Water adsorption-desorption isotherms of two-dimensional hexagonal mesoporous silica around freezing point

Zr-doped mesoporous silica with a diameter of approximately 3.8 nm was synthesized via an evaporation-induced self-assembly process, and the adsorption-desorption isotherms of water vapor were measured in the temperature range of 263-298 K. The measured adsorption-desorption isotherms below 273 K indicated that water confined in the mesopores did not freeze at any relative pressure. All isotherms had a steep curve, resulting from capillary condensation/evaporation, and a pronounced hysteresis. The hysteresis loop, which is associated with a delayed adsorption process, increased with a decrease in temperature. Furthermore, the curvature radius where capillary evaporation/condensation occurs was evaluated by the combined Kelvin and Gibbs-Tolman-Koening-Buff (GTKB) equations for the modification of the interfacial tension due to the interfacial curvature. The thickness of the water adsorption layer for capillary condensation was slightly larger, whereas that for capillary evaporation was slightly smaller than 0.7 nm.     

Distinguishing nanomaterial particles from background airborne particulate matter for quantitative exposure assessment

As the production of engineered nanomaterials quantitatively expands, the chance that workers involved in the manufacturing process will be exposed to nanoparticles also increases. A risk management system is needed for workplaces in the nanomaterial industry based on the precautionary principle. One of the problems in the risk management system is difficulty of exposure assessment. In this article, examples of exposure assessment in nanomaterial industries are reviewed with a focus on distinguishing engineered nanomaterial particles from background nanoparticles in workplace atmosphere. An approach by JNIOSH (Japan National Institute of Occupational Safety and Health) to quantitatively measure exposure to carbonaceous nanomaterials is also introduced. In addition to real-time measurements and qualitative analysis by electron microscopy, quantitative chemical analysis is necessary for quantitatively assessing exposure to nanomaterials. Chemical analysis is suitable for quantitative exposure measurement especially at facilities with high levels of background NPs.     

K-型卡拉胶/聚乙烯吡咯烷酮共混水凝胶的辐射合成

采用辐射技术合成了K 型卡拉胶 (KC) /聚乙烯吡咯烷酮 (PVP)共混水凝胶 ,研究了天然高分子KC、单体N 乙烯基吡咯烷酮 (N VP)、交联剂二甲基丙烯酸十四甘醇酯 ( 1 4G) ,辐照剂量以及剂量率等对辐射合成的KC/PVP共混水凝胶性质的影响 .实验发现 ,KC与适当比例的N VP共混后在一定剂量范围内辐照可得到高强度、高溶胀行为的KC/PVP共混水凝胶 ,随着共混凝胶内KC含量的相对增加 ,凝胶强度及溶胀性的能均显著提高 ,但合成该共混凝胶的最佳剂量却相对提前 ;加入 1 4G后降低了KC/PVP共混凝胶辐射合成最佳剂量 ,同时使KC/PVP共混凝胶的强度进一步提高 ;剂量、剂量率对KC/PVP共混凝胶的性质亦有很大的影响 .分析表明 ,KC与N VP共混后 ,在较低剂量下KC的降解被抑制 ,从而获得一种由物理交联的KC和化学交联的PVP形成的互穿网络 (IPN)凝胶     

Partial molar volumes and partial molar adiabatic compressibilities of ethylenediamine complexes in water

Densities and ultrasonic propagating velocities of aqueous solutions of ethylenediamine complexes [Co(en)₃]Cl₃, [Cr(en)₃]Cl₃, [Ni(en)₃]Cl₂, and [Cu(en)₂]Cl₂ (en=ethylenediamine), as well as the ligand ethylenediamine were measured at 25°C. The infinite dilution values of the partial molar volume V ₂ ⁰ and partial molar adiabatic compressibility K _s ⁰ were evaluated. The value of K _s ⁰ of the ligand ethylenediamine is nearly zero. The values of V ₂ ⁰ and K _s ⁰ are combined with other interaction parameters, such as the Stokes radii and the viscosity B-coefficients, and their dependece upon the charge number and the stereochemistry of the complex ions is discussed.     

