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  • Chemistry  (81,333)
  • Inorganic Chemistry  (14,880)
  • 1980-1984  (33,715)
  • 1965-1969  (23,845)
  • 1955-1959  (13,362)
  • 1925-1929
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  • 1
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1981-08-14
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Klotz, I M -- Haney, D N -- King, L C -- New York, N.Y. -- Science. 1981 Aug 14;213(4509):724-31.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/7256275" target="_blank"〉PubMed〈/a〉
    Keywords: Anemia, Sickle Cell/*drug therapy ; Aspirin/analogs & derivatives/therapeutic use ; Chemical Phenomena ; Chemistry ; *Hemoglobin, Sickle ; Humans ; Protein Binding/drug effects ; Protein Conformation ; Salicylates/*therapeutic use ; Solubility ; Structure-Activity Relationship
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  • 2
    Publication Date: 1982-09-10
    Description: Alkyl-Substituted gamma-butyrolactones were synthesized and tested for their convulsant and anticonvulsant actions in mice and guinea pigs. The alpha-substituted compounds, alpha, alpha-dimethyl-, and alpha-ethyl-alpha-methyl-gamma-butyrolactone were anticonvulsant compounds with a spectrum of activity similar to that of ethosuximide. In contrast, beta-substituted compounds were convulsant agents similar to picrotoxinin. The alpha-substituted-gama-butyrolactones represent a new class of anticonvulsant drug with experimental and clinical potential.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Klunk, W E -- McKeon, A -- Covey, D F -- Ferrendelli, J A -- GM-07200/GM/NIGMS NIH HHS/ -- GM-24483/GM/NIGMS NIH HHS/ -- NS-14834/NS/NINDS NIH HHS/ -- etc. -- New York, N.Y. -- Science. 1982 Sep 10;217(4564):1040-2.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6810462" target="_blank"〉PubMed〈/a〉
    Keywords: *4-Butyrolactone/analogs & derivatives/*therapeutic use/toxicity ; Animals ; *Anticonvulsants ; Chemical Phenomena ; Chemistry ; Convulsants ; Drug Evaluation, Preclinical ; Electroencephalography ; Epilepsy, Absence/drug therapy ; Ethosuximide/pharmacology ; *Furans/*therapeutic use ; Guinea Pigs ; Mice ; Structure-Activity Relationship ; Trimethadione/pharmacology
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  • 3
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1983-05-06
    Description: Crystalline cholesterol undergoes a phase transition a few degrees below human body temperature. The high-temperature form has an unusually complex structure with 16 independent molecules. In the transition two molecules change side chain conformation, four reorient about their long axes, and ten remain unchanged. The transition mechanism implies relatively nonspecific intermolecular interactions, qualitatively consistent with the behavior of cholesterol in biomembranes. The transition preserves a remarkably closely obeyed pseudosymmetry present in the structure.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Hsu, L Y -- Nordman, C E -- GM15259/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 1983 May 6;220(4597):604-6.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6836303" target="_blank"〉PubMed〈/a〉
    Keywords: Body Temperature ; Chemical Phenomena ; Chemistry ; *Cholesterol ; Crystallization ; Humans ; Magnetic Resonance Spectroscopy ; Molecular Conformation
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  • 4
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1984-07-20
    Description: The iron-carbon monoxide stretching mode and the iron-carbon-oxygen bending mode in carbon monoxide-bound cytochrome oxidase have been assigned at 520 and 578 cm-1, respectively. The frequencies, widths, and intensities of these modes show that the Fe-C-O grouping in carbon monoxide-cytochrome a3 is linear but tilted from the normal to the heme plane; that the iron-histidine bond in both five- and six-coordinate cytochrome a3 is strained; and that the carbon monoxide and the proximal histidine each have characteristic, well-defined orientations in all molecules. These data can account for the binding affinities of carbon monoxide and dioxygen under physiological conditions.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Argade, P V -- Ching, Y C -- Rousseau, D L -- New York, N.Y. -- Science. 1984 Jul 20;225(4659):329-31.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6330890" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; Carbon Monoxide/metabolism ; Cattle ; Chemical Phenomena ; Chemistry ; Electron Transport Complex IV/*metabolism ; Myoglobin/metabolism ; Oxidation-Reduction ; Oxygen/metabolism ; Spectrum Analysis, Raman
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  • 5
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1983-05-06
    Description: Arachidonic acid plays a central role in a biological control system where such oxygenated derivatives as prostaglandins, thromboxanes, and leukotrienes are mediators. The leukotrienes are formed by transformation of arachidonic acid into an unstable epoxide intermediate, leukotriene A4, which can be converted enzymatically by hydration to leukotriene B4, and by addition of glutathione to leukotriene C4. This last compound is metabolized to leukotrienes D4 and E4 by successive elimination of a gamma-glutamyl residue and glycine. Slow-reacting substance of anaphylaxis consists of leukotrienes C4, D4, and E4. The cysteinyl-containing leukotrienes are potent bronchoconstrictors, increase vascular permeability in postcapillary venules, and stimulate mucus secretion. Leukotriene B4 causes adhesion and chemotactic movement of leukocytes and stimulates aggregation, enzyme release, and generation of superoxide in neutrophils. Leukotrienes C4, D4, and E4, which are released from the lung tissue of asthmatic subjects exposed to specific allergens, seem to play a pathophysiological role in immediate hypersensitivity reactions. These leukotrienes, as well as leukotriene B4, have pro-inflammatory effects.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Samuelsson, B -- New York, N.Y. -- Science. 1983 May 6;220(4597):568-75.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6301011" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; Arachidonic Acids/metabolism/pharmacology/physiology ; Bronchi/drug effects ; Cats ; Chemical Phenomena ; Chemistry ; Cricetinae ; Guinea Pigs ; Haplorhini ; Humans ; Hypersensitivity, Immediate/*physiopathology ; Inflammation/*physiopathology ; Leukocytes/drug effects/metabolism ; Leukotriene B4/pharmacology/*physiology ; Mice ; Microcirculation/drug effects ; Rabbits ; Rats ; SRS-A/*physiology
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  • 6
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1984-01-20
    Description: Peptide synthesis can be used for elucidating the roles of secondary structures in the specificity of hormones, antigens, and toxins. Intermediate sized peptides with these activities assume amphiphilic secondary structures in the presence of membranes. When models are designed to optimize the amphiphilicity of the secondary structure, stronger interactions can be observed with the synthetic peptides than with the naturally occurring analogs.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Kaiser, E T -- Kezdy, F J -- HL-18577/HL/NHLBI NIH HHS/ -- New York, N.Y. -- Science. 1984 Jan 20;223(4633):249-55.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6322295" target="_blank"〉PubMed〈/a〉
    Keywords: Amino Acid Sequence ; Apolipoprotein A-I ; Apolipoproteins ; Binding Sites ; Calcitonin ; Chemical Phenomena ; Chemistry ; Corticotropin-Releasing Hormone ; Endorphins ; Glucagon ; Growth Hormone-Releasing Hormone ; *Hormones/pharmacology ; Lipoproteins, HDL ; Melitten ; Models, Structural ; *Peptides/chemical synthesis/metabolism/pharmacology ; Protein Conformation ; Structure-Activity Relationship ; beta-Endorphin
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  • 7
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1984-10-19
    Description: Fourier transform mass spectrometry will play an important role in the future because of its unique combination of high mass resolution, high upper mass limit, and multichannel advantage. These features have already found application in gas chromatography-mass spectrometry, multiphoton ionization, laser desorption, and secondary ion mass spectrometry. However, its most notable feature is the ability to store ions. This characteristic, when combined with the others, will allow expeditious study of the interaction of gas-phase ions with both photons (photodissociation) and neutral molecules, and the convenient application of this fundamental information for chemical analysis.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Gross, M L -- Rempel, D L -- 2-8423576/PHS HHS/ -- New York, N.Y. -- Science. 1984 Oct 19;226(4672):261-8.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6385250" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Fourier Analysis ; Ions ; Lasers ; *Mass Spectrometry/instrumentation/methods
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  • 8
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1984-08-31
    Description: High-resolution carbon-13 nuclear magnetic resonance (NMR) spectra of enzyme-inhibitor and enzyme-substrate complexes provide detailed structural and stereochemical information on the mechanism of enzyme action. The proteases trypsin and papain are shown to form tetrahedrally coordinated complexes and acyl derivatives with a variety of compounds artificially enriched at the site or sites of interest. These results are compared with the structural information derived from x-ray diffraction. Detailed NMR studies have provided a clearer picture of the ionization state of the residues participating in enzyme-catalyzed processes than other more classical techniques. The dynamics of enzymic catalysis can be observed at sub-zero temperatures by a combination of cryoenzymology and carbon-13 NMR spectroscopy. With these powerful techniques, transient, covalently bound intermediates in enzyme-catalyzed reactions can be detected and their structures rigorously assigned.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Mackenzie, N E -- Malthouse, J P -- Scott, A I -- New York, N.Y. -- Science. 1984 Aug 31;225(4665):883-9.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6433481" target="_blank"〉PubMed〈/a〉
    Keywords: Binding Sites ; Carbon Isotopes ; Carboxypeptidases/metabolism ; Carboxypeptidases A ; Catalysis ; Chemical Phenomena ; Chemistry ; Coenzymes/*metabolism ; Endopeptidases/metabolism ; Enzymes/*metabolism ; Freezing ; Fructose-Bisphosphate Aldolase/metabolism ; Magnetic Resonance Spectroscopy ; Papain/metabolism ; Pepsin A/metabolism ; Peptide Hydrolases/*metabolism ; Protease Inhibitors ; Pterins/metabolism ; Pyridoxal Phosphate/metabolism ; Serine Endopeptidases
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  • 9
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1984-03-09
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Maugh, T H 2nd -- New York, N.Y. -- Science. 1984 Mar 9;223(4640):1051-2.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6695193" target="_blank"〉PubMed〈/a〉
    Keywords: *Air Pollutants ; *Atmosphere ; Carbon Tetrachloride ; Chemical Phenomena ; Chemistry ; *Chlorofluorocarbons, Methane ; Free Radicals ; Nitrogen Dioxide ; Nitrous Oxide ; Oxygen ; *Ozone ; Photochemistry ; Risk ; Singlet Oxygen ; Trichloroethanes ; Ultraviolet Rays
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  • 10
    Publication Date: 1984-10-19
    Description: Pyrolysis mass spectrometry in combination with computerized multivariate statistical analysis enables qualitative and quantitative analysis of nonvolatile organic materials containing molecular assemblies of a complexity and size far beyond the capabilities of direct mass spectrometry. The state of the art in pyrolysis mass spectrometry techniques is illustrated through specific applications, including structural determination and quality control of synthetic polymers, quantitative analysis of polymer mixtures, classification and structural characterization of fossil organic matter, and nonsupervised numerical extraction of component patterns from complex biological samples.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Meuzelaar, H L -- Windig, W -- Harper, A M -- Huff, S M -- McClennen, W H -- Richards, J M -- New York, N.Y. -- Science. 1984 Oct 19;226(4672):268-74.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6484572" target="_blank"〉PubMed〈/a〉
    Keywords: Biochemical Phenomena ; Biochemistry ; Chemical Phenomena ; Chemistry ; Coal ; Enterobacteriaceae/analysis/isolation & purification ; Hot Temperature ; Mass Spectrometry/*methods ; Polymers
