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  • Organic Chemistry  (68,964)
  • Chemical Engineering  (17,982)
  • 1
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    De Gruyter | De Gruyter
    Publication Date: 2024-04-05
    Description: The essential principles of green chemistry are the use of renewable raw materials, highly efficient catalysts and green solvents linked with energy efficiency and process optimization in real-time. Experts from different fields show, how to examine all levels from the molecular elementary steps up to the design and operation of an entire plant for developing novel and efficient production processes.
    Keywords: Process Engineering ; Chemical Engineering ; Technical Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RN The environment ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RN The environment::RNU Sustainability ; 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 ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TQ Environmental science, engineering and technology
    Language: English
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  • 2
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    Frontiers Media SA
    Publication Date: 2024-04-04
    Description: The Frontiers in Chemistry Editorial Office team are delighted to present the inaugural “Frontiers in Chemistry: Rising Stars” article collection, showcasing the high-quality work of internationally recognized researchers in the early stages of their independent careers. All Rising Star researchers featured within this collection were individually nominated by the Journal’s Chief Editors in recognition of their potential to influence the future directions in their respective fields. The work presented here highlights the diversity of research performed across the entire breadth of the chemical sciences, and presents advances in theory, experiment and methodology with applications to compelling problems. This Editorial features the corresponding author(s) of each paper published within this important collection, ordered by section alphabetically, highlighting them as the great researchers of the future. The Frontiers in Chemistry Editorial Office team would like to thank each researcher who contributed their work to this collection. We would also like to personally thank our Chief Editors for their exemplary leadership of this article collection; their strong support and passion for this important, community-driven collection has ensured its success and global impact.
    Keywords: Green and Sustainable Chemistry ; Analytical Chemistry ; Theoretical and Computational Chemistry ; Polymer Chemistry ; Medicinal and Pharmaceutical Chemistry ; Organic Chemistry ; Nanoscience ; Catalysis and Photocatalysis ; Supramolecular Chemistry ; Electrochemistry ; Inorganic Chemistry ; Chemical Biology ; thema EDItEUR::P Mathematics and Science::PD Science: general issues
    Language: English
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  • 3
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    MDPI - Multidisciplinary Digital Publishing Institute
    Publication Date: 2023-06-23
    Description: The aim of this second Eng Special Issue is to collect experimental and theoretical re-search relating to engineering science and technology. The general topics of Eng are as follows: electrical, electronic and information engineering; chemical and materials engineering; energy engineering; mechanical and automotive engineering; industrial and manufacturing engineering; civil and structural engineering; aerospace engineering; biomedical engineering; geotechnical engineering and engineering geology; and ocean and environmental engineering. Therefore, the following editorial is a selection of representative works of these topics.
    Keywords: &nbsp ; Environment Management ; Environmental Engineering ; Chemical Engineering ; Materials Engineering&nbsp ; bic Book Industry Communication::T Technology, engineering, agriculture::TB Technology: general issues ; bic Book Industry Communication::T Technology, engineering, agriculture::TB Technology: general issues::TBX History of engineering & technology
    Language: English
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  • 4
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2017-04-14
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
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  • 5
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2017-04-14
    Description: The allotropes formed by carbon reflect differences in its bonding: single bonds in diamond, double bonds in graphite and graphene, and triple bonds in polyynes. Fashioning graphene sheets into bowls, monkey saddles, balls, and tubes has led to a number of molecular allotropes of carbon or carbon-rich quasi-allotropes with novel topologies and shapes. A simple ring of carbon can be reduced to practice in various forms (1): a cyclic array of carbon atoms, a “pearl necklace” of benzene rings, or a cylindrical hoop of flank-fused benzenes, just to name a few. On page 172 of this issue, Povie et al. (2) report on the synthesis of an angular-fused hoop structure, which has been a long-standing target. Author: Jay S. Siegel
    Keywords: Organic Chemistry
