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  • Chemistry
  • American Association for the Advancement of Science (AAAS)  (342)
  • Ambleside, UK  (27)
  • 1
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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
    Details
    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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    Type: monograph
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  • 2
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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
    Details
    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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  • 3
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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
    Details
    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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  • 4
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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
    Details
    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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  • 5
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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
    Details
    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
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    Type: monograph
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  • 6
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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
    Details
    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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  • 7
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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
    Details
    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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  • 8
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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
    Details
    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
    Repository Name: AquaDocs
    Type: monograph
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    Format: application/pdf
    Format: 54
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  • 9
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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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  • 10
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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
    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 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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  • 11
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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
    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 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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  • 12
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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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  • 13
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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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  • 14
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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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  • 15
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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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  • 16
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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
    Repository Name: AquaDocs
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  • 17
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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
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    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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  • 18
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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
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    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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  • 19
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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
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    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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  • 20
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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
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    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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  • 21
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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
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    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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  • 22
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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
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    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
    Repository Name: AquaDocs
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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
    Repository Name: AquaDocs
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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
    Repository Name: AquaDocs
    Type: book_section , FALSE
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    Format: application/pdf
    Format: 75-90
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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
    Repository Name: AquaDocs
    Type: book_section , FALSE
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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
    Repository Name: AquaDocs
    Type: book_section , FALSE
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    [Perspective] Molecular sieves for gas separation (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2016-07-08
    Description: Separation and purification are critical industrial processes for separating components of chemical mixtures, and these processes account for about half of industrial energy usage (1). Gas mixtures of compounds with very similar physical properties are particularly difficult to separate. On pages 137 and 141 of this issue, Cadiau et al. (2) and Cui et al. (3), respectively, show that microporous materials can be designed to have high adsorption capacity and selectivity for particular hydrocarbons, enabling energy-efficient separation. Author: Jerry Y. S. Lin
    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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    [Perspective] How to break down crystalline cellulose (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2016-05-27
    Description: Biomass-degrading microorganisms use lytic polysaccharide monooxygenase (LPMO) enzymes to help digest cellulose, chitin, and starch. By cleaving otherwise inaccessible crystalline cellulose chains, these enzymes provide access to hydrolytic enzymes. LPMOs are of interest to biotechnology because efficient depolymerization of cellulose is a major bottleneck for the production of biologically based chemicals and fuels. On page 1098 of this issue, Kracher et al. (1) compare LPMO-reducing substrates in fungi from different taxonomic groups and lifestyles, based on both biochemical and genomic evidence. The results provide insights into reductive activation of LPMO that are important for developing more efficient industrial enzymes for lignocellulose biorefineries. Author: Angel T. Martínez
    Keywords: Chemistry
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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    [Editors' Choice] Engineering open structures using DNA (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2016-03-25
    Description: Author: Marc S. Lavine
    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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    Patent law. Natural substances and patentable inventions (2003)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 2003-05-31
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Demaine, Linda J -- Fellmeth, Aaron X -- New York, N.Y. -- Science. 2003 May 30;300(5624):1375-6.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉RAND, Santa Monica, CA 90401, USA. demaine@rand.org〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/12775825" target="_blank"〉PubMed〈/a〉
    Keywords: Aluminum Oxide ; Chemical Phenomena ; Chemistry ; Natural Science Disciplines ; Patents as Topic/*legislation & jurisprudence ; Plant Extracts ; Plant Roots ; Titanium ; United States
    Print ISSN: 0036-8075
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 32
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    Chemical ecology: missed opportunities? (2002)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 2002-03-16
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Eisner, Thomas -- Berenbaum, May -- New York, N.Y. -- Science. 2002 Mar 15;295(5562):1973.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/11896239" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; Biochemical Phenomena ; *Biochemistry ; *Biological Factors/chemistry ; *Biology ; Chemical Phenomena ; Chemistry ; *Ecology ; Ecosystem ; *Molecular Biology ; Research Support as Topic ; United States
    Print ISSN: 0036-8075
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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    Characterization of a helical protein designed from first principles (1988)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1988-08-19
    Description: The question of how the primary amino acid sequence of a protein determines its three-dimensional structure is still unanswered. One approach to this problem involves the de novo design of model peptides and proteins that should adopt desired three-dimensional structures. A systematic approach was aimed at the design of a four-helix bundle protein. The gene encoding the designed protein was synthesized and the protein was expressed in Escherichia coli and purified to homogeneity. The protein was shown to be monomeric, highly helical, and very stable to denaturation by guanidine hydrochloride (GuHCl). Thus a globular protein has been designed that is capable of adopting a stable, folded structure in aqueous solution.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Regan, L -- DeGrado, W F -- New York, N.Y. -- Science. 1988 Aug 19;241(4868):976-8.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉E. I. du Pont de Nemours & Company, Central Research & Development Department, Wilmington, DE 19898.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/3043666" target="_blank"〉PubMed〈/a〉
    Keywords: Amino Acid Sequence ; Chemical Phenomena ; Chemistry ; Chromatography, Gel ; Escherichia coli/genetics ; Molecular Sequence Data ; Plasmids ; *Protein Conformation ; *Proteins/genetics
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 34
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    Sequence-specific peptide cleavage catalyzed by an antibody (1989)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1989-03-03