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  • 11
    Publication Date: 1984-08-31
    Description: The splicing of messenger RNA precursors in vitro proceeds through an intermediate that has the 5' end of the intervening sequence joined to a site near the 3' splice site. This lariat structure, which has been characterized for an adenovirus 2 major late transcript, has a branch point, with 2'-5' and 3'-5' phosphodiester bonds emanating from a single adenosine residue. The excised intervening sequence retains the branch site and terminates in a guanosine residue with a 3' hydroxyl group. The phosphate group at the splice junction between the two exons originates from the 3' splice site at the precursor.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Padgett, R A -- Konarska, M M -- Grabowski, P J -- Hardy, S F -- Sharp, P A -- P01-CA14051/CA/NCI NIH HHS/ -- P01-CA26717/CA/NCI NIH HHS/ -- R01-GM32467/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 1984 Aug 31;225(4665):898-903.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6206566" target="_blank"〉PubMed〈/a〉
    Keywords: Adenoviruses, Human/metabolism ; Base Sequence ; Chemical Phenomena ; Chemistry ; Nucleic Acid Conformation ; Nucleic Acid Precursors/analysis/*metabolism ; Oligoribonucleotides/metabolism ; Phosphates/metabolism ; RNA/analysis/*metabolism ; RNA Precursors ; *RNA Splicing ; RNA, Messenger/analysis/*metabolism ; RNA, Viral/analysis/*metabolism
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  • 12
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1984-05-11
    Description: The mechanism of lipid peroxidation and the manner in which antioxidants function is reviewed. beta-Carotene is a purported anticancer agent, which is believed by some to have antioxidant action of a radical-trapping type. However, definitive experimental support for such action has been lacking. New experiments in vitro show that beta-carotene belongs to a previously unknown class of biological antioxidants. Specifically, it exhibits good radical-trapping antioxidant behavior only at partial pressures of oxygen significantly less than 150 torr, the pressure of oxygen in normal air. Such low oxygen partial pressures are found in most tissues under physiological conditions. At higher oxygen pressures, beta-carotene loses its antioxidant activity and shows an autocatalytic, prooxidant effect, particularly at relatively high concentrations. Similar oxygen-pressure-dependent behavior may be shown by other compounds containing many conjugated double bonds.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Burton, G W -- Ingold, K U -- New York, N.Y. -- Science. 1984 May 11;224(4649):569-73.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6710156" target="_blank"〉PubMed〈/a〉
    Keywords: Antioxidants/*metabolism ; Carotenoids/*metabolism ; Chemical Phenomena ; Chemistry ; Free Radicals ; Humans ; Linoleic Acids/metabolism ; *Lipid Metabolism ; Oxidation-Reduction ; Oxygen/metabolism ; Partial Pressure ; Peroxides/metabolism ; Tetrahydronaphthalenes/metabolism ; beta Carotene
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  • 13
    Publication Date: 1983-12-16
    Description: Aplysiatoxin and debromoaplysiatoxin, which are isolated from the seaweed, Lyngbya gracilis, differ in their chemical structure only by the presence or absence of a bromine residue in the hydrophilic region. The function and the structure-activity relation of the hydrophilic region are not known. Aplysiatoxin increased malignant transformation, stimulated DNA synthesis, and inhibited the binding of phorbol-12,13-dibutyrate and epidermal growth factor to cell receptors. Debromoaplysiatoxin inhibited the binding of these two substances as strongly as aplysiatoxin but did not increase malignant transformation or stimulate DNA synthesis. These results indicate that a slight change in the chemical structure of the hydrophilic region of aplysiatoxin affects its abilities to increase cell transformation and stimulate DNA synthesis and that the abilities of the tumor promoters to inhibit the binding of phorbol-12,13-dibutyrate and epidermal growth factor are dissociable from their abilities to increase cell transformation and stimulate DNA synthesis under some circumstances.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Shimomura, K -- Mullinix, M G -- Kakunaga, T -- Fujiki, H -- Sugimura, T -- New York, N.Y. -- Science. 1983 Dec 16;222(4629):1242-4.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6316505" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; *Caenorhabditis elegans Proteins ; Carcinogens/*pharmacology ; Carrier Proteins ; Cell Line ; Cell Transformation, Neoplastic/*drug effects ; Chemical Phenomena ; Chemistry ; DNA/biosynthesis ; Epidermal Growth Factor/metabolism ; Lactones/analysis/*pharmacology ; *Lyngbya Toxins ; Mice ; Phorbol 12,13-Dibutyrate ; Phorbol Esters/metabolism ; *Protein Kinase C ; Receptor, Epidermal Growth Factor ; Receptors, Cell Surface/metabolism ; *Receptors, Drug ; Structure-Activity Relationship
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  • 14
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1984-03-16
    Description: Yeast phenylalanine transfer RNA was subjected to a 12-picosecond molecular dynamics simulation. The principal features of the x-ray crystallographic analysis are reproduced, and the amplitudes of atomic displacements appear to be determined by the degree of exposure of the atoms. An analysis of the hydrogen bonds shows a correlation between the average length of a bond and the fluctuation in that length and reveals a rocking motion of bases in Watson-Crick guanine X cytosine base pairs. The in-plane motions of the bases are generally of larger amplitude than the out-of-plane motions, and there are correlations in the motions of adjacent bases.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Harvey, S C -- Prabhakaran, M -- Mao, B -- McCammon, J A -- New York, N.Y. -- Science. 1984 Mar 16;223(4641):1189-91.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6560785" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; Computers ; Cytosine ; Guanine ; Hydrogen Bonding ; Nucleic Acid Conformation ; *RNA, Fungal ; *RNA, Transfer, Amino Acyl ; Yeasts/analysis
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  • 15
    Publication Date: 1984-11-16
    Description: Sequence-dependent variations in DNA revealed by x-ray crystallographic studies have suggested that certain DNA-reactive drugs may react preferentially with defined sequences in DNA. Drugs that wind around the helix and reside within one of the grooves of DNA have perhaps the greatest chance of recognizing sequence-dependent features of DNA. The antitumor antibiotic CC-1065 covalently binds through N-3 of adenine and resides within the minor groove of DNA. This drug overlaps with five base pairs for which a high sequence specificity exists.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Hurley, L H -- Reynolds, V L -- Swenson, D H -- Petzold, G L -- Scahill, T A -- New York, N.Y. -- Science. 1984 Nov 16;226(4676):843-4.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6494915" target="_blank"〉PubMed〈/a〉
    Keywords: Antibiotics, Antineoplastic/*metabolism ; *Base Sequence ; Binding Sites ; Chemical Phenomena ; Chemistry ; DNA/*metabolism ; *Indoles ; Leucomycins/*metabolism ; Molecular Conformation ; X-Ray Diffraction
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  • 16
    Publication Date: 1984-06-15
    Description: A new class of synthetic antifungal agents, the allylamines , has been developed by modification of naftifine , a topical antimycotic. SF 86-327, the most effective of these compounds so far, is highly active in vitro against a wide range of fungi and exceeds clinical standards in the oral and topical treatment of guinea pig dermatophytoses. SF 86-327 is a powerful specific inhibitor of fungal squalene epoxidase, a key enzyme in sterol biosynthesis.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Petranyi, G -- Ryder, N S -- Stutz, A -- New York, N.Y. -- Science. 1984 Jun 15;224(4654):1239-41.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6547247" target="_blank"〉PubMed〈/a〉
    Keywords: Allylamine/analogs & derivatives/*chemical synthesis/pharmacology ; Amines/*chemical synthesis ; Animals ; Antifungal Agents/*chemical synthesis/pharmacology ; Chemical Phenomena ; Chemistry ; Dermatomycoses/drug therapy ; Fungi/*drug effects/enzymology ; Guinea Pigs ; Naphthalenes/chemical synthesis/pharmacology ; Oxygenases/*antagonists & inhibitors ; Squalene Monooxygenase
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  • 17
    Publication Date: 1984-11-02
    Description: By recombinant DNA techniques, a disulfide bond was introduced at a specific site in T4 lysozyme, a disulfide-free enzyme. This derivative retained full enzymatic activity and was more stable toward thermal inactivation than the wild-type protein. The derivative, T4 lysozyme (Ile3----Cys), was prepared by substituting a Cys codon for an Ile codon at position 3 in the cloned lysozyme gene by means of oligonucleotide-dependent, site-directed mutagenesis. The new gene was expressed in Escherichia coli under control of the (trp-lac) hybrid tac promoter, and the protein was purified. Mild oxidation generated a disulfide bond between the new Cys3 and Cys97, one of the two unpaired cysteines of the native molecule. Oxidized T4 lysozyme (Ile3----Cys) exhibited specific activity identical to that of the wild-type enzyme when measured at 20 degrees C in a cell-clearing assay. The cross-linked protein was more stable than the wild type during incubation at elevated temperatures as determined by recovered enzymatic activity at 20 degrees C.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Perry, L J -- Wetzel, R -- New York, N.Y. -- Science. 1984 Nov 2;226(4674):555-7.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6387910" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; DNA, Recombinant/metabolism ; Escherichia coli/enzymology ; *Genetic Engineering ; Kinetics ; Muramidase/*genetics/metabolism ; Protein Denaturation
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  • 18
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1983-09-09
    Description: The structures of three proteins that regulate gene expression have been determined recently and suggest how these proteins may bind to their specific recognition sites on the DNA. One protein (Cro) is a repressor of gene expression, the second (CAP) usually stimulates gene expression, and the third (lambda repressor) can act as either a repressor or an activator. The three proteins contain a substructure consisting of two consecutive alpha helices that is virtually identical in each case. Structural and amino acid sequence comparisons suggest that this bihelical fold occurs in a number of proteins that regulate gene expression, and is an intrinsic part of the DNA-protein recognition event. The modes of repression and activation by Cro and lambda repressor are understood reasonably well, but the mode of action of CAP is still unclear.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Takeda, Y -- Ohlendorf, D H -- Anderson, W F -- Matthews, B W -- GM20066/GM/NIGMS NIH HHS/ -- GM28138/GM/NIGMS NIH HHS/ -- GM30894/GM/NIGMS NIH HHS/ -- New York, N.Y. -- Science. 1983 Sep 9;221(4615):1020-6.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6308768" target="_blank"〉PubMed〈/a〉
    Keywords: Amino Acid Sequence ; Chemical Phenomena ; Chemistry ; *DNA Helicases ; DNA-Binding Proteins ; Escherichia coli/genetics ; Gene Expression Regulation ; Models, Chemical ; Protein Conformation
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  • 19
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1984-06-08
    Description: The effect of a partial pressure of nitrogen of 50 atmospheres (5065 kilopascals ) on the hydrogen evolution reaction of nitrogenase has been investigated. Evolution of hydrogen was not blocked completely by 50 atmospheres of nitrogen in any of four experiments; rather, 27.3 +/- 2.4 percent of the total electron flux through nitrogenase was directed toward production of hydrogen. The ratio of hydrogen evolved to nitrogen fixed was close to 1:1, which implies that hydrogen evolution is obligatory in the fixation of molecular nitrogen by nitrogenase.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Simpson, F B -- Burris, R H -- AI-00848/AI/NIAID NIH HHS/ -- New York, N.Y. -- Science. 1984 Jun 8;224(4653):1095-7.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6585956" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Hydrogen ; *Nitrogen ; Nitrogen Fixation ; *Nitrogenase ; Partial Pressure
