Synthesis and characterization of multiblock copolymers composed of poly(5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one) outer blocks and poly(L‐lactide) inner blocks

Ethylene glycol (EG) initiated, hydroxyl‐telechelic poly(L ‐lactide) (PLLA) was employed as a macroinitiator in the presence of a stannous octoate catalyst in the ring‐opening polymerization of 5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one (MBC) with the goal of creating A–B–A‐type block copolymers having polycarbonate outer blocks and a polyester center block. Because of transesterification reactions involving the PLLA block, multiblock copolymers of the A–(B–A)_n–B–A type were actually obtained, where A is poly(5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one), B is PLLA, and n is greater than 0. ¹H and ¹³C NMR spectroscopy of the product copolymers yielded evidence of the multiblock structure and provided the lactide sequence length. For a PLLA macroinitiator with a number‐average molecular weight of 2500 g/mol, the product block copolymer had an n value of 0.8 and an average lactide sequence length (consecutive C₆H₈O₄ units uninterrupted by either an EG or MBC unit) of 6.1. For a PLLA macroinitiator with a number‐average molecular weight of 14,400 g/mol, n was 18, and the average lactide sequence length was 5.0. Additional evidence of the block copolymer architecture was revealed through the retention of PLLA crystallinity as measured by differential scanning calorimetry and wide‐angle X‐ray diffraction. Multiblock copolymers with PLLA crystallinity could be achieved only with isolated PLLA macroinitiators; sequential addition of MBC to high‐conversion L ‐lactide polymerizations resulted in excessive randomization, presumably because of residual L ‐lactide monomer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6817–6835, 2006     

Reactivity of DNA guanyl radicals with phenolate anions

Guanine bases are the most easily oxidized sites in DNA. Electron-deficient guanine species are major intermediates produced in DNA by the direct effect of ionizing radiation (ionization of the DNA itself) because of preferential hole migration within DNA to guanine bases. By using thiocyanate ions to modify the indirect effect (ionization of the solvent), we are able to produce these single-electron-oxidized guanine radical species in dilute aqueous solutions of plasmid DNA where the direct effect is negligible. The guanyl radical species produce stable modified guanine products. They can be detected in the plasmid by converting them to strand breaks after incubation with a DNA repair enzyme. If a phenol is present during irradiation, the yield of modified guanines is decreased. The mechanism is reduction of the guanine radical species by the phenol. It is possible to derive a rate constant for the reaction of the phenol with the guanyl radical. The pH dependence shows that phenolate anions are more reactive than their conjugate acids, although the difference for guanyl radicals is smaller than with other single-electron-oxidizing agents. At physiological pH values, the reduction of a guanyl radical entails the transfer of a proton in addition to the electron. The relatively small dependence of the rate constant on the driving force implies that the electron cannot be transferred before the proton. These results emphasize the potential importance of acidic tyrosine residues and the intimate involvement of protons in DNA repair.     

Electrochemical synthesis and characterization of conducting polymers in supercritical carbon dioxide

This contribution reports the first synthesis of conducting polymers (CPs), specifically, polyaniline (PAn) and polypyrrole (PPy), in supercritical carbon dioxide (scCO2). CPs synthesized electrochemically in scCO2 were characterized with cyclic voltammetry (CV), four-point probe conductivity, scanning electron microscopy (SEM), and UV-vis spectroscopy. Preliminary data indicate that CPs synthesized by this method exhibit novel morphology and high conductivity comparable to that synthesized by traditional methods.     

Electron transfer in the reduction of primary halides by metal hydrides

The reactions of various main-group metal hydrides with 1-halo-5-hexenes and with 1-halo-2,2-dlmethyl-5-hexenes produce both straight chain and cyclized reduction products. The formation of cyclic hydrocarbons clearly indicates the presence of radical intermediates during the course of these reactions.     

Structural and magnetic behavior of the kinked chain Cu(hfac)2(tan) and its relevance to Cu(NO3)2(tan) (hfac = hexafluoroacetylacetonate; tan = 1,4,5-triazanaphthalene)

When stoichiometric amounts of Cu(hfac)(2).H(2)O and 1,4,5-triazanaphthalene (tan) were combined in methanol, green crystals of Cu(hfac)(2)(tan) were formed. Its structure was determined at low temperature (P2(1)/c; a = 8.3308(4) A, b = 14.8945(7) A, c = 18.3046(10) A, beta = 99.298(2) degrees, V = 2241.5(3) A(3)) and found to consist of a novel kinked-chain arrangement where N atoms on opposite sides of the tan ligand bridge Cu(hfac)(2) moieties together. Long axial Cu-N bonds lead to rather weak (J/k(B) = -0.06(5) K) antiferromagnetic interactions according to a Bonner-Fisher fit of the magnetic susceptibility data. The magnetic behavior demonstrated by Cu(hfac)(2)(tan) contrasts markedly with that of Cu(NO(3))(2)(tan), as reported by Hatfield and co-workers, and is attributed to the differing orientations of the Cu d(x)2(-)(y)2 magnetic orbital.     

Substitution reactions of 4-methyldibenzothiophene

Succinoylation, acetylation and nitration of 4-methyldibenzothiophene yields 2-substituted products. Bromination however, gave 3-bromo-4-methyldibenzothiophene as the major product along with a small amount of the 2-isomer. The bromo-compounds were used to prepare related derivatives via lithium exchange. 4-Methyldibenzothiophene 5,5-dioxide was also shown to nitrate in the 3-position. The structures of the derivatives were determined by NMR analyses. An alternative synthesis of 4-methyldibenzothiophene is described.     

Covalent crosslinking of 1-D photonic crystals of microporous Si by hydrosilylation and ring-opening metathesis polymerization

Free-standing porous Si multilayer dielectric mirrors, prepared by electrochemical etching of crystalline Si, are treated with a ruthenium ring-opening metathesis polymerization (ROMP) catalyst followed by norbornene to produce flexible, stable composite materials in which poly(norbornene) is covalently attached to the porous Si matrix.     

Novel human lens metabolites from normal and cataractous human lenses

4-(2-Aminophenyl)-4-oxobutanoic acid, 4-(2-amino-3-hydroxyphenyl)-4-oxobutanoic acid and glutathionyl-kynurenine have been identified as novel metabolites in normal and cataractous human lenses following total synthesis and comparison with authentic human lens samples. Their structures are consistent with those derived from the major human lens UV filters kynurenine and 3-hydroxykynurenine, and it is proposed that these compounds also play a role as UV filters. These metabolites were isolated in pmol/mg levels (dry mass) in lenses. 4-(2-Amino-3-hydroxyphenyl)-4-oxobutanoic acid and glutathionyl-kynurenine were found to be unstable at physiological pH. Other potential metabolites, glutathionyl-3-hydroxykynurenine, kynurenine yellow and 3-hydroxykynurenine yellow, were not detected in either normal or cataractous lenses.     

A non-isothermal kinetic study of the thermal decomposition of magnesium alkoxides and amides

The thermal decomposition of alkoxides and amides of magnesium have been studied by vacuum TGA under both isothermal and non-isothermal conditions. These compounds were found to follow a unimolecular decay law, which in integrated form is ln(1  α)  kt, where α is the fraction of material reacted, and k is the Arrhenius rate constant. The rate-controlling process is random nucleation, one nucleus on each particle. Energies of activation calculated by isothermal and non-isothermal methods agree to within ±20%.