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  • 11
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Polymer International 35 (1994), S. 379-387 
    ISSN: 0959-8103
    Keywords: electrolyte ; latex ; particle size ; rate of polymerisation ; polydispersity ; adsorption ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effects of adding potassium chloride in concentrations below that required to coagulate the latex to recips of emulsion polymerisation of styrene have been investigated using different concentrations of potassium octadecanoate, which has a low critical micelle concentration (CMC), and potassium dodecanoate, which has a moderately high CMC. At relatively high concentration of octadecanoate the final particle size is significantly increased; the rate of polymerisation is initially increased but later retarded. The effects of increasing micelle size and increased rate of coalescence are dominant. At lower concentration of this emulsifier, the rate is reduced from the onset of interval II.With dodecanoate, concentrations of electrolyte up to 0.3 M accelerate the rate. No significant change in the particle size was observed up to 0.2M electrolyte, thereafter it slightly increased. The increase in micellar concentration can only partially account for these effects. It is believed that the increase in the amount of solubilised monomer inside the micelles, and later inside the latex particles, and the resistance to coalescence (because of the favourable adsorption mechanism of this emulsifier) may account for these observations.With both emulsifiers, electrolyte reduces the induction period and latices with narrow particle size distributions are produced.
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 192 (1991), S. 405-414 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In both thermal emulsion polymerization of styrene in the temperature range 60-80 °C, and peroxodisulfate-initiated polymerization at 60 °C, weight-average to number-average molecular-weight ratios (M̄w/M̄n) approach 1,5 when potassium octadecanoate is used as emulsifier. A low activation energy for thermal initiation (≈66,0 kJ/mol) was deduced which may indicate a catalytic effect of the emulsifier during the thermal initiation process. Participation of the emulsifier is probably attributed to a transfer of one of two monomer radicals, produced thermally, to the emulsifier, with subsequent desorption to the aqueous phase, leaving one radical in the polymerization locus.
    Additional Material: 4 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 1407-1412 
    ISSN: 0887-624X
    Keywords: radiochemical grafting ; anion exchange membrane ; acid dialysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the preirradiation technique a kinetic study of the grafting of the 4-vinyl pyridine (V4P) and an aliphatic ammonium monomer (ALAM) onto the copolymer film of ethylene-tetrafluoroethylene (ETFE) has been performed. The influence of dose, temperature, and concentration of monomer, reticular agent, and inhibitor were investigated. The results are discussed on the basis of the interactions between monomer diffusibility and viscosity of the medium. The characteristics of some membranes were determined. Their applicability to the recovery of acid by dialysis is demonstrated.
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  • 14
    ISSN: 1040-7685
    Keywords: fullerene-linked polymer ; fullerene-linked silica ; synthesis ; stationary phases ; microcolumns ; polycyclic aromatics ; polychlorinated biphenyls ; environmental contaminants ; liquid chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fullerenes (C60 and C70) linked to small silica or polymer particles provide novel chromatographic stationary phases with electron donor/acceptor surface interactions that may parallel those of aromatic carbons. Separations of fullerenes and aromatic compounds frequently encountered as environmental contaminants were investigated using LC microcolumns containing either particles prepared from BrHC60 linked to amino-silica (Spherisorb-NH2, Phenomenex) or porous polymers containing ca. 12% fullerene by weight. The polystyrene divinylbenzene (PSDVB)-C60/70H column had greater capacity (k') than the Si—NH—C60/70H column. Toluene and polycyclic aromatic hydrocarbons (PAHs), naphthalene, anthracene, pyrene, and perylene, were retained in the order of increasing ring number; nitro-substituents increased retention; and chlorinated-dibenzo-p-dioxins and -dibenzofurans were more strongly retained than their parent compounds. PCB congeners with no chlorine in the ortho, ortho'-positions are co-planar and are strongly retained; for these isomers, retention increased with higher chlorination. We demonstrate that surface-linked fullerenes can also accommodate further chemical modification through the addition of 2-(4-nitrophenyl)ethyl or -NH—CH2CH2NH2 moieties to yield altered electron donor/acceptor affinity. Separations appear to be derived primarily from aromatic electron induced dipole-dipole or electron-pair donor or acceptor interactions (charge transfer complexes). Except for the fullerenes, surface interactions with compounds are largely suppressed with methylene chloride as the mobile phase.
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  • 15
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Heteroatom Chemistry 5 (1994), S. 175-191 
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first stable macrocycles, 12-15, 16, 18, and 23, containing pentacovalent phosphorus have been obtained by an Atherton-Todd reaction between the bis(hydridobicyclophosphoranes) 3-7 and the corresponding binucleophile HO—(CH2)2—X—(CH2)2—OH. The tricyclic monophosphoranes 8-11 as well as the noncyclic derivative 20 have also been isolated. A pathway that accounts for the formation of all these compounds is proposed. The X-ray crystal study of two 16-membered rings, 14, 15, confirms the diequatorial placement of the macrocyclic frame on the trigonal bipyramidal phosphorus which retains the most favorable axial-equatorial-axial annelation of the bicyclic moiety. Comparison of these two molecular structures points out the effect of the nature of X on the conformation of the macrocycle.
