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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 14 (1975), S. 1623-1631 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potentiometric titrations of poly(S-carboxymethyl-L-cysteine) and poly(S-carboxy-ethyl-L-cysteine) were carried out in aqueous sodium chloride solutions and in water. For samples of both polymers of high molecular weight, a new pattern was observed concerning the change of titration curve with time; the β-coil transition became sharper and the transition free energy increased by about 100 cal mole-1 as the equilibrium was approached. This suggests that equilibrium data were not obtained in most previous studies on the titration involving the β-coil transition. It also shows that the reversbility is not necessarily sufficient to confirm the equilibrium. Another pattern, which was previously observed, was also confirmed with a low molecular weight sample of poly(S-carboxymethytl-L-cysteine). The titration curves were shown to be insensitive to polymer concentration, even when aggregation or phase separation was present. The validity of the Gouy model to describe the titration curve of the β-structure was found to depend on molecular weight as well as on the nature of the side chain.
    Additional Material: 5 Ill.
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  • 2
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of CuCl2 with poly(S-carboxymethyl-L-cysteine) (poly[Cys(CH2COOH)]) and poly(S-carboxyethyl-L-cysteine) (poly[Cys(C2H4COOH)]) were studied by absorption spectra and circular dichroism (CD). On mixing CuCl2 with polypeptide solutions, absorption bands appeared at 320-325 nm in both polypeptides, and at 255-260 nm in the case of poly[Cys(CH2COOH)]. A stable bound species was formed in the case of poly[Cys(CH2COOH)], since the apparent molar absorption coefficient of the bound species did not depend on the mixing ratio. From the absorption data, it was inferred that Cu2+ ions were complexed with the side chains, most probably with sulfur atoms and carboxyl groups. Induced optical activities were observed for the two polypeptides. The CD spectra of poly[Cys(CH2COOH)] + CuCl2 gave simpler aspects than those of poly[Cys(C2H4COOH)] + CuCl2.
    Additional Material: 8 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2525-2536 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potentiometric titration curves have been determined for aqueous solutions of poly-S-carboxyethyl-L-cysteine, which is subject to the β-coil transition by a change in pH. Reversibility and time dependence of the titration curves are examined by different methods in order to establish the conditions for obtaining equilibrium curves. The β-coil transition is manifest, at some region on the equilibrium titration curve, if pH - log (α/1 - α) is plotted against α. Assuming a value, 4.00, for pKint, the free-energy change for the β-coil transition of uncharged polymer has been evaluated from the extrapolation of the observed titration curves and is found to depend on the ionic strength and polymer concentration. The Henderson-Hasselbach plot of the titration curve yields clearer distinction between the β-form and random coil, and it permits estimation of the content of β-form at, a given pH. Comparison of the conformational titration curve with the circular dichroic measurements leads to a value of -10,000° for [θ]223 for the pure β-structure. Precipitation which occurs at low degrees of ionization and, especially, at high ionic strength does not reveal any discontinuous change of the titration curve, which suggests that, the degree of ionization of the precipitated β-form is not very different from that in solution.
    Additional Material: 8 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 19 (1980), S. 1743-1752 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sodium ion activity was measured using a Na-glass electrode in a solution of poly(S-carboxymethyl-L-cysteine) with no added salt at various degrees of neutralization and various concentrations for samples of different molecular weights. The conformational change from random coil to the β-structure was detected from the activity coefficient of counterions, as well as from CD. At a constant degree of neutralization, the activity coefficient is insensitive to a concentration change not only in the random-coil state, but also in the range of conformational change if the concentration is below about 3 × 10-2 monomolal. At high concentrations of about 5 × 10-2 monomolal, however, the activity coefficient becomes low, probably due to the occurrence of the stacking of the pleated sheets.
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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 β-coil transition of poly(S-carboxymethyl-L-cysteine) (poly[Cys(CH2CO2H)]) and poly(S-carboxyethyl-L-cysteine) (poly[Cys((CH2)2CO2H)]) was followed by CD, potentiometric titration, and viscosity in the absence of added salt. These different properties give consistent results for poly[Cys((CH2)2CO2H)]. The CD spectra of poly[Cys(CH2CO2H)] change considerably with the degree of neutralization α even for a low-molecular-weight sample incapable of forming the β-structure. Because of the superposition of this additional effect, the dependence of CD on α is inconsistent with titration data for the case of poly[Cys(CH2CO2H)], particularly when the nπ transition is used to follow the β-coil transition. The change of CD inherent to the β-coil transition is characterized by an isodichroic point: 215 nm for poly[Cys((CH2)2CO2H)] and 218 nm for poly[Cys(CH2CO2H)]. A criterion supporting the stacking of the pleated sheet is suggested based on the isodichroic point.
