2-(p-十二烷氧基苯乙炔基)吡嗪-5-羧酸的合成及成膜性

在含有吡嗪环的对位双环羧酸化合物中,2-(p-十二烷氧基苯基)吡嗪-5-羧酸具有良好的成膜性^[1,2].在苯环和吡嗪环间引入不饱和键,合成的2-(p-十二烷氧基苯乙炔基)吡嗪-5-羧酸,由于其具有较长的共轭体系,因而分子排列的取向性更好,形成的LB膜更致密.该化合物尚未见报道.本文报道该化合物的合成方法及成膜的初步结果.     

5,10,15,20—四（对—乙酯苯基）卟啉LB膜的结构

对卟啉类化合物LB膜的结构、电性质和气敏性的研究已见报道。本文利用膜天平和UV-Vis分光光度计研究了标题化合物在气-液界面上的成膜特性、分子间相互作用和LB膜的结构。5,10,15,20-四(对-乙酯苯基)卟啉(TPEPP)由5,10,15,20-四(对-氰苯基)卟啉和乙醇酯化得到。元素分析测定值与计算值相符。λ(CHCl_3,nm):421,515,550,590,645;ν(KBr压     

新型LB成膜材料—两亲性侧链取代酞菁锌的合成

本文合成了一种新型的两亲性硬脂酸侧链取代的酞菁化合物。利用LB膜技术制备了致菁化合物与正十六烷混合的单层和多层LB膜,LB膜内酞菁分子大环与基片大体平行,表明该分子具有良好的成膜性能。     

4-(2-甲氧基乙氧基)-三-4-(2,4-二特戊基苯氧基)酞菁铜的合成及其LB膜特性研究

LB膜的特性在很大程度上决定于成膜分子的结构。铜酞菁衍生物具有大π键电子共轭体系,有明显的光电特性,成膜性好,很适于作LB膜气敏材料。我们在前期工作的基础上,为探明气敏特性与化合物结构间的关系,设计并合成了标题化合物,并对其LB膜的气敏特性进行了研究。     

一种新的具有给体-受体结构的有机分子的合成及LB膜研究

本工作合成了一种新的具有给体-受体结构的长碳链有机分子, 2, 3-二(十六烷硫基)-5-(4'-硝基苯亚甲基)-1, 4-二硫代-2-环戊烯, 对其单分子膜的成膜性能进行了研究。在适宜条件下制备了单层及多层LB膜。通过电子衍射、X射线衍射、紫外-可见吸收光谱等手段对LB膜的结构进行了表征。实验结果表明, 这种化合物的成膜性能很好。单分子层膜的二次谐波测试表明该发色团分子具有较好的二阶非线性光学性。     

杯[4]芳烃双咪唑季铵盐的Langmuir-Blodgett膜性质

合成了杯[4]芳烃构建的双咪唑季铵盐化合物1(BIQ-Calix),利用表面压一面积(π-A)等温线、压缩/扩张循环等温线与膜弛豫等温线、紫外与红外光谱、原子力显微镜等手段研究了该化合物在空气/水相界面、空气/二元羧酸水溶液界面的成膜性能。结果表明:化合物1在水或者二元羧酸乙二酸,丙二酸,丁二酸水溶液的亚相表面均能很好的形成稳定的Langmuir膜,其崩溃压分别为24 mN·m-1,30 mN·m-1,33 mN·m-1和28 mN·m-1,平均单分子面积分别为2.0 nm2,2.3 nm2,2.5 nm2和2.2 nm2,并能与二元羧酸阴离子一起转移到固体基片上形成LB膜,且化合物1形成的LB膜为H-聚集体。     

单臂冠醚液晶LB膜的相变研究

研究了两种单臂冠醚液晶及配合物(1, 2及1.Eu^3^+)的LB膜的成膜特性,实验发出它们均可在气-液界面形成单分子膜, 但不易转移, 化合物1在压膜过程中出现一维相变。用CPK模型对成膜分子构型和面积进行估算, 其结果与实验相一致, 并讨论了冠醚液晶结构对LB膜相变的影响。     

新型LB成膜材料-两亲性侧链取代酞菁锌的合成

本文合成了一种新型的两亲性硬脂酸侧链取代的酞菁化合物, 利用LB膜技术制备了酞菁化合物与正十六烷混合的单层和多层LB膜, LB膜内酞菁分子大环与基片大体平行, 表明该分子具有良好的成膜性能。     

双臂胆甾醇酯型氮杂冠醚化合物的LB膜研究

研究了含有双臂胆甾基的氮杂冠醚化合物的单分子膜成膜特性,测试了其LB膜的吸收光谱和小角X-射线衍射谱。结果表明,这种化合物成膜性能和转移性能比单臂的胆甾基氮杂冠醚化合物好。结合CPK原子模型,推测了该分子在膜中的取向和构型。     

