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  • 1985-1989  (22,294)
  • 1980-1984  (18,615)
  • Polymer and Materials Science  (31,552)
  • Biochemistry and Biotechnology  (4,807)
  • Engineering General  (3,850)
  • Gas chromatography
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Year
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Archives of toxicology 63 (1989), S. 107-111 
    ISSN: 1432-0738
    Keywords: Analysis ; Biological monitoring ; Butoxyacetic acid ; Ethoxyacetic acid ; Gas chromatography ; Glycol ethers ; Metabolism ; Methoxyacetic acid ; Pentoxyacetic acid ; Urine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Alkoxyacetic acids are metabolically formed and excreted in urine after exposure to ethylene glycol monoalkyl ethers (alkoxyethanols) or their acetate esters. This paper presents a sensitive method based on extractive alkylation for determination of alkoxyacetic acids in urine. Alkoxyacetate ions were extracted from 200 μl urine into methylene chloride, with tetrabutylammonium acting as counter ion, and derivatized with pentafluorobenzyl bromide in a single step. After separation of the methylene chloride phase, evaporation, and dissolution of the residues in hexane the esters were analyzed by fused silica capillary column gas chromatography and electron capture detection. The esters formed were stable for at least 2 weeks at room temperature. The limit of quantification was estimated to 2 μM (corresponding to an injected amount of 2 pg) for methoxyacetic (MAA) and ethoxyacetic acid (EAA) in urine. The corresponding values for butoxyacetic acid (BAA) were 4 μM and 5 pg, respectively. The detector response was linear up to 80 μM and the formation of derivative at least up to 1 mM. The method error may be reduced by using a second alkoxyacetic acid derivative, EAA, BAA or 2-pentoxyacetic acid (PAA), as an internal standard. The sensitivity, stability, reduced number of extractions, and small volumes of reagents and sample needed make the present method useful in biomonitoring of occupational exposure to ethylene glycol ethers.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    International archives of occupational and environmental health 61 (1989), S. 249-254 
    ISSN: 1432-1246
    Keywords: Ethylene glycol ethers ; Alkoxyacetic acids ; Pentafluorobenzylbromide ; Gas chromatography ; Urine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A sensitive and specific method for the determination in urine of alkoxyacetic acids, the metabolites of ethylene glycol monoalkyl ethers, was developed by combining the advantages of two previously described methods. The acids were determined gas chromatographically as their pentafluorobenzylesters. The alkylation with pentafluorobenzylbromide was performed after dissolving the dry residue of lyophilized urine in methanol. Quantitative derivatization was obtained when the urinary pH was adjusted to pH 7.0, when the reagent concentration was 5% v/v, and when the reaction mixture was heated at 90°C for 3 h. Sample clean-up was performed by adding bidistilled water and the esters were extracted with methylene chloride with high yields (95%). Alkoxyacetic acid concentrations in the range of 0.1 to 200 mg/l could be determined with an average imprecision of ± 3.5%.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1612-1112
    Keywords: Gas chromatography ; FAME fingerprinting ; Animal fats ; Transesterification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The triglycerides of animal fats from milk, meat or cheese can also be characterized by the gaschromatographic pattern of the fatty acid methylesters (FAME) after conversion by an unsophisticated transesterification procedure. Even from the FAME pattern falsifications of commercial animal fats can be revealed by the fast separation of the FAME using a standard CW 20 M (polyethyleneglycol) capillary column. Characteristic patterns of FAME originating from different animals are shown. The patterns of the FAME from different races of the same animal are very similar, so that the characterisation according to the type of animal is not disturbed.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 27 (1989), S. 596-600 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Mass spectrometry ; Azines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary We have studied the gas chromatographic behaviour of several 3-methyl-2-benzothiazolone-azines. In HPLC analysis all the unsymmetrical azines show double peaks, whereas in HRGC analysis only some of these compounds show the two peaks corresponding to the Z (syn) and E (anti) isomers. By means GC/MS analysis the mass spectrum of each azine was recorded. We have assigned the E and Z configurations to the first and second gas chromtographic peaks on the basis of the ratio between the relative abundances of the two most significant framment ions at m/z 163 and 164.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 27 (1989), S. 221-224 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Large volume sample injection ; Closed on-column injector
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new simplified version of a “closed” on-column injector is introduced. Because of its design isobaric injection conditions do not have to be followed and a wide range of injection temperatures above the boiling point of the sample solvent can be chosen for on-column injections in capillary gas chromatography. Also, when following certain basic injection rules, injections of large sample volumes (≥20 μl or more) give accurate and reproducible results without further problems.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 28 (1989), S. 139-142 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Silica surface ; Silanols ; Strongly interacting sites
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The paper describes how the method of gas-phase titration of the strongest adsorption sites can be utilized to calculate a relative strength of interaction of the sites with chromatographic solutes. An excellent correlation with earlier, theoretical predictions of Giddings is noted. Significant influence of the sites on the width of a chromatographic band is observed when the interactions are an order of magnitude stronger than those of normal sites.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 28 (1989), S. 167-169 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Determination of monomer in polymers ; Sealed glass capillary sampling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Residual styrene in polystyrene and free phenol in phenolic plywood adhesive have been determined by sealing samples in glass capillary tubes. To prevent loss of sample the ends of the capillary tubes were sealed with a kind of putty made of anhydrous calcium sulfare, calcium carbonate and a small quantity of phenylmethylsilicone fluid. No volatile compounds were released from this sealing material when the capillary tubes were placed in a quartz vaporising furnace at temperatures up to 300°C.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 28 (1989), S. 237-240 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Slope of log plot ; Homologous series ; Retention index ; Retention time ; Uncertainty ; Free energy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The free energy of partition of a methylene group $$\Delta G_{CH_2 }^ \circ $$ is constant within a homologous series down to C5 and nearly constant to C3, contrary to the finding of Golovnya and Grigoryeva [5]. Retention indices are linear with carbon number: values may be extrapolated from higher carbon numbers to C5 within experimental uncertainty, to C4 with error no greater than 5 units and to C3 with error no greater than 10 units. Error in extrapolating the logarithm of the adjusted retention time, log t′R, to C5 is thus negligible, to C4 has possible error up to 5b/100 and to C3 up to 10b/100, whereb is the slope of the plot of log t′R against carbon number.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Optimization of gas-solid separations ; Plate height equation ; Computer mapping procedure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary This paper proposes an optimization model for gas-solid chromatographic separations in a non-linear programming form and an approximate equation of the plate height for the model. A computer-modified mapping procedure is also described for searching the optimum separation conditions. Just five experiments and about 20 minutes of the computer time are needed to establish the optima of column temperature and of the carrier gas linear velocity. The relative deviation between the predicted and the experimental values was found to be within 20% for the plate heights, and within 1.5% for the retention times.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 27 (1989), S. 37-43 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Methylbromide ; Charcoal tubes ; Pollution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Air sampling of methylbromide using 900 mg HBr-treated activated charcoal tubes, followed by solvent desorption and FID or ECD chromatographic analysis, makes it possible to evaluate concentrations ranging from 0.2 ppm (1 mg×m−3) to 250 ppm (1g×m−3) at ambient temperature even with a high hygrometric level. Thermal desorption does not lead to satisfactory results.
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 27 (1989), S. 60-66 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Mass loadability ; Stationary phase capacity ; Capillary columns
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary In GLC the mass load can be normalized with respect to the amount of stationary phase in one plate. This quantity can be used for a specified solute-liquid phase combination in any capillary or packed column, irrespective of the column dimensions or the number of plates. For each individual solute in a given stationary phase a unique factor β″ can be found, which accounts for the specific shape of the isotherm of this particular combination. this factor β″ corresponds well with the activity coefficients of the solutes in the stationary phase, by which a fairly good approximation of the mass loadability of the column at hand can be made without need for experiment.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 27 (1989), S. 552-558 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Radio gas chromatography ; 3H- and14C-labelled compounds ; Isotope effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Radio gas chromatography (RGC) is a valuable tool for the analysis of radioactively labelled compounds. Recent advances in capillary GC, especially in column technology and instrumentation have also induced new possibilities in this field. With regard to the preservation of the achieved separation efficiency, radioactivity detection is the main problem in capillary RGC. Based on published data and on our extensive experience in conventional RGC, a simple, reliable and versatile method has been developed for the radioactive detection: purge gas is added to the effluent of the capillary column and the RGC detection unit with conversion tube and flow-through proportional counter is used maintaining small dead volumes and dimensions. The influence of the extra-column volumes and of the total gas flow rate (of the carrier, purge and quenching gases) on the peak shape was investigated. It was also found that the isotopic effect commonly known in GC of2H- and3H-labelled compounds is hardly measurable for larger [G-14C] labelled species such as [G-14C] labelled higher fatty acids with high isotopic abundance of14C, even on the highly efficient capillary columns. The quantitative aspects of the detection method used are discussed and some applications to the analysis of labelled biochemicals (amino and fatty acids) are demonstrated.
    Type of Medium: Electronic Resource
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  • 13
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Coke oven gas evolution ; On-line gas analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A gas chromatograph will thermal conductivity detector (TCD) connected on line via a cleaning train to the semi-industrial scale Coke Oven Text Plant of the Spanish National Coal Institute (INCAR), has been used to control the evolution of the permanent gases during the coking process. The undesirable presence of oxygen in the coke oven gas can be detected with this system that will be applied to determine the end of the coking process by quantitative analysis of the gas evolved.
