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  • Polymer and Materials Science  (112,478)
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  • 101
    ISSN: 0899-0042
    Keywords: solubilization ; enhanced enantioselectivity ; chiral induction ; critical micellar concentration ; reaction place ; function of proline ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Proline and prolylproline dipeptide derived surfactants promote the asymmetric hydrogenation of (Z)-methyl α-acetamidocinnamate in water in the presence of the catalytic system [Rh(cod)2]BF4 + BPPM. Activity and enantioselectivity are enhanced significantly and the results in water are similar to those obtained with organic solvents. The possibility of a chiral induction was investigated in the presence of the optically active amino acid and peptide amphiphiles and an achiral rhodium catalyst [Rh(bdpb)(cod)]BF4. The analysis of the low optical induction gave some indications of the site where the reaction takes place within the micelle. Selected critical micelle concentrations (cmc) of the new prepared surfactants were determined by surface tension measurements. Chirality 10:754-759, 1998. © 1998 Wiley-Liss, Inc.
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  • 102
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 10 (1998), S. 779-785 
    ISSN: 0899-0042
    Keywords: optically active oxiranes ; liquid crystals ; epichlorohydrin ; glycidol ; chiral HPLC ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of racemic and optically active oxiranes, bearing mesogenic groups, precursors of liquid crystalline polyethers, has been synthesized from epichlorohydrin or glycidol. The enantiomeric excess of the optically active oxiranes has been determined by chiral stationary phase HPLC. Compounds bearing 4-cyanobiphenyl mesogenic group exhibit monotropic liquid crystalline behavior. A transfer of chirality to the mesophase has been observed for the optically active oxiranes, which present a cholesteric phase. Chirality 10:779-785, 1998. © 1998 Wiley-Liss, Inc.
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  • 103
    ISSN: 0899-0042
    Keywords: chiral HPLC ; principal component analysis (PCA) ; hierarchical clustering ; hydrogen bonding ability ; solvation of carbamate phases ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chromatographic resolution of 12 derivatives in the 4a-methyl-2,3,4,4a-tetrahydro-1H-fluorene and 4a-methyl-1,2,3,4,4a,9a-hexahydrofluoren-9-one series differing by the framework around position 9 and substitution in position 6, are reported on Chiralcel OD, Chiralpak AD, and Chiralpak AS under two elution conditions and according to the two classes of enantiomers. Results from principal component analysis (PCA) as well as hierarchical clustering show a clustering of the actual compounds depending on properties around position 9, the effect of the substituent in position 6 (methyl, chloro or fluoro) not being strong enough to intermesh the data. Carbamate phases show very different properties when they are used in the separation of a series of ketones C and α-chloroketones D, which differ in basicity and the steric requirement around the carbonyl. Analysis of the effect of 2-PrOH content in hexane on the retention is consistent with a large difference in solvation of the carbamate moiety by 2-PrOH, in the order Chiralcel OD 〉 Chiralpak AD 〉 Chiralpak AS. 4a-Methyl-2,3,4,4a-tetrahydro-1H-fluorene derivatives, which lack hydrogen bonding sites, are not discriminated on these CSPs and show identical k′ responses to 2-PrOH content changes on the three CSPs. Chirality 10:770-777, 1998. © 1998 Wiley-Liss, Inc.
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  • 104
    Electronic Resource
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    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 10 (1998), S. 786-790 
    ISSN: 0899-0042
    Keywords: enantioseparation ; peach-like aroma ; fatty acid bioconversion ; gas chromatography-mass spectrometry in selected ion monitoring mode ; Penicillium roqueforti ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Identification and enantiodifferentiation of γ-lactones produced during the bioconversion of soy bean fatty acids by Penicillium roqueforti spores in the presence of an exogenous lipase was performed using gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. It was shown that 4-dodecanolide and 4-hexanolide were first produced with an enantiomeric excess (99%) in favor of the (R) form, whereas an enantiomeric excess in favor of the (S) form (94%) is found for (6Z)-dodecen-4-olide, the major lactone produced by the fungus. If incubation was continued, mixtures of both enantiomers were found, more particularly for 4-decanolide (R/S:40/60), which was produced only after 120 hr of incubation. The results obtained can be explained by the stereoselective hydroxylation by a 10-hydratase and/or a 10-lipoxygenase of the unsaturated fatty acid precursors, oleic and linoleic acids, and by competition between different pathways. The results point out the limitations of chiral GC analysis as a criterion for the natural origin of relevant lactones, and the complexity of mechanisms involved in γ-lactone formation by microorganisms. Chirality 10:786-790, 1998. © 1998 Wiley-Liss, Inc.
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  • 105
    ISSN: 0899-0042
    Keywords: amylose ; 3,5-dimethylphenyl-carbamate ; polysaccharide phase ; tert-butyl 2-tert-butyl-4-methoxy-2,5-dihydro-1,3-imidazole-1-carboxylate; amino acid ester synthesis ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparative separation of the enantiomers of the title compound, a versatile chiral building block for the synthesis of unnatural amino acid esters, by high performance liquid chromatography on a chiral stationary phase (CSP), is reported for the first time. The CSP consists of amylose-(3,5-dimethylphenyl-carbamate), which has been coated onto the surface of macroporous aminopropyl-functionalized silica gel. The effect of mobile phase composition and the amount of amylose derivative on the silica gel has been thoroughly investigated. Using 2-propanol as organic modifier in hexane as mobile phase, on a semi-preparative column (200 mm × 40 mm ID, containing 192 g of stationary phase) about 200 mg of the racemate was separated per injection. Running the equipment under automatic conditions with repetitive injection mode allowed for the separation of 30 g per day. Both enantiomers were obtained with enantiopurities 〉99.75:0.25. Chirality 10:217-222, 1998. © 1998 Wiley-Liss, Inc.
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  • 106
    Electronic Resource
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    Chirality 10 (1998), S. 229-237 
    ISSN: 0899-0042
    Keywords: deuterium labelling ; menthocitronellol ; citronellol ; enantioselective multidimensional gas chromatography-mass spectrometry (enantio-MDGC-MS) ; dynamic headspace analysis ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mechanistic aspects of the biogenesis of the chiral monoterpenoid rose oxide in Pelargonium graveolens L'Héritier are investigated using deuterium-labelled precursors. After administration of the precursors using the cut-stem method, the dynamic headspace extracts of the plants are analysed using multidimensional gas chromatography-mass spectrometry (enantio-MDGC-MS). It is unequivocally shown that this plant is able to convert citronellol and menthocitronellol into cis-/trans-rose oxide. Menthocitronellol is converted into rose oxide with a clearly detectable enantiodiscrimination. These facts may be explained with the presence of an oxidase, which is able to oxidize citronellol and menthocitronellol in allylic position. A photooxygenation mechanism including singlet oxygen as the oxidizing agent is rather unlikely. Chirality 10:229-237, 1998. © 1998 Wiley-Liss, Inc.
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  • 107
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    Chirality 10 (1998), S. 238-245 
    ISSN: 0899-0042
    Keywords: chiral selectivity ; amino acid crystallization ; molecular recognition ; stochastic kinetics ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of chirally selective interaction in the stirred crystallization of glutamic acid and lysine is presented. The crystallization of S-glutamic acid is influenced by the presence of S-lysine but not R-lysine. Crystal nuclei in stirred systems are produced due to secondary nucleation. Secondary nucleation is an autocatalytic process in which a crystal produces secondary nuclei due to fluid motion, and due to crystal stirrer and crystal-crystal collisions. As a result of this autocatalysis, small fluctuations in the nucleation rates are amplified and the kinetics show a marked stochastic behavior. We investigate the stochastic behavior in detail and propose a kinetic mechanism that explains both the increase and the statistical distribution of the crystallization times of S-glutamic acid due to the presence of S-Lysine. Chirality 10:238-245, 1998. © 1998 Wiley-Liss, Inc.
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  • 108
    ISSN: 0899-0042
    Keywords: thalidomide enantiomers ; in vitro kinetics ; blood distribution ; human serum albumin ; chiral inversion ; plasma protein binding ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aim of this investigation was to elucidate the distribution and reactions of the enantiomers of thalidomide at their main site of biotransformation in vivo, i.e., in human blood. Plasma protein binding, erythrocyte: plasma distribution, and the kinetics of chiral inversion and degradation in buffer, plasma, and solutions of human serum albumin (HSA) were studied by means of a stereospecific HPLC assay. The enantiomers of thalidomide were not extensively bound to blood or plasma components. The geometric mean plasma protein binding was 55% and 66%, respectively, for (+)-(R)- and (-)-(S)-thalidomide. The corresponding geometric mean blood:plasma concentration ratios were 0.86 and 0.95 (at a haematocrit of 0.37) and erythrocyte:plasma distributions were 0.58 and 0.87. The rates of inversion and hydrolysis of the enantiomers increased with pH over the range 7.0-7.5. HSA, and to a lesser extent human plasma, catalysed the chiral inversion, but not the degradation, of (+)-(R)- and (-)-(S)-thalidomide. The addition of capric acid or preincubation of HSA with acetylsalicylic acid or physostigmine impaired the catalysis to varying extents. Correction for distribution in blood enhances previously observed differences between the pharmacokinetics of the enantiomers in vivo. The findings also support the notion that chiral inversion in vivo takes place mainly in the circulation and in albumin-rich extravascular spaces while hydrolysis occurs more uniformly in the body. In addition, the chiral inversion and hydrolysis of thalidomide apparently occur by several different mechanisms. Chirality 10:223-228, 1998. © 1998 Wiley-Liss, Inc.
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  • 109
    Electronic Resource
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    Chirality 10 (1998), S. 382-395 
    ISSN: 0899-0042
    Keywords: selector/selectand associates ; hydrogen bonding ; chiral separation ; chiral phases ; enantioselectivity ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The progress made in the development of chiral stationary phases based on hydrogen-bonding selector/selectand associates is reviewed here. The structure of the different selectand/selector systems was established through X-ray diffraction and other spectroscopic techniques. The structure of the energetically more stable diastereomeric-associate was then correlated to the chromatographic results, namely to the elution order and the enantioselectivity of each of the systems. Chirality 10:382-395, 1998. © 1998 Wiley-Liss, Inc.
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  • 110
    ISSN: 0899-0042
    Keywords: chirality ; helicity ; GC-stationary phase ; conformations ; 1H-NMR-studies ; molecular mechanics calculations ; enantiomer separation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The manner of hydrogen-bonding to peptide selectors in enantiomer separation is examined with the help of a structural model. This model relies on a C3-symmetric trispeptide selector, which is stabilized by a network of distinct intramolecular hydrogen bonds. A combination of experimental and theoretical tools enables us to identify the lowest-energy conformation of the trispeptide selector and the sites of selector-substrate interactions. Experimental tools include temperature dependent 1H-NMR studies, 1D-NOE-measurements, and titration experiments, with the theoretical tools being EFF and CFF91 molecular mechanics calculations. The structural information deduced from these investigations is shown to bear on the enantioseparation of the corresponding chiral stationary phase towards derivatized amino acids. These observations, taken together, help to rationalize the mode of enantiomer-separation by amide phases as involving predominantly C7-hydrogen bonding sites. Chirality 10:396-404, 1998. © 1998 Wiley-Liss, Inc.
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  • 111
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    Chirality 10 (1998), S. 195-209 
    ISSN: 0899-0042
    Keywords: molecular imprinting ; molecular recognition ; chirality ; chromatography ; catalysis ; biosensor ; immunoassay ; antibody mimic ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular imprinting is a technique for the fabrication of biomimetic polymeric recognition sites or “plastic antibodies/receptors” which is attracting rapidly increasing interest. By this technology, recognition matrices can be prepared which possess high substrate selectivity and specificity. In the development of this technology, several applications have been foreseen in which imprinted materials may be exchanged for natural recognition elements. Thus, molecularly imprinted polymers have been used as antibody/receptor binding mimics in immunoassay-type analyses, as enzyme mimics in catalytic applications and as recognition matrices in biosensors. The best developed application area for imprinted materials, though, has been as stationary phases for chromatography, in general, and chiral chromatography, in particular. This review seeks to highlight some of the more intriguing advantages of the technique as well as pointing out some of the difficulties encountered. The prospects for future development will also be considered. Chirality 10:195-209, 1998. © 1998 Wiley-Liss, Inc.
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  • 112
    ISSN: 0899-0042
    Keywords: hexahelicene ; sulphoxides ; carbohydrate carbamate ; chiral preparative ; silica ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparative enantiomeric resolutions of hexahelicen-7-yl acetic acid methyl ester and two sulphoxides were performed on cellulose tris(3,5-dimethylphenylcarbamate) coated onto aminopropylated 5-μm silica with 120-Å diameter pore. High enantiomeric purity was obtained for both enantiomers. The enantioselectivity of the amylose tris(3,5-dimethylphenylcarbamate), cellulose and amylose tris(phenylcarbamate) phases for the hexahelicen-7-yl acetic acid derivative were also investigated. Chirality 10:573-577, 1998. © 1998 Wiley-Liss, Inc.