杯芳烃-卟啉化合物及其金属配合物的Langmuir-Blodgett膜研究

通过对杯芳烃-卟啉化合物及其锌、钯配合物LB膜的表面压-表面积等温线、紫外可见光谱和傅里叶变换红外光谱的检测,研究了它们在气/液界面和Langmuir-Blodgett膜中的性质,并用量子力学方法优化了杯芳烃-卟啉化合物的构型.结果表明,成膜时3种化合物分子中卟啉环都倾斜地排列在亚相表面,且卟啉环间存在π-π相互作用.连接杯芳烃和卟啉之间的碳氢链在膜性质中起着重要的作用,杯芳烃-卟啉化合物分子中这种碳氢链的有序性小于其锌、钯配合物分子中的这种碳氢链有序性.     

(E)-脱氢二聚白藜芦醇-11,11′,13,13′-四甲醚的全合成

以3,5-二甲氧基苯甲酸(1)为起始原料, 经过甲醇酯化、氢化铝锂还原、四溴化碳溴代和Wittig-Horner反应,高产率的合成了Wittig-Horner试剂(5). 化合物5与对羟基苯甲醛(6)的羟基保护产物(7)偶联得到化合物(8),后者经去甲氧基亚甲基保护和仿生氧化偶联反应成功地全合成了(E)-脱氢二聚白藜芦醇-11,11′,13,13′-四甲醚(10). 通过1H NMR、13C NMR、IR、HRMS等测试技术确定化合物10为二聚芪类化合物(E)-脱氢二聚白藜芦醇-11,11′,13,13′-四甲醚,总收率48.93%.     

Structure elucidation of a novel analog of sildenafil detected as an adulterant in a dietary supplement using LC-UV and LC/MS

A sildenafil-related compound was detected in a dietary supplement marketed as an aphrodisiac. The compound was detected during analysis of the dietary supplement using LC-UV and LC/electrospray ionization-MS. The structure of the compound was established using high resolution MS, NMR spectrometry, and X-ray crystal structure analysis. The compound was identified as 5-(5-((3,5-dimethylpiperazin-1-yl)sulfonyl)-2-ethoxyphenyl)-l-methyl-7-((1-methyl-4-nitro-1H-imidazol-5-yl)thio)-3-propyl-1H-pyrazolo[4,3-d] pyrimidine. Based on this structure, the compound was named nitroprodenafil. The dietary supplement was found to contain 90 mg nitroprodenafil/capsule. This article describes the structural characterization of a new sildenafil-related compound. The compound was detected during analysis of a dietary supplement using LC-UV and LC/electrospray ionization (ESI)-MS. The structure was established using high resolution MS (HRMS), NMR spectrometry, and X-ray crystal structure analysis. The structures of methisosildenafil, thiomethisosildenafil, and this new analog, named nitroprodenafil (21), are shown in Figure 1. In the Demizu et al. report, the compound is named mutaprodenafil instead ofnitroprodenafil. Considering the naming right, the authors of this paper think the use of mutaprodenafil is appropriate as the compound name, although nitroprodenafil is used.     

减肥产品中非法添加西布曲明类似物的ESI-MS/MS检测与确证

通过分析西布曲明和减肥类健康产品中未知化合物质谱图的质谱信息,由高分辨串联质谱获得裂解碎片离子的精密质量数,质谱软件给出碎片的可能组成,推测了西布曲明和未知化合物的质谱裂解途径,进而推测出该化合物的结构。并通过合成该结构的化合物,采用液相色谱-串联质谱法对样品作确证检验,证实样品中添加了新的西布曲明类似物。该实验提供了一种可用于检测和确证健康产品中非法添加合成药物未知类似物的方法。     

alpha-phenylpropionic acid derivatives. Synthesis and dethiation of 5-benzoylbenzo[b]thiophene-3-carboxylic acid

The total synthesis of the title compound 8 started with p-thiocresol which was acylated with oxalyl chloride to give compound 1 . This product underwent a condensation reaction with chloroacetic acid under basic conditions yielding compound 2 . Two different synthetic pathways were used to convert compound 2 into the title compound 8 . The first consisted in decarboxylation of 2 to 3 , which was then converted to the ester 4 , which was brominated and the product 5 was subjected to a Friedel-Craft's reaction with benzene. The resulting benzyl derivative 6 was oxidized to the benzoyl stage i.e. compound 7 , which was finally hydrolyzed to 8 . The second pathway was similar to the first one so that the steps of esterification, bromination, Friedel-Craft's alkylation and oxidation started with the dicarboxylic acid 2 . Thus compounds 12–16 were obtained, and the last product was decarboxylated to 8 . The yields in both procedures were similar. Finally, the dethiation of compound 8 with Raney nickel afforded compounds 18, 19 and 20 .     