    Type of Medium: Electronic Resource
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  • 14
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Microwave plasma detector ; Thiophenes ; Shale oil distillates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A series of alkylthiophenes and dimethyl disulfide were tentatively identified in an oil shale retort gas condensate from a 6-kg bench-scale retort using gas chromatography with a microwave-induced helium plasma detector (GC-MIP). The sulfur species were present in concentrations ranging from 1.5 to 10.7 mol ppm in the undiluted offgas. The GC-MIP technique was successful in selectively detecting the sulfur components in the complex mixture. Quantitation was simplified relative to GC with flame-photometric detection because of the absence of quenching or other interference problems at the concentrations studied. Attempts to determine stoichiometry of the sulfur components by comparison of carbon, hydrogen, and sulfur ratios with those of standards were unsuccessful because of the complexity of the carbon and hydrogen chromatograms.
    Type of Medium: Electronic Resource
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  • 15
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Air pollutants ; Adsorbent enrichment ; Thermal desorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new automatic method is described for quantitative determination of some light C2–C4 hydrocarbons in urban air: ethene, ethyne, propane, propene, butane and iso-butane. This method is based on an enrichment step at room temperature using a solid sorbent and subsequent thermal desorption for gas chromatographic separation and FID detection. The instrument is built up of a small commercial gas chromatograph and a laboratory-made trap and desorption unit. The sampling parameters, sample volume, concentration and humidity of air have been investigated.
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 27 (1989), S. 159-163 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Flame photometric detector ; Sulfur compounds ; Response quenching
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The long time retardation of the main hydrocarbon peak in the chimney of the flame photometric detector greatly reduces the responses of later-eluting sulfur compounds. In the absence of hydrocarbons in the flame, the slope (s) of the log I vs. log [S] plot (where I is the sulfur response and [S] is the sulfur concentration in the sample) is of the highest value and is constant for all experimental conditions tested. Flame hydrocarbons cause the s value to decrease, and this is dependent on the oxygen to hydrogen ratio in the flame (O/H) and, under certain conditions, also on the sulfur to carbon ratio (S/C) of the sample. The abnormalities observed in the determination of methyl thiol in natural gas are explained on the basis of the present study.
    Type of Medium: Electronic Resource
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  • 17
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 27 (1989), S. 631-632 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Wide-bore glass capillary columns ; End-sealing ; Static coating
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An end-sealing method to be used for static coating of wide-bore glass capillaries is described. After the capillary was completely filled with the coating solution, one end is connected to a gas-tight syringe (10-ml volume) via silicone tubing and the other end is fixed with shortcutted silicone tubing for sealing with a plug. The method is highly successful.
    Type of Medium: Electronic Resource
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  • 18
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 27 (1989), S. 233-237 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; FTIR ; Hemoglobin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The use of N, O (S)-tert.-Butyldimethylsilyl derivatives of amino acids for capillary gas chromatography and FTIR identification of amino acids is described. Rapid identification is achieved by computerised comparison of FTIR spectra. Derivatives that are characterised by identical sets of ions in gas chromatography-mass spectrometry experiments are clearly distinguished and identified by means of their infrared spectra. This, for example, is the case with alanine, β-alanine and sarcosine, which norvaline and valine, and with norleucine, leucine and isoleucine. Unknows are also promptly detected. This is especially useful in screening biological samples for less common amino acids. Screening of hemoglogin hydrolysates for amino acid adducts is exemplified.
    Type of Medium: Electronic Resource
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  • 19
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Ethyl carbamate ; Direct injection quantification ; Cold injection system ; Optimised SIM
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An integrated procedure is described which allows direct injection quantitative screening to single figure parts per billion (μg/L) levels of ethyl carbamate in the natural matrix of distilled alcoholic beverage. Injection and detection performance was studied and optimized to allow this routine, reproducible, trace analysis without any sample pre-treatment. All aspects of the analysis including autosampler run sequences and automated internal standard report generation are initiated and controlled from a single GC/MS workstation.
    Type of Medium: Electronic Resource
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  • 20
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Trichloroethyl ester ; Dicarboxylic acid ; Urine samples ; Electron capture ; Biological monitoring
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Dicarboxylic acids were esterified by 2,2,2-trichloroethanol by using trifluoroacetic anhydride and phosphoric acid as catalysts. The method was developed to facilitate the evaluation of workers' exposure to sensitising acid anhydrides and other compounds metabolised to acids in the body. The sensitivity of the acid determination in urine was in the order of 2–4 ng ml−1 for aliphatic and alicyclic acids and 15ng ml−1 for phthalic acid.
    Type of Medium: Electronic Resource
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 27 (1989), S. 499-508 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Electron capture detector ; Space-charge model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Mathematical analysis, allowing the determination of the distribution of the electron and positive ion concentration in an electron-capture detector with a cylindrical electrode arrangement and with constant and pulsed voltage supplies, has been carried out. The measurements obtained confirm the assumptions concerning the “space change” model of the ECD introduced by Gobby et al. and cast doubt upon the general assumption of the complete removal of the electrons from the detector by the voltage pulse. The physical factors influencing the current characteristics of the detector and the possible distortions connected with the electrode geometry have been explained on the basis of the measurements carried out.
    Type of Medium: Electronic Resource
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  • 22
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 27 (1989), S. 455-460 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Surface free energy ; Silane-covered materials ; Film pressure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The surface free energy, or film pressure, π0, is measured for mica (Mica HK), silane-covered mica (Mica NP), Chromosorb W DMCS and glass beads. The film pressure is obtained from gas chromatography. The materials are used as adsorbents and benzyl alcohol and n-dodecane are used as molecular probes. Adsorption isotherms at 353 K are obtained from gas chromatography data and the surface free energy is computed with the help of the Gibbs equation. Values of π0 for a given surface are found to vary with the molecular probe. With benzyl alcohol π0 varies from 44 erg/cm2 for Mica 60 HK to 76 erg/cm2 for glass. In the case of n-dodecane π0 is found to vary in the same manner but the values range from 25 to 45 erg/cm2. The results are in good agreement with the values obtained with the contact angle method.
    Type of Medium: Electronic Resource
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  • 23
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 27 (1989), S. 469-471 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Headspace analysis ; Ethylene oxide ; Capillary column
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A headspace gas chromatographic method for determination of traces of ethylene oxide (EO) in sterilized materials has been developed. The method allows the determination of the amount of EO by putting the samples directly into acetonitrile and analysing by means of headspace GC. The procedure described is simple, sensitive, reproducible and linear. The lower limit of detection is 0.015 μg/g of sterilized material.
    Type of Medium: Electronic Resource
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  • 24
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Colloidal stationary phases ; Liquid crystals as stationary phases
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Colloid systems consisting of the nematic liquid crystals p,p′-azoxyphenetol and p,p′-methoxyethoxyazoxybenzene and high-disperse mineral particles (aerosil, carbon black) are proposed to be used as stationary phases in gas chromatography. The dependence of the retention of normal paraffins, Rohrschneider and McReynolds test solutes (benzene, ethanol, methyl ethyl ketone, nitromethane, pyridine, butanol-1, 2-pentanone, and nitropropane) on the composition of the colloid systems was investigated. The investigated colloid sorbents including liquid crystals retain their selectivity for meta/para isomers up to 50% of the aerosil content and practically at all studied carbon black concentrations.
    Type of Medium: Electronic Resource
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  • 25
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 28 (1989), S. 24-26 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Anesthetics ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A sensitive capillary gas chromatographic method is described for the simultaneous determination of lidocaine, tetracaine, procaine and dibucaine. The method was applied to the determination of anesthetics in tissue homogenates incubated at 38°C at doses between 10 and 400 mg/kg. In the liver tissue thein vitro metabolization of the studied anesthetics is most rapid for tetracaine, also fast for procaine, while for lidocaine and dibucaine the metabolization is very slow. In brain tissue thein vitro metabolization of anesthetics is very slow. The method shows good analytical parameters: linearity between 5 and 40 μg/ml; day-to-day reproducibility ca. 8% for a concentration of 20 μg/ml, precision ca. 7% for a concentration of 20μg/ml. Accuracy is also very good.
    Type of Medium: Electronic Resource
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  • 26
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Chlorinated methanes ; Activated charcoal sampling ; Pollution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A sampling method using activated charcoal, followed by percolation with ethanol and FID or ECD chromatographic analysis, depending on the concentrations to be monitored, makes it possible to evaluate concentrations of methylene chloride between 5 and 1000mg m−3, chloroform between 0.1 and 2000mg m−3, and carbon tetrachloride between 0.015 and 1000mg m−3.
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  • 27
    ISSN: 1612-1112
    Keywords: Gas chromatography ; GC/MS and headspace GC ; Elastomeric stoppers for injectables ; Trace hydrocarbons
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Elastomeric stoppers for injectables have been surveyed by means of GC/MS screening. Residual contamination by hexanes (2-methylpentane, 3-methylpentane, n-hexane, methylcyclopentane, cyclohexane) toluene and xylenes occurred in all the samples tested. A headspace GC purity test is suggested, by using these residual chemicals as purity indexes.
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  • 28
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 28 (1989), S. 313-314 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Fused-silica columns ; Static coating ; Sealing method
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary In this paper a new sealing method for the static coating of capillary columns is described. When one end of the fully filled capillary was immersed into liquid nitrogen in a Dewar flask, the coating solution at this end would be frozen and became a temporary seal, and an air-free solvent/seal interface was obtained. No bumping has ever been found at the interface, even when butane was used as solvent. By applying this sealing method, several capillary columns, including some narrow bore capillary, had been successfully coated.
