有机锡4-(4-吡啶基甲基硫代)苯甲酸酯的合成、结构与生物活性研究(英文)

通过4-(4-吡啶基甲基硫代)苯甲酸与三苯基氧化锡以及三环己基氢氧化锡反应,合成了三苯基锡4-(4-吡啶基甲基硫代)苯甲酸酯(1)及三环己基锡4-(4-吡啶基甲基硫代)苯甲酸酯(2)。它们的结构通过红外,核磁以及X-射线单晶衍射分析得到确证。化合物1表现为一维链状结构,而化合物2通过分子间的O-H…O和O-H…N氢键形成二维网状结构。生物活性测试表明,这2个化合物具有较高的抗肿瘤活性。     

双(二苄基锡杂环羧酸酯)氧化物的合成与表征

通过二苄基氧化锡与杂环取代羧酸反应,合成了8种新的双(二苄基锡杂环羧酸酯)氧化物{[(PhCH~2)~2SnO~2CR]~2O}~2(R=2-呋喃基,2-呋喃乙烯基,2-噻吩基,3-吡啶基,4-吡啶基,2-吡啶基,3-吲哚甲基,3-吲哚丙基)。生物活性测试表明,部分化合物具有一定的抗癌活性。     

3—吲哚基羧酸二（三）烃基锡配合物的红外光谱研究

研究了３－吲哚基羧酸二（三）烃基锡配合物的特征红外光谱,讨论了它们随配合物的化学结构而变化的规律。     

有机锡4-(4-吡啶基甲基硫代)苯甲酸酯的合成、结构与生物活性研究

通过4-（4-吡啶基甲基硫代）苯甲酸与三苯基氧化锡以及三环己基氢氧化锡反应,合成了三苯基锡4-（4-吡啶基甲基硫代）苯甲酸酯（1）及三环己基锡4-（4-吡啶基甲基硫代）苯甲酸酯（2）。它们的结构通过红外,核磁以及X-射线单晶衍射分析得到确证。化合物1表现为一维链状结构,而化合物2通过分子间的O-H…O和O-H…N氢键形成二维网状结构。生物活性测试表明,这2个化合物具有较高的抗肿瘤活性。     

羧酸三环己基锡盐的合成和结构分析

报导了三环己基氢氧化锡同羧酸的反应, 考察了影响产物收率的因素并合成了23个新的羧酸三环己基锡类化合物, 通过红外光谱和质谱等确定了这类化合物的结构, 并证明锡的配合物价为4.     

1-芳基-3，5-二甲基吡唑-4-羧酸有机锡酯的合成、结构及杀菌活性研究

由1-芳基-3,5-二甲基吡唑-4-羧酸与适当的有机锡反应,合成表征了一系列的1-芳基-3,5-二甲基吡唑-4-羧酸有机锡酯(1～14),并通过单晶衍射确定了1-苯基-3,5-二甲基吡唑-4-羧酸三乙基锡酯(7)的结构。该化合物与一分子水共同结晶,通过分子间O-H…O及O-H…N氢键形成二维网状结构。杀菌活性筛选表明新合成的化合物对于番茄早疫菌、花生褐斑菌、小麦赤霉菌、苹果轮纹菌及灰霉菌全部具有良好的生长抑制作用。1-苯基-3,5-二甲基吡唑-4-羧酸三乙基锡酯及1-(2-吡啶基)-3,5-二甲基吡唑-4-羧酸三乙基锡酯在50μg.mL-1浓度下的体外实验中表现出很高的生长抑制率。对于高活性的三取代锡羧酸酯进行了EC50值的测定,结果表明1-(2-吡啶基)-3,5-二甲基吡唑-4-羧酸三乙基锡酯对苹果轮纹菌的EC50值为0.06μg.mL-1,对小麦赤霉菌的EC50值为0.14μg.mL-1。     

二聚体有机锡配合物{[n-Bu2SnO2CCH(CS2NEt2)2]2O}2的合成、表征及晶体结构

近年来,有机锡(Ⅳ)的羧酸配合物因其具有很强的生物活性以及丰富的结构类型备受人们的重视．实验证明,它们的生物活性与锡原子的配位形式有关,而中心锡原子的配位形式决定于直接与锡原子相连的烃基的结构和羧酸基配体的类型。     

