Observations on the swelling characteristics of the zwitterionic hydrogel of poly(1-3-sulfopropyl)-2-vinyl-pyridinium-betaine hydrogel

Samples of poly[1-(3-sulfopropyl)-2-vinyl-pyridinium-betaine] (PSPV) have been synthesized to high conversion by free radical polymerization in aqueous solution of the zwitterionic monomer SPV with several concentrations of the crosslinker N,N′-methylene-bis-acrylamide (MBA). The densities of the resultant xerogels increased regularly with the content of MBA. Hydrogels obtained by swelling them in water and aqueous KSCN solution were examined by gravimetric and dimensional analysis. The water contents increased with decreasing content of MBA, the value of 92.7 wt% at the lowest MBA content being higher than that for other zwitterionic hydrogels. Enhanced swelling occurred in 1 M aq. KSCN at each MBA content, the total swelling being 98.1 wt% at the lowest crosslinker content. Swelling increased with increasing temperature. An approximate procedure to formulating swelling equilibrium in term of the volume fraction of water in hydrogel, in conjunction with the van’t Hoff equation, yields a small positive value for the enthalpy of swelling. This is compared with values derived similarly for other hydrogels.     

An efficient synthesis of novel spiro[[8H]indeno[2,1-b]-thiophene-8,9′-fluorene] building block for blue light-emitting materials

We have developed efficient synthetic routes to obtain a novel building block spiro[[8H]indeno[2,1-b]thiophene-8,9′-fluorene] (SITF), a monothiophene-containing spirobifluorene analogue, and constructed blue light-emitting materials, including 2′,7′-bis([1,1′-biphenyl]-4-yl)-spiro[indeno[2,1-b]thiophene-8,9′-fluorene] (BBP-SITF) and 2′,7′-bis(9,9′-spirobifluoren-2-yl)spiro[[8H]indeno[2,1-b]-thiophene-8,9′-fluorene] (BSBF-SITF). BSBF-SITF has shown to be a stable blue light-emitting material with high PL quantum efficiency (89%) and unique regioselective feature at the C2 of thiophene, which indicate that BSBF-SITF will be useful for constructing complicated optoelectronic systems.     

Xylan hydrolysis in zinc chloride solution

Xylan is the major component of hemicellulose, which consists of up to one-third of the lignocellulosic biomass. When the zinc chloride solution was used as a pretreatment agent to facilitate cellulose hydrolysis, hemicellulose was hydrolyzed during the pretreatment stage. In this study, xylan was used as a model to study the hydrolysis of hemicellulose in zinc chloride solution. The degradation of xylose that is released from xylan was reduced by the formation of zinc-xylose complex. The xylose yield was >90% (w/w) at 70°C. The yield and rate of hydrolysis were a function of temperature and the concentration of zinc chloride. The ratio of zinc chloride can be decreased from 9 to 1.3 (w/w). At this ratio, 76% of xylose yield was obtained. When wheat straw was pretreated with a concentrated zinc chloride solution, the hemicellulose hydrolysate contained only xylose and trace amounts of arabinose and oligosaccharides. With this approach, the hemicellulose hydrolysate can be separated from cellulose residue, which would be hydrolyzed subsequently to glucose by acid or enzymes to produce glucose. This production scheme provided a method to produce glucose and xylose in different streams, which can be fermented in separated fermenters.     

Multi-step polymer-assisted solution-phase (PASP) library synthesis of functionalized diaminobenzamides

A parallel solution-phase library synthesis of functionalized diaminobenzamides is described. The four-step library synthesis is accomplished using polymer-assisted solution-phase (PASP) synthesis techniques. This high-yielding, multi-step sequence utilizes sequestering resins for the removal of reactants, reactant by-products, and employs a resin capture/release strategy as a key library synthesis step. Step one of the sequence relies on the displacement of an activated fluoro-group from the aromatic ring of 1a, b with a variety of primary amines to introduce the first diversity position. Step two is hydrolysis of the benzoate ester to a benzoic acid which is subsequently captured on a polyamine resin, washed, and released to give 4a, b in pure form. Step three utilizes PASP resins to mediate the amide coupling of a benzoic acid with a variety of primary amines to give the aminonitrobenzamides 5a, b and introduces the second diversity position. Step four is the parallel reduction of the aminonitrobenzamides 5a, b to the functionalized diaminobenzamides 6a, b. This library synthesis proceeds with high overall purities which average 80 % over the 4-step sequence.     

