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  • Chemistry
  • Cell & Developmental Biology
  • Inorganic Chemistry
  • American Association for the Advancement of Science (AAAS)  (347)
  • Freshwater Biological Association  (39)
  • 1
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    The changes in various iron compounds in culture media for algae. [Translation from: Archiv fur Hydrobiologie Supplemente Band 38(1/2) 151-169, 1970.] (2021)
    Freshwater Biological Association | Windermere, UK
    In:  http://aquaticcommons.org/id/eprint/4839 | 1256 | 2011-09-29 15:49:48 | 4839 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-06
    Description: The purpose of this work is a contribution to the quantitative record of the use of iron by planktonic algae. Preliminary experiments with Chlorella to determine the rate of iron intake in the presence of inorganic sources of iron did not produce the desired result. The crucial point of this work is the investigation of the influence of various external factors on the stability of FeEDTA (FeEDTA = Ferric(III)-compound of ethylene-diamine tetra-acetic acid), since this compound appears to be particularly well-suited as a source of iron for planktonic algae (e.g. TAMIYA et al. 1953). Cultures of Chlorella fusca in a light thermostat were used in experimental research. Methods and results are discussed.
    Description: Translated from German into English
    Keywords: Chemistry ; Ecology ; Limnology ; Biometrics ; Biological sampling ; Geographical distribution ; Population density ; Population characteristics ; Population number ; Freshwater crustaceans ; Population dynamics
    Repository Name: AquaDocs
    Type: monograph
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  • 2
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    Determination of dissolved oxygen in water with leukoberbelin-blue I. A quick Winkler method. [Translation from: Z.analyt.Chem. 262 97-99, 1972.] (2021)
    Freshwater Biological Association | Windermere, UK
    In:  http://aquaticcommons.org/id/eprint/4843 | 1256 | 2011-09-29 15:49:28 | 4843 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-06
    Description: The reaction of Mn(II) with water-dissolved oxygen, to a higher manganese hydroxide in an alkaline medium, as with the longstanding classic Winkler method, is the first step in the method described here. The assumption for faultless results by the conventional and modified Winkler method is clean water, which contains no organic substances by Mn(III) or Mn(IV). In many cases, however, eg. in river and lake-water tests, it can be seen with the naked eye that after some time the originally brown-coloured precipitate of manganese hydroxide becomes more and more colourless. Oxygen content was analysed in the water samples and evaluated by raising the amount of the leuko-base and giving the corresponding dilution of the colouring matter solution formed still higher oxygen contents can be measured.
    Description: Translated from German into English
    Keywords: Chemistry ; Ecology ; Limnology ; Methodology ; Experimental research ; Dissolved oxygen ; Analytical techniques ; Water analysis
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  • 3
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    Nitrogen and phosphorus forms in water and the food requirements of algae. [Translation from: Wiadomosci Ekologiczne 19 238-244, 1973. ] (2021)
    Freshwater Biological Association | Windermere, UK
    In:  http://aquaticcommons.org/id/eprint/4848 | 1256 | 2011-09-29 15:49:18 | 4848 | Freshwater Biological Association
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    Publication Date: 2021-07-06
    Description: When dissolved in water, compounds of nitrogen and phosphorus ought to contain the basic assimilated food requirements for autotrophic plants and therefore autotrophic algae. This article summarises the occurrence of nitrogen in water, how species of algae utilize nitrogen and phosphorus forms for growth and the capacities of algae to adapt to environments of different nutrient wealth. This topic has unquestionable importance not only for the purpose of survival of a species but also in deciding indirectly about the stability of ecosystems.
    Description: Translated from Polish into English
    Keywords: Biology ; Chemistry ; Limnology ; Algae ; Nitrogen fixation ; Nitrogen ; Phosphorus ; Nutritional requirements ; Bacteria ; Organic compounds
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  • 4
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    Physiology of nitrate reduction in Pseudomonas aeruginosa. [Translation from: Z.allg.Mikrobiol. 13, 83-94, 1973.] (2021)
    Freshwater Biological Association | Windermere, UK
    In:  http://aquaticcommons.org/id/eprint/4856 | 1256 | 2011-09-29 15:48:26 | 4856 | Freshwater Biological Association
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    Publication Date: 2021-07-06
    Description: Pseudomonas aeruginosa has for some time been known as a denitrifier. Pseudomonas aeruginosa was chosen for further studies, because P. aeruginosa occurs abundantly in Plusssee and moreover there are contradictory assertions on the gas products of denitrification by this bacteria. In experimental research the pattern of growth and gas production of Pseudomonas aeruginosa on nutrient broth was studied.
    Description: Translated from German into English
    Keywords: Chemistry ; Ecology ; Limnology ; Experimental research ; Bacteria ; Freshwater lakes ; Growth ; Microbiological culture ; Plusssee
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  • 5
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    Relationship of dimensions and weight in freshwater planktonic crustaceans. [Translation from: Doklady Akademii Nauk SSSR 84(1) 153-156, 1952. ] (2021)
    Freshwater Biological Association | Windermere, UK
    In:  http://aquaticcommons.org/id/eprint/4857 | 1256 | 2011-09-29 15:48:28 | 4857 | Freshwater Biological Association
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    Publication Date: 2021-07-06
    Description: There is no doubt that determination of the biomass of zooplankton (primarily of crustaceans) will be taken into consideration in practice and limnological works, especially after the recent publication of fairly comprehensive tables of weights of a whole range of species of freshwater copepods and cladocerans. The usefulness of applying formulae of determining the biomass of marine crustaceans for freshwater copepods is discussed.
    Description: Translated from Russian into English
    Keywords: Chemistry ; Ecology ; Limnology ; Freshwater crustaceans ; Zooplankton ; Biomass ; Formulae
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  • 6
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    For the determination of iron (II) and total iron with 2,2'-dipyridyl in mineral waters. Reduction of iron (III) with ascorbic acid [Translation from: Zeitschrift fur Analytische Chemie 209 340-341, 1965] (2021)
    Freshwater Biological Association | Windermere, UK
    In:  http://aquaticcommons.org/id/eprint/4877 | 1256 | 2011-09-29 15:47:02 | 4877 | Freshwater Biological Association
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    Publication Date: 2021-07-06
    Description: The determination of bi- and trivalent iron in proximity, in mineral waters has gained in significance, on biological and technical grounds. This short paper describes the procedure of the determination of bivalent iron and total iron in a water sample.
    Description: Translated from German into English
    Keywords: Chemistry ; Limnology ; Iron ; Acids ; Analytical techniques ; Minerals ; Water analysis
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  • 7
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    Nitrification in marine ecosystems [Translation from: Rapp.Naturvardsverket SNVPM No.1213, 157-166, 1980] (2021)
    Freshwater Biological Association | Windermere, UK
    In:  http://aquaticcommons.org/id/eprint/4964 | 1256 | 2011-09-29 15:39:04 | 4964 | Freshwater Biological Association
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    Publication Date: 2021-07-07
    Description: The nitrification in the ocean is influenced by several environmental factors and the importance of these is more or less known. There are very likely many more to be discovered in the study of the interaction of nitrification bacteria and other micro-organisms in the ocean. Some of the factors to be considered will briefly be dealt with in this paper. Then the authors give the results of an incubation experiment in the Baltic Sea and from a detailed study in Gullmarn.
