1,2,3-硒二唑-5-甲酰胺类化合物的合成与生物活性研究

1,2,3-噻二唑类化合物具有广泛的生物活性[1～5],在农药领域,其商品化的品种虽不多,但具有独特的作用机制.如棉花脱叶剂TDZ,不伤害棉株,不降低产量,同时其细胞分裂素活性超过了玉米素和6-BA;而BTH则是第一个商品化的植物激活剂.1999年,日本报道1,2,3-噻二唑-5-甲酰胺类化合物对稻瘟病有很好的抑制活性[6],可有效的防止病菌菌丝对邻近健康细胞的侵入,已于今年正式上市.     

Novel plant activators with thieno[2,3-d]-1,2,3-thiadiazole-6-carboxylate scaffold： Synthesis and bioactivity

The 1,2,3-thiadiazole-carboxylate moiety was reported to be an important pharmacophore of plant activators.In this study,a series of novel plant activators based on thieno[2,3-d]-1,2,3-thiadiazole-6-carboxylate were designed and synthesized and their biological activity as plant activators was studied.The structures of the novel compounds were identifed by1H NMR,19F NMR and HRMS.The in vivo bioassay showed that these novel compounds had good effcacy against seven plant diseases.Especially,compounds 1a and 1c were more potent than the commercialized plant activator BTH.Almost no fungicidal activity was observed for the active compounds in the in vitro assay,which matched the requirements as plant activators.     

微量元素与食物

含钙高的食物:牛奶、黄豆、乳制品、海参、海带、蚕豆、豆制品、芝麻酱、虾皮、燕麦、小麦、酸奶、牛肉等。含镁高的食物:荷叶、香蕉、黄豆、蕃茄、绿豆、红小豆、蕃石榴、蜂蜜、燕麦等。含锌高的食物:牡蛎、猪肝、鱼类、高锌鸡蛋、板栗、核桃、红枣、黄鳝、海参等。含铁高的食     

钠、钾的食物来源

几乎所有的食物都含有钠和钾元素,只是植物性食品的钾含量高于钠含量,而动物性食品正好相反。体内钠主要来源于食盐,动物性食品和一些蔬菜如芹菜、榨菜、紫菜、胡萝卜等也能为体内提供少量的钠离子。发面用的小苏打,即碳酸氢钠也是体内钠离子的来源。植物性食物及动物性食物中皆有钾,饮水中也含有少量钾。豆类、马铃薯、紫菜、榨菜、花生、鳗鱼、牛肉、可可、咖啡、茶叶、蘑菇、海带等都含有丰富的钾,物别是豆类,无论是黄豆、绿豆、赤豆、豇豆、蚕豆和豌豆含钾都较高。因此,一般膳食不会缺钾。只有在肝硬变、呕吐、腹泻、糖尿病、酸中毒、大…     

以1-苯基-3-甲基-4-苯甲酰基代吡唑酮[5]萃取稀土和钍铀钛锆及其在分析化学中的某些应用

本文研究了以PMBP-苯萃取稀土和钍、铀、钛、锆的萃取行为。测定了La、Ce、Pr、Nd、Sm、Gd、Dy、Yb、Y、U(Ⅵ)、Ti、Th和Zr的pH_(1/2)值,计算了它们的萃取平衡常数。并介绍了近十年来作者将此萃取剂应用于铀、钍、稀土、鋰、钢铁合金及岩石中痕量稀土、钍和钙的分离和测定方面的工作。实践证明,PMOP合成简便、价格低廉、萃取能力较强,是比TTA更为优越的萃取剂。     

微乳及其应用

微乳在生物技术、人造血管、酶固定化、能源科学、纳米材料、涂料、医药、食品、石油、选矿、环境等方面得到了越来越广泛的关注和应用。对微乳的理论研究、组成、制备方法、性质表征及应用的研究作了阐述。微乳技术具有很好的发展前景。     