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  • 6
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2017-04-14
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 7
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2017-04-01
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 8
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2017-03-03
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 9
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2017-03-03
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 10
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2017-01-13
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 11
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-12-09
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 12
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-11-18
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 13
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-11-18
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 14
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-10-21
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 15
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-09-09
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 16
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-09-07
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 17
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-07-22
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 18
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-07-15
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 19
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-07-08
    Description: Author: Phil Szuromi
    Keywords: Organic Chemistry
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  • 20
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-07-08
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 21
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-07-01
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 22
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-06-24
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 23
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-06-10
    Description: Transition metal–catalyzed arylation of C–H bonds has been intensively studied for forming C–C bonds in complex-molecule synthesis (1). An acidic C–H bond (for example, one near a double bond or an O atom) is cleaved to form a carbon–metal bond, which then couples to arene. Many of these organometallic species can be generated catalytically. Much less research has dealt with unreactive nonacidic sp3 C–H bond functionalization (3). On page 1304 of this issue, Shaw et al. (3) report an efficient and general method that focuses on arylation of sp3 C–H bonds at carbon atoms adjacent to amines and to cyclic ethers by combining nickel, visible-light photoredox, and hydrogen-atom transfer (HAT) catalysis. Author: Corinne Fruit
    Keywords: Organic Chemistry
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  • 24
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-06-10
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 25
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-05-27
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 26
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-05-20
    Description: Antibiotics have been taking it on the chin lately. Not only has resistance to the anti-infective medications been growing, but drug companies have been dropping antibiotic research programs, because the drugs are difficult and expensive to make. Now, new help is on the way. Researchers report this week that they've found a way to churn out new members of one of the most widely used classes of antibiotics. These drugs, called macrolides, were first developed in the 1950s and now represent a major bulwark against infections. A bevy of possible new drugs in this class could lead to new weapons against antibiotic-resistant infections, and possibly save millions of lives. Author: Robert F. Service
    Keywords: Organic Chemistry
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  • 27
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-05-13
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 28
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-04-29
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 29
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-04-22
    Description: Author: Jake Yeston
    Keywords: Organic Chemistry
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  • 30
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-04-01
    Description: The SN2 nucleophilic substitution reaction, X− + RY → XR + Y−, is a paradigm reaction in organic chemistry (1). The modern understanding of the SN2 reaction mechanism is based on work of Hughes and Ingold (2), who proposed that the nucleophile (X−) approaches the carbon atom that bears the leaving group (Y−). As a result, the bond between the carbon atom and the leaving group becomes weakened. As this bond breaks and a new bond forms between the nucleophile and the carbon atom, the configuration of the carbon atom is inverted. Analyses of gas-phase reaction rates led to the suggestion of a potential energy surface (PES) with two wells connected by a central barrier transition state (3). Electronic structure calculations have confirmed this picture for some SN2 reactions (4), but recent studies have shown that the actual reaction dynamics may be considerably more complex (see the figure) (5–8). Authors: Jing Xie, William L. Hase
