能源材料的第一性原理模拟

能源问题是目前我国面临重要问题之一,这一问题的解决是我国实现可持续发展战略的重要环节.能源化学的发展对于能源问题的解决具有重要意义.理论计算与实验观测的结合可以促进能源化学更快更好地发展.目前,理论计算已经广泛应用于能源化学中的各个领域,包括碳基能源化学、电能转化与存储以及太阳能能源化学等.本文综述了理论计算在能源化学这些重要领域应用的研究现状及发展趋势,并提出了在进一步发展和应用中所面临的关键科学与技术问题.最后,文章对理论计算在能源化学中应用的未来发展方向进行了展望,建议了几个可能的重点基础研究方向,以期达到理论计算应用于在能源化学这一领域的终极目标——理论设计高效廉价的新型能源材料.国家自然科学基金(编号:21373166,21621091);;国家“青年千人”计划资助项

Studies on the Interactions between Bioactive Peroxovanadium Complexes Bearing Organic Ligands and Histidine

在合成和表征了 4种具有较强生物活性双过氧钒配合物K3 [VO(O2 ) 2 (ox) ]·2H2 O ,Na[VO(O2 ) 2 (bipy) ]·5H2 O ,K[VO(O2 ) 2 (phen) ]·3H2 O和K2 [VO(O2 ) 2 (pic) ]·2H2 O [分别缩写为pV(ox) ,pV(bipy) ,pV(phen)和pV(pic) ,其中ox为草酸根 ,bipy为 2 ,2′ 联吡啶 ,phen为邻菲咯啉 ,pic为 2 羧酸吡啶负离子 ]的基础上 ,利用多种NMR技术和电喷雾质谱 (ESI MS)研究了这 4种含有机配体双过氧钒配合物与组氨酸 (His)在溶液中的相互作用以及反应物浓度、时间、pH等对相互作用体系的影响 .51VNMR跟踪监测的结果表明 :双过氧钒配合物pV(ox)和pV(pic)与His在中性水溶液中存在强配位相互作用 ,而pV(bipy)和pV(phen)与His在中性水溶液中无明显作用 .我们还利用谱学方法确定了pV(ox)和His相互作用后所生成产物是pV(ox)分别与His咪唑基上的 3 N和 1 N配位的一对异构体. 　In order to explore the structure2activity relationship and molecular mechanism of the specific recognition between peroxovanadium (pV) complexes bearing organic ligands and the target enzymes of tyrosine phosphatase , several NMR techniques and ESI2MS were used to study the interactions of four pV complexes {pV(ox) , pV ( bipy) , pV (phen) and pV (pic) , where pV = [VO (O2 ) 2L ] n - , in which L = oxalic acid dianion (ox) , bipyridine (bipy) , 1 ,102phenanthroline (phen) , and pyridine222carboxylic acid (pic) } towards histidine. Strong coordination interactions between imidazole of histidine and vanadium of pV(ox) or pV(pic) were observed in neutral solution , while there are not obvious interactions between histidine and pV(bipy) or pV(phen) . All 13C and 1H NMR signals of 1∶1 stoichiometric mixture of pV(ox) and histidine were assigned. Spectroscopic studies demonstrated that new complexes in the mixture of pV(ox) and histidine are a pair of isomers in which the vanadium in pV(ox) binding to the 32N and 12N of the imidazole ring. Moreover , the results of effective factors on the interaction system indicated that the new isomers were stable under the condition of physiological pH and the structure2activity relationship of these pV complexes may be relevant to their specific recognition towards histidine residues in tyrosine phosphatase.国家自然科学基金 (Nos.2 0 172 0 42 ,2 9832 0 2 0 )资助项

~(51)V NMR监测[VS_4Cu_n](n≤6)簇合物自兜反应过程

采用　51VNMR监测在核磁管内模拟 (NH4 ) 3VS4 /Et4 NBr/CuBr/PPh3体系在CH2 Cl2 中的反应过程 ,研究了反应条件如反应物不同配比对生成各种 [VS4 Cun](n≤ 6)簇合物的影响 ,提供了该反应体系在CH2 Cl2 溶液中成簇过程的一些信息 .该方法不仅可用来研究反应机理 ,而且可用于指导一些条件难以确定 (溶剂、温度、酸碱度等 )的簇合物如低核数及更高核数V Cu S簇合物的合

