硫辛酸抗氧化性溶剂效应的理论研究

采用密度泛函方法,利用自洽反应场(SCRF)的Onsager模型,研究了正庚烷、苯、二氯甲烷、乙醇、二甲亚砜和水六种不同溶剂中硫辛酸分子的抗氧化性。以S-S键键解离焓(BDE)和分子电离势(IP)为理论指标评价了硫辛酸在六种溶剂中清除自由基的活性。发现随着溶剂的介电常数增大,BDE值几乎不变,而IP值则显著减小,表明溶剂效应对清除自由基的电子转移反应机理影响更大。溶剂的极性较小时,偏向于形成硫自由基的机理,而溶剂的极性较大时,偏向于电子转移机理。     

1-氨基乙内酰脲分子印迹聚合物的制备和吸附性能研究

以1-氨基乙内酰脲(AHD)为模板分子,α-甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EDMA)为交联剂,采用本体聚合方法合成了分子印迹聚合物(M IP),考察了模板分子与功能单体不同比例下制备的M IP对模板分子的吸附性能。通过Scatchard分析,表明该印迹聚合物上存在一类等价的吸附位点,其结合位点的离解常数KD=4.33mmol/L。     

甜菊叶肉细胞FDPase和UDPG焦磷酸化酶的电子显微镜细胞化学研究

本文研究了糖代谢中两种重要的酶——果糖1,6-二磷酸酶(FDPase,EC3.1.3.11)和尿苷二磷酸葡萄糖(UDPG)焦磷酸化酶(尿苷三磷酸:α-D-葡萄糖1-磷酸尿基转移酶,EC2.7.7.9)在新糖源植物——甜叶菊(Stevia rebaudiana Bertoni)叶肉细胞中的亚细胞定位和不同叶龄叶片中酶活性的变化。本实验揭示:FDPase是一种膜束缚酶,它特异性地定位于叶绿体的类囊体膜和细胞质膜。在幼叶细胞中,FDPase定位于叶绿体类囊体膜;在成叶细胞中,FDPase定位于叶绿体类囊体膜和细胞质膜。UDPG焦磷酸化酶以游离的形式分布于细胞基质中,以膜束缚的形式定位于高尔基扁平囊和高尔基小泡。本研究表明:叶绿体、细胞基质和高尔基复合体在甜菊苷合成中具有重要的作用。     

磷酸体系中微量稀土元素萃取回收技术研究

研究了从磷矿硫酸湿法制备磷酸过程中回收伴生稀土元素的萃取分离技术,首先进行了不同萃取剂的筛选,同时考察了萃取剂浓度、磷酸浓度、相比、反应温度、杂质元素等对稀土萃取率的影响.结果表明:在该体系下,P204(二(2-乙基己基)磷酸)单独萃取稀土的能力最强,而且较高的萃取剂浓度、较大相比及低的磷酸浓度有利于稀土的萃取,不同杂质对稀土萃取存在不同程度的影响;并对萃取反应机制进行了考察,得到P204在磷酸介质中萃取微量稀土的反应式,该萃取反应的焙变△H<0,为放热反应.     

采用高效液相色谱技术分析生物体内维生素B6

维生素B6(VB6)是一类2-甲基-3-羟基吡啶类化合物的总称，基本类型有吡哆醇(PN)、吡哆醛(PL)和吡哆胺(PM)，磷酸酯型有磷酸吡哆醇(PNP)、磷酸吡哆醛(PLP)和磷酸吡哆胺(PMP)，其中磷酸吡哆醛和磷酸吡哆胺为活性形式，是多种酶的辅酶，哺乳动物尿中VB6的代谢产物主要是不具有生理活性的吡哆酸(PIC)，在植物体内还发现有数种吡哆醇的糖衍生物和氨基酸衍生物。     