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  • 20
    Publication Date: 1980-01-04
    Description: In concentrates of water produced in a laboratory simulation of a drinking water treatment process, direct-acting, nonvolatile mutagens were readily detected by means of the Ames Salmonella test. The mutagens were shown to be produced by the chlorination process. Treatment of the water with chloramine resulted in less mutagenic activity than treatment with free chlorine. Dechlorination of drinking water with sulfite sharply reduced the mutagenic activity. Treatment with sulfur dioxide is proposed as an effective, inexpensive method of reducing the direct-acting mutagenic activity of drinking water and of aqueous industrial effluents.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Cheh, A M -- Skochdopole, J -- Koski, P -- Cole, L -- New York, N.Y. -- Science. 1980 Jan 4;207(4426):90-2.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6985746" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; Chloramines ; Chlorine ; Mutagens/*analysis ; Salmonella typhimurium/genetics ; Sulfites ; Water Pollutants/*analysis ; Water Pollutants, Chemical/*analysis ; Water Supply/*analysis
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  • 21
    Publication Date: 1981-10-16
    Description: The DNA/RNA Synthesizer provides a complete and automated procedure for the synthesis of DNA sequences. Each base unit is added in a 30-minute cycle, permitting a tetradecamer to be constructed in 6 1/2 hours. The complete procedure is described, including a practical procedure for isolation and purification of the desired DNA sequence.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Alvarado-Urbina, G -- Sathe, G M -- Liu, W C -- Gillen, M F -- Duck, P D -- Bender, R -- Ogilvie, K K -- New York, N.Y. -- Science. 1981 Oct 16;214(4518):270-4.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6169150" target="_blank"〉PubMed〈/a〉
    Keywords: Automation ; Chemical Phenomena ; Chemistry ; DNA/*chemical synthesis ; *Genes, Synthetic ; RNA/*chemical synthesis ; Solubility
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  • 22
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1981-05-15
    Description: Research on chitin as a marine resource is pointing to novel applications for this cellulose-like biopolymer. Discovery of nondegrading solvent systems has permitted the spinning of filaments, for example, for use as surgical sutures. New methods for preparing the bioactive alkyl glycoside of N-acetyl-D-glucosamine (the monomer unit of chitin) and a microcrystalline chitin has encouraged their use as promoters for growth of bifidobacteria and as an aid in digestion of high-lactose cheese whey by domestic animals. Chitin-protein complexes of several crustacean species show great variability in ratios of chitin to covalently bound protein and in residual protein in the "purified" chitins.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Austin, P R -- Brine, C J -- Castle, J E -- Zikakis, J P -- New York, N.Y. -- Science. 1981 May 15;212(4496):749-53.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/7221561" target="_blank"〉PubMed〈/a〉
    Keywords: Animal Feed ; Animals ; Cheese ; Chemical Phenomena ; Chemistry ; Chickens ; *Chitin ; Crystallography ; Lactose/metabolism ; Proteins/analysis ; Sutures ; *Technology
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  • 23
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1981-12-18
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Gilbert, W -- New York, N.Y. -- Science. 1981 Dec 18;214(4527):1305-12.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/7313687" target="_blank"〉PubMed〈/a〉
    Keywords: Base Sequence ; Chemical Phenomena ; Chemistry ; DNA/*genetics ; Eukaryotic Cells/physiology ; *Genes ; Hydrazines ; Lac Operon ; Methylation ; Prokaryotic Cells/physiology ; Sulfuric Acid Esters
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  • 24
    Publication Date: 1982-07-09
    Description: A new process has been developed which is called "Boradeption" to signify boronic acid--dependent phase transfer of water-insoluble agents. Highly fluorescent boronic acid dervatives, FluoroBoras, are solubilized with a physiologically compatible carrier buffer containing a receptor group for boronate adduct formation. The system can be used to stain living cells. In another variation of the Boradeption concept, an insoluble reporter molecule containing a boronate receptor is solubilized with a carrier buffer containing a boronic acid functional group. The boronate-receptor complexes, which are in dynamic equilibrium, can be designed as vital stains and reagents for a variety of biological and medical applications.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Gallop, P M -- Paz, M A -- Henson, E -- AG-00376-07/AG/NIA NIH HHS/ -- HL-20764-04A1/HL/NHLBI NIH HHS/ -- New York, N.Y. -- Science. 1982 Jul 9;217(4555):166-9.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6178158" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; *Biological Transport ; *Boron Compounds/therapeutic use ; *Boronic Acids/therapeutic use ; *Cell Membrane Permeability ; Cells, Cultured ; Chemical Phenomena ; Chemistry ; Chromogenic Compounds/metabolism ; Cricetinae ; Fibroblasts ; Fluorescent Dyes/metabolism ; Humans ; Rats ; Staining and Labeling
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  • 25
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1981-12-11
    Description: The scrapie agent causes a degenerative nervous system disease in sheep and goats. Studies with extensively purified preparations demonstrated that the agent contains a protein that is required for infectivity. Chemical modification of the scrapie agent by diethyl pyrocarbonate reduced the titer 1000-fold. Exposure of the inactivated agent to hydroxylamine, a strong nucleophile, resulted in complete restoration of infectivity. Presumably, nucleophilic residues within a scrapie agent protein undergo carbethoxylation on reaction with diethyl pyrocarbonate, and subsequent addition of hydroxylamine displaces these carbethoxy groups.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉McKinley, M P -- Masiarz, F R -- Prusiner, S B -- NS14069/NS/NINDS NIH HHS/ -- New York, N.Y. -- Science. 1981 Dec 11;214(4526):1259-61.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6795721" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; Biological Assay ; Brain/microbiology ; Chemical Phenomena ; Chemistry ; Cricetinae ; Diethyl Pyrocarbonate/pharmacology ; Histidine/pharmacology ; *Prions ; Ribonucleases/pharmacology ; Serum Albumin, Bovine/pharmacology ; Viral Proteins/*isolation & purification/pharmacology
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  • 26
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1981-01-30
    Description: The incubation of lens proteins with reducing sugars leads to the formation of fluorescent yellow pigments and cross-like similar to those reported in aging and cataractous human lenses. Called nonenzymatic browning or the Maillard reaction, this aging process also occurs in stored foods. Reducing sugars condense with the free amino group of proteins, then rearrange and dehydrate to form unsaturated pigments and cross-linked products. Although most proteins in living systems turn over with sufficient rapidity to avoid nonenzymatic browning, some, such as lens crystallins and skin collagen, are exceptionally long-lived and may be vulnerable.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Monnier, V M -- Cerami, A -- AM 19655/AM/NIADDK NIH HHS/ -- New York, N.Y. -- Science. 1981 Jan 30;211(4481):491-3.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6779377" target="_blank"〉PubMed〈/a〉
    Keywords: *Aging ; Animals ; Cattle ; Chemical Phenomena ; Chemistry ; *Crystallins ; Diabetes Mellitus/physiopathology ; Glucose ; Glucosephosphates ; In Vitro Techniques ; Lysine ; *Proteins ; Spectrophotometry, Ultraviolet
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  • 27
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1981-03-13
    Description: Great advances have been made in fundamental scientific research in recent years. The new knowledge gathered, in addition to deepening our understanding of the physical universe, contributes a range of abilities and opportunities to society that would not otherwise be available. Much research that may be called applied because it addresses needs of society is quite fundamental in character, and support of such research at the National Science Foundation is to be handled in tandem by the research directorates. Other areas that require a refocusing of support are engineering science and education, at all levels, in science and engineering. Increasing our strength in these areas is essential to achieve our national economic, social, and political goals. Steps are being taken by the National Science Foundation to make its structure better able to deal with engineering and applied research and to provide greater mutual reinforcement between applied and basic research.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Slaughter, J B -- New York, N.Y. -- Science. 1981 Mar 13;211(4487):1131-6.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/7466384" target="_blank"〉PubMed〈/a〉
    Keywords: Cell Biology ; Chemical Phenomena ; Chemistry ; *Forecasting ; Geological Phenomena ; Geology ; *Government Agencies ; Molecular Biology ; Neurochemistry ; Physical Phenomena ; Physics ; Research Support as Topic ; United States
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  • 28
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1982-12-10
    Description: The discovery that cis-diamminedichloroplatinum(II) (cis-DDP) has clinically useful antitumor properties and can form platinum blues spawned an extensive investigation of its chemistry in water. Several new molecules have been synthesized, some rather old ones have been characterized for the first time, and clues have begun to emerge about the chemical interaction of cis-DDP with its likely biological target, DNA.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Lippard, S J -- New York, N.Y. -- Science. 1982 Dec 10;218(4577):1075-82.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6890712" target="_blank"〉PubMed〈/a〉
    Keywords: Chemical Phenomena ; Chemistry ; *Cisplatin ; *Dna ; Hydrolysis ; Pigments, Biological
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  • 29
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1982-12-03
    Description: The visual response is initiated by light reception and transduction into chemical and electrical energy in the outer-segment membranes of rod and cone cells. Recent research on the molecular events controlled by light has clarified the roles of some of the rod outer-segment biomolecules. These developments and the current unresolved questions are described.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉O'Brien, D F -- New York, N.Y. -- Science. 1982 Dec 3;218(4576):961-6.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6291153" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; Blood Proteins/metabolism ; Calcium/metabolism ; Chemical Phenomena ; Chemistry ; Enzyme Activation ; Enzymes/metabolism ; GTP-Binding Proteins ; Light ; Membranes/metabolism ; Models, Biological ; Phosphoric Diester Hydrolases/biosynthesis ; Photoreceptor Cells/*metabolism ; Receptors, Cell Surface/metabolism ; Rhodopsin/metabolism ; Rod Cell Outer Segment/*metabolism ; Vision, Ocular/*physiology
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  • 30
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 1983-06-10
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Krenitsky, T A -- Beauchamp, L -- New York, N.Y. -- Science. 1983 Jun 10;220(4602):1106.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6857236" target="_blank"〉PubMed〈/a〉
    Keywords: Acyclovir/metabolism ; *Antiviral Agents/metabolism ; Chemical Phenomena ; Chemistry ; Humans ; Vidarabine/metabolism
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  • 31
    Publication Date: 1983-05-06
    Description: Resonance Raman spectra of photolyzed carbonmonoxyhemoglobin obtained with 10-nanosecond pulses are compared with the spectra of photolyzed carbonmonoxyhemoglobin stabilized at 80 K. In comparing the deoxy with the photodissociated species, the changes in the Raman spectra are the same for these two experimental regimes. These results show that at ambient and cryogenic temperatures the heme pocket in liganded hemoglobin is significantly different from that of deoxyhemoglobin. It is concluded that measurements of the properties of intermediate species from photodissociated hemoglobin stabilized at low temperatures can be used to probe the short-lived metastable forms of hemoglobin present after photodissociation under biologically relevant solution conditions.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Ondrias, M R -- Friedman, J M -- Rousseau, D L -- New York, N.Y. -- Science. 1983 May 6;220(4597):615-7.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6836305" target="_blank"〉PubMed〈/a〉