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  • 113
    Electronic Resource
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    Chirality 10 (1998), S. 587-591 
    ISSN: 0899-0042
    Keywords: snuff ; chewing tobacco ; Turkish tobacco ; Burley tobacco ; Virginia tobacco ; transdermal patches ; gum ; nasal spray ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantiomeric composition of nicotine in 18 smokeless tobaccos, 3 strains of tobacco leaf, 8 pharmaceutical products, and 4 commercial reagents was determined. The relative amount of the minor enantiomeric component, (R)-(+)-nicotine, ranged from ∼0.1% to ∼1.2% of the total nicotine in all samples. In some cases it appears that (R)-(+)-nicotine may be considered one of the five most common alkaloids in tobacco products. The highest level of (R)-(+)-nicotine was found in a commercial transdermal patch. The extraction and purification processes used in obtaining commercial (S)-(-)-nicotine supplies from tobacco do not appear to decrease the amount of (R)-(+)-nicotine present. Chirality 10:587-591, 1998. © 1998 Wiley-Liss, Inc.
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  • 114
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    Chirality 10 (1998), S. 600-618 
    ISSN: 0899-0042
    Keywords: steroidal bile acids ; inclusion compounds ; crystal structures ; facial molecules ; amphiphilic molecules ; amphiphilic sheets ; hydrogen-bonding networks ; head-to-tail ; head-to-head ; tail-to-tail ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral compounds, N-methyl-, N-ethyl-, and N-n-propylcholamides, form crystalline inclusion compounds with water or small organic substances. The compounds were analyzed by X-ray diffraction methods. It was found that the crystals have bilayered structures accumulated by chiral molecular sheets. The chiral molecules associate in a unique head-to-head/tail-to-tail and right-to-left motif to give chiral and amphiphilic sheets. Such sheets stack by adhesions between the hydrophilic sides and between the lipophilic sides. The alkyl groups of the amides prompt the formation of a hydrogen-bonding network between the tails instead of a cyclic one between the head and tail. The guest molecules are accommodated into small cavities between the steroidal side chains. Chirality 10:600-618, 1998. © 1998 Wiley-Liss, Inc.
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  • 115
    ISSN: 0899-0042
    Keywords: chiral separation ; chiral selector ; separation of enantiomers ; liquid chromatography ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A chiral stationary phase (CSP 1) prepared starting from (R)-4-hydroxyphenylglycine and then grafting (R)-N-butanoyl-4-allyloxyphenylglycine N-propyl amide to silica gel was found to be very effective in separating the enantiomers of N-(3,5-dinitrobenzoyl)-α-amino amides. From the chromatographic behaviors of the resolution of N-propyl amides, N,N-diethyl amides and ethyl esters of N-(3,5-dinitrobenzoyl)-α-amino acids and the resolution of various N-(substituted benzoyl)leucine N-propyl amides, the hydrogen bonding and the π-π donor-acceptor sites of the analyte for the interaction with the CSP have been proposed. Similarly, the hydrogen bonding donor and acceptor sites of the CSP for the interaction with the analyte have been proposed from the comparison of the chromatographic behaviors of the resolution of various N-(3,5-dinitrobenzoyl)-α-amino N-propyl amides on modified CSPs (CSP 7 containing trifluoroacetyl group instead of the butanoyl group of CSP 1 and CSP 8 containing N,N-diethyl group instead of the N-propyl group of CSP 1) with those on CSP 1. By correlating the interaction sites of the CSP and their complementary interaction sites of the analyte, a chiral recognition mechanism which utilizes the two hydrogen bonding interactions and the π-π donor-acceptor interaction between (R)-CSP 1 and more retained analytes, (S)-N-(3,5-dinitrobenzoyl)-α-amino amides, has been proposed. Chirality 10:592-599, 1998. © 1998 Wiley-Liss, Inc.
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  • 116
    ISSN: 0899-0042
    Keywords: nucleophilic aromatic substitution ; optical resolution ; asymmetric synthesis ; diastereoselective reaction ; Grignard reaction ; atrolactic acid derivatives ; biaryl coupling reaction ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel 1-aryl-9H-fluoren-9-ols 1 were conveniently synthesized by using the ester-mediated nucleophilic aromatic substitution on 2,6-dimethoxybenzoate 2 by aryl Grignard reagents as the key step. Racemic 1-phenylfluorenol 1a was converted to the diastereomeric esters 8 of (S)-2′-methoxy-1,1′-binaphthyl-2-carboxylic acid, which were readily separable by silica-gel column chromatography. Reduction of the optically pure diastereomer (+)-8 with LiAlH4 accompanied an appreciable racemization to give (+)-1a of 89% ee, which provides the first isolation of an optically active fluorenol of defined enantiomeric purity. Intrinsic chiral induction abilities of the 9-fluorenols 1 were examined in the atrolactic acid synthesis from phenylglyoxylates 9 and methylmagnesium iodide with diastereoselectivity of up to 85% de and the binaphthyl coupling of 1-methoxy-2-naphthoates 11 with 2-methoxy-1-naphthylmagnesium bromide with up to 73% de. Chirality 10:619-626, 1998. © 1998 Wiley-Liss, Inc.
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  • 117
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    Chirality 10 (1998), S. 661-666 
    ISSN: 0899-0042
    Keywords: chiral dendrimers ; dendrimers ; axial chirality ; (R)-(+)-1,1′-bi-2,2′-naphthol ; optical rotation ; circular dichroism ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and optical activity of novel chiral dendrimers with axial chirality are reported. The dendrimers were constructed by coupling of the polyether dendritic bromides with (R)-(+)-1,1′-bi-2-naphthol (1). The uniform (2, 3, 4) and non-uniform double-O-alkylated (8, 9, 10) as well as mono-O-alkylated (5, 6, 7) products were thus obtained. These chiral molecules were characterized by 1H- and 13C-NMR, elemental analysis, optical rotation, adsorption spectra, and circular dichroism. It was found that the specific rotation decreases with the increase of the number of generation for each group of dendrimers (2-4, 5-7, and 8-10, respectively). In terms of the molar rotation, it was quite different; the molar rotation increased sharply for dendrimers, 2-4, but only slightly for dendrimers 5-7. The dihedral angle change of bi-naphthyl in the synthesized dendrimers was discussed based on the CD spectra. Chirality 10:661-666, 1998. © 1998 Wiley-Liss, Inc.
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  • 118
    ISSN: 0899-0042
    Keywords: avoparcin ; macrocyclic antibiotics ; enantiomeric separations ; chiral stationary phases ; verapamil ; thyroxine ; mephenytoin ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Avoparcin is a macrocyclic glycopeptide antibiotic structurally related to vancomycin, teicoplanin, and ristocetin A. When attached to 5-μm spherical silica gel, the avoparcin proved to be an effective chiral stationary phase (CSP) that could be used in the reversed-phase, normal-phase, and polar-organic modes. The avoparcin CSP was complimentary to the other macrocyclic glycopeptide CSPs in that it could resolve some racemates that the others could not, and vice versa. Some important compounds resolved on the avoparcin CSP include verapamil, thyroxine, mephenytoin, and 2-imidazolidone-4-carboxylic acid. The use of this CSP and the optimization of separations on it are discussed. Avoparcin appears to be a useful addition to this family of CSPs. Chirality 10:627-660, 1998. © 1998 Wiley-Liss, Inc.
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  • 119
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    Chirality 10 (1998), S. 693-698 
    ISSN: 0899-0042
    Keywords: Pseudomonas cepacia ; lipase PS ; transesterification ; kinetic resolution ; 2-substituted 3-hydroxy ester ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic resolution of 2-substituted 3-hydroxy esters was examined by lipase PS catalyzed transesterification using vinyl acetate as an acyl donor. Resolution of (±)-syn- and -anti-1a, -1e possessing a small methyl group at the C-3 position was accomplished enantioselectively. The outcome of the resolution seems to be related to the differences in size of the substituents at the stereocenter bearing a secondary hydroxy group. Chirality 10:693-698, 1998. © 1998 Wiley-Liss, Inc.
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  • 120
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    Chirality 10 (1998), S. 676-681 
    ISSN: 0899-0042
    Keywords: β-glucosidase from almond ; reverse hydrolysis ; transglucosylation ; enantioselectivity ; enantiomeric excess ; absolute configuration ; alkyl β-D-glucopyranoside ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Almond β-glucosidase was used to catalyze the synthesis of alkyl β-d-glucopyranosides 1b-3b starting from either d-glucose (4) or phenyl-β-d-glucopyranoside (5) and the racemic alcohols 1a-3a. The enzymic reactions were provided in different acetonitrile/water mixtures [9:1 (v/v) for the reverse hydrolysis, and 1:9 (v/v) for the transglycosylation]. Both enzymic reactions, that is, the reverse hydrolysis and the transglucosylation, are enantioselective processes. The enantiomeric purity of products 1b-2b of the enzymic reactions varied between 75 and 86% ee, the values of which were based on the analysis of the aglyconic parts (1c-2c) of the alkyl β-d-glucopyranoside molecules (1b-2b). Chirality 10:676-681, 1998. © 1998 Wiley-Liss, Inc.
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  • 121
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    Chirality 10 (1998), S. 682-692 
    ISSN: 0899-0042
    Keywords: optically active ; epichlorohydrin ; 3-chloro-1,2-propanediol ; microbial resolution ; dehalogenation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Production of highly optically active C3 and C4 chlorohydrins was developed by using the bacteria stereoselectively dehalogenating and assimilating the racemic substrate: Pseudomonas sp. and Alcaligenes sp. These bacteria stereoselectively assimilate (RS)-2,3-dichloro-1-propanol (DCP) and (RS)-3-chloro-1,2-propanediol (CPD) followed by microbial preparation of (R)- and (S)-DCP, and (R)- and (S)-CPD with 〉99% ee. A novel dehalogenating enzyme, halohydrin dehydro-dehalogenase from one of the above strains, Alcaligenes sp. DS-S-7G, was applicable for preparation of optically active 1,2-diols with 60-99% ee. Moreover, microbial resolution of C4 chlorohydrins with whole cells of Pseudomonas sp. was carried out. This resolution reaction using the resting cells gave (R)- and (S)-4-chloro-3-hydroxybutyrate (CHB) and (S)-4-chloro-3-hydroxybutyronitrile (BN) with 〉98% ee. In the case of the resting cells of Enterobacter sp., both (R)-CHB (〉99% ee) and (S)-3-hydroxy-γ-butyrolactone (95% ee) with excellent yield were obtained. Also, some typical synthetic applications using the above chiral C3 and C4 synthons were introduced: ferroelectric liquid crystals, optically active β-blockers, and other chiral pharmaceuticals. Chirality 10:682-692, 1998. © 1998 Wiley-Liss, Inc.
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  • 122
    ISSN: 0899-0042
    Keywords: polysilane ; circular dichroism ; exciton couplet ; helix ; fluorescence ; poor solvent ; good solvent ; conformational property ; helix reversal ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An optically active, rigid rodlike helical polysilane with 6,9,12-trioxatetradecyl and (S)-2-methylbutyl substituents (1) was newly obtained as a very high molecular weight polymer of several million. Due to the presence of trietheral substituent, 1 was readily soluble in a polar solvent such as ethanol and a mixture of ethanol and water, but was insoluble in pure water. Polysilane 1 in pure ethanol at room temperature exhibited an intense and narrow ultraviolet (UV) and circular dichroism (CD) absorptions at 323 nm, associated with an almost mirror imaged fluorescence (FL) at 328 nm, that are characteristic of rigid rodlike, single-screw-sense helical polysilanes reported previously. When solution temperature was changed from 60°C to -104°C, a global shape of 1 expanded associated with an increase of segment length, whereas a screw pitch tended to be wound tightly. On the other hand, as a solvent polarity became poor, a global shape of 1 shrunk associated with an decrease of segment length and formed a chiral motif with an M-helicity between two helical segments with a kink. At a ratio of 50% of ethanol/water of 50:50 (v/v), 1 became insoluble and formed aggregates. Chirality 10:667-675, 1998. © 1998 Wiley-Liss, Inc.
