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  • 1
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a study of A-B type block copolymers of γ benzyl-L-gultamate and β-benzyl-L-aspartate use has been made of the observations: (1) that for poly aspartate esters the chemical shifts of the α-CH and NH resonances are sensitive to the helix sense, (2) that in both helical and random coil conformations the same resonances of poly-γ-benzyl-L-glutamate are well separated from those of poly aspartates. Since the sense of poly-β-benzyl-L-aspartate is very sensitive to the inclusion of γ-benzyl-L-glutamate residues, the degree of overlap between the blocks can be studied by monitoring the helix sense of the aspartate. The ability of the NMR method to make separate observation of the two blocks removes the necessity of relying on an overall ORD parameter such as b0. The copolymers studied include those having lefthanded, righthanded, and mixed-sense aspartate, corresponding to differing degrees of overlap.
    Additional Material: 5 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 6 (1968), S. 837-850 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An alcoholysis method is described for the modification of high molecular weight poly(β-benzyl L-asparatate); by this method the benzyl groups in the polypeptide have been replaced by methyl, ethyl, isopropyl, n-propyl, and phenethyl groups to give a series of copolymers of each of the corresponding aspartate esters with benzyl L-aspartate. By repeating the reactions, replacement of better than 99% has been achieved in some cases to give in effect the homopolymer. Optical rotatory dispersion studies show that of all the systems studied only poly(β-methyl L-aspartate) has the left-handed helix sense, the others are right-handed. It is shown further that the helix sense is not an intrinsic property of the nature of the aspartate side chain. Raising the temperature of chloroform solutions of the right-handed form of the copolymers of benzyl L-aspartate and ethyl L-aspartate results in a transition to the left-handed helix, the temperature of the transition being dependent on the composition of the copolymer. Also poly(β-n-propyl L-aspartate) undergoes a transition from the right- to the left-handed helix form at 59°C. These results suggest a general pattern of behavior of poly(aspartate esters) and that with suitable conditions of solvent and temperature they may be in either the right- or left-handed helical form.
    Additional Material: 9 Ill.
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  • 3
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has already been show that the helix senses of poly(β-benzyl L-aspartate) and poly(β-methyl L-aspartate) are left-handed, while the poly esters of n-propyl, isopropyl, n-butyl, and phenethyl L-asparate are all right-handed. The effect of changes in helix sense from the left-handed to the right-handed α-helical form on the infrared spectra of copolymers of benzyl L-aspartate with ethyl, n-butyl, isopropyl, n-propyl, and phenethyl L-aspartate have been studied. Those show that for the right-handed helical form the amide band frequencies fall within the range given by Elliott,7 while for the left-handed form the frequencies are higher. The frequency ranges for the two helix senses are given and have been used to show that poly (β-n-propyl L-aspartate) in chloroform solution undergoes a transition from the right-handed to the left-handed helix form on heating. Polarized infrared studies of the different copolymers show that the disposition of the side chain ester groups is different for the two forms. Although methyl L-aspartate forms a left-handed α-helix similar to benzyl L-aspartate, the introduction of methyl L-aspartate residues into poly (β-benzyl L-aspartate) prevents the formation of the ω-helix. The factors involved in the formation of this helix form are discussed.
    Additional Material: 5 Ill.
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  • 4
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-resolution NMR is used to study two series of benzyl-L- or D-glutamate: benzyl-L-aspartate random copolymers. The helix sense of the L-aspartate residues determined from the αCH and NH chemical shifts agrees with that obtained from ORD. The stability of the helical copolymers to TFA addition shows a minimum at the composition of helix-sense inversion for the L-glutamate:L-aspartate copolymers but no minimum for the lefthanded D-glutamate: L-aspartate series. The helix-coil transition of the glutamate and aspartate residues in each polymer is compared. For the D-glutamate: L-aspartate series no differences are found, indicating random copolymerization. In the L-glutamate:L-aspartate series significant differences between the transition midpoints are interpreted as resulting from irregular distribution of component residues along the chain.
    Additional Material: 4 Ill.
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  • 5
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The helix-coil transition has been studied by high-resolution NMR for three water-soluble polypeptides. Such systems are better models for protein behavior than those in TFA-CDCl3 solvent. An upfield shift of ∼7 cps is observed for the α-CH peak of poly(L-glutamic acid) and poly-L-lysine as the helix content increases over the transition. No such shift is found for copoly(L-glutamic acid42, L-lysine28, L-alanine30). The width of the α-CH peak for poly L-lysine increases rapidly as helix content rises but for poly L-glutamic acid and the copolymer, the width of this peak remains unchanged up to 60% helicity. This demonstrates a rapid rate of interconversion between helical and random conformations in partly helical polymer for the latter two polypeptides. All three polymers however, show no apparent α-CH peak at 100% helicity. Side-chain resonance lines also broaden as helix content increases and, to a greater extent, the closer the proton is to the main chain.
    Additional Material: 11 Ill.
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