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  • 1
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Schiff's bases of ortho-, meta- and para-hydroxybenzaldehydes with poly(L-α,γ-diaminobutyric acid) and poly(L-lysine) were investigated in solution of methanol and methanol-water mixtures by circular dichtroism, absorption spectroscopy and equilibrium dialysis techniques. The results so far obtained allow us to propose a molecular model, which fully justifies the stereospecific binding of ortho-hydroxybenzaldehyde with the polypeptide chain; moreover it is able to explain the dramatic change of the chemical equilibrium in the hydrolysis reaction.
    Additional Material: 7 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 97 (1966), S. 113-127 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die SCHULZsche Theorie über die chromatographische Fraktionierung mittels BAKERWILLIAMS-Säulen wurde auf das System Poly-γ-benzyl-L-glutamat/Methanol/Methylenchlorid angewandt.Es wurde gefunden, daß die Trennung sehr wirksam ist, wenn die Fraktionierungsbedingungen sorgfältig ausgewählt werden. Darüber hinaus stimmen die Ergebnisse mit dem vermuteten Mechanismus der mit primären Aminen initiierten N-Carboxyanhydrid-(NCA)-Polymerisation gut überein. An den Ergebnissen der Fraktionierung wurde erkannt, daß das Zahlenmittel des Polymerisationsgrades P̄n annähernd dem Verhältnis der Monomeranfangskonzentration zur Initiatorkonzentration ([M]0/[I]0) gleich ist. Eine sehr große Uneinheitlichkeit wurde mit P̄w/P̄n ≃ 7 in Übereinstimmung mit älteren Literaturdaten gefunden1.
    Notes: The SCHULZ theory on the chromatographic fractionation with a BAKER and WILLIAMS column was applied to the system poly-γ-benzyl-L-glutamate/methanol/methylenechloride.It was found that the separation is very efficient if the fractionation conditions are carefully selected. Moreover the results are in good agreement with the suggested mechanism of N-carboxyanhydride (NCA) polymerization initiated by primary amines. In fact from the fractionation data it was found that the number average degree of polymerization P̄n is approximatively equal to the ratio between the initial concentrations of monomer and initiator ([M]0/[I]0). A very large inhomogeneity was found with P̄w/P̄n ≃ 7, in agreement with previous literature data1.
    Additional Material: 5 Ill.
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  • 3
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden die Bildung, die optischen Eigenschaften und die Strukturen der Bis(o-hydroxybenzylidenamin)Kupfer(II)-Chelate von Poly(L-lysin), Poly(L-ornithin) und Poly(L-α,γ-diaminobuttersäure) untersucht.Aus den Versuchsergebnissen ging hervor, daß diese Polykomplexe in alkoholisch wäßriger Lösung eine bestimmte Struktur besitzen. Aus den strukturellen Eigenschaften resultierte, daß die asymmetrischen Polypeptid-Ketten die Metall-Chelate stereospezifisch binden.Auf Grund dieser Ergebnisse kann man stereoselektive Reaktionen der Kupfer(II)-polykomplexe von Bis(o-hydroxybenzylidenamin) erwarten.
    Notes: Formation, optical properties and structures of bis(o-hydroxybenzylideneamine)copper(II) chelates of poly(L-lysine), poly(L-ornithine), and poly(L-α,β-diaminobutyric acid) were investigated.Experimental evidence was obtained for a definite structure of these polycomplexes in alcoholic/aqueous solution. Structural features showed that asymmetric polypeptide matrices bind metal chelates stereospecifically. On the basis of these results stereoselective reactions on bis(o-hydroxybenzylideneamine)copper(II) polycomplexes are expected.
    Additional Material: 11 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 28 (1989), S. 225-246 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The major immunodominant region of the coating protein of Plasmodium falciparum sporozoites contains multiple tandem copies of the sequence Asn-Ala-Asn-Pro (NANP). Current efforts for the development of an antisporozoite vaccine are focused on the synthesis of polypeptides reproducing part of the circumsporozoite protein repeat sequence and, in an attempt to relate conformational properties and biological response, 1H-nmr one- and two-dimensional studies of the synthetic models (NANP)2NA and (NANP)6 were carried out in water and water/methanol mixtures, at 400 and 500 MHz. In water, (NANP)6 undergoes fast conformational averaging. At variance, in water/methanol, the molecule appears to adopt an extensive structure, but detailed analysis is impaired by high spectral degeneracy. Based on the results obtained with (NANP)2NA and from preliminary expermints in water/trifluoroethanol, an interpretation is suggested for the (NANP)6 data in water/methanol in terms of a mixed sequence of βI-turns and half-turns (or/and γI-turns) around the positions Ni-1-Pi-Ni+1.
