Synthesis,Crystal Structure and Na~+/K~+-ATPase Inhibitory Activity of △~(14,15)-anhydro-24-thiocarbonylbufalin

The title compound △14,15-anhydro-24-thiocarbonylbufalin(1) was prepared by the reaction of natural product bufalin with Lawesson reagent. The crystal structure of 1, C24H30O2S·C24H30O2S, was determined by single-crystal X-ray diffraction analysis. It belongs to monoclinic, space group C2, with a = 30.9845(2), b = 6.8036(3), c = 22.5791(15) , V = 4241.7(4) 3, Mr = 384.21, Z = 4, Dc = 1.204 g/cm3, μ = 1.463 mm-1, F(000) = 1664, S = 1.064, R = 0.0487 and wR = 0.0645 for 4683 unique reflections, of which 3757 were observed(I 2■(I)). The asymmetric unit contains two independent molecules(I and Ⅱ), which are closely similar to each other except for the orientation of the lactone ring. Both conformations of I and Ⅱ are in good agreement with the solution structure in methanol as indicated by 1H-NMR analysis. Due to the presence of heavy atom sulfur in the molecules, the final refinement resulted in a small Flack parameter 0.02(3), permitting the assignments of the absolute configuration. In the solid state, intermolecular hydrogen bonds involving thiocarbonyl group in the lactone moiety and the hydroxyl groups in the steroid moiety ester linked adjacent molecules into a three-dimensional network. Compound 1 showed weak inhibition on Na+/K+-ATPase in contrast to the strong inhibitory activity of the parent compound bufalin, suggesting that the carbonyl group in lactone moiety and the hydroxyl group at C-14 play important roles for the inhibition of Na+/K+-ATPase.     

Antihyperglycaemic mechanisms of an aceteoside polymer from rose flowers and a polysaccharide–protein complex from abalone mushroom

Oral administration of an aceteoside polymer from rose Rosa rugosa (P_1-b) and a polysaccharide–peptide complex from abalone mushroom Pleurotus abalonus (LB-1b), both with antioxidant activity, produced antihyperglycaemic effects in alloxan-induced diabetic mice. The expression of insulin, superoxide dismutase and pancreas duodenum homeobox factor-1 essential for pancreatic islet function as estimated by real-time PCR was augmented. The reactive oxygen species-scavenging ability of the rose constituent was notably stronger than the mushroom constituent. Thus, the two biomolecules protected the pancreas from oxidative stress, elevated pancreatic insulin expression and lowered circulating glucose level.     

中空纤维碳纳米管/正辛醇固-液协同微萃取机理及其应用

讨论了以中空纤维为载体的碳纳米管/正辛醇固-液协同微萃取机理,建立了中空纤维碳纳米管/正辛醇固-液协同微萃取-高效液相色谱法同时测定复杂样品中微量咖啡酸、阿魏酸和肉桂酸含量的方法.以2.5 cm长的聚偏氟乙烯中空纤维为碳纳米管正辛醇分散液载体,供相为分析物的HCl(pH 2.1)溶液,接受相为pH 12.7的NaOH溶液,在35℃下,搅拌萃取60 min,萃取液进行高效液相色谱紫外检测.在优化的实验条件下,分析物的线性范围均在0.05～50 μg/L,r＞0.9990 (n=5);检出限均为0.015μg/L;日内与日间精密度均小于9.8％(n=9),平均回收率为93.8％～115.2％;富集倍数分别为514,942和1084倍.在以中空纤维为支持体的碳纳米管/正辛醇微萃取中,碳纳米管/正辛醇分散液嵌入中空纤维管壁上的微孔中形成了碳纳米管/正辛醇固-液微萃取单元束,对苯丙烯酸类化合物起到协同萃取作用.     

混沌映射和神经网络互扰的新型复合流密码

提出了一种将新型的神经网络互学习模型和常见的多混沌系统融合互扰的复合流密码方案. 首先利用三个Logistics混沌映射产生的随机序列作为神经网络互学习模型中三个 隐含层神经元的随机输入, 神经网络交互学习达到内部权值同步后, 再将同步权值映射为随机序列并与三个Logistics序列复合产生最终的密钥流. 实验表明, 产生的密钥流具有更好的随机性, 混沌流加密应用效果好. 关键词： 混沌映射 神经网络 权值同步 随机密钥流     

扫描探针显微术在巯醇自组装单分子膜纳米刻蚀中的应用

介绍了近十年来扫描探针显微术(SPM)在巯醇自组装单分子膜纳米刻蚀中的应用. 依据扫描探针的工作原理, 依次讨论了扫描隧道显微镜、原子力显微镜和导电原子力显微镜的工作特点和适用范围. 同时也讨论了自组装单分子膜纳米刻蚀术在生物分子传感器、超高密度信息存储等领域的应用前景.     

CO在Ag掺杂的氧化锰八面体分子筛上吸附的TAP研究

利用产物瞬时分析反应器中进行的单脉冲实验, 考察了393～493 K温度范围内CO在Ag掺杂的氧化锰八面体分子筛上的吸附行为. 实验表明: CO在催化剂表面发生化学吸附, 并与晶格氧反应生成CO₂. 通过对该过程反应物及产物脉冲响应曲线的模拟, 得到了各基元反应的动力学参数. CO和CO₂在该催化剂表面的脱附活化能分别为83和31 kJ/mol, CO与晶格氧的反应活化能为116 kJ/mol.     

抽运-自旋定向-探测技术及其应用

抽运-自旋定向-探测是最近发展起来的一种新型瞬态测量技术,该技术在胶体纳米结构电荷分离超快动力学探测中具有独特的优势.本文在比较传统的两光束载流子抽运-探测以及自旋抽运-探测的基础上,深入分析了三光束抽运-自旋定向-探测技术的特点、光路配置及其在胶体量子点光致负荷电、正荷电探测中的应用.最后对三光束抽运-自旋定向-探测技术的更多应用前景作出展望.     

一类多频激励相对转动非线性动力学模型的重正规化解

用摄动理论研究了一类多频激励下具有非线性弹性力和摩阻力的相对转动非线性动力学模型.探讨了各种组合频率之间的关系,给出了使多种类型共振同时发生的条件,并用重正规化方法得出了模型在各相应条件下解的渐近表达式.     

素养导向的高中化学项目教学中教师有效行为研究——以“探秘神奇的医用胶”项目教学为例

以“探秘神奇的医用胶”为主题设计实施了素养导向的项目教学。从教师行为的角度,对本次项目教学的课堂录像编码分析,发现本次项目教学的3个关键过程、7种高频行为类型、7种高频和次高频问题类型。根据编码结果回顾课堂录像,分析讨论教师在项目教学中如何通过高频行为类型、高频和次高频问题类型帮助学生建立有机物和有机反应的认识角度和认识思路,促进学生化学学科核心素养的发展。