Studies on the interactions between bioactive peroxovanadium complexes bearing organic ligands and histidine

In order to explore the structure-activity relationship and molecular mechanism of the specific recognition between peroxovanadium. (pV) complexes bearing organic ligands and the target enzymes of tyrosine phosphatase, several NMR techniques and ESI-MS were used to study the interactions of four pV complexes {pV(ox), pV(bipy), pV(phen) and pV(pic), where pV=[VO(O-2)(2)L](n-), in which L=oxalic acid dianion (ox), bipyridine (bipy), 1, 10-phenanthroline (phen), and pyridine-2-carboxylic acid (pic)} towards histidine, Strong coordination interactions between imidazole of histidine and vanadium of pV(ox) or pV(pic) were observed in neutral solution, while there are not obvious interactions between histidine and pV(bipy) or pV (phen). All C-13 and H-1 NMR signals of 1:1 stoichiometric mixture of pV (ox) and histidine were assigned. Spectroscopic studies demonstrated that new complexes in the mixture of pV (ox) and histidine are a pair of isomers in which the vanadium in pV(ox) binding to the 3-N and 1-N of the imidazole ring. Moreover, the results of effective factors on the interaction system indicated that the new isomers were stable under the condition of physiological pH and the structure-activity relationship of these pV complexes may be relevant to their specific recognition towards histidine residues in tyrosine phosphatase

Co-Ti合金中γ相粗化动力学的实验研究和相场模拟（英文）

本研究结合实验和相场法研究了反相Co-19.7Ti合金中无序γ析出相的组织演变和粗化行为。实验和模拟结果皆表明γ相的形貌随时效时间增加由近球形转变成条状。γ相平均粒径的粗化动力学遵循r~3=kt,可获得如下■texp[-349890RT]。γ相平均粒径随时效时间的变化分为两个阶段,阶段I增长快速而阶段II增长速度减缓。时效温度由700℃增至750℃,γ相粒径分布的峰值变大以及粒径分布的宽度变窄,模拟结果与实验结果取得良好的一致性。National Key R&D Program of China(2017YFB0702901,2016YFB0701401)Ministry of Science and Technology of China(2014DFA53040)Fundamental Research Funds for the Central Universities(20720180072

Studies on the Interactions between Bioactive Peroxovanadium Complexes Bearing Organic Ligands and Histidine

【中文摘要】 在合成和表征了 4种具有较强生物活性双过氧钒配合物K3 [VO(O2 ) 2 (ox) ]·2H2 O ,Na[VO(O2 ) 2 (bipy) ]·5H2 O ,K[VO(O2 ) 2 (phen) ]·3H2 O和K2 [VO(O2 ) 2 (pic) ]·2H2 O [分别缩写为pV(ox) ,pV(bipy) ,pV(phen)和pV(pic) ,其中ox为草酸根 ,bipy为 2 ,2′ 联吡啶 ,phen为邻菲咯啉 ,pic为 2 羧酸吡啶负离子 ]的基础上 ,利用多种NMR技术和电喷雾质谱 (ESI MS)研究了这 4种含有机配体双过氧钒配合物与组氨酸 (His)在溶液中的相互作用以及反应物浓度、时间、pH等对相互作用体系的影响 .51VNMR跟踪监测的结果表明 :双过氧钒配合物pV(ox)和pV(pic)与His在中性水溶液中存在强配位相互作用 ,而pV(bipy)和pV(phen)与His在中性水溶液中无明显作用 .我们还利用谱学方法确定了pV(ox)和His相互作用后所生成产物是pV(ox)分别与His咪唑基上的 3 N和 1 N配位的一对异构体 【英文摘要】 In order to explore the structure-activity relationship and molecular mechanism of the specific recognition between peroxovanadium (pV) complexes bearing organic ligands and the target enzymes of tyrosine phosphatase, several NMR techniques and ESI-MS were used to study the interactions of four pV complexes {pV(ox), pV(bipy), pV(phen) and pV(pic), where pV=[VO(O 2) 2L] n-, in which L=oxalic acid dianion (ox), bipyridine (bipy), 1,10-phenanthroline (phen), and pyridine-2-carboxylic acid (pic)} towards h...国家自然科学基金 (Nos.20172042 ,29832020 )资助项