    Description: Monoclonal antibodies have been induced that are capable of catalyzing specific hydrolysis of the Gly-Phe bond of peptide substrates at neutral pH with a metal complex cofactor. The antibodies were produced by immunizing with a Co(III) triethylenetetramine (trien)-peptide hapten. These antibodies as a group are capable of binding trien complexes of not only Co(III) but also of numerous other metals. Six peptides were examined as possible substrates with the antibodies and various metal complexes. Two of these peptides were cleaved by several of the antibodies. One antibody was studied in detail, and cleavage was observed for the substrates with the trien complexes of Zn(II), Ga(III), Fe(III), In(III), Cu(II), Ni(II), Lu(III), Mg(II), or Mn(II) as cofactors. A turnover number of 6 x 10(-4) per second was observed for these substrates. These results demonstrate the feasibility of the use of cofactor-assisted catalysis in an antibody binding site to accomplish difficult chemical transformations.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Iverson, B L -- Lerner, R A -- New York, N.Y. -- Science. 1989 Mar 3;243(4895):1184-8.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Molecular Biology, Research Institute of Scripps Clinic, La Jolla, CA 92037.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2922606" target="_blank"〉PubMed〈/a〉
    Keywords: Amino Acid Sequence ; Animals ; *Antibodies, Monoclonal ; Antigens/immunology ; Binding Sites, Antibody ; Catalysis ; Chemical Phenomena ; Chemistry ; Cobalt/immunology/metabolism ; Glycine/metabolism ; Haptens/immunology ; Hydrogen-Ion Concentration ; Hydrolysis ; Immunization ; Metals/metabolism ; Mice ; Molecular Sequence Data ; Molecular Structure ; Oligopeptides/*metabolism ; Phenylalanine/metabolism ; Trientine/immunology
    Print ISSN: 0036-8075
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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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
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 36
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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
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  • 37
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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
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  • 38
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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
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 39
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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
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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
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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
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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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
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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
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 44
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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
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    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 45
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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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  • 46
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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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  • 47
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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
    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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  • 48
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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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  • 49
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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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    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
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    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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  • 56
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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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    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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    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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  • 64
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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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    Molecular mechanisms and forces involved in the adhesion and fusion of amphiphilic bilayers (1989)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 1989-11-17
    Description: The surface forces apparatus technique was used for measuring the adhesion, deformation, and fusion of bilayers supported on mica surfaces in aqueous solutions. The most important force leading to the direct fusion of bilayers is the hydrophobic interaction, although the occurrence of fusion is not simply related to the force law between bilayers. Bilayers do not need to "overcome" some repulsive force barrier, such as hydration, before they can fuse. Instead, once bilayer surfaces come within about 1 nanometer of each other, local deformations and molecular rearrangements allow them to "bypass" these forces.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Helm, C A -- Israelachvili, J N -- McGuiggan, P M -- New York, N.Y. -- Science. 1989 Nov 17;246(4932):919-22.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemical and Nuclear Engineering, University of California, Santa Barbara 93106.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2814514" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Lipid Bilayers ; Models, Biological ; Models, Structural ; Phosphatidylcholines ; Phosphatidylethanolamines
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    "Chemzymes" mimic biology in miniature (1989)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1989-07-28
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Waldrop, M M -- New York, N.Y. -- Science. 1989 Jul 28;245(4916):354-5.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2756423" target="_blank"〉PubMed〈/a〉
