Polyesterification of aromatic dicarboxylic acids and bisphenols with tosyl chloride/dimethylformamide/pyridine promoted by the improvement of the difficult solubility of the activated diacids with lithium chloride

The solution polyesterification of dicarboxylic acids in pyridine, the activated intermediates of which were difficult to dissolve in tosyl chloride/dimethylformamide/pyridine, was investigated in the presence of lithium chloride. The solubility of the activated dicarboxylic acids was largely improved by the presence of the salt, and the polycondensation with bisphenols was greatly facilitated. The salt was more effectively added to a pyridine solution of dicarboxylic acids than to the activated dicarboxylic acids in pyridine. The favorable additive effect on the improved solubility was attributed to a lowered degree of association of the activated dicarboxylic acids, which led to distributions of the resulting oligomers from bisphenols at an earlier stage closer to the theoretical ones and yielded better polycondensation results. The reaction, which proceeded through favorable distributions of the co‐oligomers, produced copolymers of higher inherent viscosities and slightly block sequence distributions determined by NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2725–2733, 2004     

TTF-porphyrin dyads as novel photoinduced electron transfer systems

A TTF-linked porphyrin dyad and its zinc complex have been synthesized as novel photosystems with a redox-active pendant. The two chromophores of these dyads are not interactive in the absorption spectra, but the fluorescence of the porphyrin chromophore is dramatically quenched by intramolecular electron transfer from the TTF pendant.     

Effect of adsorbed water on the electrorheology of silica suspensions

Monodisperse silica particles were formed by hydrolyzing tetraethylorthosilicate in an ethanol solution and the silica suspensions dispersed in a silicone oil were prepared by a different procedure. The effects of adsorbed water on the electrorheological (ER) behavior were studied under oscillatory shear. The amounts of adsorbed water and surface silanol groups were determined by thermogravimetric analysis. The magnitude of the complex viscosity, |η^*|, increases with the application of electric fields. The physically adsorbed water is primarily responsible for the ER effect. However, the fluids containing large amounts of adsorbed water do not always show excellent ER performance. The surface silanol groups have an important role in promoting the ER effect. Not only the amount but also the situation of silanol groups determines the ER activity of adsorbed water.     

Photodimerization of benzene -photochromism of layered dithiacyclophane-

A novel cage compound was obtained by irradiation of a quadruple-layered dithiacyclophane and showed thermally reverse reaction.     

Micropore-free surface-activated carbon for the analysis of polychlorinated dibenzo-p-dioxins-dibenzofurans and non-ortho-substituted polychlorinated biphenyls in environmental samples

2,3,7,8-Substituted polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs) and non-ortho-substituted polychlorinated biphenyls (PCBs) account for almost all of the total toxic equivalents (TEQ) in environmental samples. Activated carbon columns are used to fractionate the samples for GC-MS analysis or bioassay. Micropore-free surface-activated carbon is highly selective for PCDD/Fs and non-ortho-PCBs and can improve the conventional activated carbon column clean-up. Along with sulfuric acid-coated diatomaceous earth columns, micropore-free surface-activated carbon provides a rapid, robust, and high-throughput sample preparation method for PCDD/Fs and non-ortho-PCBs analysis.     

Synthesis and characterization of monodispersed core-shell spherical colloids with movable cores

Gold nanoparticles have been conformally coated with amorphous silica (using a sol-gel method) and then an organic polymer (via surface-grafted, atom transfer radical polymerization) to form spherical colloids with a core-double-shell structure. The thickness of silica and polymer shells could be conveniently controlled in the range of tens to several hundred nanometers by changing the concentration of the reagent and/or the reaction time. Selective removal of the silica layer (through etching in aqueous HF) led to the formation of hollow polymer beads containing movable gold cores. This new form of core-shell particles provides a unique system for measuring the feature size and transport property associated with hollow particles. In one demonstration, we showed that the thickness of a closed polymer shell could be obtained by mapping the electrons backscattered from the core and shell. In another demonstration, the plasmon resonance band of the gold cores was used as an optical probe to follow the diffusion kinetics of chemical reagents across the polymer shells.     