    Keywords: Organic Chemistry
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  • 31
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-04-01
    Description: Author: Julia Fahrenkamp-Uppenbrink
    Keywords: Organic Chemistry
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  • 32
    Publication Date: 2016-03-19
    Description: Exploiting binding affinities between molecules is an established practice in many fields, including biochemical separations, diagnostics, and drug development; however, using these affinities to control biomolecule release is a more recent strategy. Affinity-controlled release takes advantage of the reversible nature of noncovalent interactions between a therapeutic protein and a binding partner to slow the diffusive release of the protein from a vehicle. This process, in contrast to degradation-controlled sustained-release formulations such as poly(lactic-co-glycolic acid) microspheres, is controlled through the strength of the binding interaction, the binding kinetics, and the concentration of binding partners. In the context of affinity-controlled release--and specifically the discovery or design of binding partners--we review advances in in vitro selection and directed evolution of proteins, peptides, and oligonucleotides (aptamers), aided by computational design.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Pakulska, Malgosia M -- Miersch, Shane -- Shoichet, Molly S -- Canadian Institutes of Health Research/Canada -- New York, N.Y. -- Science. 2016 Mar 18;351(6279):aac4750. doi: 10.1126/science.aac4750.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemical Engineering and Applied Chemistry, Institute of Biomaterials and Biomedical Engineering, and Donnelly Centre, University of Toronto, Toronto, Ontario, Canada. ; Department of Molecular Genetics, University of Toronto, Toronto, Ontario, Canada. ; Department of Chemical Engineering and Applied Chemistry, Institute of Biomaterials and Biomedical Engineering, and Donnelly Centre, University of Toronto, Toronto, Ontario, Canada. Department of Chemistry, University of Toronto, Toronto, Ontario, Canada.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/26989257" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Engineering ; Combinatorial Chemistry Techniques ; Delayed-Action Preparations/*chemistry ; Directed Molecular Evolution ; *Drug Design ; Humans ; Lactic Acid/*chemistry ; Microspheres ; Polyglycolic Acid/*chemistry ; Proteins/*administration & dosage
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  • 33
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 2014-11-29
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Langer, Robert S -- Gura, Trisha -- New York, N.Y. -- Science. 2014 Nov 28;346(6213):1146. doi: 10.1126/science.346.6213.1146.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Trisha Gura is a freelance writer who lives in Boston. For more on life and careers visit www.sciencecareers.org.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/25430772" target="_blank"〉PubMed〈/a〉
    Keywords: Biotechnology ; *Career Choice ; Chemical Engineering ; *Entrepreneurship ; *Science
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  • 34
    Publication Date: 2014-10-04
    Description: Ethanol toxicity in the yeast Saccharomyces cerevisiae limits titer and productivity in the industrial production of transportation bioethanol. We show that strengthening the opposing potassium and proton electrochemical membrane gradients is a mechanism that enhances general resistance to multiple alcohols. The elevation of extracellular potassium and pH physically bolsters these gradients, increasing tolerance to higher alcohols and ethanol fermentation in commercial and laboratory strains (including a xylose-fermenting strain) under industrial-like conditions. Production per cell remains largely unchanged, with improvements deriving from heightened population viability. Likewise, up-regulation of the potassium and proton pumps in the laboratory strain enhances performance to levels exceeding those of industrial strains. Although genetically complex, alcohol tolerance can thus be dominated by a single cellular process, one controlled by a major physicochemical component but amenable to biological augmentation.〈br /〉〈br /〉〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4401034/" target="_blank"〉〈img src="https://static.pubmed.gov/portal/portal3rc.fcgi/4089621/img/3977009" border="0"〉〈/a〉   〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4401034/" target="_blank"〉This paper as free author manuscript - peer-reviewed and accepted for publication〈/a〉〈br /〉〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Lam, Felix H -- Ghaderi, Adel -- Fink, Gerald R -- Stephanopoulos, Gregory -- R01 GM035010/GM/NIGMS NIH HHS/ -- R01-GM035010/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 2014 Oct 3;346(6205):71-5. doi: 10.1126/science.1257859. Epub 2014 Oct 2.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemical Engineering, Massachusetts Institute of Technology (MIT), Cambridge, MA, USA. Whitehead Institute for Biomedical Research, Cambridge, MA, USA. ; Department of Chemical Engineering, Massachusetts Institute of Technology (MIT), Cambridge, MA, USA. ; Whitehead Institute for Biomedical Research, Cambridge, MA, USA. gfink@wi.mit.edu gregstep@mit.edu. ; Department of Chemical Engineering, Massachusetts Institute of Technology (MIT), Cambridge, MA, USA. gfink@wi.mit.edu gregstep@mit.edu.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/25278607" target="_blank"〉PubMed〈/a〉