    Keywords: *Catalysis ; Chemical Phenomena ; Chemistry ; *Enzymes ; Technology, Pharmaceutical
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    A base dispute (1990)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 1990-08-03
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Waldrop, M M -- New York, N.Y. -- Science. 1990 Aug 3;249(4968):472-3.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2382127" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Information Systems ; Jurisprudence ; Societies, Scientific ; United States
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    Clathrate hydrate formation in amorphous cometary ice analogs in vacuo (1991)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 1991-10-25
    Description: The presence of clathrate hydrates in cometary ice has been suggested to account for anomalous gas release at large radial distances from the sun as well as the retention of volatiles in comets to elevated temperatures. However, how clathrate hydrates can form in low-pressure environments, such as in cold interstellar molecular clouds, in the outer reaches of the early solar nebula, or in cometary ices, has been poorly understood. Experiments performed with the use of a modified electron microscope demonstrate that during the warming of vapor-deposited amorphous ices in vacuo, clathrate hydrates can form by rearrangements in the solid state. Phase separations and microporous textures that are the result of these rearrangements may account for a variety of anomalous cometary phenomena.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Blake, D -- Allamandola, L -- Sandford, S -- Hudgins, D -- Freund, F -- New York, N.Y. -- Science. 1991 Oct 25;254:548-51.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Planetary Biology Branch, Ames Research Center, Moffett Field, CA 94035, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/11538372" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; Crystallography ; Earth (Planet) ; Hydrocarbons/chemistry ; Ice/*analysis ; *Meteoroids ; Microscopy, Electron ; *Solar System
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    Molecular recognition and metal ion template synthesis (1989)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 1989-05-26
    Description: Methods for the design and synthesis of ligands intended to be specific for a metal ion have been a recent chemical development. This article describes how this process can be inverted so that the specifics of the coordination environment around the metal ion can be used as a template in large-scale ligand synthesis. The synthesis of macrobicyclic ligands for ferric ion has been accomplished by using active esters of catechol ligands in which catecholate coordination to iron is a prelude to the organic chemical reactions that link the coordination subunits together into one ligand system surrounding a central metal ion coordination site. The lanthanide(III) ions, which are among the most labile metal ions known, have coordination numbers of 8 or higher, and thus their encapsulation into a macrobicyclic structure is a challenging problem. Lanthanide amine complexes have been used as metal templates in the synthesis of such macrobicyclic lanthanide complexes. There is evidence that such a complex is inert to exchange in aqueous solution.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉McMurry, T J -- Raymond, K N -- Smith, P H -- New York, N.Y. -- Science. 1989 May 26;244(4907):938-43.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Radiation Oncology Branch, National Cancer Institute, Bethesda, MD 20892.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2658057" target="_blank"〉PubMed〈/a〉
    Keywords: Cations ; Chemical Phenomena ; Chemistry ; Iron/metabolism ; *Ligands ; Macromolecular Substances ; Metals/*metabolism ; Metals, Rare Earth/metabolism ; Molecular Structure ; Templates, Genetic
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    Polymer synthesis and organotransition metal chemistry (1989)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 1989-02-17
    Description: Mechanistic and synthetic studies in organometallic chemistry have provided considerable insight into olefin metathesis and Ziegler-Natta polymerization. New homogeneous olefin metathesis catalysts based on high oxidation state transition metals have opened new opportunities in polymer synthesis by providing unprecedented control in ring-opening polymerization of cyclic alkenes. The recent development of living coordinative polymerization systems has led to the preparation of a number of new, interesting materials, including block copolymers, conducting polymers or precursors, and ionophoric polymeric substrates.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Grubbs, R H -- Tumas, W -- New York, N.Y. -- Science. 1989 Feb 17;243(4893):907-15.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉California Institute of Technology, Pasadena 91125.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2645643" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Organometallic Compounds ; *Polymers
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  • 73
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    Direct measurement of forces between linear polysaccharides xanthan and schizophyllan (1990)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 1990-09-14
    Description: Direct osmotic stress measurements have been made of forces between helices of xanthan, an industrially important charged polysaccharide. Exponentially decaying hydration forces, much like those already measured between lipid bilayer membranes or DNA double helices, dominate the interactions at close separation. Interactions between uncharged schizophyllans also show the same kind of hydration force seen between xanthans. In addition to the practical possibilities for modifying solution and suspension properties through recognition and control of molecular forces, there is now finally the opportunity for theorists to relate macroscopic properties of a polymer solution to the microscopic properties that underlie them.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Rau, D C -- Parsegian, V A -- New York, N.Y. -- Science. 1990 Sep 14;249(4974):1278-81.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Laboratory of Biochemistry and Metabolism, National Institute of Diabetes and Digestive and Kidney Diseases, National Institues of Health, Bethesda, MD 20892.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2144663" target="_blank"〉PubMed〈/a〉
