L-鼠李糖基(氨基)硫脲类化合物的合成

以L-鼠李糖为起始原料, 制备1-溴-2,3,4-三-O-乙酰基-β-L-吡喃型鼠李糖, 然后在甲苯中与Pb(SCN)₂作用, 得到中间体2,3,4-三-O-乙酰基-α-L-吡喃型鼠李糖基异硫氰酸酯(1). 利用2,3,4-三-O-乙酰基-α-L-吡喃型鼠李糖基异硫氰酸酯易发生亲核加成的性质, 在不同溶剂中, 与取代的苯并噻唑胺(2a～2f)、取代的苯并噻唑肼(2g～2l)、氧化和非氧化的哒嗪酮甲酰肼(2m, 2n)以及取代的嘧啶胺(2o, 2p)反应, 合成了16种新的(氨基)硫脲类化合物3a～3p. 所有化合物的结构均经IR, ¹H NMR, LC-MS和元素分析确证, 并对它们的生物活性做了初步测试.     

Anti-Inflammatory,Antidiabetic Properties and In Silico Modeling of Cucurbitane-Type Triterpene Glycosides from Fruits of an Indian Cultivar of Momordica charantia L.

Diabetes mellitus is a chronic disease and one of the fastest-growing health challenges of the last decades. Studies have shown that chronic low-grade inflammation and activation of the innate immune system are intimately involved in type 2 diabetes pathogenesis. Momordica charantia L. fruits are used in traditional medicine to manage diabetes. Herein, we report the purification of a new 23-O-β-d-allopyranosyl-5β,19-epoxycucurbitane-6,24-diene triterpene (charantoside XV, 6) along with 25ξ-isopropenylchole-5(6)-ene-3-O-β-d-glucopyranoside (1), karaviloside VI (2), karaviloside VIII (3), momordicoside L (4), momordicoside A (5) and kuguaglycoside C (7) from an Indian cultivar of Momordica charantia. At 50 µM compounds, 2–6 differentially affected the expression of pro-inflammatory markers IL-6, TNF-α, and iNOS, and mitochondrial marker COX-2. Compounds tested for the inhibition of α-amylase and α-glucosidase enzymes at 0.87 mM and 1.33 mM, respectively. Compounds showed similar α-amylase inhibitory activity than acarbose (0.13 mM) of control (68.0–76.6%). Karaviloside VIII (56.5%) was the most active compound in the α-glucosidase assay, followed by karaviloside VI (40.3%), while momordicoside L (23.7%), A (33.5%), and charantoside XV (23.9%) were the least active compounds. To better understand the mode of binding of cucurbitane-triterpenes to these enzymes, in silico docking of the isolated compounds was evaluated with α-amylase and α-glucosidase.     

Two New Sesquiterpenes from Eupatorium lindleyanum

Various germacrane sesquiterpenes have been isolated from many species of the Eupatorium.In recent years these compounds have been increasing interest due to their insecticidal,cytotoxic,antitumor-promoting and insect-antifeedant activities1.In our present study,we have investigated the chemical constituents of Eupatorium lindleyanum DC.,which is a geo-authentic medicine of Jiangsu province.It is used as a antipyretic drug.Two novel germacrane sesquiterpenes(Figure1)were found by us from th…     

Different catalysis role of in‐loop and out‐of‐loop waters in assisting HNS/HSN proton transfer isomerizations: Bridging vs. surrounding effect

In this work, a density function theory (DFT) study is presented for the HNS/HSN isomerization assisted by 1–4 water molecules on the singlet state potential energy surface (PES). Two modes are considered to model the catalytic effect of these water molecules: (i) water molecule(s) participate directly in forming a proton transfer loop with HNS/HSN species, and (ii) water molecules are out of loop (referred to as out‐of‐loop waters) to assist the proton transfer. In the first mode, for the monohydration mechanism, the heat of reaction is 21.55 kcal · mol^?1 at the B3LYP/6‐311++G** level. The corresponding forward/backward barrier lowerings are obtained as 24.41/24.32 kcal · mol^?1 compared with the no‐water‐assisting isomerization barrier T (65.52/43.87 kcal · mol^?1). But when adding one water molecule on the HNS, there is another special proton‐transfer isomerization pathway with a transition state 10T′ in which the water is out of the proton transfer loop. The corresponding forward/backward barriers are 65.89/65.89 kcal · mol^?1. Clearly, this process is more difficult to follow than the R–T–P process. For the two‐water‐assisting mechanism, the heat of reaction is 19.61 kcal · mol^?1, and the forward/backward barriers are 32.27/12.66 kcal · mol^?1, decreased by 33.25/31.21 kcal · mol^?1 compared with T. For trihydration and tetrahydration, the forward/backward barriers decrease as 32.00/12.60 (30T) and 37.38/17.26 (40T) kcal · mol^?1, and the heat of reaction decreases by 19.39 and 19.23 kcal · mol^?1, compared with T, respectively. But, when four water molecules are involved in the reactant loop, the corresponding energy aspects increase compared with those of the trihydration. The forward/backward barriers are increased by 5.38 and 4.66 kcal · mol^?1 than the trihydration situation. In the second mode, the outer‐sphere water effect from the other water molecules directly H‐bonded to the loop is considered. When one to three water molecules attach to the looped water in one‐water in‐loop‐assisting proton transfer isomerization, their effects on the three energies are small, and the deviations are not more than 3 kcal · mol^?1 compared with the original monohydration‐assisting case. When adding one or two water molecules on the dihydration‐assisting mechanism, and increasing one water molecule on the trihydration, the corresponding energies also are not obviously changed. The results indicate that the forward/backward barriers for the three in‐loop water‐assisting case are the lowest, and the surrounding water molecules (out‐of‐loop) yield only a small effect. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