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  • 29
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Renewal theory ; Monte-Carlo simulation ; Prediction of retention and peak widths
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new method for prediction of gas chromatographic retention times and peak half widths is based on the renewal theory. The only requirements are the heats of vaporization of the compounds to be separated and one calibration measurement. With this data, retention times and peak half widths can be predicted for isothermal as well as temperature-programmed gas chromatography. For the separation of non-polar substances on non-polar stationary phases the prediction error for retention times is approx. 1–2%. First simulations of polar molecules and polar stationary phases indicate that this method is also applicable in these cases but some extension will be required.
    Type of Medium: Electronic Resource
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  • 30
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 5 (1989), S. 125-131 
    ISSN: 0887-3585
    Keywords: protein conformation ; dynamics ; Monte Carlo simulation ; conformational energy ; minimization ; plastic deformation ; conformational heterogeneity ; hierarchy in dynamics ; trypsin inhibitor ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Differences in atom packing are studied in the minimum energy conformations derived from the record of the Monte Carlo simulation of conformational fluctuation in the native state of a globular protein, bovine pancreatic trypsin inhibitor. It is found that local deformations observed among the minima which are found in the previous paper are accompanied by rearrangement of atom packing. Spatial locations of the local deformations in the three-dimensional folded structure are also studied. It is foundthat the local deformations are distributed in space in several clusters inthe folded structure. The size and location of the clusters characterize the respective fluctuations of the first and the second levels observed in the simulation. In the fluctuations of the first level local deformations, each of which usually involves a few side chains and one main chain local segment, are thermally exited independently of each other near thesurface of the molecule. The observed fluctuation of the second level involves a cooperative deformation involving many side chains and local main chain segments all in one cluster, which goes though the core of the molecule. The collective local deformations observed both in the first and second levels are plastic in the sense that they are accompanied with rearrangement of atom packing.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 31
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Proteins: Structure, Function, and Genetics 5 (1989), S. 139-148 
    ISSN: 0887-3585
    Keywords: protein architecture ; packing ; evolutionary relationships ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: α/β barrel structures very similar to that first observed in triose phosphate isomerase are now known to occur in 14 enzymes. To understand the origin of this fold, we analyzed in three of these proteins the geometry of the eight-stranded β-sheets and the packing of the residues at the center of the barrel. The Packingin thisregion is seen in its simplest form in glycolate oxidase. It consists of 12 residues arranged in three layers. Each layer contains four side chains. The packing of RubisCO and TIM can be understood in terms of distortions of this simple pattern, caused by residues with small side chains at someof the positions inside the barrel. Two classes of packing are found. In one class, to which RubisCO and TIM belong, the central layer is formed by a residue from the first, third, fifth, and seventh strands; the upper and lower layers are formed by residues fromthe second, fourth, sixth, and eighth strands. In the second class, to which GAO belongs, this is reversed: it is side chains from the even-numbered strands that form the central layer, and side chains from the oddnumbered strands that form the outer layers. Our results suggest that not all proteins with this fold are related by evolution, but that they represent a common favorable solution to the structural problems involved in the creation of a closed β barrel.
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  • 32
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    Proteins: Structure, Function, and Genetics 5 (1989), S. 170-182 
    ISSN: 0887-3585
    Keywords: modeling ; flavodoxin ; structure prediction ; side chains ; database ; structure analysis ; protein ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The tertiary structure of flavodoxin has been model build from only the X-ray crystallographic α-carbon coordinates. Main-Chain atoms were generated from a dictionary of backbone structures. Side-chain conformations were initially set according to observed statistical distributions, clashes were resolved with reference to other knowledge-based parameters, and finally, energy minimization was applied. The RMSD of the model was 1.7 Å across all atoms to the native structure. Regular secondary structural elements were modeledmore accurately than other regions. About 40%of the ξ1 torsional angles were modeled correctly. Packing of side chains in the core was energetically stable but diverged significantly from the native structure in some regions.The modeling of protein structures is increasing in popularity but relatively few checks have been applied to determine the accuracy of the approach. In this work a variety of parameters have been examined. It was found that close contact, and hydrogen-bonding patterns could identifypoorly packed residues. These tests, however, did not indicate which residues had a conformation different from the native structure or how to move such residues to bring them into agreement. To assist in the modeling of interacting side chains a database of known interactions has been prepared.
    Additional Material: 8 Ill.
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  • 33
    ISSN: 0887-3585
    Keywords: yeast hexokinase II ; dimerization ; in vivo functions ; glucose repression ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The function of the N-terminal amino acids of Saccharomyces cerevisiae hexokinase II was studied in vivo using strains producing a form of hexokinase II lacking its first 15 amino acids (short form).This short form of hexokinase II was produced from a fusion between the promoter region of the PGK1 gene and the HXK2 coding sequence except the first 15 codons. As expected, the in vitro analysis of the short from protein by gel filtration chromatography indicates that the short protein does not form dimers under conditions where the wild-type protein dimerizes. Kinetic studies show that the enzymatic activities are very similarto wild-type behavior. The physiological experiments performed on the strains containing the fusion allele demonstrate that the short form ofthe enzyme is similar to the wild-type both in terms of phosphorylation of hexoses and glucose repression. We conclude that the N-terminalamino acids of hexokinase II are not required in vivo either for phosporylation of hexoses or for glucose repression.
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  • 34
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    Proteins: Structure, Function, and Genetics 5 (1989), S. 289-312 
    ISSN: 0887-3585
    Keywords: aconitase ; iron-sulfur enzyme ; crystal structure ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The crystal structure of the 80,000 Da Fe—S enzyme aconitase has been solved and refined at 2.1 Å resolution. The protein contains four domains; the first three from the N-terminus are closely associated around the [3Fe-4S] cluster with all three cysteine ligands to the cluster being provided by the third domain. Associationof the larger C-terminal domain with the first three domains createsan extensive cleft leading to the Fe—S cluster. Residues from all four domains contribute to the active site region, which is defined by the Fe—S cluster and a bound SO42-ion. This region of the structure contains 4 Arg, 3 His, 3 Ser, 2 Asp, 1 Glu, 3 Asn, and 1 Gln residues, as well asseveral bound water molecules. Three of these side chains reside on a threeturn 310 helix in the first domain. The SO42-ion is bound 9.3 Å from the center of the [3Fe-4S] cluster by the side chains of 2 Arg and 1 Gln rsidues. Each of 3 His side chains in the putative active site is paired with Asp or Glu side chains.
    Additional Material: 13 Ill.
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  • 35
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    Proteins: Structure, Function, and Genetics 5 (1989), S. 271-280 
    ISSN: 0887-3585
    Keywords: antifluorescyl monoclonal antibody ; high-affinity binding site ; effects of MPD on hapten binding ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The crystal structure of a fluorescein-Fab (4-4-20) complex was determined at 2.7 Å resolution by molecularreplacement methods. The starting model was the refined 2.7 Å structure of unliganded Fab from an autoantibody (BV04-01) with specificity for single-stranded DNA. In the 4-4-20 complex fluorescein fits tightly into a relatively deep slot formed by a network of tryptophan and tyrosine side chains. The planar xanthonyl ring of the hapten is accommodated at the bottom of the slot while the phenylcarboxyl group interfaces with solvent. Tyrosine 37 (light chain) and tryptophan 33 (heavy chain) flank the xanthonyl group and tryptophan 101 (light chain) provides the floor of the combining site. Tyrosine 103 (heavy chain) is situated near the phenyl ring of the hapten and tyrosine 102 (heavy chain) forms part of the boundary of the slot. Histidine 31 and arginine 39 of the light chain are located in positions adjacent to the two enolic groups at opposite ends of the xanthonyl ring, and thus account for neutralization of one of two negative charges in the haptenic dianion. Formation of an enol-arginine ion pair in a region of low dielectric constant may account for an incremental increase in affinity of 2-3 orders of magnitude in the 4-4-20 molecules relative to other members of an idiotypic family of monoclonalantifluorescyl antibodies. The phenyl carboxyl group of fluorescein appearsto be hydrogen bonded to the phenolic hydroxyl group of tyrosine 37 of the light chain. A molecule of 2-methyl-2,4-pentanediol (MPD), trapped in the interface of the variable domainsjust below the fluorescein binding site, may be partly responsible for the decrease in affinity for the hapten in MPD.
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  • 36
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    Proteins: Structure, Function, and Genetics 5 (1989), S. 355-373 
    ISSN: 0887-3585
    Keywords: protein ; structure ; prediction ; primary ; secondary ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A new approach is introduced for analyzing and ultimately predicting protein structures, defined at the level of Cα coordinates. We analyze hexamers (oligopeptides of six amino acid residues) and show that their structure tends to concentrate in specific clusters rather than vary continuously. Thus, we can use a limited set ofstandard structural building blocks taken from these clusters as representatives of the repertoire of observed hexamers. We demonstrate that protein structures can be approximated by concatenating such building blocks. We have identified about 100 building blocks by applying clustering algorithms, and have shown that they can “replace” about 76% ofall hexamers in well-refined known proteins with an error of less than 1 Å, and can be joined together to cover 99% of the residues. After replacing each hexamer by a standard building block with similar conformation, we can approximately reconstruct the actual structure by smoothly joining the overlapping building blocks into a full protein. The reconstructed structures show, in most cases, high resemblance to the original structure, although using a limited number of building blocks and local criteria of concatenating them is not likely to produce a very precise global match. Since these building blocks reflect, in many cases, some sequence dependency, it may be possible to use the results of this study as a basis for a protein structure prediction procedure.
