荧光碳点的制备及其荧光特性的研究和应用

围绕具有优良荧光发光特性的无机纳米材料——碳点,设计一个本科化学实验。通过"自下而上"的方法分别制备蓝色、绿色荧光碳点溶液;考察荧光碳点溶液的荧光激发和发射光谱关系,相对法测定荧光量子产率;探究不同浓度和pH条件下的荧光光谱变化;并将荧光碳点应用到防伪技术领域,加深学生对荧光材料的相关荧光概念和表征手段如荧光激发光谱、荧光发射光谱、荧光量子产率,术语如Stokes位移和荧光影响因素等理论知识的理解,同时通过防伪应用开拓学生的思维,鼓励学生将课堂所学应用到实际生产生活中。     

照相明胶荧光特性的研究

利用荧光分析法研究了照像明胶的荧光特性,结果表明,除了公认的苯丙氨酸和酪氨酸两种荧光物质外,还存在一种未知的荧光杂质,其最大激发峰为240 nm,荧光峰为395 nm,性能试验表明,该荧光杂质可能为卟啉类络合物或某种色素物质。     

基于喹啉单元的荧光探针的研究进展

喹啉及其衍生物是一种很好的金属螯合剂,而且它们具有良好的荧光性能,所以喹啉及其衍生物一直是荧光探针领域研究的热点.本文综述了近几年来含喹啉单元的荧光探针的研究进展,介绍了含喹啉单元类的荧光探针对Zn~(2+)、Cd~(2+)、Al~(3+)、Fe~(3+)、Cu~(2+)和含喹啉单元与金属离子的复合型荧光探针对阴离子荧光传感性能,并展望了含喹啉单元的荧光探针的理论和应用前景.     

荧光指示剂载体对荧光法溶氧传感器荧光膜性能的影响

以沉淀白炭黑、气相白炭黑和MQ树脂负载荧光指示剂Ru(dpp)3Cl2,添加到二甲基硅橡胶,制备氧敏感荧光膜,研究指示剂载体和用量对荧光膜荧光输出的影响。结果表明:纯硅橡胶荧光膜的荧光输出很低,SiO2填料可作荧光指示剂的载体提高指示剂的分散和荧光效率,SiO2填料提高荧光效率的能力为MQ树脂>气相白炭黑>沉淀白炭黑。含10%SiO2载体的硅橡胶制备的荧光膜,其荧光输出随指示剂用量线性增加,直至指示剂用量达0.1%,但SiO2填料降低荧光膜的响应速度。     

水溶液中金属增强荧光的研究进展

本文综述了水溶液中金属增强荧光的研究进展,重点阐明如何通过控制荧光物质与金属纳米粒子表面的距离,实现水溶液中的金属增强荧光。荧光物质与金属纳米粒子表面的距离主要通过有机分子和无机分子Si O2层控制,只有当距离合适才能达到最大的金属增强荧光。金属增强荧光提高了荧光检测的灵敏度,扩大了荧光技术的应用范围,已广泛应用到DNA、蛋白质检测、生物标记、生物成像和免疫分析中。     

基于铕配合物的荧光分子印迹的制备及其选择性检测痕量2,4,6-三氯苯酚

设计并制备了用于检测2,4,6-三氯苯酚的荧光分子印迹。由于铕配合物对模板分子的荧光淬灭作用,可用于荧光检测工具。荧光分子印迹在模板分子浓度范围0~70 nmol·L~(-1)内具有良好的荧光线性响应,相关系数为0.996 28。荧光分子印迹展现出了良好的灵敏度,其最低检出限为3.12 nmol·L~(-1)。荧光分子印迹具有较好的热稳定性,同时选择性检测实验证明荧光分子印迹对2,4,6-三氯苯酚具有良好的特异选择性。实验结果说明荧光分子印迹可用于选择性荧光检测低浓度氯酚类物质。     

荧光碳点的合成及对酿酒酵母的毒性研究

以葡萄糖为碳源采用溶剂热法合成了荧光碳点。紫外吸收光谱、荧光光谱以及透射电镜照片表明,所合成的荧光碳点发光性能优异,分散性好,且无团聚现象。荧光碳点原溶液出现浓度淬灭现象,稀释60倍情况下荧光最强。以酿酒酵母为模型生物,考察了不同生长时期(调整期、对数期早期、对数期中期)的酿酒酵母与不同浓度的荧光碳点共培养后的生长曲线。结果表明,即使荧光碳点浓度在27.75 mmol.L-1条件下也没有影响酵母菌的生长曲线,可认为基本没有细胞毒性。比较了相同荧光强度下的荧光碳点与CdTe量子点对酿酒酵母的细胞毒性,结果表明荧光碳点的毒性显著低于量子点的毒性。     

稀土元素荧光分析的进展

稀土元素的荧光分析是稀土元素发光分析的一部分,但有关无机荧光分析的文献未见对稀土元素作专门研究。该类分析通常包括溶液荧光分析和固体荧光分析,本文对溶液荧光分析的荧光光度分析法进行了讨论。     

基于BODIPY衍生物的氟离子荧光比例探针的研究

利用有机合成中Si-O键受氟离子（F-）作用断裂形成O-的机理,开展了以荧光染料BODIPY-PhOSi作为荧光探针检测溶液中的微量氟离子的研究。BODIPY-PhOSi受氟离子作用形成BODIPY-PhO-,引起荧光强度变化,从而达到检测微量氟离子的作用。实验通过有机反应合成了荧光探针BODIPY-PhOSi,然后采用荧光光谱仪进行低浓度溶液中微量氟离子滴定实验,得到不同浓度氟离子的荧光光谱曲线,谱图分析表明荧光探针BODIPY-PhOSi对氟离子的响应呈比例比色型,通过数据计算得到荧光探针的最小检测限,在对比实验中氟离子检测表现出了良好的选择性。     

有机锡缩聚物荧光染料的开发和研究

国际上在活性、荧光和还原三大染料工业中,荧光染料越居第二位。有机锡缩聚物荧光染料是近几年才开发的新型荧光材料。本文就荧光发射的基本原理,荧光物质的吸光发光的结构特征,染料高分子化的优点,以及影响荧光性能诸方面进行了论述。本文还简述了有机锡缩聚物荧光化合物的合成,荧光量子产率和荧光寿命的测定,以及其应用前景。     

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.     

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%).     

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.     

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.