羧酸稀土配合物的合成及其对LDPE膜和农膜光敏化效果的研究

合成了６种羧酸和羧酸混合稀土配合物。通过元素分析，热重－差热分析、红外光谱和紫外光谱研究了它们的组成和性质，用红外光谱法测定了含羧酸铈或羧酸共生稀土的低密度聚乙烯ＵＶ光氧化羰基指数，研究了羧酸铈和羧酸共生稀土对ＬＤＰＥ膜ＵＶ光氧化速度及其粘均分子量的影响，并探讨了它们在敏化ＬＤＰＥ膜光氧化降解方面的作用机理。     

三苄基锡羧酸酯的合成及其结构表征

本文以(三苄基锡)氧化物和相应的羧酸反应, 合成了20个三苄基锡羧酸酯, 由波谱对结构的研究表明, 红外光谱的酰基振动频率与羧基上取代基的空间和电子效应密切相关, 三苄基锡羧酸酯的结构微小变化, 明显地反映了^1^1^9Sn和^1^3CNMR化学位移的差异, ^1^1^9Sn化学位移与三苄基锡取代的苯甲酸酯的对位取代基Hammett常数(σ)之间存在着良好的线性关系: δ~1~1~9~S~n=15.48σ+14.23, n=7, r=0.995, 去烃基化是这一类化合物质谱裂解的特点。     

氯代二苯基锗杂环羧酸酯的合成与表征

以二苯基二氯化锗和杂环羧酸钠为原料,合成了8种氯代二苯基锗杂环羧酸酯Ph2Ge(Cl)O2CR(R=2-呋喃基,2－呋喃乙烯基,2－噻吩基,2－吡啶基,3－吡啶基,4－吡啶基,3－吲哚甲基,3－吲哚丙基）。利用元素分析,红外光谱、核磁共振谱和质谱表征了这些化合物的结构。结果表明杂环羧酸是以单齿形式与锗原子键合,生成了四配位的有机锗化合物,生物活性测试表明,该类化合物具有较高的体外抗癌活性。     

Probing the differential effects of infrared light sources IR1072 and IR880 on human lymphocytes: evidence of selective cytoprotection by IR1072

Light therapy, both laser and LED, have been shown to provide clinical benefit in many therapeutic arenas. The effects of IR1072 and IR880 were investigated, using a range of single and multiple irradiation protocols, for their effect on freshly prepared human lymphocytes stimulated with phytohemagglutinin. Viable cell numbers remained significantly higher after irradiation with IR1072 and were significantly lower after IR880 irradiation compared to untreated controls, following a daily single irradiation over a 5-day period. Cell numbers were significantly higher after pre-treatment with IR1072 and exposure to UVA, compared to cells treated with UVA only. Cells irradiated twice on Day 3 post-harvest with various wavebands confirm on Day 5, an increase in % cell viability after IR1072, and IR1072 alternating with IR1268 irradiation, and a decrease in % cell viability after IR880 irradiation alone. Further, wavebands tested displayed no significant differences compared to the control. Cells were collected after exposure on Days 3 and 5 with IR1072 and IR880 treatments and protein levels were compared using quantitative immunoblotting probed with an anti-iNOS antibody. Following IR1072, but not IR880, treatment there was a 4.9+/-2.1-fold higher iNOS protein expression in treated cells compared to the control on Day 5 post-treatment.     

