)amine to the “amides” (SRe)/(RRe)-(PinCp*)Re(NO)(PPh3)[CONHCH(CH3)C10H7] [(SRe)/(RRe) = 1:1]. Fractional crystallisation separates the (SRe) isomer with an optical purity of 〉 98%. The latter compound has been characterized by X-ray structure analysis. By treating the (SRe)-amide with CF3CO2H and NaBF4, (SRe)-(PinCp*)Re(CH3)(NO)(PPh3) can be generated. Protolysis of this compound with HBF4/Et2O in CD2Cl2 at -78 °C leads to the solvent-stabilized complex (SRe)-[(PinCp*)Re(NO)(PPh3)(ClCD2Cl)]+BF4-. The thermal and configurational stability of this chiral Lewis acid is investigated at various temperatures. The syntheses of [PinCp*RhCl2]2, PinCp*TiCl3 and PinCp*M(CO)2(NO) (M = Mo, W) are also described. Starting with PinCp*M(CO)2(NO), the relatively stable 16-VE complexes PinCp*MCl2(NO) and PinCp*W(CH2SiMe3)2(NO) are synthesized.
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  • 70
    ISSN: 1434-1948
    Keywords: 2,2′-Bipyridines ; Chelate complexes ; Hydrogen bonding ; π-π stacking ; Crystal structure ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new synthetic route for the synthesis of 5,5′-diamino-2,2-bipyridine (5) based on the coupling of 2-chloro-5-aminopyridine in the presence of NiCl2 × 6 H2O/PPh3/Zn in dimethylformamide is described. The reactions of the potentially ambidentate ligand 5 with salts of the transition metals Mn, Fe, Ni, Cu, Zn, Ag, and Cd gave a variety of 13 metal-ligand complexes depending on the anion, the crystallization conditions and the metal-to-ligand ratio. The complexes obtained were characterized by thermal analyses, NMR including 113Cd-NMR, IR, and for the iron complex 57Fe-Mößbauer spectroscopy. The structure of eight of the compounds was elucidated by X-ray crystallography. All of these metal complexes show a bipyridine-metal coordination. The amino functionality was never involved in metal coordination. The intermolecular arrangement is dictated by hydrogen bonding from the amino functionality and by π-π stacking of the bipyridine rings.Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2005/1999/99078_s.pdf or from the author.
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  • 71
    ISSN: 1434-1948
    Keywords: Iron(III) ; Peroxo Complexes ; Kinetics ; Hydrogen Peroxide ; Catalase ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new diiron complex [Fe2(tbpo){O2As(CH3)2}(CH3O)(CH3OH)](ClO4)3 · 5 CH3OH · 2 H2O (1) containing a (μ-alkoxo)(μ-dimethylarsinato)diiron(III) core was synthesized using the heptadentate ligand N,N,N′,N′-Tetrakis(2-benzimidazolylmethyl)-1,3-diamino-2-propanol (Htbpo). The complex was characterized structurally by X-ray crystallography. 1reproduces the coordination mode and the stoichiometry of the proposed purple acid phosphatase-arsenate inhibitor complex. More importantly, 1 is a good functional model for the activation of small molecules, since the solvent molecule in the coordination sphere of each iron ion can be substituted very easily by a small substrate molecule. This is confirmed by the comparatively high pH-dependent catalase-like activity of 1. In order to study the influence of the cacodylate bridge on the formation of the metastable adduct with hydrogen peroxide, the analogous hydroxo-bridged complex [Fe2(tbpo)(OH)(NO3)2](NO3)2 · CH3OH · 2 H2O (2) was employed. The reactions of 1and 2 with H2O2 were studied as a function of [H2O2], pH, temperature, and pressure, and the kinetic results including the activation parameters are reported. In the case of compound 2 the reaction proceeds in one step, and the observed first order rate constant, kobs, shows a linear dependence on the hydrogen peroxide concentration with a zero intercept. For complex 1 the kinetic traces could be fitted to two exponential functions. One of the observed pseudo-first-order rate constants, kobs1, exhibits a linear dependence on the hydrogen peroxide concentration with a zero intercept, whereas the other rate constant, kobs2, was independent of the hydrogen peroxide concentration. A mechanistic interpretation is presented.Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2005/1999/99068_s.pdf or from the author.
