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  • 1
    Electronic Resource
    Electronic Resource
    Modulation of Prohormone Convertase mRNA by Second Messenger Activators and Drugs (1996)
    Oxford, UK : Blackwell Publishing Ltd
    Annals of the New York Academy of Sciences 780 (1996), S. 0 
    Details
    ISSN: 1749-6632
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Natural Sciences in General
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1111/j.1749-6632.1996.tb15117.x
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  • 2
    Electronic Resource
    Electronic Resource
    Studies on the application of matrix-assisted-laser-desorption-ionisation time-of-flight mass spectrometry to the determination of chain transfer coefficients in free radical polymerization (1998)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 2403-2408 
    Details
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The chain transfer coefficient (Cs) has been determined for 2-methyl-2-propanethiol (t-Bu-SH) in the solution polymerization of methyl methacrylate (MMA). Three different analytical methods were investigated. The Mayo and chain length distribution (CLD) methods yielded consistent Cs values of 0.12 and 0.13, respectively, at 60°C. A third, new approach to the evaluation of Cs values was also attempted using Matrix-Assisted-Laser-Desorption-Ionisation (MALDI) Time-Of-Flight Mass Spectrometry to analyse the end-groups of the polymer chains. The values of Cs obtained from MALDI analyses were not consistent with the other two methods and the relative intensities of the peaks with different end-groups were found to be dependent on the selection of cation.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Critically evaluated rate coefficients for free-radical polymerization, 2.Part 1: cf. ref.1. Propagation rate coefficients for methyl methacrylate (1997)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 198 (1997), S. 1545-1560 
    Details
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Pulsed-laser polymerization (PLP) in conjunction with molar mass distribution (MMD) measurement is the method of choice for determining the propagation rate coefficient kp in free-radical polymerizations. The authors, members of the IUPAC Working Party on Modeling of kinetics and processes of polymerization, collate results from using PLP-MMD to determine kp as a function of temperature T for bulk free-radical polymerization of methyl methacrylate at low conversions and ambient pressure. Despite coming from several different laboratories, the values of kp are in excellent agreement and obey consistency checks. These values are therefore recommended as constituting a benchmark data set, one that is best fitted by \documentclass{article}\pagestyle{empty}\begin{document}$ k_p = 10^{6,427} {\rm L} \cdot {\rm mol}^{ - 1} \cdot {\rm s}^{ - 1} \exp \left( {\frac{{ - 22,36{\rm kJ} \cdot {\rm mol}^{ - 1} }}{{R \cdot T}}} \right) $\end{document}The 95% joint confidence interval for these Arrhenius parameters is also given. In so doing, we describe the most appropriate statistical methods for fitting kp(T) data and then obtaining a joint confidence interval for the fitted Arrhenius parameters. As well, we outline factors which impose slight limitations on the accuracy of the PLP-MMD technique for determining kp, factors which may apply even when this technique is functioning well. At the same time we discuss how such systematic errors in kp can be minimized.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1997.021980518
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  • 4
    Electronic Resource
    Electronic Resource
    Synthesis of porous hydrogel structures by polymerizing the continuous phase of a microemulsion (1995)
    New York, NY [u.a.] : Wiley-Blackwell
    Polymer International 36 (1995), S. 219-226 
    Details
    ISSN: 0959-8103
    Keywords: microemulsion ; hydrogel ; poly(2-hydroxyethyl methacrylate) ; equilibrium water content ; oxygen permeability ; scanning electron microscopy ; 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: A series of microemulsions have been formulated, with 2-hydroxyethyl methacrylate (HEMA) or HEMA/water/propanol mixtures as the continuous phase and methylcyclohexane as the discontinuous phase. The effect of surfactant type was investigated with the utilization of both anionic and nonionic surfactants. The microemulsion continuous phase was polymerized by UV radiation and a thermal post-cure. The resultant polymers were extracted to remove the discontinuous phase and the surfactant. On swelling, the majority of the polymers became opaque, although transparent PHEMA hydrogels were synthesized with an improved equilibrium water content (EWC). The cause of opacity was shown by field emission scanning electron microscopy (FESEM). The breakdown in the microemulsion on polymerization is caused by unfavourable interactions between the PHEMA and the stabilizing surfactants causing agglomerization of the discontinuous phase. All the hydrogels were found to have higher water retention than PHEMA, with EWCs of up to 70%. The modified polymers also demonstrated an increased rate of water diffusion into the matrix. A preliminary study of oxygen permability revealed that a significant improvement had been made over standard PHEMA membranes. The porous structure of the PHEMA gels has been shown to be dependent on the type of surfactant used during synthesis.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pi.1995.210360301
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  • 5
    Electronic Resource
    Electronic Resource
    The effect of solvent on the homo-propagation rate coefficients of styrene and methyl methacrylate (1997)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2311-2321 
    Details
    ISSN: 0887-624X
