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71.
The coil/helix transition of a synthetic, branched-chain polymeric polypeptide (poly (Lys(Glu(1)-DL-Ala(3))EAK), 50-Lys residues long in the backbone, as a function of increasing molarities of methanol in solution, is here studied by both, circular dichroism (CD) and capillary zone electrophoresis. CD spectra showed that, at 75% v/v methanol, the transition from random coil to fully helical structure was obtained, in a pH 1.1 HCI solution in the presence of 20 mM NaCI. CZE studies, run in parallel, exhibited the classical unfolding to folding sigmoidal transition, with mid-point at 60% v/v methanol concentration, plateauing at ca. 80% v/v organic solvent. Surprisingly, though, such unfolding to folding transition was accompanied by an expansion, rather than a contraction, of the resulting ordered polypeptide. As the charge of the polypeptide (a pure polycation at a pH of 2.1 in CZE) was kept rigorously constant, a plot of the radius of the polymer along the sigmoidal transition clearly showed that the radius of gyration of the helical, structured polypeptide was in fact larger than that of the random coil. Such results were confirmed by molecular dynamics simulations, which indicated that the dimensions of such polypeptide, in alpha-helix configuration, were 8.5 nm (in length) and 3.2 nm (in diameter), whereas those of the corresponding random coil were 7.2 nm (in length) and 5.1 nm (length of shorter axis). It would thus appear that the randomized structure assumes the shape of a more compact object, roughly resembling a "rugby ball". 相似文献
72.
Ferenc F. Gaál Biljana F. Abramovi Ferenc B. Szebenyi Velimir D. Cani 《Fresenius' Journal of Analytical Chemistry》1977,286(3-4):222-225
Summary Amperometric and potentiometric methods at a small constant current were developed to follow the course of catalytic titrations. In ammoniacal medium EDTA was determined by titration with 0.1 M copper(II) chloride in the presence of hydrogen peroxide as the indicator. Amounts of 42.26–126.87 mg of EDTA were determined with a maximal average deviation of 0.55 %. The results obtained are in good agreement with those of comparable methods.
Bestimmung von ÄDTA mit Hilfe der katalytischen amperometrischen und der katalytischen potentiometrischen Titration bei kleinem konstantem Strom
Zusammenfassung Die amperometrische und die potentiometrische Methode bei kleinem konstantem Strom wurden für die Verfolgung katalytischer Titrationen ausgearbeitet. ÄDTA wurde in Ammoniakmedium mit 0,1 M Kupfer(II)-chlorid in Anwesenheit von Wasserstoffperoxid als Indicator titriert. Mengen von 42,26–126,87 mg ÄDTA wurden mit einer mittleren Abweichung von 0,55% bestimmt. Die Ergebnisse stimmen gut mit denen vergleichbarer Methoden überein.
The authors thank the SIZ for researchs of SAP Vojvodina for the partial financial support of the present work. 相似文献
73.
74.
75.
Lajos Simon S. Gizella Talpas Ferenc Fülp Gbor Bernth Gyula Argay Alajos Klmn PL Sohr 《Journal of heterocyclic chemistry》1995,32(1):161-167
trans-Perhydro-1,4-benzoxazepin-3-ones 2a-c were synthesized and transformed to condensed-skeleton perhydro-trans-1,4-benzoxazepines 3a,b , the thiones 4a,b , the urea derivatives 5a,b , and N-acylated compounds 6a-e . Compounds 6b,d were ring-opened by hydrochloric acid in ethanol to yield trans-2-(1-carbethoxyethoxy)-1-acylaminomethylcyclohexane derivatives 7b,d . The 1H- and 13C-nmr investigation and X-ray analysis of 5b and 6c,d proved that the expected N-acylated derivatives were formed and that both rings of the trans anellated compounds have a chair conformation. 相似文献
76.