Electrochemical preparation and structural characterization of Co thin films and their anomalous IR properties

Nanometer scale cobalt thin films of different structures and thicknesses supported on glassy carbon were prepared by electrochemical deposition under cyclic voltammetric conditions (denoted nm-Co/GC(n)). The thickness of Co thin films was altered systematically by varying the number (n) of potential cycling within a defined potential range in electrodeposition. Electrochemical in situ scanning tunneling microscopy (STM) and ex situ scanning electron microscopy (SEM) were employed to characterize the surface structure of Co thin films. It has been illustrated that the Co thin films were uniformly composed of Co nanoparticles, whose structure and size varied with increasing n. The structure of nanoparticles inside the Co thin films underwent a transition from bearded nanoparticles to multiform nanoparticles and finally to hexagonal nanosheets, accompanying with an increase of average size. In situ FTIR reflection spectroscopic studies employing CO adsorption as probe reaction revealed that the Co thin films all exhibited anomalous IR properties; that is, along with their different nanostructures they presented abnormal IR effects, Fano-like IR effects, and surface-enhanced IR absorption effects. CO adsorbed on Co thin films dominated by bearded nanoparticles yielded abnormal IR absorption bands; that is, the direction of the bands is inverted completely, with enhanced intensity in comparison with those of CO adsorbed on a bulk Co electrode. The enhancement of abnormal IR absorption has reached a maximal value of 26.2 on the nm-Co/GC(2) electrode. Fano-like IR features, which describe the bipolar IR bands with their positive-going peak on the low wavenumbers side, were observed in cases of CO adsorbed on Co thin films composed mainly of multiform nanoparticles, typically on the nm-Co/GC(8) electrode. IR features were finally changed into surface-enhanced IR absorption as CO adsorbed on the nm-Co/GC(30) electrode, on which the Co thin film is dominated by Co hexagonal nanosheets.     

三氯化铝烷基氯化咪唑盐结构和红外光谱的模拟计算

采用量子化学密度泛函的方法计算了三氯化铝烷基氯化咪唑盐的红外光谱, 预测了三氯化铝烷基氯化咪唑盐的分子结构和光谱. 合成了三氯化铝1-丁基-3-甲基-咪唑盐[(BMIM)AlCl4], 并测试了其红外光谱, 对预测的分子结构和红外光谱进行了验证.     

Polymeric micelleplexes for improved photothermal endosomal escape and delivery of siRNA

Effective endosomal escape is required for practical application of nucleic acid therapeutics. In this study, we prepared siRNA micelleplexes with photothermally triggered endosomal escape and improved gene silencing activity in vitro. The micelleplexes were prepared from cholesterol‐modified and CXCR4‐inhibiting poly(amido amine)s (PAMD‐Ch). Near‐infrared dye IR780 was encapsulated in cationic PMAD‐Ch micelles, which then were used to form IR780 micelleplexes with siRNA. The micelleplexes displayed improved gene silencing efficiency upon laser irradiation, which was attributed to enhanced endosomal escape because of the photothermal effects of the encapsulated IR780. The IR780 micelleplexes retained the CXCR4 antagonism and inhibition of cancer cell invasion of the parent PAMD. Overall, this study validates codelivery of IR780 in siRNA micelleplexes as promising photothermally controlled siRNA delivery approach.     

IR125和HDITCP在不同烷基链长阳离子离子液体中的光异构化动力学

利用稳态吸收和荧光光谱以及时间相关单光子计数实验,分别测得近红外花菁分子IR125和HDITCP在不同烷基链长阳离子离子液体中的荧光量子产率和荧光寿命,并通过计算获得了它们各自在相应离子液体中的光异构化速率.发现IR125和HDITCP在不同离子液体中的光异构化速率没有随着离子液体粘度的增大而产生明显变化.与IR125和HDITCP在与离子液体具有相同粘度的甘油水溶液中的光异构化速率对比,发现IR125和HDITCP在离子液体中的光异构化能垒比它们在甘油水溶液中的光异构化能垒增大约2 kJ?mol-1,这表明在高粘度的离子液体中IR125或HDITCP与离子液体之间特殊的相互作用会阻碍它们各自的光异构化过程.     