    Keywords: styrene ; methyl methacrylate ; pulsed-laser polymerization ; “living” free radical ; propagation rate coefficient ; solvent effects ; benzyl alcohol ; N-methyl pyrrolidinone ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The free radical propagation rate coefficients of both Methyl Methacrylate (MMA) and Styrene (STY) have been measured using Pulsed-Laser Polymerization. The effect of solvents on the propagation rate coefficient, kp, is reported for several solvents, namely, bromobenzene, chlorobenzene, dimethyl sulphoxide, diethyl malonate, diethyl phthalate, benzonitrile, and benzyl alcohol, at 26.5°C. This preliminary data indicated that benzyl alcohol (BzA) had a large effect on the MMA propagation reaction. As earlier work indicated that N-methyl pyrrolidinone (NMP) would also have a large effect on the kp of MMA, Arrhenius parameters were evaluated for both MMA and STY at two different concentrations of monomer in BzA and NMP. BzA had a significant effect (at 95% confidence) increasing both the activation energy (Ea) and the preexponential factor (A) for MMA and STY. In NMP, a similar trend is observed for MMA polymerization; however, while a solvent effect on STY was observed, the effect on Ea and A was too small to discern with confidence. A series of additional experiments was performed to evaluate the influence of camphorsulfonic acid (CSA) as an additive in STY polymerization. There was no effect of CSA on kp, confirming that the strong effect CSA has on “living” radical polymerization of styrene does not originate from complexation leading to an accelerated propagation step but rather by altering the ratio of active-to-dormant chains in the reaction. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2311-2321, 1997
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Catalytic chain transfer for molecular weight control in the emulsion homo- and copolymerizations of methyl methacrylate and butyl methacrylate (1997)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 859-878 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The behavior of catalytic chain transfer in semi-batch emulsion polymerization has been studied for two monomers, viz, methyl and n-butyl methacrylate. Two different catalytic chain transfer reagents were used with different water solubilities: cobaloxime boron fluoride (COBF), which was found to partition approximately equally between organic and aqueous phases, and tetra-phenyl cobaloxime boron fluoride (COPhBF), which was found to reside predominantly in the organic phase. The difference in hydrophilicity between the two transfer agents was found to affect the polymerization mechanism. COBF exhibited superior transfer behavior in all cases, whereas the restricted mobility of the COPhBF had a deleterious effect on the efficiency of the transfer mechanism. The best results were achieved under monomer flooded conditions using COBF. MALDI-TOF mass spectrometry analysis shows catalytic chain transfer to be the dominant mechanism initiating and stopping chain growth as none of the chains appear to have initiator fragment end groups. Analysis of copolymers by MALDI-TOF mass spectrometry reveals both molecular weight and composition data. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 859-878, 1997
    Additional Material: 21 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Application of dielectric spectroscopy and DSC to the study of relaxations in some copolymeric hydrogels (1995)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 56 (1995), S. 397-404 
    Details
    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 nature of water in copolymeric N-vinyl pyrrolidone/methyl methacrylate hydrogels has been investigated using dielectric thermal analysis (DETA) and differential scanning calorimetry (DSC). Dielectric tan δ measurements are reported over a frequency range 500 Hz-20 kHz and a temperature range of -140 to +20°C. The observed complex relaxations were attributed to the mobility of water and the relaxation processes of the copolymer matrix. In addition DSC was used to measure the melting endotherm of water in gels partially swollen to a pseudoequilibrium. The resultant data were fitted to a two-phase approximation model. © 1995 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1995.070560310
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  • 8
    Electronic Resource
    Electronic Resource
    Atom transfer radical copolymerization kinetics (1998)
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 19 (1998), S. 371-375 
    Details
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Starting from the basic radical mechanism of atom transfer radical polymerization (ATRP), simple expressions are derived for the description of atom transfer radical copolymerization kinetics. It is shown that kinetic parameters are interchangeable between atom transfer and conventional free-radical copolymerization, which is important for two reasons. Firstly, it enables the prediction of the average equilibrium constant (and hence average rate of polymerization) in an ATRP system with two monomers if the corresponding conventional kinetic parameters are known. Secondly, it enables the determination of the relative fractions of propagating radicals by a detailed ATRP study.
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Solvent effects in copolymerization (1995)
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 16 (1995), S. 207-210 
    Details
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Extension of the Mayo-Lewis Model of copolymerization concerning solvent effects in free-radical polymerization is discussed on the basis of the bootstrap and penultimate unit effects.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/marc.1995.030160309
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  • 10
    Electronic Resource
    Electronic Resource
    Simulation of free radical addition reactions modified by the presence of cobalt macrocycles (1995)
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 4 (1995), S. 195-208 
    Details
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Free radical addition reactions in the presence of cobaloximes and related compounds have been modelled. Several mechanisms are presented and similarities with the “persistent radical effect” noted by Daikh and Finke are discussed. Cobaloximes and salophenSystem. name: N-acetyl-p-aminophenyl salicylate. derivatives are widely used in organic synthesis to build carbon-carbon bonds, whereas in polymer synthesis they are used as catalytic chain transfer agents in the production of oligomers. This work shows that these reactions are closely related and also demonstrates the influence that an external radical source has on the overall reaction kinetics.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/mats.1995.040040114
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