    Keywords: Carbohydrate Sequence ; Chemical Phenomena ; Chemistry ; Gels ; *Glycosaminoglycans ; Macromolecular Substances ; Molecular Sequence Data ; Osmosis ; *Polysaccharides, Bacterial ; *Sizofiran ; Solutions ; Viscosity
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  • 74
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    Common features of protein unfolding and dissolution of hydrophobic compounds (1990)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1990-02-02
    Description: Protein unfolding and the dissolution of hydrophobic compounds (including solids, liquids, and gases) in water are characterized by a linear relation between entropy change and heat capacity change. The same slope is found for various classes of compounds, whereas the intercept depends on the particular class. The feature common to these processes is exposure of hydrophobic groups to water. These observations make possible the assignment of the heat capacity change to hydrophobic solvation and lead to the description of protein stability in terms of a hydrophobic and a nonhydrophobic contribution. A general representation of protein stability is given by the heat capacity change and the temperature.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Murphy, K P -- Privalov, P L -- Gill, S J -- New York, N.Y. -- Science. 1990 Feb 2;247(4942):559-61.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry and Biochemistry, University of Colorado, Boulder 80309.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2300815" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Protein Denaturation ; *Proteins ; Thermodynamics
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    Interparticle collisions driven by ultrasound (1990)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1990-03-02
    Description: Ultrasound has become an important synthetic tool in liquid-solid chemical reactions, but the origins of the observed enhancements remained unknown. The effects of high-intensity ultrasound on solid-liquid slurries were examined. Turbulent flow and shock waves produced by acoustic cavitation were found to drive metal particles together at sufficiently high velocities to induce melting upon collision. A series of transition-metal powders were used to probe the maximum temperatures and speeds reached during such interparticle collisions. Metal particles that were irradiated in hydrocarbon liquids with ultrasound underwent collisions at roughly half the speed of sound and generated localized effective temperatures between 2600 degrees C and 3400 degrees C at the point of impact for particles with an average diameter of approximately 10 microns.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Doktycz, S J -- Suslick, K S -- New York, N.Y. -- Science. 1990 Mar 2;247(4946):1067-9.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉School of Chemical Sciences, University of Illinois, Urbana 61801.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2309118" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Metals ; Microscopy, Electron, Scanning ; Microspheres ; *Ultrasonics
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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    Changes in mean concentration, phase shifts, and dissipation in a forced oscillatory reaction (1990)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1990-01-12
    Description: Experiments are presented that confirm earlier predictions that the mode of supply of reactants to a nonlinear (bio)chemical reaction determines or controls concentrations at steady states far from equilibrium. The oxidation of nicotinamide adenine dinucleotide (NADH) catalyzed by the enzyme horseradish peroxidase with continuous input of oxygen was studied; NAD+ is continuously recycled to NADH through a glucose-6-phosphate dehydrogenase system. A comparison of steady-state concentrations is made with an oscillatory oxygen input and a constant input at the same average oxygen input for both modes. By varying the frequency and amplitude of the perturbation (O2 influx), the following may be changed: the average concentration of NADH; the Gibbs free energy difference delta G of the reactants and products at steady state; the average rate of the reaction; the phase relation between the oscillatory rate and delta G; and the dissipation. These results confirm the possibility of an "alternating current chemistry," of control and optimization of thermodynamic efficiency and dissipation by means of external variation of constraints in classes of nonlinear reactions and biological pumps, and of improvements of the yield in such reactions (heterogeneous catalysis, for example).〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Lazar, J G -- Ross, J -- New York, N.Y. -- Science. 1990 Jan 12;247(4939):189-92.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, Stanford University, CA 94305.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2294601" target="_blank"〉PubMed〈/a〉
    Keywords: Adenosine Triphosphate/metabolism ; Chemical Phenomena ; Chemistry ; Glucosephosphate Dehydrogenase/*metabolism ; Horseradish Peroxidase/*metabolism ; Kinetics ; NAD/*metabolism ; Oxidation-Reduction ; Oxygen/metabolism ; Peroxidases/*metabolism ; Thermodynamics
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    An antibody binding site on cytochrome c defined by hydrogen exchange and two-dimensional NMR (1990)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1990-08-17