草酸/四丙基溴化铵体系中磷酸锆晶体的离子热合成与表征

采用离子热合成方法, 在草酸/四丙基溴化铵离子型低共熔混合物中对磷酸锆骨架材料的合成进行了系统地研究, 通过改变反应条件合成了2种不同的磷酸锆, α-Zr(HPO₄)₂•H₂O和 (NH₄)Zr₂(PO₄)₃. 体系中的四丙基季铵阳离子对磷酸锆骨架没有体现出模板作用, 后者是在较高的反应温度下(220 ℃)以四丙基季铵离子的热分解产物( )作为模板而生成. 通过向该体系中添加少量的氮杂环化合物(哌嗪), 合成了一种三维开放骨架的8-元环磷酸锆微孔材料, 位于孔道中的质子化哌嗪起到模板作用并平衡骨架负电荷. 研究结果表明, 草酸/四丙基溴化铵低共熔混合物可以作为一种离子热反应介质, 通过向体系中引入少量的有机碱可以起到模板作用来诱导磷酸锆骨架的生成.     

碱性磷酸酶的体外检测和体内成像研究进展

碱性磷酸酶(Alkaline phosphatase,ALP)是一种水解酶,可以催化蛋白质、核酸和碳水化合物中磷酸基团的去除.ALP广泛存在于原核生物和真核生物中,具有调节细胞分裂、增殖、凋亡和信号转导等生物功能.ALP的活性失调与心血管疾病、糖尿病和癌症等疾病密切相关,是一种重要的生物标志物.ALP的超灵敏检测对临床...     

组合肽配体库技术富集蛋白研究进展

低丰度蛋白是生物体中重要的活性物质,参与新陈代谢、转录和翻译等多种生理及病理过程,因此对低丰度蛋白的研究具有重要意义。组合肽配体库技术(CPLL)是富集低丰度蛋白的一种有效方法,通过CPLL富集作用可以实现低丰度蛋白的检测与鉴定。该文总结了CPLL应用于不同领域中(包括人体、动物源、植物源等蛋白研究方面)低丰度蛋白样品的富集研究,可为CPLL的进一步应用提供参考。     

有机络合剂去除活化法生产活性炭的回收磷酸液中铁离子

用磷酸液活化活性炭,磷酸液可重复回收利用,由于木屑、炭屑等原材料的影响,用于反复活化浸渍的磷酸液中铁含量将从小于10 μg/g上升到几百μg/g,甚至更高,不能满足医药、食品等行业对活性炭中铁离子含量低的要求。对回收来的磷酸液进行除铁纯化具有一定的经济意义。探讨了一种通过用二甲胺(33%)、氢氧化钠(15%)（或氢氧化钾）、二硫化碳三种药品于一定条件下,制得的有机络合沉淀剂,常温下可将回收来的磷酸母液中铁离子除去,除铁效果显著,达到50 μg/g以下,从而使回收的磷酸液能满足医药、食品等行业用活性炭的生产之需。方法工艺简单、成本低,是一种值得推广的应用技术。     

多酸含量对无机/高分子复合薄膜结构及光致变色性能的影响

制备了一系列不同浓度的钨磷酸/聚乙烯醇(PWA/PVA)复合薄膜, 通过红外光谱、原子力显微镜、紫外-可见吸收光谱对复合薄膜的结构和光致变色性能进行了研究. 红外光谱分析结果表明, Keggin结构钨磷酸和聚乙烯醇分子的基本结构在复合薄膜中仍然存在, 钨磷酸分子与高分子底物间存在氢键作用, 形成电荷转移桥. 原子力显微镜(AFM)结果表明复合前后PVA薄膜表面形貌发生了显著变化, 复合膜表面形貌随钨磷酸含量的不同而不同. 在紫外光照射下, 复合薄膜由无色变为蓝色. 复合膜的升色速度和褪色速度均随着钨磷酸含量的增加而加快. 这些结果表明钨磷酸含量对复合膜的微结构存在影响, 从而导致了复合膜具有不同的光致变色性能.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.