    Keywords: *Biofuels ; Cation Transport Proteins/genetics ; Cell Culture Techniques ; Cell Membrane/metabolism ; Chemical Engineering ; *Drug Resistance, Fungal/genetics ; Ethanol/*metabolism/pharmacology ; Fermentation ; Genetic Engineering ; Glucose/metabolism ; Hydrogen-Ion Concentration ; Phosphates/*metabolism ; Potassium Compounds/*metabolism ; Proton Pumps/genetics ; Proton-Translocating ATPases/genetics ; Saccharomyces cerevisiae/drug effects/genetics/*metabolism ; Saccharomyces cerevisiae Proteins/genetics ; Up-Regulation ; Xylose/metabolism
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 2012-11-28
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Savage, Phillip E -- New York, N.Y. -- Science. 2012 Nov 23;338(6110):1039-40. doi: 10.1126/science.1224310.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Chemical Engineering Department, University of Michigan, Ann Arbor, MI 48109, USA. psavage@umich.edu〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/23180853" target="_blank"〉PubMed〈/a〉
    Keywords: *Biofuels ; Cell Culture Techniques ; Chemical Engineering ; Chlorophyta/*chemistry/growth & development ; *Hot Temperature ; *Hydrostatic Pressure ; *Water
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  • 36
    Publication Date: 2007-11-17
    Description: Artificial biochemical circuits are likely to play as large a role in biological engineering as electrical circuits have played in the engineering of electromechanical devices. Toward that end, nucleic acids provide a designable substrate for the regulation of biochemical reactions. However, it has been difficult to incorporate signal amplification components. We introduce a design strategy that allows a specified input oligonucleotide to catalyze the release of a specified output oligonucleotide, which in turn can serve as a catalyst for other reactions. This reaction, which is driven forward by the configurational entropy of the released molecule, provides an amplifying circuit element that is simple, fast, modular, composable, and robust. We have constructed and characterized several circuits that amplify nucleic acid signals, including a feedforward cascade with quadratic kinetics and a positive feedback circuit with exponential growth kinetics.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Zhang, David Yu -- Turberfield, Andrew J -- Yurke, Bernard -- Winfree, Erik -- New York, N.Y. -- Science. 2007 Nov 16;318(5853):1121-5.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Computation and Neural Systems, California Institute of Technology, MC 136-93, 1200 East California Boulevard, Pasadena, CA91125, USA. dzhang@dna.caltech.edu〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/18006742" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; Catalysis ; Chemical Engineering ; *Computers, Molecular ; DNA/*chemistry ; Entropy ; Equipment Design ; Feedback, Physiological ; Mice ; Nanotechnology ; Nucleic Acid Hybridization ; Rabbits
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 37
    Keywords: Biomass conversion ; Biotechnology ; Chemical Engineering ; Chemistry industry ; Industrial Chemistry ; Kent ; Riegel ; biochemical engineering
    Description / Table of Contents: Substantially revising and updating the classic reference in the field, this handbook offers a valuable overview and myriad details on current chemical processes, products, and practices. No other source offers as much data on the chemistry, engineering, economics, and infrastructure of the industry. The Handbook serves a spectrum of individuals, from those who are directly involved in the chemical industry to others in related industries and activities. It provides not only the underlying science and technology for important industry sectors, but also broad coverage of critical supporting topics. Industrial processes and products can be much enhanced through observing the tenets and applying the methodologies found in chapters on Green Engineering and Chemistry (specifically, biomass conversion), Practical Catalysis, and Environmental Measurements; as well as expanded treatment of Safety, chemistry plant security, and Emergency Preparedness. Understanding these factors allows them to be part of the total process and helps achieve optimum results in, for example, process development, review, and modification. Important topics in the energy field, namely nuclear, coal, natural gas, and petroleum, are covered in individual chapters. Other new chapters include energy conversion, energy storage, emerging nanoscience and technology. Updated sections include more material on biomass conversion, as well as three chapters covering biotechnology topics, namely, Industrial Biotechnology, Industrial Enzymes, and Industrial Production of Therapeutic Proteins.
