吖啶橙-氧化石墨烯荧光猝灭法测定多巴胺

在酸性介质中氧化石墨烯对吖啶橙的荧光发生猝灭作用,此时加入适量多巴胺,则导致体系的荧光强度增强,且增强程度与多巴胺的加入量成正比.据此建立了吖啶橙-氧化石墨烯荧光光度法测定多巴胺的方法.多巴胺的质量浓度在0.05～12.0μmol/L范围内呈线性,线性方程为ΔIF=3.9+57.8c(μmoL/L),相关系数r=0.9...     

基于金纳米簇探针的荧光猝灭检测铁离子

以D-色氨酸为保护剂和还原剂, 采用水热法快速制备了具有强荧光的金纳米簇(D-Trp@AuNCs); 以其作为荧光探针, 建立了基于荧光猝灭的选择性高灵敏检测Fe³⁺的传感方法. 利用透射电子显微镜(TEM)、 紫外-可见光谱(UV-Vis)和红外光谱(IR)等手段对制备的金纳米簇进行了表征, 并利用荧光光谱研究了D-Trp@AuNCs的荧光性能. 结果表明, D-Trp@AuNCs具有较好的生物相容性, 其最大激发波长为370 nm, 最大发射波长为460 nm; 向金纳米簇溶液中加入Fe³⁺后, D-Trp@AuNCs的荧光发生明显猝灭, 其猝灭程度与Fe³⁺的浓度在0.3~500.0 μmol/L范围内呈现良好的线性关系, 检出限为33.1 nmol/L(S/N=3). 将该荧光探针用于实际水样中Fe³⁺的检测, 回收率为86.6%~106.5%.     

罗丹明6G荧光猝灭法测定痕量肝素

在pH 8.0的缓冲体系中,肝素使得罗丹明6G的荧光发生明显猝灭,罗丹明6G的荧光猝灭程度在一定范围内与肝素的浓度成正比,据此建立了荧光猝灭法测定痕量肝素的方法,并对体系的荧光猝灭机理进行了讨论。体系的激发波长为482 nm,发射波长为560 nm,线性范围为0.05~3.0 mg/L,检出限为6.1μg/L。方法已应用于肝素钠注射液中肝素含量的测定。     

银纳米簇荧光探针测定水样中铜(Ⅱ)

制备了银纳米簇并考察其光学性能,最大吸收波长和荧光激发波长均在340 nm,荧光发射波长为462 nm。Cu2+可使银纳米簇的荧光发生明显猝灭,且其它金属离子干扰较小。依据Cu2+银纳米簇荧光强度猝灭率与Cu2+的相关性,建立了Cu2+测定方法,采用4参数S曲线方程拟合,对Cu2+检出限为0.1μmol/L。方法用于水样中Cu2+检测,可以满足环境水样中Cu2+的检测要求。     

恒波长同步荧光猝灭法测定饮用水中微量溴酸根

在HCl介质中,Δλ=20nm,溴酸根对罗丹明123的恒波长同步荧光有猝灭作用,且猝灭程度与溴酸根的含量呈线性关系,据此建立了恒波长同步荧光猝灭测定饮用水中的微量测定溴酸根的新方法。该方法的线性范围为0～200μg/L,检出限为3.0ng/mL。该方法可用于化学试剂和各种饮用水中溴酸盐含量的测定。     

双发射碳量子点的一步合成及其用于卡托普利比率测定的研究

以间苯二胺(MPD)为唯一碳源，在乙酸存在条件下，一步水热法合成了新型双发射碳量子点(m-CQDs)。在305 nm波长激发下，m-CQDs于345 nm与511 nm波长处具有独立的双发射峰。在对m-CQDs结构表征和发光性能研究的基础上，实验发现，加入KMnO₄可使m-CQDs双发射峰中345 nm波长处荧光猝灭，其后再加入卡托普利(CAP),可使345 nm波长处猝灭后的荧光信号重新线性恢复，而511 nm波长处荧光信号基本不变。据此，以m-CQDs 345 nm波长峰强度为荧光响应信号，511 nm波长峰强度为参比信号，基于该m-CQDs探针直接形成“响应-参比”信号，可构建用于CAP测定的“猝灭-恢复”比率型荧光探针。该探针对CAP检出限为5.2×10^-8 mol/L,CAP浓度在8.0×10^-8 mol/L～1.0×10^-5 mol/L范围内，与荧光信号比值F₃₄₅/F₅₁₁呈良好线性关系。通过比对紫外-可见吸收光谱和不同温度对猝灭常数的影响，...     