    Keywords: Carboxyhemoglobin ; Chemical Phenomena ; Chemistry ; Freezing ; *Hemoglobins ; Humans ; Ligands ; Spectrum Analysis, Raman ; Temperature
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  • 32
    Publication Date: 1983-04-15
    Description: Alkylating agents that display strong selectivity for opiate receptor types delta or mu were prepared by appropriate modification of the structures of the strong analgesics fentanyl, etonitazene, and endoethenotetrahydrooripavine. The availability of these substances should facilitate studies of the structural basis of receptor specificity and of the physiologic roles of these receptors.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Rice, K C -- Jacobson, A E -- Burke, T R Jr -- Bajwa, B S -- Streaty, R A -- Klee, W A -- New York, N.Y. -- Science. 1983 Apr 15;220(4594):314-6.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6132444" target="_blank"〉PubMed〈/a〉
    Keywords: Alkylation ; Animals ; Benzimidazoles/analogs & derivatives/metabolism ; Brain/physiology ; Cells, Cultured ; Chemical Phenomena ; Chemistry ; Enkephalin, Methionine/analogs & derivatives/metabolism ; Fentanyl/analogs & derivatives/metabolism ; *Isothiocyanates ; Ligands ; Rats ; Receptors, Opioid/*metabolism/physiology ; Thebaine/analogs & derivatives/pharmacology
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  • 33
    Publication Date: 1980-10-01
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Bumb, R R -- Crummett, W B -- Cutie, S S -- Gledhill, J R -- Hummel, R H -- Kagel, R O -- Lamparski, L L -- Luoma, E V -- Miller, D L -- Nestrick, T J -- Shadoff, L A -- Stehl, R H -- Woods, J S -- New York, N.Y. -- Science. 1980 Oct;210(4468):385-90.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6159682" target="_blank"〉PubMed〈/a〉
    Keywords: Air Pollutants/analysis ; Chemical Phenomena ; Chemistry ; Chromatography, High Pressure Liquid ; *Dioxins/analysis ; *Fires ; Power Plants ; Smoke/analysis ; Soil Pollutants/analysis ; Tetrachlorodibenzodioxin/analysis ; Vehicle Emissions/analysis ; Water Pollutants, Chemical/analysis
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  • 34
    Publication Date: 1984-05-25
    Description: Polypeptide analogs of the known members of the corticotropin-releasing factor (CRF) family were synthesized and tested in vitro and in vivo for enhanced potency or competitive antagonism. Predictive methods and physicochemical measurements had suggested an internal secondary alpha-helical conformation spanning about 25 residues for at least three members of the CRF family. Maximization of alpha-helix-forming potential by amino acid substitutions from the native known sequences (rat/human and ovine CRF, sauvagine, and carp and sucker urotensin 1) led to the synthesis of an analog that was found to be more than twice as potent as either of the parent peptides in vitro. In contrast, certain amino-terminally shortened fragments, such as alpha-helical CRF or ovine CRF residues 8 to 41, 9 to 41, and 10 to 41, were found to be competitive inhibitors in vitro. Selected antagonists were examined and also found to be active in vivo.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Rivier, J -- Rivier, C -- Vale, W -- AA03504/AA/NIAAA NIH HHS/ -- AM20917/AM/NIADDK NIH HHS/ -- AM26741/AM/NIADDK NIH HHS/ -- etc. -- New York, N.Y. -- Science. 1984 May 25;224(4651):889-91.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/6326264" target="_blank"〉PubMed〈/a〉
    Keywords: Adrenocorticotropic Hormone/secretion ; Animals ; Binding, Competitive ; Chemical Phenomena ; Chemistry ; Corticotropin-Releasing Hormone/*antagonists & inhibitors ; Rats
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  • 35
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 15 (1980), S. 79-101 
    ISSN: 1432-1432
    Keywords: Molecules ; Interstellar ; Chemistry ; Isotopes ; Solar system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The study of interstellar molecules broadly includes two areas of interest. One area uses the unique ability of molecules to act as probes of the physical conditions in the cold, dense, visually opaque component of the interstellar medium. The physical properties of this and other components of the interstellar medium are summarized. The other area deals with the chemistry of interstellar molecules, recent aspects of which are emphasized in this review. Gas-phase chemistry, shock chemistry, and grain surface chemistry are discussed in the context of recent observations. No present observations suggest that surface reactions are relevant, but neither can they be ruled out. Ion-molecule reactions are clearly operative, at least for the simpler species. Chemical isotope fractionation is reviewed, andd it is concluded that the complexities of the chemistry allow no cosmological conclusions to be drawn from observations of deuterium in interstellar molecules, while the presence of13C in interstellar molecules permits an estimate of the12C/13C ratio which is consistent with the current concepts of the nucleosynthesis history of the Galaxy. Possible connections between interstellar molecules and the early molecular history of the solar system are discussed.
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  • 36
    Electronic Resource
    Electronic Resource
    Springer
    Pure and applied geophysics 118 (1980), S. 128-151 
    ISSN: 1420-9136
    Keywords: Galactic cosmic rays ; Solar proton events ; Particle precipitation ; Chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract An assessment is made of the relative contribution of certain classes of energetic particle precipitation to the chemical composition of the middle atmosphere with emphasis placed on the production of odd nitrogen and odd hydrogen species and their subsequent role in the catalytic removal of ozone. Galactic cosmic radiation is an important source of odd nitrogen in the lower stratosphere but since the peak energy deposition occurs below the region where catalytic removal of O3 is most effective, it is questionable whether this mechanism is important in the overall terrestrial ozone budget. The precipitation of energetic solar protons can periodically produce dramatic enhancement in upper stratospheric NO. The long residence time of NO in this region of the atmosphere, where catalytic interaction with O3 is also most effective, mandates that this mechanism be included in future modelling of the global distribution of O3. Throughout the mesosphere the precipitation of energetic electrons from the outer radiation belt (60°≲Λ≲70°) can sporadically act as a major local source of odd hydrogen and odd nitrogen leading to observable O3 depletion. Future satellite studies should be directed at simultaneously measuring the precipitation flux and the concomitant atmosphere modification, and these results should be employed to develop more sophisticated models of this important coupling.
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  • 37
    ISSN: 1432-0827
    Keywords: Bacterial amphophile ; Purification ; Chemistry ; Resorption ; Ca influx ; Cyclic AMP
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary The bone resorptive factor and amphipathic antigen (AcA) previously identified by us in preparations fromActinomyces viscosus have been partially purified, characterized chemically, and compared. They elute at the same location on chromatography with Ac 22. The fatty acid composition of AcA and the bone resorptive factor is the same. Some differences in carbohydrate composition are observed. TheActinomyces factor does not affect calcium influx or cyclic AMP in isolated bone cells. Therefore it is concluded that AcA stimulates resorption either by gaining entrance into bone cells or by way of a yet undetermined second messenger.
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  • 38
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The two-state theory of protein denaturation, in which it is assumed that a protein exists as two species, native and denatured, is examined by three approaches in this paper. First, the point is made that denaturation of an isolated molecule involves a continuous shift in the probabilities of occurrence of many states generated by the partition function for the protein. It is argued that the maximum term approximation does not lead to a two-state mechanism of denaturation, and that the extent of cooperation implied by the two-state theory should give very much sharper transitions than are actually found in proteins. Second, the two-state theory is applied to the various model systems treated in this series of papers, and is found to be inadequate. Since the detailed behaviour of the models is known, it is possible to deduce the effect of the incorrect application of the two-state theory to a system that “denatures” by gradual unwinding. This exercise is useful when, thirdly, we examine experimental data that seem to depart radically from a two-state interpretation. We conclude that a mechanism of gradual unwinding is the most generally valid assumption, and that the two-state theory has no theoretical or experimental support.
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  • 39
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    Biopolymers 3 (1965), S. 481-489 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three types of band-forming centerpieces useful in band centrifugation in the analytical ultracentrifuge are described. The mode of filling and the advantages and disadvantages of each type are discussed.
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  • 40
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    Biopolymers 3 (1965), S. 497-508 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ability of periodate-oxidized amylose to form aggregates in aqueous solution was studied by sedimentation, light scattering, and viscosity analyses. Ultracentrifuge schlieren patterns show that aggregation can be appreciable at pH 3.0 and 1.0. The hydroxyl ion-catalyzed degradation of the oxidized amylose is faster at pH 3.0 than at pH 1.0. Viscosity and sedimentation analyses conducted at pH 3.0 show that a minimum in the degree of aggregation of the oxidized molecules is obtained at 15-25% oxidation. Solubulity studies and x-ray diffraction patterns on retrograded amylose show that maximum solubility of the retrograded amylose is obtained by oxidizing to the extent of 25-35%. It was therefore concluded that in the general range of 20-30% periodate oxidation, the oxidized amylose has a minimum ability to form intermolecular hydrogen bonds. Outside of this range, oxidized amylose readily forms aggregates in aqueous solutions.
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  • 41
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    Biopolymers 3 (1965), S. 491-496 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Calorimetric measurements of the heat of the addition of the second strand of poly U to poly (A + 2U) to form the three-stranded poly (A + 2U) complex in 0.1M and 0.5M NaCl at 24 and 37°C. are reported. A value of ΔH = -3800 cal./mole of poly (A + 2U) formed was found to be fairly insensitive to the experimental conditions employed. The heat of the addition of the third strand to the preformed poly (A + U) helix is considerably less exothermic than the heat of reaction between poly A and poly U to form poly (A + U). The insensitivity of the heat of addition of the third strand (poly U) to changes in salt concentration and temperature lends qualitative support to the earlier hypothesis that the major portion of the variation of the ΔH of the poly A and poly U reaction with experimental conditions arises from differences in the conformation of poly A. Combining the information obtained in this study for the ΔH of the reaction forming poly (A + 2U) with data for the ΔH of the formation of poly (A + U) indicates that the conversion of poly (A + U) to poly (A + 2U) is opposed by an enthalpy change which increases with temperature. Extrapolation of these values to 52°C. where poly (A + U) is transformed to poly (A + 2U) in 0.5M NaCl leads to a value of ΔH = +3800 cal./mole (A + 2U) formed and ΔS = 11.5 cal./mole of (A + 2U) formed. It is concluded from the calorimetric data that the driving force for the poly (A + U) to poly (A + 2U) conversion reaction is the favorable entropy change.
