SYNTHESIS AND PROPERTIES OF ANILING ANILING AND 0-AMINOBENZENESULFONIC ACID COPOLYMER*

Poly(aniline- co-o-aminobenzenesulfonic acid) (PAOABSA) as a water soluble conducting polymerwas synthesized by chemical polymerization. The productivity and the room-temperature conductivity of thecopolymer were measured as a function of the reaction conditions, such as reaction temperature, the ratio ofoxidant to monomer and the degree of sulfonation defined as the ratio of sulfur to nitrogen atoms(S/N). Themain results obtained are summarized as follows : (1) lower reaction temperature (at about 0℃) is favorablefor the enhancement of the room-temperature conductivity of the copolymer; (2) higher content of oxidant isunfavorable for increasing the room-temperature conductivity of the copolymer; (3) both productivity androom-temperature conductivity of the copolymer decrease with increase of the degree of sulfonation whichwas always lower than 0.5 even an excess of o-aminobenzenesulfonic acid was added, probably because thereactivity ratio of aniline (γ=2.99± 0.05) is much higher than that of o-aminobenzenesulfonic acid (γ_2 = 0.06±0.02) estimated by using Fineman-Ross method and least square method.     

Real‐Time Measurement of the Size Distribution of Diesel Exhaust Particles using a Portable 4‐stage Electrical Low Pressure Impactor

For this study, a 4 stage electrical low pressure impactor was designed to measure the real‐time size distribution of diesel particulate matter (DPM). For the performance evaluation, sodium chloride (NaCl) particles and dioctyl sebacate (DOS) particles were used. After evaluating the collection efficiency of each stage of the impactor, the size distributions of test particles were estimated using electrical current data and their inversion algorithm, and this was found to agree with the results obtained by a scanning mobility particle sizer (SMPS). For measurement of DPM, a common‐rail direct injection (CRDI) diesel engine, for engine speeds of 1,200 rpm and 1,500 rpm at 2.7 kgf·m, was used. Therefore, it was found that the size distribution of the DPM could be easily obtained, with the currents measured by the impactor and the data inversion algorithm, in less than 5 seconds. Furthermore, the effective density of the DPM could be obtained using the calculated results and the SMPS data.     

Single-Ion Conduction and Electrochemical Characteristics of Poly (Oxyethylene)/ Lithium Methoxy Oligo(Oxyethylene) Sulfate Blend

Abstract

The ion conduction of a blend of poly(oxyethylene) (PEO) and lithium methoxy oligo(oxyethylene) sulfate (SAL₈) and its electrochemical characteristics were studied. The maximum ambient conductivity of the blend reaches 1.2 × 10^?6 S/cm. The blend exhibits single-ion conduction, excellent mechanical performance, and electrochemical stability. A battery of Li/PEO + SAL₈/Li_1+xV₃O₈ has a constant discharge capacity at different discharge current densities up to a certain voltage, while the discharge capacity of Li/P (MEO_16-AM) + LiClO₄/Li_1+xV₃O₈ decreases with an increase of the discharge current density.     

Liquid chromatographic resolution of racemic rasagiline and its analogues on a chiral stationary phase based on (+)‐(18‐crown‐6)‐2,3,11,12‐tetracarboxylic acid

A liquid chromatographic chiral stationary phase based on (+)‐(18‐crown‐6)‐2,3,11,12‐tetracarboxylic acid was applied to the resolution of 15 analytes, including racemic rasagiline, a chiral drug for the treatment of Parkinson's disease, and its analogues. The composition of mobile phase was optimized to be ethanol/acetonitrile/acetic acid/triethylamine (80:20:0.2:0.3, v/v/v/v) by evaluating the chromatographic results for the resolution of five selected analytes under various mobile phase conditions. Under the optimized mobile phase conditions, racemic rasagiline was resolved quite well with a separation factor of 1.48 and resolution of 2.71 and its 14 analogues were also resolved reasonably well with separation factors of 1.06–1.54 and resolutions of 0.54–2.11. Among 15 analytes, racemic rasagiline was resolved best except for just one analyte. The analyte structure–enantioselectivity relationship indicated that racemic rasagiline has the most appropriate structural characteristics for resolution on the chiral stationary phase.     

Organocatalytic Conjugate Addition of Azide Ion to α,β‐Unsaturated Aldehydes

An efficient and simple amine‐catatalyzed azide conjugate addition to α,β‐unsaturated aldehydes has been developed. In the presence of a catalytic amount of tertiary amine with a 1:1 mixture of NaN₃ and 37% HCl in CH₂Cl₂, α,β‐unsaturated aldehydes provided β‐azido aldehydes, which could be transformed into 1,3‐amino alcohols.     

Surface-Modified Sb2S3 Nanoparticles and Their Tribological Behaviors in Liquid Paraffin

Sb₂S₃ nanoparticles surface-modified with S-tetradecyl N, N-dihydroxyethyl dithiocarbamate (C₁₄DTC-Sb₂S₃) have been synthesized via extraction of Sb₂S₃ colloidal particles from ethylene glycol into toluene in the presence of C₁₄DTC. The obtained products were characterized by high-resolution transmission electron microscope (HRTEM) and Fourier transformation infrared (FTIR), and their tribological behaviors as an additive in liquid paraffin were investigated using a four-ball tribometer. The results show that C₁₄DTC-Sb₂S₃ nanoparticles can significantly improve the friction reduction, anti-wear, and load-carrying properties of base oils. The preliminary lubrication mechanism was discussed based on the SEM and XPS investigation of the rubbed surfaces.     