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  • 123
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    Chirality 10 (1998), S. 711-716 
    ISSN: 0899-0042
    Keywords: stereospecific polymerization ; chiral α-substituted acrylate ; stereoregularity ; chiroptical property ; isotactic polymer ; regular arrangement ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel chiral monomer, benzyl α-[(1-phenylethoxy)methyl]acrylate was synthesized, and the stereoregularity and chiroptical property of the polymers obtained by radical and anionic polymerizations were investigated. Anionic polymerization in toluene provided a polymer with high isotacticity regardless of optical purity of the monomer and difference of counter cations, Li+ and Mg2+, while radical polymerization appears to yield an atactic polymer. The isotactic copolymers anionically obtained from a mixture of (R)- and (S)-monomers showed peak splitting probably due to the triad arrangement of (R) and (S) groups of side chains in the resonance of 13C-NMR spectra. The isotactic polymer prepared from enantiomerically pure (R)-monomer ([α] 25 365 = +157°) with n-BuLi in toluene exhibited higher specific rotation ([α] 25 365 = +262°) than that of the radical polymer ([α] 25 365 = +162°). This may be explained by regular arrangement of optically active groups along the polymer chain of the isotactic polymer. Chirality 10:711-716, 1998. © 1998 Wiley-Liss, Inc.
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  • 124
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    Chirality 10 (1998), S. 699-704 
    ISSN: 0899-0042
    Keywords: ormeloxifene ; chiral separation ; sulfated cyclodextrin ; enantiomers ; capillary electrophoresis ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (-)-Ormeloxifene, a drug candidate under development, was separated from (+)-ormeloxifene using capillary electrophoresis (CE) with sulfated β-cyclodextrin as chiral buffer additive. With conventional long-end injection the method showed high efficiency, since the theoretical plate number for (-)-ormeloxifene was over 1 million per m and the enantiomeric resolution was more than 100. However, the relatively long separation time of ∼22 min was a limiting factor. In order to reduce separation time, short-end injection experiments were carried out. By using the instrumental limits for capillary dimensions and field strength, the separation time was reduced to 〈40 sec. A further and significant reduction was achieved by applying extended short-end injection, which is a novel injection technique presented in this paper. With the extended short-end injection procedure, a plug of run buffer is injected after the sample has been injected, thus moving the sample closer to the detector and resulting in very short effective capillary lengths. Using the extended short-end injection technique, the separation was performed on 1.8 cm capillary (effective length) and the enantiomers were separated within 10 sec, which is a reduction of the original separation time by a factor of ∼155. Chirality 10:699-704, 1998. © 1998 Wiley-Liss, Inc.
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  • 125
    ISSN: 0899-0042
    Keywords: preferential enrichment ; enantiomeric enrichment ; mixed crystal ; solid solution ; racemic compound crystals ; X-ray crystallography ; chiral ammonium sulfonate ; reversal of chirality ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The X-ray crystal structure of (±)-[2-[4-(3-ethoxy-2-hydroxypropoxy)phenylcarbamoyl]ethyl]dimethylammonium p-nitrobenzenesulfonate [(±)-NNMe2], which shows the novel enantiomeric resolution phenomenon Preferential Enrichment, has been compared with that of (±)-[2-[4-(3-ethoxy-2-hydroxypropoxy) phenylcarbamoyl]ethyl]dimethylammonium p-toluenesulfonate [(±)-NTMe2], which does not show the phenomenon. The stable crystalline form of (±)-NNMe2 is a racemic compound, while that of (±)-NTMe2 is a mixed (disordered) crystal composed of the two enantiomers. The intermolecular hydrogen bonding mode in the crystal of (±)-NNMe2 was very different from that of (±)-NTMe2. Chirality 10:705-710, 1998. © 1998 Wiley-Liss, Inc.
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  • 126
    ISSN: 0899-0042
    Keywords: zirconium ; binaphthol (BINOL) ; allylation ; asymmetric activation ; enantioselective carbon-carbon bond formation ; chiral high-performance liquid chromatography ; induction period ; product-like activator ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The asymmetric activation of binaphthol (BINOL)-zirconium catalysts is described on the enantioselective allylation of benzaldehyde with allyltin reagents. This model reaction has been used with the intention of establishing a protocol for a zirconium-based catalyst system, to be followed by structural studies. Initial results are reported that characterise a number of interesting features, namely the influence of an induction period and a high level of asymmetric activation obtained after addition of a product-like activator. Chirality 10:717-721, 1998. © 1998 Wiley-Liss, Inc.
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  • 127
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    Chirality 10 (1998), S. 95-99 
    ISSN: 0899-0042
    Keywords: β-amino alcohols ; enantiopure ; chiral ligands ; regioselective ; stereoselective ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Both enantiomers of the important chiral β-amino alcohols erythro-2-amino-1,2-diphenylethanol were obtained via the separation of diastereoisomeric N-chlorinated derivatives of racemic trans-stilbene oxide and (S)-α-methylbenzylamine. The incorporation of chlorine in these precursors facilitated both the separation of diastereoisomers and the removal of the α-methylbenzyl chiral adjuvant. Each enantiopure β-amino alcohol was converted (Mitsunobu conditions) into the corresponding trans-2,3-diphenylaziridine in good overall yield. Chirality 10:95-99, 1998. © 1998 Wiley-Liss, Inc.
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  • 128
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    Chirality 10 (1998), S. 120-124 
    ISSN: 0899-0042
    Keywords: libraries ; asymmetric reduction ; oxazaborolidine ; chiral hplc ; chiral benz- hydrols ; borane ; combinatorial chemistry ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The advantages and disadvantages of the one-pot multi-substrate screening in asymmetric catalysis are discussed. The specific case of asymmetric reduction of ketones has been studied and is examplified by borane reduction catalyzed by an oxazaborolidine derived from (S)-diphenylproline. Chirality 10:120-124, 1998. © 1998 Wiley-Liss,Inc.
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  • 129
    ISSN: 0899-0042
    Keywords: chiral CE ; maltooligosaccharides ; cellooligosaccharides ; cis-diltiazem ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Twelve different disaccharides and a series of noncyclic malto- and cello-oligosaccharides were used as chiral selectors in capillary electrophoresis (CE). Most saccharides resolved the enantiomers of atropisomeric 1,1′-binaphthyl-2,2′-diyl hydrogen phosphate (BDHP) depending on the type (α or β) and position of the linkage between monosaccharides. The effect of chain length of malto- and cello-oligosaccharides on enantioseparation of BDHP was also investigated. The nature of cations in background electrolytes affected significantly the separation of BDHP enantiomers. Chirality 10:134-139, 1998. © 1998 Wiley-Liss,Inc.
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  • 130
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    Chirality 10 (1998), S. 125-133 
    ISSN: 0899-0042
    Keywords: molecular topology ; catenane ; trefoil knot ; template effect ; circular dichroism ; enantiomers ; resolution methods ; 1,10-phenanthroline ; (S)-(+)-1,1′-binaphthyl-2,2′-diyl phosphate ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantiomers of topologically chiral molecular objects cannot be interconverted by a continuous deformation. It must be noted that this behavior is opposite to that of molecules showing classical or Euclidian chirality. Interlocked oriented rings and the trefoil knot are prototypical topologically chiral objects. We have been designing a transition-metal templated route to the corresponding real molecules (i.e., [2]-catenanes and molecular knots) using copper(I) as the template and 2,9-diphenyl-1,10-phenanthroline (dpp) based ligands. The precursor to the catenane species was a tetrahedral Cu(dpp)2+ complex in which the two ligands fit in around Cu(I), thereby allowing the interlocking process. In the case of the knot, the precursor was a double-stranded helical complex in which two bis-phenanthroline ligands wrap around two Cu(I) ions. The compounds were obtained as racemates and were resolved as their Cu(I) complexes either by HPLC on chiral stationary phases or by diastereoselective crystallization. For the trefoil knot (K · 2Cu+), the latter method proved to be the most efficient. It took advantage of the dicationic nature of the species to be resolved. The original triflate anion was exchanged by an optically pure anion (S)-(+)-1,1′-binaphthyl-2,2′-diyl phosphate ((+)-BNP-) and the diastereomer (+)-K · 2Cu+ · 2(+)BNP- was selectively crystallized in a mixture of nitromethane and benzene. Removal of the Cu(I) ions by treatment with cyanide afforded an enantiomerically pure molecular knot (K), showing an optical rotatory power close to +2,000° · mol-1 · L · dm-1. Chirality 10:125-133, 1998. © 1998 Wiley-Liss,Inc.
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  • 131
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    Chirality 10 (1998), S. 106-119 
    ISSN: 0899-0042
    Keywords: porphyrin ; chiral ; oxidation ; mechanism ; enantioselective ; asymmetric catalysis ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantioselective catalytic epoxidation of olefins is an important problem from both practical and mechanistic points of view. The origins of chiral induction by asymmetric porphyrin and salen complexes were investigated by FT-NMR T1 relaxation techniques. A new chiral vaulted porphyrin (1) that carries (S)-binaphthyl-L-alanine straps across both faces of the porphyrin macrocycle was synthesized and characterized. (R)-styrene oxide was obtained in 〉90% ee in the initial stages of styrene epoxidation with F5PhIO catalyzed by 1-Fe(III)Cl. The transition state for olefin epoxidation with high-valent metal-oxo species was modeled by coordinating epoxides to paramagnetic copper complexes of the corresponding ligands. The epoxide enantiomer that better fit the chiral cavity of the catalyst, as revealed by T1 relaxation measurements, was also the major product of catalytic olefin epoxidation. These results are consistent with the “lock-and-key” mechanism of asymmetric catalysis by metalloporphyrins. The copper complex of a chiral salen ligand showed no differentiation in terms of T1 relaxation rates between the enantiomers of cis-β-methylstyrene oxide in contrast to the high enantioselectivity observed for catalytic epoxidation. Chirality 10:106-119, 1998. © 1998 Wiley-Liss,Inc.
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  • 132
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    Chirality 10 (1998), S. 140-146 
    ISSN: 0899-0042
    Keywords: enantioselective chromatography ; chiral selectands ; chiral selectors ; peak coalescence ; enantiomer separation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Six scenarios of peak coalescence are distinguished in enantioselective chromatography. Where appropriate, they are verified by an experiment. Chirality 10:140-146, 1998. © 1998 Wiley-Liss, Inc.
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    Chirality 10 (1998), S. 154-158 
    ISSN: 0899-0042
    Keywords: polycyclic aromatic hydrocarbons ; arynes ; cyclopentadienones ; conformation ; steric hindrance ; rotational barriers ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two exceptionally crowded derivatives of octaphenylnaphthalene bearing ortho-methyls on the phenyl substituents - 2,3,5,6,7,8-hexaphenyl-1,4-di(o-tolyl)naphthalene (2) and 2,3,6,7-tetraphenyl-1,4,5,8-tetra(o-tolyl)naphthalene (3) - were prepared by the addition of tetraarylbenzynes to tetraarylcyclopentadienones. Both compounds exist as a mixture of conformational isomers which do not interconvert at ordinary temperatures. The yield of 2 and its distribution of conformers is strongly influenced by the choice of precursors in the final cycloaddition; one method gives a high yield of a 55:45 trans-2:cis-2 mixture, while another gives a very low yield of a 15:85 trans-2:cis-2 mixture. Kinetic epimerization of the latter indicated that the barrier to rotation about the tolyl-naphthalene bonds is 33.1 kcal/mol. Chirality 10:154-158, 1998. © 1998 Wiley-Liss, Inc.
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    Chirality 10 (1998), S. 147-153 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of the chiral 9,12-dimethyl-4-oxa[7]paracyclophane 3 was achieved by the dithia route with subsequent sulfone pyrolysis. The conformational flexibility of the oxamethylene bridge with local Cs symmetry is evident from low temperature NMR experiments. Experimentally, an activation enthalpy of 11.4 kcal/mol is found for this process, which is in good agreement with the rotational barrier derived from semiempirical AM1 calculations (10.2 kcal/mol). Ab initio Hartree-Fock geometry optimizations have been performed for 3 and the corresponding hydrocarbon 9,12-dimethyl[7]paracyclophane 4. The distance of the O-atom to the center of the benzene ring in the structure of 3 is only 2.784 Å, i.e., significantly closer than the analogous C4-benzene ring distance in the slightly more strained 4 (3.112 Å). The enantiomeric separation of (±3) has been achieved by HPLC and the circular dichroism (CD) spectrum is reported. Ab initio all-electron DFT/SCI calculations of the CD spectrum are in good agreement with the experimental data and reveal the importance of p(O-atom)→ π* charge-transfer type excited states at relative low energies (6.6 eV, 188 nm) responsible for an intense negative CD band. The benzene type π → π* states are energetically lowered by 0.4-0.8 eV due to the boat-type deformation of the benzene moiety. By comparison of theoretical and experimental CD data the absolute configuration of 3 is assigned as (-)-(S). Chirality 10:147-153, 1998. © 1998 Wiley-Liss, Inc.