    Description: The interaction of a protein antigen, horse cytochrome c (cyt c), with a monoclonal antibody has been studied by hydrogen-deuterium (H-D) exchange labeling and two-dimensional nuclear magnetic resonance (2D NMR) methods. The H-exchange rate of residues in three discontiguous regions of the cyt c polypeptide backbone was slowed by factors up to 340-fold in the antibody-antigen complex compared with free cyt c. The protected residues, 36 to 38, 59, 60, 64 to 67, 100, and 101, and their hydrogen-bond acceptors, are brought together in the three-dimensional structure to form a contiguous, largely exposed protein surface with an area of about 750 square angstroms. The interaction site determined in this way is consistent with prior epitope mapping studies and includes several residues that were not previously identified. The hydrogen exchange labeling approach can be used to map binding sites on small proteins in antibody-antigen complexes and may be applicable to protein-protein and protein-ligand interactions in general.〈br /〉〈br /〉〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3432411/" target="_blank"〉〈img src="https://static.pubmed.gov/portal/portal3rc.fcgi/4089621/img/3977009" border="0"〉〈/a〉   〈a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3432411/" target="_blank"〉This paper as free author manuscript - peer-reviewed and accepted for publication〈/a〉〈br /〉〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Paterson, Y -- Englander, S W -- Roder, H -- GM 31847/GM/NIGMS NIH HHS/ -- GM 35926/GM/NIGMS NIH HHS/ -- R01 GM031847/GM/NIGMS NIH HHS/ -- S07-RR-05415-28/RR/NCRR NIH HHS/ -- New York, N.Y. -- Science. 1990 Aug 17;249(4970):755-9.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Microbiology, University of Pennsylvania, Philadelphia 19104.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/1697101" target="_blank"〉PubMed〈/a〉
    Keywords: Antibodies, Monoclonal/immunology/metabolism ; Antigen-Antibody Complex ; *Binding Sites, Antibody ; Chemical Phenomena ; Chemistry ; Cytochrome c Group/*immunology ; Deuterium ; Epitopes/immunology ; Hydrogen/*metabolism ; Hydrogen Bonding ; Kinetics ; *Magnetic Resonance Spectroscopy ; Molecular Structure ; Protein Conformation
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    Manifest destiny at the Scripps Research Institute (1991)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 1991-07-12
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Baskin, Y -- New York, N.Y. -- Science. 1991 Jul 12;253(5016):140-2.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/1853198" target="_blank"〉PubMed〈/a〉
    Keywords: *Academies and Institutes ; Biology ; California ; Chemical Phenomena ; Chemistry ; Research Support as Topic
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    Studies of unusual simple molecules by neutralization-reionization mass spectrometry (1990)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1990-02-23
    Description: Reactive or unstable molecules are key intermediates in many important reactions, but can be difficult to prepare for experimental studies. Species with missing (:CH-OH) or extra (H3) substituents can often be formed conveniently in the gas phase by neutralizing a beam of a more stable ionic counterpart (CH = O+H, H3+). Reionization of the neutral after approximately 10(-6) seconds tests its stability, whereas its unimolecular chemistry can be probed by preparing it with different amounts of internal energy. The resulting neutral products are reionized and mass analyzed. Isomers are then characterized by ion dissociation and a third mass-analysis step. Many unusual molecules have been characterized with this technique, which can also be used to probe complex unimolecular chemistry, such as that of cyclobutadiene and ethylene oxide.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉McLafferty, F W -- GM-16609/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 1990 Feb 23;247(4945):925-9.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Cornell University, Baker Laboratory, Ithaca, NY 14853-1301.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2305261" target="_blank"〉PubMed〈/a〉
    Keywords: Butadienes ; Chemical Phenomena ; Chemistry ; Ethylene Oxide ; Free Radicals ; Hydrocarbons ; *Ions ; *Mass Spectrometry ; Methane/analogs & derivatives ; Molecular Structure ; Thermodynamics
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    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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    Inhibition of FKBP rotamase activity by immunosuppressant FK506: twisted amide surrogate (1990)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 1990-05-18
    Description: The immunosuppressive agents cyclosporin A and FK506 inhibit the transcription of early T cell activation genes. The binding proteins for cyclosporin A and FK506, cyclophilin and FKBP, respectively, are peptidyl-prolyl-cis-trans isomerases, or rotamases. One proposed mechanism for rotamase catalysis by cyclophilin involves a tetrahedral adduct of an amide carbonyl and an enzyme-bound nucleophile. The potent FKBP rotamase inhibitor FK506 has a highly electrophilic carbonyl that is adjacent to an acyl-pipicolinyl (homoprolyl) amide bond. Such a functional group would be expected to form a stabilized, enzyme-bound tetrahedral adduct. Spectroscopic and chemical evidence reveals that the drug interacts noncovalently with its receptor, suggesting that the alpha-keto amid of FK506 serves as a surrogate for the twisted amide of a bound peptide substrate.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Rosen, M K -- Standaert, R F -- Galat, A -- Nakatsuka, M -- Schreiber, S L -- GM-38627/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 1990 May 18;248(4957):863-6.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, Harvard University, Cambridge, MA 02138.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/1693013" target="_blank"〉PubMed〈/a〉