    Description: Translated from Swedish into English
    Keywords: Chemistry ; Ecology ; Oceanography ; Marine ecology ; Nitrification ; Experimental research ; Sediment analysis ; Bacteria ; Carbon fixation ; Nitrosococcus oceanus ; Nitrococcus mobilis
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  • 8
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    Ratio of natural isotopes of nitrogen. I. Primary results: soils of Dombes [Translation from: Revue d'Ecologie et de Biologie du Sol 14, 279-287, 1977] (2021)
    Freshwater Biological Association | Windermere, UK
    In:  http://aquaticcommons.org/id/eprint/4967 | 1256 | 2011-09-29 15:36:52 | 4967 | Freshwater Biological Association
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    Publication Date: 2021-07-07
    Description: Utilization of the heavy isotope of nitrogen as a tracer has found numerous applications in soil biology. It allows better definition of different stages of the nitrogen cycle, in particular the immobilization-mineralization cycle. In this work, the authors report the results of calculations of natural isotope ratios of nitrogen in samples of water, soil and vegetation prevailing in Dombes and discuss the possibilities of errors and coefficients of fractionation.
    Description: Translated from French into English
    Keywords: Chemistry ; Ecology ; Limnology ; Nitrogen isotopes ; Soils ; Tracers ; Bacteria ; Nitrogen compounds ; France ; Dombes
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  • 9
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    Experiments on the production of a highly dispersible calcium carbonate. ('Experimental section' only) [Translation from: Szklo i Ceramiki 30, 133-136, 1979] (2021)
    Freshwater Biological Association | Windermere, UK
    In:  http://aquaticcommons.org/id/eprint/4963 | 1256 | 2011-09-29 15:39:01 | 4963 | Freshwater Biological Association
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    Publication Date: 2021-07-07
    Description: This short translation summarises experiments on the production of a highly dispersible precipitate of calcium carbonate. The translation covers the 'Experimental section' (of the original larger paper) only.
    Description: Translated from Polish into English
    Keywords: Chemistry ; Limnology ; Experimental research ; Calcium carbonates ; Magnetic fields ; Ultrasonic devices
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  • 10
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    Chemical composition of Iraq water resources (abbreviated translation) [Translation from: Vodnye Resursy 1975(4,) 173-185] (2021)
    Freshwater Biological Association | Windermere, UK
    In:  http://aquaticcommons.org/id/eprint/4988 | 1256 | 2011-09-29 15:36:31 | 4988 | Freshwater Biological Association
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    Publication Date: 2021-07-07
    Description: This abbreviated translation summarises the chemical composition of Iraq water resources. Among the described water bodies are the River Euphrates, Shatt al Arab River and a number of standing waters.
    Description: Translated from Russian into English
    Keywords: Chemistry ; Ecology ; Limnology ; Inland water environment ; Inland waters ; Water analysis ; Iraq
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  • 11
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    Mechanism of mass transfer in the formation of hydrothermal deposits of sulphides [Translation from: Trudy Inst.Geol.rudn.Mesterozh. 16, 80 [pages 44-46 ”Solubility of sulphides of iron” only], 1958] (2021)
    Freshwater Biological Association | Windermere, UK
    In:  http://aquaticcommons.org/id/eprint/4980 | 1256 | 2011-09-29 15:38:06 | 4980 | Freshwater Biological Association
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    Publication Date: 2021-07-07
    Description: This partial translation of the original paper provides the summary of this study of the mechanism of mass transfer in the formation of hydrothermal deposits of sulphides. For determining the solubility of sulphides of iron, the radioactive isotope Fe59 was used. The solubility of two sulphides was determined.
    Description: Translated from Russian into English
    Keywords: Chemistry ; Ecology ; Limnology ; Sulphide deposits ; Sulphides ; Hydrothermal deposits ; Iron isotopes ; Solubility
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  • 12
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    Some data on the content of organic carbon in rivers in the winter months. [Translation from: Gidrochim. Mat. 23, 36-38, 1955] (2021)
    Freshwater Biological Association | Windermere, UK
    In:  http://aquaticcommons.org/id/eprint/5054 | 1256 | 2011-09-29 15:29:08 | 5054 | Freshwater Biological Association
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    Publication Date: 2021-07-08
    Description: Observations are reported on the content of organic matter in the Moscow region in 1941. Some data is given on alkalinity, oxygen content and colourisation of the rivers.
    Description: Translated from Russian into English
    Keywords: Biology ; Chemistry ; Limnology ; Rivers ; Organic matter ; Alkalinity ; Dissolved oxygen ; Colour
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  • 13
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    Final report on the updating service on environmental chemicals in freshwater for the period 9.1.89 to 9.7.89 (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5238 | 1256 | 2011-09-29 15:13:42 | 5238 | Freshwater Biological Association
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    Publication Date: 2021-07-09
    Description: This report presents five batches of data which have been despatched to the Joint Research Centre, Ispra. The data as been allocated to various ECDIN (Environmental Chemicals Data and Information Network) files. The data comprises environmental chemicals in the freshwater environment, taking in paricular consideration: aquatic toxicity, bioaccumulation, metabolism and elimination biodegradation.
    Keywords: Chemistry ; Ecology ; Limnology ; Data ; Data processing ; Data collections ; Chemical compounds ; Toxicity ; Bioaccumulation ; Biodegradation ; Metabolism
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  • 14
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    Changes of water quality and sediment phosphorus of a small productive lake following decreased phosphorus loading (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5293 | 1256 | 2011-09-29 15:08:09 | 5293 | Freshwater Biological Association
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    Publication Date: 2021-07-09
    Description: Esthwaite Water is the most productive or eutrophic lake in the English Lake District. Since 1945 its water quality has been determined from weekly or biweekly measurements of temperature, oxygen, plant nutrients and phytoplankton abundance. The lake receives phosphorus from its largely lowland-pasture catchment, sewage effluent from the villages of Hawkshead and Near Sawrey, and from a cage-culture fish farm. From 1986 phosphorus has been removed from the sewage effluent of Hawkshead which was considered to contribute between 47% and 67% of the total phosphorus loading to the lake. At the commencement of phosphorus removal regular measurements of phosphorus in the superficial 0-4 cm layer of lake sediment were made from cores collected at random sites. Since 1986 the mean annual concentration of alkali-extractable sediment phosphorus has decreased by 23%. This change is not significant at the 5% level but nearly so. There has been no marked change in water quality over this period. Summer dominance of blue-green algae which arose in the early 1980s after decline of the previous summer forms, Ceratium spp., has been maintained. Improvement in water quality is unlikely to be achieved at the present phosphorus loading.
    Keywords: Chemistry ; Limnology ; Pollution ; Eutrophication ; Freshwater lakes ; Limnological surveys ; Phosphorus ; Phytoplankton ; Primary production ; Sediment analysis ; Water quality ; England ; Esthwaite Water
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  • 15
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    The changing chemical composition of chalk streams and rivers (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5157 | 3949 | 2011-09-29 15:19:58 | 5157 | Freshwater Biological Association
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    Publication Date: 2021-07-08
    Description: The area studied was the River Frome system below Dorchester. The main river has its origins mainly in chalk springs, although some of its tributaries have surface run-off from farm lands and heath-lands. Thus the chemistry of the river is affected by changes in land practice and differences in the geology of the catchment area. Regular chemical analysis of chalk waters started at the River Laboratory in 1964, Regular weekly analyses have been carried out since 1965 at Bere Stream (a small chalk stream) and the River Frome (a large chalk stream); also single samples have been analysed to provide preliminary information. In 1970-71 an attempt was made to discover the contribution each main source made to the flow and chemical composition of the River Frome. Results of these investigations are presented in the paper.
    Keywords: Chemistry ; Environment ; Chemical analysis ; Chemical composition ; Rivers ; Stream flow ; Annual report ; England ; Dorset
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  • 16
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    Geochemistry of lipids in lacustrine sediments (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5171 | 3949 | 2011-09-29 15:18:48 | 5171 | Freshwater Biological Association
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    Publication Date: 2021-07-08
    Description: An explanation of the basic premises of the subject and its terminology is given. The article then outlines aspects of research on the organic material found in lacustrine sediments, and the analytical methods involved.