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    Chirality 10 (1998), S. 159-168 
    ISSN: 0899-0042
    Keywords: symmetry ; conformation ; chirality ; stereochemistry ; NMR ; rotational barrier ; interconversion graph ; gear meshing ; molecular propellers ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The static and dynamic stereochemistries of tricyclohexylmethane, tetracyclohexylmethane, and tetracyclohexylethene are reviewed. Chirality 10:159-168, 1998. © 1998 Wiley-Liss, Inc.
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    Chirality 10 (1998), S. 430-433 
    ISSN: 0899-0042
    Keywords: Whelk-O 1 ; chromatography ; HPLC ; enantiodifferentiation ; heterocycles ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In concert with a larger study of the processes by which chiral stationary phase CSP 1 differentiates between enantiomers, we have investigated the chromatographic separation of the enantiomers of a series of aryl-substituted heterocycles of systematically varied structure. A mechanistic picture of how these and similar resolutions occur is emerging. The mechanistic hypothesis described herein is of predictive value. Chirality 10:430-433, 1998. © 1998 Wiley-Liss, Inc.
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  • 137
    ISSN: 0899-0042
    Keywords: ristocetin A ; macrocyclic antibiotic ; enantiomeric separations ; underivatized amino acids ; chiral stationary phase ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The macrocyclic glycopeptide, ristocetin A, was covalently bonded to a silica gel support and evaluated as a liquid chromatographic (LC) chiral stationary phase (CSP). Over 230 racemates were resolved in either the reversed-phase mode, the normal-phase mode, or the polar-organic mode. The retention behavior and selectivity of this CSP were examined in each mode. Optimization of separations on this column is discussed. The ristocetin A CSP appeared to be complimentary to other glycopeptide CSPs (i.e., vancomycin and teicoplanin). Column stability was excellent. The CSP was not irreversibly altered when going from one mobile phase mode to another. Chirality 10:434-483, 1998. © 1998 Wiley-Liss, Inc.
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  • 138
    ISSN: 0899-0042
    Keywords: salbutamol ; chiral separation ; validated assay ; fluorescence detection ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A sensitive enantioselective high-performance chromatographic (HPLC) method was developed and validated to determine low levels of (-)-R and (+)-S-albuterol in plasma. Baseline resolution was achieved by using a teicoplanin-based chiral stationary phase with a polar organic mobile phase consisting of methanol/acetonitrile/glacial acetic acid/diethylamine, 40:60:0.3:0.2, (v/v/v/v) and a flow-rate of 1.0 ml/min. Enantioselectivity (α) equaled 1.18 and resolution (Rs) equaled 1.8. By using fluorescence detection maximized at 230 and 310 nm for excitation and emission, respectively, concentrations of each enantiomer could be measured down to 125 pg/ml from a 1-ml plasma sample. Initially, the method was applied to plasma samples from a small single-dose inhalation study of racemic albuterol in a human volunteer and, later, to in vivo samples from a canine inhalation study of the single enantiomer, (-)-R-albuterol. Results from the canine study showed that no chiral inversion of (-)-R-albuterol occurs in the dog. Chirality 10:484-491, 1998. © 1998 Wiley-Liss, Inc.
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  • 139
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    Chirality 10 (1998), S. 492-498 
    ISSN: 0899-0042
    Keywords: racemate ; enantiomer ; HPLC ; chiral stationary phase ; benzoylcellulose ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The advantages that can be gained from derivatization of various racemic aliphatic and aromatic alcohols prior to enantiomeric chromatographic separation have been systematically investigated for a series of benzoate derivatives. Three cellulose-based CSPs available in the pure polymeric form - tribenzoyl cellulose (TBC), meta-methylbenzoyl cellulose (MMBC), and para-methylbenzoyl cellulose (PMBC) - were selected and several benzoate derivatives varying in the nature and the position of the substituent on the benzoyl group were prepared and analysed. TBC clearly gives the broadest application range, and among the different benzoate esters the best selectivity was generally obtained with either the 4-methoxybenzoate or the 4-methylbenzoate derivatives. Based on these results, some empirical rules could be formulated for optimizing the enantiomeric separation of racemic alcohols, which make up one of the most important classes of chemical substances used as drugs and biocides, or as building blocks for their synthesis. An application of this approach to the preparative separation of the enantiomers of a drug intermediate is also shown. Chirality 10:492-498, 1998. © 1998 Wiley-Liss, Inc.
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    Chirality 10 (1998), S. 499-504 
    ISSN: 0899-0042
    Keywords: enantioselective capillary gas chromatography ; cyclodextrin derivatives ; stereochemistry of terpenes ; monoterpenes ; essential oils ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Capillary gas chromatography employing the unique selectivities of specifically substituted cyclodextrins is highly suited for stereochemical investigations of terpenoid compounds. The analysis of many essential oils have shown that monoterpene derivatives regularly occur as enantiomeric mixtures. In the case of sesquiterpene hydrocarbons, liverworts (Hepaticae) and other lower organisms usually biosynthesize compounds of opposite stereochemistry as compared to higher plants and enantiomeric mixtures occur only occasionally. The investigation of diterpene hydrocarbons has so far shown no indication of the presence of both enantiomers in the same plant. Chirality 10:499-504, 1998. © 1998 Wiley-Liss, Inc.
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  • 141
    ISSN: 0899-0042
    Keywords: CBH I ; cellulase ; cation ; sodium ; potassium ; enantioselectivity and temperature ; ionic strength ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An increase in both retention and enantioselectivity for some β-blocking agents was observed when exchanging potassium to sodium ion in the buffer used as mobile phase. A large effect of ionic strength on retention was observed, while the enantioselectivity was constant. Chirality 10:513-518, 1998. © 1998 Wiley-Liss, Inc.
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    Chirality 10 (1998), S. 519-521 
    ISSN: 0899-0042
    Keywords: optical activity of enantiomers ; weak interactions ; stability of optical activity ; racemization ; tunneling effect ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Assuming the active molecule as a two-level system, we calculate the racemization, due to the tunneling effect, taking into account the effects of the weak interactions and of an external potential. We show that the weak interactions would block the tunneling racemization of enantiomers in compressed gases and liquids. Chirality 10:519-521, 1998. © 1998 Wiley-Liss, Inc.
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    Chirality 10 (1998), S. 507-512 
    ISSN: 0899-0042
    Keywords: chiroptical method ; drug analysis ; β-lactam antibiotics ; CD spectroscopy ; human fluids ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the applicability of circular dichroism (CD) for the determination of drug levels in human serum is described and a new method for the quantitative determination of optically active absorbing drugs having Cotton effects at wavelengths above 250 nm in human serum and/or plasma is proposed. The principal advantages of this method are speed, economy, and simplicity, no derivatization or chromatographic separation steps being needed. The validity of the CD determination was confirmed by analysis of variance, β-lactam antibiotics being chosen as model drugs. In addition, the validation studies performed confirm the accuracy and precision of the proposed method. For β-lactam antibiotics lacking Cotton effects above 250 nm, an alternative method based on the extraction of the drug from serum is considered. Chirality 10:507-512, 1998. © 1998 Wiley-Liss, Inc.
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    Chirality 10 (1998), S. 46-52 
    ISSN: 0899-0042
    Keywords: dendrimers ; circular dichroism ; accidental degeneracy ; cryptochirality ; solketal ; dendritic wedges ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of both enantiomers of 2-(benzyloxy)-1- [3,5-bis[[3,5-bis(benzyloxy)]benzyloxy]benzyloxy]-3-[[3,5-bis(benzyloxy)]benzyloxy] propane (S-7 and R-7) are described. The chirality is based on the linkage of three constitutionally different, but chemically similar, dendritic wedges with a chiral glycerol derived core. Both enantiomers are synthesized from the same starting material: S-(+)-Solketal. Despite their enantiomeric purity, S-7 and R-7 lack any optical activity and may be regarded as the first macromolecular analogues of the well-known organic molecules with “accidental degeneracy” or “cryptochirality.” Chirality 10:46-52, 1998. © 1998 Wiley-Liss,Inc.
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  • 145
    ISSN: 0899-0042
    Keywords: grazing-incidence X-ray diffraction ; topochemical photodimerization ; 4-alkoxycinnamic acid ; 4-alkoxycinnamamide ; 2-D crystallites on water surfaces ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A direct relationship between the structures of two-dimensional (2-D) crystallites of 4-octadecyloxy-E-cinnamic acid and 4-octadecyloxy-E-cinnamamide amphiphiles at the air-water interface and their photochemical behavior, is presented. The detailed packing arrangements of the monolayers were determined, close to the atomic level, from the diffraction pattern measured, in situ on the water surface, by the grazing incidence X-ray diffraction (GID) technique using synchrotron radiation. The products of the photochemical reaction, performed by irradiating the monolayer films directly on the water surface, were collected and analyzed. While the acid crystallites yield a β-truxinic acid product together with the cis-isomer, the amide undergoes only trans-cis isomerisation, in full agreement with the 2-D crystalline packing arrangements of the two amphiphiles on the water surface. Chirality 10:60-65, 1998. © 1998 Wiley-Liss,Inc.
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  • 146
    ISSN: 0899-0042
    Keywords: capillary electrophoresis ; enantiomer separation ; chiral drugs ; γ-cyclodextrin ; gamma-cylcodextrin ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Following an extended chiral drug screening program by capillary zone electrophoresis (CZE), the enantioseparation of 86 racemic drugs was tested with γ-cyclodextrin as a chiral solvating agent. Unified conditions were applied to all experiments. In total, 18 drug racemates were separated, 13 entries thereof that had not been separated at the lower CSA concentration applied in an earlier stage of the project. A comparison of the data with the results obtained for α- and β-cyclodextrin points to the significance of partial penetration (“side-on binding”) of aryl groups into the cyclodextrin cavity. Chirality 10:548-554, 1998. © 1998 Wiley-Liss, Inc.
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  • 147
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    Chirality 10 (1998), S. 78-87 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The syntheses of two types of conformationally switched podand ionophores and their ionophoric properties are described. Both feature cyclohexane rings with polyether groups as trans 1,2 substituents. In the “switched off” forms of the ionophores, the two podand substituents are constrained to a diaxial orientation and cannot chelate a metal ion. In both cases, a chemical reaction, hydrolysis of a ketone acetal, is used to remove the constraint allowing the two podand substituents to achieve a diequatorial orientation. In this conformation, the two diequatorial podand substituents can chelate a potassium ion and the ionophoric properties are “switched on.” In one case, the chains can be held in the diaxial orientation by a large group, an acetyle group derivatized as the ethylene glycol acetal, in the 4 position. When the size of the group is lowered, the polyether groups become equatorial and can complex a potassium ion as evidenced by a conformational change measured by low temperature NMR spectroscopy. In the second example, an annulated ring holds the cyclohexane ring rigidly in the non-complexing conformation. When the restraint is removed, complexation can occur as evidenced by transport of potassium picrate through a liquid membrane (chloroform layer). In both cases, the ionophoric properties are “switched on” by hydrolysis of a ketone acetal. Chirality 10:78-87, 1998. © 1998 Wiley-Liss, Inc.
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  • 148
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    Chirality 10 (1998), S. 88-90 
    ISSN: 0899-0042
    Keywords: allylic oxidation ; dihydroxylation ; chiral lactam ; chiral indolizidines ; phenyl glycinol ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The concise and highly diastereoselective synthesis of the titles azasugars was accomplished using nonracemic bicyclic lactams. Chirality 10:88-90, 1998. © 1998 Wiley-Liss, Inc.
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  • 149
    ISSN: 0899-0042
    Keywords: β-lactams ; carbapenem antibiotics ; titanium enolates ; imines ; stereoselective synthesis ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A short stereoselective synthesis of the acetoxy azetidinone (1), an important precursor of several biologically active β-lactam antibiotics, has been accomplished in seven steps and 32.8% overall yield from the easily available and inexpensive (R) ethyl 3-hydroxybutanoate. Chirality 10:91-94, 1998. © 1997 Wiley-Liss, Inc.
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  • 150
    ISSN: 0899-0042
    Keywords: chiral separation ; chiral stationary phases ; hydroxyphosphonates ; chiroptical study ; enantiomeric excess ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantiomers of 17 α-hydroxybenzylphosphonate diethylesters containing para, or ortho substituents or other aromatic rings (1-naphthyl, 2-naphthyl, and 2-thienyl) have been successfully separated by HPLC on a Whelk-O 1 chiral stationary phase which is superior to other CSPs. The effect of the substituents, particularly halogens, on the enantioselectivity was investigated and related to a chiral recognition model. The absolute configurations of 4-methyl and 2-methyl substituted α-hydroxybenzylphosphonates were obtained by measurement of the circular dichroism spectra of the isolated enantiomers. Chirality 10:100-105, 1998. © 1998 Wiley-Liss,Inc.
