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Anion cascade reactions Ⅲ:Synthesis of 3-isoquinuclidone bridged polycyclic lactams

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Chinese Chemical Letters 2024年第2期35卷 426-430页

作者： Zhiguo Zhang Bingbing Shi Xiyang Cao nana ma Hao Wu Xingjie Zhang Guisheng Zhang Key Laboratory of Green Chemical Media and Reactions Ministry of EducationCollaborative Innovation Centre of Henan Province for Green Manufacturing of Fine ChemicalsNMPA Key Laboratory for Research and Evaluation of Innovative DrugSchool of Chemistry and Chemical EngineeringHenan Normal UniversityXinxiang 453007China

Bridged polycyclic lactams are important structural units in organic functional materials,natural products,and pharmaceuticals.A flexible and efficient anion cascade reaction was developed for the preparation of bridged polycyclic lactams from readily available malonamides and 1,4‑*** highly substituted bridged polycyclic lactams were synthesized in good to excellent yields by tandem nucleophilic sequences in the presence of t BuOK in commercially available EtOH solvent at 60℃.Notably,the simple reactions can be run on a gram ***,bis-Michael addition reaction and hemiaminalization reactions are involved in the tandem transformation.

关键词： Anion cascade reactions 3-Isoquinuclidone Bridged polycyclic lactams Bis-Michael addition reaction Hemiaminalization

黄刺多糖中单糖含量与体外降血糖活性相关性分析

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食品科学 2024年第8期45卷 122-133页

作者：岳庆明韩丽娟邓永蓉马娜娜赵玉欣青海大学农牧学院青海西宁810016

基于糖脂毒性(glucolipotoxicity,GLTy)诱导的RIN-m5F胰岛细胞模型及α-葡萄糖苷酶和α-淀粉酶活性共同探究不同产地黄刺多糖(Berberi dasystachya polysaccharides,BDPs)降血糖活性,以期探究其单糖含量与降血糖活性之间的相关性。以青... 详细信息

基于糖脂毒性(glucolipotoxicity,GLTy)诱导的RIN-m5F胰岛细胞模型及α-葡萄糖苷酶和α-淀粉酶活性共同探究不同产地黄刺多糖(Berberi dasystachya polysaccharides,BDPs)降血糖活性,以期探究其单糖含量与降血糖活性之间的相关性。以青海省5个地区黄刺浆果为原料,采用超声辅助热水浸提法提取5种不同产地BDPs(Ⅰ~Ⅴ),明确BDPs化学组成及初级结构,探讨BDPs体外降血糖活性及对GLTy损伤的胰岛细胞的保护作用,揭示BDPs单糖含量与降血糖活性之间的相关性。结果表明,不同产地BDPs均是由β-糖苷键连接且具有吡喃糖环骨架构型的不具备三螺旋构象的杂多糖,在200℃以下表现出优良的热稳定性。另外不同产地BDPs单糖组成及分子质量存在较大差异。不同产地BDPs均展现了良好的体外降血糖活性,其中BDPs-I对α-淀粉酶具有显著的抑制效果,抑制率高达67.41%(P<0.05)。此外,不同产地BDPs对GLTy诱导的RIN-m5F胰岛细胞具有良好的保护作用,其中BDPs-I具有最优的细胞增殖活性,可有效清除活性氧水平,显著降低肿瘤坏死因子-α含量。最后,通过相关性分析发现葡萄糖、半乳糖、鼠李糖等单糖与α-淀粉酶抑制率呈现较强的正相关关系,甘露糖与活性氧之间存在较强的负相关性。本研究为黄刺浆果资源在降血糖活性方面的利用及开发提供一定理论依据。

关键词：黄刺多糖单糖 RIN-m5F胰岛细胞体外降血糖活性糖脂毒性相关性分析

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L-quantum spaces

Science China(Information Sciences) 2016年第3期59卷 153-161页

作者： Bin ZHAO nana ma College of mathematics and Information Science Shaanxi Normal University

In this paper, based on a complete residuated lattice L, we introduce the definitions of L-quantum spaces and continuous mappings. Then we establish an adjunction between the category of stratified L-quantum spaces and the opposite category of two-sided L-quantales. We also prove that the category of sober L-quantum spaces is dually equivalent to the category of spatial two-sided L-quantales.