    Keywords: Amino Acid Isomerases/*antagonists & inhibitors ; Anti-Bacterial Agents/metabolism/*pharmacology ; Binding Sites ; Carrier Proteins/antagonists & inhibitors/metabolism ; Chemical Phenomena ; Chemistry ; Cloning, Molecular ; Cyclosporins/metabolism/pharmacology ; Escherichia coli/genetics ; Gene Expression ; *Immunosuppressive Agents ; Lymphocyte Activation ; Magnetic Resonance Spectroscopy ; Molecular Structure ; Peptidylprolyl Isomerase ; Recombinant Proteins ; T-Lymphocytes/immunology ; Tacrolimus
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    At the crossroads of chemistry and immunology: catalytic antibodies (1991)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1991-05-03
    Description: Immunochemistry has historically focused on the nature of antigenicity and antibody-antigen recognition. However, in the last 5 years, the field of immunochemistry has taken a new direction. With the aid of mechanistic and synthetic chemistry, the vast network of molecules and cells of the immune system has been tapped to produce antibodies with a new function--catalytic antibodies. Because antibodies can be generated that selectively bind almost any molecule of interest, this new technology offers the potential to tailor-make highly selective catalysts for applications in biology, chemistry, and medicine. In addition, catalytic antibodies provide fundamental insight into important aspects of biological catalysis, including the importance of transition-state stabilization, proximity effects, general acid and base catalysts, electrophilic and nucleophilic catalysis, and strain.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Lerner, R A -- Benkovic, S J -- Schultz, P G -- New York, N.Y. -- Science. 1991 May 3;252(5006):659-67.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, Scripps Research Institute, La Jolla, CA 92037.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2024118" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; *Antibodies/chemistry/immunology/metabolism ; Antibodies, Monoclonal/immunology/metabolism ; Antibody Specificity ; Antigens/chemistry/immunology/metabolism ; Binding Sites, Antibody ; *Catalysis ; Chemical Phenomena ; Chemistry ; Haptens ; Hydrogen-Ion Concentration ; Hydrolysis ; Metals ; Molecular Conformation ; Recombinant Proteins ; Thermodynamics ; Zinc
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    Evolution. Darwin for all seasons (2006)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 2006-07-22
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Szathmary, Eors -- New York, N.Y. -- Science. 2006 Jul 21;313(5785):306-7.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Institute of Biology, Eotvos University Budapest, and Collegium Budapest (Institute for Advanced Study), 2 Szentharomsag utca, H-1014 Budapest, Hungary. szathmary@colbud.hu〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/16857926" target="_blank"〉PubMed〈/a〉
    Keywords: *Biological Evolution ; Chemical Phenomena ; Chemistry ; Computational Biology ; Cooperative Behavior ; Cultural Evolution ; Exobiology ; Humans ; Language ; Models, Biological ; Models, Theoretical ; Molecular Biology ; Origin of Life ; *Research ; Selection, Genetic
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    Herve This profile. The joy of evidence-based cooking (2006)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 2006-11-25
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Enserink, Martin -- New York, N.Y. -- Science. 2006 Nov 24;314(5803):1235-6.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/17124302" target="_blank"〉PubMed〈/a〉
    Keywords: Chemistry ; *Cooking ; *Food ; France ; History, 20th Century ; History, 21st Century
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    Cyberinfrastructure for e-Science (2005)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 2005-05-10
    Description: Here we describe the requirements of an e-Infrastructure to enable faster, better, and different scientific research capabilities. We use two application exemplars taken from the United Kingdom's e-Science Programme to illustrate these requirements and make the case for a service-oriented infrastructure. We provide a brief overview of the UK "plug-and-play composable services" vision and the role of semantics in such an e-Infrastructure.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Hey, Tony -- Trefethen, Anne E -- New York, N.Y. -- Science. 2005 May 6;308(5723):817-21.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Engineering and Physical Sciences Research Council, Polaris House, North Star Avenue, Swindon SN2 1ET, UK.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/15879209" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; Combinatorial Chemistry Techniques ; *Computational Biology ; *Computer Communication Networks ; *Computing Methodologies ; Databases as Topic ; Graves Disease/genetics ; *Internet ; *Research ; *Software ; Williams Syndrome/genetics
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    Profile: Marina Protopopova (2004)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 2004-05-29
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Malakoff, David -- New York, N.Y. -- Science. 2004 May 28;304(5675):1283.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/15166364" target="_blank"〉PubMed〈/a〉
    Keywords: Biotechnology ; Career Choice ; Chemistry ; Emigration and Immigration ; History, 20th Century ; History, 21st Century ; Siberia ; United States
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    The class of 2005. United States: two scientists and a baby (2005)
    American Association for the Advancement of Science (AAAS)
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    Publication Date: 2005-10-22
    Description: If you trust the conventional wisdom, Amy Palmer and Alexis Templeton did a lot of things wrong in their job search. Then why did things turn out so right?〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Austin, Jim -- New York, N.Y. -- Science. 2005 Oct 21;310(5747):518-9.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/16239480" target="_blank"〉PubMed〈/a〉
    Keywords: *Career Choice ; *Career Mobility ; Chemical Phenomena ; Chemistry ; Education, Graduate ; *Faculty ; Microbiology ; *Research ; United States ; *Universities