新型螺环六氢山酮素-氧化吲哚-苯并呋喃酮类拼接物的合成及其抗白血病细胞增殖活性

以色酮-氧化吲哚合成子与3-烯基苯并呋喃酮为原料,在催化剂1,8-二氮杂二环十一碳-7-烯作用下,在二氯甲烷中发生Michael/Michael加成关环反应,合成了6个未见文献报道的螺环六氢山酮素-氧化吲哚-苯并呋喃酮类拼接物(3a^3f),产率75%~87%,dr值3/1~5/1,其结构经1H NMR,13C NMR和HR-MS(ESI-TOF)表征。采用MTT法研究了3a^3f对人白血病细胞(K562)的体外抗增殖活性。结果表明:化合物3c,3e和3f对K562增殖有一定的抑制活性。     

松干蚧性信息素Matsuone C(7)～C(13)片段的合成

以甾体皂甙元降解工业废弃物中获取的(R)-5-溴-4-甲基戊酸甲酯为原料, 通过三步反应合成了松干蚧性信息素Matsuone的C(7)～C(13)片段-(R)-4,6-二甲基庚醛, 三步合成的总收率为41.6%.     

Oxygen Atom Adsorption and Diffusion on Pd Low-index Surfaces and （311） Stepped Surface

Introduction Atom adsorption on transition metal surfaces has attracted special attention as a base for understanding the fundamental processes of oxidative catalysis. Particularly interesting is the adsorption and diffusion of oxygen on well-defined metal surfaces. An oxygen covered palladium surface, for example, plays a central role in several important reactions such as oxidation of carbon monoxide and ammonia. In particular, the (100), (111), (110) surfaces and the interactions with oxyge…     

新型反相微乳液制备纳米结构甲烷催化燃烧催化剂La0.95Ba0.05MnAl11O19-α的研究

提出一种由水, 异丙醇, 正丁醇组成的新型微乳液, 并以其为反应介质制备了甲烷高温燃烧La_0.95Ba_0.05MnAl₁₁O_19-a催化剂. 采用¹H NMR, FT-IR, 电导法及激光粒度散射法研究了新型微乳液中水的结构及相特性. 新型微乳液中水的体积分数小于一定值时, 电导率与水含量成非线性关系, k～φ曲线上存在一临界值(φ^P＝0.15). 水质子的化学位移随水含量的降低移向高场. 加入4% D₂O测定的O—D键的伸缩振动随水含量增加而向高波数方向移动. 异丙醇铝在新型微乳液中水解形成的Al(OH)₃ 胶体粒子的粒径范围为226～329 nm. 采用新型微乳液作为反应介质制备的Ba_0.05La_0.95MnAl₁₁O_19-α催化剂的粒径在30 nm, 明显小于纯水制备的样品(100 nm). BET 比表面积为65 m²/g, 比纯水制备样品高出约一倍. XRD结果显示, 1200 ℃焙烧10 h即可获得含单一β-Al₂O₃相的催化剂. Ba_0.05La_0.95MnAl₁₁O_19-α催化剂甲烷催化燃烧的T₁₀为420 ℃, 比纯水制备样品下降了90 ℃. 甲烷催化燃烧活性提高是由于含有较多Mnⁿ+纳米结构六铝酸盐的形成.     

具有双螺旋链的新型二维无机-有机骨架晶体材料Ni(PDC)(H2O)2的合成与结构

本文报道由H2PDC合成的新型维层状无机-有机骨架晶体Ni(PDC)(H2O)2(H2PDC=吡啶-2,5-二羧酸), 该化合物的一层是由右手螺旋Ni—O—C链与左手螺旋Ni-pdc链组成, 而邻近的一层则是由左手螺旋Ni—O—C链与右手螺旋Ni-pdc链组成, 层与层之间通过氢键作用形成了三维超分子结构. 用ICP、TG、IR和X射线单晶衍射分析等手段对其结构进行表征.     

CH4, CO2和H2O在非金属原子修饰石墨烯表面的吸附

煤层气(矿井瓦斯)是一种有望替代传统化石燃料，如煤、石油和天然气的非常规气体. 作为可得的清洁能源，它的利用被认为是节能和经济的选择. 在本工作中，非金属原子X(X=H，O，N，S，P，Si，F，Cl)修饰的石墨烯(Gr)被用来代表具有结构异性的煤表面模型. 通过密度泛函理论系统地研究了煤层气组分Y(Y=CH₄，CO₂，H₂O)在非金属原子修饰石墨烯上的吸附作用. 结果表明Y在非金属原子修饰石墨烯上的吸附均为物理吸附. 态密度和差分电荷密度共同表明了这种弱的相互作用.其中，H和Cl对CH₄的作用较大； N、O、F、Cl对CO₂的作用较强； N，Cl对H₂O的影响不容忽视. 总的来说，吸附能大小依次为：H₂O>CO₂>CH₄. 因此，在CH₄富集的煤层里注入H₂O或CO₂可以与CH₄形成竞争吸附，进而提高煤层气采收率. 本工作提供了在分子水平下煤层气与非金属原子修饰石墨烯之间的相互作用的详情，并为煤层瓦斯的开采与分离提供了有用的信息.