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  • 42
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    Biopolymers 3 (1965) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 43
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    Biopolymers 3 (1965), S. 461-480 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of salt type and concentration on the transformation of an oriented crystalline collagen tendon into a crosslinked network under conditions of equilibrium swelling was investigated. Our main observations are the following. The degree of swelling of crystalline tendons increases at low salt concentration Cs, and decreases at higher Cs for a wide variety of salts. The observation is not reconcilable with swelling taking place in interfibrillar spaces or structural voids. Within the tropocollagen units and at their ends, regions of reduced organization are postulated (as suggested by Bear and by Schmitt) which are able to interact with the diluent in the amorphous-like manner. At least four different factors should be considered in assessing the role of salt and salt concentration on the shrinkage temperature Ts under isoelectric conditions. They are: (1) specific effects, (2) diluent effects, (3) crosslinking effects, and (4) nonequilibrium effects. The diluent effects are correlated with the salting-in-salting-out power of the ions which was characterized in Part I of this series. Smaller amounts of diluents are generally available to the tendon when the salt has a higher salting-out power, and this corresponds to higher shrinkage temperatures, other conditions being the same. The crosslinking effect raises Ts due to a reduction of the diluent content and, probably for p-benzoquinone and formaldehyde, also to a reduction of the conformational entropy in the molten state. Nonequilibrium effects arise from the fact that shrinkage and recrystallization are kinetically hindered when the tendon is highly deswollen in strong salting-out solutions, or when the salt has a crosslinking power. The specific effect is the only effect which is not related to the amount of diluent present in the tendon. Its origin is less clear. For anions such as Cl- and SCN-, it is possibly related to an ability of the ion to prevent intersegmental hydrogen bonding and water carbonyl bridges. The competition of several of the above effects for a given salt solution makes possible various types of dependence of Ts upon Cs: Ts may either continuously decrease or continuously increase with increasing Cs, or it may go through a minimum. In absence of salt, the cooperative character of the transition at the pH at which maximum swelling occurs appears extremely reduced. The large swelling maintains the tendon in the elongated state and this simulates a continuous decrease of Ts on lowering pH. In presence of small quantities of salt, which reduce swelling, the transition is sharp and Ts is decreased with pH up to pH 2, when maximum swelling occurs, and then reincreases on further lowering of the pH. The dependence of Ts upon Cs is more complex than under isoelectric conditions. There is generally an increase of Ts with Cs which is equivalent to an increase of the denaturation temperature with Cs for helical polyelectrolytes in solution. At higher salt concentrations, however, Ts may decrease again, and possibly increase again at still higher salt concentrations, depending upon the effect of the salt solution in the isoelectric zone.
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  • 44
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: By using the Nemethy-Scheraga theory of water structure, a calculation was made of the energy changes for the rupture of a DH…A solute-solute hydrogen bond in water. A partition function was also obtained for the binding of water and other solutes to the DH and A groups in the special case where these are the NH and CO groups of a random coil polypeptide chain. In subsequent papers of this series, these calculated quantities will be used in a statistical mechanical treatment of the helix-coil transition for polypeptides in water.
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  • 45
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A partition function is derived for a simple model of interacting helices in a short (20 residues) chain of poly-L-alanine. It is found that interhelical hydrophobic bonds effect a marked stabilization of helical forms, and give rise to a sharp transition of the type found in many proteins.
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  • 46
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The electric birefringence of collagen solutions has been measured over a wide range of field strength with the pulse technique. The soluble collagen was from rat tail tendon. The solvent used was dilute acetic acid. Very pronounced saturation of the electric birefringence was observed, permitting calculation of the optical anisotropy factor. The Kerr constant was determined by extrapolation to zero field strength. From the dependence on field strength of the birefringence, the permanent dipole moment and the anisotropy of polarizability were separately determined. The contribution of the former to the Kerr constant was found to be twice as large as that of the latter. The same conclusion was obtained from the initial slope of the rise curves of the birefringence at low fields. The permanent dipole moment was 1.5 × 104 Debye, and the anisotropy of polarizability was about 3 × 10-15 cm.3. The magnitude of the latter indicates that the ion atmosphere polarization is important. Effects of added salt and thermal denaturation on the electric birefringence were explored.
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  • 47
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    Biopolymers 4 (1966), S. 595-599 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The γ-benzyl-L-glutamate N-carboxyanhydride (NCA) polymerization initialed by diisopropylamine was studied in dimethylformamide (DMF)-dioxane mixtures of different compositions. It was found that the shape of the conversion versus time plots and the molecular weights of the polymers depend on the solvent composition. Auto-catalysis is present only when dioxane predominates in the solvent mixtures. Moreover, the molecular weight of the final polymer depends strongly on the precipitation conditions when the polymerization is carried out in DMF.
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  • 48
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crosslinked synthetic polypeptides of poly Glu51Lys33Tyr16 (mol. wt. 31,000) and of poly Glu52Lys33Tyr15 (No. 3) (mol. wt. 52,000) containing from one to six crosslinks per molecule have been prepared by use of FFDNB, WRK and ICD reagents.The monomeric fractions of these derivatives were isolated by Sephadex G-100 chromatography. The number of crosslinks per molecule of DNPene derivatives was determined by total hydrolysis of the derivatives, isolation of O, N∊-DNPene-Tyr-Lys bridges by paper chromatography and then spectrophotometric quantitation. The number of the amide-type crosslinks in Am derivatives was established by their deamination followed by total hydrolysis and quantitation of the remaining lysine residues. Crosslinked derivatives appear to have a more compact structure, as judged by their behavior on the Sephadex columns and by their intrinsic viscosities. They were further characterized in regard to their amino acid composition, average number of the crosslinks per molecule, nitrogen content, solubility, root-mean-square end-to-end distance, and their spectral properties. Their properties recommend them as useful models for the study of the tertiary structure of proteins in solution.
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  • 49
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The introduction of intramolecular amide bonds into synthetic polypeptides produces molecules with organized spatial structure which are good models for the tertiary structure of proteins. Polarization of fluorescence measurements were used to study the internal structure and the overall rigidity of the intramolecularly crosslinked polypeptides. The graph of [(1/p) + (1/3)] against T/η changes from a straight line to a continuous curve: the temperature at which this change occurs and the slope of the straight line segment measure the stability of the internal structure of the molecule. The introduction of one to six crosslinks produces an organized internal structure that becomes more stable as the number of crosslinks increases. In contrast to the fluorescence measurements, the intrinsic viscosities, reflecting the overall hydrodynamic domain of the molecules, change (decrease) to the same extent whether one, four, or six intramolecular crosslinks are present. The overall rigidity of the polymers can be assessed by the rotational relaxation time ρh and the polarization at 10°C. p10. Both of these criteria show that the presence of six crosslinks significantly increases the rigidity, but one or four does not. The various hydrodynamic measurements may be fitted into a hierarchy of discrimination: intrinsic viscosity, sedimentation, and diffusion for size and shape; rotational relaxation time and polarization of fluorescence at a given temperature for overall molecular rigidity; and transition temperature and rate at which it is attained for internal molecular detail.
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  • 50
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    Biopolymers 3 (1965), S. 57-68 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theory for the dependence of the net thermodynamic solvation of a macroion in an electrolyte solution is presented. The solvation in moles salt/mole macroion is shown to approach - |Zp|/v in the limit of infinite dilution of salt and macroion. The solvation in moles water/mole macroion is shown to approach zero at zero water activity. Isopiestic determinations of the hydration of sodium deoxyribonucleate in NaCl, Na2SO4, and NaClO4 solutions indicate that short-range interactions of the NaDNA with solvent account for more than half of the observed solvation. The net hydration appears to be predominantly influenced only by water activity.
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  • 51
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    Biopolymers 3 (1965), S. 69-78 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cohesive energy densities (CED) of three amylose derivatives have been estimated from viscosity measurements in a range of solvents, by using methods proposed by Mangaraj and Bristow and Watson. The values assigned to the triacetate, (2.5) nitrate, and tricarbanilate are 92 ± 2, 90 ± 2, and 87 ± 2 cal./cc., respectively. The CED of unsubstituted amylose has been measured and found to be 154 ± 4 cal./cc. The results are discussed in relation to solvent power, structure, and possible correlation with the internal pressure of the polymer.
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  • 52
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    Biopolymers 3 (1965), S. 115-119 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Viscosity measurements and calculated rotary diffusion constants show that collagen undergoes photopolymerization when irradiated with ultraviolet light of 2537 A. Fibril formation at the same time is inhibited. The results are correlated with the aromatic amino acid content of the dangling peptides protruding from the rigid portion of the macromolecule.
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  • 53
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: It is shown how the technique of fluorescence may be used to assess conclusions about conformation which are based on a statistical mechanical treatment of simple protein models. Specifically, the state of bonding and distance between two chromophores in a molecule depend on the overall conformation, which can be computed for model systems. On the assumption that the intensity and polarization of fluorescence are affected by exciton transfer between the chromophores, it is possible to compute the effect of conformation on fluorescence. It is demonstrated that the conformational changes computed in the preceding paper will give rise to marked changes in the intensity and polarization of fluorescence.
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  • 54
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    Biopolymers 3 (1965), S. 421-437 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Intrinsic viscosity-temperature studies for isoelectric gelatin in KCl and KSCN aqueous solutions and equilibrium degree of swelling, ν-1, measurements for amorphous crosslinked rat tail tendons in the same solutions were carried out. On increasing salt concentration Cs, both [η] and ν-1 increase, go through a maximum, and then decrease at high Cs, KCl being more effective than KSCN in bringing about this decrease. The trend observed is similar to the variation of solubility of polypeptides and soluble proteins with Cs. By regarding a water-salt solution of a given Cs as a single diluent interacting with the protein modified by solvation and binding of ions, usual polymer solution theories were applied to the experimental results. Thus, quantities related to the entropy and enthalpy components of the excess chemical potential of the diluents were obtained. The data indicate that the initial increase of [η] and ν-1 with Cs results from the balance of an enthalpy component which, on increasing Cs, becomes less favorable to dilution and an entropy component which, conversely, becomes more favorable. The subsequent decrease of [η] and ν-1 with Cs is due to the prevailing of the enthalpy component. The maximum is reached at higher Cs for KSCN than for KCl, primarily because of the large increase in the entropy component operated by the former salt. The increase of the entropy parameter with Cs is associated to a breaking down of the coordinated water structure and to an alteration of the conformation of the macro molecules due to ion-dipole interaction and to ion absorption. The decrease in exothermicity of dilution with Cs indicates a reduced thermodynamic affinity of the diluent toward the polymer which probably results from alteration of the nature of both polymer and diluent.
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  • 55
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nine samples of poly-γ-benzyl-L-glutamate (PBLG), ranging in M̄w from 19,000 to 410,000, were examined viscomctrically and by ultracentrifugation with dimethylforma-mide (DMF) at 25°C. as helicogenic solvent. The data for [η] and s0 (limiting sedimentation coefficient) as functions of M̄w were fitted well by the theories for a rigid prolate ellipsoid of revolution whose major axis increases linearly with M̄w, but whose minor axis is independent of M̄w. This implies that the overall shape of the PBLG molecule in DMF is represented by a straight cylinder whose cross section is independent of its length. The length per monomeric residue h evaluated from [η] is about 1.3 A., whereas that from s0 is about 1.6 A. No adequate explanation for this difference in h can be found at present. More serious is the fact that these hydrodynamically evaluated values of h are appreciably larger than, the value obtained from our light-scattering measurements reported previously. All these values of h from our studies are not consistent with the value characteristic of the α-helix, for which h is 1.5 A. The concentration dependence of s0 was found to agree well with the recent theoretical prediction of Peterson for cylindrical macromolecules.