    Keywords: Chemistry ; Earth Sciences ; Diagenesis ; Freshwater lakes ; Geochemistry ; Lipids ; Sediment analysis ; Annual report
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    Format: 45-56
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  • 17
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    Joint research project on the aquatic ecotoxicity of organo-aluminium: Chemical reactions. First interim report (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5225 | 1256 | 2011-09-29 15:12:36 | 5225 | Freshwater Biological Association
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    Publication Date: 2021-07-09
    Description: The overall goal of the joint research project is to relate the chemical reactions involved in the formation of organo-aluminium complexes under acid conditions to their toxic effects on the physiology of aquatic organisms. Finally, this research is intended to predict toxic effects arising from acidity and aluminium under varying environmental conditions. This interim report examines the chemical modelling of ion-binding by humic substances where a computer model has been developed and is being tested using field data, and conditions required for the precipitation of aluminium in surface waters.
    Keywords: Chemistry ; Limnology ; Pollution ; Modelling ; Models ; Humic acids ; Surface water ; Aluminium compounds ; Aluminium ; Ions ; Toxicity ; England ; Duddon River
    Repository Name: AquaDocs
    Type: monograph
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  • 18
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    Decomposition in lake sediments: bacterial action and interaction (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5239 | 3949 | 2011-09-29 15:13:47 | 5239 | Freshwater Biological Association
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    Publication Date: 2021-06-24
    Description: This review discusses the processes involved in the decomposition of organic carbon derived initially from structural components of algae and other primary producers. It describes how groups of bacteria interact in time and space in a eutrophic lake. The relative importance of anaerobic and aerobic processes are discussed. The bulk of decomposition occurs within the sediment. The role of bacteria in the nitrogen cycle and the iron cycle, and in sulphate reduction and methanogenesis as the terminal metabolism of organic carbon are described.
    Keywords: Biology ; Chemistry ; Anaerobic bacteria ; Bacteria ; Biodegradation ; Carbon cycle ; Eutrophic lakes ; Fresh water ; Geochemical cycle ; Iron ; Manganese ; Nitrates ; Nitrogen cycle ; Organic carbon ; Oxygen consumption ; Partical size ; Sedimentation ; Sulphates ; Sulphur ; Annual report
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  • 19
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    Biological and climatic influences on the dace Leuciscus leuciscus in a southern chalk-stream (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5247 | 3949 | 2011-09-29 15:08:19 | 5247 | Freshwater Biological Association
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    Publication Date: 2021-07-09
    Description: The dace, Leuciscus leuciscus (L.) is an important cyprinid in terms of population biomass in chalk streams of southern England. Dace recruitment has been shown to vary widely from year to year and it is thought that this variation is largely as a result of the influence of abiotic factors, chiefly water temperature. From 1968 to 1981 there was a thirteen-fold difference in the year class structure index between the minimum index (0.25 in 1972) and the maximum (3.21 in 1976). The problems of such variation, especially those that could ensue from a succession of poor year-classes, are offset by the spread of reproductive effort by each female over several years.
    Keywords: Biology ; Chemistry ; Fisheries ; Abiotic factors ; Age composition ; Annual variations ; Climate ; Fecundity ; Fish eggs ; Fish larvae ; Freshwater fish ; Life history ; Mortality ; Population dynamics ; Predation ; Recruitment ; Sexual reproduction ; Survivial ; Water temperature ; Cyprinidae ; Leuciscus leuciscus ; England ; Dorset ; Chalk streams ; Annual report
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  • 20
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    Analysis and adsorption of phosalone on aquatic sediment (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5257 | 1256 | 2011-09-29 15:09:23 | 5257 | Freshwater Biological Association
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    Publication Date: 2021-07-09
    Description: Phosalone is a non systematic, wide spectrum organophosphate pesticide which was discovered in 1961 in the laboratories of the Societe des Usines Chimique Rhone-Poulenc in France. It has been approved for commercial use since 1964 in France, in Australia since 1966, in the United Kingdom in 1967 and in many other countries including Japan, Egypt, USSR and the USA. This study provides a full literature review on all aspects of phosalone including its physical, biological and chemical characteristics, and analytical methods of analysis with particular reference to soils/sediments. Furthermore, it aims to develop a method for the determintion of phosalone in aquatic sediments and to determine the adsorption of phosalone onto kaolinite.
    Keywords: Chemistry ; Limnology ; Pollution ; Insecticides ; Metabolism ; Toxicity ; Biodegradation ; Adsorption
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  • 21
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    Petroleum hydrocarbons in fresh waters: a preliminary desk study and bibliography (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5278 | 1256 | 2011-09-29 15:11:09 | 5278 | Freshwater Biological Association
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    Publication Date: 2021-07-09
    Description: A literature survey was carried out into the effects of petroleum hydrocarbons in freshwater, from the toxicity, biodegradability and concentration aspects. It was supplemented by a selective search on hydrocarbons in the marine environment for comparison. The aim was to determine the major inputs of these hydrocarbons, their accumulation, effects and fate in freshwaters. The search was confined to the period 1965-1978. The bibliography contains 390 references, divided by subject.
    Keywords: Chemistry ; Limnology ; Pollution ; literature reviews ; petroleum ; toxicity ; biodegradation
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  • 22
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    Concentrations of major ions in the stream water of the River Duddon, England, 1970-1974 [Dataset] (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5349 | 1256 | 2011-05-13 11:55:43 | 5349 | Freshwater Biological Association
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    Publication Date: 2021-07-10
    Description: This dataset provides raw data of chemical analyses made during studies on seasonal variations of some major ions in the stream water of the River Duddon in Cumbria. Measurements of sodium, calcium, potassium, magnesium and chloride ions and pH were taken at 5 stations in the River Duddon between January 1970 and August 1974.
    Description: This data was used in the publication: Carrick, T.R. & Sutcliffe, D.W.: Concentrations of Major Ions in Streams on Catchments of the River Duddon (1971-1974) and Windermere (1975-1978), English Lake District. Freshwater Biological Association, Ambleside, UK, 1983 (FBA Occasional Publications 22)
    Keywords: Chemistry ; Limnology ; Calcium ; chlorides ; fresh water ; ions ; magnesium ; potassium ; seasonal variations ; sodium ; water analysis ; dataset
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  • 23
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    Analysis of stream waters in the catchment of Lake Windermere (1975-1978), England [Dataset] (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5351 | 1256 | 2011-05-13 11:55:21 | 5351 | Freshwater Biological Association
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    Publication Date: 2021-07-10
    Description: This dataset provides raw data of chemical analyses made during studies on seasonal variations of some major ions in the stream water of the catchment of Lake Windermere in Cumbria. Measurements of sodium, calcium, potassium, magnesium, chloride ions and pH were taken at 37 stations in the catchment between 1975 and 1978.
    Description: This data was used in the publication: Carrick, T.R. & Sutcliffe, D.W.: Concentrations of major ions in streams on catchments of the River Duddon (1971-1974) and Windermere (1975-1978), English Lake District. Freshwater Biological Association, Ambleside, UK, 1983 (FBA Occasional Publications 22)
    Keywords: Chemistry ; Limnology ; Calcium ; chlorides ; fresh water ; ions ; magnesium ; potassium ; seasonal variations ; sodium ; water analysis ; England ; Lake Windermere ; dataset
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  • 24
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    Concentrations of major ions in 182 tarns in the English Lake District (1953-1978) [Dataset] (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5354 | 1256 | 2011-09-16 12:01:28 | 5354 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-10
    Description: This dataset provides raw data of chemical analyses made during studies on seasonal variations of 182 tarns in the English Lake District, Cumbria. Measurements of sodium, calcium, potassium, magnesium, pH, chloride ions, alkalinity, sulphite, strong acids and nitrate were taken between 1953 and 1978.