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  • 72
    ISSN: 1434-1948
    Keywords: Ruthenium ; Coordination chemistry ; Paramagnetic complexes ; Magnetic properties ; Ion exchange ; Antitumor agents ; Colon tumors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Indazolium trans-tetrachlorobis(indazole)ruthenate(III) exhibits excellent results against different tumor models in vitro and in vivo. To improve the water solubility necessary for the introduction of this tumor-inhibiting compound into clinical trials, we synthesized the corresponding sodium salt in a two-step ion exchange via the tetramethylammonium salt. The sodium salt shows a 35-fold higher solubility in water relative to the indazolium salt. We also synthesized the n-butylammonium, n-octylammonium, and tetraphenylphosphonium salts, all of which showed improved solubility in organic solvents. The X-ray crystal structure of the latter could be solved, proving the trans configuration of the complex anion. In spite of the paramagnetic RuIII center an assignement of the coordinated indazole protons could be made with the help of a COSY experiment.
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  • 73
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    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2355-2368 
    ISSN: 1434-1948
    Keywords: Phosphane complexes ; Lithium ; Aminophosphanes ; Hydrazides ; (N-lithioamino)diorganophosphanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Butyllithium (nBuLi) deprotonates Ph2P-NHtBu in ether to give (Ph2P-NLitBu)2·OEt2. There is no Li···P interaction in this molecule. Three compounds of the type R′P(NLiR)2 have been obtained by lithiation of R′P(NHR)2, isolated as [BuP(NLitBu)2·OEt2]2, [PhP(NLiPh)2·OEt2]2 and [PhP(NLiPh)2]2. Reaction of nBuLi with MeP(NHiPr)2 in hexane/THF leads to [MeP{N(Li)iPr]2·THF}4 with an asymmetric cluster structure comprising one LiP3, three LiPN2, three LiP2N and one LiN3 cluster units. The molecular structures of these compounds as determined by X-ray structure analysis show that they are best depicted as N-lithioaminophosphanes and not as the isomeric P-lithioiminophosphoranes.
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  • 74
    ISSN: 1434-1948
    Keywords: Alkylation ; Carbonyl complexes ; Lewis acids ; Phosphaalkenes ; Protonation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of the carbonyl-functionalized phosphaalkenes RC(O)P=C(NMe2)2 [R = tBu (2a), Ph (2b)] with protic acids and alkylating reagents occurred at the two-coordinate phosphorus atom to give the phosphanyl-substituted carbocations 3a,b and 4a,b. In contrast, treatment with Me3SiOSO2CF3 resulted in attack at the oxygen atom by the silyl group, and the formation of [RC(OSiMe3)=PC(NMe2)2]SO3CF3 (5a,b). Similarly, the Lewis acids B(C6F5)3, Al(tBu)2Cl and AlMe3 were ligated to the oxygen atom of the carbonyl group. Two equivalents of GaMe3 were added to the oxygen and phosphorus atom of the phosphaalkene to yield the thermolabile complexes [RC(OGaMe3)=P(GaMe3)C(NMe2)2] (10a,b). In contrast, one molecule of InMe3 was bound to the phosphorus center of the phosphorus compound. Reaction of the phosphaalkenes with [Ni(CO)4], [Fe2(CO)9] or [{(Z)-cyclooctene}Cr(CO)5] also took place at the pnictogen atom, resulting in complexes of the type [RC(O)P{M(CO)n}C(NMe2)2] (R = tBu, Ph; M = Ni, n = 3; Fe, n = 4; Cr, n = 5). The chemical transformations reported here underline the versatile chemistry of phosphaalkenes and emphasize a relationship between carbonyl-functionalized phosphaalkenes and the well-investigated class of phosphorus ylides. X-ray structures of compounds 6b, 7b*, 10a, 11a and 12a are reported.