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    [This Week in Science] Synthetic twists among lipids (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2016-04-29
    Description: Author: Jake Yeston
    Keywords: Chemistry
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    [This Week in Science] Temporarily caught in a bind (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2016-03-18
    Description: Author: Marc S. Lavine
    Keywords: Chemistry
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    [Perspective] Quantum dynamics in the smallest water droplet (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2016-03-18
    Description: Water plays a central role in scientific disciplines ranging from geology to astronomy to biology. Yet it is an extraordinarily dif cult liquid to understand because of its complex, ever-changing patterns of hydrogen bonds. Studies of small water clusters have provided important insights into the concerted hydrogen-bond motions that can occur in water. These studies are also crucial for developing an accurate potential function for simulating the properties of liquid water and ice (1). On page 1310 of this issue, Richardson et al. (2) provide evidence for a concerted type of motion in which two hydrogen bonds in a water cluster are broken simultaneously (see the figure). The results have implications for many areas of scientific study, including the chemistry of polar solvents, the conformations of proteins, and the dissolution of ions in minerals. Author: David C. Clary
    Keywords: Chemistry
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    [Editors' Choice] Beyond blank slates in the lab notebook (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2016-03-18
    Description: Author: Jake Yeston
    Keywords: Chemistry
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    [Perspective] Surprised by selectivity (2016)
    American Association for the Advancement of Science (AAAS)
    In: Science
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    Publication Date: 2016-03-04
    Description: Lower olefins, particularly ethylene (C2H4), propylene (C3H6), and butylene (C4H8), are important intermediates in the manufacture of products such as plastics, solvents, paints, and medicines. They are produced worldwide in amounts exceeding 200 million tons per year (see the photo) (1), mostly from crude oil. More recent approaches use methanol or synthesis gas (syngas; a mixture of carbon monoxide and hydrogen) as feedstocks, but capital investments are high and/or selectivities to lower olefins limited. A bifunctional catalyst reported by Jiao et al. on page 1065 of this issue (2) enables the direct conversion of synthesis gas to lower olefins with a surprisingly high selectivity. Author: Krijn P. de Jong
    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
    Details
    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
    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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    Steps to smaller rings (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-11-02
    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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  • 95
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    Pinpointing the role of geometric phase (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-12-14
    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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  • 96
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    Salt and iron ease the way to amines (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-10-26
    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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  • 97
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    Catalytic palladium-oxyallyl cycloaddition (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    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
    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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  • 98
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    Heterocycles meet and marry on phosphorus (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-11-16
    Keywords: Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 99
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    DNA binding by proteins (1988)
    American Association for the Advancement of Science (AAAS)
    Details
    Publication Date: 1988-09-02
    Description: Study of proteins that recognize specific DNA sequences has yielded much information, but the field is still in its infancy. Already two major structural motifs have been discovered, the helix-turn-helix and zinc finger, and numerous examples of DNA-binding proteins containing either of them are known. The restriction enzyme Eco RI uses yet a different motif. Additional motifs are likely to be found as well. There is a growing understanding of some of the physical chemistry involved in protein-DNA binding, but much remains to be learned before it becomes possible to engineer a protein that binds to a specific DNA sequence.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Schleif, R -- New York, N.Y. -- Science. 1988 Sep 2;241(4870):1182-7.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Graduate Department of Biochemistry, Brandeis University, Waltham, MA 02254.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/2842864" target="_blank"〉PubMed〈/a〉
    Keywords: Amino Acids/metabolism ; Binding Sites ; Chemical Phenomena ; Chemistry ; DNA/metabolism ; DNA Restriction Enzymes/metabolism ; DNA-Binding Proteins/*metabolism ; Deoxyribonuclease EcoRI ; Electrochemistry ; Nucleic Acids/metabolism ; Protein Conformation ; Zinc
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 100
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    A rapid screen for complex reactants (2018)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2018-08-10
    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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