Determination of norfloxacin in pharmaceuticals,human serum,and urine using a luminol—dissolved oxygen chemiluminescence system

A sensitive chemiluminescence method, based on the enhancive effect of norfloxacin on the reaction between luminol and dissolved oxygen in a flow injection system, was proposed for the determination of norfloxacin. The increment of the chemiluminiscence intensity was proportional to the concentration of norfloxacin, giving a calibration graph linear over the concentration from 0.4 ng mL⁻¹ to 400.0 ng mL⁻¹ (r ² = 0.9988) with the detection limit of 0.1 ng mL⁻¹ (3 × σ _noise). At the flow rate of 2.0 mL min⁻¹, a complete determination of norfloxacin, including sampling and washing, could be accomplished in 30 s with the relative standard deviation lower than 3.0 %. The proposed method was applied successfully to determine norfloxacin in pharmaceuticals, human urine, and serum. Possible mechanism of the reaction was also discussed.     

Direct Synthesis, Crystal Structure and Thermal Kinetics of Supramolecular Complex [Co（H2O）6]·（Hnip）2·（H2nip）2·（DMA）2·（H2O）8 （nip=5-nitroisophthalate, DMA=CH3NHCH3）

The crystal of [Co（H2O）6]·（Hnip）2·（H2nip）2·（OMA）2·（H2O）8 has been cultured using direct method and characterized by X-ray single crystal diffractometry, elemental analysis and FTIR spectroscopy. It crystallizes in triclinic system, P-1 space group with the cell parameters of a=0.7012（1） nm, b=1.1378（2） nm, c=1.6612（3） nm, α= 84.92（3）°, β=85.19（3）°, γ=85.91（3）°, V= 1.3128（5） nm^3, Z=1, Dc= 1.573 g·cm^-3. Final R indices [1〉2σ（I）] are： R1 =0.0279, wR2=0.0765 while R indices for all data are： R1 =0.0327, wR2=0.0806. The Co coordination octahadra are each surrounded by two Hnip, two H2nip, two DMA and eight water molecules that are linked by hydrogen bonds and π-π stacking interactions. Thermal analyses of DSC and TG-DTG have been performed on the complex to predict its thermal decomposition mechanism and determine the most probable kinetic model function using Kissinger, Ozawa, integral and differential methods.     

Extremely facile ring inversion and rearrangement in fluorobicyclo[2.1.0]pentanes

cis-1,2,3,4,5,5-Hexafluorobicyclo[2.1.0]pentane and 1,2,4,5-tetrafluorobicyclo[2.1.0]pentane have been synthesized from hexafluorobenzene. The former hydrofluorocarbon, which exists entirely in the endo configuration, rearranges to cis-1,2,3,3,4,5-hexafluorocyclopentene below room temperature (E_a = 21.9 kcal/mol, log A = 13.4). The latter undergoes degenerate ring inversion with extraordinary ease (ΔG^‡ = 6.8 ± 0.2 kcal/mol at −55 °C). Density functional calculations indicate that significant bonding between the bridgehead carbons is retained in the ring inversion transition state. Analogous calculations predict for hexafluorobicyclo[1.1.0]butane a considerably lower barrier for ring inversion and more 1,3-bonding in the transition state.     

Quantitative determination of glutathione in single human erythrocytes by capillary zone electrophoresis with electrochemical detection

Glutathione (GSH) in single human erythrocytes is determined by capillary zone electrophoresis with end-column amperometric detection at a gold/mercury amalgam microelectrode. A capillary of 10 microm inner diameter is suitable for determination of GSH in an individual erythrocyte with a good signal-to-noise ratio. The limit of detection is 1 x 10(-7) mol/L or 26 amol and the linear dynamic range is 2 x 10(-7) to 2 X 10(-5) mol/L for the capillary. In this method, the calibration line is obtained with a capillary adsorbed before a certain amount of hemoglobin can be used for the quantification of GSH in the external standardization. The whole cell injection and the lack of necessity of a derivatization reaction lead to more accurate and precise results, which are closer to the macroscopic values of glutathione in human red blood cell (i.e., hemolysate) than those determined by indirect laser-induced fluorescence detection.     

单臂冠醚液晶LB膜的相变研究

研究了两种单臂冠醚液晶及配合物(1, 2及1.Eu^3^+)的LB膜的成膜特性,实验发出它们均可在气-液界面形成单分子膜, 但不易转移, 化合物1在压膜过程中出现一维相变。用CPK模型对成膜分子构型和面积进行估算, 其结果与实验相一致, 并讨论了冠醚液晶结构对LB膜相变的影响。     

Determination of Osmium(VIII) by Flow Injection-Kinetic Methods Using Bromopyrogallol Red and Hydrogen Peroxide

A new flow injection-kinetic method has been developed for the determination of trace amount of osmium(WI), based on its catalytic effect on the bromopyrogallol red and hydrogen peroxide reaction. The reaction is followed spectrophotometrically by measuring the decrease in absorbance at 559 nm. The calibration graph for osmium(VIII) is linear over the range from 0.0040 to 0.10 μg/ml and the detection limit and sampling frequency are 0.0030 μg/ml and 47 per hour, respectively. The proposed method was applied to the determination of trace amounts of osmium in refined ores and chlorination residues with satisfactory results.