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  • 37
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    Proteins: Structure, Function, and Genetics 6 (1989), S. 20-31 
    ISSN: 0887-3585
    Keywords: ribonuclease ; active site ; conformational change ; protein-nucleic ; acid interactions ; fluorescence depolarization ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Molecular dynamics simulations were performed on free RNase T1 and the 2′GMP-RNase T1 complex in vacuum and with water in the active site along with crystallographically identified waters, allowing analysis of both active site and overall structural and dynamics changes due to the presence of 2′GMP. Difference in the active site include a closing in the presence of 2′GMP, which is accompanied by a decrease in mobility of active site residues. The functional relevance of the active site fluctuations is discussed. 2′GMP alters the motion of Tyr-45, suggesting a role for that residue in providing a hydrophobic environment for the protein-nucleic acid interactions responsible for the specificity of RNase T1. The presence of 2′GMP causes a structural change of the C-terminus of the α-helix, indicating the transmission of structural changes from the active site through the protein matrix. Overall fluctuations of both the free and 2′GMP enzyme forms are in good agreement with X-ray temperature factors. The motion of Trp-59 is influenced by 2′GMP, indicating difference in enzyme dynamics away from the active site, with the calculated changes following those previously seen in time-resolved fluorescence experiments.
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  • 38
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    Proteins: Structure, Function, and Genetics 6 (1989), S. 324-337 
    ISSN: 0887-3585
    Keywords: aspartyl protease ; HIV/AIDS ; yeast expression ; polyprotein processing ; α-factor ; secretion ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The protease of the human immunodeficiency virus type I (HIV1) was expressed both intracellularly and extracellularly in Saccharomyces cerevisiae. Intracellular expression of the protease was achieved by fusing a 179 amino acid precursor form of the protease to human superoxide dismutase (hSOD). Self-processing of the viral enzyme from the hybrid precursor was demonstrated to ocur within the yeast host. Secretion of the protease was achieved by fusing the leader sequence of yeast α-factor to the precursor form of the protrease or to the 99 amino acid mature form of the protease. Authentic and active forms of the retroviral enzyme were detected in yeast supernatants of cells expressing the precursor or the mature form of the protease. A D25E active site variant of the retroviral enzyme exhibited diminished autocatalytic activity when expressed intracellularly or secreted from yeast. The wild-type protease was active in an in vitro assay on the natural substrate, myristylated gag precursor, Pr53gag. Correct processing of Pr53gag at the Tyr 138-Pro 139 junction was confirmed by amino terminal sequence analysis of the resulting capsid protein (CA, p24). The secreted protease was purified to homogeneity from yeast media using preparative isoelectric focusing and reverse-phase HPLC. Amino terminal sequence analysis showed a sequence beginning at amino acid 1 of the mature enzyme (Pro) and another sequence beginning at amino acid 6 (Trp). This shorter sequence may represent a natural autolytic product of the proteaseaspartyl protease.
    Additional Material: 7 Ill.
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  • 39
    ISSN: 0887-3585
    Keywords: protein tertiary structure ; incorrect and correct folding ; molecular surfaces ; solvation free energy ; solution and crystal structure ; disulfide connectivity determination ; squash inhibitor family ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Refinement of distance geometry (DG) structures of EETI-II (Heitz et al.:Biochemistry 28:2392-2398, 1989), a member of the squash family trypsin inhibitor, have been carried out by restrained molecular dynamics (RMD) in water. The resulting models show better side chain apolar/polar surface ratio and estimated solvation free energy than structures refined “in cacuo.” The consistent lower values of residual NMR constraint violations, apolar/polar surface ration and solvation free energy of one of these refined structures allowed prediction of the 3D folding and disulfide connectivity of EETI-II. Except for the few first residues for which no NMR constraints were available, this computer model fully agree with X-ray structures of CMTI-I (Boe et al.: FEBS Lett. 242:285-292, 1989) and EETI-II complexed with trypsin that appeared after the RMD simulation was completed. Restrained molecular dynamics n water is thus proved to highly valuable for refinement of DG structures Also, the successful use of apolar/polar surface ratio and solvation free energy reinforce the analysis of Novotny et al. (Proteins 4: 19-30, 1988) and shows that these criteria are useful indicators of correct versus misfolded models.
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  • 40
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    Proteins: Structure, Function, and Genetics 5 (1989) 
    ISSN: 0887-3585
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 41
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    Proteins: Structure, Function, and Genetics 6 (1989), S. 155-167 
    ISSN: 0887-3585
    Keywords: protein structure comparison ; dihedral angles ; protein conformation ; hemoglobin structure ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: An efficient algorithm was characterized that determines the similarity in main chain conformation between short protein substructures. The algorithm computes Δt, the root mean square difference in φ and ψ torsion angles over a small number of amino acids (typically 3-5). Using this algorithm, large number of protein substrates comparisons were feasible. The parameter Δt was sensitive to variations in local protein conformation, and it correlates with Δr, the root mean square deviation in atomic coordinates. Values for Δt were obtained that define similarity thresholds, which determine whether two substructure are considered structurally similar. To set a lower bound on the similarity threshold, we estimated the component of Δt due to measurement noise fromcomparisons of independently refined coordinates of the same protein. A sample distribution of Δt from nonhomologous protein comparisons identified an upper bound on the similarity threshold, one that refrains from incorporating large numbers of nonmatching comparisons large numbers of nonmatching comparisons. Unlike methods based on Cα atoms alone, Δt was sensitive to rotations in the peptide plane, shown to occur in several proteins. Comparisons of homologus proteins by Δt showed that the active site torsion angles are highly conserved. The Δt method was applied to the α-chain of human hemoglobin, where it readily demonstrated the local differences in the structures of different ligation states.
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  • 42
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    Proteins: Structure, Function, and Genetics 6 (1989), S. 193-209 
    ISSN: 0887-3585
    Keywords: protein folding ; simulated annealing ; empirical potentials ; Monte Carlo dynamics ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The current work describes a simplified representation of protein structure with uses in the simulation of protein folding. The model assumes that a protein can be represented by a freely rotating rigid chain with a single atom approximately the effect of each side chains. Potentials describing the attraction or repulsion between different types of amino acids are determined directly from the distribution of amino acids in the database of known protein structures. The optimization technique of simulated annealinghas been used to dynamically sample the conformations available to this sample model, allowing the protein to evolve from an extended, random coil into a compact globular structure. Many characteristics expected of true proteins, such as the sequence-dependent formation of secondary structure, the partitioning of hydrophobic residues, and specific disulfide, suggestion the model may accurately simulate the folding process.
    Additional Material: 8 Ill.
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  • 43
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    Proteins: Structure, Function, and Genetics 6 (1989), S. 249-258 
    ISSN: 0887-3585
    Keywords: DNA binding domain ; etheno-M13 DNA ; single-stranded DNA affinity chromatography ; proteolytic fragments ; truncated topoisomerase ; protein-DNA interaction ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Limited digestion of E. coli DNA topoisomerase I with trypsin or papain generated a DNA-binding domain of MW 14,000 corresponding to the carboxyl terminal of the enzyme. This fragment binds to single-stranded DNA agarose as tightly as the intact enzyme. It required around 400 mM NaCl for elution. A truncated topoisomerase that lacks this C-terminal domain was purified. It was eluted from the single-stranded DNA agarose column at around 150 mM NaCl. Although the truncated enzyme could relax negatively supercoiled DNA as efficiently as the intact enzyme at low ionic strength, its processivity was more sensitive to increasing salt concentration. Measurement of binding to fluorescent etheno-M13 DNA also demonstrated that the presence of the C-terminal domain confers higher affinity to DNA for the enzyme.
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  • 44
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    Proteins: Structure, Function, and Genetics 6 (1989), S. 275-283 
    ISSN: 0887-3585
    Keywords: mutagenesis ; structure-function relationships ; enzymatic catalysis ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Site saturation mutagenesis has been carried out at Ala-237 in RTEM-1 β-lactamase to assess the role of this site in modulating differences in specificity of β-lactamases for penams vs. cephams as substrates. (An Ala-237 Thr mutation had previously been shown to increase activity on cephems by about 30-80%.1,2) Screening of all 19 possibles mutants on penams and cephems revealed the even more active Ala-237 Asn mutant. Detailed kinnetic analysis showns that this mutant has about four times the activity toward cephalothin and cephalosporin C as the wild-type enzyme. Both mutations reduce the activity toward penams to about 10% that of RETM-1 β-lactamase and lower by about 5°C the tempreature at which the enzyme denatures. Functional properties of the other mutants have also been surveyed. The most intresting aspect of these results is that two quite disparate amino acids, theronine and asparagine, when intorduced for Ala-237, cause such similar changes in enzyme specificity while more similar residues do not alter the catalytic properties of the enzyme to such a significant degree.
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  • 45
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    Proteins: Structure, Function, and Genetics 6 (1989), S. 338-340 
    ISSN: 0887-3585
    Keywords: cytochrome c ; axial ligand ; semisynthesis ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Semisynthesis has been employed to replace the axial methionine in horse heart cytochrome c with histidine. The reduction potential of the His-80 protein (cyt c-His-80) is 41 mV vs NHE (0.1 M phosphate; pH 7.0; 25°C). The absorption spectra of oxidized and reduced cyt c-His-80 are very similar to those of the native protein in the porphyrin region, but the 695 nm band is absent in the oxidized His-80 protein.