    Pages: Online-Ressource (XIV, 1562 pages)
    ISBN: 9780387278438
    Language: English
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  • 38
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 115-117 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel oxygen induced reduction of α,β-unsaturated carbonyl compounds is discovered. The reduction of the carbon-carbon double bond of α,β-unsaturated carbonyl compounds by benzeneselenol was caused by an introduction of molecular oxygen into the reaction system. This reduction is likely to proceed via a radical chain pathway involving an SH2 type reaction between a phenylseleno radical and a 1,2-adduct of benzeneselenol to the carbonyl group of the α,β-unsaturated carbonyl compound to give an allylic radical which absracts a hydrogen atom from benzeneselenol to form the reduction product.
    Additional Material: 1 Tab.
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  • 39
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 191-195 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The photochemical reaction of MAQO with various aromatic amines were studied by ESR. The results show that nitroxide radicals are stable productrs of the photooxidation of both diphenylamines and phenylamines. The photolyzed phenothiazine does not yield nitroxide as the final product, instead it gives the neutral radical as the stable final product.
    Additional Material: 4 Ill.
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  • 40
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 26-34 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A set of 4-monosubstituted cyclopentenes, , were synthesized and their relative rates (kX/kH) for bromination and chlorination were determined in methanol, ethanol and acetic acid at 25 °C by competitive method. log(kX/kH) for most of the substituents can be correlated by means of Taft's equation, log(kX/kH) = ρI σI + C. In methanol ρI, Br2 = -2·91, ρI, Cl2 = -0·49, in ethanol ρI, Br2 = -3·07, ρI, Cl2 = -0·70 and in acetic acid ρI, Br2 = -1·64, ρI, Cl2 = -0·65. The presence of C(〈0) is due to a constant steric effect. The deviation of X = H is ascribed to the absence of the steric effect and that of X = CO2Me and CO2Et is accounted for in terms of anchimeric assistance. For chlorination no anchimeric assistance was observed.
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  • 41
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 57-88 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cation radical vinylcyclobutane (VCB) rearrangement is found to be a reaction of substantial scope, synthetic utility, and exceptional kinetic facility. In conjuction with cation radical cyclobutanation, it constitutes an effective method for net (indirect) Diels-Alder addition to electron rich dienophiles. Reactions can be carried out with either aminium salt or photosensitized electron transfer (PET) initiation and are powerfully facilitated by ionizable substituents such as p-anisyl, phenylthio, and phenoxy at the 2-position of the vinylcyclobutane. The intramolecularity of the reaction is clearly established and in four discrete systems preferred sr (suprafacial/retention) stereochemistry is observed. A theoretical basis for sr stereochemistry in the cation radical VCB rearrangement is advanced. The transition state for the reaction is considered to be similar to that for the direct cation radical Diels-Alder cycloaddition, another cation radical pericyclic reaction which converges on the same product. This model of the VCB rearrangement transition state is used to rationalize the strong rate-retarding effect of a Z-methyl substituent attached to the vinyl group and of a methyl substituent at the 4-position of the vinylcyclobutane ring cis to the vinyl substituent.
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  • 42
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 333-349 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New series of platinum complexes of cyclopropenylidenes of the types of PtX2(CP)2 and trans-PtX(PBu3)2(CP) have been synthesized, where CP is di-t-butylcyclopropenylidene (BCP) or bis(diisopropylamino)cyclopropenylidene (ACP). The 13C-NMR chemical shifts, and 13C-195Pt coupling constants (1JPtC) for the complexes are discussed in comparison with those values derived from closely related series of compounds, trans-PtCl(PR3)2L; L — —CH3, —C6H5 and —C≡CBu-t. An excellent linear relationship through the origin was obtained between 1JPtC and the formal ‘s’ % character of the carbon directly bonded to Pt for the series trans-PtCl(PR3)2L in which the Pt—C bond is regarded as a pure σ-linkage, whereas 1JPtC deviates largely from this relationship when pπ—dπ bonding interaction possibly exists in the Pt—C bond. The NMR data suggest the strong nmr trans-influence of the cyclopropenylidenes and that in the Pt—CP bond the σ-interaction is appreciable but the π-interaction is negligible.
    Additional Material: 3 Ill.
