酰腙类衍生物作为阴离子荧光探针的研究

本文设计合成了含偶氮酰腙类受体分子1,2-羟基-5-(4-硝基苯偶氮基)苯甲醛-p-硝基苯甲酰腙。用UV-Vis和荧光光谱考察了其与AcO-、H2PO4-、F-、Cl-、Br-和I-阴离子的作用。当加入AcO-、F-和H2PO4-时,受体分子的吸收光谱发生明显的红移,同时溶液颜色由无色变为紫红色。更为重要的是受体1对阴离子表现出荧光光谱的比率变化。最后通过在DMSO-d6中的核磁滴定实验研究受体1和F-相互作用的本质。     

新型含酚羟基Schiff碱化合物的比色阴离子传感器

设计合成了一种含酚羟基Schiff碱类受体1-羟基-4-氯-二苯甲酮-2,4-硝基苯腙受体分子1.利用紫外-可见吸收光谱、荧光光谱考察了其与AcO -,H2PO4-,F-,Cl-,Br-,I-等阴离子的作用.当加入AcO -,F-和H2PO4-时,导致紫外光谱的可见光区明显变化(大约130nm红移),同时伴随着从亮黄色到粉红色的“裸眼”颜色变化.通过在DMSO-d6核磁滴定实验进一步研究了探针1和F-相互作用的本质.     

高选择性氟离子受体的合成与识别性能研究

设计合成了一种新型腙类阴离子受体1。利用紫外-可见吸收光谱,荧光光谱考察了其与Ac O-,H2PO4-,Cl-,Br-,I-和F-几种阴离子之间的作用。当加入F-时,导致紫外光谱的可见光区明显变化(大约115nm红移),同时伴随着浅黄色变为蓝紫色的"裸眼"颜色变化。而加入其他离子后溶液颜色几乎没有发生颜色。据此建立了裸眼比色法检测F-的方法。     

酰胺硫脲类衍生物对阴离子的识别作用研究

应用紫外-可见吸收光谱和荧光光谱考察了一种酰胺硫脲类衍生物在二甲基亚砜(DMSO)中与F-、C1-、Br-、CH3CO2-、H2PO4-和HSO4-的相互作用.结果表明,该类主体分子能与阴离子形成结合比为1:1的氢键配合物,荧光光谱显示它们对F-和H2PO4-有突出的响应灵敏度,可选择性识别F-和H2PO4-.     

N3染料对F-的高选择性光学传感性质

采用紫外-可见吸收光谱和荧光光谱滴定方法研究了N3染料, cis-Ru(H2dcbpy)2(NCS)2 (H2dcbpy=4,4’-二羧酸-2,2’-联吡啶), 在二甲基亚砜(DMSO)溶液中对F-、Cl-和Br-的识别行为. 结果表明, F-能引起N3的吸收光谱和荧光光谱的明显变化, 能作为高选择性的荧光和比率色度F-传感器. N3与F-相互作用产生一个大的荧光增强因子40, 在已报道的基于Ru(II)配合物的F-传感器中较为罕见.     

一种双腙受体的合成及阴离子识别性能研究

设计合成了一种含双腙类阴离子受体1(5-甲基双水杨醛-2,4-二硝基苯腙)。用紫外-可见吸收光谱、荧光光谱考察了其与AcO-,H2PO4-,F-,Cl-,Br-和I-阴离子的作用。当加入AcO-、F-和H2PO4-时,受体分子1的吸收光谱发生明显的红移,与此同时溶液颜色由浅粉色变为紫色,而加入其他阴离子则无变化。通过在DMSO-d6核磁滴定实验进一步研究受体1和F-相互作用的本质。     

基于苯腙类衍生物的阴离子光学传感器的研究

本文设计合成了一种简单的比色阴离子受体1,5,5'-亚甲基双水杨醛-2,4-二硝基苯腙。利用UV-vis光谱和荧光光谱研究了受体1与阴离子AcO-,H2PO4-,F-,Cl-,Br-和I-的相互作用。当加入AcO-,F-和H2PO4-时,受体分子的吸收光谱发生明显的红移,与此同时溶液颜色由浅黄色变为红色,而加入其他阴离子则无变化。最后通过1HNMR滴定进一步研究了1与阴离子AcO-的相互作用的本质。     

N3染料对F-的高选择性光学传感性质

采用紫外-可见吸收光谱和荧光光谱滴定方法研究了N3染料,cis-Ru(Hedcbpy)2(NCS)2(H2dcbpy=4,4'-二羧酸-2,2'-联吡啶),在二甲基亚砜(DMSO)溶液中对F-、Cl-和Br-的识别行为.结果表明,F-能引起N3的吸收光谱和荧光光谱的明显变化,能作为高选择性的荧光和比率色度F-专感器.N3与P相互作用产生一个大的荧光增强因子40,在已报道的基于Ru(Ⅱ)配合物的F-传感器中较为罕见.     