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  • 56
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    Biopolymers 4 (1966), S. 247-258 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Precipitation of soluble forms of collagen from solutions containing the soluble protein-polysaccharide (PP-L) of bovine nasal cartilage, followed by centrifugation at 100,000 g, resulted in the formation of coherent elastic pellets whose wet weights increased with the concentration of PP-L in the initial solution. Dry weights and uronic acid contents of these pellets showed that the amount of water held in the wet pellet was nearly constant for any one kind and concentration of collagen, and ranged from 20 to 100 mg./mg. PP-L in the pellet. Soluble collagens from four different sources and PP-L from three kinds of cartilage showed similar effects. Precipitation of soluble collagen in the presence of hyaluronate or dextran yielded pellets of much smaller size than those formed in the presence of PP-L. The presence of chondroitin sulfate had only a slight effect on wet pellet weights. Wet weights of pellets formed in the presence of PP-L decreased with increasing ionic strength. A model involving entanglement between insoluble collagen fibrils and the relatively stiff chondroitin sulfate chains of branched PP-L seems qualitatively capable of accounting for these results.
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  • 57
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    Topics: Chemistry and Pharmacology
    Notes: The conformations of oligopeptides derived from L-alanine and co-oligomers of L-alanine with γ-methyl-L-glutamate were studied in several solvents via optical rotation and far-ultraviolet spectroscopy. Calculated values for optical rotation based on model compounds were compared with experimental values for the oligomers. In trifluoroacetic and dichloroacetic acids, the oligomers and co-oligomers exhibit rotations in close agreement with predicted values based on model compounds. Thus, in these solvents only nonhelical conformations exist. In trifluoroethanol, the experimental points of molar rotation for the pentamer and larger oligomers no longer follow the predicted values. In addition, the benzyloxycarbonyl and acetyl cononamers show b0 values of about -150, which demonstrates the presence of stable helical forms for these peptides. We also examined the molar extinction coefficients of oligopeptides in the 190 mμ region and determined the values for nonhelical peptide groups. The molar extinction coefficients per amide bond for the benzyloxycarbonyl and acetyl cononamers show extensive hypo-chromism, once again indicating the presence of stable helices for these compounds in trifluoroethanol.
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  • 58
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    Biopolymers 4 (1966), S. 1046-1050 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 59
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 60
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    Biopolymers 4 (1966), S. 1081-1090 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies were made of the influence of hydrostatic pressure on the helix-coil transitions of poly (A + U) and poly (A + 2U). The results were analyzed by a thermodynamic treatment which emphasized the cooperative aspect of the transitions. The helix-to-coil volume changes were found to be small and negative indicating pressure stabilization of the coil form. The significance of the results with respect to other denaturation measurements was discussed.
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  • 61
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    Biopolymers 4 (1966), S. 1091-1104 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical rotatory dispersion curves of the proflavine cation were measured in the spectral range 400-500 mμ. No optical activity was observed for the free cation but a large positive Cotton effect appeared in the presence of DNA. The effect of ionic strength, denaturation of the DNA, and the DNA/proflavine ratio were studied. The dependence of the magnitude of the Cotton effect on the DNA/proflavine ratio suggests that a nearest-neighbor interaction between bound proflavine molecules is necessary for optical activity. A simple statistical treatment was made which indicated that only a small number of proflavine molecules are required in close proximity for optical activity to occur. Denaturation of the DNA did not destroy the optical activity, which shows that long runs of DNA double helix are not necessary for optical activity of the ligand molecules. The optical rotatory dispersion curves of acridine orange which was bound to DNA were also measured. Two Cotton effects of opposite sense could be distinguished, the relative magnitudes of which depended on the DNA/acridine orange ratio and the state of denaturation of the DNA. The apparent differences from the proflavine-DNA system can to a large extent be explained in terms of the tendency of acridine orange to form aggregates.
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  • 62
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  • 63
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    Biopolymers 5 (1967), S. 1-4 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Investigations have been made on the optical rotatory dispersion properties of E. coli ribosomes and their constituent RNA and proteins. The results indicate that (1) no conformational changes are involved in the formation of a 70S particle from the 50S and 308 subunits, (2) the E. coli ribosomal proteins are similar to most globular proteins with little α-helix content, and (3) the conformation of RNA and proteins inside the ribosome is very similar to that in the free state.
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  • 64
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    Topics: Chemistry and Pharmacology
    Notes: The iodine which is added to an aqueous amylose solution is bound only partly by the amylose while forming the blue complex and partly remains free. The equilibrium normality of the free and the bound iodine at half-saturation of amylose by iodine is designated as [If]v and [Ib]w, respectively. The stability of the poly iodine chain formed within the axis of amylose helices depends on its length, i.e., indirectly on the DP of the amylose helices: the greater this stability, the lower the [If]v value. The amylose molecule consists of helical segments. Such a molecule may behave as a random coil. The average length of the helical segments in freshly prepared amylose-iodine complexes depends on temperature, pH, iodide concentration, the presence of other complex-forming agents, and the DP of the amylose. This latter factor is investigated in the present paper. By the aid of an automatically recording photometrictitrating device the coherent values of [Ib] and [If] were determined. Plotting these values against DPn for mechanochemically degraded as well as for periodateo-xidized amyloses resulted in curves consisting of two linear sections. The break of the curves occurred between DPn 110 and 130. It was concluded that below DPn = 100 the DP of helical segments (= sDPn) is identical to the DPn of the total molecule, i.e., the molecule consists of only a single, relatively stiff helix. Above this limit the molecule contains several helical segments. The DP of these helical segments can be calculated as follows: sDPn = 141.1 - 10.2 × 105[If]v. This equation is considered to be valid for 0.5-0.6 mg. amylose in 100 ml. 0.1N HCl at 20°C., λ = 650 mμ, euuvet diameter 3.4 cm., the feed rate of the iodate-iodide titrating solution (in acid medium resulting in a 5 × 10-3N I2 solution with a molar iodide to iodine ratio of 1.5) is 0.4ml./min. Amylose molecules of, e.g., DPn = 1380 consist of an average of 11.4 segments having a DP of about 120 and consisting of an average of 15-18 helical turns.
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  • 65
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    Biopolymers 5 (1967), S. 61-68 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrochemical possibilities for investigation of nucleic acids with high molecular weight are restricted to the determination of the adsorption behavior. According to our experience the alternating current polarography (Breyer-polarography) is mainly appropriate for the characterization of changes in the secondary structure of DNA. The Breyer-polarogram shows the alternating current of the dropping electrode in dependence on their potential which varied from 0-2 v. negative against the normal calomel electrode (NCE). By addition of native DNA to the supporting electrolyte (buffer solution) the current drops down in the range of adsorption between 0 and 1 v. At 1.16 v. against NCE the desorption takes place together with the formation of a rounded desorption peak. The investigation was carried out in phosphate buffer solution 0.1m with 0.075m NaCl or in a phosphate buffer 0.18m with 0.03m NaCl. In the pH range above pH 8 NaOH was added to realize the higher pH values. A calf thymus DNA sample having a mean molecular weight of about 18 million was used. The concentration of DNA was 5 × 10-3-1 × 10-1 wt.-%. The polarographic measurements were performed with an a.c./d.c.-polarograph “GWP 564” from Akademiewerkstätten für Forschungsbedarf der Deutschen Akademie der Wissenschaften zu Berlin (DAW). The denaturation of the double helix causes a sharp desorption peak at negative potentials of the alternating current polarogram. This new criterion for the helix-coil transition is due to formation of unpaired bases. These nearly free bases undergo a specific adsorption and the desorption takes place within a narrow potential range. Nevertheless, at present time an electron transfer to particular bases cannot be excluded at special conditions. The increase of the sharp peak permits to estimate: (a) the melting curve of the double helix in agreement with spectroscopic measurements; (b) the photolysis of the double helix; (c) the strand separation in acid and alkaline solution. In the alkaline range the sharp peak increases and reaches its maximum at pH 〉 12. In the acid range, however, no sharp peak is observed and the rounded desorption peak decreases. Therefore, the best way of following the conformation changes is to measure the current difference between the curves of the solutions with and without DNA at electrocapillary-zero-potential. On the classical d.c.-polarogram one can measure small current steps only, which may be caused mainly by capacity changes. Moreover, the scission of the molecule by ultrasonic action can be followed. In this case the rounded peak of DNA increases but the sharp peak does not appear. Similar alternating current polarograms are obtained with poly-A in the native state, because helical and unordered regions coexist in the same molecule. The very rapid indication of these structure changes allows one to carry out kinetic measurements at a fixed potential with this method.
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    Biopolymers 5 (1967), S. 135-148 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The theory of Kirkwood for the translational frictional coefficients of structures composed of subunits has been generalized in two ways in order to consider aggregates of nonidentical subunits. One of these generalizations fails when the sizes of subunits are too disparate; the other, derived from a surface shell distribution of frictional elements, is effective over the whole range of relative sizes. It is shown that, in the limit of a continuous surface distribution, a shell model reproduces Stoke's law for a sphere. Comparison is made between the frictional coefficients of spheres, ellipsoids, and rods modeled by finite numbers of subunits and by continuous shells of frictional elements, and those calculated from other theories. Agreement is generally good, though the shell model for prolate ellipsoids of revolution deviates by a few per cent from the Perrin value.
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    Biopolymers 4 (1966), S. 677-682 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction, V amylose hydrate ⇄ H2O + V amylose dehydrate, where the amylose hydrate and dehydrate are pseudohexagonal, helical species with packing diameters of 13.7 and 13.0 A., respectively, has been studied. The V amyloses were exposed to water vapor pressures at various temperatures, with phase determination obtained by identifying solid reactant and product from their x-ray patterns. Reversibility of reaction was found to occur over a 50-96°C. range. A Clausius-Clapeyron plot yields a ΔH of reaction of 10.4 kcal./mole of water released, which value is close to analogous heats of reaction of many common hydrate systems.
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    Biopolymers 4 (1966), S. 663-676 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal helix-coil transition of DNA was studied by means of dielectric constant measurements. The dielectric dispersion of native helical DNA is characterized by a large dielectric increment and a large relaxation time, whereas that of denatured coil DNA is characterized by a small dielectric increment and a small relaxation time. The dielectric dispersion of partially denatured DNA is of particular interest. At the intermediate stage of the helix-coil transition, dispersion curves which are different from either that of helix DNA or that of coil DNA appear. This is particularly pronounced for large DNA. This indicates the presence of an intermediate form of DNA. Flow birefringence measurements were carried out simultaneously. The negative birefringence of helical DNA diminishes as the helix-coil transition proceeds. However, the extinction angle remains constant, as long as it can be measured. These results indicate the absence of intermediate forms during the helix-coil transition. The discrepancy between dielectric and birefringence measurements can be resolved by assuming that the intermediate forms are not birefringent. The size distribution of native DNA and of the indicated intermediate form of DNA was studied. It is found that a logarithmic normal distribution function explains the distribution of size of DNA reasonably well.
