二茂钛含氟有机酸衍生物的质谱研究

本文研究了二茂钛含氟长链有机酸衍生物(1～3)和具有环状结构的新型二茂钛全氟有机酸(4～7)的电子轰击质谱(EIMS)和负离子化学电离质谱(NICIMS)。在EI谱中出现弱的或不出现M~+,1～7均以CpTiF_2离子为基峰。高质量区的主要特征碎片离子有[M-·cp]~+、[M-R]~+(1～3)和氟重排离子。在低质量区出现一系列二茂钛及茂钛氟重排离子。 1、4～7的NICI(CH_4)质谱中,4、5出现强的M~-离子峰,1出现[M-1]-离子峰,有两个钛的环状结构化合物6和7出现双电荷M~=离子峰,而不出现M~-。     

A New Total Synthesis of D-threo-L-talo-Octose

A new approach to the total, asymmetric synthesis of D -threo-L -talo-octose ((?)- 1 ) and its derivatives is presented. It is based on the chemoselective Wittig-Horner monoolefination of a 5-deoxy-D -ribo-hexodialdose derivative 4 obtained by selective reduction of (?)-5-deoxy-2.3-O-isopropylidene-/β-D -ribo-hexofuranurono-6,1-lactone ((?)- 3 ). Allylic bromination of the resulting methyl (E)-oct-6-enofuranuronate (+)- 5 followed by intramolecular nucleophilic displacement of the so-obtained bromides gave a 13.3:1 mixture of (?)-methyl (E)-l,4-anhydro-6,7-dideoxy-2,3-O-isopropylidene-β-L -talo-oct-6-enopyranuronate ((?)- 8 ) and methyl (E)-l,4-anhydro-6,7-dideoxy-2,3-O-isopropylidene-α-D -allo-oct-6-enopyranuronate ( 9 ). The double hydroxylation of the enoate (?)- 8 followed Kishi's rule and gave the corresponding D -threo-β-L -talo-octopyranuronate derivative (?)- 11 with a good diastereoselectivity. Reduction of ester (?)- 11 and deprotection led to pure (?)- 1 .     

Asymmetric Synthesis VIII: Enantioselective Synthesis of (R) or (S)-α-Substituted Benzylamines VIA Chiral Pinanone Ketimine Template

An excellent asymmetric synthesis of both (R) and (S)-α-substituted benzylamines in optical purity 90.4–99.9% has been achieved by alkylation of a chiral ketimine, prepared from pinanone and benzylamine. Diastereoselectivity in the alkylation is not dependent on the alkyl halides.     

钙蛋白酶-10 基因SNP-19 与多囊卵巢综合征相关性研究

目的 探讨钙蛋白酶-10 基因（CAPN-10）单核苷酸多态性-19（SNP-19）与多囊卵巢综合征（PCOS）的相关性。 方法 采用聚合酶链反应- 限制性片段长度多态性（PCR-RFLP）技术,对107 例PCOS患者（PCOS 组）及111 例健康体检者（对照组）的CAPN-10 SNP-19 进行分析,并测定其性激素和生化指标。PCOS组再根据BMI与胰岛素抵抗（IR）稳态模型指数（HOMA-IR）分为肥胖组与非肥胖组、IR 组与非IR 组,分析CAPN-10 SNP-19 与其关系。结果 与对照组相比,PCOS 组BMI、空腹血糖（FPG）、TG、TC、LDL、黄体生成素（LH）、黄体生成素/ 卵泡刺激素（LH/FSH）、睾酮（T）均升高（均P＜0.01）。PCOS 组CAPN-10 SNP-19 1等位基因及1/2基因型频率均高于对照组（均P＜0.05）;且CAPN-10 SNP-19 1/2基因型PCOS 发病风险较1/1、2/2 基因型增加约2倍（OR=1.9,95％CI=1.1~3.3,P＜0.05）。CAPN-10 SNP-19 1、2等位基因频率PCOS 肥胖组与非肥胖组、IR 组与非IR组比较均无统 计学差异（均P＞0.05）;PCOS 肥胖组和IR组CAPN-10 SNP-19 1/2基因型频率分别高于非肥胖组和非IR 组,但差异均无统计学意义（均P＞0.05）。结论 CAPN-10 SNP-19 与PCOS 遗传易感性有关,可能与PCOS 肥胖及IR 无关。     