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    AIChE Journal 41 (1995), S. 185-189 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 76
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    AIChE Journal 41 (1995), S. 190-194 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 41 (1995), S. 58-67 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Theoretical models of gas diffusion and permeation in microporous molecularsieve membranes are presented. The effect of the adsorbed diffusant on the total transmembrane flow is insignificant for permanent gases. For highly adsorbable gases the effect of the adsorbed molecules on the total transmembrane flux may be high at low temperatures. The activation energy of diffusion increases when the kinetic diameter of the diffusant increases. The activation energy of gas diffusion compares well with the values calculated based on the Lennard-Jones potential. Maximum possible permeability coefficients calculated for He in the molecular-sieve membranes do not exceed ˜30,000 Barrer at room temperature. The experimentally observed value for He permeability is ˜1,000 Barrer (T=30°C) because of the high tortuosity (τ≍ 25) and low porosity (θ = 0.22) of the membrane porous structure.
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  • 78
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    AIChE Journal 41 (1995), S. 68-77 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A pH-stat MSMPR crystallizer is used to obtain the nucleation rate equation of calcite formed in the Na2CO3-CaCl2 reacting system. The experiments are conducted for seeded and unseeded runs. Effects of breakage and agglomeration on the crystalsize distribution are demonstrated. In a continuous operation, the agglomeration of nuclei followed by the breakage of agglomerates occurs at the transient state, while the agglomeration is significant at the steady state. Taking crystal agglomeration into account, the corrected nucleation rate and agglomeration rate are obtained simultaneously. The agglomeration rate is a function of relative supersaturation and magma density, and the corrected nucleation rate is approximately two- to five-fold of the apparent nucleation rate, which is the nucleation rate without considering the agglomeration effect. Discussed also is the formation of calcium carbonate polymorphism.
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  • 79
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    AIChE Journal 41 (1995), S. 135-147 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Research on exothermic reactor operation has been based mostly on the classic two-state continuous stirred tank reactor model, implicitly assuming that the cooling jacket temperature dynamics are negligible. In this case, the cooling jacket temperature is the manipulated input instead of the cooling jacket flow rate for feedback control of reactor temperature. Adding a cooling jacket energy balance results in much more complex behavior than a simple lag effect. A stabilizing inner-loop cascade controller is assumed in the two-state CSTR model, because the three-state model incorporating cooling jacket temperature dynamics may be open-loop unstable when the two-state model is open-loop stable. The influence of design parameters on the multiplicity behavior of a three-state model is considered. Elementary catastrophe theory is used to study the effect of process parameters such as the cooling jacket flow rate, heat-transfer coefficient, heat of reaction, and cooling jacket feed temperature on the steady-state multiplicity of the three-state model. This multiplicity analysis is particularly relevant for control because the primary bifurcation parameter is the cooling jacket flow rate, the manipulated input for feedback control in the three-state model. This multiplicity analysis guides improvements in process design and/or operation to eliminate difficult operating regions associated with steady-state multiplicities; the presence of multiple steady states results in safety and operation problems due to ignition/extinction phenomena. Reactor scale-up affects the presence of these infeasible reactor operating regions. Certain design parameter changes that remove multiplicities in the two-state model cannot remove multiplicities in the three-state model.
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  • 80
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    AIChE Journal 41 (1995), S. 346-356 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Brownian and molecular dynamics simulations are used to study rapid bimolecular reactions at near-infinite dilution in near-critical and supercritical fluids. We probe the dynamics of both nonreactive and reactive collisions and measure rate constants for reaction and collision. Collision rate constants are nearly independent of bulk solvent density, but affected by local solute-solute density enhancements at a given density: their magnitudes depend on the length scale for molecular encounters (cybotactic radius) in the reaction through the equilibrium solute-solute radial distribution function. In contrast, reaction rate constants asymptotically approach the gas-kinetic limit at low densities and the Smoluchowski liquid-like limit at high densities. They also display the same radial dependence as collision rate constants at lower densities and a direct dependence on the cybotactic radius at higher densities (as in the Smoluchowski theory). Their behavior is explained in terms of a transition from a collision-limited regime at low densities to a diffusion-limited regime at higher densities. The transition between these regimes depends on the cybotactic radius and the density of the system, the interplay of which causes shifts in the transition region which depend not only on the properties of the near-critical solvent: they differ for different reactions, even at the same solvent density. This explains some of the apparent inconsistencies among previous experimental and computational studies of reactions in supercritical fluid media.