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  • 151
    ISSN: 0899-0042
    Keywords: 1,4-benzoxazine-2-carboxylic acids ; X-ray crystal structure determination ; 1-phenylethylamine ; 2-amino-1,4-benzoxazin-3-ones ; racemization ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Both enantiomers of 2-methyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazine-2-carboxylic acid 2 and 2,4-dimethyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazine-2-carboxylic acid 3 were prepared via resolution of the corresponding racemic carboxylic acids with (R)- and (S)-1-phenylethylamine, respectively. Absolute configuration of (-)-(R)-2-methyl-3-oxo-3,4-dihydro-2H-1,4-benzoxazine-2-carboxylic acid was determined by X-ray crystallography. Curtius rearrangement of acyl azides prepared from enantiomers of these heterocyclic carboxylic acids carried out in benzyl alcohol afforded enantiomers of the corresponding benzyl carbamates, which upon hydrogenolysis gave racemic 2-amino-2-methyl-3,4-dihydro-2H-1,4-benzoxazin-3-one 4 and 2-amino-2,4-dimethyl-3,4-dihydro-2H-1,4h-benzoxazin-3-one 5. Chirality 10:791-799, 1998. © 1998 Wiley-Liss, Inc.
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  • 152
    ISSN: 0899-0042
    Keywords: β2-agonist drugs ; sulfotransferase ; M-form phenolsulfotransferase ; sulfation ; isoproterenol ; metaproterenol ; terbutaline ; albuterol ; salbutamol ; salmeterol ; formoterol ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The β2-receptor agonist class of drugs is metabolized in humans almost exclusively by sulfate conjugation. The objective of this investigation was to determine the influence of chemical structure on the stereoselectivity of the sulfoconjugation of these chiral drugs. The pure enantiomers of six β2-agonists, including those clinically most widely used, were all effectively sulfated both by the cytosol of the human intestine and the recombinant human M-form phenolsulfotransferase (PST). Whereas the apparent Km values (Km,app) for the sulfation of the individual drug enantiomers by the intestinal cytosol varied widely, ranging from 4.8 μM for (S)-isoproterenol to 889 μM for (S)-albuterol, these Km,app values were highly correlated with those obtained with M-PST (correlation coefficient 0.994). In contrast, the M-PST Vmax,app values were similar for all drug enantiomers, ranging from 276 to 914 pmol min-1 mg-1 protein, implying that substrate binding to M-PST by far is the main determinant of the sulfation activity. For isoproterenol, the Km,app for M-PST was 6.1 times higher for the active (R)- than for the inactive (S)-enantiomer. For other β2-agonists, the stereoselectivity decreased towards unity as the Km,app increased. However, for albuterol, containing a hydroxymethyl substituent at the aromatic ring, the stereoselectivity was dramatically reversed, with 10 times higher Km,app for the inactive (S)- than for the active (R)-enantiomer. Chirality 10:800-803, 1998. © 1998 Wiley-Liss, Inc.
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  • 153
    ISSN: 0899-0042
    Keywords: 2,3-epoxyalcohols ; enantiomeric elution order ; protective groups ; chain length influence ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of 2,3-epoxy alcohol derivatives (1-16), obtained either as racemates or through the Sharpless asymmetric epoxidation reaction, were studied on a Chiralcel OD column. Nearly all compounds exhibit good enantioselective resolution on this chiral support. The order of elution of enantiomers is reversed between nerol and geraniol compounds. For 2,3-epoxy alcohols bearing a remote alkoxy (or silyloxy) group, the order of the enantiomeric elution alternates with the number n (n = 1-3) of methylenic groups present between the epoxide ring and the terminal OR (R = p - BrBn or OSitBuPh2) functionality. In the case of trans 2,3-epoxy alcohols for the same number n, the order of elution is reversed when changing the terminal group -OSi to -OR. The latter group greatly improves the separation of the two enantiomers. Chirality 10:804-807, 1998. © 1998 Wiley-Liss, Inc.
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  • 154
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    Chirality 10 (1998), S. 1-2 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 155
    ISSN: 0899-0042
    Keywords: quinuclidine derivatives ; chromatographic separation ; borane complexes ; fractional crystallization ; resolution ; X-ray crystallography ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The four stereoisomers of the antimuscarinic 3-(2,3-dihydrobenzofuran-2-yl)quinuclidine have been prepared by a method involving chromatographic separation of the racemic diastereoisomers as borane complexes. The relative and absolute configurations of the stereoisomers were determined by X-ray crystallographic methods. The crystal structure of (2′R,3R)-3-(2,3-dihydrobenzofuran-2-yl)quinuclidine · HCl · H2O contains two independent molecules with different conformations of both the quinuclidine moiety and the dihydrofuran ring. Chirality 10:813-820, 1998. © 1998 Wiley-Liss, Inc.
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  • 156
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    Chirality 10 (1998), S. 405-414 
    ISSN: 0899-0042
    Keywords: chiral-discrimination ; homochirality ; stereospecificity ; self-assembly ; supercoiling ; cholesteric mesophase ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nucleic acids are characterized by a predominant right-handed helical configuration that derives from the chirality of the sugar moiety. Hitherto, only “local” effects of this helical asymmetry, exemplified by DNA interactions with small compounds, have been documented. The results described in this study indicate that an enhanced asymmetry is required for the manifestation of chiral effects in DNA self-assembly processes or for chiral discrimination upon interactions with peptides. Two cases in which the intrinsic DNA asymmetry is enhanced are reported: rod-like superhelical species derived from linear DNA molecules, and topologically constrained supercoiled DNA. In the first case, the superhelical grooves within the DNA rods allow for a stereospecific complexation with peptides, resulting in chiral discrimination. In the second case, it is shown that the properties of cholesteric assemblies derived from supercoiled DNA are strictly determined by the enhanced asymmetry associated with molecular supercoiling. The results allow for new reflections on the concept of molecular complementarity, and indicate that spontaneously obtained chiral DNA mesophases might have played a key role in determining terrestrial homochirality. Chirality 10:405-414, 1998. © 1998 Wiley-Liss, Inc.
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  • 157
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    Chirality 10 (1998), S. iii 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 158
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    Chirality 10 (1998), S. 169-172 
    ISSN: 0899-0042
    Keywords: stereochemistry ; chirality ; circular dichroism ; isoquinoline ; enantiomers ; alkaloids ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Circular dichroism (CD) spectra were determined for the bioactive (+)-enantiomers of 1 · HCl, 3 · HCl, and 4 · HBr to characterize the chiroptical properties of these pyrroloisoquinoline antidepressants. The compounds showed a low-intensity negative CD band with much fine structure between 252 and 272 nm, a medium negative CD band with fine structure between 215 and 225 nm, and a high-intensity negative CD maximum between 198 and 203 nm. Except for amplitude variation, the three CD spectra were essentially superimposable in sign and position of the bands. The CD curves for the (-)-enantiomers of 1 · HCl and 4 · HBr were opposite in sign and comparable within 5% to the (+)-enantiomers. The results are consistent with the previously assigned (Maryanoff et al. J. Med. Chem. 30:1433-1454, 1987) absolute configurations of (6S, 10bR) for 1 and 3, and (6R, 10bR) for 4. Chirality 10:169-172, 1998. © 1998 Wiley-Liss, Inc.
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  • 159
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    Chirality 10 (1998), S. 173-179 
    ISSN: 0899-0042
    Keywords: chirality at low and high resolution ; functional groups ; fuzzy density fragments ; continuum models ; fuzzy sets ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mislow's Label Paradox and the chirality preserving or abandoning properties of deformation paths of polyhedral models are extended to simple representations of electron density continua of molecules. Chirality 10:173-179, 1998. © 1998 Wiley-Liss, Inc.
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  • 160
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    Chirality 10 (1998), S. 180-189 
    ISSN: 0899-0042
    Keywords: hypercoordinate silicon in naphthylsilanes ; X-ray structures ; NMR spectra ; reinterpretation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hexacoordinate silicon has been claimed to occur in bis(8-dimethylamino-naphth-1-yl)silanes on the basis of X-ray data and NMR spectra. Very much the same effects are shown by a bis(8-dimethylamino-naphth-1-yl)carbinol, pointing to essentially the same bonding in the Si and C compounds. Faced with the choice that either the carbon in the carbinol is hexacoordinate, too, or that the silicon in the silanes is, in fact, tetracovalent, we prefer the latter conclusion. Chirality 10:180-189, 1998. © 1998 Wiley-Liss, Inc.
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  • 161
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    Chirality 10 (1998), S. 190-193 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 162
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    Chirality 10 (1998), S. 53-59 
    ISSN: 0899-0042
    Keywords: macromolecular chirality ; chiral dendrimers ; cryptochirality ; fuzzy chirality ; starburst polymers ; cascade polymers ; chiral catalysts ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation, chiroptical properties and potential application of chiral dendritic polymers are reviewed. Mislow's analysis of the manifestation of chirality, cryptochirality and fuzzy chirality is useful in studying these unique chiral macromolecules. Chirality 10:53-59, 1998. © 1998 Wiley-Liss,Inc.
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  • 163
    ISSN: 0899-0042
    Keywords: polymers ; polyisocyanates ; helical conformation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A class of polymers synthesized at DuPont in the late 1950's, the polyisocyanates, are the simplest analogs of the Nylons and have proven valuable as experimental models for theories of wormlike macromolecules. The macromolecular dimensional properties associated with all wormlike polymers arise from a strongly preferred local conformation of the chain and in the polyisocyanates this conformation is helical with an interesting additional property in that the mirror helical senses are of equal probability. Recent experiments have shown that discrimination between the helical senses can be accomplished with surprisingly small chiral influences indicating high cooperativity which arises from a conformational state in which long sections of one helical sense are separated from the other sense by infrequent helical reversals. This can be seen to be analogous to theoretical ideas about one-dimensional paramagnetic materials in which the spin states and the domain boundaries are analogs to the helical sense and the helical reversals in the polyisocyanates. The mathematical formalisms of the one-dimensional magnetic materials precisely describe the chiral properties of the polyisocyanates. Chirality 10:41-45, 1998. © 1998 Wiley-Liss,Inc.
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  • 164
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    Chirality 10 (1998), S. 722-725 
    ISSN: 0899-0042
    Keywords: R- and S-isomer ; chiral compound ; enthalpy of mixing ; propane-1,2-diol ; methyllactate ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enthalpies of mixing of chiral isomers R- and S- of propane-1,2-diol and methyllactate, respectively, have been measured over the whole range of mole fraction at 298.15 K. All the enthalpies of mixing measured are very small. The enthalpic differences between the interactions of molecules of like-configuration and those of opposite configuration have been evaluated precisely. Mixing of R- and S-enantiomers of propane-1,2-diol gives slight enthalpic stabilisation over the whole range of mole fraction, however methyllactate has shown the opposite effect on mixing. Chirality 10:722-725, 1998. © 1998 Wiley-Liss, Inc.
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  • 165
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    Chirality 10 (1998), S. 246-252 
    ISSN: 0899-0042
    Keywords: sulfoxides ; chloroperoxidase ; asymmetric oxidation ; enantioselective ; episulfide ; gas chromatography ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Asymmetric sulfoxidation by means of a chloroperoxidase from Caldariomyces fumago and hydrogen peroxide as the oxygen source was studied for a series of sterically well-defined substrates. The stereochemistry of the sulfoxidation was the same for all substrates studied. While 2,3-dihydrobenzo[b]thiophene (1) is an excellent substrate (giving 99.5% yield and 99% e.e. of the (R)-sulfoxide), replacement of a methylene group by either a more sterically demanding group or a heteroatom caused a substantial decrease in reactivity or in reactivity as well as enantioselectivity. A further investigation of the lowered catalytic efficiency of chloroperoxidase with these substrates has been carried out in a series of competitive reactions. Thus, benzo[1,3]oxathiole (5) acted as a competitive inhibitor of the enzyme, whereas 1-thiochroman (2) and 1-thiochroman-4-one (3) were shown to be too sterically demanding to significantly compete for the active site. For the oxidation of 2, 3, and 5, it was found that in the low CPO concentration range the chemical yield after 60 min reaction time increased almost linearly with the amount of CPO used. The products from 2 and 3 could be obtained in over 80% yield with an e.e. exceeding 96%. Chloroperoxidase was also found to be an effective catalyst in the oxidation of labile episulfides, yielding the corresponding anti-sulfoxides quantitatively and giving 12% e.e. of (1R, 2R)-sulfoxide in the oxidation of propylene sulfide. Chirality 10:246-252, 1998. © 1998 Wiley-Liss, Inc.