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  • 43
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 1-14 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of aromatic nucleophilic substitutions by amines in protic solvents is well established; on the contrary the mechanism/s of the reactions in aprotic solvents is/are still subject of controversy. The present paper describes several systems for which fourth-order kinetics (third-order in amine) were observed. A mechanism is proposed to account for this as well as other observation such as: overall negative energies of activation, quadratic dependence of kA with non-nucleophilic tertiary bases, spectacular effects of hydrogen-bond donor (HBD) and hydrogen-bond acceptor (HBA) catalysts, etc. Other alternative mechanisms are also discussed.
    Additional Material: 5 Ill.
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  • 44
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics and mechanisms of the reactions between 1-phenylethyl benzenesulfonates (1-PEB) with N,N-dimethylanilines are investigated in methanol at 35·0°C. Reactivity and selectivity trends were found to be similar to those for the reactions of 1-PEB with anilines, but the magnitudes of cross interaction constants, ρXZ, between substituents X in the nucleophile and Z in the leaving group were substantially smaller indicating no hydrogen-bond bypass bridge formation in the transition state. However, the magnitude of ρXZ suggested a direct electrostatic interaction between the reaction centers in the nucleophile and leaving group in the frontside nucleophilic attack with a loose transition state structure.
    Additional Material: 6 Tab.
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  • 45
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 183-186 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The harmonic vibrational frequencies were calculated analytically at the 6-31** level for azetidine using the GAUSSIAN 82 program. The results strongly indicate the presence of several errors in a recent assignment of the fundamentals of azetidine based on a normal coordinate analysis and a revised assignment is suggested. It is concluded that reliable vibrational data for azetidine in the gas phase are needed in order to resolve the remaining ambiguities in the interpretation of the spectra.
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  • 46
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 47
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 110-116 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The transamination reaction of α-amino acids with glyoxylic acid as catalyzed by copper(II) ions was investigated kinetically in an aqueous medium at pH 5·0 and 30·0°C. L-Phenylalanine transferred its amino group to glyoxylic acid most readily among seven different amino acids used here in the single-walled bilayer vesicle formed with N,N-dihexadecyl-Nα-[6-(trimethylammonio)hexanoyl]-L-histidinamide bromide (N+C5His2C16). Such rate enhancement was found to originate from the cooperative trifunctional catalysis: a coordination effect exercised by copper(II) ions, a general acid-base catalysis by the imidazolyl group of the lipid, and a hydrophobic field effect provided by the bilayer vesicle. Lack of any of the three functions failed to give out significant rate enhancement. As regards correlation between the reactivity and the nature of α-amino acids, the copper(II)-catalyzed transamination was progressively enhanced as hydrophobicity of the α-amino acid was increased in the N+C5His2C16 vesicle.
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  • 48
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 49
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 123-131 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photolysis of N-alkyl-N-(3-aryl-3-butenyl) ureas (1) in acetonitrile gave cyclization products, 3-aryl-3-methyl-pyrrolidines, in good yields, whereas irradiation of 1 in methanol afforded methanol adducts as well as the cyclization products. Both the reactions are singlet reactions, and the cyclization is presumed to proceed via 1,6-hydrogen transfer from exciplexes with charge transfer character.
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  • 50
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 143-151 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dependence of the catalytic efficiencies of sodium carboxymethylamylose (NaCMA) for the hydrolysis of N-lauryl-3-acetoxypyridinium iodide (1) and p-nitrophenyl dodecanoate (3) on its degree of substitution (D. S. = 0·00, 0·12, 0·18, 0·24, 0·29 and 0·35) and on the pH values of the solutions (pH = 7·32, 7·80, 8·10 and 9·30) have been studied. At fixed D. S. values, the observed hydrolysis rates of 1 and 3 increase with increasing concentrations of NaCMA and follow saturation kinetics. At fixed concentration of NaCMA, the rates increase with decreasing D. S. values until they reach maxima at D. S. = 0·00. Furthermore, at any D. S. value the catalytic efficiency increases with increasing pH values of the solutions. All these results indicate that the hydroxyl groups are actually the principal catalyzing groups.
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