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  • 1
    Electronic Resource
    Electronic Resource
    Equilibrium constants and the prediction of miscibility windows for polymer blends containing poly(tetrafluoroethylene-alt-vinyl alcohol) (1993)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 31 (1993), S. 2039-2056 
    Details
    ISSN: 0887-624X
    Keywords: blends ; hydrogen bonding ; miscibility ; phase behavior ; equilibrium constants ; fluoropolymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Theoretical calculations of miscibility windows for binary polymer blends in which one component is an essentially alternating copolymer of tetrafluoroethylene and vinyl alcohol (FVOH) are reported. FVOH has an inherently low solubility parameter [≈ 6.2 (cal. cm-3)0.5] that is outside the range commonly encountered in miscible polymer blends and thus represents a stringent test of the predictive capabilities of an association model we have used in previous work. The application of this model requires that we determine dimensionless equilibrium constants describing the self-association of a model compound 3,4-pentafluorobutan-2-ol (PFB) at 25°C from infrared spectroscopic data. Analogous equilibrium constants for FVOH were scaled from those of PFB by taking into account differences in the molar volume of the model and the specific repeat of the copolymer (see M. M. Coleman, J. F. Graf, and P. C. Painter: Specific Interactions and the Miscibility of Polymer Blends, Technomic, Lancaster, PA, 1991). Equilibrium constants describing the inter-association of FVOH with ester type carbonyl groups were obtained from spectroscopic studies of miscible blends with poly(ethyl methacrylate). These equilibrium constant values were then used to calculate theoretical miscibility windows for the complete range of blends of FVOH with polymethacrylates, ethylene-co-methyl acrylate, styrene-co-methyl acrylate, and ethylene-co-vinyl acetate copolymers. Experimental results performed in our laboratories confirm the general validity of the predicted miscibility windows. © 1993 John Wiley & Sons, Inc.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1993.080310811
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  • 2
    Electronic Resource
    Electronic Resource
    General theory of stationary random sequences with applications to the tacticity of polymersPaper presented at the 142nd Meeting of the American Chemical Society, Atlantic City, New Jersey, September 1962. (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1635-1649 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When, in a poly-α-olefin, the probability that a given placement be isotactic depends upon the tacticity of only a finite number of immediate predecessors, the resulting diastereosequence distribution obeys the theory of Markoff chains. When this is not the case, one says that the resulting diastereosequence distribution is non-Markoffian. A special case of a Markoffian distribution is given by a simple Markof chain in which the tacticity of a given placement is assumed to be affected by only the tacticity of the immediately preceding placement. Another special case is, of course, the Bernoulli trial distribution in which the probability that a given placement be isotactic is independent of the tacticity of all other placements. A high resolution NMR spectrum can sometimes yield a quantitative determination of the concentrations of isotactic and syndiotactic placements and the concentrations of the three types of possible adjacent pairs of such placements (i.e., isotactic, syndiotactic, and heterotactic pairs). When this is the case, the spectrum can be used to determine whether or not a given diastereosequence distribution is Bernoullian. However, because the longest diastereosequences whose concentration can be measured by NMR spectroscopy involve only two placements, an NMR spectrum cannot check whether a given non-Bernoullian distribution be simple Markoffian or Markoffian in general. In fact, non-Markoffian distributions are compatible with existing NMR spectra on polymers prepared by anionic polymerizations. In this paper we work within the framework of Kac's theory of stationary statistical processes and point out some general results which are valid for both Markoffian and non-Markoffian processes. The results are applied to NMR spectroscopy and it is pointed out which calculations used to check the self-consistency of NMR data and to obtain the mean length of closed diastereosequences are valid for both Markoffian and non-Markoffian distributions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1996.838
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  • 3
    Electronic Resource
    Electronic Resource
    A comparison of models for hydrogen bonding in polymer blends (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1189-1193 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080320622
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  • 4
    Electronic Resource
    Electronic Resource
    Hexafluoro-2-hydroxy-2-propyl-modified polyisoprene blends (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1817-1827 
    Details
    ISSN: 0887-624X