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    Chirality 10 (1998), S. 273-280 
    ISSN: 0899-0042
    Keywords: direct chiral separation ; mobile phase composition ; NSAIDs ; retention model ; vancomycin ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fused silica-packed capillary columns containing vancomycin immobilized by reductive amination on an aldehyde-silica were used to separate enantiomers of some non-steroidal anti-inflammatory drugs. Attempts have been made to qualitatively explain the influence of various mobile phase compositions on the enantioselective retention. The effects of mobile phase pH, buffer, and organic modifier concentrations were investigated as well as the influence of salts of hydrophobic ions added to the mobile phase to induce ion pair retention. Chirality 10:273-280, 1998. © 1998 Wiley-Liss, Inc.
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  • 167
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    Chirality 10 (1998), S. 262-272 
    ISSN: 0899-0042
    Keywords: airway ; beta2-agonist ; racemic ; eutomer ; distomer ; hyperreactivity ; bronchospasm ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Airways of asthma patients can become hyperresponsive to airway spasmogens following regular use of isoprenaline or β2-selective sympathomimetics. Hyperreactivity that results from acute exposure of animals to these drugs is pre-empted by vagal section (a procedure which does not influence spasmolytic efficacy of sympathomimetics), is not diminished by antagonism of β2-adrenoceptors and is not associated with loss of responsivity of β2-adrenoceptors in the airways. Since activation, modulation, or blockade of β2-adrenoceptors does not determine this form of hyperreactivity, the possibility that distomers may induce hyperreactivity must be considered. Ocular and vascular responses to distomers of sympathomimetics have long been recognised and, more recently, comparable observations have been made for the airways. Thus, reactivity of guinea-pig airways to spasmogens was increased following exposure to S-isoprenaline, S-salbutamol, or S-terbutaline and exposure to S-isoprenaline or S-salbutamol can intensify symptoms in asthmatics. Regular exposure to the racemate, especially during or following an allergic reaction, predisposes to expression of hyperreactivity, which is nullified, acutely, by the eutomer. These observations imply that biological effects of sympathomimetic distomers may contribute to morbidity and mortality in asthma patients. Chirality 10:262-272, 1998. © 1998 Wiley-Liss, Inc.
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    Chirality 10 (1998), S. 281-281 
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 169
    ISSN: 0899-0042
    Keywords: chiroptical properties ; Cotton effect ; atropisomerism ; quantum-mechanical calculation ; AM1 ; CNDO/S ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rotational strengths calculated on the basis of quantum-mechanically obtained minimum energy geometries were used to determine the absolute configurations of axially chiral 3-aryl-4(3H)-quinazolinones from the sign of the observed Cotton effects (CEs). For the spectral data, CNDO/S calculations were used; for the geometries, ab initio (RHF/6-31G) and semiempirical (AM1) theories were used. Oscillator and rotational strengths of all excited states down to 200 nm were compared to experimental absorption and circular dichroism (CD) data. It was found that the sign of the 1Lb Cotton effects obtained for the enantiomers of methaqualone and derivatives of 3-aryl-2-alkylthio-4(3H)-quinazolinones can be correlated unambiguously with the absolute configuration. Furthermore, the sign of the Cotton effect of the π-π* transition of the thiocarbonyl chromophore of 3-aryl-2-mercapto-4(3H)-quinazolinones is suitable for a successful stereochemical correlation. Chirality 10:253-261, 1998. © 1998 Wiley-Liss, Inc.
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    Chirality 10 (1998), S. 289-293 
    ISSN: 0899-0042
    Keywords: chirality ; time reversal symmetry ; asymmetric synthesis ; enantiomerism ; isomerism ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: If a molecule is identified not only by its static spatial constructions, but also by the motions at the sub-molecular level, application of time reversal symmetry operation to a certain molecule could lead to another distinguishable from the original in the sense of sub-molecular motions, a phenomenon now defined as time reversal isomerism. Assessment of the consideration of certain enantiomers as distinguishable time reversal isomers is suggested in order to evoke a comprehensive interpretation of a likely correlation between the two types of isomerisms. The conceptual basis of a connection between absolute asymmetric synthesis under the influence of external fields and the intrinsic time reversal symmetry violation at the molecular level is also established to encourage new experimental investigations on this theme. Chirality 10:289-293, 1998. © 1998 Wiley-Liss, Inc.
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  • 171
    ISSN: 0899-0042
    Keywords: chiral HPLC ; cellulose carbamates ; enantiomeric resolution ; warfarin ; flurbiprofen ; lorazepam ; oxazepam ; pindolol ; tertatolol ; nicardipine ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four cellulose mixed 10-undecenoate/carbamate derivatives, simultaneously bearing 10-undecenoyl and variously substituted phenylaminocarbonyl groups, were chemically bonded on allylsilica gel. The study of the effect of these substitutions on the performance of the resulting chiral supports, and a comparison with the recently described 10-undecenoate/3,5-dimethylphenylcarbamate derivative, are presented. In this study heptane/2-propanol or heptane/chloroform mixtures were used as mobile phases. Chirality 10:283-288, 1998. © 1998 Wiley-Liss, Inc.
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  • 172
    ISSN: 0899-0042
    Keywords: cellulose ; regioselective derivatization ; chiral stationary phases ; liquid chromatography ; enantioseparation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various cellulose-2,3-bis-arylcarbamate-6-O-arylesters and cellulose-2,3-bis-arylester-6-O-arylcarbamates, designed to test the possible combined effects of the known tris-arylcarbamate and tris-arylester classes, were synthesized with high regioselectivity at O-C(6), and their use as CSPs in liquid chromatography for enantiomeric separations was investigated. The separations obtained with the synthesized CSPs were compared to the separations achieved on a self-packed reference column, consisting of cellulose-tris-(3,5-dimethylphenyl-carbamate) as CSP standard. Among the synthesized, regioselectively substituted cellulose derivatives, 2,3-bis-O-(3,5-dimethylphenylcarbamate)-6-O-benzoate-cellulose and 2,3-bis-O-(benzoate)-6-O-(3,5-dichlorophenylcarbamate)-cellulose gave the best CSPs for the separation of the test racemates. CSPs from regioselectively substituted cellulose derivatives seem to exhibit higher selectivities than cellulose-tris-(3,5-dimethylphenylcarbamate) for certain classes of racemic compounds. Chirality 10:294-306, 1998. © 1998 Wiley-Liss, Inc.
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  • 173
    ISSN: 0899-0042
    Keywords: configurational stability ; pH ; temperature ; ionic strength ; phosphate buffer concentration ; plasma protein affinity ; native cyclodextrins ; cyclodextrin derivatives ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The configurational stability of (+)- and (-)-diethylpropion [(+)- and (-)-2-(diethyl)-1-phenyl-1-propanone or (+)- and (-)-DEP] was investigated systematically from chemical, pharmaceutical, and pharmacological aspects. The enantiomeric ratio was monitored directly with a recently developed stability-indicating enantioselective HPLC method.In aqueous solutions, the rate of racemization increased non-linearly with increasing pH and with increasing phosphate buffer concentration. The racemization rate showed a positive slope with increasing temperature and decreasing ionic strength.The racemization rates of (+)- and (-)-DEP in the presence of cyclodextrins (CDs) did not differ significantly. CDs that were added to (+)- and (-)-DEP in a molar ratio 5:1 showed the following effects after dissolution in 10 mM phosphate buffer (final pH 6.7): sulfobutyl ether-β-CD (SBE-β-CD) and methylated-β-CD (Me-β-CD) retarded racemization; whereas hydroxypropyl-β-CD (HP-β-CD), acetyl-γ-CD (Ac-γ-CD), acetyl-β-CD (Ac-β-CD), γ-CD, and β-CD showed a weak destabilising effect. In contrast to the described CDs, α-CD distinctly accelerated the rate of racemization.The configurational stability of (+)- and (-)-DEP was also studied under physiological conditions. The half-life of racemization in heparinised human plasma was for both enantiomers determined to be approximately 23-25 min.In phosphate buffer (10 mM, pH 7.4), rac-DEP showed a high, but unselective affinity towards human α1-acid glycoprotein (orosomucoid) immobilised on silica (Chiral AGP).The rate of racemization of the free base of (-)-DEP dissolved in organic solutions generally increases with the polarity of the solvating agent. Chirality 10:307-315, 1998. © 1998 Wiley-Liss, Inc.
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  • 174
    ISSN: 0887-6266
    Keywords: liquid crystal ; block copolymer ; polyester block ; polymethacrylate block ; magnetic field ; X-ray diffraction ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phase and orientational behaviors of a series of liquid crystalline (LC) AB-type diblock copolymers comprising thermotropic main-chain (MC) polyester and side-group (SG) polymethacrylate blocks were investigated by X-ray diffraction. The MC and SG blocks were phase separated and gave rise to their individual mesophases that coexisted at equilibrium. The samples were oriented by using either a magnetic field or a mechanical field. In magnetically aligned samples both the MC and SG microphases were oriented with their smectic planes orthogonal to the magnetic field direction, independent of the copolymer composition. Mechanically aligned, fiber samples showed different orientations of the MC and SG smectic planes for different sample compositions. In this case the disposition of the smectic planes of the MC and SG blocks was driven by the relative length of the two blocks. Some features of the X-ray patterns of the copolymers were compared to those of the MC and SG homopolymers. In addition, the MC smectic domains crystallized on annealing without affecting the orientation that had been achieved by applying a magnetic field. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 21-29, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 31-38 
    ISSN: 0887-6266
    Keywords: liquid crystals ; thermosets ; smectic epoxy ; nematic ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Deformation experiments were carried out for densely crosslinked smectic-like networks obtained from diepoxy monomers with twin mesogen architecture. For the initially unoriented smectic networks, the network could be aligned up to an orientation parameter of 0.35 by applying 8 MPa of external stress in the rubbery regime. X-ray diffraction measurements revealed that the deformed smectic network possesses both smectic-A like and smectic-C like structure. It is thought that after extension domains initially oriented parallel to the external stress displayed a smectic-A-like structure, whereas domains initially tilted with respect to the tensile direction showed a stress-induced smectic-C like structure. A smectic network oriented under a.c. electric fields with an orientation parameter of 0.4 had a smectic-A like structure and possessed linear elasticity in the rubbery regime. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 31-38, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 39-48 
    ISSN: 0887-6266
    Keywords: poly-p-phenylenebenzobisoxazole ; X-ray scattering ; transmission electron microscopy ; Young's modulus ; tenacity ; crystal size ; orientation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Morphological survey on new PBO fiber (Zylon®) was conducted by X-ray and transmission electron microscopic studies. Crystal size, orientation of the crystal, fibrils, microvoids, and fine structure were discussed. It was found that the molecule in the fiber showed high orientation (more than 0.99 in Hermann's orientation function for heat-treated fiber) and relatively small crystal sizes in the longitudinal (160 Å) and the transverse (110 Å) directions. Crystal modulus estimated by extrapolation to perfect orientation on the plot of the fiber modulus as a function of fiber orientation (Northolt's method) shows discrepancy from the crystal modulus directly obtained by X-ray scattering. This discrepancy means that the Northolt's model is insufficient to describe the Young's modulus of PBO fiber. Microvoids elongated to the fiber direction were examined by small-angle X-ray scattering and transmission electron microscopic methods. The diameter of the microvoids was 20 Å to 30 Å and the fiber had a very thin microvoids-free layer (0.2 μm). Preferential orientation of the a-axis of crystal in the fiber was also confirmed. Summarizing these results, a structure model of the PBO fiber was proposed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 39-48, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 991-997 
    ISSN: 0887-6266
    Keywords: poly(methyl methacrylate-co-lithium methacrylate)(P(MMA-co-LiMA)) ; ionomer ; polymer electrolyte ; ion content ; ion conductivities ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have prepared polymer electrolytes composed of poly(methyl methacrylate-co-lithium methacrylate) ionomer (P(MMA-co-LiMA)), low molecular weight PEG, and LiCF3SO3 salt. The ion groups in P(MMA-co-LiMA) could enhance the miscibility between the MMA units and PEG in the polymer electrolytes. This miscibility enhancement made the pathway of ion transport less tortuous, and consequently led to the increase in ion conductivity. The maximum ambient ion conductivities in these systems were measured to be in the range of 10-4-10-5 S/cm. The polymer electrolytes became transparent at the higher ion content owing to the enhanced miscibility. The mechanical stability of the polymer electrolytes was also improved through the introduction of ion groups into the PMMA. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 991-997, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1025-1035 
    ISSN: 0887-6266
    Keywords: polymer thin films ; thermosets ; microelectronics ; moisture ; physical aging ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In polymers for microelectronics applications, moisture is known to have a deleterious effect upon device reliability. In this paper, the moisture transport behaviors of a newly developed family of all-aromatic and aromatic/aliphatic copolyester thermosetting films were described. The moisture uptake as a function of temperature, relative humidity, sample thickness, and processing conditions were presented via conjugate moisture sorption tests.1 It was found that the post curing near but below Tg resulted in an increase in both total moisture uptake and diffusion coefficient due to the effect of physical aging and the generation of sample defect volume. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1025-1035, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1013-1024 
    ISSN: 0887-6266
