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  • GEOPHYSICS  (57)
  • Chemistry  (53)
  • 1995-1999  (32)
  • 1985-1989  (71)
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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 633-642 
    ISSN: 0887-624X
    Keywords: free radicals ; grafting ; kinetics ; methacrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of grafting a basic monomer, 2-(dimethylamino)-ethyl methacrylate (DMAEMA) to hydrocarbon substrates have been investigated. These systems were chosen as models for the grafting of a homopolymerizable monomer to polyolefins such as polyethylene. The reactions with squalane and n-eicosane were initiated by an organic peroxide, 2,5-dimethyl 2,5 dit-butylperoxy)-3-hexyne; grafting yields become significant at high reaction temperatures and low monomer concentrations. In squalane, the order of reaction with respect to monomer increased from about 1.1 for 0.22-0.44M DMAEMA to almost 2 at 0.69M DMAEMA; the order with respect to initiator was 0.56. The overall activation energy in the 130-160°C temperature range was, however, surprisingly low, 42±5 kJ mol-1. When analytical data were used to separate the overall rate into those for grafting and homopolymerization, different kinetic paths were observed for the competing reactions. These results are interpreted in terms of two different mechanisms; intramolecular chain transfer plays an important role in grafting, while depropagation becomes a major factor in homopolymerization at temperatures above 150°C. © 1995 John Wiley & Sons, Inc.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 3517-3525 
    ISSN: 0887-624X
    Keywords: peroxide ; vinylsilane ; grafting ; polymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The peroxide-initiated grafting of vinyltrimethoxysilane (VTMS) onto dodecane has been examined as a model for grafting onto polyethylene. At 160°C, 2% v/v VTMS and 0.08% v/v initiator, the monomer was grafted onto dodecane with a 59% conversion and an average of 2.37 VTMS grafts per dodecane. These values were obtained by separation of the grafted material through reduced pressure distillation then characterization with FTIR and NMR spectroscopy, mass spectrometry, and gel permeation chromatography. NMR studies strongly indicate that the multiple grafts consist predominantly of multiple single grafts rather than homopolymer grafts. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3517-3525, 1997
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1573-1582 
    ISSN: 0887-624X
    Keywords: amic acid ; secondary amine ; maleic anhydride ; melt reaction kinetics ; model compounds ; polymer-bound functional groups ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This study examines the legitimacy of using the reaction kinetics of low molecular weight model compounds in solution to predict the chemical kinetics of polymer-bound species in a homogeneous melt. The reaction under study takes place between an aliphatic secondary amine, diisooctadecylamine (DiOA), and a 5-membered anhydride ring, saturated maleic anhydride (MA), forming an amic acid product. The MA species was present as a pendant graft on either a model compound, dodecane-g-(maleic anhydride) (dodecane-g-MA), or a polymer chain, linear low-density polyethylene-g-(maleic anhydride) (LLDPE-g-MA). Pseudo-second-order kinetics of the anhydride consumption are followed by infrared spectroscopy, either in situ in dodecane solution or by scanning frozen film samples taken from a linear low-density polyethylene melt. It was found that the LLDPE-g-MA/DiOA system reacted at a slightly slower rate than the dodecane-g-MA/DiOA system in the low-viscosity solution at 140°C. In the melt, the dodecane-g-MA/DiOA system experienced a small decrease in the overall reaction rate compared to the same reaction carried out in dodecane. However, the LLDPE-g-MA/DiOA system underwent a 65% decrease in the observed second-order rate constant on going from a solution to the melt. To explain these phenomena, the effects of diffusion, miscibility, and chain entanglements in the melt are examined here. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1573-1582, 1998
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  • 4
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermospray LC/MS methods with internal standardization were developed for the quantification of the antimalarial arteether and six of its metabolites at the 1-10 μg/ml level in liver microsome preparations without the use of solvent extraction. The thermospray mass spectra of arteether and most of its metabolites exhibited strong [M + NH4]+ and [M - OR]+ peaks arising from the molecular ion adduct and the loss of the alkoxy or hydroxy group of the side chain. In addition to the six metabolites for which authentic reference standards were available, three additional metabolites were detected. The major metabolites of arteether were found to be dihydroartemisinin, deoxydihydroartemisinin, 3-hydroxydeoxydihydroartemisinin, two isomers of hydroxyarteether, and 3-hydroxydeoxyarteether. Deoxyartheether was not found at significant concentrations in the microsome preparation.
    Additional Material: 11 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 27 (1985), S. 355-361 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Batch hydrolysis kinetics of paper birch (Betula papyrifera) xylan and its associated acetyl groups in dilute sulfuric acid have been measured for acid concentrations of between 0.04 and 0.18M and temperatures of between 100 and 170°C. Only 5% of the cellulose was hydrolyzed for up to 85% xylan removal. Rate data were correlated well by a parallel reaction model based on the existence of reactive and resistant xylan portions. The resulting rate equation predicts the experimental xylan concentrations in the residue to within 10%. Hydrolysis of xylan-associated acetyl groups was found to occur at the same rate as that of xylan, except at 100°C, where acetyl is released preferentially. No effect of acid concentration on the rate of acetyl removal relative to that of xylan was evident.