    Keywords: polymer blends ; hydrogen bonding ; miscibility ; phase behavior ; equilibrium constants ; hexafluoroisopropanol groups ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dimensionless equilibrium constants describing the self-association of the hexafluoro-2-alkyl-2-propanol group have been determined from infrared spectroscopic data. Corresponding values of these equilibrium constants for a fully modified polyisoprene containing the hexafluoroisopropanol group (PHFPI) were calculated by taking into account differences in the molar volume of the model and the specific repeat unit of the polymer. Equilibrium constants describing the inter-association of PHFPI with methacrylate, acrylate, and acetoxy type carbonyl groups were obtained from spectroscopic studies of miscible PHFPI blends with poly(n-butyl methacrylate), poly(methyl acrylate), and an ethylene-co-vinyl acetate copolymer containing 70 wt% vinyl acetate. The set of equilibrium constant values were then used to calculate theoretical miscibility windows for the complete range of PHFPI blends with poly(n-alkyl methacrylate)s and four copolymers, ethylene-co-methyl methacrylate, styrene-co-methyl acrylate, ethylene-co-methyl acrylate, and ethylene-co-vinyl acetate. Experimental infrared studies confirm the general validity of the predicted miscibility windows. © 1994 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321003
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  • 5
    Electronic Resource
    Electronic Resource
    Commentary: Reflections on “General theory of stationary random sequences with applications to the tacticity of polymers,” by Bernard D. Coleman and Thomas G Fox, J. Polym. Sci. A, 1, 3183 (1963) (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1631-1632 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1996.836
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  • 6
    Electronic Resource
    Electronic Resource
    Computer-Aided models for optimization of eluent parameters in chiral liquid chromatography (1992)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 4 (1992), S. 316-322 
    Details
    ISSN: 0899-0042
    Keywords: chiral LC ; drug enantiomers ; modelling ; central composite desire ; optimization ; β-cyclodextrin ; response surface ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The application of a central composite design to the enantiomeric separation of the antifungal drug tioconazole is investigated. The design involves application of a mathematical model to the data to model the response in regions of the factor space not investigated in the experimental design. The significance of the variable terms in the model is assessed statistically and those terms declared not significant are removed from the model. The statistical adequacy of these reduced models is discussed, together with an examination of the prediction errors of the models. Three-dimensional predicted response surfaces for the complete models are presented and the predictive performance assessed. © 1992 Wiley-Liss, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530040510
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  • 7
    Electronic Resource
    Electronic Resource
    Method development in liquid chromatography with a charged cyclodextrin additive for chiral resolution of rac-amlodipine utilising a central composite design (1996)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 8 (1996), S. 466-476 
    Details
    ISSN: 0899-0042
    Keywords: rac-amlodipine ; amlodipine ; liquid chromatography ; chiral ; charged cyclodextrin ; optimisation ; central composite design ; mobile phase additive ; experimental design ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A negatively charged derivative of β-cyclodextrin, sulphobutyl ether-β-cyclodextrin (SBE-β-CD), was examined as a chiral mobile phase additive in reversed-phase high-performance liquid chromatography for the enantiomeric resolution of the calcium channel blocker rac-amlodipine. Theoretical and practical aspects are discussed for setting up a central composite design applicable to any analytical method. These include the correct location of factor points for maintaining orthogonality within the design and the augmentation of centrepoint experiments to allow a larger factor space by increasing the distance of axial star points. Optimised separation was achieved using a reverse-phase column with eluent comprising: acetonitrile (ACN) - potassium dihydrogen phosphate (pH 3.93) containing 2.66 mM SBE-bgr;-CD (26.5:73.5% v/v) at a flow rate of 1.0 ml/min. This yielded a Kaiser peak separation index, Pi = 0.96, at tR2 = 52 min with satisfactory reproducibility, relative standard deviation values: tR1, 0.39%; tR2, 0.47% (n = 5). These experimental results were in excellent agreement with those predicted by the SAS software package for a chromatographic response function model. Multiple regression analysis in four dimensions, with three response models based on Rs, Pi, and a function of Pi, produced response surfaces which revealed zones of optimum robustness and illustrated the interactions involved between the key chromatographic factors. Putative proposals for a mechanism involving the interaction of each of the positively charged enantiomers with the negatively charged cyclodextrin are also discussed. These examine the possibility of ion-pairing and inclusion phenomena to account for the excellent resolution observed. © 1996 Wiley-Liss, Inc.