    Keywords: nonlinear optical polymer ; pressure ; chromophore reorientation ; poly(alkyl methacrylates) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Activation volumes for chromophore reorientation were measured for a series of guest-host polymeric materials, indicating a significant coupling between chromophore motion and the glassy α and β relaxation dynamics of the polymer host. The specific systems studied were formed by individually dissolving N,N-dimethyl-p-nitroaniline (DpNA), 4-(dimethylamino)-4′-nitrotolane (DMANT), 4-(diethylamino)-4′-nitrotolane (DEANT), and 1-((4-(dimethylamino)phenyl)ethynyl)-4-((4-nitrophenyl)ethynyl)benzene (DMAPEANT) in poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), and poly(isobutyl methacrylate) (PiBMA). In each of these systems, the isothermal, sub-Tg decay of the second-order optical susceptibility χ(2) was monitored as a function of pressure using second harmonic generation. In each system, the observed decay of χ(2) was represented by a stretched exponential equation from which the decay time τ0 and decay distribution width βKWW were determined. For each dopant molecule, the decrease in activation volume with the increasing size of the polymer host's alkyl side group and the pressure dependence of βKWW were indicative of partial coupling between chromophore rotation and the glassy β relaxation dynamics of the polymer host. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1013-1024, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1037-1050 
    ISSN: 0887-6266
    Keywords: polymer glasses ; glass transition ; diluents ; antiplasticization ; mixtures ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A mathematical model to describe the specific volume of glassy mixtures of a polymer and a low molecular weight diluent or additive is presented. The model is based on understandable physical assumptions and relies on parameters that can be determined experimentally or estimated from methods available in the literature. The predictions of the model show good agreement with the experimental data for mixtures of four polymers with diluents that in the pure state are liquid, glassy, or crystalline. The observed negative departure from volume additivity, as defined by simple additivity of the specific volume of the pure glassy polymer and the pure amorphous diluent, is the result of the relaxation of the excess volume of the glassy mixture relative to the equilibrium state caused by mixing two components with different glass transition temperatures. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1037-1050, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1051-1060 
    ISSN: 0887-6266
    Keywords: polymer mixtures ; film casting ; solvent selectivity ; incompatibility ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Blends of polystyrene/poly(oxyethylene) (PS/POE) and polystyrene/poly-(methyl methacrylate) (PS/PMMA) have been obtained by casting from solution. Differential Scanning Calorimetry, Optical Microscopy, and Scanning Electron Microscopy showed that two incompatible polymers can present relatively good miscibility (formation of domains smaller than 5 μm) when the solvent from which the films are obtained does not present any noticeable selectivity towards the two polymers of the blends. An increase of the casting temperature increases the miscibility of PS and PMMA because the selectivity of the solvent used, towards these polymers decreases with increasing temperature. On the contrary, an increase of the casting temperature in the case of the PS and POE mixture decreases their miscibility because the selectivity of the solvent used increases with increasing temperature. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1051-1060, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1061-1080 
    ISSN: 0887-6266
    Keywords: polymer blends ; dilatometry ; free volume ; specific volume ; excess volume ; compressibility ; thermal expansivity ; equation of state ; scaling parameters ; crystallinity ; glass transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melt-miscible polymer blends of poly(ethylene oxide)/atactic poly(methyl methacrylate (PEO/a-PMMA)) were prepared by melt-mixing and characterized by pressure-volume-temperature (PVT) dilatometry in the pressure and temperature range of 0 to 200 MPa and 20 to 200°C, respectively. The PVT data were analyzed in terms of two equations of state (EOS). The empirical Tait EOS was applied in the glassy, semicrystalline, and equilibrium melt state, and the Simha-Somcynsky EOS theory was applied in the equilibrium melt and glassy state. The Simha-Somcynsky EOS theory contains a free volume function. The temperature, pressure, and composition dependence of the free volume fraction h calculated from the Simha-Somcynsky EOS theory was studied. As a function of blend composition we observe that the free volume fraction, thermal expansivity, and compressibility all deviate mainly positively from linearity while the specific volume deviates mainly negatively from linearity. These findings are reconciled with composition-dependent free volume parameters, the free volume and cell volume as well as with self- and cross-interaction parameters derived from the Simha-Somcynsky EOS theory as applied to polymer mixtures. Moreover, the pressure dependence of glass and melting transitions as well as crystallization kinetics have been investigated. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1061-1080, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 673-679 
    ISSN: 0887-6266
    Keywords: scanning force microscopy ; hectorite ; polystyrene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Many important layered silicate-polymer nanocomposite materials may be synthesized using an in-situ polymerization process. Using this technique, organic monomers are intercalated into the interlayer regions of the hosts, where subsequent polymerization may then occur. In this paper, we report on the in-situ polymerization of styrene in Cu(II)-exchanged hectorite thin films. Scanning force microscopy (SFM) images of the polymer surface reveal that the surface polystyrene is generally aggregated into groups of elongated strands. SFM imaging of the interclay regions, in conjunction with X-ray diffraction (XRD) and electron spin resonance (ESR) data, indicates that approximately 20-30% of these regions contain polystyrene, with minimal reduction in the majority of Cu2+ sites observed. XRD data shows little or no intercalation of the monomer into the true intergallery regions. Instead, the polymer likely forms in intercrystallite or planar defect regions. In addition, two distinct phases of polymeric material are found within these defect regions, a highly polymerized polystyrene in addition to a polystyrene form exhibiting greater material stiffness. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 673-679, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 693-703 
    ISSN: 0887-6266
    Keywords: phase separation ; NMR spectroscopy ; block copolymers ; reaction injection molding ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The microphase separation (MPS) in polyureas based on methylene diphenyl diisocyanate (MDI) hard segment, diethyltoluenediamine chain extender, and amino-terminated polypropylene glycol soft segment prepared by reaction injection molding (RIM) was studied by advanced solid-state NMR spectroscopy. Incomplete microphase separation leads to the presence of mobilized hard segments dispersed in the soft segment domains as well as immobilized soft segments residing in the hard domains. This is detected by 1H-NMR spectra recorded under spinning at the magic angle (MAS) as well as two-dimensional wide-line separation (WISE) NMR spectra. The sizes of the various domains as well as the interfaces between them are quantified by spin diffusion measurements. In this way the impact of annealing, method of polymerization, and hard segment content on MPS is studied. Whereas annealing at temperatures up to 170°C results in improving the MPS, major changes are observed after annealing at higher temperatures (190°C), where the system changes from “soft-in-hard” to “hard-in-soft” behavior. The MPS decreases with increasing hard segment content. The highest MPS is observed for solution polymerized samples. The various NMR experiments clearly reveal the nonequilibrium nature of RIM systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 693-703, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 681-692 
    ISSN: 0887-6266
    Keywords: high-density polyethylene ; nonisothermal crystallization kinetics ; plateau temperature ; regime transition ; crystallinity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The quiescent nonisothermal bulk crystallization kinetics of two high-density polyethylene resins were investigated by a modified light-depolarizing microscopy (LDM) technique. The technique allows studies at average cooling rates up to 2500°C/min. The polymer was found to crystallize at a pseudo-isothermal temperature even at these very high cooling rates. The overall bulk crystallization rate increased rapidly as the cooling rate and supercooling increased. Crystallization kinetics was analyzed by Avrami analysis. Avrami exponents near 3 suggested spherical growth geometry and instantaneous nucleation at predetermined sites. Observation of spherulites by optical microscopy together with a number density of spherulites that changed little with increase in cooling rate or supercooling supported this model of crystallization behavior. Analysis of the half-time of crystallization based on the Lauritzen and Hoffman secondary nucleation theory indicated that the regime II-III transition was found to occur at a degree of supercooling of approximately 22°C. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 681-692, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1107-1114 
    ISSN: 0887-6266
    Keywords: polyelectrolytes ; conformational change ; water-acetone mixture ; viscosity and conductivity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of a polyelectrolyte poly(methacryloylethyl trimethylammonium methylsulfate), PMETMMS, with molar masses Mw = 22-25 × 106 were examined with viscosity, static light scattering, and conductivity measurements in a water-acetone solvent. Because acetone is a nonsolvent for this polymer the measurements were performed to determine the influence of the solvent composition, the polymer concentration, and the presence of added ions on the conformation of the polyelectrolyte in mixed solvents. The possible influence of a hydrodynamic field on the polymer conformation was also studied. The viscosity of the polymer solutions as a function of polymer concentration, as well as of the solvent composition, was studied using a broad range of shear rates. When the mass fraction of acetone in the solvent, γ, is below 0.5, the solutions show a usual polyelectrolyte behavior. When γ ≥ 0.80, the polymer adopts a compact conformation. This is observed as a decrease of the radius of gyration, Rg, second virial coefficient, A2, the viscosity, and also as a change in the conductivity of the solution. The change in the polymer conformation may be induced also by dilution. When 0.60 ≤ γ 〈 0.80, a gradual decrease in the polymer concentration leads to a sudden decrease of the reduced viscosity, which indicates a decrease in the particle size. The values of Mw measured by static light scattering were constant in all experiments. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1107-1114, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 395-402 
    ISSN: 0887-6266
    Keywords: syndiotactic polypropylene ; form-IV ; form II ; kink bands ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The packing of the chains in (T6G2T2G2)n conformation of the form IV of s-PP is revisited on the basis of packing energy and structure factor calculations. According to this analysis, an alternative mode of packing has been suggested. A monoclinic structural model, with the unit cell centered on the C face, is obtained, after small changes of the atomic coordinates in the triclinic structural model as proposed by Chatani et al. The monoclinic model presents a lower packing energy than the triclinic model and a good agreement between the calculated and observed structure factors. The triclinic structural model implies that all the chains are rotated by the same amount around the chain axis with respect to the monoclinic structural model. Since clockwise and counter clockwise rotations are equivalent, the monoclinic structural model may be taken as descriptive of the order in the long range, for the form IV of s-PP, or in other terms, descriptive of an average structure (space group C2, unit cell constants equal to am = 14.17 Å, bm = 5.72 Å, cm = 11.6 Å, and βm = 108.8°). The triclinic structural model for this polymorph, instead (space group P1, unit cell constants equal to at = 5.72 Å, bt = 7.64 Å, ct = 11.60 Å, αt = 73.1°, βt = 88.8°, γt = 112.0°) is probably more properly descriptive of local situation of order (the symmetry, locally, is broken). Analogies between the monoclinic limit ordered structural model for the form IV and the orthorhombic limit ordered structural model for the form II (with chains in the more stable (TTGG)n conformation) of s-PP are also provided. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 395-402, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1153-1165 
    ISSN: 0887-6266
    Keywords: even-odd nylons ; lamellar crystals ; structure ; hydrogen-bonding schemes ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nylon 6 9 has been shown to have structures with interchain hydrogen bonds in both two and in three directions. Chain-folded lamellar crystals were studied using transmission electron microscopy and sedimented crystal mats and uniaxially oriented fibers studied by X-ray diffraction. The principal room-temperature structure shows the two characteristic (interchain) diffraction signals at spacings of 0.43 and 0.38 nm, typical of α-phase nylons; however, nylon 6 9 is unable to form the α-phase hydrogen-bonded sheets without serious distortion of the all-trans polymeric backbone. Our structure has c and c* noncoincident and two directions of hydrogen bonding. Optimum hydrogen bonding can only occur if consecutive pairs of amide units alternate between two crystallographic planes. The salient features of our model offer a possible universal solution for the crystalline state of all odd-even nylons. The nylon 6 9 room-temperature structure has a C-centered monoclinic unit cell (β = 108°) with the hydrogen bonds along the C-face diagonals; this structure bears a similarity to that recently proposed for nylons 6 5 and X3. On heating nylon 6 9 lamellar crystals and fibers, the two characteristic diffraction signals converge and meet at 0.42 nm at the Brill temperature, TB · TB for nylon 6 9 lamellar crystals is slightly below the melting point (Tm), whereas TB for nylon 6 9 fibers is ≅ 100°C below Tm. Above TB, nylon 6 9 has a hexagonal unit cell; the alkane segments exist in a mobile phase and equivalent hydrogen bonds populate the three principal (hexagonal) directions. A structure with perturbed hexagonal symmetry, which bears a resemblance to the reported γ-phase for nylons, can be obtained by quenching from the crystalline growth phase (above TB) to room temperature. We propose that this structure is a “quenched-in” perturbed form of the nylon 6 9 high-temperature hexagonal phase and has interchain hydrogen bonds in all three principal crystallographic directions. In this respect it differs importantly from the γ-phase models. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1153-1165, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1167-1189 
    ISSN: 0887-6266