1,8-萘酰亚胺修饰的卟啉及其作为F-识别化学传感器的研究

合成了新型的具有识别F-能力的1,8-萘酰亚胺修饰的卟啉化合物,在F-的作用下,紫外-可见光谱和荧光光谱都发生明显的变化,而且可以被肉眼识别,该传感器可以作为具有F-选择性的比色和荧光化学传感器。     

基于分子内电荷转移的阴离子比率荧光分子探针

设计合成了一种基于4-甲基-1-羟基二苯甲酮对硝基苯腙的比色和比率荧光阴离子受体1。此类受体以羟基和腙单元为识别位点,以硝基苯基为信号报告基团。向受体1的DMSO溶液中加入AcO-、H2PO4-、F-后,溶液颜色由黄色变为紫红色,而加入所研究的其它阴离子则无变化,从而实现对AcO-、H2PO4-、F-这三种离子的裸眼识别。利用紫外-可见吸收光谱、荧光光谱考察了其与AcO-,H2PO4-,F-,Cl-,Br-,I-等阴离子的识别作用。1H NMR滴定为受体分子与阴离子之间氢键作用本质提供了有力证据。     

Novel fluorogenic probe for fluoride ion based on the fluoride-induced cleavage of tert-butyldimethylsilyl ether

A highly sensitive and selective fluorogenic probe for fluoride ion, 4-methylumbelliferyl tert-butyldimethylsilyl ether (4-MUTBS), was designed and synthesized. 4-MUTBS was a weakly fluorescent compound and was synthesized via the one-step reaction of 4-MU with tert-butyldimethylsilyl chloride. Upon incubation with fluoride ion in acetone-water solution (7:3, v/v), the Si-O bond of 4-MUTBS was cleaved and highly fluorescent 4-methylumbelliferone (4-MU) was released, hence leading to the fluorescence increase of the reaction solution. The fluorescence increase is linearly with fluoride concentration in the range 50-8000 nmol l(-1) with a detection limit of 19 nmol l(-1) (3sigma). Because of the high affinity of silicon toward fluoride ion, the proposed probe shows excellent selectivity toward fluoride ion over other anions. The method has been successfully applied to the fluoride determination in toothpaste and tap water samples.     

1,5-二芳基-3-(2-羟基-4,6-二甲氧基苯基)-2-吡唑啉的合成及氟离子荧光探针行为

设计合成了8个1,5-二芳基-3-(2-羟基-4,6-二甲氧基苯基)-2-吡唑啉化合物4a~4h. 它们的结构经由IR、1H NMR、MS和元素分析确认. 测定了它们的紫外光谱和荧光光谱, 研究了它们对氟离子的选择性识别作用, 发现化合物4a,4c和4d均可选择性地识别氟离子, 其中4a和4c作为识别氟离子的荧光探针, 受常见离子干扰较小, 选择性较高.     

Novel side‐chain naphthalimide polyphenylacetylene as a ratiometric fluorescent chemosensor for fluoride ion

Novel polyphenylacetylene ( P1 ) containing naphthalimides units in the side chain was designed and synthesized. The structure and properties of the polymer were characterized and evaluated by IR, NMR, UV, and PL. The measurements of sensing behavior to various halide anions, that is, F^?, Cl^?, Br^?, and I^?, reveal that the polymer is a ratiometric fluorescent chemosensors for fluoride ion. The polymer sensor shows spectral shifts and intensity changes in the presence of fluoride, in a wavelength‐ratiometric and ‐colorimetric manner, which can detect fluoride concentrations in range of 10–100 μM at visible wavelengths. The obvious colorless‐to‐yellow color change and blue‐to‐orange emission color change on the addition of fluoride ion are easily observed by naked eyes. It provides a feasible way to construct a ratiometric fluorescent chemosensors for fluoride ion. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1544–1552, 2009     

对氟苯酚-过氧化氢-辣根过氧化物酶体系酶联荧光免疫分析研究──Ⅰ.对氟苯酚直接法及铝-钙指示剂偶合法测定人血清中乙肝表面抗原和表面抗体

对氟苯酚在辣根过氧化物酶（HRP）的催化下可被H2O2氧化，生成本酚及F-。测定对氟苯酚荧光猝灭程度及用铝－钙指示剂荧光体系检测酶促反应释放的F－，可分别建立HRP及其标记物的两种分析方法。铝－钙指示剂偶合法测定HRP的线性范围为0．031～31U／L，检测限（3δ）为0．0093U／L。两种方法分别用于测定人血清中乙肝表面抗原及抗体，结果令人满意。     