关键词： L-quantum space L-quantale adjunction stratified L-quantum space spatial two-sided L quantale

Theoretical study on second-order nonlinear optical properties of 1,10-phenanthroline Ru(Ⅱ) complexes

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Science China Chemistry 2012年第7期55卷 1421-1427页

作者： WANG CunHuan ma nana SUN ShiLing QIU YongQing Institute of Functional material Chemistry Faculty of ChemistryNortheast Normal UniversityChangchun 130024China

The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru（II） complexes were carried out using density functional theory （DFT）. The results indicate that these complexes have large second-order nonlinear optical （NLO） responses. Specially, complex 6b has a maximal first hyperpolarizability βtot value. The first hyperpolarizabilities can be tuned by changing the ancillary ligand, introducing electron-acceptor group NO2 and/or increasing r-conjugation on phenanthroline. Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer （ILCT）, while the complexes in series b exhibit metal-to-ligand charge transfer （MLCT） and lig- and-to-ligand charge transfer （LLCT） transition at relatively low-energy absorptions.

关键词： 1,10-phenanthroline Ru(II) complexes NLO property DFT

黄刺多糖对STZ诱导的Ⅰ型糖尿病大鼠糖脂代谢的调节作用

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食品工业科技 2024年第16期45卷 348-357页

作者：马娜娜韩丽娟杨永晶索有瑞院珍珍叶英青海大学农牧学院青海西宁810016 中国科学院西北高原生物研究所青海西宁810001 中国科学院大学北京100049

为探究黄刺多糖(Berberis dasystachya ***,BDP)对链脲佐菌素(STZ)诱导的I型糖尿病大鼠的糖脂代谢的调节作用,本文采用STZ诱导I型糖尿病大鼠模型,糖尿病模型大鼠随机分为模型对照组、多糖低剂量组(BDP-L,100 mg/kg)、中剂量组(BDP-M,200... 详细信息

为探究黄刺多糖(Berberis dasystachya ***,BDP)对链脲佐菌素(STZ)诱导的I型糖尿病大鼠的糖脂代谢的调节作用,本文采用STZ诱导I型糖尿病大鼠模型,糖尿病模型大鼠随机分为模型对照组、多糖低剂量组(BDP-L,100 mg/kg)、中剂量组(BDP-M,200 mg/kg)、高剂量组(BDP-H,400 mg/kg)。灌胃28 d后,监测大鼠体重及血糖变化,测定血脂水平、脂代谢酶活性及体内抗氧化酶活等指标。结果表明:黄刺多糖给药第28 d,与模型组相比BDP给药组的血糖、血脂水平均显著降低(P<0.05),其中高剂量组血糖下降39.16%(P<0.01)。BDP给药组的血清胰岛素水平、肝糖原(HG)水平有所增加(P<0.05或P<0.01),其中高剂量组的大鼠血清胰岛素水平增加1.28倍(P<0.01),HG水平增加89.79%(P<0.01)。相比较模型组大鼠,经BDP给药后大鼠/血清和胰腺中的过氧化氢酶(CAT),超氧化物歧化酶(SOD)和还原型谷胱甘肽(CSHPx)以剂量依赖性方式显著增加(P<0.05或P<0.01),丙二醛(MDA)含量显著减少(P<0.05)。综上,黄刺多糖通过改善Ⅰ型糖尿病大鼠氧化应激从而保护胰岛β细胞的损伤,进而改善糖尿病大鼠的糖脂代谢。

关键词：黄刺多糖 Ⅰ型糖尿病糖脂代谢氧化应激

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Synthesis of[60]Fullerene-Fused Allylbenzofurans via Palladium-Catalyzed Migration Reaction

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中国化学:英文版 2023年第14期41卷 1733-1739页

作者： Tong-Xin Liu Panting Yang nana ma Xiaojun Li Xin Wang Jinliang ma Guisheng Zhang Collaborative Innovation Center of Henan Province for Green manufacturing of Fine Chemicals Key Laboratory of Green Chemical Media and ReactionsMinistry of EducationSchool of Chemistry and Chemical EngineeringHenan Normal UniversityXinxiangHenan453007 China

Chemical functionalization of fullerenes has been an important topic in fullerene chemistry. Herein, an unprecedented Pd-catalyzed migration reaction of [60]fullerene with allyloxy-tethered aryl iodides is present for the preparation of novel [60]fullerene-fused allylbenzofurans. The use of 1,2-bis(diphenylphosphino)benzene (DPPBz) as a ligand is crucial for the success of the transformation. The reaction shows high chemo- and regioselectivity, and is flexible with regard to allyl-migration site, providing a new and efficient approach to rare [60]fullerene-fused benzofurans. Control experiments disclose that the reaction most probably undergoes a sequential C—O bond cleavage/allyl-migration/intermolecular cycloaddition cascade process.