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    AIChE Journal 41 (1995), S. 402-414 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Many motile bacteria exhibit chemotaxis, the ability to bias their random motion to ward or away from increasing concentrations of chemical substances which benefit or inhibit their survival, respectively. Since bacteria encounter numerous chemical concentration gradients simulatneously in natural surroundings, it is necessary to know quantitatively how a bacterial population responds in the presence of more than one chemical stimulus to develop predictive mathematical models describing bacterial migration in natural systems. This work evaluates three hypothetical models describing the integration of chemical signals from multiple stimuli: high sensitivity, maximum signal, and simple additivity. An expression for the tumbling probability for individual stimuli (Brown and Berg, 1974) is modified according to the proposed models and incorporated into the cell balance equation for a 1-D attractant gradient (Ford and Cummings, 1992). Random motility and chemotactic sensitivity coefficients, required input parameters for the model, are measured for single stimulus responses. Theoretical predictions with the three signal integration models are compared to the net chemotactic response of Escherichia coli to co- and antidirectional gradients of D-fucose and α-methylaspartate in the stopped-flow diffusion chamber assay. Results eliminate the high-sensitivity model and favor the simple additivity over the maximum signal. None of the simple models, however, accurately predict the observed behavior, suggesting a more complex model with more steps in the signal processing mechanism is required to predict responses to multiple stimuli.
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    AIChE Journal 41 (1995), S. 426-429 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 41 (1995), S. 439-443 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 84
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    AIChE Journal 41 (1995), S. 446-455 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Studies of heat and mass transfer in packed beds, which disagree substantially in their findings, have nearly all been done with beds of regular particles of uniform size, whereas oil-shale retorting involves particles of diverse irregular shapes and sizes. We, in 349 runs, measured mass-transfer rates from naphthalene particles buried in packed beds by passing through air at room temperature. An exact analogy between convection of heat and mass makes it possible to infer heat-transfer coefficients from measured mass-trans-fer coefficients and fluid properties. Some beds consisted of spheres, naphthalene and inert, of the same, contrasting or distributed sizes. In some runs, naphthalene spheres were buried in beds of crushed shale, some in narrow screen ranges and others with a wide size range. In others, naphthalene lozenges of different shapes were buried in beds of crushed shale in various bed axis orientations. This technique permits calculation of the mass-transfer coefficient for each active particle in the bed rather than, as in most past studies, for the bed as a whole.The data are analyzed by the traditional correlation of Colburn jD vs. Reynolds number and by multiple regression of the mass-transfer coefficient on air rate, sizes of active and inert particles, void fraction, and temperature. Principal findings are: local Reynolds number should be based on the active-particle size, not the average for the whole bed; differences between shallow and deep beds are not appreciable; mass transfer is 26% faster for spheres and lozenges buried in shale than in all-sphere beds; orientation of lozenges in shale beds has little or no effect on mass-transfer rate; and for mass or heat transfer in shale beds, log(j·∊) = - 0.0747 - 0.6344logNRe + 0.0592log2 NRe.
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    AIChE Journal 41 (1995), S. 456-468 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The thermodynamics and transport properties of Lennard-Jones particles in pillared catalytic clays are studied by molecular dynamics simulation. The clays are represented by parallel sheets separated by a given distance and connected by pillars of a given size. Two different spatial distributions of the pillars are studied to determine their effect on the properties of the system. Calculations did not indicate a strong dependence of the diffusivity on the spatial distribution of the pillars, except at low porosities. The solvation force increases monotonically with decreasing porosity of the clays and increasing density of the molecules. The percolation threshold ϕc of the system is estimated from the diffusivity measurements in the limit of infinitely low sorbate densities. Near ϕc the diffusivity D vanishes according to the power law, D ˜ (ϕ - ϕc)n, where ϕ is the porosity of the system, and n is a universal constant. The simulations yield n ⋍ 1.7. Since 2- percolation systems require n ⋍ 1.3 and 3-D systems n ⋍ 2.0, pillared clays behave as a system with an effective dimensionality between 2 and 3.
