(-)-双(薄荷基甲酰基)苯基氧化膦的合成及在自由基光聚合中的螺旋选择性

以苯基二氯化膦和薄荷基甲酸为原料, 合成了一种手性双酰基膦氧化物光引发剂(-)-双(薄荷基甲酰基)苯基氧化膦. 采用核磁共振谱、 质谱及元素分析确定了该化合物的结构, 并测定了其螺旋诱导能力. 结果表明, (-)-BMPPO在引发自由基光聚合大位阻的单体甲基丙烯酸-1-苯基二苯并环庚酯(PDBSMA)的反应中具有螺旋选择性. 所得聚合物具有高度全同结构并显示出光学活性, 说明该聚合物形成了稳定的单手性螺旋链构象. 降低单体与引发剂的投料比及提高聚合温度有利于增加反应的螺旋选择性. 在手性薄荷醇溶剂中, 由(2,4,6-三甲基苯甲酰基)二苯基氧化膦(TPO)引发单体PDBSMA的光聚合反应也具有螺旋选择性, 但螺旋选择性很小.     

Ergosta-7,9(11),22-trien-3β-ol Rescues AD Deficits by Modulating Microglia Activation but Not Oxidative Stress

Ergosta-7,9(11),22-trien-3β-ol (EK100) was isolated from the Taiwan-specific medicinal fungus Antrodia camphorata, which is known for its health-promotion and anti-aging effects in folk medicine. Alzheimer’s disease (AD) is a major aging-associated disease. We investigated the efficacy and potential mechanism of ergosta-7,9(11),22-trien-3β-ol for AD symptoms. Drosophila with the pan-neuronal overexpression of human amyloid-β (Aβ) was used as the AD model. We compared the life span, motor function, learning, memory, oxidative stress, and biomarkers of microglia activation and inflammation of the ergosta-7,9(11),22-trien-3β-ol-treated group to those of the untreated control. Ergosta-7,9(11),22-trien-3β-ol treatment effectively improved the life span, motor function, learning, and memory of the AD model compared to the untreated control. Biomarkers of microglia activation and inflammation were reduced, while the ubiquitous lipid peroxidation, catalase activity, and superoxide dismutase activity remained unchanged. In conclusion, ergosta-7,9(11),22-trien-3β-ol rescues AD deficits by modulating microglia activation but not oxidative stress.     

Effect of NaCl doped into Bphen layer on the performance of tandem organic light-emitting diodes

To improve the performance of tandem organic light-emitting diodes （OLEDs）, we study the novel NaCl as n-type dopant in Bphen：NaCl layer. By analyzing their relevant energy levels and cartier transporting characteristics, we discuss the mechanisms of the effective charge generation layer （CGL） of Bphen：NaCl （6 wt%）/MoO3. In addition, we use the Bphen：NaC1 （20 wt%） layer as the electron injection layer （ELL） combining the CGL to further improve the performance of tandem device. For this tandem device, the maximal current efficiency of 9.32 cd/A and the maximal power efficiency of 1.93 lm/W are obtained, which are enhanced approximately by 2.1 and 1.1 times compared with those of the single- emissive-unit device respectively. We attribute this improvement to the increase of electron injection ability by introducing of Bphen：NaCl layer. Moreover, the CGL is almost completely transparent in the visible light region, which is also important to achieve an efficient tandem OLEDs.     

Direct asymmetric Mannich reaction of phthalides: facile access to chiral substituted isoquinolines and isoquinolinones

The first Mannich reaction employing phthalides using a quinidine-based multifunctional catalyst has been developed. The reported method led to the synthesis of 3,3-disubstituted phthalide derivatives in excellent yields, with good diastereo- and enantioselectivities. Convenient synthesis of chiral isoquinolinones and isoquinolines has also been demonstrated.     

Hydrosilane and bismuth-accelerated palladium catalyzed aerobic oxidative esterification of benzylic alcohols with air

In a palladium-catalyzed oxidative esterification, hydrosilane can serve as an activator of palladium catalyst with bismuth, thus leading to a novel ligand- and silver-free palladium catalyst system for facile oxidative esterification of a variety of benzylic alcohols in good yields.     

钛/活细胞界面原位EIS研究

设计了原位电解池用于生物材料/活细胞界面电化学交流阻抗谱(EIS)的测量, 原位观测了钛/MG63细胞界面EIS行为及其随时间的变化. 原位电解池中引入Ag/AgCl作为参比电极, 解决了EIS测量过程中高频部分信号失真的问题. 钛/MG63细胞界面EIS研究初步结果表明: 活细胞在钛电极表面附着, 可改变界面双电层结构和电极的表面状态, 进而影响界面的电化学性质. 实验发现, 由于钛电极表面氧化层的阻抗信号处于中低频段, 而细胞膜层自身的电化学阻抗响应位于高频范围, 由此, 可分别分析不同的电极过程, 解析其相互关系, 研究活细胞在生物材料表面的作用机理.     

非化学化工专业“大学化学”课程考核方法改革实践与探索

对"大学化学"课程的考核方法进行了改革。引入过程考核，降低期末考试在总成绩中的权重，在教学过程中增加理论联系实际的课外作业，以巩固基础理论知识的学习，并锻炼学生分析问题、解决问题的能力，作为考核指标记入总成绩。鼓励学生全程学习，避免突击应试。问卷调查结果表明大部分学生认同该考核方法。     

Highly efficient phosphine-catalyzed aza-Michael reactions of α,β-unsaturated compounds with carbamates in the presence of TMSCl

Aza-Michael reactions of enones with carbamates took place efficiently in the presence of a catalytic amount of phosphine and TMSCl to afford the total products in high yields. The new catalytic system was also efficient in the aza-Michael reaction of chalcone, which was difficult to react with carbamates by transition metal salts catalysts.     

Combined Dynamic Kinetic Resolution and C−H Functionalization for Facile Synthesis of Non-Biaryl-Atropisomer-Type Axially Chiral Organosilanes

Although asymmetric C−H functionalization has been available for the synthesis of structurally diverse molecules, catalytic dynamic kinetic resolution (DKR) approaches to change racemic stereogenic axes remain synthetic challenges in this field. Here, a concise palladium-catalyzed DKR was combined with C−H functionalization involving olefination and alkynylation for the highly efficient synthesis of non-biaryl-atropisomer-type (NBA) axially chiral oragnosilanes. The chemistry proceeded through two different and distinct DKR: first, an atroposelective C−H olefination or alkynylation produced axially chiral vinylsilanes or alkynylsilanes as a new family of non-biaryl atropisomers (NBA), and second, the extension of this DKR strategy to twofold o,o′-C−H functionalization led to the multifunctional axially chiral organosilicon compounds with up to >99 % ee.     

Efficient Pyrazolo[5,4-f]quinoxaline Functionalized Os(II) Based Emitter with an Electroluminescence Peak Maximum at 811 nm

Upon fusing the pyrazinyl pyrazole entity in giving pyrazolo[3,4-f]quinoxaline chelate, the corresponding Os(II) based NIR emitter exhibited “invisible” and efficient electroluminescence with a peak maximum at 811 nm. A maximum external quantum efficiency of 0.97 % and a suppressed efficiency roll-off till a current density of 300 mA cm⁻² was also exhibited.