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  • 46
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    Proteins: Structure, Function, and Genetics 6 (1989) 
    ISSN: 0887-3585
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 47
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    Proteins: Structure, Function, and Genetics 6 (1989), S. 372-381 
    ISSN: 0887-3585
    Keywords: cytochromec ; Saccharomyces cerevisiae ; protein secondary structures ; protein design ; protein engineering ; protein folding ; protein evolution ; modular exchange ; loop swap ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Ω(Omega)-loops are protein secondary structural elements having small distance between segment termini. It should be possible to delete or replace certain of these Ω-loops without greatly distorting the overall structure of the remaining portion of the molecule. Functional requirements of regions of iso-1-cytochrome c from the yeast Saccharomyces cerevisiae were in investigated by determining the biosynthesis and activity in vivo of mutant forms in which four different Ω-loops were individually deleted, or in which one Ω-loop was replaced with five different segments. Deletion encompassing amino acid positions 27-33 and79-83 either prevented synthesis of the holoprotein, or produced highly labile iso-1-cytochromes c, whereas deletions encompassing position 42-45 and 48-55 allowed partial synthesis and activity. These two latter regions, therefore, are not absolutely required for any biosynthetic process such as heme attachment, mitochondrial import, or for enzymatic interactions. All replacements in Loop A (residue position 24-33) with the same size (10 amino acid residues), longer (13 and 15 amino acid residues), or shorter segments (6 amino acid residues), resulted in strains having at least partial levels of iso-1-cytochrome c; however, the relative activities ranged from zero to almost the normal level. Thus, Loop A does not appear to be essential for such biosynthetic steps as heme attachment and mitochondrial import. In contrast, the full range of relative activities suggest that this region interacts with physiological partners to carry out efficient electron transport.
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  • 48
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    Proteins: Structure, Function, and Genetics 6 (1989), S. 418-423 
    ISSN: 0887-3585
    Keywords: accessible area ; power law fit ; bootstrap analyses ; fractal structure ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The coefficients in a power low fit of accessible area versus molecular weight for high-reslution monomeric protein structures are assessed with respect to statistical accuracy using bootstrap analyses, and with respect to physical significance using model systems and the concept of roughness or fractal structure of the protein surface.
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  • 49
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 139-145 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of benzil and thioxanthone triplets with triethylamine leads to the production of free radicals that are able to initiate the polymerization of methylmethacrylate and vinyl acetate. The process is mediated by a charge transfer complex. The initiation efficiency is higher in benzene than in acetonitrile, a result explained in terms of competition between back electron transfer, production of free ions and ketyl radical formation. The initiation efficiency decreases when the carbonyl concentration increases, because of the occurrence of a radical molecule reaction such as The α-hydroxy radicals produced in this reaction are unable to initiate the polymerization chain.
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  • 50
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 171-183 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(enamine-ketones) were prepared by the nucleophilic (Michael-type) addition of various aromatic diamines to 1,1′-(1,3- or 1,4-phenylene)bis(2-propyn-1-one)(1,3 or 1,4-PPO) in m-cresol at 5-23°C. The low molecular weight polymers (inherent viscosity of 0.25 dL/g) exhibited limited solubility in organic solvents. Glass transition temperatures were generally undetectable by differential scanning calorimetry while polymer decomposition temperatures (10% weight loss), as measured by thermogravimetric analysis, were observed from 355 to 419°C. Polymers prepared from 1,4-PPO were semi-crystalline as shown by wide-angle X-ray diffraction. The poly(enamine-ketone) structure was confirmed by matching infrared spectral characteristics of the polymers with those of well-characterized model enamine ketones.
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  • 51
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 971-977 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monomers and polymers of 2-benzylidene-1,3-dithioles (dithiafulvenes) were synthesized. Polymerization of substituted dithiafulvenes with diacid chlorides, p-phenylene diisocyanate, or terephthalaldehyde yielded yellow polymers with inherent viscosities ranging from 0.10 to 0.21 dL/g.
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  • 52
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 989-997 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The syntheses, characterizations, and electrical properties of four regiospecifically substituted poly(phenylacetylene)s are described. Tungsten(VI) chloride/tetra-n-butyltin (WCl6/n-Bu4Sn) catalyst system (Higashimura-Masuda, H.-M. catalyst) was used to polymerize 3-bromo-, 3-chloro-, 3-trimethylsilyl-, and 3-trimethylstannylphenylacetylenes in order to obtain high-molecular-weight and soluble materials. Characterizations of these polymers were done by IR and UV spectroscopic methods, GPC, DSC, and elemental analysis. The electrical conductivities of the polymers were measured on the surface of pressed pellets by a four-point probe.
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  • 53
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 999-1015 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of polymethacrylates and polyacrylates containing 4-methoxy-4′-hydroxy-α-methylstilbene side groups attached either directly or through flexible spacers containing eleven, eight, six, three, and respectively two methylenic units, and of the polysiloxanes containing the same mesogenic group connected through flexible spacers containing eleven, eight, six, and respectively three methylenic units are described. All polymers exhibit thermotropic liquid crystallinity. The nature of the mesophase is determined by the spacer length. However, the nature of the polymer backbone determines the thermal stability of the mesophase. That is, for the same spacer length and similar polymer molecular weight, the most flexible polymer backbone leads to the highest isotropization temperature.
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  • 54
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 979-988 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polyarylates having inherent viscosities of 0.4-1.1 dL/g was prepared by the two phase polycondensation of 1,1,3-trimethyl-3-(4-chloroformylphenyl)indanecarbonyl chloride with various bisphenols in an organic solvent-aqueous alkaline solution system in the presence of a phase transfer catalyst. Similarly, copolyarylates of high molecular weights were prepared from a mixture of the phenylindanedicarbonyl chloride, terephthaloyl chloride, and 2,2-bis(4-hydroxy-phenyl)propane. All the polyarylates were characterized by their amorphous nature and high solubility in organic solvents. They gave transparent and tough films by the solution casting. The films had tensile strength of 33-46 MPa, elongation at break of 3-16%, and tensile modulus of 1.2-1.6 GPa. These polyarylates had glass transition temperatures in the range of 205-310°C, and began to decompose at ca. 350°C in air.
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  • 55
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The temperature dependence of the binding of butyl orange by a homopolymer of 2-dimethylaminoethyl methacrylate (DMAEMA) and copolymers of DMAEMA and N-vinyl-2-pyrrolidone (VPy) has been examined at various pH's. The binding is very much dependent upon the temperature of the system, the pH of the binding medium, and the DMAEMA content in the polymer. In this case maximal binding is obtained at approximately 15-25° in the temperature range measured, although in most cases which have been examined, the degree of binding increases steadily with increasing temperature. This peculiar temperature dependence of the binding becomes more pronounced as the pH and the DMAEMA content are increased. The appearance of the peculiarity is discussed in terms of the pH-induced conformational changes of the polymer and the hydrophobicity of the polymer.
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  • 56
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 343-355 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidative degradation of polybutadiene-styrene-acrylonitrile (ABS) copolymer was extensively investigated. Three factors were studied: the influence of ageing temperature on the rate of the oxidation of the copolymer; the efficiency of β-carotene as chain breaking antioxidant; and the effect of butadiene content on the rate of the oxidative degradation of the ABS copolymer.
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  • 57
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 389-392 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 58
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 397-397 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 59
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 399-408 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When PVC films containing zinc(II) chloride were heated in the temperature range 65-95°C, broad absorptions developed in the 250-900 nm region with maxima around 610 nm. The development of the color, the rate of which was proportional to the ZnCl2 content, was preceded by an induction period, the length of which depended on the temperature. The activation energy of the process decreased as the ZnCl2 content of the film increased. Color developments in air and in vacuum were compared.
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  • 60
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 423-430 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolyamides of nylon-4,6 and nylon-4,T were prepared by a two-step method: (1) a prepolymerization in an autoclave (40 min at 210°C) and (2) a postcondensation in the solid state (4 h, 260°C). On these materials was studied the melting behavior with DSC, the crystalline structure with WAXS, the water absorption, and the mechanical properties with a torsion pendulum. In these copolyamides the order was found to remain high, but the crystalline structures of -4,6 and -4,T were not isomorphous. The torsion moduli increased with -4,T content both at RT and at 140°C.
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  • 61
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 431-446 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diacids with variable spacer length were prepared by condensation of trimellitic anhydride and ω-amino acids. From these diacids, homopolyesters were prepared by thermal condensation with the acetates of hydroquinone or 4,4′-dihydroxy biphenyl and a series of copolyesters containing 4-hydroxy benzoic acid. The same LC poly(ester imide)s could also be prepared in a “one-pot procedure” from trimellitic anhydrid, lactams, and bisphenol acetates. The differential scanning calorimetry (DSC) traces of most poly(ester imide)s exhibit two endotherms representing the solid → LC phase transition (Tm1) and the LC phase → isotropic melt transition (Tm2). Observation under the polarizing microscope and wide-angle X-ray scattering (WAXS) measurements suggest that the LC phase formed immediately above the melting points (Tm1) have a smectic character. Poly(ester imide)s of 4,4′-dihydroxybiphenyl possess higher melting points and a broader temperature range of the LC phase than those of hydroquinone. The copolyesters possess a nematic melt over a broad temperature range. Thermomechanical analyses under low pressure (0.05 kg/mm2) gave heat distortion temperatures close to the melting points (Tm1), and under high pressure (1 kg/mm2), values between Tm1 and the glass transition temperatures (Tg). Thermogravimetric measurements indicate that processing from the melt is feasible up to temperatures around 340°C.