实验室认可的发展与体会

介绍实验室认可的发展过程与发展趋势。实验室认可的内涵是按章行事、全员参与、服务客户、实施预防、强化技术和不断完善。全面、灵活、文件资料多和要求严格是实验室认可的特点。组织落实、文件编制、人员培训、仪器档案整理、量值溯源、内审及管理评审是实施实验室认可的重要工作。     

电感耦合等离子体原子发射光谱法测定钨钢中硅、锰、磷、铬、镍、铜、钼、钒和钨

采用电感耦合等离子体原子发射光谱法测定钨钢中硅、锰、磷、铬、镍、铜、钼、钒和钨的含量。试样用盐酸、柠檬酸铵、硝酸溶解。基体效应采用基体匹配法消除。硅、锰、磷、铬、镍、铜、钼、钒、钨的分析谱线依次为288.158,257.610,177.495,267.716,213.604,327.396,204.598,310.230,239.709nm。9种元素的质量分数在一定的范围内与其发射强度呈线性关系,方法的检出限(3s)在0.000 3%~0.004 8%之间。方法用于两种标准物质的测定,测定结果与认定值相符,测定值的相对标准偏差(n=5)在0.74%~2.1%之间。方法的回收率在95.0%~107%之间。     

《国际结晶学会通讯》讯息

《国际结晶学会通讯》分发给 39个国家的 587个图书馆和 1 50 0 0名结晶学家 (结晶学工作者 ) ,及其他感兴趣的个人。有特色的文章、会议通知、研究报告、研究信息或其它结晶学家感兴趣的文章 ,任何时候都可以交给编辑。无论来稿是电子邮件、手抄文稿、幻灯片或照片 ,均要求用快邮方式投寄。编辑将根据需要 ,选择内容、形式及时间合适的来稿刊登。编辑有权进行删改。发表费用由澳大利亚、哥伦比亚、克罗地亚、古巴、捷克共和国、法国、印度、意大利、日本、马来西亚、新西兰、波兰、南非、瑞士、台湾、荷兰、泰国和委内瑞拉等国家或地区的结…     

《色谱》投稿须知(2018)

正《色谱》是中国化学会和中国科学院大连化学物理研究所主办、中国科学技术协会主管、国内外公开发行的专业性学术期刊,月刊。主要报道色谱学科的基础性研究成果、色谱及其交叉学科的重要应用成果及其进展,包括新方法、新技术、新仪器在各个领域的应用,色谱仪器与部件的研制和开发。被Medline、ESCI、CA、CSA、JST、AA、CHI、MSB-S、AJ、IC、SCOPUS等收录。是百种中国杰出学术期刊、中国最具国际影响力学术期刊、中国科学院优秀期刊、中国科协优秀期刊、中文核心期刊、中国科技核心期刊、中国精品科技期刊,入选中国科协精品科技期刊工程项目。     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

关于"对‘燃料电池物理及化学性能的有限时间热力学分析方法'的讨论”答复

把有限时间热力学理论用于化学过程的研究,将会得到一系列新的结论,开展这方面的研究是很有意义的.文献[1]以燃料电池为例,在同时考虑化学反应及传热不可逆性的情况下,研究了燃料电池的性能界限,文献[2]指出了文献[1]计算化学反应及传热不可逆性而引起系统与有关环境的总熵产生率的错误以及由此而导致的结论所存在的问题,并进行了富有启发性的分析与讨论.但文献[2]对于系统与有关环境的总熵产生率的计算也是不正确的,由此得到的其它结论自然不能成立.本文将就此情况下系统与有关环境的总熵产生率的计算再次进行讨论,并给出电池功率和效率的有限时间热力学性能界限.     

Regiospecific synthesis of quercetin O-β-d-glucosylated and O-β-d-glucuronidated isomers

Quercetin, the polyphenolic compound, which has the highest daily intake, is well known for its protective effects against aging diseases and has received a lot of attention for this reason. Both quercetin 3-O-β-d-glucuronide and quercetin 3′-O-β-d-glucuronide are human metabolites, which, together with their regioisomers, are required for biological as well as physical chemistry studies. We present here a novel synthetic route based on the sequential and selective protections of the hydroxyl functions of quercetin allowing selective glycosylation, followed by TEMPO-mediated oxidation to the glucuronide. This methodology enabled us to synthesize the five O-β-d-glucosides and four O-β-d-glucuronides of quercetin, including the major human metabolite, quercetin 3-O-β-d-glucuronide.     

