羟乙基皂仁胶水溶胶和凝胶体系流变性的研究——不含交联剂溶胶体系的粘度

研究了羟乙基皂仁胶水溶胶体系的粘度对浓度、温度和切变速率的依赖性。溶胶的表观粘度进行了非牛顿校正,其表观粘度的切变速率依赖性可用幂律模型描述。采用Spencer-Dillon方程求得的体系零切粘度与浓度的关系可用Onogi公式描述。对于溶剂和较稀溶液,温度对粘度的影响可用Andrade公式描述,但对较浓溶液,此式不再适用。     

Systems-based design of bi-ligand inhibitors of oxidoreductases: filling the chemical proteomic toolbox

Genomics-driven growth in the number of enzymes of unknown function has created a need for better strategies to characterize them. Since enzyme inhibitors have traditionally served this purpose, we present here an efficient systems-based inhibitor design strategy, enabled by bioinformatic and NMR structural developments. First, we parse the oxidoreductase gene family into structural subfamilies termed pharmacofamilies, which share pharmacophore features in their cofactor binding sites. Then we identify a ligand for this site and use NMR-based binding site mapping (NMR SOLVE) to determine where to extend a combinatorial library, such that diversity elements are directed into the adjacent substrate site. The cofactor mimic is reused in the library in a manner that parallels the reuse of cofactor domains in the oxidoreductase gene family. A library designed in this manner yielded specific inhibitors for multiple oxidoreductases.     

食品中化学性有害物的质谱软电离裂解规律及筛查技术研究进展

食品中化学性有害物是导致食品安全问题的重要原因，质谱是对食品中化学性有害物进行定性定量分析的有效方法。该文按照化合物结构类别，综述了食品中重要化学性有害物的质谱软电离裂解机理，包括农药、兽药、真菌毒素，以及其他化学污染物。对于每类化合物，重点综述化合物质谱裂解产生的特征碎片、中性丢失等，以及这些质谱软电离裂解机理在食品中化学性有害物筛查及发现中的应用。研究化合物的质谱裂解机理可以帮助研究者对化合物进行结构解析和结构确证，为食品中同类结构新型化学性有害物的发掘提供理论依据。     

纳米氧化铝微柱富集-等离子体发射光谱法测定植物中痕量稀土元素

以负载了1-苯基-3-甲基-4-苯甲酰基-吡唑酮[5](PMBP)的纳米氧化铝为微柱吸附材料，采用等离子体原子发射光谱法(ICP-AES)，系统地研究了其在动态条件下对稀土离子Sc^3 、Y^3 和La^3 的吸附性能，并确定了最佳吸附及解脱条件。实验结果表明：在pH为4．5时，分析物均可被上述吸附材料定量吸附；用0．5moL／L盐酸溶液可将吸附在微柱上的稀土离子完全解脱。本法对Sc^3 、Y^3 和La^3 的检出限分别为0．16、0.19和0．39μg／L；相对标准偏差(RSD)分别为2．7％、3．2％和1．6％(n=9，C=0．5mg／L)。方法应用于植物标样中痕量Sc、Y和La的测定，其测定值与标样值吻合很好。     

Continuous electrophoretic separation of106Ru species in sea water and uptake of the separated fractions by sea algae

¹⁰⁶Ru chloro and nitrosyl-nitrato complexes in sea water were separated into several species by continuous electrophoresis on a filter paper curtain. Biological uptake experiments were carried out on sea algae Fucus virsoides with fractionated¹⁰⁶Ru chloro and nitrosyl-nitrato complex species in sea water. The biological uptake of¹⁰⁶Ru chloro complex species was about 8 times higher than the uptake of¹⁰⁶Ru nitrosyl-nitrato species. Electrophoretically most mobile electrically positively charged cationic species in both systems also showed about 8 times higher biological uptake than the most mobile negatively charged anionic species. A close relation of the biological uptake to the sign of the electrical charge and the electrophoretic mobility of the species is demonstrated. The results are discussed with respect to possible danger to the biological environment as a consequence of the aging of ruthenium species in sea water resulting from¹⁰⁶Ru waste disposal to the sea from a nuclear reprocessing plant. On leave of absence from the National Institute of Radiological Sciences, 9-1, 4-chome, Anagawa, Chiba-shi, Japan, on a fellowship from The Science and Technology Agency of the Japanese Govemment.     

Nanosized aluminum nitride hollow spheres formed through a self-templating solid-gas interface reaction

Nanosized aluminum nitride hollow spheres were synthesized by simply heating aluminum nanoparticles in ammonia at 1000 °C. The as-synthesized sphere shells are polycrystalline with cavity diameters ranging from 15 to 100 nm and shell thickness from 5 to 15 nm. The formation mechanism can be explained by the nanoscale Kirkendall effect, which results from the difference in diffusion rates between aluminum and nitrogen. The Al nanoparticles served as both reactant and templates for the hollow sphere formation. The effects of precursor particle size and temperature were also investigated in terms of product morphology. Room temperature cathode luminescence spectrum of the nanosized hollow spheres showed a broad emission band centered at 415 nm, which is originated from oxygen related luminescence centers. The hollow structure survived a 4-h heat treatment at 1200 °C, exhibiting excellent thermal stability.     

