铜(Ⅱ)及其多胺螯合物催化抗坏血酸有氧氧化动力学

抗坏血酸与自由钢(Ⅱ)及其多胺螯合物不发生直接的氧化还原反应。铜(Ⅱ)与抗坏血酸有络合作用。螯合齿数大于2的铜(Ⅱ)-多胺螯合物对抗坏血酸的有氧氧化无催化活性。当配位数为2时, 铜(Ⅱ)-乙二胺的1:1螯合物的催化反应符合酶催化动力学。自由铜(Ⅱ)催化反应对铜(Ⅱ)及抗坏血酸均显一级。实验结果说明钢(Ⅱ)在催化抗坏血酸有氧氧化时, 只能有2个配位位置被占据。其它位置必须是空位或容易被取代。实验事实支持三元络合物形成的机制。     

Well-defined BiOCl colloidal ultrathin nanosheets: synthesis,characterization, and application in photocatalytic aerobic oxidation of secondary amines

We demonstrate the first colloidal synthesis of single-crystalline BiOCl ultrathin nanosheets (UTNSs) that feature a well-defined square morphology. Unlike BiOCl nanomaterials prepared by hydrothermal routes, our colloidal BiOCl UTNSs exhibit hydrophobic surface properties and high activity and selectivity toward the photocatalytic aerobic oxidation of secondary amines to corresponding imines at room temperature. Hence, the application of BiOCl nanomaterials has been successfully extended from the widely studied photodecomposition of pollutants in aqueous solution to the synthesis of fine chemicals in organic solvent using a green approach.     

Pharmacokinetics and bioavailability of gelsenicine in mice by UPLC–MS/MS

Gelsenicine is an indole alkaloid isolated from Gelsemium elegans Benth. In recent years, the role of G. elegans Benth preparations in anti‐tumor, analgesic, dilatation and dermatological treatment has attracted attention, and it has been applied clinically, but it is easy to cause poisoning with its use. An UPLC–MS/MS method was established to determine the gelsenicine in mouse blood, and the pharmacokinetics of gelsenicine after intravenous (0.1 mg/kg) and intragastric (0.5 and 1 mg/kg) administration was studied. Deltalin was used as internal standard; a UPLC BEH C₁₈ column was used for chromatographic separation. The mobile phase consisted of acetonitrile and 10 mmol/L ammonium acetate (0.1% formic acid) with a gradient elution flow rate of 0.4 mL/min. Multiple reaction monitoring mode was used for quantitative analysis of gelsenicine in electrospray ionization positive interface. Proteins from mouse blood were removed by acetonitrile precipitation. A validation of this method was performed in accordance with the US Food and Drug Administration guidelines. In the concentration range of 0.05–100 ng/mL, the gelsenicine in the mouse blood was linear (r > 0.995), and the lower limit of quantification was 0.05 ng/mL. In the mouse blood, the intra‐day precision RSD was <12%, the inter‐day precision RSD was <15%, the accuracy ranged from 89.8 to 112.3%, the average recovery was >76.8%, and the matrix effect was between 103.7 and 108.4%, which meet the pharmacokinetic research requirements of gelsenicine. The UPLC–MS/MS method is sensitive, rapid and selective, and has been successfully applied to the pharmacokinetic study of gelsenicine in mice. The absolute bioavailability of gelsenicine is 1.13%.     

NaCl、KCl在CH3OH+DMF或DMSO混合溶剂中的溶解度, 278、288、298、303、313 K

本工作测定了NaCl、KCl在CH_3OH与DMF及CH_3OH与DMSO全组成范围混合溶剂中的溶解度。实验温度分别是; 对NaCl:278、288、298、303、313 K, 对KCl:288、303、313 K。随着溶剂组成变化KCl和NaCl的溶解度曲线皆有一极大值。溶解度温度系数分别为正和负, 随着溶剂中CH_3OH组份的减少温度系数减小。根据实验结果, 计算得NaCl和KCl自甲醇至混合溶剂的转移自由能和熵。对离子在此混合物中的溶剂化、结构影响和盐的溶解倾向作了初步解释。     

基于超快超声多普勒的三维脑损伤成像方法研究

三维超声微血管成像可直观呈现血流信息,对于脑血管疾病诊断和治疗具有重要意义。本文旨在将超快超声成像技术、超快超声功率多普勒技术和机械扫描相结合,实现脑血管三维成像和脑缺血区域评价。通过工程实现,完成了可同步控制微型线性位移平台移动和超声阵列超快发射、高速采集与压缩存储的三维扫描数据采集序列与系统。利用GPU并行运算,高效实现了超声图像波束合成方法,对原始射频超声数据完成重建。进而,基于SVD杂波滤除技术,从重建三维超声数据中提取了脑部的动态小血管信号,并获得了各切面的功率多普勒成像和冠状面彩色多普勒超声小血管成像。最后,采用体素方法对三维脑血管进行重建。大鼠在体实验结果表明,该成像系统可用于三维脑血管网络在体成像,以及脑血管损伤区域定位与量化评价。本工作对脑病检测技术发展与诊断方法研究具有一定的借鉴意义。此外,相关检测系统和成像算法具有一定普适性,对其他富含微血流血管的组织检测也有一定的参考价值。     

Note on Magic Squares and Magic Cubes on Abelian Groups

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不同介质中热处理TS-1的表征及催化性能

 分别以水汽和空气为介质对TS－1进行热处理，并采用XRF，XRD，FT－IR，UV－Vis，27AlMASNMR，29SiMASNMR，31PMASNMR和NH3－TPD等手段对TS－1热处理后骨架结构变化及B酸中心和酸量变化进行了分析．以丙烯环氧化反应为探针，考察了酸中心变化对TS－1催化性能的影响．结果表明，TS－1中的微量铝随着热处理温度的升高而减少，导致B酸中心数量及总酸量减少，环氧丙烷选择性提高，以水汽为介质热处理时脱铝更明显．热处理温度达到750℃时，TS－1分子筛中的硅氧四面体发生变化，不同的介质对骨架钛产生不同的影响．     

Photo-affinity labeling strategy to study the binding site of G protein-coupled receptors

G protein-coupled receptors (GPCRs) are involved in the control of every aspect of our behavior and physiology. GPCR can be involved in pathological processes as well and are linked to numerous diseases, including cardiovascular and mental disorders, retinal degeneration, cancer, and AIDS. This article reviews the methods of approaching photo-affinity labeling strategy to obtain the possible G protein-coupled receptors’s binding site.     

Ultrafast and Highly Selective Uranium Extraction from Seawater by Hydrogel‐like Spidroin‐based Protein Fiber

For the practical extraction of uranium from seawater, adsorbents with high adsorption capacity, fast equilibrium rate, high selectivity, and long service life are needed. Herein, a chimeric spidroin‐based super uranyl‐binding protein (SSUP) fiber was designed by fusing the gene of super uranyl‐binding protein (SUP) with the gene of spidroin. SUP endowed the SSUP fiber with high affinity and selectivity to uranium, and spidroin gave the SSUP fiber with high mechanical strength and high reusability. The wet SSUP fiber is a water‐rich hydrogel‐like structure, which provided abundant hydrophilic intermolecular space for the entrance of uranyl ions, and could accelerate the rate for uranium adsorption. In seawater, the SSUP fiber achieved a breakthrough uranium extraction capacity of 12.33 mg g^?1 with an ultrashort equilibration time of 3.5 days, suggesting that SSUP fiber might be a promising adsorbent for uranium extraction from the natural seawater.