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  • 16
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 179-196 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To examine the importance of the aromatic side chains of enkephalin on opiate activity, we report the synthesis and conformational analysis of a series of analogues related to enkephalin with β-naphthylalanine in place of phenylalanine at the fourth position. Three linear analogues (Tyr-D-Ala-Gly-(L and D)-β Nal(1)-Leu-NH2 and Tyr-D-Ala-Gly-β Nal(2)-Leu-NH2) were initially synthesized to examine the effect of the substitution on biological activity. The increased activity of these peptides at the μ-opiate receptor, compared to native Leu-enkephalin, prompted us to examine the more conformational constrained analogues, Tr-c[D-A2bu-Gly-(L and D)-β Nal(1)-Leu], incorporating a α,γ-diaminobutyric acid at the second position and cyclization to the carboxylic end of the leucine. These two cyclic analogues provide insight into the necessity for the L chirality of the aromatic residue at position 4. The Tyr-c[D-A2bu-Gly-L-β Nal(1)-Leu] analogue is highly potent and displays a slight preference for the μ receptor. The conformational analysis indicates that despite the high flexibility of the tyrosine side chain, the aromatic rings of the tyrosine and naphthylalanine are relatively distant from each other. The presence of two intramolecular hydrogen bonds help maintain the conformation of the 14-membered backbone ring that keeps the side chains directed away from each other. These findings are in agreement with our model of an extended structure required for μ selectivity and a folded form with close aromatic ring placement for δ selectivity.
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  • 17
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to study structure-activity relationships of enkephalin-related analogues, we report the biological activity and conformational analysis of four 14-membered cyclic enkephalin analogues with β-(1-naphthyl)alanine in place of phenylalanine at the fourth position, Tyr-c[D-A2bu-Gly-(L and D)-βNal(1)-(L and D)-Leu]. The L-βNal(1)-containing analogues display higher activity at both the μ and δ receptors than the corresponding analogues with the L-Phe residue. In contrast to the linear enkephalins, the cyclic analogues with the D-βNal(1) residue are also active at the μ receptor since the relative spatial arrangement of functional groups required for biological activity is achieved by the constrained nature of the cyclic molecules. A comparison of the findings from the conformational analysis and biological assays establishes that relatively extended structures, in which the two aromatic side chains are oriented in opposite directions with a ∼ 14Å separation, is required for activity at the μ receptor. On the other hand, folded conformations with nearly parallel orientations and a close proximity ( 〈 10Å) of the aromatic rings of the Tyr and βNal(1) residues are required for activity at the δ receptor. It should be noted that the overall structures and thus the biological profiles of the 14-membered cyclic enkephalin analogues are strongly dependent on the conformation of the second residue. The folded conformations with parallel orientation of the two aromatic side chains of Tyr-c [D-A2bu-Gly-L-βNal (1)-D-Leu] is stabilized by an interaction between the Tyr phenolic OH proton and βNal(1) C*O groups. This analogue, which shows the highest activity at both the μ and δ receptors among the four stereoisomers studied, displays an increase of the fraction of the side-chain χ1 = t conformer for the βNal(1) residue. It is concluded that the incorporation of the D-Leu residue at the fifth position increases the relative fraction of the folded conformations with parallel orientation of the aromatic side chains, and hence enhances activity at the δ receptor as compared to the corresponding L-Leu containing analogue.
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  • 18
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have investigated the conformational effects of modifying the amide group in model dipeptides. The N-methyl amide ψ[CO-NMe], N-hydroxy amide ψ[CO-N(OH)], N-amino amide ψ[ CO-N (NH2)], retro amide ψ[ NH-CO], reduced amide in the neutral ψ[CH2-NH] and protonated ψ[CH2-N + H2] state, and hydrazide ψ[CO-NH-NH] have been introduced as surrogates of the amide link in pseudopeptide derivatives of the Pro-Gly or Ala-Gly model dipeptides protected on both termini by an amide group. These compounds have been studied in solution by proton nmr and ir spectroscopy, and in the solid state by x-ray diffraction, giving an extended data set of experimental structural and conformational information on pseudopeptide sequences. The conformational effects depend both on the nature and the position of the modified amide link. Some modifications appear to have no intrinsic conformational induction (N-amino and retro amide), but destabilize any local folded structure by hydrogen-bond breaking. Because of the formation of strong intramolecular interactions, others are capable of stabilizing a β-turn (for example protonated reduced amide), or of inducing a particular local conformation such as a β- or γ-like turn (for example N-hydroxy amide). The particular geometry of the cis N-methyl amide and of the “hydrazino” proline favors the formation of a sharp turn of the main chain. All these structural data are of interest to the design of bioactive peptide mimics. © 1993 John Wiley & Sons, Inc.
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  • 19
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 46 (1992), S. 1121-1124 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Additional Material: 5 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 195 (1994), S. 2947-2964 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Glycidyl (2,3-epoxypropyl) esters are convenient reagents for the fixation of carboxylic acid moieties on polymeric support of the polyacid type. This way of synthesis was applied to 1-naphthylacetic acid on poly(methacrylic acid). Esterification of 1-naphthylacetyl chloride by glycidol (2,3-epoxy-1-propanol) and addition of 1-naphthylacetic acid on epichlorohydrin (1-chloro-2,3-epoxypropane) with subsequent reformation of the oxirane ring have been used for the synthesis of the glycidyl ester but the reaction of the potassium salt of the acid with epichlorohydrin leads to a better yield. Addition of 1-naphthylacetic acid on glycidyl acetate was studied in N,N-dimethylformamide (DMF) and acetonitrile. The best results were obtained in DMF. The reaction is of first order with respect of epoxide, but 2nd order applies when the solvent is acetonitrile. The same reaction conditions as for glycidyl acetate were used for the chemical modification of poly(methacrylic acid) with glycidyl 1-naphthylacetate except that methanol was used as the solvent.
    Additional Material: 9 Ill.
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