    Description: This data was used in the publication: Carrick, T.R. & Sutcliffe, D.W.: Concentrations of major ions in lakes and tarns on the English Lake District (1953-1978). Freshwater Biological Association, Ambleside, UK, 1982 (FBA Occasional Publications 16)
    Keywords: Chemistry ; Limnology ; Calcium ; chlorides ; fresh water ; ions ; magnesium ; potassium ; seasonal variations ; sodium ; water analysis ; alkalinity ; England ; Lake District ; dataset
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    Analyses of treated sewage effluent from Grasmere Treatment Unit (1974-1976), England [Dataset] (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5352 | 1256 | 2012-07-04 19:32:47 | 5352 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-10
    Description: This dataset provides raw data of chemical analyses made during studies on seasonal variations of treated sewage effluent from Grasmere Treatment Unit in Cumbria. Measurements of sodium, calcium, potassium, magnesium and chloride ions were taken between 1974 and 1976.
    Description: This data was used in the publication: Carrick, T.R. & Sutcliffe, D.W.: Concentrations of major ions in streams on catchments of the River Duddon (1971-1974) and Windermere (1975-1978), English Lake District. Freshwater Biological Association, Ambleside, UK, 1983 (FBA Occasional Publications 22)
    Keywords: Chemistry ; Limnology ; Calcium ; chlorides ; fresh water ; ions ; magnesium ; potassium ; seasonal variations ; sodium ; water analysis ; England ; Grasmere ; dataset
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    Concentrations of major ions in the stream water of the upper basin of the River Duddon, England, 1972-1974 [Dataset] (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5350 | 1256 | 2011-05-13 11:56:03 | 5350 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-10
    Description: This dataset provides raw data of chemical analyses made during studies on seasonal variations of some major ions in the stream water of the upper basin of the River Duddon in Cumbria. Measurements of sodium, calcium, potassium, magnesium and chloride ions and pH were taken at 26 stations in the River Duddon basin between 1972 and 1974.
    Description: This data was used in the publication: Carrick, T.R. & Sutcliffe, D.W.: Concentrations of Major Ions in Streams on Catchments of the River Duddon (1971-1974) and Windermere (1975-1978), English Lake District. Freshwater Biological Association, Ambleside, UK, 1983 (FBA Occasional Publications 22)
    Keywords: Chemistry ; Limnology ; Calcium ; chlorides ; fresh water ; ions ; magnesium ; potassium ; seasonal variations ; sodium ; water analysis ; England ; River Duddon ; dataset
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    Major ions in 25 frequently sampled tarns in the English Lake District (1954-56, 1974-1976) [Dataset] (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5353 | 1256 | 2012-07-04 19:33:33 | 5353 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-10
    Description: This dataset provides raw data of chemical analyses made during studies on seasonal variations of 25 frequently sampled tarns in Cumbria. Measurements of sodium, calcium, potassium, magnesium, pH, chloride ions, alkalinity, sulphite, strong acids and nitrate were taken between 1954 and 1956 and between 1974-1976.
    Description: This data was used in the publication: Carrick, T.R. & Sutcliffe, D.W.: Concentrations of major ions in streams on catchments of the River Duddon (1971-1974) and Windermere (1975-1978), English Lake District. Freshwater Biological Association, Ambleside, UK, 1983 (FBA Occasional Publications 22)
    Keywords: Chemistry ; Limnology ; Calcium ; chlorides ; fresh water ; ions ; magnesium ; potassium ; seasonal variations ; sodium ; water analysis ; alkalinity ; England ; Lake District ; dataset
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    Type: other
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    Changes in the phytoplankton (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5111 | 3949 | 2011-09-29 15:23:22 | 5111 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-08
    Description: An article discussing changes observed in phytoplankton of the Lake District. An overview is given of previous phytoplankton studies undertaken in the area, detailing some changes found in various waterbodies. Water quality changes in Lake Windermere are mentioned, including the gradual increase of dissolved organic matter (DOM), believed to be caused by the increase of sewage to the lake. The lakes in the Alps are given as an example of a similar anthropogenic pollution scenario. The treatment of a Lake District tarn with bone meal is described. The article goes on to discuss the composition of plankton throughout the year under a variety of climatic conditions. A figure shows seasonal variation in the consistuents of phytoplankton in Windermere (north basin).
    Keywords: Biology ; Chemistry ; Limnology ; Phytoplankton ; Limnology ; Dissolved organic matter ; Seasonal variations ; Sewage ; Water quality ; Annual reports ; England ; Lake District
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    The chemical budget of a lake (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5107 | 3949 | 2011-09-29 15:23:50 | 5107 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-08
    Description: A progress report on research undertaken on the chemical budget of a lake, outlining the importance of nitrogen and phosphorus in governing the production of life in freshwater. The report uses the Rivers Brathay and Leven, which flow into Windermere, as examples. The report also refers to the Rivers Rothay, Troutbeck and Cunsey. A table is including which shows the monthly average nitrate content (mg per litre) of the River Brathey and River Leven for 1937 into 1938. The report also includes a figure showing Windermere lake levels, discharge and rainfall during 1937. It also briefly considers possible anthropogenic influences on water quality.
    Keywords: Chemistry ; Ecology ; Limnology ; Phosphorus ; Organic compounds ; Sewage ; Diatoms ; Algae ; Sediment chemistry ; Seasonal variations ; Annual reports ; Nitrates ; River discharge ; England
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    Bacteria in freshwaters (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5114 | 3949 | 2011-09-29 15:21:32 | 5114 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-08
    Description: An article looking at the numerical distribution of bacteria in lakes, the types most commonly present and the nitrogen-cycle, in Lake Windermere. The methodology is explained, including the sampling frequency and depths, and bacteria culturing techniques. Water bodies other than Lake Windermere were also sampled and these are detailed, including a water reservoir. A summary of the work into horizontal of bacteria is given, including a table showing the number of bacteria per millilitre at different distances from inflow into Windermere. A summary of the work into vertical distribution is also given, including two figures, one showing seasonal variation during 1938-9 in numbers of bacteria at different depths in Winderemere, and the other showing the relationship between the numbers of bacteria at 10 metres depth in Windermere and the rainfull during the previous 7 days. A summary of the types of bacteria found, as well as work on the nitrogen cycle in Esthwaite Water, Lake Windermere and Blelham Tarn are given.
    Keywords: Biology ; Chemistry ; Limnology ; Nitrogen cycle ; Bacteria ; Freshwater ecology ; Limnology ; Seasonal variations ; Water column ; Water reservoirs ; Annual reports ; England ; Lake District
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    Changes in physical and chemical variables (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5112 | 3949 | 2011-09-29 15:23:20 | 5112 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-08
    Description: An article reviewing the work undertaken looking at the seasonal variation of chemical conditions in water at various depths in lakes. The laboratory tests undertaken for the research is outlined, as well as details of the sampling locations and the staff involved with the work. One figure shows the seasonal variation in the amounts of dissolved substances in the surface water of Windermere during 1936. Another figure shows seasonal varation inthe dry weight of phyto- and zooplankton in Windermere. Seasonal changes are discussed further and a table is included showing chemical conditions in winter and summer for Windermere.
    Keywords: Biology ; Chemistry ; Limnology ; Limnology ; Chemistry ; Seasonal variations ; Diatoms ; Phytoplankton ; Zooplankton ; Water column ; Surface water ; Annual reports ; England ; Lake District
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    Biological surveillance of chalk-streams (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5122 | 3949 | 2011-09-29 15:22:47 | 5122 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-08
    Description: An article reviewing the methods of biological surveillance of chalk-streams developed and commonly used at that time, with a focus on their application to the River Frome catchment in Dorset. In evaluating the surveillance methods, the author looks at sampling methods (including cores and kick-sampling), the level of identification of macroinvertebrates, and temporal and spatial variations. Responses of indices to organic pollution are also discussed. A number of accompanying figures are also included.