基于CdSe/ZnS量子点构建多巴胺荧光检测方法的研究

以CdSe/ZnS量子点为荧光探针,基于多巴胺对CdSe/ZnS量子点的荧光猝灭效应,建立了一种可快速测定多巴胺的荧光检测方法。在最优实验条件下(pH7.4,反应时间20min),多巴胺浓度在0.01~0.7μmol/L范围内与CdSe/ZnS量子点的荧光猝灭强度比值呈良好的线性关系(r=0.996),方法检出限为1.6×10-4μmol/L,相对标准偏差为1.2%。与文献报道的方法相比,该方法的检出限更低,更为灵敏,可用于多巴胺注射液及人体尿样中多巴胺的快速检测。     

基于5-氨基水杨酸的碳量子点用于测定高锰酸根

采用简单的水热法制备了以5-氨基水杨酸为前驱体的氮掺杂碳量子点(N-CQDs)。合成的NCQDs呈球形,平均粒径3.45 nm,表面含有丰富的功能基团。在紫外灯照射下,N-CQDs发出绿色荧光,荧光量子产率为10.4%,最大激发和发射波长分别为340 nm和502 nm。加入MnO₄^-后,N-CQDs的荧光强度呈浓度依赖性猝灭,基于此,构建了灵敏的“开-关”型纳米探针。通过考察紫外-可见吸收光谱、荧光寿命和Stern-Volmer常数,MnO₄^-猝灭N-CQDs荧光归因于内滤效应和静态猝灭。在优化条件下,N-CQDs检测MnO₄^-的线性范围为0～14μmol/L,检出限(LOD)为0.14μmol/L。N-CQDs对水中常见的其他阳离子和阴离子表现出优良的选择性和抗干扰能力。该方法已成功应用于湖水中MnO₄^-的测定。     

脯氨酸保护的铜纳米团簇的制备及其在三硝基苯酚检测中的应用

以脯氨酸(Pro)为保护剂,盐酸羟胺为还原剂,通过一步化学还原法制备脯氨酸稳定的铜纳米团簇(Cu NCs)。采用分子荧光仪和紫外可见吸收仪对Cu NCs的光学性质进行分析,通过透射电子显微镜(TEM)、X射线光电子能谱(XPS)和傅里叶变换红外波谱仪(FTIR)对Cu NCs的结构进行表征。TEM图像显示Cu NCs的形貌为球状,平均直径为1.89 nm。Cu NCs溶液在紫外光下呈蓝色,最大激发和发射波长分别为397和458 nm。Cu NCs的荧光可以选择性地被三硝基苯酚(PA)猝灭。该探针对PA的线性响应范围为0.5~15μmol/L和20~70μmol/L,检测限为0.092μmol/L(S/N=3)。可能的检测机理是静态猝灭和内滤效应。此外,该荧光探针已成功应用于实际水样品中PA的测定。     

水溶性阳离子荧光共轭聚合物作为荧光探针测定三磷酸腺苷

利用荧光光谱研究了三磷酸腺苷(ATP)与水溶性阳离子荧光共轭聚合物的相互作用,发现加入ATP后,聚合物的荧光强度被显著猝灭,且猝灭程度与ATP的加入量成正比,据此建立了测定ATP的方法.荧光光谱的激发波长选择395 nm,发射波长为521 nm,激发狭缝宽度为10.0 nm,发射狭缝宽度为10.0 nm.在0 05 mol/L Tris-HCl缓冲溶液(pH=7.4)中,测定ATP的线性范围为8.0×10-8～1.0×10-5 mol/L; 检出限为2.0×10-8 mol/L; 回收率在93.6%～105.6%之间; 相对标准偏差在2.2%～6.9%之间.本方法用于三磷酸腺苷二钠药片和鲫鱼肉中ATP的测定,获得满意结果.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

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%).     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

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.