    Keywords: poly(dimethylsiloxane) ; silica ; hydrolysis ; condensation ; gelation ; composites ; filled elastomers ; stress-strain isotherms ; reinforcement ; X-ray scattering ; neutron scattering ; fractal geometry ; disordered systems ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various synthetic protocols were used to prepare several classes of polysiloxane-silica filler systems. The structures of these fillers and their interactions with the polysiloxane matrices were studied using small-angle X-ray and neutron scattering. In addition, the mechanical properties of the composites were characterized using equilibrium stress-strain isotherms in elongation. The results indicated that manipulation of the chemical reactions used to generate the filler can lead to a wide range of complex structures and unusual properties. Some of the observed mechanical properties were correlated with information on the composite structures and on elastomer-filler interactions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1167-1189, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1201-1209 
    ISSN: 0887-6266
    Keywords: polymer electrolytes ; NMR ; conductivity ; glasses ; Arrhenius and VTF dependences ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have studied the temperature variation of conductivity and 1H NMR linewidth of (PEG)xNH4ClO4 (x = 20, 30, 46, 100, 200, & 1000) polymer electrolyte systems. The temperature dependence of the conductivity shows two distinct behaviors, the low temperature VTF dependence crossing over to Arrhenius dependence at higher temperatures. The departure from the VTF behavior is found to be composition dependent. NMR spectra indicate the presence of large fractions of crystalline regions that start to melt around the crossover temperature. We understand the deviation from the VTF behavior as a consequence of this crystalline to elastomer transition. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1201-1209, 1998
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 447-453 
    ISSN: 0887-6266
    Keywords: polyethylene terephthalate ; low density polyethylene ; isocyanate functional group ; compatibility ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To evaluate the compatibilizing effects of isocyanate (NCO) functional group on the polyethylene terephthalate/low density polyethylene (PET/LDPE) blends, LDPE grafted with 2-hydroxyethyl methacrylate-isophorone diisocyanate (LDPE-g-HI) was prepared and blended with PET. The chemical reaction occurred during the melt blending in the PET/LDPE-g-HI blends was confirmed by the result of IR spectra. In the light of the blend morphology, the dispersions of the PET/LDPE-g-HI blends were very fine over the PET/LDPE blends. DSC thermograms indicated that PET microdispersions produced by the slow cooling of the PET/LDPE-g-HI blends were largely amorphous, with low crystallinity, due to the chemical bonding. The tensile strengths of the PET/LDPE-g-HI blends were higher than those of the PET/LDPE blends having a poor adhesion. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 447-453, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 455-462 
    ISSN: 0887-6266
    Keywords: photoreactive polymer blends ; photocrosslinking kinetics ; photodimerization of anthracene ; Kohlrausch-Williams-Watts relaxation ; poly(vinyl methyl ether) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mixtures of polystyrene derivatives (PSCS) and poly(vinyl methyl ether) (PVME) were made photocrosslinkable by chemically labeling PSCS chains with photoreactive anthracene. Miscibility of these anthracene-labeled PSCS/PVME blends was examined by light scattering under several crosslinking conditions in the one-phase region via photodimerization of anthracenes. As the reaction proceeds, the coexistence curve of PSCS/PVME blends shifts toward the low temperature side. By following the changes in concentration of anthracenes with irradiation time, it was found that the crosslinking reaction of PSCS chains in the blends does not follow the mean-field kinetics. However, it can be well expressed by the Kohlrausch-Williams-Watts (KWW) relaxation mechanism, indicating that the crosslinking reaction proceeds inhomogeneously in the blends. By scaling the reaction time with the average reaction rate obtained from the KWW equation modified for the reaction kinetics, all the crosslinking data obtained in the miscible region of the reacted blends fall on a single master curve. These experimental results suggest the universal behavior of the photocrosslinking kinetics obtained under the “shallow quench” conditions in the region far away from the coexistence curve of the reacting blends. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 455-462, 1998
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  • 193
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1219-1225 
    ISSN: 0887-6266
    Keywords: poly(ethylene terephthalate) ; oligomer ; poly(ethylene glycol) ; epoxy resin ; concentrated solution ; crystallinity ; thermoreversible gel ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(ethylene terephthalate) (PET) was rapidly crystallized through thermoreversible gelation in a liquid ethylene glycol oligomer or in epoxy resin. The solutions formed gel rapidly on cooling. Polarized light microscopy and small-angle light scattering showed that these gels contain large, regular PET spherulites. The gels may be formed by two consecutive processes: the phase separation and crystallization, and gelation by formation of a three-dimensional PET network in the oligomer solvents, where the nodes of the network are PET spherulites. The crystallinity of PET recovered from polymer/oligomer gels is near 72% measured by wide-angle X-ray diffraction method, which is about 20% higher than PET samples crystallized by solution crystallization in small molecule solvent, high temperature annealing, and stretching techniques. It takes only a few minutes to form the highly crystalline phase PET in the PET/oligomer system, and the crystallinity of the dried gel is independent of the concentration of the original solution. Excimer-fluoresence and Raman spectroscopic studies indicated that PET recovered from the gels are in an ordered state with few chain entanglements. The entanglement density of the recovered PET recovered from a 20 wt % solution in ethylene glycol oligomer is as low as that of freeze-extracted PET from a 0.5 wt % solution in phenol. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1219-1225, 1998
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  • 194
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1227-1233 
    ISSN: 0887-6266
    Keywords: FTIR spectroscopy ; isotactic polystyrene ; crystallization process ; induction period ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melt crystallization process of isotactic polystyrene (i-PS) was studied by means of in situ Fourier transform infrared (FTIR) spectroscopy, with a focus on the conformational changes during the induction period. The spectra obtained during the induction period suggested the occurrence of some ordered structure that is characterized by higher regularity and packing of the helical moieties than observed in the melt. This ordered structure was clearly different from the amorphous structure, and close to the crystal structure. The Avrami analysis indicated that the formation process of the ordered structure at the late stage of the induction period is similar to the growth process of the crystallites after the induction period. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1227-1233, 1998
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  • 195
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 827-840 
    ISSN: 0887-6266
    Keywords: polyimides ; imidization ; perylenetetracarboxydiimide ; electron transfer ; fluorescence quenching ; polyimide blends ; miscibility ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Perylenetetracarboxydiimide (PEDI) molecularly dispersed in polyamic acid (PAA) and polyimide (PI) films has unique fluorescence properties. An originally strong fluorescence of PEDI is efficiently quenched in the PAA films. The systematic variation of the chain structure of the PAA matrices revealed that the aromatic amide groups in the PAA chains function as a quencher. When a PAA derived from 3,4,3′4′-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA), BPDA/PDA, was used as a matrix polymer, the fluorescence of the dye dispersed in the film increased abruptly as imidization of the matrix proceeds. But annealing at temperatures higher than 320°C in the step-heating process caused a gradual decrease in the fluorescence intensity. The decreased intensity results from the dye-PDA units interactions intensified by the denser molecular packing of the matrix polymer chains. PEDI shows significant dependence of the fluorescence intensity on the chain structure of the PI matrices. In the various PI films containing a fixed diamine component, the dye fluorescence intensity reduces linearly with an increase in the intramolecular charge transfer ability of the PI matrices. From the result, we propose a fluorescence quenching mechanism through multistep electron transfer processes. The BPDA/PDA polyimide matrix leads to a strong PEDI fluorescence whereas the pyromellitic dianhydride (PMDA)-based PI matrices do not. For the blends composed of these PIs, the fluorescence of PEDI bound into the main chains provides a valuable indicator of the miscibility on the molecular level. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 827-840, 1998
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  • 196
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 851-859 
    ISSN: 0887-6266
    Keywords: poly(aryl ether ketone)s ; dielectric relaxation spectroscopy ; dynamic mechanical analysis ; α-relaxation ; β-relaxation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relaxation behavior of four amorphous poly(aryl ether ketone)s was investigated using dielectric relaxation spectroscopy and dynamic mechanical analysis. The temperature dependence of the relaxation times of the glass transition process and the cooperative nature of this process were unaffected by changes in polymer structure. The temperature location of the loss peaks for all polymers progressed smoothly between the low frequency of the mechanical measurements and the higher frequencies of the dielectric probe. Differences were observed in mechanical activation energy and dielectric relaxation strength for one polymer which contained a significant concentration of meta linkages, compared with the para-linked polymers, while relaxation broadness was generally greater in the dynamic mechanical mode. Changes in chemical structure had little effect on the shape, intensity, and location of the β-relaxation peak, the main observation being that the Arrhenius activation energy measured by dynamic mechanical analysis was significantly higher than that calculated from the dielectric data. The dielectric β-relaxation was sensitive to absorbed moisture. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 851-859, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1275-1281 
    ISSN: 0887-6266
    Keywords: chitosan ; polyethylene glycol polyblend ; intermolecular interaction ; viscometry ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular structures of polyethylene glycol (PEG) and chitosan (CS) are illustrated as follows: 1CS2PEG\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm HO} \hbox{--} {\rm CH}_2 {\rm CH}_2 \rlap{--} ({\rm O} \hbox{--} {\rm CH}_2 {\rm CH}_2 \rlap{--} {\rm O} \hbox{--} {\rm CH}_2 {\rm CH}_2 \hbox{--} {\rm OH} $$\end{document} The intermolecular interactions between these two polymers were studied by viscometry with a thermodynamic parameter α, which was first proposed by Sun et al. The weight additive rule of the intrinsic viscosity of polyblend relating to the values of each polymeric constituent was attested to with PEG/CS polyblend. The calculation formula of Huggins coefficient for polyblend, km, was theoretically deduced, and a very simple expression of α was obtained. First, the values of α for PEG/CS blends with different PEG molecular weight were estimated from the experimental viscosity data of the polyblends with different mixed ratio. According to these values of α, it can be predicted that an attractive interaction exists between the molecule of PEG and that of CS. Second, the viscosity of CS was measured in pseudo-solvents (PEG dissolved in 0.01N sodium chloride aqueous solution) with different PEG concentrations. From these viscosity data, the values of cross Huggins coefficient are calculated to be all larger than the values of the Huggins coefficient both for CS and for PEG. On the revised α criterion, the dissimilar molecular interaction in PEG/CS polyblend is demonstrated to be attractive too. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1275-1281, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 537-542 
    ISSN: 0887-6266
    Keywords: sulfonated polyelectrolytes ; gelatin ; complex stoichiometry ; size-exclusion chromatography ; flow field-flow fractionation ; hydrodynamic size ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 543-553 
    ISSN: 0887-6266
    Keywords: polyacrylonitrile ; polyimine ; isotacticity ; dynamic mechanical analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyacrylonitrile (PAN) films have been “grafted” onto copper electrodes by cathodic polarization and analyzed by infrared spectroscopy and dynamic mechanical thermal analysis (DMTA). The dynamic mechanical response shows two or three transitions depending on the film thickness and the potential deposition. The viscoelastic properties of “ungrafted” PAN films, e.g., solvent cast films of commercially available PAN, are deeply different from those of “electrografted” films. The experimental data support that “ungrafted” chains are paracrystalline in contrast to the “grafted” ones which are essentially amorphous. Moreover, the irreversible transformation of the “grafted” PAN chains observed beyond 225°C is confirmed by Fourier transform infrared (FTIR) analysis and ascribed to an intramolecular cyclization of PAN into polyimine. This reaction occurs rapidly and at a comparatively low temperature with respect to “ungrafted” PAN, which suggests that the “grafted” chain configuration might be predominantly isotactic. The isotacticity and the amorphous structure appear to decrease as the thickness of the PAN film is increased. Literature data and the herein reported observations would suggest a dependence of the amorphous structure of PAN on the chain isotacticity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 543-553, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 555-565 
    ISSN: 0887-6266
    Keywords: polyester ; annealing ; birefringence ; mechanical loss factor ; orientation ; density ; crystalline ; profile ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyester (Egyptian) fibers were annealed at constant temperature (190°C) with different annealing times. Density, crystallinity, mean square density fluctuation, mechanical loss factor, and molecular orientation were calculated. Densities and mechanical loss factor were determined using an acoustic method. Changes in the molecular orientation were evaluated from the resulting optical data using the polarizing Pluta interference microscope. Correlation of data obtained by one method with another leads to relational changes in optothermal properties and in the molecular orientation. Changes of refractive index profiles of annealed PET fibers are provided. Illustrations using graphs and microinterferograms are shown. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 555-565, 1998
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