CdTe量子点与L-天冬氨酸相互作用的研究及其分析应用

水相中合成了谷胱甘肽(GSH)修饰的CdTe量子点(GSH-CdTe QDs). 利用紫外-可见吸收光谱(UV-vis)、共振瑞利散射(RRS)光谱、荧光光谱(FL)和傅里叶变换红外光谱(FTIR)研究了GSH-CdTe QDs与L-天冬氨酸(L-Aspartic acid, L-Asp)的相互作用机理. 在pH为5.3 的BR缓冲溶液中, GSH-CdTe QDs与L-Asp主要通过静电引力和氢键作用在GSH-CdTe QDs周围形成了粒径较大的聚集体, 导致体系的RRS显著增强和GSH-CdTe QDs的荧光急剧猝灭. 在一定浓度范围内RRS增强和荧光猝灭均与L-Asp的浓度成正比, 其中RRS法灵敏度更高（对L-Asp检出限为14.2 ng•mL^–1）, 据此建立了以GSH-CdTe QDs作RRS探针测定L-Asp的一种新方法. 同时讨论了反应条件和共存物质对体系RRS强度的影响. 用于实际尿样中L-Asp的测定, 实验结果满意.     

小分子生物硫醇荧光探针研究进展

半胱氨酸(Cys)、同型半胱氨酸(Hcy)和还原型谷胱甘肽(GSH)等小分子生物硫醇在人的生理活动中起着重要作用.近年来,生物和环境样品中小分子生物硫醇的检测引起科学家们极大的兴趣,生物硫醇荧光探针和比色传感器得到快速发展.根据探针与生物硫醇的反应机理,包括利用小分子生物硫醇中巯基与探针反应、巯基和氨基协同与探针反应,综述两年来生物硫醇小分子荧光探针的设计、合成与应用进展.     

配体对CdTe量子点与BSA的选择性相互作用的影响

以巯基乙酸(TGA)、巯基丙酸(MPA)、巯基甘油(TG)、L-半胱氨酸(L-cys)和谷胱甘肽(GSH)等5种巯基分子为稳定剂, 水相合成了5种CdTe量子点. 以牛血清白蛋白(BSA)作为靶分子, 通过吸收光谱、荧光光谱和时间分辨荧光动力学等手段研究了各种配体分子稳定的CdTe量子点与BSA的直接相互作用. 结果表明, 5种量子点均能有效猝灭BSA的荧光, 其猝灭程度按配体次序为GSH>L-cys>TGA>TG>MPA; 而BSA对不同配体稳定的CdTe量子点的荧光光谱的影响则具有明显的选择性. BSA对TGA-CdTe和MPA-CdTe量子点的荧光先敏化增强而后猝灭下降; L-cys分子由于同时具有氨基和羧基而与BSA的相互作用较强, 因此BSA能显著猝灭L-cys-CdTe量子点的荧光; 而BSA对TG-CdTe量子点的荧光猝灭程度较小; GSH分子的空间效应使GSH-CdTe量子点的荧光被BSA猝灭的程度最小. 吸收光谱和时间分辨荧光动力学研究表明, 5种量子点与BSA之间的相互作用均为静态过程. 探讨了量子点的配体分子结构与蛋白质的相互作用机理.     

一种“硫醇-色烯点击反应”的荧光探针的合成及应用

本文设计合成了一种基于硫醇-色烯点击反应的荧光探针CHMPC-Ac,用于半胱氨酸(Cys)、同型半胱氨酸(Hcy)和谷胱甘肽(GSH)的识别检测.这些生物硫醇因巯基的强亲核性而与探针的不饱和酮发生迈克尔加成反应,导致色烯分子开环等分子内级联反应,生成具有强荧光的香豆素衍生物,分别使荧光强度增强107、69和66倍. CHMPC-Ac具有灵敏度高(Cys:15 nM; Hcy:26 nM; GSH:22 nM)和响应快(Cys:20 s; Hcy:50 s; GSH:30 s)等优点,并已应用于HepG 2细胞和斑马鱼体内生物硫醇的识别检测.     

CdTe/CdS半导体量子点作为农药百草枯的高灵敏传感器

用硫普罗宁(Tiopronin, TP)作为稳定剂合成了水溶性的高荧光CdTe/CdS量子点. 研究了该量子点与10种农药的相互作用. 实验发现, 当农药浓度为4.76×10^-6 mol/L时, 农药百草枯(Paraquat)能显著猝灭CdTe/CdS量子点的荧光, 使其荧光强度下降87.3%, 而分别加入乙酰甲胺磷及辛硫磷等其它9种农药, 仅能使CdTe/CdS量子点的荧光强度下降0.1%～5.1%, 显示了该CdTe/CdS量子点对百草枯的特异性传感作用. 采用吸收光谱和时间分辨荧光动力学研究了百草枯对CdTe/CdS量子点的荧光猝灭机理. 计算得出荧光强度猝灭的Stern-Volmer常数K为2.03×10⁶, 而寿命猝灭的Stern-Volmer常数K为4.25×10⁵. 结果表明, 百草枯对CdTe/CdS量子点的荧光猝灭主要为静态过程, 而动态过程的贡献较小. 利用二者的猝灭作用建立了对农药百草枯的高灵敏检测新方法, 校正曲线的线性范围为9.90×10^-9～1.50×10^-6 mol/L, 检出限为6.35×10^-9 mol/L, R=0.999. 用该方法对3种食品和3种水样中残留农药进行了检测, 加标回收率均在82.2%～98.5%之间, 其相对标准偏差为2.62%~8.35%.     