    Additional Material: 7 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 23 (1984), S. 1333-1346 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of three cationic surfactants, dodecylammonium chloride (DAC), dodecyldimethylammonium chloride (DDAC), and dodecyldimethylammonium chloride (DTDAC), on the conformation of poly(L-glutamic acid) and at neutral pH were examined by CD. The maximum extent of the α-helix induction occurs for each surfactant when the mixing ration is about unity. Different effects specific to each surfactant, as described below, appear in the range of mixing ratios larger than that required for the maximum induction. In the case of DTAC, the α-helices disintegrate into random coils. In the case of DDAC, the aggregation of α-helices takes place eventually leading to precipitation. Solubilization of the precipitates occurs at high mixing ratios. The most complex behavior is seen in the case of DAC; aggregation of α-helices occurs only to a small extent and the formation of a small complex predominates over aggregation takes place again as DAC concentration increases further. Induction of the α-helix is favored by dilution at a constant mixing ratio but is suppressed by the addition of NaCl.
    Additional Material: 8 Ill.
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  • 7
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Carboxyanhydride of S-carbobenzoxymethyl-L-cysteine was polymerized by the addition of ethylamine as an initiator at anhydride-initiator ratios A/I = 3, 4, 6, 8, 12, and 16. Acetylation of the amino terminal was carried out with p-nitrophenylacetate. After debenzylation, low-molecular-weight samples of poly(S-carboxymethyl-L-cysteine) were obtained for A/I = 8, 12, and 16. These samples were fractionated by ion-exchange chromatography (DEAE-cellulose). About six fractions of narrow molecular-weight distributions were obtained. Their degrees of polymerization (DP) ranged from 8 to 16, as determined from proton nmr and also estimated based on their elution volumes on the ion-exchange chromatography at constant ionic strengths. This range of DP covered the range of interest concerning the formation of the β-structure in aqueous solutions; a fraction did not form the β-structure, whereas another fraction did. The results of the gel filtration (Biogel P-10) of the fractionated samples were consistent with the estimated DPs.
    Additional Material: 10 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 483-490 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Light-scattering measurements were carried out on chick-embryo cartilage proteoglycan type H (PG-H) in three different media. The number of uronates per PG-H was obtained as a measure of the molecular weight: 2.3 × 103 in 4M GdnHCl, 7.1 × 103 in 0.3M NaCl, and 5.7 × 103 in 0.04 g/dL SDS + 0.1M NaCl (GdnHCl, guanidine hydrochloride; SDS, sodium dodecylsulfate). Self-association of PG-H occurred in 0.3M NaCl and 0.04 g/dL SDS + 0.1M NaCl.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 11 (1972), S. 95-104 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Counterion activity of poly-S-carboxyethyl-L-cysteine in salt-free solutions neutralized to various degrees with sodium hydroxide was determined either directly from the e.m.f measurements of concentration cells formed across a Na-glass electrode, or from the potentiometric titrations at different sodium chloride concentrations assuming the additivity rule.From e.m.f. measurements, the activity coefficient of counterions was confirmed to display the β-structure random coil transition of the polymer.For random coil state, both methods gave identical results. Observed values of the activity coefficient was generally smaller than those for other randomly coiled polypeptides. The activity coefficient was found to decrease with the increase of the polymer concentration.The activity coefficient of counterions for β-structure was extremely small as compared with that for random coil at the same degree of neutralization. The activity coefficient obtained from titrations was almost independent of degree of neutralization and increased with the increase of the polymer concentration.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 12 (1973), S. 2121-2133 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The visible phase separation encountered in aqeuous system involving the β-coil transition is investigated on poly-S-carboxyethyl-L-cysteine at a constant ionic strength of 0.2 molal. Solubility of the polymer decreases as the average charge density or pH is decreased, indicating that short-range interactions favor the phase separation. The titration curve of the gel phase (i.e., of the pure β-structure) is obtained by using the solubility data. Circular dichroism of the solution phase in equilibrium with the gel shows that the β-structure is present in the solution phase. To isolate the two phases, centrifugal force is applied and it is demonstrated that the polymers in the two phases are in true equilibrium with each other. The effect of total concentration on the solubility of polymer and the degree of neutralization in each phase is interpreted in terms of the poly-dispersity of the sample.
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