The IR spectra and hydrogen bonding of toluene-2,6-bis(methyl) and 4,4′-diphenylmethane-bis(methyl) carbamates

The IR spectroscopy has been used to study models of polyurethanes containing different hard segments. The spectra of toluene-2,6-bis(methyl) and 4,4′-diphenylmethane-bis(methyl) carbamates at different temperatures were studied. The absorption curves of the free and associated carbamate molecules were compared with experimental IR spectra. The characteristic features of toluene-2,6-bis(methyl) carbamate and methyl-N-methyl carbamate clusters were revealed. The IR spectra for the two most stable toluene-2,6-bis(methyl) carbamate conformations were compared. The origin of the multiplet structure of bands in the experimental IR spectra of polyurethanes was discussed. The results obtained can be used for the analysis of the chemical and physical transformations in urethanes and polyurethanes.     

不同尺度和分散状态的钯纳米粒子红外光学性能研究

运用CO分子探针红外光谱研究不同尺度和分散状态的钯纳米粒子的红外光学性能.结果表明,粒子尺度为6.6nm分散的球型钯纳米粒子(Pdn)和粒子尺度为100～150nm分散的立方体型钯纳米粒子(Pdncube)均给出两个不同吸附方式的桥式CO红外谱峰,其吸收峰位置约在1970cm-1和1910cm-1.将Pdn引入到电极表面后,通过界面电化学诱导使之形成团聚体(Pdnag),其红外光学性能发生显著变化,表现为随着界面电化学诱导时间的增加,其1970cm-1处的谱峰方向从正常转为异常.本研究进一步证明红外谱峰方向的倒反是由于粒子间的相互作用引起的.     

A Platinum(II) Complex of Heptamethine Cyanine for Photoenhanced Cytotoxicity and Cellular Imaging in Near‐IR Light

Controlled generation of cytotoxic agents with near‐IR light is a current focus of photoactivated cancer therapy, including that involving cytotoxic platinum species. A heptamethine cyanine scaffolded Pt^II complex, IR797‐Platin exhibits unprecedented Pt?O bond scission and enhancement in DNA platination in near‐IR light. This complex also displayed significant singlet oxygen quantum yield thereby qualifying as a near‐IR photodynamic therapeutic agent. The complex showed 30–60 fold enhancement of cytotoxicity in near‐IR light in various cancer cell lines. The cellular imaging properties were also leveraged to observe its significant co‐localization in cytoplasmic organelles. This is the first demonstration of a near‐IR light‐initiated therapy involving the cytotoxic effects of both active cisplatin and singlet oxygen.     

独立成分分析结合在线红外技术研究3,4-双(4'-氨基呋咱基-3')氧化呋咱的合成反应机理

利用在线红外技术监测3,4-双(4'-氨基呋咱基-3')氧化呋咱(DATF)的合成过程,并结合核独立成分分析算法对反应过程中获得的实时红外光谱数据进行解析,得到了反应物、中间体及产物各组分纯物质的红外光谱图.采用密度泛函理论B3LYP法,在6-31+G(d,p)基组水平上求得中间体的红外振动光谱,验证了所分离红外光谱图的正确性,从而推导出合理的合成反应机理.结果表明,核独立成分分析算法能合理地解析红外光谱在线数据,并有效捕捉合成反应的中间体,对合成反应机理的研究具有重要的指导意义.     

Matrix-free infrared soft laser desorption/ionization

Infrared soft laser desorption/ionization was performed using a 2.94 µm Er : YAG laser and a commercial reflectron time-of-flight mass spectrometer. The instrument was modified so that a 337 nm nitrogen laser could be used concurrently with the IR laser to interrogate samples. Matrix-assisted laser desorption/ionization (MALDI), laser desorption/ionization and desorption/ionization on silicon with UV and IR lasers were compared. Various target materials were tested for IR soft desorption ionization, including stainless steel, aluminum, copper, silicon, porous silicon and polyethylene. Silicon surfaces gave the best performance in terms of signal level and low-mass interference. The internal energy resultant of the desorption/ionization was assessed using the easily fragmented vitamin B₁₂ molecule. IR ionization produced more analyte fragmentation than UV-MALDI analysis. Fragmentation from matrix-free IR desorption from silicon was comparable to that from IR-MALDI. The results are interpreted as soft laser desorption and ionization resulting from the absorption of the IR laser energy by the analyte and associated solvent molecules. Copyright © 2004 John Wiley & Sons, Ltd.