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    AIChE Journal 41 (1995), S. 337-345 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The monolith froth reactor, involving two-phase flow and a monolith catalyst, is developed. The flow within monolith channels, consisting of trains of gas bubbles and liquid slugs, is produced by forming a two-phase froth in a chamber immediately below the bottom of the monolith. The froth then flows upward into the monolith channels through pressure forces, which differs from previous methods since it may be carried out for a commercial-scale reactor. Because the liquid film which develops between the gas phase and the surface of the catalyst is extremely thin, two-phase flow within a monolith can provide reaction rates which are near their intrinsic values. Catalytic oxidation of aqueous phenol over copper oxide supported on γ-Al2O3 is used as a model reaction for investigating reactor performance. Generation of a froth is confirmed by visual inspection; the average bubble size is approximately that predicted by a force balance. The effect of externally controllable process variables (liquid and gas flow rates, temperature, and pressure) on the rate of phenol oxidation was investigated. Reaction rate increases with temperature or pressure increase and decreases with gas flow rate increase, achieving a maximum with respect to liquid flow rate. The activation energy calculated from the apparent reaction rate measured in the monolith froth reactor is similar to that of intrinsic value, suggesting minimal mass-transfer limitations.
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  • 87
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    AIChE Journal 41 (1995), S. 377-388 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A thermogravimetric analyzer is used to study the synthesis of TiN from Ti powder over a wide range of temperature, conversion and heating rate, and for two Ti precursor powders with different morphologies. Conversions to TiN up to 99% are obtained with negligible oxygen contamination. Nonisothermal initial rate and isothermal data are used in a nonlinear least-squares minimization to determine the most appropriate rate law. The logarithmic rate law offers an excellent agreement between the experimental and calculated conversions to TiN and can predict afterburning, which is an important experimentally observed phenomenon. Due to the form of the logarithmic rate law, the observed activation energy is a function of effective particle size, extent of conversion, and temperature even when the intrinsic activation energy remains constant. This aspect explains discrepancies among activation energies obtained in previous studies. The frequently used sedimentation particle size is a poor measure of the powder reactivity. The BET surface area indicates the powder reactivity much better.
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    AIChE Journal 41 (1995), S. 430-434 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 41 (1995), S. 435-438 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 41 (1995), S. 501-508 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A primary method of reducing membrane fouling during cross-flow microfiltration is periodic reverse filtration. This in situ method of cleaning the membrane forces clear fluid in the reverse direction through the membrane and readjusts the particle or solute accumulation on the retentate side of the membrane. This work focuses on the design of a high-frequency, reverse-filtration strategy to maximize the flux for washed yeast suspensions through 0.2- μm cellulose acetate flat sheet membranes. Several experiments were conducted with reverse-filtration times ranging from 0.5-4 s and forward-filtration times ranging from 1-40 s. For every back-filtration time, there exists an optimum forward-filtration time that gives the maximum global average flux. The optimum average flux increases with decreasing back filtration times and feed concentrations, but shows little dependence on cross-flow velocity and reverse filtration transmembrane pressure. The optimum flux with rapid backflushing is 20 to 30 times higher than the long-term flux in the absence of backflushing. A theory presented assumes that cake formation during forward filtration follows dead-end filtration theory and the cake is instantly removed during reverse filtration. The measured average flux per cycle follows the trends predicted by the theory, but the measured values exceed the predictions, presumably due to brief delays in cake removal and cake formation at the start of reverse and forward filtration, respectively, during each cycle.
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    AIChE Journal 41 (1995), S. 868-879 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Fluidized-bed polyethylene reactors are prone to unstable behavior and temperature oscillations (Choi and Ray, 1985b). Their work is extended to show the effects of ethylene feed system operation, reactor cooling system design, catalyst properties, and gas composition on reactor stability and dynamics. The analysis is performed using a well-mixed model, because heat- and mass-transfer resistances between multiple phases are small and are not required to account for the observed bifurcation phenomena. The addition of a gas recycle and heat exchanger system to the model significantly affects dynamic performance, including the formation of limit cycles. The size and dynamics of the heat exchanger, however, have little effect on the overall stability. In contrast, automation of the ethylene feed system to replace the monomer in the reactor as it is consumed leads to substantially different dynamic behavior than if the ethylene feed is maintained at a constant rate. Catalyst properties (multiple sites, activation energy, and deactivation) significantly affect dynamics and stability, whereas comonomer and other gases affect them only mildly. The results confirm that without proper temperature control, gas-phase polyethylene reactors are prone to instability, limit cycles, and excursions towards unacceptable high-temperature steady states.
