Electronic polarizability-based stereochemical model for Sharpless AD reactions

Softness really is the hard force! Reported here was the critical yet long-overlooked role of electronic polarizability (i.e., softness) effect in controlling absolute stereochemical courses of general asymmetric induction events. Thus, a sensitive dependence of the sense of chiral induction on an alkene substrate’s substituent electronic polarizability character was uncovered from a range of structurally highly comparable Sharpless asymmetric dihydroxylation (AD) systems, from which a new polarizability-based stereochemical model of predictive power was suggested.     

双通道差分式阻抗谱检测技术及仪器研究

阻抗谱检测的目的在于获取不同物质之间微弱的介电差异信息或同一物质的介电变化信息,并据此对其组成、结构及其变化特征进行分析.常规单通道的阻抗谱检测技术对于物质间的差异和变化信息检测易受传感器和样品体系等基底信号的影响.本研究提出了一种基于AD5933阻抗转换芯片简化阻抗测量的双通道差分式阻抗谱检测技术,并研制了检测仪器,在1 ～ 91 kHz频率范围内,对比分析了基底信号分别为200,400和1000 mV,响应信号增加量0～100 mV时双通道差分和单通道检测的灵敏度,并考察了在激励峰峰值为18 V的条件下,汽油、柴油、喷气燃料及润滑油共7个样品在单通道,以空气及喷气燃料为参比的双通道差分检测的灵敏度差异.结果表明,单通道检测受基底信号影响较大,随基底信号增加,检测灵敏度降低;双通道差分式检测技术的灵敏度为单通道检测的1～2个数量级,且不受基底信号影响;以喷气燃料为参比的差分检测灵敏度分别是以空气为参比的差分检测及单通道检测的5 ～10倍及9～12倍,证实了通过合理选择参比样品,双通道差分检测能够极大地提高阻抗检测灵敏度.     

基于AChE和BuChE靶标的查尔酮衍生物的合成及生物活性研究

为了探寻治疗阿尔茨海默症（AD）的潜在双靶标活性化合物,本研究设计合成了5个新的查尔酮衍生物,并对它们的生物活性进行了评价。酶活性测定结果表明,化合物C1～C5对乙酰胆碱酯酶（AChE）和丁酰胆碱酯酶（BuChE）均具有显著的抑制活性。其中,化合物C4对AChE和BuChE有明显的抑制作用,IC₅₀分别为6.00和2.63μmol/L。细胞实验表明,化合物C4对Glu、H₂O₂和Aβ_1-42诱导的神经母细胞瘤SH-SY5Y损伤具有显著的保护作用,且呈剂量依赖性。Y迷宫和Morris水迷宫研究表明,C4能改善东莨菪碱诱导的小鼠的认知障碍和背景记忆能力,且对小鼠自主活动无影响,具有毒副作用小的优点。此外,C4能显著降低小鼠皮层总胆碱酯酶和丙二醛含量,提高谷胱甘肽过氧化物酶和超氧化物歧化酶含量。分子模拟显示,化合物C4能够结合AChE和BuChE的催化活性位点和外周阴离子位点。因此,化合物C4可能是一种很有前途的双靶向活性分子,值得做进一步的结构优化和活性评价,以期发现更安全高效的AD治疗药物。     

Acridin-9(10H)-one-based blue thermally activated delayed fluorescence materials: improvement of color purity and efficiency stability

A series of donor-acceptor-donor (D-A-D) type blue thermally activated delayed fluorescence (TADF) emitters, namely, 2,7-DtBuCz-AD, 3,6-DtBuCz-AD, 3,6-DMAC-AD, and 3,6-DMAC-AD-CF₃, were developed with highly rigid acridin-9(10H)-one (i.e. acridone [AD]) as acceptor. The regioisomeric effect study revealed that the attachment of donors at 3,6-sites of AD ring dramatically enhanced TADF ratio in comparison with the 2,7-site isomer. On the one hand, by varying donors from dimethylacridine (DMAC) to tert-butylcarbazole (tBuCz) at 3,6-sites of AD ring, the emission color purity of blue TADF emitters was improved from sky blue to deep blue. On the other hand, by introducing trifluoromethyl (CF₃) onto 9-site phenyl ring of 3,6-DtBuCz-AD, the efficiency stability of the sky blue emission for 3,6-DMAC-AD-CF₃ was remarkably improved. The deep blue organic light-emitting diode (OLED) of 3,6-DtBuCz-AD exhibited a maximum external quantum efficiency (EQE_max) of 17.88% with CIE coordinates of (0.15, 0.08), which is among the best performances ever reported for deep blue TADF-OLEDs. The sky-blue OLED of 3,6-DMAC-AD realized an EQE_max of 23.16%. And with the incorporation of CF₃, the sky blue device of 3,6-DMAC-AD-CF₃ exhibited extremely low efficiency loss of only 5.1% at the high brightness of 1,000 cd/m².     