    Keywords: Biology ; Chemistry ; Ecology ; Environment ; Chalk ; Water management ; Cores ; Aquatic communities ; Freshwater ecology ; Invertebrate larvae ; Biological surveys ; Temporal variations ; Spatial variations ; Annual reports ; England
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    The design and development of the Windermere Profiler. An instrument for measuring how various environmental parameters vary with depth in lakes, reservoirs and rivers (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5123 | 3949 | 2011-09-29 15:22:51 | 5123 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-08
    Description: A review article detailing the background, development and functionality of the Windermere Profiler, a multi parameter environmental monitoring instrument for use in lakes, reservoirs and rivers. The article explains the requirement for regular data collection by the Freshwater Biological Association at Windermere. The article covers the requirements of a profiling instrument, the design considerations, the electronic circuitry, the computer program, the operation of the computer software, the profiler in use and further developments to the design. A number of figures and images accompany the article.
    Keywords: Chemistry ; Environment ; Limnology ; Profilers ; Inland water environment ; Water reservoirs ; Lakes ; Rivers ; Temperature data ; Electrical conductivity ; Dissolved oxygen ; Depth measurement ; Light attenuation ; Annual reports ; England ; Lake District
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    The growth of brown trout (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5117 | 3949 | 2011-09-29 15:22:21 | 5117 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-08
    Description: An article discussing the factors affecting the rate of growth of brown trout, detailing the research udnertaken at Wray Castle, designed to clarify the influencing factors in different waters and investigate what would be required to increase their size. The article considers factors such as alkalinity, total hardness, the presence of coarse fish in the waterbodies and competition for food. Previous work undertaken on brown trout in Ireland by other authors is reviewed. A figure showing average growth rate of brown trout in five lakes, as determined from their scales (Lough Derg, Windermere, Loch Leven, Ullswater, Haweswater).
    Keywords: Biology ; Chemistry ; Limnology ; Coarse fish ; pH effects ; Water hardness ; Food availability ; Limnology ; England ; Lake District
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    Acid precipitation and its effects on aquatic systems in the English Lake District (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5189 | 3949 | 2011-09-29 15:16:49 | 5189 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-09
    Description: There is no evidence of an increase in the acidity (lower pH or alkalinity) of water-bodies in the Lake District over the last 50 years. Brown trout occur in acid streams and upland tarns where pH is 4.5-5.2 throughout the year. Their occurrence in such waters in Britain and Ireland has been known for most of this century and there is no previous evidence of harmful effects on salmonid fisheries, though numbers of fish are naturally low. However, many benthic invertebrates that are common in hill-streams where pH is above 5.7 do not occur in more acid streams. This phenomenon occurs in the headwaters of several western rivers in Cumbria. It is not a recent response to "acid rain". Harmful effects of pH are undoubtedly more pronounced in waters that are poor in other dissolved ions. Low concentrations of sodium, potassium, calcium and chloride are especially important and may limit the distributions of some aquatic animals even where pH is above 5.7. The concentration of sulphate ions is usually relatively high but this is not important to the fauna; concentrations are at least two times higher in productive alkaline water-bodies than they are in unproductive acid waters.
    Keywords: Chemistry ; Ecology ; Limnology ; Acid rain ; Acidification ; Alkalinity ; Freshwater pollution ; pH ; Pollution effects ; Invertebrata ; Salmonidae ; England ; Lake District ; Annual report
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    Studies of chemical speciation in naturally anoxic basins (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5181 | 3949 | 2011-09-29 15:17:17 | 5181 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-09
    Description: The chemical speciation of both metals and non-metals, the use of polarographic techniques, and application to the study of the chemistry of anoxic waters are considered. In the first part of the paper unfamiliar terminology is explained and then an example of simple lake chemistry is presented to illustrate why the concept of speciation is necessary.
    Keywords: Chemistry ; Limnology ; Chemical speciation ; Anoxic basins ; Annual report
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    The kinetics of calcite precipation and related processes (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5195 | 3949 | 2011-09-29 15:15:06 | 5195 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-09
    Description: This review is concerned with the kinetics of calcium carbonate formation and related processes which are important in many hard waters.
    Keywords: Chemistry ; Calcite ; Calcium carbonates ; Chemical precipitation ; Fresh water ; Geochemical cycle ; Annual report
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    Treading in Mortimer's footsteps: the geochemical cycling of iron and manganese in Esthwaite water (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5193 | 3949 | 2011-09-29 15:15:03 | 5193 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-09
    Description: A study of the geochemical cycling of iron and manganese in a seasonally stratified lake, Esthwaite water is described. This work is based on speculative ideas on environmental redox chemistry of iron which were proposed by C.H. Mortimer in the 1940's. These observations have been verified and some speculations confirmed, along with a new understanding of the manganese cycle, and detailed information on the particulate forms of both iron and manganese. Details on the mechanisms and transformations of iron have also emerged.
    Keywords: Biology ; Chemistry ; Chemical precipitation ; Freshwater lakes ; Iron ; Manganese ; Oxidation ; Redox potential ; Reduction ; Stratification ; England ; Esthwaite Lake ; Annual report
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    Long-term natural acidification of upland sites in Cumbria: Evidence from post-glacial lake sediments (2021)
    Freshwater Biological Association | Ambleside, UK
    In:  http://aquaticcommons.org/id/eprint/5197 | 3949 | 2011-09-29 15:15:33 | 5197 | Freshwater Biological Association
    Details
    Publication Date: 2021-07-09
    Description: Studies by the Freshwater Biological Association over the last 25 years have supplied data relevant to the levels of acidity in local soils and water before the onset of industrial pollution and current interest in acid rain. This article reviews published analysis from cores of lake sediments, in or near the catchment of the River Duddon. Electron spin resonance spectra of humic acids and iodine values confirm evidence from pollen analysis for a history of progressive acidification of the source material of lake sediments since before 5000 radiocarbon years, in upland catchments of the Lake District. Processes involved included: removal of basic ions from soils by rainfall, the effects of which were intensified by removal by man of deciduous forest; acidification of soils and waters by decomposition products of Calluna and further acidification of waters by Sphagnum species which colonized habitats where drainage became impeded by paludification processes.
    Keywords: Biology ; Chemistry ; Earth Sciences ; Acid rain ; Acidification ; Freshwater lakes ; Lake Basins ; Lake deposits ; pH ; Palnology ; England ; Cumbria ; Annual report
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    Left- or right-handed C-H bond activation (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-02-16
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
    Published by American Association for the Advancement of Science (AAAS)
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  • 41
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    Comment on "Selective anaerobic oxidation of methane enables direct synthesis of methanol" (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-02-16
    Description: The comment and response concerning the report of oxidation of methane to methanol by water (Reports, 5 May 2017, p. 523) do not fully capture the implications of thermodynamic limitations. A nonisothermal process in which each cycle requires a large temperature swing and permits only substoichiometric methane conversion surely could not be carried out on any practical scale.
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 42
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    Response to Comment on "Selective anaerobic oxidation of methane enables direct synthesis of methanol" (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-02-16
    Description: Labinger argues that stepwise reaction of methane with water to produce methanol and hydrogen will never be commercially feasible because of its substoichiometric basis with respect to the active site and the requirement of a large temperature swing. This comment is not touching any new ground, beyond describing the thermodynamic feasibility, thermal cycling, and the role of water as discussed previously. Most important, it does not have a solid numerical basis.