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  • 62
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 1099-1114 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water-soluble graft copolymers of well-defined structure having hydrophobic polymethacrylate branches with different ester groups were prepared by the macromonomer method. Methacrylate macromonomers of controlled molecular weights having a methacryloyloxyl end group were synthesized by radical polymerization of the corresponding monomer in the presence of thioglycolic acid followed by the reaction of glycidyl methacrylate with the terminal carboxyl group. These macromonomers were copolymerized with methacrylic acid and methyl methacrylate to prepare tailor-made graft copolymers composed of a hydrophlic backbone and different kinds of hydrophobic branches, which were characterized by elemental analysis, NMR, and GPC. The viscosities of the aqueous solutions of the sodium salts of these graft copolymers were measured. It was found that the viscosity of the dilute solution of the graft copolymer was remarkably high compared with the corresponding random copolymer irrespective of the ester group in branch segments. Solubilizing behavior of Orange-OT in aqueous solutions of the graft copolymers and the random copolymer were also investigated to study the nature of the hydrophobic domain of the graft copolymers.
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  • 63
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3451-3463 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this study, a radiation-induced copolymer, namely, polyethylene-g-acrylic acid and EVA-g-acrylic acid, in the form of a membrane, particulate, or tube was used as a substrate. The carboxyl groups of the grafted acrylic chains were oxidized into peracids. Optimal conditions for the oxidation, including the catalyst, reaction time, and temperature were investigated. Novel bigraft copolymers were then synthesized from the grafted polymeric peracid. A third component (e.g., 2-hydroxyethyl methacrylate) was grafted through the decomposition of peracid groups. Abnormality in morphology of the acrylic acid grafted and HEMA bigraft membrane was investigated by SEM and TEM observation, which showed the levelling effect of the third component and manifested a third circular domain generated inside the membrane at high degree of grafting.
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  • 64
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3495-3501 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Plasma polymerization of perfluorobenzene/sulfur dioxide (PFB/SO2) mixture was investigated by elemental analysis, infrared spectroscopy, and XPS. Plasma polymer films like Nafion were obtained from the plasma polymerization of PFB/SO2 mixture. The plasma polymerization deposited fluoropolymers with sulfur moieties including sulfonate and sulfonic acid groups. The elemental composition, F/C, and S/C atomic ratio of the formed plasma polymers were 0.65-0.67 and 0.24-0.27, respectively, which were independent of the starting mixture composition. The polymers showed cation-exchange ability of which the capacity was 0.49 meq/g polymer, and initiated the polymerization of pyrrole.
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  • 65
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3531-3531 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 66
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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  • 67
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3551-3567 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Methacryloxy-2,3,5,6-tetrabromobenzyl phosphonates (MTBBP) are prepared by the reaction of corresponding 4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonates (HTBBP) with methacryloyl chloride. Comparisons of flame retardancy among the copolymers of methylmethacrylate (MMA) with MTBBP or with 4-methacryloxy-2,3,5,6-tetrabromotoluene(MTBT) and the mixture of poly(methyl methacrylate) (PMMA) with triphenyl phosphite reveal that the combination of phosphorus and bromine elements produces a synergistic effect on flame retardancy, and the chemical grafting of the fire-resistant elements into the polymer backbone gives a better effect than the physical mixing of their compounds with polymer. The unsatisfactory results of homopolymers of the synthesized methacrylate monomers prepared by free radical polymerization in solution may be due to their less reactivities; however, they can readily copolymerize with a liquid vinyl monomer such as MMA by means of bulk polymerization.
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  • 68
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3569-3587 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new approach is presented to calculate both the distribution of particles with iradicals and the average number of radicals per particle in emulsion polymerizations carried out using oil-soluble initiators. The convergence and accuracy of the approach were examined. It was found that, in agreement with previously published experimental results, the present approach predicts a kinetic behavior similar to that found for water-soluble initiators. This effect is primarily due to the desorption of initiator radicals from the polymer particles rather than the contribution of the fraction of oil-soluble initiator dissolved in the aqueous phase.
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  • 69
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3589-3602 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optically active polynucleotide analogs were prepared by grafting nucleic acid base derivatives onto poly(vinyl alcohol). The (R)-ethyl 2-(5-bromouracil-1-yl)propanoate was obtained either by reaction of 5-bromouracil sodium salt with (S)-ethyl 2-[(methylsulfonyl)oxy]propanoate or reaction of 5-bromouracil with (S)-ethyl lactate in the presence of triphenyl phosphine and diethyl azodicarboxylate. Subsequent hydrolysis of the ester is aqueous acid provided the optically pure (R)-bromouracilypropanoic acid. The monomer model compounds were prepared by an esterification reaction of the pendant groups with 3-pentyl alcohol in the presence of dicyclohexylcarbodiimide and a catalytic amount of 4-pyrrolidinopyridine. Poly(vinyl alcohol) underwent reaction with the (R)-bromouracilylpropanoic acid or the (R)-adeninylpropanoic acid in the presence of dicyclohexylcarbodiimide and a catalytic amount of 4-pyrrolidinopyridine. The resulting polymers were optically active and percents grafting were almost quantitative.
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  • 70
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3603-3618 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Undecyl and phenyl oxazolines were synthesized. They were copolymerized in different mole ratios using methyl nosylate as initiator. A series of di- and triblock copolymers with narrow molecular weight distributions as indicated by GPC were obtained. A three-armed block copolymer was also obtained by using 1,3,5-tris(bromomethyl)benzene as initiator. When the nonpolar undecyl block crystallized as a coating, the critical surface energy approached 21.0 dyn/cm, and the contact angle of water on the surface could be higher than 107°. The melting point increased as the chain length of crystallizable undecyl block increased, and the melting peak on DSC was very sharp when the length was equal to or longer than 25 monomer units. When these copolymers were coated on substrates, the work of adhesion with pressure sensitive adhesives was greatly reduced.
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  • 71
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3637-3649 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The anionic polymerization of ∊-caprolactam (CLM) has been shown to proceed at high reaction rate when catalyzed by metallic lactamates and initiated by acyllactams. The role of initiator and catalyst concentration on the process of ∊-caprolactam anionic polymerization has been explored, with the aim of selecting the most suitable experimental conditions for reaction injection molding (RIM). The overall polymerization rates and physical properties for reaction injection molding of star-shaped nylon 6 homopolymer have been studied by the quasi-adiabatic process. In order to model the actual rapid molding conditions, time vs. temperature reaction profiles were measured, and the relative rates of polymerization subsequently determined from these data.
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  • 72
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3829-3835 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper reports that 60Co γ-ray irradiation can convert cis-polyphenylacetylene (cis-PPA) films prepared with rare-earth coordination catalysts to highly photosensitive materials. The dependence of the photosensitivity on irradiation dose, preparation methods, and microstructure of the PPA films has been investigated by means of a potential discharge technique. The photosensitivity was enhanced with increasing irradiation dose. The critical dose to produce a light response was 5 × 103 Gy. The maximum surface potential discharge rate was 618 V/s, and the dark decay was approximately 2 V/s for cis-PPA films irradiated with 60Co γ-ray (dose: 2 × 105 Gy). The cis-transoidal-PPA and an electrophotographic photoreceptor device incorporating cis-PPA showed a higher irradiation effect. The structure and properties of 60Co γ-ray irradiated rare-earth PPA films are similar to the unirradiated films.
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  • 73
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly[N,N′-(sulfo-phenylene)phthalamid]es and poly[N,N′-(sulfo-p-phenylene)pyromellitimide] were prepared in water-soluble form and were found to have unique solution properties, similar in some respects to xanthan. The polymer most investigated, poly[N,N′-(sulfo-p-phenylene)terephthalamide] (PPT-S), is produced as the dimethylacetamide (DMAC) salt by the solution polymerization of 2,5-diaminobenzenesulfonic acid with terephthaloyl chloride in DMAC containing LiCl. The isolated polymer requires heating in water to dissolve; the resulting cooled solutions are viscous or gels at concentrations as low as 0.4%. They are highly birefringent, exhibit circular dichroism properties, and are viscosity-sensitive to salt. Solutions of this polymer mixed with those of guar or hydroxyethyl cellulose give significantly enhanced viscosity. The polymer is relatively low molecular weight, ca. 5000 estimated from viscosity data. Some meta and para isomeric analogs of PPT-S were prepared; these polymers have similar properties except they are more soluble in water, and higher concentrations are required to obtain significant viscosity. Poly[N,N′-(sulfo-p-phenylene) pyromellitimide] (PIM-S) was prepared similarly from 2,5-diaminobenzenesulfonic acid and pyromellitic dianhydride. Its aqueous solution properties are similar to those of PPT-S. It appears that these relatively low-molecular-weight rigid-chain polymers associate in water to form a network that results in viscous solutions at low concentrations.
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  • 74
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3895-3901 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aromatic polyamides (aramids) having pendant t-butyl group were synthesized by the direct polycondensation of 5-t-butylisophthalic acid with various aromatic diamines in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. The aramids having inherent viscosities of 0.6-2.4 dL/g were obtained in quantitative yields. These polymers were readily soluble in various solvents such as NMP,N,N-dimethylacetamide, dimethyl sulfoxide, and pyridine, and gave transparent, tough and flexible films by casting from the NMP solutions. The aramids had glass transition temperatures between 250 and 330°C, and started to lose weight around 350°C, with 10% weight loss being recorded at about 450°C in air.