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    AIChE Journal 41 (1995), S. 924-927 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The Maxwell equal area rule is a basic construct for determining saturated phase volumes from equations of state. The fundamental idea is that for a pure substance a horizontal line drawn through the trace of an isotherm, which equalizes the van der Waals loops area above and below the line, intersects the isotherm at the saturated volumes.Another basic construct exists for determining the phase compositions in a binary mixture by establishing the tangent line to the total Gibbs energy curve plotted against composition. We demonstrate that finding the tangent also reduces to an equal area construction for the derivative of the total Gibbs energy plotted against composition. An efficient algorithm suggested effects such equal area determinations. The trial-and-error procedure normally converges in one to three steps to the correct solution given any resonable starting guess. Implementation using modern calculators with graphics capabilities is simple and straightforward.
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  • 93
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 959-973 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The interaction between a winter flounder antifreeze polypeptide and an ice/water interface was studied using Molecular Dynamics computer simulation techniques to study the mechanism of action of this class of antifreeze molecules. Simple Point Charge models were used for the water molecules, and a molecular mechanics program (CHARMM) was used to construct the model for the polypeptide. A (2021) face was exposed on the ice surface, as this is believed to be the experimentally favored ice face for peptide binding. The polypeptide binds strongly to the ice surface even though it was placed with its four polar threonine (Thr) groups pointing away from the ice surface. This tested the previously advanced hypothesis that adsorption occurs primarily between these groups and the ice due to a matching of the spacing between oxygen atoms in the ice lattice and the polar Thr residues. As well as contacts with other polar groups on the peptide, the binding to the ice produces a good steric fit of the peptide with the corrugated ice interface. The presence of the peptide did not induce any melting of the ice at 200 K.
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  • 94
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 985-990 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Computer simulation studies of refolding pathways and the formation of intermediates for a simple, 2-D lattice protein model are presented. The sequence of the 20-bead model protein chain is chosen so that hydrophobic beads will reside in the protein interior in the native state. Nonbonded hydrophobic beads attract each other with strength ∊ decreasing the |∊/kT| mimics increasing the concentration of the denaturant. Dynamic Monte Carlo simulations and exhaustive conformational searches have been performed on an isolated model protein sequence at different levels of |∊| (different denaturant concentrations). As the denaturant is withdrawn, the model protein exhibits a transition from a random coil state to a compact native state with a hydrophobic core. The refolding process is observed to be cooperative in that the chain does not start folding until the middle section has folded correctly, and proceeds along preferred pathways that are populated by distinct, partially folded intermediates.
    Additional Material: 9 Ill.
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  • 95
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 974-984 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A theoretical model for investigating physical phenomena underlying immune complex formation was developed, based on the statistical mechanical theory of associating fluids that identifies each molecule as a hard sphere with a nested point charge and vector dipole. The interaction between binding molecules (epitope-paratope binding) is represented as a cone truncated by two concentric spheres in which the potential energy is a modified square well with respect to particle separation and a square well with respect to mutual molecular orientation. Equilibrium binding results predicted by the model show good agreement with results obtained experimentally for a model system containing a single antigen and a single monoclonal antibody [bovine serum albumin (BSA) - anti-BSA antibody]. Moreover, values obtained for the system isothermal compressibility and the second virial coefficient by both the model and light scattering experiments also show good agreement with one another.
    Additional Material: 10 Ill.