Inhibition Effects of Some Bioactive Peroxovanadium Complexes on the Tyrosine Phosphatase

为研究过氧钒配合物降血糖作用的构效关系规律和构效关系的分子机制 ,从牛心分离纯化了电泳纯的低分子量牛心酪氨酸磷酸酶 (BHPTPase)。合成并用51VNMR和13CNMR以及IR等谱学表征了 4种具有很强生物活性的过氧钒配合物K3[VO(O2 ) 2 (ox) ]·2H2 O、Na[VO(O2 ) 2 (bipy) ]·5H2 O、K[VO(O2 ) 2 ( phen) ]·3H2 O和K2 [VO(O2 ) 2 ( pic) ]·2H2 O。4种配合物对BHPTPase都有极显著的抑制作用 ,抑制强度的IC50 分别为 0 .2 2、0 .3 6、0 .90和0 .2 8μmol/L ,并根据实验结果讨论了过氧钒配合物的氧化能力和有机配体的空间位阻对构效关系的影响。　In order to study the st ructure2activity relationship and molecular mechanism of insulin2mimetic peroxovanadium complexes , the low2molecular2weight BHPTPase f rom bovine heart has been purified mainly by chromatography of DEAE2cellulose and Sephadex G275 , which was showed homogenicity on SDS2PAGE. Four bioactive peroxovanadium(pV) complexes bpV(ox) , bpV(bipy) , bpV(phen) and bpV(pic) , [VO(O2) 2L ] n - , where L = oxalic acid dianion(ox) , bipyridine (bipy) , 1 ,102phenanthroline (phen) , pyridine222carboxylic acid (pic) have been synthesized ; the bonding properties of center metal and it s ligand were characterized by 51V NMR , 13 C NMR , IR and elemental analysis. The complexes displayed remarkable inhibitory effect s on the bovine heart tyrosine phosphatase. Their IC50 were 0. 22 , 0. 36 , 0. 90 and 0. 28μmol/ L , respectively. The st ructure2activity relationship of the complexes were discussed by their oxidizing ability and through the steric space hindrance of the organic ligands.国家自然科学基金重点项目资助（No .2 983 2 0 2 0）;国家自然科学基金资助项目（No .196 0 5 0 0 4

2D NMR Study on the Chemical Structure of Natural Product Bergenin

The compound bergenin w asisolated from theaerialpartsofBergenia pur- purascens. Allprotonsand carbons ofthe com pound w ereassigned and its structure was char- acterized as 4-m ethoxy-2-[tetrahydro-3,4,5-trihydroxy-6-(hydroxym ethyl)pyran-2-yl]-α-re- sorcylic acid δ-lactone by using 1H-1H DQF-COSY, 1H-13CHMQCand HMBC. This work will be helpfulto the chem icalstructure studies ofthe sim ilar new ArylC-glycoside com pounds by means of NMR spectroscopy.国家自然科学基金(19605004 和29832020);教育部材料和生命过程分析科学开放实验室资助

Probing self-assembling process of [VS4-Cu-n] (n <= 6) clusters by V-51 NMR

V-51 NMR was used as a new pseudo in situ and nondestructive analytical tool to monitor and identify possible products of [VS4-Cu-n] (n less than or equal to 6) clusters. The reaction of (NH4)(3)VS4/Et4NBr/CuBr/PPh3 systems with various molar ratios in CH2Cl2 were mimicked in NMR tubes. The reaction conditions for the formation of the [VS4-Cu-n] clusters with different coordinate number of copper atoms n were studied. The results show the influence of the ratio among the reactants on the products and reveal the reaction mechanism in solution. This method not only provides some information about reaction mechanism, but also provides a guide in the synthesis of some clusters such as V-Cu-S clusters with less or more coordinate copper number whose reaction conditions (solvent, temperature, pH etc,) are difficult to be determined

