溶剂在丁腈基聚氨酯中的溶解和扩散

用石英弹簧法和示差扫描量热法 (DSC)、红外分光光度计 (FTIR)研究了苯、乙醇、丙酮、醋酸乙酯和1,2 二氯乙烷五种溶剂在端羟基聚丁二烯 丙烯腈共聚物为软段的聚氨酯中的溶解和扩散行为 .结果表明所有溶剂在丁腈聚氨酯中的扩散均为非费克扩散 ,且随着溶剂蒸汽压增大偏离费克扩散的程度增大 .相同相对蒸汽压下 1,2 二氯乙烷和醋酸乙酯偏离费克 (Fickian)扩散的程度较大 ,而乙醇、丙酮和苯则较小 ,这主要与它们和丁腈软段溶解度参数的极性分量和氢键分量有关 .1,2 二氯乙烷和苯在HTBN PU中的溶解度较高 ,而乙醇 ,醋酸乙酯和丙酮较低 ,主要与它们和丁腈软段溶解度参数的色散分量有关 .所有溶剂均表现出近似Flory Huggins型等温吸收曲线 .红外表明吸收溶剂后 ,氨基甲酸酯基团的氢键化程度有不同程度的下降 ,和溶剂与之形成氢键的能力大小有关 .力学性能表明非极性溶剂苯对材料的力学性能影响较小 ,而乙醇 ,醋酸乙酯和丙酮由于可与氨酯基团形成氢键 ,对原HTBN PU中氨酯键氢键的破坏大 ,力学性能下降大     

High levels of soluble herpes virus entry mediator in sera of patients with allergic and autoimmune diseases

Herpes virus entry mediator (HVEM) is a newly discovered member of the tumor necrosis factor receptor (TNFR) superfamily that has a role in herpes simplex virus entry, in T cell activation and in tumor immunity. We generated mAb against HVEM and detected soluble HVEM (SHVEM) in the sera of patients with various autoimmune diseases. HVEM was constitutively expressed on CD4(+) and CD8(+) T cells, CD19(+) B cells, CD14(+) monocytes, neutrophils and dendritic cells. In three-way MLR, mAb 122 and 139 were agonists and mAb 108 had blocking activity. An ELISA was developed to detect sHVEM in patient sera. sHVEM levels were elevated in sera of patients with allergic asthma, atopic dermatitis and rheumatoid arthritis. The mAbs discussed here may be useful for studies of the role of HVEM in immune responses. Detection of soluble HVEM might have diagnostic and prognostic value in certain immunological disorders.     

A Novel Carbon Nanotube-Supported NiP Amorphous Alloy Catalyst and Its Hydrogenation Activity

A carbon nanotube-supported NiP amorphous catalyst (NiP/CNT) was prepared by induced reduction. Benzene hydrogenation was used as a probe reaction for the study of catalytic activity. The effects of the support on the activity and thermal stability of the supported catalyst were discussed based on various characterizations, including XRD, TEM, ICP, XPS, H2-TPD, and DTA. In comparison with the NiP amorphous alloy, the benzene conversion on NiP/CNT catalyst was lower, but the specific activity of NiP/CNT was higher, which is attributed to the dispersion produced by the support, an electron-donating effect, and the hydrogen-storage ability of CNT. The NiP/CNT thermal stability was improved because of the dispersion and electronic effects and the good heat-conduction ability of the CNT support.     

QuEChERS前处理结合HPLC-Q-TOF/MS非靶向快速筛查凉茶中的非法添加物

建立了QuEChERS法净化,结合高效液相色谱-四极杆-飞行时间质谱法(HPLC-Q-TOF/MS)非靶向快速筛查凉茶中未知非法添加物的方法。凉茶中的非法添加物经0.5%乙酸-乙腈提取,氨丙基粉净化,C_(18)色谱柱(100 mm×2.1 mm,1.7μm)分离,HPLC-Q-TOF/MS测定。利用8种质控化合物建立的筛查方法检出限为2.0～10μg/kg,定量下限为5.0～25μg/kg。3个不同加标水平的平均回收率为75.8%～95.6%,RSD(n=6)为2.1%～6.5%。在该定量方法基础上利用目标化合物特征离子的精确质量数、同位素匹配、二级碎片信息进行数据库匹配,无标准品情况下非靶向筛查非法添加物。结果表明,该方法无需标准品即可快速筛查凉茶中的非法添加西药,能应用于凉茶样品的实际筛查。应用该方法对50份散装凉茶样品进行测定,其中10份凉茶样品检出对乙酰氨基酚,含量为4.14～2 188 mg/kg。该方法快速、准确、分析通量高,可为凉茶中非法添加物的快速筛查和质量控制提供重要依据。     