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  • 96
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 855-867 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: For a triplet competitive-consecutive halogenation sequence forming mono-, di- and trihalogenated products of the form, A + B → R + B → S + B → T, under semibatch operation adding B to A, if perfect mixing could be assumed at all scales, the product distribution would be unchanged on scaling up. However, if the reaction rates are reasonably faster than the mixing rate, the semibatch addition of B to A will be imperfectly backmixed, exhibiting macroscale concentration gradients. This partial segregation of the primary reagents is capable of modifying the selectivity and corresponding appearance of R, S and T in the course of the batch. Imperfect mixing is quantified using the networks-of-zones model. The effect of scaling up at equal tip speed is examined for a lab-scale 0.3-dm3 reactor, a semitech 30-dm3 reactor, and a production-scale 3,000-dm3 vessel. The intensity of partial segregation is weak at the lab scale, but very severe at the production scale. The lab-scale reactor is therefore close to perfectly backmixed, and the primary, secondary and tertiary products appear in sequence. At the semitech scale the increased partial segregation causes the final product to initially precede the secondary product paradoxically but lag the initial product. At the large scale the more severe segregation between A and B gives an even greater paradox, whereby the final product appears ahead of both the primary and secondary ones. The segregated concentration fields of A and B are visualized as sectional image reconstructions for networks comprising on the order of 1,000 zones. Localized intensive plumes of B emanating from the addition point cause the paradoxical reversals of product sequences. The calculations are directly relevant to real industrial miscible liquid halogenations for which product distribution paradoxes have been observed (Haywood, 1990).
    Additional Material: 14 Ill.
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  • 97
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 907-914 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Microporous solids made by polymerizing the organic phase of bicontinuous microemulsions stabilized with didodecyldimethylammonium bromide show surface areas as high as 70 m2/g. Small-angle X-ray scattering measurements on microporous copolymers containing polymethylmethacrylate show that these areas result from structures larger than 250 Å that are generated during polymerization. These X-rays measurements also show that the 17-Å structures characteristics of the original microemulsion are retained during polymerization, but destroyed when the detergent is extracted and the solid is dried.
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  • 98
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 938-947 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method-based on evaporation of a constant-composition droplet containing two components that differ markedly in volatility accurately estimates activity coefficients of both components. This new technique is developed to simultaneously determine the evaporation rate and composition of a droplet from intensity peaks observed in the light scattered by the droplet. It has no upper or lower limits on the relative volatility of the system and is particularly suitable for systems containing one relatively nonvolatile component. The data on the glycerol-ethanol system, obtained from evaporation of glycerol droplets in ethanol vapor and correlated with Margules and Wilson equations, are thermodynamically consistent. The results of this study agree with ethanol activity coefficients calculated from the total pressure vs. solution composition data previously reported.
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  • 99
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 1184-1193 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mobile-phase additives, commonly used to modulate absorbate retention in gradient elution chromatography, are usually assumed to be either linearly retained or unretained. Previous theoretical work from our laboratory has shown that these modulators, such as salts in ion-exchange and hydrophobic interaction chromatography and organic modifiers in reversed-phase chromatography, can absorb nonlinearly, giving rise to gradient deformation. Consequently, adsorbate peaks that elute in the vicinity of the head of the deformed gradient may exhibit unusual shapes, form shoulders, and/or be concentrated. These effects for a reversed-phase sorbent with aqueous acetonitrile (ACN) as the modulator are verified experimentally. Gradient deformation is demonstrated experimentally and agrees with simulations based on ACN isotherm parameters that are independently determined from batch equilibrium studies using the layer model. Unusual adsorbate peak shapes were found experimentally for single-component injections of phenylalanine, similar to those calculated by the simulations. A binary mixture of tryptophan and phenylalanine is used to demonstrate simultaneous concentration and separation, again in agreement with simulations. The possibility of gradient deformation in ion-exchange and hydrophobic interaction chromatography is discussed.
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  • 100
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 1550-1562 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method for treating three-dimensional current and temperature distributions in large-scale battety modules is described. Simulations are presented for a module consisting of cells formed with a lithium metal anode, a polymer electrolyte, and a vanadium oxide cathode. The calculations illustrate the nonlinear dependence of power output on system temperature, which for the investigated lithium-polymer battery module is determined primarily by the influence of temperature on the electrochemical reaction rates and ionic conductivity. An appendix is devoted to the estimation of physicochemical parameters, some of which are not available from the current literature, but are nonetheless important model inputs.
    Additional Material: 11 Ill.
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