关键词： Fullerenes Transition-metal catalysis Cross-coupling Cycloaddition Oxygen heterocycles

Iridium complex of porphycene:a new member of metalloporphycene

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Science China Chemistry 2020年第5期63卷 682-686页

作者： Yi Chang Fei Zhao Fan Wu nana ma Xiaoming ma Yue Zhao Kin Shing Chan Zhen Shen State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical EngineeringNanjing UniversityNanjing 210046China Key Laboratory of Green Chemical Media and Reactions Ministry of EducationSchool of Chemistry and Chemical EngineeringHenan Normal UniversityXinxiang 453007China

Iridium(Ⅲ)porphycene complex was synthesized and structurally characterized for the first *** introduction of the posttransition iridium(Ⅲ)ion not only significantly enhances the absorption intensity at the end of visible region,but also displays efficient singlet oxygen quantum yield(76%),which is applicable for photodynamic therapy in living cells.

关键词： porphycene iridium complex magnetic circular dichroism singlet oxygen photodynamic therapy

Quantum chemical studies on tuning the second-order nonlinear optical molecular switching of triarylborane derivatives

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Chinese Science Bulletin 2012年第15期57卷 1772-1780页

作者： LI Xue SUN ShiLing ma nana QIU YongQing FU Qiang Institute of Functional material Chemistry Faculty of ChemistryNortheast Normal UniversityChangchun 130024China

In this work, density functional theory (DFT) combined with the finite field (FF) method has been adopted to analyze the second-order nonlinear optical (NLO) properties of the triarylborane (TAB) derivatives obtained by introducing different inductive electron groups into the phenylene ring of the TAB (RTAB, where R=2-C6H5-C2B10H10(1),R=F(2), R=Me(3),R=NO2(4),R=NH2(5)). The static first hyperpolarizabilities (βtot) of the RTAB molecules can be switched by binding one F- to the boron center (RTAB′) or one-electron reduction (RTAB"). The DFT-FF calculations show that the βtot values of 2′, 3′ and 5′ decrease while those of 1′ and 4′ increase compared with the values of their neutral molecules, which was attributed to the fact that the charge transfers of 2, 3 and 5 become smaller and those of 1 and 4 become larger by binding one F- ion to the boron center, according to time-domain DFT (TD-DFT) analysis. However, the incorporation of one electron enhances the second-order NLO properties of the RTAB molecules remarkably, especially for system 1. It is notable that the βtot value of reduced form 1″ is 508.69×10-30 esu, i.e. about 578 times larger than that of system 1. Frontier molecular orbital (FMO) and natural bond orbital (NBO) analyses suggest that the reversal of the charge distribution between the neutral molecules and their reduced forms leads to low HOMO-LUMO energy gaps (E0) and thus large βtot values for the reduced forms.

关键词：二阶非线性光学性质分子开关衍生物三芳基硼烷化学研究 TD-DFT 单电子还原

Copper（I）-Catalyzed Intramolecular N-N Coupling of Cyclopropyl O-Acyl Ketoximes： Synthesis of Spiro-fused Pyrazolin-5-ones

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Chinese Journal of Chemistry 2016年第12期34卷 1309-1320页

作者： Zhiguo Zhang Junlong Li Guoqing Huang Kai Sun Guisheng Zhang nana ma Qingfeng Liu Tongxin Liu Collaborative Innovation Center of Henan Province for Green manufacturing of Fine Chemicals Key Laboratory of Green Chemical Media and Reactions Ministry of Education School of Chemistry and Chemical Engineering Henan Normal University Xinxiang Henan 453007 China Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis Northeast Normal University Changchun Jilin 130024 China Handan Purification Equipment Research Institute Handan Hebei 056027 China College of Chemistry and Chemical Engineering Anyang Normal University Anyang Henan 455000 China

A convenient copper-catalyzed approach has been developed for the synthesis of substituted spiro-fused pyrazolin-5-ones from readily available cyclopropyl O-acyl ketoximes via an intramolecular N-N bond formation reac... 详细信息

关键词： copper-catalyzed N-Nbond formation O-acyl ketoximes pyrazolin-5-ones cyclopropyl oximes