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  • 75
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3915-3926 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water-soluble comb-shaped polymers were prepared through grafting of poly(ethylene glycol) monomethyl ethers (MPEG) onto acrylic and methacrylic ester copolymers by transesterification reactions. The grafting was alkali-catalyzed, and performed in refluxing toluene solution or in melt at 155°C. The grafting efficiency was found to be on the order of 1 graft/10 monomer units. Epoxy groups in glycidyl methacrylate copolymers were also utilized for grafting. The crude graft copolymers were purified through chromatography and characterized by NMR and IR spectroscopy. Polymers prepared from MPEG 2000 were crystalline with melting points 10-15°C lower than the MPEG used. All polymers were shown to be surface active with CMC on the order of 1.5 g/L, and surface tensions of 38-45 dyn/cm. When used as emulsifiers the graft copolymers containing bulky lipophilic ester groups (2-ethylhexyl t-butyl) gave oil-in-water (o/w) and water-in-oil (w/o) emulsions from xylene/water with higher stability than those containing straight chain ester groups (methyl nbutyl n-docecyl). The most stable emulsions were obtained by dissolving the polymers in the organic phase.
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  • 76
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 3977-3983 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Initiation of polymerization of methyl methacrylate with redox system montmorillonite (with lattice Fe3+)-thiourea has been achieved. The rates are dependent on both clay mineral and thiourea. Amidosulfenyl radicals are believed to initiate the polymerization on the clay surface. The polymerization produced nonextractable clay-polymer adduct up to an extent of 70 wt %. The pH of the medium (in the acidic range) did not affect the polymerization rate.
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  • 77
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4013-4033 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new family of polynucleotide analogs were prepared by grafting nucleic acid base derivatives onto polytrimethylenimine. Several new optically pure α-nucleic acid base substituted propanoic acids were prepared as pendant groups. The (R)-ethyl adeninylpropanoate was obtained from adenine and (S)-ethyl lactate by utilizing a diethyl azodicarboxylate-triphenyl phosphine method. Subsequent hydrolysis of the ester in aqueous acid gave the (R)-adeninylpropanoic acid without racemization. The reaction of cytosine sodium salt with (S)-ethyl 2-[(methylsulfonyl)oxy] propanoate produced the 20% racemized (R)-ethyl 2-(cytosin-1-yl)propanoate. The optically pure ester was obtained by recrystallization from ethyl alcohol, which was hydrolyzed in aqueous acid to give the (R)-acid with 66% enantiomeric excess. The (R)-2-(hypoxanthin-9-yl)propanoic acid was prepared by reaction of (R)-2-(adenin-9-yl)propanoic acid with sodium nitrite. The pendant groups were allowed to react with N-hydroxy compounds in the presence of dicyclohexylcarbodiimide to give the active esters. These active esters underwent reaction with N,N-dipropylamine to provide monomer model compounds. The pendant groups were grafted onto polytrimethylenimine by using the active ester method. The racemization reactions were observed in the grafting reactions. The resulting polymers showed a range of percent grafting from 60 to 80%.
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  • 78
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4035-4049 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interactions of H2 and NH3 plasmas with the surfaces of various poly(alkylmethacrylate)s and of poly(phenylmethacrylate) have been studied with XPS and SSIMS. Experiments on poly(methylmethacrylate) reveal that during short treatment times with the NH3 plasma chain, scission takes place and nitrogen is not incorporated into the surface. The chain scission also takes place with the H2 plasma. With the aid of SSIMS results, the nature of the chain scission could be deduced. Comparison of these results with those on poly(n-butylmethacrylate) and poly(t-butylmethacrylate) reveals a reaction mechanism in which hydrogen atoms generated in both plasmas play an important role in the chain scission process. After longer treatment time with the NH3 plasma, the poly(methylmethacrylate) surface becomes deoxygenated and nitrogen is incorporated into surface structures of low molecular weight. Experiments on poly(phenylmethacrylate) reveal that already during short treatment times with the NH3 plasma, nitrogen is incorporated into the aromatic ring. Chain scission does not play an important role. One of the processes with the H2 plasma is hydrogenation of the aromatic ring, leading to poly(cyclohexylmethacrylate).
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  • 79
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4087-4097 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solutions of 3-methoxythiophene (MeOT) in dimethylformamide (DMF) were electrolyzed at controlled electrode potentials. The polymerizations were studied under homogeneous conditions in solutions in which the polymer was soluble in the medium, and no coating of the electrodes occurred. The reaction proceeded at high coulombic efficiency and a first order dependence on monomer concentration was observed. The molecular weights of the polymers were determined by gel permeation chromatography. All samples showed a narrow distribution of molecular weights, with Mw/Mn ranging from 1.01 to 1.07. The molecular weight was low (about 3000 Daltons) and did not change in magnitude during the course of the reaction from 10 to 86% conversion, or with change in electrode potential from 1.55 to 1.65 V vs. SCE. The data are interpreted on a model based upon the competitive formation of chemically unreactive bipolarons.
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  • 80
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4129-4141 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of preparation history upon the thermal cyclodehydration reaction of polyhydrazide samples has been investigated. Solid polyhydrazide samples were prepared from DMSO solutions using the phase-inversion technique. Significant differences in conversion rates were observed between samples prepared by nonsolvent immersion precipitation and by evaporation of solvent. It appeared that contact with the nonsolvent water during the sample preparation process has considerable influence on the conversion rate. Not only does the immersion in and washing with water lead to a better removal of the solvent also the pH of the water determines the rate of conversion. A distinct change in the conversion rate is found for washing water at a pH of 7. Basic washing solutions showing lower conversion rates than acid ones. A mechanism explaining these phenomena is proposed.
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  • 81
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4169-4179 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polysulfides (PI and PII) having spiroorthocarbonate moiety in the main chain were synthesized by the polyaddition of unsaturated spiroorthocarbonate (1 or 2) and dithiols in excellent yields. It is confirmed by DSC and x-ray measurement that PII is the crystalline polymer. PI and PII were treated with a cationic catalyst such as BF3 · OEt2 and BzS+SbF6- to afford the crosslinked polymer and to partially undertake the main chain scission. Further, it was also found in the reaction of PI and PII with adipoyl chloride as the crosslinking reagent that PI underwent cleavage of the main chain, but PII mainly gave crosslinked polymers.
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  • 82
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4181-4190 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Vinyl anthraquinone has been polymerized, via radiation-induced initiation, in dimethyl-sulphoxide and in dichloromethane. Solvent to monomer ratios of 1 : 0.030 to 1 : 0.0167 mol have been examined for dose rates in the range 0.035 to 0.129 Gy s-1 and exposure times in the range 1.44 × 104 to 4.32 × 106 s. Rates of polymerization were found to lie in the range from 2.4 × 10-8 to 1.92 × 10-6 mol L-1 s-1. Values for the chain transfer constant to dimethyl-sulphoxide and to dichloromethane have been calculated. In addition, values of the kinetic ratio kp2/kt, for the polymerization of 2-vinyl anthraquinone have been estimated. The dependence of Rp on the monomer concentration and on the radiation intensity have been shown to be in broad agreement with a simplified steady-state kinetic scheme. A value of G(radical) for 2-vinyl anthraquinone was obtained via electron spin resonance studies, and shown to be 0.24. This G(radical) value and those obtained indirectly from kinetic data are discussed in relation to the molar mass values obtained from the poly(2-vinyl anthraquinone) products.
    Additional Material: 8 Ill.
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  • 83
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4227-4227 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 84
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4281-4289 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the apparent reaction rate constants of phenylacetylene polymerized in CCl4 in the presence of light-activated W(CO)6 and of the molecular weight of the resulting polymer indicates that the propagating centers are conserved to high monomer conversions, though some chain transfer to monomer occurs, limiting molecular weights to about 100,000. Although solutions of the polymer are deep red in color, the molecular conformation is more coil-like than rod-like. The NMR spectra suggest that the steric purity of the polymer is limited, so that it can only be referred to as trans-rich polyphenylacetylene, confirming other results on tungsten-catalyzed polyphenylacetylene.
    Additional Material: 6 Ill.
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  • 85
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4305-4318 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of 10 acetylene-terminated aromatic amide monomers was synthesized by the triethylamine-promoted reaction of bis[p-(m-chlorocarbonylphenoxy)phenyl] sulfone or bis[p-(m-chlorocarbonylphenoxyl)phenyl]ketone with o- or p-ethynyl- and o- or p-trimethylsilylethynylaniline. Yields were essentially quantitative. Structures were verified by infrared and nuclear magnetic resonance spectroscopy and mass spectral data. Thermal characteristics of the monomers were investigated by means of differential scanning calorimetry and thermogravimetric analysis. The initial glass transition temperatures were generally well below the onset of cure which occurred in the 160-225°C range for the terminal ethynyl monomers and in the 260-295°C range for their trimethylsilylethynyl analogs. Onset of decomposition in air for the resinified terminal ethynyl monomers took place in the 400-485°C range, while resins from the trimethylsilylethynyl monomers underwent breakdown at substantially lower temperatures.
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  • 86
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4257-4265 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two-dimensional NMR spectra of commercially available poly(N-vinylcarabazole) are presented and analyzed. Complete assignments for the aromatic region of the carbon spectrum are made using the edited spectrum and literature references for model compounds. The proton spectrum is assigned from its correlations with the carbon spectrum and with a J-correlated two-dimensional spectrum. One of the protons (number 1) is shifted to rather unusual high fields by the stacked structure of the carbazole rings, independent on the polymer tacticity. From the aliphatic carbon spectrum a meso probability of 0.45 is estimated for the commercial polymer, and another J-correlated two-dimensional spectrum helps assigning the triad and tetrad splittings in the aliphatic proton spectrum.