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  • 6
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Aspen (Populus tremuloides) and black cottonwood (Populus trichocarpa) organosolv pulps produced in a wide range of solvent composition (between 30 and 70% by volume of methanol) and catalysts (H2SO4 and H3PO4) such that the cooking liquor pH ≤ 3 are easily digested by enzymes. The total yields of hydrolysis residues (pulps) are in the 40-60% range; the acid-catalyzed delignification followed by enzyme hydrolysis can generate 70-88% of the original six-carbon sugars contained in the wood. Glucomannan and arablnogalactan are dissolved into the pulping liquor in the pH range of 2-4.5. Lower pH (≤3) leads to additional solubilization of six-carbon sugars. These sugars may be fermented directly. From the insoluble hydrolysis residues, 36-41% conversions of wood into fermentable sugars were obtained after enzyme hydrolysis; the starting feedstocks contain 50.8 and 46.6% hexosans, respectively, for aspen and black cotton-wood. The kinetics of enzymatic hydrolysis of cellulose can be formally treated as two simultaneous pseudo-first-order reactions in which fast and slow hydrolyses of cellulose occur. Correlations between the glucan digestibility and the effect of the pretreatment have been made. The higher residual xylan content reduces the amount of the rapidly hydrolyzable glucan fraction and lowers the glucan digestibility. The proposed simple kinetic treatment is very helpful in assessing the effect of the pretreatment on pulp enzyme hydrolyzability.
    Additional Material: 3 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 1108-1115 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A lab-scale nonflowing reactor was built to study chemical vapor deposition reactions. Mass spectrometry is used to follow reaction pathways and to determine instantaneous reaction rates throughout film growth. In each experiment, the kinetic rate dependence on concentration for a wide range of concentrations is observed as reactants convert to products. This method of obtaining kinetic data is efficient in terms of sample loading, gas usage, and time, since over 200 instantaneous rate/composition pairs can be determined from one 30-min deposition. Because the rate is determined from gas-mass balance, rather than film-thickness measurements, an unlimited number of rate studies can be made on one sample. As a test case, the SiH4 reduction of WF6, used to deposit tungsten during integrated-circuit production, was investigated in the 0.64-L nonflowing laboratory reactor. Gas compositions were measured 2 mm from the growing surface, throughout time, with a mass spectrometer equipped with a capillary sampling tube. Tungsten was deposited on the 95°C surface, and SiHF3 was the primary silicon fluoride reaction product for most tested conditions. A multiple-regression analysis of 1,975 instantaneous composition/rate pairs gives orders of 1.22 in silane, 0.27 in hydrogen, and -2.17 in WF6. The ratio of SiF4 to SiHF3 stays low and constant until the gas becomes silane-rich. The evolution of the instantaneous rate over time implies that a minimal level of thermal activation of the reactive gases is necessary for the deposition to be surface-rate-limited. Preliminary heat-transfer models of the wire substrate imply that heat transfer to the gas phase is in the Knudsen regime.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 31 (1988), S. 321-327 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A combination of ionic strength reduction and diafiltration of Trichoderma reesei cellulate complex through a hollow fiber apparatus of 5000 molecular weight (MW) cutoff and subsequent passage of filtrate over a Spherogel-TSK 3000-SW column provided extracts that had the ability to generate microfibrils in filter paper and to disrupt filter paper and corn leaf tissue. Milligram quantities of material obtained from these extracts released small amounts of soluble carbohydrate from filter paper, required ferric iron for increased activity, and contained amino acids. Short fiber formation and disruption of filter paper during interaction with these extracts was enhanced by prior acid treatment and eliminated by prior base treatment. The amount of soluble carbohydrate hydrolyzed in 24 h from filter paper by whole cellulase complex was not changed by first disrupting the substrate with the extracts.
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  • 9
    ISSN: 0899-0042
    Keywords: microbial chiral inversion ; 2-phenylpropionic acid ; kinetic isotope effect ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Previous investigations have described the development of nongrowing suspension of Verticillium lecanii as a microbial model of the mammalian chiral inversion of the 2-arylpropionic acids (2-APAs). Mechanistic studies in mammals have shown that inversion involves loss of the α-methine proton but retention of the original atoms at the β-methyl position, and a mechanism has been proposed involving enzymatic epimerisation of acyl-CoA thioester derivatives of the substrate. Inversion of the 2-APAs by V. lecanii exhibits extensive intersubstrate variation in the presence, rate, extent, and direction of inversion, which are different from those observed in mammalian systems, possibly indicating differences in the mechanism of inversion between mammalian and microbial cells. This study involved the investigation of proton/deuterium exchange by 1H-nuclear magnetic resonance following incubation of deuterated derivatives of 2-phenylpropionic acid (2-PPA), a model compound, in cell suspensions of V. lecanii and incubation of undeuterated 2-PPA in cell suspensions containing D2O. The results indicated that the inversion of 2-PPA by V. lecanii also involved exchange of the α-methine proton but complete retention on the original atoms at the β-methyl position. No kinetic deuterium isotope effect was observed, indicating that loss of the α-methine proton is not the rate-limiting step of the inversion process. This suggests that the observed differences between microbial and mammalian systems probably involve the stereoselective acyl-CoA thioester formation step and not the subsequent epimerisation of the resultant diastereomers. Chirality 9:254-260, 1997. © 1997 Wiley-Liss, Inc.
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  • 10
    ISSN: 0899-0042
    Keywords: stereoselective synthesis ; carboxyibuprofen diastereoisomers ; circular dichroism ; chiral LC separation ; ibuprofen ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chromatographic resolution of the four stereoisomers of carboxyibuprofen, a major metabolite of ibuprofen in man, was achieved using a Chiralpak AD chiral stationary phase (CSP) (J.T. Baker, Milton, Keynes, UK). The elution order of the stereoisomers was determined to be 2′S,2R; 2′R,2R; 2′R,2S; 2′S,2S by a combination of stereoselective synthesis of diastereoisomeric mixtures and analysis of the two diastereoisomers isolated from human urine following the administration of (S)-ibuprofen. The individual stereoisomers were isolated by semipreparative chiral phase chromatography and characterized by circular dichroism spectroscopy. Chirality 9:75-87, 1997. © 1997 Wiley-Liss, Inc.
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