Determination of cadmium by suction-flow liquid-liquid extraction combined with inductively-coupled plasma atomic emission spectrometry

The flow manifold described permits suction-flow liquid-liquid extraction of cadmium in a discrete aqueous sample as its diethyldithiocarbamate into carbon tetrachloride. The organic extract is fed into the nebulizer of an inductively-coupled plasma atomic emission spectrometer by a peristatic pump. An increase in sensitivity of ca. 250-fold is achieved in comparison with direct aspiration of the aqueous solution. The sampling frequency is 20 h^?1 and the consumption of carbon tetrachloride and 5% (w/v) sodium diethyldithiocarbamate solution are each 0.6 ml min^?1. The 3σ detection limit is 0.4 ng ml^?1 cadmium, and the calibration is linear up to 300 ng ml^?1. The relative standard deviation for 10 replicate measurements is 1.5% for 50 ng ml^?1 cadmium. The flow interferences observed can be decreased or eliminated by the addition of citrate to the buffer solution. Results of analysis of some certified biological reference materials are given.     

A facile and novel synthesis of 5-phenylimidazo[4,5-c][1,8]naphthyridin-4(5H)-ones

A convenient and regioselective synthesis of a new heterocycle, 5-phenyl-1H or 3H-imidazo[4,5-c][1,8]-naphthyridin-4(5H)-one 1-a or 1-b , is described. Methyl 2-anilinonicotinate 15 was transformed into the valuable intermediate, N-phenyl-3-azaisatoic anhydride 4 using trichloromethyl chloroformate (TCF). Treatment of 4 with the anion of ethyl nitroacetate gave 4-hydroxy-3-nitro-1-phenyl-1,8-naphthyridin-4(5H)-one 3 . Compound 3 was chlorinated, aminated, reduced, and cyclized to afford 5-phenylimidazo[4,5-c][1,8]naphthyridin-4(5H)-one 1 . Regioselective substitution at the 1 or 3-position in the imidazole moiety of 1 was achieved by minor changes of the above scheme.     

Miniaturized HPTLC of Vitamin B12 Compounds in Foods

High-performance thin-layer chromatography (HPTLC) is a separation technique commonly used to identify and quantify compounds in chemical mixtures. Preliminary experiments indicated that Lichrospher silica gel 60 F254s HPTLC sheets were the most suitable for analyzing vitamin B₁₂ compounds. This study revealed the advantages of miniaturized Lichrospher HPTLC for analyzing authentic vitamin B₁₂ compounds as short migration distances (5 cm) and short development times (<45 min) in combination with high separation efficiency and sensitivity (>25 pmol at 254 nm). The practicability of using miniaturized HPTLC was demonstrated by the separation and identification of vitamin B₁₂ compounds purified from foods using an immunoaffinity column.     

Coherent oscillations in ultrafast fluorescence of photoactive yellow protein

The ultrafast photoinduced dynamics of photoactive yellow protein in aqueous solution were studied at room temperature by femtosecond fluorescence spectroscopy using an optical Kerr-gate technique. Coherent oscillations of the wave packet were directly observed in the two-dimensional time-energy map of ultrafast fluorescence with 180 fs time resolution and 5 nm spectral resolution. The two-dimensional map revealed that four or more oscillatory components exist within the broad bandwidth of the fluorescence spectrum, each of which is restricted in the respective narrow spectral region. Typical frequencies of the oscillatory modes are 50 and 120 cm(-1). In the landscape on the map, the oscillatory components were recognized as the ridges which were winding and descending with time. The amplitude of the oscillatory and winding behaviors is a few hundred cm(-1), which is the same order as the frequencies of the oscillations. The mean spectral positions of the oscillatory components in the two-dimensional map are well explained by considering the vibrational energies of intramolecular modes in the electronic ground state of the chromophore. The entire view of the wave packet oscillations and broadening in the electronic excited state, accompanied by fluorescence transitions to the vibrational sublevels belonging to the electronic ground state, was obtained.