Ag2S基近红外II区荧光量子点的水相合成优化探究

具有近红外II区荧光的Ag₂S量子点(QDs)因具有带隙窄、Stokes位移大及光稳定性好等优点而在生物成像领域具有广阔应用前景. 然而, 传统有机相合成的Ag₂S量子点水溶性与生物相容性较差, 而水相合成Ag₂S量子点的荧光又很难到近红外II区, 这严重制约了Ag₂S量子点的生物医学应用推广. 因此, 优化探究具有近红外II区荧光发射的Ag₂S基量子点的水相合成方法具有重要意义. 采用核掺杂ZnS、表面阳离子(Zn²⁺)改性以及调控表面配体制备出一系列Ag₂S基量子点, 发现核掺杂和表面阳离子改性均使Ag₂S基量子点的荧光呈现剂量依赖性蓝移; 而将表面配体由树枝状短链(Captopril)更换为长直链(11-巯基十一烷酸, MUA)时, Ag₂S基量子点的发射峰红移至1105 nm(近红外II区)且半峰宽更窄. 本研究发现, 相比核掺杂和表面阳离子改性, 优化表面配体更容易在水相中制备出具有近红外II区荧光的Ag₂S基量子点. 本工作为近红外荧光量子点的水相合成及优化提供了基础研究数据.     

谷胱甘肽稳定水溶性CdTe/ZnTe量子点的制备与表征

用还原型谷胱甘肽(GSH)作为稳定剂, 合成了水溶性的CdTe/ZnTe核壳结构的半导体量子点. 考察了Zn/Cd反应物配比及GSH用量对CdTe/ZnTe量子点的性能影响. 用高分辨透射电子显微镜(HRTEM)和X射线粉末衍射(XRD)光谱对CdTe和CdTe/ZnTe的形貌和晶体结构进行了表征. 荧光光谱结果表明, 核壳结构的CdTe/ZnTe量子点比单一的CdTe量子点具有更高的荧光量子产率和更好的光活化性能.     

高性能CdTe/CdS核壳型量子点的制备及应用于小麦面粉中呕吐毒素的荧光免疫检测研究

量子点荧光免疫法的广泛应用迫切需要提高量子点的发光强度和抗体的稳定性. 分别采用巯基乙酸和谷胱甘肽作稳定剂, 水相合成CdTe量子点, 再包覆CdS制备核壳型CdTe/CdS量子点. 以EDC/NHS作交联剂将CdTe/CdS量子点标记到呕吐毒素抗体上, 然后用牛血清蛋白封闭抗体. 研究发现, 谷胱甘肽稳定剂优于巯基乙酸. 与CdTe量子点相比, 谷胱甘肽修饰的CdTe/CdS量子点其荧光的强度和稳定性分别提高6倍和2倍以上. 谷胱甘肽碳链较长, 减少了量子点对抗体尤其是活性位点处的空间构型影响, 从而大大提高抗体的稳定性. 监测不同储藏时间(4 ℃)的CdTe/CdS量子点-抗体偶联复合物与呕吐毒素免疫反应前后荧光强度变化值, 结果显示抗体至少可以稳定7 d. 基于谷胱甘肽稳定的高性能CdTe/CdS量子点, 我们建立了一种新的呕吐毒素荧光免疫检测方法. 呕吐毒素浓度在0～0.9 ng•mL^－1之间相对荧光强度呈线性关系, 相关系数(R²)为0.9992, 检出限是0.038 ng•mL^－1. 方法的灵敏度高于文献报道的其它方法, 如GC-ECD, HPLC和HPLC-MS, 已成功应用于小麦面粉样品中痕量呕吐毒素的测定.     

水溶性量子点碲化镉测定同型半胱氨酸的研究

以巯基丙酸为稳定剂,在水溶液中一步合成了CdTe量子点,以该量子点为荧光探针,基于荧光增敏法对同型半胱氨酸(Hcy)进行选择性测定,考察了缓冲体系、缓冲液浓度、缓冲液pH值、反应时间、量子点浓度等多种因素的影响.在0.05 mol/L、pH 8.8的磷酸二氢钠-磷酸氢二钠缓冲液中,当量子点浓度为1.2 mmol/L、反应时间为10 min时,该方法的线性区间为0.1 ～60 μmol/L,检出限为8×10-8 mol/L.     

基于碳点荧光恢复法测定生物巯基化合物

碳点(CDots)是一种新型荧光纳米材料,Cu2+可以有效猝灭其荧光;而当有生物巯基化合物存在时,碳点-Cu2+体系的荧光可以恢复.基于此原理,我们成功地构建了检测生物体内总巯基化合物的新方法.该方法具有很好的选择性,常见氨基酸和金属离子对谷胱甘肽(GSH)、半胱氨酸(Cys)和高半胱氨酸(Hcy)的检测无影响.最佳实验条件下,谷胱甘肽、半胱氨酸、高半胱氨酸的浓度在6.0×10-6mol/L～1.0×10-4mol/L与相对荧光强度呈线性,R>0.996,检出限为2.0×10-6mol/L.该体系成功用于血清样品中总巯基化合物的检测.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

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.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

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.     

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.