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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 1363-1371 
    ISSN: 0887-624X
    Keywords: liquid chromatography ; column packing ; bare silica gel ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Liquid chromatography of macromolecules at the critical adsorption point (LC CAP) presents a potentially very powerful method for molecular characterization of complex polymers. However, LC CAP applicability is limited due to various experimental problems. The pore sizes and surface chemistry of the column packings belong to the most important weak points of the method. The LC CAP behavior of poly(methyl methacrylate)s was investigated using bare silica gels of 6, 12, and 100 nm pore sizes and with various amounts of surface silanols. Tetrahydrofuran as the adsorption suppressing liquid and toluene as the adsorption promoting liquid were mixed to form the “nearly critical” eluents. Both pore size and surface chemistry of silica were found to strongly influence the retentive characteristics of the system in the critical adsorption area. Macromolecules that were large enough to be excluded from the packing pores hardly followed the LC CAP rules: their retention volumes changed irregularly with the polymer molar mass and their recovery dropped sharply. The narrow pore silica gel-packed column governed the elution patterns of the whole column set composed of silica gels with different pore sizes. This makes the conventional LC CAP characterization of common polymers with broader molar mass distribution impractical and even not feasible. A hybrid column system was proposed containing narrow pore nonadsorptive column added in series to the meso- and macroporous LC CAP silica gels. This narrow pore column would allow separation of gas, impurities, and system peaks from the polymer peaks. The possible successive changes of the surface of silica gel, e.g., due to formation of silanols by hydrolysis or due to irreversible adsorption of some admixtures from the sample or eluent may make the LC CAP irrepeatable. Pronounced peak broadening was observed in the critical adsorption area and this effect increased strongly with the polymer molar mass. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1363-1371, 1998
    Additional Material: 7 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 2337-2340 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 261-272 
    ISSN: 0894-3230
    Keywords: 1-substituted 2-pyrrolidinones ; C=O stretching frequencies ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an effort to model solute-solvent interactions, the C=O stretching frequencies of five 1-substituted 2-pyrrolidinones and four other carbonyl-containing compounds were measured for 30 common solvents. These were then correlated with four empirical parameter sets and one theoretical (computational) parameter set. While an empirical parameter set gave the best correlation equations, the theoretical parameter equations are physically and statistically significant. Solvent volume, polarizability and hydrogen bond donor acidity (capacity) terms are significant in the correlation equations. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 14 Tab.
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  • 4
    ISSN: 1040-0397
    Keywords: DNA, Metronidazole ; Modified electrodes ; Nucleic acids ; Biosensors ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electroanalytical performance at three electrodes: DNA-modified galssy carbon electrode, mercury thin film electrode and glassy carbon electrode, for the study of the electrochemical reduction of metronidazole is compared. All three electrodes showed a similar trend in the reduction mechanism for metronidazole, depenent on pH in the acid and neutral region and independent in alkaline media, although there was a shift in the peak potentials to more negative values when a bare glassy carbon electrode was used compared to the other two. Besides the advantage of using a solid electrode for the reduction of metronidazole, the DNA-modified galssy carbon electrode enables a lower detection limit of 1.0 μM owing to the preconecentration of the drug on the electrode surface, which is not the case for the mercury thin film or bare glassy carbon electrodes.
    Additional Material: 6 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 1 (1995), S. 149-156 
    ISSN: 1075-4261
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: A series of copper bilirubinate complexes (CuBR) was synthesized in solution and in solid state to mimic the black color of the black-pigment gallstone and to explore the formation mechanism of the gallstonein vitro. The variation of the copper contents of these samples indicated that CuBR also exhibits nonstoichiometric characteristics from the FTIR study, i.e., both the so-called acid and neutral copper complex moieties exist in CuBR. The NH groups in pyrrole and lactam groups of bilirubin (H2BR) are binding to the copper ions. An EPR study demonstrates the generation of free radicals and the variation of its electronic structure and conjugation system in the skeleton of H2BR molecule during complex formation. A polymer of CuBR may form through the reaction of H2BR with copper ions. © 1995 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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  • 6
    ISSN: 1040-0397
    Keywords: Gold ; Microelectrodes ; Array electrodes ; Fabrication ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple and inexpensive way to fabricate arrays of gold microelectrodes is proposed. Integrated circuit chips are sawed through their middle, normal to the longest axis, leading to destruction of the silicon circuit and rupture of the gold wires that interconnect it with the external terminals. Polishing the resulting rough surface converts the tips of the wires embedded in the chip halves into arrays of gold microdisks of about 25 μm diameter. The number of active microelectrodes (MEs), of an array depends on the number of pins in the chip, n, being typically (n/2)-4. These MEs can be used individually or externally interconnected in any combination. X-ray images of the chips and micrographs of the resulting surface of the polished arrays have revealed variable distances between neighbor MEs, which are however, larger than 10 times the radius of the disks. This feature of the MEs prevents diffusional cross-talk between electrodes. The use of these microdisk electrodes for analytical purposes exhibits sigmoidal voltammograms, and chronoamperometric experiments confirm the nonlinear i vs. t1/2 plots, typical for processes where radial diffusion prevails, Satisfactory uniformity was observed for the response of each electrode of an array, indicating similarity of geometry and disk areas. The potentialities of these MEs were demonstrated by the determination of cadmium at ppb levels using square wave voltammetry with preconcentration. Due to the relative ease with which these MEs can be manufactured and their good performance in (chemical) analysis, wide applications in electrochemistry and electroanalysis is envisioned.
