Copper-catalyzed enantioselective addition of alcohols to isatin-derived ketimines

The first copper-catalyzed enantioselective addition of alcohols to imines was described. In the presence of 1?mol% Cu(OAc)₂ complexed with chiral cyclohexane-based N,P-ligand L4, chiral isatin-derived N,O-aminals were obtained in excellent yields (93–99%) and good-to-excellent enantioselectivities (up to 93% ee) under mild conditions.     

全媒体时代仪器分析实验课程的教学改革研究

随着现代信息技术的迅猛发展,声音、图像、视频等多种媒体在课程教学中广为应用,学生在任何时间、任何地点利用信息终端完成线上自主学习成为常态,课程教学的信息全媒体时代随之而来,全媒体对实验教学带来全新要求。本文在总结近年来仪器分析实验全媒体教学经验的基础上,开展全媒体时代背景下仪器分析实验的实践教学设计、资源库建设、新型教学模式构建、课堂教学考评、教学团队建设的研究,以期提高学生自主综合学习能力和高阶思维能力,提升仪器分析实验课程的教学效果,为深入开展全媒体教学改革提供参考。     

超高效液相色谱-串联质谱法测定蛋白胨中9种B族维生素

建立了能够同时测定蛋白胨中9种B族维生素的超高效液相色谱-串联质谱法（UPLC-MS/MS）。样品经水溶解后,滤液经Syncronis C₁₈色谱柱分离,采用电喷雾电离源,正离子、多反应监测模式进行检测,分析时间8 min,外标法定量。结果表明,9种B族维生素在各自质量浓度范围内线性良好,相关系数（R²）均大于0.999,方法的检出限为0.09~1.67 μg/L,方法的相对标准偏差均<3%（n=6）;9种B族维生素不同添加水平下的平均回收率为80.2%~103.9%。该方法简便、准确,灵敏度高,适用于蛋白胨中B族维生素的测定。     

超高效液相色谱-串联质谱法测定人血浆中苯海索

建立了灵敏、高通量的超高效液相色谱-串联质谱（UPLC-MS/MS）定量测定人血浆中苯海索的方法,用于盐酸苯海索片生物等效性研究,并确证食物对苯海索体内药代动力学行为的影响。以甲醇为沉淀剂进行蛋白质沉淀,苯海索-d11为内标,采用Waters Acquity UPLC BEH C8色谱柱（50 mm×2.1mm,1.7 μm）,以0.1%（v/v）甲酸水溶液（含5 mmol/L醋酸铵）和乙腈-水（95：5,v/v）为流动相进行梯度洗脱;采用电喷雾电离（ESI）源,在正离子模式下进行多反应监测（MRM）扫描。苯海索在0.1~40 ng/mL范围内线性关系良好。应用该方法测定中国健康受试者空腹及餐后单次口服2 mg盐酸苯海索片后的血药浓度,结果显示最大血药浓度（C_max）、血药浓度-时间曲线下面积（AUC_0-t、AUC_0-∞）的90%置信区间均在80.0%~125.0%范围内,表明两种制剂在空腹和餐后均生物等效。     

A Multi‐Functional Silicon Nanoparticle Designed for Enhanced Osteoblast Calcification and Related Combination Therapy

Implant materials applied in bone defect commonly focus on the inducement of bone regeneration and neglect to cure complications including bacterial infection and inflammation, which may result in delayed unions or even amputation. In this study, a microporous silica nanoparticle‐poly(N‐isopropylacrylamide‐b‐(2‐(dimethylamino)ethyl methacrylate) is synthesized for loading DXMS and the ECM‐derived peptide (Sequence: Succinic acid‐GTPGPQGIAGQRGVV) in order to enhance the osteoblast calcification and relieve related symptoms. Positively charged PDMA blocks endow the nanoparticle with the antimicrobial property. Moreover, the combination of DXMS makes it have the ability of anti‐inflammation and promoting calcification formation. Furthermore, incorporation of the peptide leads to a significant improvement of mineralization and alkaline phosphatase expression in the preosteoblast. After intramuscular implantation in mice for four weeks, the results indicate the composite nanoparticle can promote ectopic bone formation. These combined properties make the composite silicon nanoparticle a promising osteogenic drug appropriate for further study in bone repair and related combination therapy.     