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 43
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    Silicon smooths the way to vinyl cations (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-07-27
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-07-27
    Description: Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium–weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond–forming reactions, including carbon-hydrogen (C–H) insertion into unactivated sp 3 C–H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C–H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 45
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    Separation of enantiomers by their enantiospecific interaction with achiral magnetic substrates (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-06-22
    Description: It is commonly assumed that recognition and discrimination of chirality, both in nature and in artificial systems, depend solely on spatial effects. However, recent studies have suggested that charge redistribution in chiral molecules manifests an enantiospecific preference in electron spin orientation. We therefore reasoned that the induced spin polarization may affect enantiorecognition through exchange interactions. Here we show experimentally that the interaction of chiral molecules with a perpendicularly magnetized substrate is enantiospecific. Thus, one enantiomer adsorbs preferentially when the magnetic dipole is pointing up, whereas the other adsorbs faster for the opposite alignment of the magnetization. The interaction is not controlled by the magnetic field per se, but rather by the electron spin orientations, and opens prospects for a distinct approach to enantiomeric separations.
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 46
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    Inspiration from a vitamin (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-06-29
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
    Published by American Association for the Advancement of Science (AAAS)
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  • 47
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    Observation of the geometric phase effect in the H + HD -〉 H2 + D reaction (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-12-14
    Description: Theory has established the importance of geometric phase (GP) effects in the adiabatic dynamics of molecular systems with a conical intersection connecting the ground- and excited-state potential energy surfaces, but direct observation of their manifestation in chemical reactions remains a major challenge. Here, we report a high-resolution crossed molecular beams study of the H + HD -〉 H 2 + D reaction at a collision energy slightly above the conical intersection. Velocity map ion imaging revealed fast angular oscillations in product quantum state–resolved differential cross sections in the forward scattering direction for H 2 products at specific rovibrational levels. The experimental results agree with adiabatic quantum dynamical calculations only when the GP effect is included.
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
    Published by American Association for the Advancement of Science (AAAS)
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  • 48
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    Photocatalytic upgrading of natural gas (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-17
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
    Published by American Association for the Advancement of Science (AAAS)
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  • 49
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    Radically transforming light hydrocarbons (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-17
    Keywords: Chemistry
    Print ISSN: 0036-8075
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Stereodivergent synthesis of 1,4-dicarbonyls by traceless charge-accelerated sulfonium rearrangement (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-17
    Description: The chemistry of the carbonyl group is essential to modern organic synthesis. The preparation of substituted, enantioenriched 1,3- or 1,5-dicarbonyls is well developed, as their disconnection naturally follows from the intrinsic polarity of the carbonyl group. By contrast, a general enantioselective access to quaternary stereocenters in acyclic 1,4-dicarbonyl systems remains an unresolved problem, despite the tremendous importance of 2,3-substituted 1,4-dicarbonyl motifs in natural products and drug scaffolds. Here we present a broad enantioselective and stereodivergent strategy to access acyclic, polysubstituted 1,4-dicarbonyls via acid-catalyzed [3,3]-sulfonium rearrangement starting from vinyl sulfoxides and ynamides. The stereochemistry at sulfur governs the absolute sense of chiral induction, whereas the double bond geometry dictates the relative configuration of the final products.
    Keywords: Chemistry
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    Four varieties of carbonyl sandwich (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-17
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Selective functionalization of methane, ethane, and higher alkanes by cerium photocatalysis (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-17
    Description: With the recent soaring production of natural gas, the use of methane and other light hydrocarbon feedstocks as starting materials in synthetic transformations is becoming increasingly economically attractive, although it remains chemically challenging. We report the development of photocatalytic C–H amination, alkylation, and arylation of methane, ethane, and higher alkanes under visible light irradiation at ambient temperature. High catalytic efficiency (turnover numbers up to 2900 for methane and 9700 for ethane) and selectivity were achieved using abundant, inexpensive cerium salts as photocatalysts. Ligand-to-metal charge transfer excitation generated alkoxy radicals from simple alcohols that in turn acted as hydrogen atom transfer catalysts. The mixed-phase gas/liquid reaction was adapted to continuous flow, enabling the efficient use of gaseous feedstocks in scalable photocatalytic transformations.
    Keywords: Chemistry
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    Hot lithium-oxygen batteries charge ahead (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-24
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    A preference for acids (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-24
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    18 electrons and counting (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-31
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Directional control of a processive molecular hopper (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-31
    Description: Intrigued by the potential of nanoscale machines, scientists have long attempted to control molecular motion. We monitored the individual 0.7-nanometer steps of a single molecular hopper as it moved in an electric field along a track in a nanopore controlled by a chemical ratchet. The hopper demonstrated characteristics desired in a moving molecule: defined start and end points, processivity, no chemical fuel requirement, directional motion, and external control. The hopper was readily functionalized to carry cargos. For example, a DNA molecule could be ratcheted along the track in either direction, a prerequisite for nanopore sequencing.
    Keywords: Chemistry
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    Unlocking P(V): Reagents for chiral phosphorothioate synthesis (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-09-21
    Description: Phosphorothioate nucleotides have emerged as powerful pharmacological substitutes of their native phosphodiester analogs with important translational applications in antisense oligonucleotide (ASO) therapeutics and cyclic dinucleotide (CDN) synthesis. Stereocontrolled installation of this chiral motif has long been hampered by the systemic use of phosphorus(III) [P(III)]–based reagent systems as the sole practical means of oligonucleotide assembly. A fundamentally different approach is described herein: the invention of a P(V)-based reagent platform for programmable, traceless, diastereoselective phosphorus-sulfur incorporation. The power of this reagent system is demonstrated through the robust and stereocontrolled synthesis of various nucleotidic architectures, including ASOs and CDNs, via an efficient, inexpensive, and operationally simple protocol.
    Keywords: Chemistry
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    Self-assembly of lattices with high structural complexity from a geometrically simple molecule (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-09-21
    Description: Here we report an anomalous porous molecular crystal built of C–H···N-bonded double-layered roof-floor components and wall components of a segregatively interdigitated architecture. This complicated porous structure consists of only one type of fully aromatic multijoint molecule carrying three identical dipyridylphenyl wedges. Despite its high symmetry, this molecule accomplishes difficult tasks by using two of its three wedges for roof-floor formation and using its other wedge for wall formation. Although a C–H···N bond is extremely labile, the porous crystal maintains its porosity until thermal breakdown of the C–H···N bonds at 202°C occurs, affording a nonporous polymorph. Though this nonporous crystal survives even at 325°C, it can retrieve the parent porosity under acetonitrile vapor. These findings show how one can translate simplicity into ultrahigh complexity.
    Keywords: Chemistry
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    Two ways out of an oxetane (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-09-28
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Arenes and amides from a single source (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-09-28
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 61
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    Interrupted carbonyl-olefin metathesis via oxygen atom transfer (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-09-28
    Description: Some of the simplest and most powerful carbon-carbon bond forming strategies take advantage of readily accessible ubiquitous motifs: carbonyls and olefins. Here we report a fundamentally distinct mode of reactivity between carbonyls and olefins that differs from established acid-catalyzed carbonyl-ene, Prins, and carbonyl-olefin metathesis reaction paths. A range of epsilon, zeta-unsaturated ketones undergo Brønsted acid–catalyzed intramolecular cyclization to provide tetrahydrofluorene products via the formation of two new carbon-carbon bonds. Theoretical calculations and accompanying mechanistic studies suggest that this carbocyclization reaction proceeds through the intermediacy of a transient oxetane formed by oxygen atom transfer. The complex polycyclic frameworks in this product class appear as common substructures in organic materials, bioactive natural products, and recently developed pharmaceuticals.