离子液体载催化剂和载试剂在有机合成中的应用

综述了离子液体载催化剂和载试剂在有机合成中的应用进展. 离子液体载催化剂是针对离子液体中催化剂难以回收利用的问题提出来的, 它不仅可以实现均相催化, 而且反应产物容易分离, 催化剂可以循环使用. 离子液体载有机试剂合成, 又称为离子液体相有机合成, 具有固相反应产物纯度高和液相反应反应快的优点. 在离子液体载无机试剂的反应中, 反应物毒性降低, 反应条件温和, 产物选择性好.     

Direct determination of rare earth impurities in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry

A novel method was developed for the direct determination of trace quantities of rare earth elements (REEs) in high purity erbium oxide dissolved in nitric acid by inductively coupled plasma mass spectrometry (ICP-MS) in this work. The mass spectra overlap interferences arose from Er matrix on the neighbouring and monoisotopic analytes of ¹⁶⁵Ho(100) and ¹⁶⁹Tm(100) were eliminated by adjusting instrumental peak resolution value from 0.7 to 0.3 amu. The matrix suppression effect of Er on the ion peak signals of REEs impurities was effectively compensated with spiking In as internal standard element. The limit of quantitation (LOQ) of REEs impurities was from 0.0090 to 0.025 μg g⁻¹, the recoveries of spiked sample for REEs were found to be in the range of 90.3-107% through using the proposed method and relative standard deviation (R.S.D.) varied between 2.5% and 6.7%. The novel methodology had been found to be suitable for the direct determination of trace REEs impurities in 99.999-99.9999% high purity Er₂O₃ and the results obtained from this method keep in good agreement with that acquired from high resolution ICP-MS.     

1,3-Dipolar cycloaddition of azides with electron-deficient alkynes under mild condition in water

We report a simple synthetic protocol for the 1,3-dipolar cycloaddition of azides with electron-deficient alkynes. Alkyne with at least one neighboring electron-withdrawing group proceeds with the cycloaddition successfully without any catalysts at room temperature in water. Under this simple condition, we evaluated a series of small molecule model reactions and then coupled an azido-DNA molecule with electron-deficient alkynes for the formation of [1,2,3]-triazole heterocycle, providing a potential method for introducing functional groups to DNA under biological conditions.     

铬系乙烯齐聚和聚合催化剂

综述了近年来国内外铬系催化剂的最新研究进展。介绍了该类催化剂齐聚和合的性能研究和应用，讨论了该催化剂长期引起争议的活性中心，活性价态，以及反应机理，并同时预测了铬系催化剂在工业和纳米技术方面的发展趋势。     

Conformation of poly(S-(2-N-carbazolylethyl)-L-cysteine) in the solid state

The β-forming characteristics of poly(S-(2-N-carbazolylethyl)-L -cysteine), (CELC)_n, were examined by infrared (IR) spectroscopy. The film of (CELC)₃₉ cast from tetrahydrofuran (THF) showed the typical spectrum of the antiparallel β-form with the amide I band at 1630 cm^?1, whereas that of (CELC)₂₀₀ from dimethylformamide (DMF) or pyridine exhibited the amide I band at 1640 cm^?1 which shifted to 1630 cm^?1 on heating at 100°C for 5 min. As a result of the examination of the spectral variation due to the degree of polymerization, casting solvents, casting temperatures, and heat treatment, together with the evaluation of interaction constants for intermolecular hydrogen bonds, the band at 1640 cm^?1 was attributed to the antiparallel-chain pleated sheet (designated as β′-form) with weaker hydrogen bond strength than that of the usual antiparallel β-form. The β′-β-transformation is discussed in terms of the rigidity of the side-chain region.     

硝酸、硫化钠溶液浸取冷原子荧光法选择性测定土壤及河流沉积物中硫化汞

本文研究了饱和硫化钠溶液对土壤样品中硫化汞的浸取效率(其加标回收率达100%),以及用硝酸和硫化钠溶液对样品中汞的选择性浸取并研究了土壤中硫化汞垂直分布。提出了利用硝酸、饱和硫化钠溶液浸取,由冷原子荧光法选择性测定土壤及河流沉积物中硫化汞的新方法。用该方法对同一样品进行8次测定,其相对标准偏差为7.1%。