    Additional Material: 10 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: Through the joint use of CD, Fourier transform ir (FTIR), and attenuated total reflectance FTIR we have found that synthetic polypeptide models of the Plasmodium falciparum circumsporozoite (CS) protein repeat domain bind calcium ions in helicogenic environments. Ca2+-(NANP)n complexes (n ≥ 20) interact vectorially with model phospholipid membranes orienting their polypeptide axes preferentially along those of the lipid acyl chains. It is proposed that the P. falciparum CS protein central region, rather than acting as a molecular lure helping the parasite to evade host immune control, plays, as a specific Ca2+ macroligand, a critical functional role during attachment, invasion, and development of the malaria parasite in the hepatic cell.
    Additional Material: 4 Ill.
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  • 6
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several cyclic hemopeptides containing L-azetidine-2-carboxylix acid (Aze) - an imino acid homologous with proline but containing one less methylene group in its cyclic side chain - have been prepared. The peptides reported include (Aze)2, cyclo(Aze)3, and cyclo(Aze)6. The synthesis and spectral characterization of these cyclic peptides are described, and the results discussed in terms of the rigidity and steric constraints attributable to Aze-containing peptides. CD spectra of these materials in several solvents are reported and compared with those of proline analogs; the similarity between the CD spectra of cyclo(Aze)3 and cyclo (Pro)3, is noted.
    Additional Material: 8 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 13 (1974), S. 2209-2225 
    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 of poly-N5-(3-hydroxypropyl)-L-glutamine (PHPLG) has been studied in methanol-water by CD and cmr spectroscopy. For polydisperse PHPLG, two separate peaks arising from residues in helical and random-coil conformations are observed during the transition for both main-chain carbons. These results are discussed and compared to those observed in the case of a polymer sample obtained by racemization of PHPLG in 0.1 M NaOH and of PHPLG samples of controlled molecular weight and dispersity. The dominant influence of the molecular-weight heterogeneity on the double-peak phenomenon has been verified. The linewidths and chemical shift of the 13C resonances are discussed in terms of side-chain-main-chain interactions and side-chain solvation.
    Additional Material: 9 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 13 (1974), S. 2405-2405 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 6 (1968), S. 1477-1486 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Circular dichroism (CD) measurements were carried out on various copolymers of L-tryptophan and γ-ethyl L-glutamate in ethylene glycol monomethyl ether as the solvent. On increasing the L-tryptophan content of the copolymers a gradual change in the CD spectra was observed. The typical spectrum of the right-handedα-helix becomes more and more evident as the L-tryptophan content decreases. On the basis of these results we assumed that no conformational transition occurs on proceeding from pure poly (γ-ethyl L-glutamate) to pure poly-L-tryptophan in ethylene glycol monomethyl ether: therefore the conformation of poly-L-tryptophan should be that of a right-handed α-helix. Moreover we observed that the change in the CD spectra of the copolymers is gradual but not linear on increasing the tryptophan content. The deviations from linearity were attributed to interactions among side-chain chromophores whose contributions to the optical activity are not simply additive. An x-ray analysis carried out on oriented films of poly-L-tryptophan casted from solutions of the polymer in dimethylformamide shows conclusively that the solid-state conformation of the polymer is that, of an α-helix.
    Additional Material: 4 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 6 (1968), S. 963-971 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A block copolymer [γ-Et-DL-Glu]m [L-Trp]n was prepared using N-carboxy anhydrides (NCA) of L-tryptohan and γ-ethyl DL-glutamate. The block copolymer, dissolved in trifluoroethanol (TFE)-dichloroacetic acid (DCA) mixtures, exhibited a sharp change in the specific rotation at 546 mμ when the solvent composition reached 70-75% DCA content. Optical rotatory dispersion (ORD) and circular dichroism (CD) measurement were carried out in TFE solution in the spectral range 180-350 mμ. Indole side-chain chromophores were found to be optically active in the polymer. On the other hand, these groups exhibit very small optical activity in the model compound C6H3—CH2—O—CO—(L-Trp)2—O—CH3. Indole groups therefore appear to be in a dissymmetric environment only in the polymer. From these data it was concluded that poly-L-Trp is in some type of helical conformation in TFE. Strong overlapping of CD bands from side-chain chromophores and peptides chromophores in the wavelength range 185-240 mμ does not allow definite conclusions to be drawn about the type of helical conformation which exists in poly-L-Trp in TFE solution.
    Additional Material: 4 Ill.
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