Species Diversity and Secondary Metabolites of Sarcophyton-Associated Marine Fungi

Soft corals are widely distributed across the globe, especially in the Indo-Pacific region, with Sarcophyton being one of the most abundant genera. To date, there have been 50 species of identified Sarcophyton. These soft corals host a diverse range of marine fungi, which produce chemically diverse, bioactive secondary metabolites as part of their symbiotic nature with the soft coral hosts. The most prolific groups of compounds are terpenoids and indole alkaloids. Annually, there are more bio-active compounds being isolated and characterised. Thus, the importance of the metabolite compilation is very much important for future reference. This paper compiles the diversity of Sarcophyton species and metabolites produced by their associated marine fungi, as well as the bioactivity of these identified compounds. A total of 88 metabolites of structural diversity are highlighted, indicating the huge potential these symbiotic relationships hold for future research.     

石墨烯表界面化学修饰及其功能调控

石墨烯属于碳纳米材料家族中的一员,是一种单层的二维原子晶体,具有高硬度、高导热性、高载流子迁移率等诸多优良特性,被认为是新一代电子学器件的重要基础材料.近年来我们课题组利用石墨烯的这些优良特性在其表界面化学修饰及其功能调控方面开展了一系列研究工作.我们对石墨烯表界面进行了共价或非共价化学修饰,在一定程度上打开了石墨烯的带隙,并发展了具有传感功能的石墨烯器件.我们还制备了基于石墨烯的纳米电极,发展了新一代分子电子器件的普适性制备方法,实现了单分子器件的功能化.展望未来,以石墨烯为代表的碳基纳米材料将继续在纳电子器件研究领域发挥重要作用.     

基于双向循环神经网络的汉语语音识别*

当前基于深度神经网络模型中,虽然其隐含层可设置多层,对复杂问题适应能力强,但每层之间的节点连接是相互独立的,这种结构特性导致了在语音序列中无法利用上下文相关信息来提高识别效果,而传统的循环神经网络虽然做出了改进,但是只能对上文信息进行利用。针对以上问题,该文采用可以同时利用语音序列中上下文相关信息的双向循环神经网络模型与深度神经网络模型相结合,并应用于语音识别。构建具有5层隐含层的模型,其中第3层为双向循环神经网络结构,其他层采用深度神经网络结构。实验结果表明:加入了双向循环神经网络结构的模型与其他模型相比,较好地提高了识别正确率;噪声对双向循环神经网络汉语识别有重要影响,尤其是训练集和测试集附加噪声类型不同时,单一的含噪声语音的训练模型无法适应不同噪声类型的语音识别;调整神经网络模型中隐含层神经元数量后,识别正确率并不是一直随着隐含层中神经元数量的增加而增加,神经元数量数目增加到一定程度后正确率出现了降低的趋势。     

红茶提取液在盐酸中对碳钢的缓蚀作用

采用动电位极化曲线和交流阻抗（EIS）研究了红茶提取液（BLE）在盐酸介质中对碳钢的缓蚀性能和缓蚀机理。 研究结果表明,采用索氏提取法从红茶茶叶中提取的缓蚀剂,对碳钢在1.0 mol/L盐酸溶液中具有良好的缓蚀性能,随着提取物浓度的增加,缓蚀效率增大。 红茶提取液中的有效缓蚀成分为抑制阴阳极反应的混合型缓蚀剂,在碳钢表面的吸附符合Langmuir等温式,属于单分子层吸附。     

Efficient synthesis of 2,3-dihydro-1,4-benzoxazines via intramolecular copper-catalyzed O-arylation

A highly efficient synthetic approach to 2,3-dihydro-1,4-benzoxazines is described. The method involves a mild intramolecular copper-catalyzed O-arylation of β aminoalcohol, which works well without N-protection.     

A facile synthesis of novel endo-selective polycyclic spiropyrrolidine oxindoles via 1,3-dipolar cycloaddition of α,γ-dialkylallenoate esters

Novel polycyclic spiropyrrolidine oxindoles that bear two vicinal quaternary centers and an exocyclic CC double bond have been synthesized by a three-component reaction involving α,γ-dialkylallenoate esters, isatin derivatives and amino acids, by way of an endo-selective 1,3-dipolar cycloaddition. These reactions proceed in high yields and diastereoselectivities. The structures and relative stereochemistry of products were confirmed by NMR, HRMS and X-ray crystallography.