    Additional Material: 11 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Chiral recognition in liquid chromatography utilising chargeable cyclodextrins for resolution of doxazosin enantiomers (1997)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 9 (1997), S. 184-190 
    Details
    ISSN: 0899-0042
    Keywords: rac-doxazosin ; doxazosin ; liquid chromatography ; chiral ; carboxymethyl-β-cyclodextrin ; optimisation ; central composite design ; mobile phase additive ; experimental design ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chromatographic resolution of rac-doxazosin using reversed-phase high performance liquid chromatography (HPLC) with the chargeable chiral mobile phase additive, carboxymethyl-β-cyclodextrin (CM-β-CD), is described. The effects of different modifiers (acetonitrile, methanol and tetrahydrofuran), pH, temperature, and cyclodextrin concentration were investigated to (a) assess the key chromatographic parameters for subsequent chemometric optimisation, and (b) explore the enantioselective mechanism. Assuming a 1:1 complex between each doxazosin enantiomer and CM-β-CD, studies of the relationship between the capacity factors (k′) and functions of CM-β-CD concentration indicate that the mechanisms for retention and chiral selectivity are comparable with those proposed earlier by Sybilska et al.1 Stability constants (KG) calculated for rac-doxazosin complexed with CM-β-CD (647 ± 55 and 594 ± 45 M-1 for each enantiomer respectively) are significantly larger than those calculated for the barbiturates complexed with β-CD (ca. 101-108 M-1).1 Investigations on pH indicate an ionic or ion-pair interaction between the anionic CM-β-CD and the cationic doxazosin enantiomers.A central composite design was used to optimise the key chromatographic parameters: pH, methanol (v/v) and CM/β-CD concentration. The Kaiser peak separation index, Pi, was used for the response function. The predicted response for this chiral separation has been compared with that observed experimentally and samples of the four-dimensional response surface have been assessed for their value in showing robustness. Chirality 9:184-190, 1997. © 1997 Wiley-Liss, Inc.
    Additional Material: 11 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Central composite design for the rapid optimisation of ruggedness and chiral separation of amlodipine in capillary electrophoresis (1995)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 7 (1995), S. 226-234 
    Details
    ISSN: 0899-0042
    Keywords: central composite design ; liquid chromatography ; capillary electrophoresis ; amlodipine ; cyclodextrin ; ruggedness ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Systematic optimisation with central composite design offers an efficient route for rapid optimisation of resolution with multiple interacting parameters in chiral CE. This is illustrated by separations of amlodipine with α-CD as chiral selector in the running buffer, for which the predicted performance of central composite design is assessed. The utility of response surface methodology for locating optimum ruggedness in CE is also described. © 1995 Wiley-Liss, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530070408
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  • 10
    Electronic Resource
    Electronic Resource
    Analysis of gases containing inorganic and organic compounds using a combination of a thick-film capillary column and a packed adsorption column (1985)
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 8 (1985), S. 112-118 
    Details
    ISSN: 0935-6304
    Keywords: Gas chromatography, GC ; Fused silica capillary columns ; Packed absorption columns ; Thick liquid phase films ; Natural, refinery, and reactor gas analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A gas chromatographic system consisting of one multiport valve, two (hot-wire and flame-ionization) detectors and two analytical columns (one thick-film capillary and one packed adsorption column) is used for the analysis of gas samples containing a number of inorganic compounds (hydrogen, argon, oxygen, nitrogen, carbon monoxide, and carbon dioxide) and organic compounds. Examples include samples containing hydrocarbons up to n-nonane and benzene and toluene. The system also permits the analysis of more complicated samples containing, for example, alcohols, in addition to hydrocarbons.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jhrc.1240080302
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