Rapid Removal of Organics and Oil Spills from Waters Using Silicone Rubber “Sponges”

We have developed a simple, robust, and efficient technology utilizing cheap and recoverable materials based on commercially available silicone elastomer networks for removing organic solvents and crude oil from waters. Hydrophobic and oleophilic properties of silicone elastomers endow poly(dimethyl siloxane) (PDMS) with the capacity to absorb a large variety of organics, including benzene (B), toluene (T), ethylbenzene (E), and xylene (X), commonly referred to as BTEX, and also crude oils, while at the same time enabling the organic “sponges” to float on waters, which facilitates straightforward handling. We developed a method for generating PDMS particles with variable sizes (ranging from hundreds nanometers to few millimeters) by drop-wise depositing siloxane/cross-linker mixtures into warm water, a process which leads to the cross-linking of the PDMS components. We have tested the capability of the PDMS particles to remove toluene and benzene from water. We also performed similar experiments by utilizing PDMS sheets. In both instances we observed a rapid sorption of the organic phase into PDMS; the amount of absorbed organic solvent depended on the concentration in water and the total mass (volume) of PDMS and did not depend on the geometry of the PDMS “sponge.” In addition, we have examined the uptake of toluene and benzene from toluene/benzene (T/B) mixtures dissolved in water. Our results indicate that the amount of benzene absorbed from the T/B mixtures into PDMS increases relative to the uptake from pure benzene/water solutions. This behavior is associated with toluene acting as a “surfactant” that effectively replaces the more unfavorable PDMS/B contacts with less costly T/B ones. Finally, a simple experiment demonstrates qualitatively that PDMS is also capable of removing crude oils from oil-contaminated waters.     

Synthesis and mesomorphism of 4,4'-bis(omega-hydroxyalkoxy)-alpha-methylstilbenes

A homologous series of 4,4'-bis(omega-hydroxyalkoxy)-alpha-methylstilbenes, denoted HAMS-n, has been synthesized. Here n is the carbon atom length of the peripheral n-alkyl chain; in this work n = 2 to 8 and 11. The composition, microstructure, thermal properties, and mesomorphism of the homologues were determined using elemental analysis, ¹H NMR, FTIR, DSC, wide angle X-ray diffraction, and polarizing optical microscopy with a heating stage. The influence of the length and the even/odd numbers of methylene units of the peripheral chains on the variants of mesomorphism and the stability of mesophases, as well as on their transition temperatures, are discussed. The homologues with n = 8 and 11 were enantiotropic monomorphic, CrG (or CrH). The odd homologues showed monotropic trimorphism on cooling, while the even homologues exhibited enantiotropic trimorphism. A pronounced even/odd effect on the melting temperatures was observed.     

Naphthalene and benzene levels in microenvironments associated with potential exposure: new and old apartments with moth repellents,and cabins of passenger cars

A lesser degree of information is available with respect to microenvironments associated with potential exposure to naphthalene, in comparison with other volatile organic compounds. The current study investigated the levels of benzene as well as naphthalene, both in the indoor and outdoor air of apartments and in the cabins of passenger cars. Two groups of 20 apartment buildings (20 new and 20 old) were chosen on the basis of the selection criteria (apartment location and size). In addition, 10 actual commuters were recruited for this study. The equal number of drivers was recruited for the study for comparison of two types of fuels for vehicles (five drivers of gasoline-fuelled and five drivers of diesel-fuelled passenger cars). Indoor naphthalene concentrations were similar between old and new apartments, while the benzene concentrations in new apartments were significantly higher than those of old apartments. The naphthalene concentrations in bedrooms, where wardrobes with moth repellent (MRs) were placed, were significantly higher than those for living rooms where no MRs were present. In turn, these indoor concentrations were significantly higher than outdoor levels. It is noteworthy that the mean and median values of naphthalene measured in the bedrooms exceeded the USEPA RfC (inhalation reference concentration) of 3?µg?m^?3, and the living room values were close to the RfC, while the residential benzene levels exceeded the European benzene limit of 5?µg?m^?3. In contrast, the maximum outdoor levels were well below that of the RfC. The use of passenger cars appeared to be a significant daily activity for both naphthalene and benzene exposure. The naphthalene-to-benzene ratios varied with the type of microenvironments. Both the indoor naphthalene and benzene concentrations in the present study were much higher than those of other studies.     

Exploring the Reactivity of Multicomponent Photocatalysts: Insight into the Complex Valence Band of BiOBr

The band structure of multicomponent semiconductor photocatalysts, as well as their reactivity distinction under different wavelengths of light, is still unclear. BiOBr, which is a typical multicomponent semiconductor, may have two possible valence‐band structures, that is, two discrete valence bands constructed respectively from O 2p and Br 4p orbitals, or one valence band derived from the hybridization of these orbitals. In this work, aqueous photocatalytic hydroxylation is applied as the probe reaction to investigate the nature and reactions of photogenerated holes in BiOBr. Three organic compounds (microcystin‐LR, aniline, and benzoic acid) with different oxidation potentials were selected as substrates. Isotope labeling (H₂¹⁸O as the solvent) was used to determine the source of the O atom in the hydroxyl group of the products, which distinguishes the contribution of different hydroxylation pathways. Furthermore, a spin‐trapping ESR method was used to quantify the reactive oxygen species (^.OH and ^.OOH) formed in the reaction system. The different isotope abundances of the hydroxyl O atom of the products formed, as well as the reverse trend of the ^.OH/^.OOH ratio with the oxidative resistance of the substrate under UV and visible irradiation, reveal that BiOBr has two separate valence bands, which have different oxidation ability and respond to UV and visible light, respectively. This study shows that the band structure of semiconductor photocatalysts can be reliably analyzed with an isotope labeling method.