Online Separation and Preconcentration of Gold and Palladium on Amidinothiourea Immobilized Glass Bead for Interference-Free Flame Atom Absorption Spectrometry Determination

Amidinothiourea immobilized glass bead (AGB) was applied as the microcolumn packing for the flow-injection online separation and preconcentration of Au(III) and Pd(II) coupled with FAAS determination. The peak-area absorbance (A) and the peak-height absorbance (H) were all used as the evaluating modes. Au(III) and Pd(II) in 0.50 M HCl solution were absorbed onto AGB completely and then eluted into AAS with thiourea solution. Base metal ions with a concentration of 2.0 mg/mL and anions with a concentration of 20.0 mg/mL caused no interference in the determination of Au(III) and Pd(II). The LODs of Au(III) and Pd(II) for a preconcentration time of 60 s with a sampling flow rate of 5.0 mL/min for 0.20 μg/mL of Au(III) and 0.30 μg/mL of Pd(II) were 2.7 and 6.5 ng/mL with the H mode and 4.6 and 10.2 ng/mL with the A mode, respectively. The RSD of seven replicate determinations of 0.20 μg/mL of Au(III) and 0.30 μg/mL of Pd(II) were 0.018 and 0.024 for the H mode and 0.013 and 0.018 for the A mode, respectively. The method was successfully applied to the determination of Au and Pd in real samples. __________ From Zhurnal Analiticheskoi Khimii, Vol. 60, No. 10, 2005, pp. 1023–1029. Original English Text Copyright ? 2005 by Liu, Pu, Su. The text was submitted by the authors in English.     

Effect of microstructure on molecular oxygen permeation through condensed phospholipid monolayers

A method is presented that allows novel measurement of the effect of microstructure on the oxygen permeability of highly condensed, polycrystalline phospholipid monolayers. Oxygen permeability of the polycrystalline shell coating a stationary microbubble is measured directly using an apposing microelectrode in the induced transfer mode and modeling oxygen flux through the shell and intervening aqueous medium. Varying cooling rate through the phospholipid main phase transition permits control of shell microstructure by manipulation of crystalline domain size and shape. Domain boundary density, defined as the ratio of the mean domain perimeter to the mean domain area, of the microbubble shell is determined by fluorescence microscopy. Oxygen permeability was shown to increase linearly with domain boundary density at a constant phospholipid acyl chain length and, accordingly, was shown to decrease exponentially with increasing chain length at a constant domain boundary density. Modification of the energy barrier theory to account for microstructural effects, in terms of the domain boundary density, provides a general equation to model passive transport through polycrystalline monolayer films. Results from this method show promise in determining the gas transport kinetics of medical microbubbles and the gas exchange characteristics of biological monolayers.     

Synthesis and crystal structure of two novel nickel (imidazole) complexes having hydrogen-bonded networks

Two nickel (imidazole) complexes, Ni(im)₆Cl₂·4H₂O (1) and Ni(im)₆(NO₃)₂ (2) (im=imidazole) have been synthesized and characterized by elemental analysis, IR, UV, TG and single crystal X-ray diffraction. 1 crystallizes in the triclinic space group P-1 with a=8.800(6) Å, b=9.081(6) Å, c=10.565(7) Å, =75.058(9)°, β=83.143(8)°, γ=61.722(8)°, V=718.3(8) Å³, Z=1 and R₁ (wR₂)=0.0469 (0.1497). 2 crystallizes in the trigonal space group R-3 with a=12.370(6) Å, b=12.370(6) Å, c=14.782(14) Å, =90.00°, β=90.00°, γ=120.00°, V=1959(2) Å³, Z=3 and R₁ (wR₂)=0.0358 (0.0955). 1 and 2 exhibit different supramolecular network due to their different counter anions and different hydrogen bonding connection. In compound 1, [Ni(im)₆]²⁺ cation and counter anions Cl⁻ alternatively array in an ABAB fashion via N–HCl hydrogen bonding. In compound 2, the plane of each NO₃²⁻ is almost parallel and each NO₃²⁻ connect three different [Ni(im)₆]²⁺ cations via N–HO hydrogen bonding.     

Resonance Rayleigh scattering, frequency doubling scattering and second-order scattering spectra of the heparin-crystal violet system and their analytical application

In pH 6.0-11.2 Britton-Robinson buffer solution, binding of heparin with crystal violet (CV) can result in a significant enhancement of resonance Rayleigh scattering (RRS) and resonance non-linear scattering, such as frequency doubling scattering (FDS) and second-order scattering (SOS). Their maximum scattering wavelengths, λ_ex/λ_em, appear at 492 nm/492 nm for RRS, 984 nm/492 nm for FDS and 492 nm/984 nm for SOS, respectively. The optimum conditions of the reaction, the influencing factors and the relationship between the three scattering intensities and the concentration of heparin have been investigated. New methods for the determination of trace amounts of heparin based on the RRS, FDS and SOS methods have been developed. The methods exhibit high sensitivities, the detection limit for heparin is 2.9 ng ml⁻¹ for the RRS method, 3.5 ng ml⁻¹ for the FDS method and 3.3 ng ml⁻¹ for the SOS method. The methods have good selectivity and were applied to the determination of heparin in heparin sodium injection samples with satisfactory results.