Supramolecular hydrogels and organogels based on novel l-valine and l-isoleucine amphiphiles

New low-molecular-weight gelators based on l-valine and l-isoleucine gelators, which have a positively charged terminal group, can gel not only pure water and aqueous solutions containing inorganic acids and salts but also some organic solvents and oils.     

STRUCTURE AND STABILITY OF γ-CRYSTALLINS-V. COVALENT AND NONCOVALENT PROTEIN-PROTEIN INTERACTIONS IN PHOTOSENSITIZED REACTIONS

Abstract— Irradiation of γ-crystallins with 300 nm light or with the photosensitizers riboflavin or methylene blue (MB) leads to intermolecular cross-linking and insolubilization. Sodium dodecyl sulfate polyacrylamide gel electrophoresis studies reveal that these cross-links are composed of nondisulfide covalent bonds. The water-insoluble phase is stabilized by noncovalent forces, as denaturants readily dissolve it. High-performance liquid chromatography and electrophoresis results further indicate that the higher multimers are part of this water-insoluble fraction only, with the exception of MB-sensitized reactions, which are also able to produce a water-soluble, high-molecular-weight protein of at least 1 million. Labeling the external sulfhydryl groups with iodoacetamide does not prevent the photoreac-tions; however, a reducing agent such as dithiothreitol does. A mechanism involving initial oxidation and interaction of sulfhydryl groups (forming an intramolecular disulfide) buried within the protein as a necessary precursor to polymerization and precipitation has been proposed in the preceding paper. The present study provides support for this mechanism.     

pH-regulated formation of amyloid-like beta-sheet assemblies from polyglutamate grafted polyallylamine

A novel artificial protein with simple primary structure, poly(gamma-methyl-L-glutamate)-grafted polyallylamine, has been prepared and the resultant peptide has shown a unique property of pH-regulated conformation and morphology.     

Volumetric study on the inclusion complex formation of α- and β-cyclodextrin with 1-alkanols at different temperatures

The partial molar volumes (V_a) of 1-alkanols (carbon number, m=5, 6, 7) in - and -cyclodextrin (CD) solutions at 5.00 mmol kg^–1 have been determined as a function of alkanol concentration (C_a) between 293.2 and 308.2 K by using a dilatometer. It has been observed that with an increase in C_a, V_a increased in -CD solution but decreased in -CD solution, asymptotically to a value of V_a in CD-free water. The dependence of V_a on C_a provided the binding constant (K) of 1:1 complex, the volume change in complex formation, and the partial molar volume of complex itself. The complex formation mechanism has been discussed on the basis of these values and their carbon number dependences in the respect of geometric behavior, hydrophobic interaction, and van der Waals interaction. It is concluded that the CD cavity in water is not rigid but flexible for fitting in nicely with guest molecule.     

Theoretical study of the electronic structure of the lower states of the [Cr2Cl9]3- and [Mo2Cl9]3- ions

The electronic structure of the lower states of a trigonal Cr3+ pair and Mo3+ pair, which occur in the Cs3M2Cl9 crystal (M=Cr,Mo), were studied by theoretical calculations carried out according to several methods: multireference singly and doubly excited configuration interaction, second-order configuration interaction, and multireference coupled-pair approximation. We employed a model of a [M2Cl9]3- anion embedded in a cage of point charges, which were arranged so as to simulate the anion in the crystal. The model core potential was utilized, where the relativistic effect was included for Mo. Results of the Cr complex showed that there were no direct bonds between the Cr metals. The lower electronic spectra of the [Cr2Cl9]3- ion were interpreted in terms of the electronic spectra of [CrCl6]3-. The lowest state of simultaneous excitation in both metals was considered. The [Mo2Cl9]3- ion exhibited a single direct bond between the metals. Reflecting this single bond, the observed singlet-triplet splitting was much larger than that in the case of Cr and the calculated splitting was in good agreement with the observed one. We account for the electronic spectra of the [Mo2Cl9]3- complex, which exhibited quite different features in the electronic excitation spectra in comparison with those of the Cr complex.