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  • 69
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    Topics: Chemistry and Pharmacology
    Notes: Poly-γ-berizyl-L-glutamate prepared by polymerization of γ-benzyl-L-glutamate NCA in dimethylformamide (DMF) with the use of diisopropylamine as the initiator was precipitated from the polymerization mixture under different conditions. A portion of the almost completely polymerized solution was treated with an excess of isopropylamine and then precipitated into diethyl ether (sample A). The remaining portion of the polymerization mixture was concentrated in a rotating evaporator, stored at room temperature for a few days, and then diluted with DMF and precipitated into diethyl ether (sample B). The molecular weight distributions of the two polymer samples were determined by the chromatographic procedure of Baker and Williams. The molecular weight of sample B is roughly three times that of sample A. However both samples have the “most probable” distribution of molecular weight. The results are interpreted according to Bamford's polymerization mechanism.
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    Biopolymers 4 (1966) 
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    Biopolymers 4 (1966), S. 747-757 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The sedimentation coefficient of T2 phage DNA has been studied by zone centrifugation in sector-shaped preparative centrifuge tubes over a concentration range of 0.02-2.0 μg./ml. DNA. These results have been compared to a similar study in the analytical centrifuge of T4 DNA over the range of 0.50-5.75 μg./ml. DNA. A value for the sedimentation coefficient of 60.7 ± 1.8 S. was obtained by the first method and a value of 61.3 ± 1.5 S. by the second.
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    Biopolymers 4 (1966), S. 705-708 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 5 (1967), S. 589-613 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of matrix rank analysis has been applied to a large body of experimental data to determine and identify the minimum number of independent spectral components that, were contained within it. The optical rotatory dispersion of TMV RNA was measured in the wavelength region 230-350 mμ, for a wide range of temperatures and ionic strengths. Over the whole range of conditions considered, the observed optical rotatory dispersion spectra were found to be a superposition of two basic spectra only. Evidence is put forward relating these spectra to the single-strand and double-strand helical forms of the molecule. A model is proposed to explain the observed spectral changes in terms of an equilibrium between these two conformations, which leads to a direct calculation of the percentage composition of the double strand at any of the conditions considered. This equilibrium, while simple in general description, appears multi-state and complex in detail. This method of analysis is both powerful and of wide applicability, since it is independent of the source of the data.
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  • 74
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    Topics: Chemistry and Pharmacology
    Notes: An infinite series solution to the Mason-Weaver equation is presented for the case in which a synthetic boundary is formed originally between solution and solvent. Digital computations based on this series, and confirmed independently, have been made for a range of parameters. For given conditions, the maximum rate of change of concentration at the meniscus and the time at which it occurs can be easily estimated by means of the curves presented. In equilibrium experiments which commence with formation of a sharp boundary, this enables the fringes to be identified with certainty.
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  • 75
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    Topics: Chemistry and Pharmacology
    Notes: The course of the reversible helix formation of poly(γ-benzyl L-glutamate) (PBG) dissolved in a mixture of dichloroacetic acid (DCA) and 1,2-dichloroethane (EDC) was followed by measuring the heat capacity and the optical rotation of the system through the transition region. The results of these measurements indicate that the transition enthalpy ΔH the transition temperature Tc, and the Zimm-Bragg parameter σ depend considerably on the PBG concentration as well as on the composition of the solvent. For the standard state of infinite dilution, however, a linear extrapolation of the measured ΔH if values results in a standard value ΔH° = 950 cal./mole, independent of the solvent composition. The results of the calorimetric measurements are discussed in relationship to changes in optical rotation. Some peculiarities in the measured thermodynamic and optical properties in solutions with relatively high content of dichloroacetic acid are reported.
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    Biopolymers 5 (1967), S. 673-679 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Helical conformations of infinite polymer chains may be described by the helical parameters, d and θ (the translation along the helix axis and the angle of rotation about the axis per repeat unit), pi (the distance of the ith atom from the axis), dij, and dij (the translation along the axis and the angle of rotation, respectively, on passing from the ith atom to the jth). A general method has been worked out for calculating all those helical parameters from the bond lengths, bond angles, and internal-rotation angles. The positions of the main chain and side chain atoms with respect to the axis may also be calculated. All the equations are applicable to any helical polymer chain and are readily programmed for electronic computers. A method is also presented for calculating the partial derivatives of helical parameters with respect to molecular parameters.
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    Biopolymers 5 (1967), S. 685-689 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A dilatometric technique is employed to measure the volume changes occurring on denaturation of collagen solutions and tendons. Partial specific volumes of tropocollagen are calculated to be 0.686 ml./g. in water and 0.689 ml/g in 0.1M citrate buffer. From data on non-aqueous solutions, it is estimated that most of the volume change arises from changes in polymer configuration rather than from changes in solvation.
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    Biopolymers 5 (1967), S. 697-713 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have generated solutions to the Lamm equation to examine the effects of concentration dependence on velocity experiments. Two forms of c dependence are considered: s/s0 = 1 - kc and s/s0 = (1 + kc)-1. Features of these solutions are discussed. The magnitude of the errors resulting from the usual procedure of measuring the rate of movement of schlieren maxima or of the position at which the concentration is one half the plateau value have been examined. These errors are usually negligible after sufficient centrifugation time. The errors in using the half-plateau concentration are less than those using the movement of the peak. We have also examined a technique due to Fujita for determining D from boundary spreading when s/s0 = (1+kc)-1. This method is satisfactory when s/s0 is actually of this form, or under certain limitations when s/s0 = (1 + kc)-1. Creeth has shown that under certain conditions the concentration gradient, curve remains virtually unchanged in shape after separating from the meniscus. When this occurs it is possible to estimate s/D from the data. The condition for such a steady state is that kc0 be sufficiently large. Numerical confirmation of this method is presented in the final section.
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    Biopolymers 5 (1967), S. 723-726 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preliminary experiments have been carried out which measure the variation in the intensity of the light scattered by DNA solutions under the influence of an electric field. Data have been collected on the length of DNA molecules, their electric polarizability, and their dispersion behavior.
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  • 80
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    Topics: Chemistry and Pharmacology
    Notes: Information concerning the structures of rA-rU, rA-rU2 rI-rC, rA-rI2, and acid rA helices in solutions is reported. Through the use of diquaternary ammonium salts of the general structure, \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm R}_1 {\rm R}_2 {\rm R}_3 \mathop {\rm N}\limits^ + ({\rm CH}_2 )n\mathop {\rm N}\limits^ + {\rm R}_1 {\rm R}_2 {\rm R}_3 \cdot 2{\rm Br}^ - $\end{document} (I), it is shown that (1) the distances between adjacent negatively charged oxygen atoms on the helix increases in the following order rA-rI2 〈 rI-rC 〈 rA-rU ≤ rA-rU2; (2) the density of the helices increases in the order. rA-rI2 〈 rA-rU 〈 rA-rU2 〈 rI-rC; (3) there is a large hydrophobia site in rA-rI2 and possibly also in rA-rU, rA-rU2, and rI-rC helices; (4) the results of the interactions between the salts of type I and the helices may be formulated in semi-quantitative terms by the use of two parameters, α, and β which are shown to be related to the charge separation and the density of the helices, respectively; (5) the studies in solutions compare favorably with the x-ray studies on the fibers; and (6) the acid rA helix differs significantly from the other helices by the fact that the electrostatic interstrand interactions between the negatively charged oxygen atom of a phosphate group and the positively charged 10-amino group of adenine contribute significantly to the stabilization of the helix, and thus it is found that the presence of the salts, I, leads to a significant destabilization of the acid rA helix.
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  • 81
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    Topics: Chemistry and Pharmacology
    Notes: The half molecules of 186 DNA have been isolated by the Hg(II)-Cs2SO4 density gradient centrifugal ion technique. The buoyant densities of the two halves in CsCI at 25°C. are 1.713 and 1.709 g./cm.3, corresponding to GC contents of 54% and 50%, respectively. Similarly, 5-bromouracil labeled λ DNA halves were separated. The isolation of the four DNA halves made it possible to test for homology in base sequences between the cohesive ends of λ and those of 186. There was no indication of any significant homology in base sequences between the cohesive ends of the two DNA's, as indicated by the absence of a band with intermediate buoyant density in CsCI when either half of 186 DNA was annealed with either half of 5-bromouracil labeled λ DNA and then centrifuged. The lack of cohesion between the two DNA's made it possible to demonstrate unequivocally the formation of interlocked rings (catenanes) between the two DNA's. The existence of a dimeric catenane is evidenced by the formation of a species of intermediate buoyant density when 5-bromouracil labeled λ DNA is cyclized in the presence of cyclic 186 DNA of a relatively high concentration. The molecular weight of one DNA relative to the other can be calculated from the position of the dimeric catenane in a density gradient by using the method of Baldwin. The result was in complete agreement with our previous measurements from the sedimentation coefficients and by electron microscopy. The probability of dimeric catenane formation when one DNA is cyclized in the presence of another DNA is discussed. The experimental results agree with the theoretical expectation.
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    Biopolymers 4 (1966), S. 1035-1041 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Based on the four electrodes technique, an apparatus is described which measures the Very Low Frequency (VLF) conductivity of ionic solutions, all electrode effects being completely eliminated. It is thus possible to measure the conductivity frequency dependence between 0.8 and 500 cps, with a relative error of 10-4. Applying this method to DNA solutions, one always finds a conductivity dispersion in the VLF range, which disappears when the biopolymer is heat-denatured. The relaxation time is different from one solution to another, but is always greater than 10 msee. approximately, sometimes even greater than 0.1 sec., the upper limit which one can estimate with our apparatus. The different, explanations of the DNA very low frequency polarization, assuming that its relaxation is connected with the rotational diffusion of the biopolymer long axis, is discussed.
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    Biopolymers 4 (1966), S. 1051-1052 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 5 (1967) 
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    Biopolymers 4 (1966), S. 1067-1072 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies of the properties of copolymers of N-carboxy sarcosine anhydride with other N-carboxy α-amino acid anhydrides have shown that the secondary structure may be a function of the type of initiator used. In particular, when polysarcosine is the initiator, and the “chain effect” becomes possible, blocklike character appears in the copolymer. This is the result of selective and rapid polymerization of N-unsubstituted N-carboxy α-amino acid anhydrides by the chain-effect mechanism. In suitable circumstances, therefore, the latter may be used to induce order into copolymerizations of this type.
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    Biopolymers 5 (1967), S. 815-820 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sterically allowed forms of the poly-N-methyl-L-alanine chain were found by calculation of conformational energies as a function of the rotation angles of its chain bonds. The lowest energy form seems to be a right-handed, approximately threefold helix.
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    Biopolymers 5 (1967), S. 837-845 
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    Topics: Chemistry and Pharmacology
    Notes: Oriented amylose fibers in the V form were prepared and subjected to x-ray analysis. Unit cells and the probable space group of P212121 were determined for the V anhydrous and V hydrate forms of amylose; the analysis confirms previous predictions of these structures based on x-ray powder patterns. Chain folding in V amyloses is discussed in view of crystallographic evidence and folding experiments conducted with space-filling models. Reported also is evidence for amylose helices having diameters intermediate between 13.0 and 13.7 A.