    Additional Material: 6 Ill.
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  • 7
    ISSN: 1075-4261
    Keywords: brown pigment stone ; PAGE ; mid-IR spectroscopy ; far IR spectroscopy ; FT-Raman ; bezoar ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Spectroscopic studies of various types of gallstones carried out in China are reviewed. Three basic classes of gallstones are surveyed: cholesterol stones, brown pigment stones, and black pigment stones. The emphasis of this review is on brown gallstones. The primary spectroscopic methods used in the studies surveyed are Fourier transform infrared absorption and Fourier transform Raman scattering. Chemical components studied in gallstones include cholesterol, bile pigments, glycoproteins, proteins, bilirubin metal complexes, and salts of calcium and other metals. Further studies are needed characterize the relationship of these components to more complex features of gallstones. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 371-380, 1997
    Additional Material: 13 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 317-330 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Samples of poly(etherether ketone) (PEEK) were subjected to large plastic deformations under uniaxial tension and simple shear by means of a new video-controlled testing method at constant true strain rate. The “equivalent” stress-strain curves obtained under the two loading modes are close at the yield point, but diverge drastically at large strains, with a rapidly increasing hardening in tension and a moderate hardening under simple shear. X-ray diffraction goniometry shows that these contrasting behaviors are associated with the different textures developed in the crystallite orientations. Under tension, the PEEK lamellae are progressively tilted in such a way that the chain axis becomes oriented parallel to the tensile axis; in the other mode, the final chain orientation is near to the shear axis. DSC analyses of deformed samples in both modes are carried out. The results show that the tension loading induces a fragmentation of the thin lamellae, while the shear mode generates less fragmentation. A quantitative model is presented that involves a composite approach: (i) the viscoplastic deformation of the crystalline lamellae, which is controlled by chain slip and transverse slip systems on planes parallel to the c axis, and (ii) the hyperelastic deformation of the amorphous phase, which depends on the affine unfolding of statistically distributed subchains. A discussion of the influence of the CRSS values on the stress-strain curves and textures is developed by means of this model.
    Additional Material: 19 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2085-2098 
    ISSN: 0887-6266
    Keywords: polypropylene ; CP/MAS NMR ; spunbonded fabrics ; crystal structure ; melting ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The double melting endotherm of spunbonded isotactic polypropylene (iPP) fabrics was investigated by monitoring changes in the solid-state NMR spectrum that result from thermal annealing. The DSC melting thermogram was found to change from a double to a single endotherm at anneal temperatures ≥156°C, with a concomitant increase in percent crystallinity. All of the carbon resonances in the CP/MAS NMR spectrum of the purely crystalline phase of iPP were found to be composed of multiple peaks with relative intensities that depend on anneal temperature. By monitoring the changes in the distribution of intensity among the various peaks of a given resonance, a transition temperature of 156°C was identified. Arguments are presented that this redistribution of intensity within a given carbon resonance characterizes the transformation from the α1 to the α2 monoclinic crystal form. The exothermicity associated with this transformation is responsible for the observation of a double melting endotherm by DSC. The splitting patterns observed in the NMR spectrum are discussed in terms of interlayer distances between layers of isochiral helices and the density of exposed methyls at the contact faces of these interlayers. © 1996 John Wiley & Sons, Inc.
    Additional Material: 15 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 60 (1996), S. 1575-1578 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The flowability and thermal behavior of waxy solutions with and without an ethylene-vinyl acetate copolymer (EVA) have been studied. The drastic changings of pour point depression (ΔTpp) and the crystallization in four waxy solutions were observed. These changes were linear with the U-interaction parameters between EVA and wax in different solvents, suggesting that the efficiency of EVA pour point depressent depends on its compatibility with wax, which is affected by solvent. © 1996 John Wiley & Sons, Inc.
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