耐辐射奇球菌抗辐射物质的研究

本研究分析了耐辐射奇球菌(Deinococcus radiodurans)生长过程中产生的色素物质。紫外照射实验结果表明这种物质具有很强的抗紫外辐射能力。紫外扫描、高压液相测定和显色反应表明这种抗辐射物质含有萜类双键,主要吸收峰在310nm处,保留时间为4．632min,其含量占总量的53．04%,初步确定这种色素物质为类胡萝卜素。     

多孔金属片载杂多化合物膜的催化性能

用组合化学法合成了Ｃｕ１．３Ａｓ０．３ＰＶＭｏ１１高元杂多化合物,并用红外和差热－热重分析技术进行了表征;将高元杂多化合物制成高分子催化膜,用于几种醇的选择性催化氧化反应,结果表明,高元杂多化合物膜具有优异的催化性能,更坦 步探索了多孔金属片载杂多化合物膜催化技术的应用。     

WYE‐120318, a ring contraction product of methylnaltrexone,and structure revision of coniothyrione

A contracted ring degradation product, WYE‐120318 (compound 2), was discovered during the development phase for methylnaltrexone bromide (compound 1) drug substance. The compound was isolated by high‐performance liquid chromatography fractionation, and its structure was determined by spectroscopic data analyses. WYE‐120318 is formed from methylnaltrexone through a benzyl‐benzilic acid type rearrangement reaction to yield an α‐hydroxy‐cyclopentanecarboxylic acid substructure. The proposed structure and the formation mechanism are confirmed by the synthesis of WYE‐120318 from methylnaltrexone (compound 1). A similar benzyl‐benzilic acid type rearrangement reaction can be envisioned as the biological origin of remisporine A (compound 3), a naturally occurring cyclopentadienyl compound that autocatalytically dimerizes to remisporine B (compound 4). The structure of remisporine A was deduced from its dimer 4. Coniothyione (compound 5) can be considered as the first example of a stable natural product bearing the remisporine A skeleton. However, the regiochemistry of the chlorosubstitution in the coniothyrione structure needs to be revised to compound 6 on the basis of the nuclear magnetic resonance data and biogenesis analysis. Copyright © 2012 John Wiley & Sons, Ltd.     

三苯胺甲醛二苯腙的合成及其光电性能研究

合成了一种新型的三苯胺类载流子传输材料三苯胺甲苯二苯腙,通过一系列手段对该化合物性能进行了表征,并以此化合物为载流子空穴传输材料,Y-型酞菁氧钛为载流子产生材料制备了光导器件,测定了该光电器件的光电性能,显示出良好的光电性能(E_1/2=1.0lx.s),可以替代常用的载流子传输材料二乙基苯甲醛二苯腙.     

12-钼磷酸-葡聚糖包合物固容体的光致变色

通过DSC曲线,IR光谱,电子光谱和XRD谱分析,发现12-钼磷酸与葡聚糖在水溶液中可形成黄色包合物。以ESR,XPS,IR和电子光谱等手段研究此黄色包合物在紫外光照射下的光致变蓝紫色,是由于其光电子转移反应产物多价态钼(Ⅵ,Ⅴ,Ⅳ)配合物呈蓝紫色,而另一产物带部分羰基葡聚糖为无色所致。由DSC曲线,电子光谱,IR光谱和XRD谱测试结果得知,随着光化反应产物的生成,两者分子间产生包合作用,从而提高光致变色的稳定性。     

Pharmacokinetic and brain distribution study of an anti-glioblastoma agent in mice by HPLC–MS/MS

Previously compound I showed great anti-glioblastoma activity without toxicity in a mouse xenograft study. In this study, a sensitive and rapid high-performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS) method was developed and validated to investigate the pharmacokinetics and brain distribution of compound I in mice. The protein precipitation method was applied to extract the compound from mouse plasma and brain homogenates, and it was then separated using a Kinetex C₁₈ column with a mobile phase consisting of acetonitrile–0.1% formic acid water (50:50, v/v). The analytes were detected with multiple reaction monitoring for the quantitative response of the compounds. The inter- and intra-day precisions were <8.29 and 3.85%, respectively, and the accuracy range was within ±7.33%. The method was successfully applied to evaluate the pharmacokinetics of compound I in mouse plasma and brain tissue. The peak concentration in plasma was achieved within 1 h. The apparent elimination half-life was 4.06 h. The peak concentration of compound I in brain tissue was 0.88 μg/g. The results indicated that compound I was rapidly distributed and could cross the blood–brain barrier. The pharmacokinetic profile summarized provides valuable information for the further investigation of compound I as a potential anti-glioblastoma agent.