基于状态关联性的Boost变换器混沌与反混沌控制

混沌控制与反混沌控制是一对逆问题. 通过研究系统状态变量的关联性, 分析了在电流型连续电流模式Boost变换器关联系数变化的情况下, 实现系统的混沌控制与反混沌控制的方法, 为实际应用打下理论基础. 建立了系统的离散数学模型, 利用单值矩阵理论解释了变换器混沌控制与反混沌控制的机理. 研究结果表明, 在只改变系统状态变量的关联系数的情况下, 该控制策略能够将处于任意状态的Boost变换器控制到周期1, 2, 4轨道以及混沌态, 系统的输出可实现混沌与反混沌控制. 仿真结果证明了所提出方法以及研究结果的正确性.     

无源LC传感器信号读取系统扫频源设计

针对连续快速的高频线性扫频信号源在无源LC传感器信号读取中的应用需求,设计并实现了0～400MHz任意频率段的线性扫频源系统。该系统的核心器件为直接数字频率合成器(DDS)AD9910,采用该芯片的RAM模式和数字斜坡模式,详细介绍各模式工作原理及寄存器的具体配置过程,并分别以这两种模式实现了输出扫频信号。测试结果表明,两种方式均可实现高频高速捷变稳定信号的连续扫频。该扫频源具有高精度、稳定性好、频率捷变快和小型化的等特,为LC传感器的工程应用提供技术基础。     

Enantioseparation of racemic paroxol on an amylose‐based chiral stationary phase by supercritical fluid chromatography

The separation of racemic paroxol, a key precursor of trans‐(?)‐paroxetine, on Chiralpak AD‐H, an amylose‐based chiral stationary phase, by supercritical fluid chromatography was studied. Pulse experiments were investigated using supercritical carbon dioxide modified with methanol (MeOH), ethanol and 2‐propanol at 35°C and 15 MPa. Retention and separation factors were determined under analytical conditions for different mobile phase compositions. Among the modifiers used, MeOH was shown to be the best additive, and 5% v/v of MeOH was the preferable concentration at which selectivity of 1.14 and resolution of 3.0 was obtained. In order to evaluate the potential with respect to preparative separations, the adsorption isotherms of individual enantiomers of paroxol were estimated using the elution by characteristic point method. Isotherm parameters were determined from the overloaded elution profiles that were collected at pressure ranging from 15 to 24 MPa. The isotherms obtained were further validated by comparing experimentally recorded elution profiles with the predictions based on the equilibrium‐dispersive model. The results are important to the process design and optimization of preparative supercritical fluid chromatography application.     

Workshop lecture on products of Fréchet spaces

The general question, “When is the product of Fréchet spaces Fréchet?” really depends on the questions of when a product of α₄ Fréchet spaces (also known as strongly Fréchet or countably bisequential spaces) is α₄, and when it is Fréchet. Two subclasses of the class of strongly Fréchet spaces shed much light on these questions. These are the class of α₃ Fréchet spaces and its subclass of ℵ₀-bisequential spaces. The latter is closed under countable products, the former not even under finite products. A number of fundamental results and open problems are recalled, some further highlighting the difference between being α₃ and Fréchet and being ℵ₀-bisequential.     

模拟朗缪尔探针伏安特性的非线性电子负载的设计与样机研制

研发了一套模拟朗缪尔探针伏安特性的非线性电子负载,由载波相移正弦脉宽调制(CPS-SPWM)技术的级联型H桥变流器与双向DC/DC变换器两部分组成.通过对电子负载设计方案开展建模仿真验证及样机初步测试表明,该系统基本达到了预期要求,可用于探针电源相关参数的测试及探针后端电子学系统的联合调试.