Cl+F2→ClF+F和F+ClF′→ClF+F′反应机理的密度泛函理论研究

用密度泛函理论(DFT)B3LYP方法, 在6-311G基组下,计算研究了反应Cl+F2→ClF+F和对称反应F+ClF′→ClF+F′的机理。求得前者的过渡态为三角形,活化能为15.57 kJ*mol-1;后者的过渡态为线形和三角形,活化能分别为11.52和196.25 kJ*mol-1。结果均经过振动分析和IRC计算验证。     

丙三醇浓溶液玻璃化转变与结构松弛参数DSC分析

In order to examine the effects of water contents and heating/cooling rates on the glass transition and the structure relaxation parameters of glycerol/water mixtures, five aqueous solutions (60%, 70%, 80%, 90% and 100%) were investigated using the differential scanning calorimetry. Four scanning rates (10, 15, 20, 25 K/min) were used to obtain the glass transition parameters. The fitting results of plasticization constants indicated that Gordon-Taylor relationship could not be used effectively without considering scanning rates and that point on calorimetric step was chosen as the glass transition temperature. The specific heat changes during glass transition processes were relative not only to water content but also to heating rates. With the increasing of water contents in glycerol aqueous solutions, the structure relaxation activation energies and dynamic fragilities were decreased. Since the thermodynamic fragilities were increased with the increasing of water content, so the dynamic fragility and thermodynamic fragility were changed inversely if the water contents were changed in glycerol/water mixtures.     

Deuterodehalogenation—a mild method for synthesising deuterated heterocycles

We report a mild and efficient method for introducing deuterium into a range of heterocycles by reacting readily available halide analogues in a deuterodehalogenation reaction using D₈-IPA or Et₃SiD under palladium-catalysed conditions.     

The conversion of 2-cyano cyanothioformanilides into 3-aminoindole-2-carbonitriles using triphenylphosphine

2-Cyano cyanothioformanilide 3a reacts with triphenylphosphine in the presence of water to give 2-(cyanomethyleneamino)benzonitrile 4a, 2-(cyanomethylamino)benzonitrile 5, 3-aminoindole-2-carbonitrile 2a and (2-cyanoindol-3-yl)iminotriphenylphosphorane 6a. In the presence of p-toluenesulfonic acid in MeOH the reaction between 2-cyano cyanothioformanilide 3a and triphenylphosphine (2 equiv) gives 3-aminoindole-2-carbonitrile 2a in 90% yield. Under the same conditions 2-(cyanomethyleneamino)benzonitrile 4a gives anthranilonitrile 8a, 3-aminoindole-2-carbonitrile 2a and N-(2-cyanophenyl)formamide 9. In addition, substituted 2-cyano cyanothioformanilides 3b-f react with triphenylphosphine and p-toluenesulfonic acid in MeOH to give 3-aminoindole-2-carbonitriles 2b-f in 63-75% yields. Under analogous conditions 2-cyano-4,5-dimethoxyphenyl cyanothioformanilide 2g gives only 4,5-dimethoxyanthranilonitrile 8g and 4,6,7-trimethoxyquinazoline-2-carbonitrile 14g, but in refluxing dry PhMe in the absence of p-toluenesulfonic acid 2-cyano-4,5-dimethoxyphenyl cyanothioformanilide 3g, (2-cyano-5,6-dimethoxyindol-3-yl)iminotriphenylphosphorane 6g and 2-(cyanomethyleneamino)-4,5-dimethoxybenzonitrile 4g are obtained. The structure of 2-(cyanomethyleneamino)-4,5-dimethoxybenzonitrile 4g is supported unambiguously via independent synthesis and comparison to the isomeric 6,7-dimethoxyquinazoline-2-carbonitrile 15. All new compounds are fully characterised and a tentative mechanism for the transformation of 2-cyano cyanothioformanilides to indoles is proposed.