Syntheses of 5H-[1,2,4]triazolo[5′,1′:2,3][1,3]thiazino[5,4-c]quinolines 8, 5H-[1,2,4]triazolo[3′,4′:2)3][1,3]thiazino[5,4-c]quinolines 9, 5H-[1,2,4]triazolo[5′,1′:2,3][1,3]thiazino[5,6-c]quinolines 14 and 5H-[1,2,4]triazolo[3′,4′:2,3][1,3]thiazino[5,6-c]quinolines 15 are described starting from 4-chloro-3-chloromethylquinaldine (4) and 1,2,4-triazole-5-thiols 5 taking advantage of different reactivity of the chlorine atoms of 4 under different reaction conditions. The structures of products 8, 9, 14 and 15 and the intermediates leading to them were confirmed by desulfurization, unequivocal syntheses and nmr spectroscopy as well. 相似文献
77.
Szpakowska M Czaplicka I Płocharska-Jankowska E Nagy OB 《Journal of colloid and interface science》2003,261(2):451-455
It is shown that liquid membrane oscillators with cationic surfactants have more complex oscillation patterns than observed previously. The actual details of the oscillations depend strongly on the nature of the membrane material, disclosing even the presence of parallel molecular events. It appears that sampling topology also has a great influence on the observed oscillatory behavior. Variation of oscillation patterns with diffusion path length in the membrane demonstrated the decisive role played by the actual timing of molecular events. The new evidences produced complete usefully the actual views concerning the mechanism of oscillations. 相似文献
78.
79.
The complexes of 4-chloro-2-methoxybenzoic acid anion with Mn2+,
Co2+, Ni2+, Cu2+
and Zn2+ were obtained as polycrystalline solids
with general formula M(C8H6ClO3)2·nH2O and colours typical for M(II) ions (Mn – slightly pink, Co –
pink, Ni – slightly green, Cu – turquoise and Zn – white).
The results of elemental, thermal and spectral analyses suggest that compounds
of Mn(II), Cu(II) and Zn(II) are tetrahydrates whereas those of Co(II) and
Ni(II) are pentahydrates. The carboxylate groups in these complexes are monodentate.
The hydrates of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II)
and Zn(II) heated in air to 1273 K are dehydrated in one step in the range
of 323–411 K and form anhydrous salts which next in the range of 433–1212
K are decomposed to the following oxides: Mn3O4,
CoO, NiO and ZnO. The final products of decomposition of Cu(II) complex are
CuO and Cu. The solubility value in water at 293 K for all complexes is in
the order of 10–3 mol dm–3.
The plots of χM
vs.
temperature of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II)
follow the Curie–Weiss law. The magnetic moment values of Mn2+,
Co2+, Ni2+ and Cu2+
ions in these complexes were determined in the range of 76−303 K and
they change from: 5.88–6.04 μB for Mn(C8H6ClO3)2·4H2O, 3.96–4.75
μB for Co(C8H6ClO3)2·5H2O, 2.32–3.02 μB for Ni(C8H6ClO3)2·5H2O and 1.77–1.94
μB for Cu(C8H6ClO3)2·4H2O. 相似文献
80.
Krisztina Sebk‐Nagy Lszl Biczk Akimitsu Morimoto Tetsuya Shimada Haruo Inoue 《Photochemistry and photobiology》2004,80(1):119-126
Effects of solvent, pH and hydrogen bonding with N‐methylimidazole (MIm) on the photophysical properties of 1‐hydroxyfluorenone (1HOF) have been studied. Fluorescence lifetime, fluorescence quantum yield and triplet yield measurements demonstrated that intersystem crossing was the dominant process in apolar media and its rate constant significantly diminished with increasing solvent polarity. The acceleration of internal conversion in alcohols paralleled the strength of intermolecular hydrogen bonding. The faster energy dissipation from the singlet‐excited state in cyclohexane was attributed to intramolecular hydrogen bonding. The pKa of 1HOF decreased from 10.06 to 5.0 on light absorption, and H3O+ quenched the singletexcited molecules in a practically diffusion‐controlled reaction. On addition of MIm in toluene, dual fluorescence was observed, which was attributed to reversible formation of excited hydrogen‐bonded ion pair. Rate constants for the various deactivation pathways were derived from the combined analysis of the steady‐state and the time‐resolved fluorescence results. 相似文献