    Keywords: Chemistry
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    Arylsulfonylacetamides as bifunctional reagents for alkene aminoarylation (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-09-28
    Description: Alkene aminoarylation with a single, bifunctional reagent is a concise synthetic strategy. We report a catalytic protocol for the addition of arylsulfonylacetamides across electron-rich alkenes with complete anti-Markovnikov regioselectivity and excellent diastereoselectivity to provide 2,2-diarylethylamines. In this process, single-electron alkene oxidation enables carbon-nitrogen bond formation to provide a key benzylic radical poised for a Smiles-Truce 1,5-aryl shift. This reaction is redox-neutral, exhibits broad functional group compatibility, and occurs at room temperature with loss of sulfur dioxide. As this process is driven by visible light, uses readily available starting materials, and demonstrates convergent synthesis, it is well suited for use in a variety of synthetic endeavors.
    Keywords: Chemistry
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    Activating plasmonic chemistry (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-10-05
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Hot carriers reducing thermal barriers (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-10-05
    Keywords: Chemistry
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  • 65
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    Quantifying hot carrier and thermal contributions in plasmonic photocatalysis (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-10-05
    Description: Photocatalysis based on optically active, "plasmonic" metal nanoparticles has emerged as a promising approach to facilitate light-driven chemical conversions under far milder conditions than thermal catalysis. However, an understanding of the relation between thermal and electronic excitations has been lacking. We report the substantial light-induced reduction of the thermal activation barrier for ammonia decomposition on a plasmonic photocatalyst. We introduce the concept of a light-dependent activation barrier to account for the effect of light illumination on electronic and thermal excitations in a single unified picture. This framework provides insight into the specific role of hot carriers in plasmon-mediated photochemistry, which is critically important for designing energy-efficient plasmonic photocatalysts.
    Keywords: Chemistry
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    An acid inaccessible to aldol products (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-10-12
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Iodine smooths the way to ketyl radicals (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-10-12
    Keywords: Chemistry
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    Ketyl radical reactivity via atom transfer catalysis (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-10-12
    Description: Single-electron reduction of a carbonyl to a ketyl enables access to a polarity-reversed platform of reactivity for this cornerstone functional group. However, the synthetic utility of the ketyl radical is hindered by the strong reductants necessary for its generation, which also limit its reactivity to net reductive mechanisms. We report a strategy for net redox-neutral generation and reaction of ketyl radicals. The in situ conversion of aldehydes to α-acetoxy iodides lowers their reduction potential by more than 1 volt, allowing for milder access to the corresponding ketyl radicals and an oxidative termination event. Upon subjecting these iodides to a dimanganese decacarbonyl precatalyst and visible light irradiation, an atom transfer radical addition (ATRA) mechanism affords a broad scope of vinyl iodide products with high Z -selectivity.
    Keywords: Chemistry
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  • 69
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    Confined acids catalyze asymmetric single aldolizations of acetaldehyde enolates (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-10-12
    Description: Reactions that form a product with the same reactive functionality as that of one of the starting compounds frequently end in oligomerization. As a salient example, selective aldol coupling of the smallest, though arguably most useful, enolizable aldehyde, acetaldehyde, with just one partner substrate has proven to be extremely challenging. Here, we report a highly enantioselective Mukaiyama aldol reaction with the simple triethylsilyl (TES) and tert -butyldimethylsilyl (TBS) enolates of acetaldehyde and various aliphatic and aromatic acceptor aldehydes. The reaction is catalyzed by recently developed, strongly acidic imidodiphosphorimidates (IDPi), which, like enzymes, display a confined active site but, like small-molecule catalysts, have a broad substrate scope. The process is scalable, fast, efficient (0.5 to 1.5 mole % catalyst loading), and greatly simplifies access to highly valuable silylated acetaldehyde aldols.
    Keywords: Chemistry
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    Breaking through the nitrogen ceiling (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-12-21
    Keywords: Chemistry
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    Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-12-21
    Description: Single-molecule magnets (SMMs) containing only one metal center may represent the lower size limit for molecule-based magnetic information storage materials. Their current drawback is that all SMMs require liquid-helium cooling to show magnetic memory effects. We now report a chemical strategy to access the dysprosium metallocene cation [(Cp i Pr5 )Dy(Cp*)] + (Cp i Pr5 , penta-iso-propylcyclopentadienyl; Cp *, pentamethylcyclopentadienyl), which displays magnetic hysteresis above liquid-nitrogen temperatures. An effective energy barrier to reversal of the magnetization of U eff = 1541 wave number is also measured. The magnetic blocking temperature of T B = 80 kelvin for this cation overcomes an essential barrier toward the development of nanomagnet devices that function at practical temperatures.
    Keywords: Chemistry
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    Carbon nanotubes help nickel work in water (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-10-19
    Keywords: Chemistry
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    Chiral Lewis acids integrated with single-walled carbon nanotubes for asymmetric catalysis in water (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-10-19
    Description: The development of highly reactive and stereoselective catalytic systems is required not only to improve existing synthetic methods but also to invent distinct chemical reactions. Herein, a homogenized combination of nickel-based Lewis acid–surfactant-combined catalysts and single-walled carbon nanotubes is shown to exhibit substantial activity in water. In addition to the enhanced reactivity, stereoselective performance and long-term stability were demonstrated in asymmetric conjugate addition reactions of aldoximes to furnish chiral nitrones in high yields with excellent selectivities. The practical and straightforward application of the designed catalysts in water provides an expedient, environmentally benign, and highly efficient pathway to access optically active compounds.
    Keywords: Chemistry
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    Steps to smaller rings (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-11-02
    Keywords: Chemistry
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    Pinpointing the role of geometric phase (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-12-14
    Keywords: Chemistry
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    Salt and iron ease the way to amines (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-10-26
    Keywords: Chemistry
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    Catalytic palladium-oxyallyl cycloaddition (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-11-02
    Description: Exploration of intermediates that enable chemoselective cycloaddition reactions and expeditious construction of fused- or bridged-ring systems is a continuous challenge for organic synthesis. As an intermediate of interest, the oxyallyl cation has been harnessed to synthesize architectures containing seven-membered rings via (4+3) cycloaddition. However, its potential to access five-membered skeletons is underdeveloped, largely due to the thermally forbidden (3+2) pathway. Here, the combination of a tailored precursor and a Pd(0) catalyst generates a Pd-oxyallyl intermediate that cyclizes with conjugated dienes to produce a diverse array of tetrahydrofuran skeletons. The cycloaddition overrides conventional (4+3) selectivity by proceeding through a stepwise pathway involving a Pd-allyl transfer and ring closure sequence. Subsequent treatment of the (3+2) adducts with a palladium catalyst converts the heterocycles to the carbocyclic cyclopentanones.
    Keywords: Chemistry
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    Heterocycles meet and marry on phosphorus (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-11-16
    Keywords: Chemistry
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    A rapid screen for complex reactants (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-08-10
    Keywords: Chemistry
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  • 80
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    Mapping the dark space of chemical reactions with extended nanomole synthesis and MALDI-TOF MS (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-08-10
    Description: Understanding the practical limitations of chemical reactions is critically important for efficiently planning the synthesis of compounds in pharmaceutical, agrochemical, and specialty chemical research and development. However, literature reports of the scope of new reactions are often cursory and biased toward successful results, severely limiting the ability to predict reaction outcomes for untested substrates. We herein illustrate strategies for carrying out large-scale surveys of chemical reactivity by using a material-sparing nanomole-scale automated synthesis platform with greatly expanded synthetic scope combined with ultrahigh-throughput matrix-assisted laser desorption/ionization–time-of-flight mass spectrometry (MALDI-TOF MS).