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  • 88
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    Notes: Conformational energies of the poly-N-methyl-L-alanine chain have been calculated as a function of the rotational angles of its skeletal bonds, taking into account torsional potentials, van der Waals repulsions, and London attractions. Four pronounced minima in the energy were found; the relative magnitudes of the energies at these minima suggest that the preferred conformation of this chain is either a right-handed, approximately threefold helix, or a slightly distorted, left-handed α-helix. Inclusion of an estimate of the dipolar contribution to the total conformational energy does not significantly affect this conclusion.
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  • 89
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    Topics: Chemistry and Pharmacology
    Notes: The equilibrium normality [If] of free iodine in amylose-iodine complex formation is a function of the length of the polyiodine chains. This length depends on the DP of helical segments of amylose (sDPn). Values of [If] and of the concentration of the bound iodine [Ib] were determined by the continuous photometric titration with automatic recording. Plots of [Ib] versus [If] give an integral distribution curve. Since the relation between [If] and sDPn is known, the graphic differentiation of the [Ib] versus [lf] curve furnishes the differential distribution curve, representing the mass distribution of the helical segments according to their DP. The peak of this curve is characteristic of the percentage and DP of those helical segments, which occur in the largest amount. On the basis of the differential distribution curve the polymolecularity of the investigated sample may be judged. The titration of amylose samples degraded by various methods gives different distribution curves. Titrating mixtures of samples with widely differing average DP values results in differential curves having more than one maximum.
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    Biopolymers 5 (1967), S. 79-94 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electronic absorption and circular dichroism spectra of the DNA-acridine orange complex have been measured over a range of ionic strength, pH, and DNA phosphate to dye (P/D) ratios. Three circular dichroism bands associated with the long wavelength absorption band of acridine orange are induced on complex formation with DNA. Two of the dichroism bands, due mainly to dimeric dye molecules, are favored by low ionic strength, low pH (3.2), and a low P/D ratio (∼3), while the third, deriving primarily from monomeric dye, is optimum at high ionic strength, neutral pH, and a larger P/D ratio (9). The data suggest that monomeric acridine orange binds to DNA in the form of a left-handed helical array with four dye molecules per turn, while the bound dimer has a skewed sandwich conformation which is itself dissymmetric. The stereochemical relations between the bound monomer dye and the DNA are consistent with a modified intercalation model for the DNA-acridine complex.
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    Biopolymers 5 (1967), S. 69-77 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The degree of helicity θ of a series of homologous polypeptides as a function of solvent composition was investigated. The polypeptides studied were: poly-N5-(3-hydroxypropyl)-L-glutamine (PHPG) as well as the corresponding 2-hydroxyethyl and 4-hydoxybutyl derivatives (PHKG and PHBG, respectively). PHPG, which is nonhelical in formic acid, attains helicity on addition of relatively small amounts of formates, formamide, and urea to its solution in formic acid. This demonstrates that the high acidity of pure formic acid is largely responsible for its helix-breaking power-probably through protonation of the peptide bonds. In formic acid-water mixtures all three polymers show a maximum in degree of helicity at a mole fraction of about 0.3 formic acid. This is interpreted as being due to interaction between the two helix-breaking solvents, which results in the formation of an inactive molecular species. It is shown that solvent-induced transitions with helicity maxima are predicted by the Bixon-Lifson treatment when applied to this system.
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  • 92
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In aqueous solutions of the amylase-iodine complex the concentration of free iodine [If]v after reaching equilibrium (or closely approximating it) is determined by the following factors: temperature, pH, concentration of iodide ions and amylose, and DP of amylose. In the present paper the role of temperature, amylose concentration, and DP has been investigated. At half-saturation of amylose by iodine, the reciprocal value of free iodine defines the equilibrium constant: 1/[If]v = K. The relation between [If]v, in normality and temperature is the following: 5 + log [If]v = -(2.132/T) + 8.52, for DPn = 1290, 0.4 mg. amylose in 100 ml. 0.1N HCl. The value of the energy of activation Ea between 2 and 52°C. is 9.72 kcal./mole. The influence of amylose concentration [Am] on photometrically determined [If]v, at 20°C, in the range of 0.1-1.2 mg./100 ml. 0.1 N HCl for DPn = 1290 is: 5 + log [If]v = 0.209 - 0.047 log [Am]. At [Am] = 0.6 mg. amylose/ 100 ml. 0.1 N HCl and 20°C, the value of [If]v depends on DPn as follows: 5 + log [If]v = 0.085 = + 0.222 log (104/DPn). These above equations are summarized by the relation: [If]v = exp {16.865 - (Ea/RT)}[Am]0.047(104/DPn)0.222 ×10-5 Considering that the determination of [If]v by automatic photometric titration can be performed quickly and with appropriate reproducibility, this method is convenient for a rapid empirical and approximate determination of DP of amylose on a microscale. The iodine-binding capacity [IBC] as well as the value of λmax, have been also investigated as functions of DPn, by photometric and by amperometric titration.
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  • 93
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    Biopolymers 5 (1967), S. 879-886 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dielectric properties of human and horse hemoglobin were studied at frequencies ranging from 20 kc./sec. to 7 Mc./sec. The relative errors in the measurements were usually less than 10-3 even for mildly conducting solutions (10-3M KCl). The experimental setup allowed us variation and measurement of the degree of oxygenation of the protein and to determine its dielectric parameters. Our main conclusion is that it was not possible to find any variation of the dielectric increment for hemoglobin oxygenation levels of 25, 50, 75, and 100%, approximately. This result is at variance with some previous reports. We cannot give the reason for this discrepancy but discuss some possible explanations. The specific dielectric increment, Δεs/c, of human hemoglobin was shown to be significantly smaller than that of horse hemoglobin (0.28 against 0.32). This physical property is lowered with increasing ionic strength I: Δεs/c = 0.28 and 0.20 for I = 10-4 and 10-3, respectively (human protein).
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  • 94
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    Biopolymers 6 (1968), S. 415-430 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transient electric birefringence behavior of bacteriophage T2 and the T2 ghost or protein coal was studied. The field free relaxation measurements show both the intact virus and its ghost to have two rotary diffusion coefficients. These coefficients have values of 555 ± 54 and 111 ± 22 sec.-1 for the intact virus and 688 ± 89 and 161 ± 29 sec.-l for the ghost. The equivalent ellipsoids for the fast and slow relaxation coefficients were obtained by use of Perrin's equation and were related to the bacteriophage structure in terms of a possible extension of the tail fibers or an enlargement of the head structure. The saturation of the specific birefringence of the phage and the ghost when compared with the specific birefringence of the free nucleic acid gave an average optical orientation of 10 to 18% of the nucleic acid parallel to the main axis of the phage. The analysis of the birefringence versus applied field strength in the Kerr region gave the following values for the anisotropy of the polarixability. αe,33 - αe,11 and intrinsic dipole, μ, of both phage and ghost : for T2 phage αe,33 - αe,11 = 5.0 × 10-14 cm.3 and μ = 64,400 Debyes; for T2 ghost αe,33 - αe,11 = 7.9 × 10-14cm.3 and μ = 57,200 Debyes. The high intrinsic dipole for phage and ghost is interpreted as to be associated with the mechanisms of the virus for attachment, to the host cell wall.
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  • 95
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    Biopolymers 6 (1968) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 96
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    Biopolymers 6 (1968), S. 431-440 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydration of several polyacids has been investigated with special attention to the effects of neighboring charged groups and hydrophobic groups on the hydration regions. The molar volume change due to the structural change of water by the hydration was obtained by the method of refractivity measurement. The polyacids employed were poly(acrylic acid), poly(methacrylic acid), poly(L-glutamic acid), and a copolymer of maleic acid and vinyl acetate. The measurement of the refractive index was performed for the solutions of these polymers neutralized to varying degrees by tetrabutyl-ammonium hydroxide and sodium hydroxide. The results confirm the characteristics of the previous model of the hydration of polyelectrolytes, that is, the cooperative action of neighboring charged groups induce the second hydration region in addition to the intrinsic hydration region. The stiff structure of water in these regions restricts the mobility of counterions forced to enter into these regions by the strong electrostatic potential of polyions. The results indicate also that hydrophobic groups induce an additional hydration region around their neighboring charged groups. Small but negative volume changes were observed for conformational changes of poly(L-glutamic acid) and poly(methacrylic acid) induced by the neutralization of carboxyl groups.
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  • 97
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    Biopolymers 6 (1968), S. 441-448 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The heat of solution of a series of three polyglutamates as a function of solvent composition was measured. The abrupt increase in heat of solution at the solvent composition of the helix-coil transition (as evidenced by optical rotation data) allows the estimation of the transition enthalpy change. The difference of side chain in the three polyglutamates has no appreciable effect on the transition enthalpy, although it affects the helix stability, as judged from the solvent composition at the transition points. These facts are discussed on the basis of existing models of the transition.
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  • 98
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    Biopolymers 6 (1968), S. 469-477 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Single crystals of poly(γ-benzyl L-glutamate) were formed by epitaxial crystallization from solution in mesitylene on NaCl, KI, and KCl (001) cleavage faces. From electron microscopy and diffraction studies, the structure of these overgrowths was determined to be that of lamellae containing chain-folded α-helical macromolecules. The usual type of crystal perfection, that of ordered helix axes and disordered side groups, was exhibited by this synthetic polypeptide. Unique orientation regimes were observed with each substrate.
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  • 99
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    Biopolymers 6 (1968), S. 479-490 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As a model for a variety of reaction processes on long chain molecules, for example, helix formation, a kinetic theory on a linear lattice is presented. Each reaction site can undergo reversible transitions between two states (0 and 1) with rates depending on the slate of its nearest neighbors. The system of coupled rate equations for the frequencies of specified runs of 0's and 1's is infinite for an infinite chain. In contrast to the case of irreversible processes, the system cannot, be written down by inspection. A procedure for the systematic derivation of the rate equations is developed which can be programmed on a computer. Explicit expressions for runs up to length four, involving runs up to length five are obtained without recourse to the computer. For the solution of the rate equations a closure must necessarily be imposed, and a possible procedure is pointed out. Furthermore the equilibrium relations following from the model are considered. The well-known equilibrium results for nearest-neighbor interactions represent a special case of these equations.
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  • 100
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    Biopolymers 6 (1968), S. 1355-1377 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Measurements of specific heat of wool-water systems were made at approximately 5°C intervals over the temperature range -70 to 100°C. Ten different, samples were used, each with a different amount of absorbed water in the range from dry ness to saturation at 0°C. The graph of specific heat against temperature for dry wool is precisely linear over the complete temperature range, suggesting that thermal motion is entirely vibrational. When absorbed water is present the data can be conveniently discussed in terms of behavior below and above an amount of absorbed water of 22.7 g in 100 g of wool (22.7% of absorbed water). Below 22.7% there is only one temperature range in which the results indicate an appreciable transition in heat absorbing properties. The temperature of transition depends on water content but is higher than 0°C. Above 22.7% a second transition appears in the range -30 to 0°C and grows rapidly larger with increase of water content. The first transition is tentatively ascribed to a slightly cooperative breakdown of polar bonds in wool, and the second to a process analogous to melting in the absorbed water. The results are discussed in these terms as well as with reference to specific heat theories, the heat absorption of the wool component and the water component, and enthalpy differences between the various samples.
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