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  • 87
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 1883-1890 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Amphiphilic block copolymers, i.e., poly(methyl methacrylate)-b-poly(2-dimethylethylammoniumethyl methacrylate), were synthesized by the reaction between two prepolymers. Carboxyl-terminated poly(methyl methacrylate) and hydroxyl-terminated poly(2-dimethylaminoethyl methacrylate) were prepared by radical polymerization of the corresponding monomers in the presence of thioglycolic acid and 2-mercaptoethanol as a chain transfer agent, respectively. Two condensation methods, i.e., DCC and the acid chloride method, were used for the reactions of these prepolymers. The subsequent quarternization produced the amphiphilic block copolymers. Surface property of poly(methyl methacrylate) films containing this amphiphilic block copolymer was examined by measuring contact angles for water. The addition of only 0.5 wt% of the block copolymer was sufficient to make poly(methyl methacrylate) surfaces hydrophilic. The block copolymer formed a polymeric micelle in acetone-water mixed solvent.
    Additional Material: 4 Ill.
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  • 88
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4297-4303 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A procedure for synthesizing an open-chain polyimide has been developed. O-Substituted hydroxylamines were found to behave as difunctional nucleophiles in acylation under appropriate conditions, and thus the reaction of equimolar amounts of benzyloxyamine and terephthaloyl chloride gave rise to the corresponding novel type of polyimide, an open-chain polyimide. The results of polymerization under various conditions indicated the reaction to proceed efficiently in N, N-dimethylacetamide in the presence of an acid acceptor system composed of double the molar quantity of triethylamine and the molar quantity of pyridine to give the polyimide with a high molecular weight. In contrast to the conventional polyimides having cyclic imide structures, the resulting open-chain polyimide exhibited remarkable solubility in common organic solvents and a low glass transition temperature.
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  • 89
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4329-4339 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cationic polyacrylamides (C-PAM) which contain both primary and quaternary amines were prepared according to the Hofmann reaction by adding choline chloride to a solution of polyacrylamide in water. The reaction was 90% complete after 60 min at 20°C. The degree of amination was over 70% and the proportion of primary and quaternary amines could be altered widely by controlling the relative concentrations of NaOH, NaOCl, and choline chloride.C-PAM was dansylated (fluorescently labeled) in a homogeneous system using aqueous dimethylformamide as solvent. The optimum excitation wavelength for dansylated C-PAM in water at room temperature (22 ± 1°C) was 333 nm and the corresponding emission wavelength 538 nm. The fluorescence intensity was almost constant at pH levels above 5, but decreased rapidly below pH 4 and was almost zero at pH 2.
    Additional Material: 8 Ill.
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  • 90
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4365-4374 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyaniline-tetracyanoethylene (TCNE) complexes can be synthesized either from emeraldine base or emeraldine hydrochloride by a relatively simple method. The complexes demonstrate greater stability than the emeraldine hydrochloride at elevated temperatures and under high current densities. The electrical conductivity of the complexes synthesized from emeraldine base can be varied from 〈 10-6 to 0.2 S/cm by varying the amount of TCNE incorporated. The complexes synthesized from emeraldine hydrochloride are slightly more conductive than the starting emeraldine hydrochloride. In both types of complexes, it appears that electron transfer between the polyaniline and TCNE has occurred resulting in the formation of some positively charged polyaniline nitrogen and TCNE anions.
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  • 91
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 1925-1933 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymers of N-vinyl-2-pyrrolidone and 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-dimethylaminoethyl acrylate, or 2-dimethylaminopropyl acrylamide have been prepared. Studies were made of the binding of a “binding probe,” methyl orange, by the copolymers in aqueous solution. The first binding constants accompanying the binding were evaluated. Furthermore, the intensity of fluorescence of a hydrophobic fluorescent probe, 2-p-toluidinylnaphthalene-6-sulfonate, in the presence of these polymers was investigated. The nature and phenomena of dye binding and hydrophobic fluorescent probe binding with the polymers are discussed.
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  • 92
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    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 1915-1923 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of a monodisperse hydrophilic polyamide was achieved in the anionic polymerization of a bicyclic oxalactam, 8-oxa-6-azabicyclo[3.2.1]octan-7-one (abbreviated BOL) with the use of N-benzoyl BOL and potassium pyrrolidonate (2 and 0.5 mol % to BOL, respectively) in dimethyl sulfoxide at 25°C. The number-average molecular weight of the polyamide increased in direct proportion to the monomer conversion, and was consistent with the value calculated from the amounts of the consumed monomer and activator. The molecular weight distribution (MWD) of the polyamide obtained until the middle stage of polymerization (polymerization time, 〈 10 min; monomer conversion, 〈 60%) was found to be narrow (Mw/Mn = 1.1). The MWD was gradually broadened in the later stage of the polymerization, which may result from the redistribution of molecular weight of the resulting polyamide not only by the polymerization-depolymerization equilibrium, but also by transamidation between polymer chains.
    Additional Material: 7 Ill.
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  • 93
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 1935-1956 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Graft polymerization of acrylates and acrylamide complexes of Mn(II), Cr(III), Fe(III), Co(II), Ni(II), and Cu(II) from alcohol solutions onto a polyethylene powder preirradiated in air up to total doses of 10-300 kJ/kg was studied. Graft copolymers with a metal content of as high as 1.7 mass% were obtained. The addition of a σ- or a coordinate-bound metal atom to the monomer molecule (acrylic acid, acrylamide) was shown to decelerate the process of thermal homopolymerization by 4 to 8 times, significantly reduce the reaction order in respect with monomer concentration in solution, and in most cases produce no effect on the polymer chain termination mechanism. The grafting of metal-containing monomers was found not to alter the structure of the monomer unit, valent state, and coordination of the metal atom, either. The graft polymerization of the monomers from solution is distinguished by a weak effect of the radical reaction inhibitors. The effective activation energies for the grafting of the metal-containing monomers lie within 42-60 kJ/mol.
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  • 94
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 1957-1965 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 7,8-Dicyano-7,8-diphenylquinodimethane (DCDPQ) was prepared by oxidation of the dianion of α,α′-dicyano-α,α′-diphenylxylene. 1H-NMR of a solution of the purified compound showed that the cis and trans isomers were present in a 1:1 ratio. Following further spectroscopic and electronic characterization the polymerizability of the title compound was investigated. DCDPQ did not homopolymerize at 65°C in the presence of AIBN. DCDPQ copolymerized with p-methoxystyrene and p-aminostyrene in the presence of AIBN at 65°C. Characterization of the latter two copolymers indicated that they were nearly alternating. The copolymerization between DCDPQ and p-aminostyrene proceeded in the absence of AIBN.
    Additional Material: 2 Ill.
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  • 95
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 2189-2201 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation and properties of highly crystalline ionomers formed by the copolymerization of propylene and low levels of ethylcholoroaluminium 10-undecenoate have been investigated. Few of the variables studied had dramatic effects on the copolymerization. Thus, a five-fold increase in undecenoate concentration gave only about a 20% increase in acid incorporation into the copolymer. Increasing temperature resulted in increased acid content, but handling problems in a I gal stirred reactor limited polymerization of 80°C. Rates were lowered in the presence of complex, but the effect was minimized by hydrogen. Rheological measurements showed an increase in low shear melt viscosity of the pottasium salts by up two orders of magnitude relative to the acid from. Ionomers containing two or more carboxyl groups as their potassium salts, and having a broad molecular weight distribution, had an extended rubbery plateau range, covering most of the shear ranges of normal processing. The zero-shear activation energy for viscous flow was 42 kcal, comparable to ABS and polystyrene. These ionomers are promising candidates for thermoforming applications
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  • 96
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 2357-2366 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: p-Divinylbenzene (DVB) 13C-labeled at the methine carbon of the vinyl group was copolymerized in suspension with styrene at 70, 70-95, and 135-155°C using 2,2′-azobisisobutyronitrile (AIBN) as the initiator. The number of unreacted vinyl groups in each copolymer was determined by 13C CP-MAS NMR analysis of solid samples, direct polarization 13C-NMR analysis of CDCl3-swollen gels, and bromination. Results from the three methods agree methods agree qualitatively. Even the 1% DVB-crosslinked networks contained 40% unreacted DVB-vinyl groups when prepared by high conversion polymerization at 70°C and 16% unreacted DVB-vinyl groups when polymerization was finished at 95°C. The analyses were also applied to some commercial crosslinked polystyrenes. Every sample examined contained pendent vinyl groups
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  • 97
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 2483-2486 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 98
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 2487-2487 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 99
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 2457-2482 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of converting wood into thermoplastic materials was undertaken to develop a new technique in effective utilization of wood wastes. Thermoplasticizatoin of wood carried out by means benzylation. Various reaction parameters, such as alkalinity of reaction media, reaction temperature, and time were taken into account to produce benzylated wood with different degrees of substitution (based on weight gain) FTIR, DSC, DMTA, SEM and x-ray crystallography were used to characterize the chemical and mechanical properties of benzylated wood. Experimental data showed that preswelling and reaction temperature had critical effects on benzylation reaction. Lignin in wood appeared to inhibit benzylation but extractives had little effect. Different species showed some variation in reaction rates. The thermoplasticized wood exhibited good melting properties and were readily molded into bulk materials or extruded into films and sheets. A wide range of glass transition temperatures from 66 to 280°C for the benezylatedwoods was achieved, and they were larely dependent on the weight gain. The molded and extruded products exhibited acceptable mechanical strength for structural engineering applications. The property and structure relationship for the thermoplasticized wood were discussed
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  • 100
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 2491-2496 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-(Ethylene)phthalimidyl acrylate was synthesized starting from phthalimide or phthalic anhydride using two different routes. Free radical or anionic polymerization of the ester resulted in low-molecular-weight polymers.
    Additional Material: 3 Ill.
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