Relaxation of the remanent resistance of granular HTSC Y-Ba-Cu-O + CuO composites after magnetic field treatment

The hysteresis of magnetoresistance R(H) and relaxation of the remanent resistance R _rem with time after magnetic field treatment of HTSC (Y-Ba-Cu-O) + CuO composites are studied. Such a composite constitutes a network of Josephson junctions wherein the nonsuperconducting component (CuO) forms Josephson barriers between HTSC grains. By comparing the experimental R _rem(t) and R(H) dependences, it is shown that the relaxation of the remanent resistance is caused by the decreased magnetic field in the intergrain medium due to relaxation of magnetization. The reason is uncovered for the differences between the published values of pinning potentials determined by measuring the relaxation of magnetization or resistance and fitting them by the Anderson law.     

衰减全反射红外光谱法快速测定糠醛抽出油烃族组成含量方法研究

提出了一种衰减全反射红外光谱法快速测定糠醛抽出油烃族组成含量的方法,设计了一套重油烃族组成快速分析系统。实验收集了62个减压蜡油经糠醛精制后的抽出油样品,采用NB/SH/T0509-2010方法测定其饱和烃、芳烃含量,由差减法求得胶质和沥青质总含量。采用偏最小二乘法(PLS)分别建立了糠醛抽出油饱和烃、芳烃和胶质+沥青质含量的定量校正模型,其SEC分别为1.43%,0.91%和1.61%,SEP分别为1.56%,1.24%和1.81%,均小于NB/SH/T0509-2010方法规定的再现性误差,模型预测精密度小于标准方法的重复性误差要求。与现行标准方法相比,该方法速度快,操作简单,可显著提高糠醛抽出油烃族组成分析效率。该分析系统也可用于其他重油分析,具有很好的推广应用前景。     

CH3CH2O+HCHO反应机理及主通道速率常数

采用CCSD(T)/cc-pVDZ//B3LYP/6-311++G(d,p)双水平计算方法研究了CH₃CH₂O+HCHO反应的微观反应机理. 结果表明, 标题反应主要存在5个抽氢和3个氢迁移异构化反应通道, 其中抽氢通道R→ IMa(CH₃CH₂O…CH₂O)→TS1→ IM1b→P1(CH₃CH₂OH+CHO)为优势通道, 其表观活化能为14.65 kJ/mol. 利用变分过渡态理论(CVT)并结合小曲率隧道效应模型计算了主通道R1在275~1000 K温度范围内的速率常数k^TST, k^CVT和k^CVT/SCT, 在此温度区间内表观反应速率常数三参数表达式为k^CVT/SCT=2.26×10^-17 T^0.57 exp(-1004/T), 显示具有正温度系数效应.     

后修饰法合成介孔钴金属有机框架及其催化烯烃环氧化

通过后修饰水热合成法制备了新型Co2+配位的金属有机框架材料,并采用红外、电感耦合等离子分析和N2吸附等技术手段对其进行了表征。 在氧气/异丁醛反应体系中,介孔钴金属有机框架对烯烃环氧化反应表现出较高的活性。 其中,环辛烯的转化率及环氧环辛烷的选择性分别达到了94%和91%,转化频率(TOF)值为509 h-1。 催化剂循环使用5次之后,其结构和活性无明显变化。     

Andreev reflection and tunneling spectrum in a superlattice of metal-superconductor junctions

The tunneling spectrum of an electron and a hole in a superlattice of NS junctions is computed using the BTK approach and the transfer matrix method. It shows sharp resonances at some energies above the superconducting gap. The sharper the resonance is the more layers the superlattice has. We find for the first time a mechanism to balance the incident and outgoing currents on the superlattice by averaging over the phase between the incident electron and the incident hole. This mechanism is more natural and physical than those in literatures.