Aripiprazole versus other atypical antipsychotics for schizophrenia

BACKGROUND: In most western industrialised countries, second generation (atypical) antipsychotics are recommended as first line drug treatments for people with schizophrenia. In this review we specifically examine how the efficacy and tolerability of one such agent - aripiprazole - differs from that of other comparable second generation antipsychotics. OBJECTIVES: To evaluate the effects of aripiprazole compared with other atypical antipsychotics for people with schizophrenia and schizophrenia-like psychoses. SEARCH METHODS: We searched the Cochrane Schizophrenia Group Trials Register (November 2011), inspected references of all identified studies for further trials, and contacted relevant pharmaceutical companies, drug approval agencies and authors of trials for additional information. SELECTION CRITERIA: We included all randomised clinical trials (RCTs) comparing aripiprazole (oral) with oral and parenteral forms of amisulpride, clozapine, olanzapine, quetiapine, risperidone, sertindole, ziprasidone or zotepine for people with schizophrenia or schizophrenia-like psychoses. DATA COLLECTION AND ANALYSIS: We extracted data independently. For dichotomous data we calculated risk ratios (RR) and their 95% confidence intervals (CI) on an intention-to-treat basis based on a random-effects model. Where possible, we calculated illustrative comparative risks for primary outcomes. For continuous data, we calculated mean differences (MD), again based on a random-effects model. We assessed risk of bias for each included study. MAIN RESULTS: We included 12 trials involving 6389 patients. Aripiprazole was compared to olanzapine, risperidone and ziprasidone. All trials were sponsored by an interested drug manufacturer. The overall number of participants leaving studies early was 30% to 40%, limiting validity (no differences between groups).When compared with olanzapine no differences were apparent for global state (no clinically important change: n = 703, 1 RCT, RR short-term 1.00 95% CI 0.81 to 1.22; n = 317, 1 RCT, RR medium-term 1.08 95% CI 0.95 to 1.22) but mental state tended to favour olanzapine (n = 1360, 3 RCTs, MD total Positive and Negative Syndrome Scale (PANSS) 4.68 95% CI 2.21 to 7.16). There was no significant difference in extrapyramidal symptoms (n = 529, 2 RCTs, RR 0.99 95% CI 0.62 to 1.59) but fewer in the aripiprazole group had increased cholesterol levels (n = 223, 1 RCT, RR 0.32 95% CI 0.19 to 0.54) or weight gain of 7% or more of total body weight (n = 1095, 3 RCTs, RR 0.39 95% CI 0.28 to 0.54).When compared with risperidone, aripiprazole showed no advantage in terms of global state (n = 384, 2 RCTs, RR no important improvement 1.14 95% CI 0.81 to 1.60) or mental state (n = 372, 2 RCTs, MD total PANSS 1.50 95% CI -2.96 to 5.96).One study compared aripiprazole with ziprasidone (n = 247) and both the groups reported similar change in the global state (n = 247, 1 RCT, MD average change in Clinical Global Impression-Severity (CGI-S) score -0.03 95% CI -0.28 to 0.22) and mental state (n = 247, 1 RCT, MD change PANSS -3.00 95% CI -7.29 to 1.29).When compared with any one of several new generation antipsychotic drugs the aripiprazole group showed improvement in global state in energy (n = 523, 1 RCT, RR 0.69 95% CI 0.56 to 0.84), mood (n = 523, 1 RCT, RR 0.77 95% CI 0.65 to 0.92), negative symptoms (n = 523, 1 RCT, RR 0.82 95% CI 0.68 to 0.99), somnolence (n = 523, 1 RCT, RR 0.80 95% CI 0.69 to 0.93) and weight gain (n = 523, 1 RCT, RR 0.84 95% CI 0.76 to 0.94). Significantly more people given aripiprazole reported symptoms of nausea (n = 2881, 3 RCTs, RR 3.13 95% CI 2.12 to 4.61) but weight gain (7% or more of total body weight) was less common in people allocated aripiprazole (n = 330, 1 RCT, RR 0.35 95% CI 0.19 to 0.64). Aripiprazole may have value in aggression but data are limited. This will be the focus of another review. AUTHORS' CONCLUSIONS: Information on all comparisons are of limited quality, are incomplete and problematic to apply clinically. Aripiprazole is an antipsychotic drug with a variant but not absent adverse effect profile. Long-term data are sparse and there is considerable scope for another update of this review as new data emerges from the many Chinese studies as well as from ongoing larger, independent pragmatic trials