Cooperative C-F...Si interaction in optically active helical polysilanes

Cooperative amplification of the C-F...Si weak interaction between side chains and the main chain was found to afford rigid rodlike helical polysilanes with a preferential screw sense.     

Synthesis of multisubstituted 1,3-butadienes using the ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynylboronates

The ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynes developed by Dixneuf and co-workers was applied to the synthesis of 2-alkyl- or 2-aryl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-bis(trimethylsilyl)-1,3-butadienes by use of alkynylboronates instead of alkynes. Di- and tetrasubstituted 1,3-butadienes were prepared from a 2-boryl-1,4-disilyl-1,3-butadiene, using the Suzuki-Miyaura coupling reaction, iodolysis of the alkenylsilane moieties with N-iodosuccinimide and hydrolysis of the carbon-silicon bonds with trifluoroacetic acid. The same compound was converted also to a bicyclic compound, a trisubstituted 1,3-butadiene and a dienone through the Diels-Alder reaction, oxidation of the alkenylboronate moiety and the Mukaiyama aldol reaction.     

An unusual twist conformation of 2-O-methyl-1,3,4,5-tetrakis-O-tert-butyldiphenylsilyl-myo-inositol

The ring conformation of 2-O-methyl-1,3,4,5-tetrakis-O-tert-butyldiphenylsilyl-myo-inositol was in a twist form both in solid state and in solution. This is the first observation of a stable twist conformer induced by the introduction of bulky silyl protecting groups.     

Crystal structure of poly(p-benzamide)

Redetermination of the crystal structure of poly(p-benzamide) was made by using newly collected intensity data. The molecular conformation is TCTC, where the internal rotation angles about the N? C bond of the amide group and about the virtual bond of N-phenyl-C are T (trans) and C (cis) conformations, respectively. Two molecular chains pass through a rectangular unit cell with dimension, a = 7.75 Å, b = 5.30 Å, c (fiber axis) = 12.87 Å, and the space group, P2₁2₁2₁-D. The reflection observed at the spacing of 010 may be attributed to the reflection due to another crystal polymorph or the diffuse scattering due to disorder. © 1993 John Wiley & Sons, Inc.     

Preparation and thermosensitivity of naturally occurring polypeptide poly(gamma-glutamic acid) derivatives modified by propyl groups

Poly(gamma-glutamic acid) (gamma-PGA) is a biosynthetic polymer, and the carboxyl groups are able to undergo a chemical modification. In this study, poly(alpha-propyl gamma-glutamate) (gamma-PGA propylate) was synthesized by the esterification of these carboxyl groups to yield a thermosensitive and biodegradable polymer. In aqueous solution, the gamma-PGA propylate can impart thermosensitivity by controlling the hydrophobic-hydrophilic balance of the gamma-PGA polymeric chains.     

Self-oscillation of polymer chains induced by the Belousov-Zhabotinsky reaction under acid-free conditions

A novel self-oscillating polymer was prepared by utilizing the Belousov-Zhabotinsky (BZ) reaction. In this study, a sulfonic acid group was newly introduced as a pH-control site into the copolymer of N-isopropylacrylamide, and the ruthenium complex was introduced as a catalyst site. By introducing the pH-control site, we succeed in causing the soluble-insoluble self-oscillation of the polymer solution under acid-free conditions in which only two BZ substrates, malonic acid and sodium bromate, were present as added agents. The self-oscillating behavior was remarkably influenced by the temperature and polymer concentration, which reflects the intermolecular aggregative capacity of the polymer chains in the reduced state to change the lower critical solution temperature. This achievement of self-oscillation of polymer chains under acid-free conditions may lead to their practical use as novel biomimetic materials under biological conditions.     

Beta-1,3-glucan polysaccharides as novel one-dimensional hosts for DNA/RNA, conjugated polymers and nanoparticles

Beta-1,3-glucan polysaccharides have triple-stranded helical structures whose sense and pitch are comparable to those of polynucleotides. We recently revealed that the beta-1,3-glucans could interact with certain polynucleotides to form triple-stranded and helical macromolecular complexes consisting of two polysaccharide-strands and one polynucleotide-strand. This unique property of the beta-1,3-glucans has made it possible to utilize these polysaccharides as potential carriers for various functional polynucleotides. In particular, cell-uptake efficiency of the resultant polysaccharide/polynucleotide complexes was remarkably enhanced when functional groups recognized in a biological system were introduced as pendent groups. The beta-1,3-glucans can also interact with various one-dimensional architectures, such as single-walled carbon nanotubes, to produce unique nanocomposites, in which the single-walled carbon nanotubes are entrapped within the helical superstructure of beta-1,3-glucans. Various conductive polymers and gold nanoparticles are also entrapped within the helical superstructure in a similar manner. In addition, diacetylene monomers entrapped within the helical superstructure can be photo-polymerized to afford the corresponding poly(diacetylene)-nanofibers with a uniform diameter. These findings indicate that the beta-1,3-glucans are very attractive and useful materials not only in biotechnology but also in nanotechnology. These unique properties of the beta-1,3-glucans undoubtedly originate from their inherent, very strong helix-forming character which has never been observed for other polysaccharides.     

Palladium-catalysed dimerization of vinylarenes using indium triflate as an effective co-catalyst

A palladium-indium triflate catalyst was found to be much more active for the dimerization of vinylarenes compared with generally used cationic palladium(II) catalysts.     

Modeling the adsorption of U(VI) onto animal chitin using coupled mass transfer and surface complexation

This paper reports the development of a treatment system, using animal chitin as a passive biosorbent, for removing U(VI) from aqueous waste streams. An integral part of this system is a model that provides for the optimization of the treatment system through simulation of U(VI) removal efficiency based on the characteristics of the influent waste stream. The model accounts for changing solution matrix conditions through the coupling of surface complexation and mass transfer models. Complexation of U(VI) by chitin surface sites was modeled using FITEQL. Application of FITEQL in the “forward” mode provided the sorbed and aqueous phase concentrations needed for the mass transfer model. The mass transfer model was derived for both batch and continuously stirred tank reactor (CSTR) configurations using Fick's Law, reactor mass balances and rate law expressions. The coupled model was successfully validated using CSTR data at pH 6.5 and rate constants determined from batch sorption experiments. The CSTR configuration yields a steady-state, eighty percent U(VI) removal for 1 μM influent U(VI) with a solution-phase pH of 6.5 and 3.9 g l⁻¹ chitin.