    Keywords: Chemistry
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    High-affinity adsorption leads to molecularly ordered interfaces on TiO2 in air and solution (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-24
    Description: Researchers around the world have observed the formation of molecularly ordered structures of unknown origin on the surface of titanium dioxide (TiO 2 ) photocatalysts exposed to air and solution. Using a combination of atomic-scale microscopy and spectroscopy, we show that TiO 2 selectively adsorbs atmospheric carboxylic acids that are typically present in parts-per-billion concentrations while effectively repelling other adsorbates, such as alcohols, that are present in much higher concentrations. The high affinity of the surface for carboxylic acids is attributed to their bidentate binding. These self-assembled monolayers have the unusual property of being both hydrophobic and highly water-soluble, which may contribute to the self-cleaning properties of TiO 2 . This finding is relevant to TiO 2 photocatalysis, because the self-assembled carboxylate monolayers block the undercoordinated surface cation sites typically implicated in photocatalysis.
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    Tiny cargos ferried along a track (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-31
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 83
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    Carbonyls in the s block (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-08-31
    Keywords: Chemistry
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    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 84
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    Observation of alkaline earth complexes M(CO)8 (M = Ca, Sr, or Ba) that mimic transition metals (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-31
    Description: The alkaline earth metals calcium (Ca), strontium (Sr), and barium (Ba) typically engage in chemical bonding as classical main-group elements through their n s and n p valence orbitals, where n is the principal quantum number. Here we report the isolation and spectroscopic characterization of eight-coordinate carbonyl complexes M(CO) 8 (where M = Ca, Sr, or Ba) in a low-temperature neon matrix. Analysis of the electronic structure of these cubic O h -symmetric complexes reveals that the metal–carbon monoxide (CO) bonds arise mainly from [M(d )] -〉 (CO) 8 backdonation, which explains the strong observed red shift of the C-O stretching frequencies. The corresponding radical cation complexes were also prepared in gas phase and characterized by mass-selected infrared photodissociation spectroscopy, confirming adherence to the 18-electron rule more conventionally associated with transition metal chemistry.
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 85
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    A radical approach to soot formation (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-09-07
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 86
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    Resonance-stabilized hydrocarbon-radical chain reactions may explain soot inception and growth (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-09-07
    Description: Mystery surrounds the transition from gas-phase hydrocarbon precursors to terrestrial soot and interstellar dust, which are carbonaceous particles formed under similar conditions. Although polycyclic aromatic hydrocarbons (PAHs) are known precursors to high-temperature carbonaceous-particle formation, the molecular pathways that initiate particle formation are unknown. We present experimental and theoretical evidence for rapid molecular clustering–reaction pathways involving radicals with extended conjugation. These radicals react with other hydrocarbon species to form covalently bound complexes that promote further growth and clustering by regenerating resonance-stabilized radicals through low-barrier hydrogen-abstraction and hydrogen-ejection reactions. Such radical–chain reaction pathways may lead to covalently bound clusters of PAHs and other hydrocarbons that would otherwise be too small to condense at high temperatures, thus providing the key mechanistic steps for rapid particle formation and surface growth by hydrocarbon chemisorption.
    Keywords: Chemistry
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  • 87
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    Enantioselective four-component Ugi reactions (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-09-14
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 88
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    Plastics recycling with a difference (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-04-27
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 89
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    Light and acid steer a radical addition (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-04-27
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 90
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    Catalytic enantioselective Minisci-type addition to heteroarenes (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-04-27
    Description: Basic heteroarenes are a ubiquitous feature of pharmaceuticals and bioactive molecules, and Minisci-type additions of radical nucleophiles are a leading method for their elaboration. Despite many Minisci-type protocols that result in the formation of stereocenters, exerting control over the absolute stereochemistry at these centers remains an unmet challenge. We report a process for addition of prochiral radicals, generated from amino acid derivatives, to pyridines and quinolines. Our method offers excellent control of both enantioselectivity and regioselectivity. An enantiopure chiral Brønsted acid catalyst serves both to activate the substrate and induce asymmetry, while an iridium photocatalyst mediates the required electron transfer processes. We anticipate that this method will expedite access to enantioenriched small-molecule building blocks bearing versatile basic heterocycles.
    Keywords: Chemistry
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  • 91
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    Reduction can make cobalt act precious (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-05-25
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 92
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    Transforming nitrogen without carbon (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-05-25
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 93
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    Efficient access to unprotected primary amines by iron-catalyzed aminochlorination of alkenes (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-10-26
    Description: Primary amines are essential constituents of biologically active molecules and versatile intermediates in the synthesis of drugs and agrochemicals. However, their preparation from easily accessible alkenes remains challenging. Here, we report a general strategy to access primary amines from alkenes through an operationally simple iron-catalyzed aminochlorination reaction. A stable hydroxylamine derivative and benign sodium chloride act as the respective nitrogen and chlorine sources. The reaction proceeds at room temperature under air; tolerates a large scope of aliphatic and conjugated alkenes, including densely functionalized substrates; and provides excellent anti-Markovnikov regioselectivity with respect to the amino group. The reactivity of the 2-chloroalkylamine products, an understudied class of amphoteric molecules, enables facile access to linear or branched aliphatic amines, aziridines, aminonitriles, azido amines, and homoallylic amines.
    Keywords: Chemistry
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  • 94
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    The staying power of electron-poor ligands (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-11-09
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 95
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    Enantiodivergent Pd-catalyzed C-C bond formation enabled through ligand parameterization (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-11-09
    Description: Despite the enormous potential for the use of stereospecific cross-coupling reactions to rationally manipulate the three-dimensional structure of organic molecules, the factors that control the transfer of stereochemistry in these reactions remain poorly understood. Here we report a mechanistic and synthetic investigation into the use of enantioenriched alkylboron nucleophiles in stereospecific Pd-catalyzed Suzuki cross-coupling reactions. By developing a suite of molecular descriptors of phosphine ligands, we could apply predictive statistical models to select or design distinct ligands that respectively promoted stereoinvertive and stereoretentive cross-coupling reactions. Stereodefined branched structures were thereby accessed through the predictable manipulation of absolute stereochemistry, and a general model for the mechanism of alkylboron transmetallation was proposed.
    Keywords: Chemistry
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  • 96
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    Heterobiaryl synthesis by contractive C-C coupling via P(V) intermediates (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-11-16
    Description: Heterobiaryls composed of pyridine and diazine rings are key components of pharmaceuticals and are often central to pharmacological function. We present an alternative approach to metal-catalyzed cross-coupling to make heterobiaryls using contractive phosphorus C–C couplings, also termed phosphorus ligand coupling reactions. The process starts by regioselective phosphorus substitution of the C–H bonds para to nitrogen in two successive heterocycles; ligand coupling is then triggered via acidic alcohol solutions to form the heterobiaryl bond. Mechanistic studies imply that ligand coupling is an asynchronous process involving migration of one heterocycle to the ipso position of the other around a central pentacoordinate P(V) atom. The strategy can be applied to complex drug-like molecules containing multiple reactive sites and polar functional groups, and also enables convergent coupling of drug fragments and late-stage heteroarylation of pharmaceuticals.
    Keywords: Chemistry
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  • 97
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    The dynamic art of growing COF crystals (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-07-06
    Keywords: Chemistry
    Print ISSN: 0036-8075
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 98
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    Imaging CF3I conical intersection and photodissociation dynamics with ultrafast electron diffraction (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-07-06
    Description: Conical intersections play a critical role in excited-state dynamics of polyatomic molecules because they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wave-packet trajectories through these intersections directly. Here, we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF 3 I molecules using ultrafast gas-phase electron diffraction. In the two-photon channel, we have mapped out the real-space trajectories of a coherent nuclear wave packet, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitation of both the umbrella and the breathing vibrational modes in the CF 3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab initio nonadiabatic dynamics calculations.
    Keywords: Chemistry
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  • 99
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    Femtosecond structural photobiology (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2018-07-13
    Keywords: Chemistry
    Print ISSN: 0036-8075
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 100
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    Feel the dielectric force (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-06-22
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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