The characteristic fragment ions and visualization of cationic starches on pulp fiber using ToF‐SIMS

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) was used to investigate the distribution of cationic starch on pulp fiber. To identify the characteristic fragment ions of the cationic starches, deuterium‐labeled cationic starches were prepared and analyzed using ToF‐SIMS. The starch 2‐hydroxypropyltrimethylammonium chloride derivative generated characteristic fragments at m/z 58 and 59, which were identified as [H₂C?N(CH₃)₂]⁺ and [N(CH₃)₃]^+·, respectively. The fragmentation patterns were also suggested. From the imaging analysis, the adsorption of the cationic starch on fibers was uneven on individual fibers, as well as between fibers. This may have been on account of fiber morphology and structure. On examining scanning electron microscope (SEM) images, the quaternary ammonium starch derivative (QS) did not penetrate the fiber. No migration of cationic starch was observed under various drying conditions. Copyright © 2007 John Wiley & Sons, Ltd.     

A simple and simultaneous determination of acyclovir and ganciclovir in human plasma by high-performance liquid chromatography

A simple high-performance liquid chromatographic method was developed for the simultaneous determination of the therapeutic levels of acyclovir and ganciclovir in human plasma. After precipitation of plasma proteins with 6% perchloric acid, acyclovir and ganciclovir were simultaneously determined by reversed-phase chromatography with spectophotometric detection at 254 nm. The peak heights for acyclovir and ganciclovir were linearly related to their concentrations ranging from 0.063 to 2.080 micro g/mL. The recovery was 100.48-102.84% for acyclovir and 99.26-103.07% for ganciclovir. The intra- and inter-day relative standard deviation values were in the range 0.186-8.703% for acyclovir and 0.137-6.424% for ganciclovir. The detection limits for both compounds were 0.01 micro g/mL determined as the signal-to-noise ratio of 3. The present method is applicable to therapeutic monitoring during antiviral medication.     

Loss and recovery in hydrophobicity of silicone rubber exposed to corona discharge

This paper describes the loss and recovery in the hydrophobicity of unfilled high temperature vulcanized silicone rubber (HTV-SR) resulting from corona discharge. In this study, HTV-SR specimens were exposed to corona stress generated by a parallel needle-plane electrode system, and physicochemical analyses on the surface layer of SR before and after corona discharge treatment were carried out by using Fourier transform infra-red (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). It is demonstrated that hydrophilic OH groups that are by-products of ageing can be formed instead of hydrophobic CH₃ groups on the surface of aged SR and the corona discharge plays an important role on the temporary loss of hydrophobicity. After a substantial period of ‘rest’, the hydrophobic recovery of SR results from the diffusion of low-molecular weight (LMW) silicone fluid from the bulk onto the aged layer.     

Control of photoinduced energy- and electron-transfer steps in zinc porphyrin-oligothiophene-fullerene linked triads with solvent polarity

The dramatic changes of the lifetimes of the charge-separated (CS) states were confirmed in zinc porphyrin (ZnP)-oligothiophene (nT)-fullerene (C(60)) linked triads (ZnP-nT-C(60)) with the solvent polarity. After the selective excitation of the ZnP moiety of ZnP-nT-C(60), an energy transfer took place from the (1)ZnP moiety to the C(60) moiety, generating ZnP-nT-(1)C(60). In polar solvents, the CS process also took place directly via the (1)ZnP moiety, generating ZnP(*+)-nT-C(60)(*-), as well as the energy transfer to the C(60) moiety. After this energy transfer, an indirect CS process took place from the (1)C(60) moiety. In the less polar solvent anisole, the radical cation (hole) of ZnP(*+)-nT-C(60)(*-) shifted to the nT moiety; thus, the nT moiety behaves as a cation trapper, and the rates of the hole shift were evaluated to be in the order of 10(8) s(-1); then, the final CS states ZnP-nT(*+)-C(60)(*-) were lasting for 6-7 mus. In the medium polar solvent o-dichlorobenzene (o-DCB), ZnP-nT(*+)-C(60)(*-) and ZnP(*+)-nT-C(60)(*-) were present as an equilibrium, because both states have almost the same thermodynamic stability. This equilibrium resulted in quite long lifetimes of the CS states (450-910 mus) in o-DCB. In the more polar benzonitrile, the generation of ZnP-nT(*+)-C(60)(*-) was confirmed with apparent short lifetimes (0.6-0.8 mus), which can be explained by the fast hole shift to more stable ZnP(*+)-nT-C(60)(*-) followed by the faster charge recombination. It was revealed that the relation between the energy levels of two CS states, which strongly depend on the solvent polarity, causes dramatic changes of the lifetimes of the CS states in ZnP-nT-C(60); that is, the most appropriate solvents for the long-lived CS state are intermediately polar solvents such as o-DCB. Compared with our previous data for H(2)P-nT-C(60), in which H(2)P is free-base porphyrin, the lifetimes of the CS states of ZnP-nT-C(60) are approximately 30 times longer than those in o-DCB.