1-dicarboxymethylaminomethyl-2-hydroxy-3-naphthoic acid as a sensitive and selective fluorimetric reagent for beryllium,and for lanthanum and lutetium in presence of the other lanthanides

1-Dicarboxymethylaminomethyl-2-hydroxy-3-naphthoic acid (DHNA) forms fluorescent complexes with Al, Be, Ga, Hf, In, La, Lu, Mg, Sc, Th, Y, and Zr. The Be, La and Lu complexes have a metal : ligand ratio of 1:1. The beryllium complex shows maximal fluorescence at pH 6.8 with excitation-fluorescence maxima at 360 and 450 nm; linear calibration curves are obtained in the range 0.09–1.8 μg Be. In the presence of the calcium-EDTA complex, of 25 cations studied, only > 100-fold molar ratios of aluminium and > 10-fold molar ratios of magnesium and scandium caused interference in the determination of 0.1 μ mole of beryllium. Amongst 15 anions, > 100-fold molar ratios of phosphate, > 50-fold molar ratios of arsenate or oxalate and > 10-fold molar ratios of citrate, fluoride and tartrate caused low results. Lanthanum and lutetium can be determined at PH 10 and 370/460 nm in the range 7–28 μg even in the presence of a 3-fold molar ratio of the other lantlianides without interference.     

Photophysical and density functional studies of the interaction of a flavone derivative with the halides

The synthesis, photophysical behavior, and anion-sensing ability of a fluorescent molecular system, N-(3-methoxy-4-oxo-2-phenyl-4H-chromen-7-yl)-benzamide (1H), designed and developed with a view to sensing fluoride ions, are reported. NMR and density functional studies on the system have been carried out to determine the nature of the interaction between 1H and X- (X = halogen atom) responsible for fluoride-induced dramatic changes in the absorption and emission properties of 1H. The color change of 1H, which can be observed by the naked eye, is found specific to fluoride ion; it is unaffected by the presence of a large excess of Cl-, Br-, and I-, thus rendering 1H as a selective fluoride ion sensor in micromolar concentration in the visible region. The changes in the fluorescence behavior of 1H, specifically, the formation of an additional long-wavelength emission band in the presence of fluoride ion, allow ratiometric fluorescence signaling of the fluoride ion as well. The results suggest that abstraction of the acidic proton of 1H by the F- leading to the formation of 1- is responsible for the spectral changes that allow signaling of the F-. Density functional calculations of the optimized geometrical parameters and charge densities of the 1H...halide complexes confirm the proton abstraction mechanism of the signaling of F-. Calculations of the transition energies of the 1H, 1-, and 1H...F- (hydrogen-bonded complex) show that only 1- is responsible for the long-wavelength absorption and emission band observed in the presence of F-.     

Fluoride ion detection by 8-hydroxyquinoline-Zr(IV)-EDTA complex

A simple fluorescent detection based on the ligand exchange mechanism is proposed for the fluoride ion in aqueous media. This procedure is based on the exchange of 8-hydroxyquinoline (oxine) coordinated to Zr(IV) by fluoride ion without interference from other common anions. The ternary complex of oxine with [Zr(H(2)O)(2)EDTA].2H(2)O formed by replacing two water molecules in aqueous solution provides a sensitive signalling system for fluoride ion in the concentration range from 6 x 10(-7)M to 8 x 10(-4)M. The green fluorescence (lambda(max)=532 nm) exhibited by the complex upon excitation at 247 nm decreases in intensity with fluoride addition with a detection limit of 12 ppb. The complexation reaction between oxine and Zr(IV)-EDTA and the ligand exchange reaction with fluoride ion has been investigated by UV-vis and fluorescence spectroscopies combined with the PM3 semi-empirical quantum chemical calculations. Job's method of continuous variation and the molar ratio method ascertain a 1:1 stoichiometry composition of the chelate in aqueous media.     

A coumarin-based fluorescent and colorimetric chemosensor for rapid detection of fluoride ion

A novel coumarin-based compound 1 featuring thiosemicarbazone as binding unit, was reported as a colorimetric and fluorescent probe for the detection of fluoride anion. The addition of F^? to a solution of probe 1 in tetrahydrofuran resulted in evident naked-eye color change from green-yellow to orange-red under daylight and obvious fluorescence quenching within 3 s. And the detection limit toward F^? was calculated to be as low as 2.16 × 10^?7 mol/L. ¹H NMR titrations proved that the interaction between 1 and fluoride ion: hydrogen bond at low fluoride ion concentration, deprotonation at high fluoride ion concentration. Besides, it exhibited highly sensitivity and selectivity for F^? over other examined ions (Cl^?, Br^?, I^?, AcO^?, NO₃^?, HSO₄^?, H₂PO₄^?) in tetrahydrofuran solution.     

Unique hydrogen bonds between 9-anthracenyl hydrogen and anions

Unique hydrogen bonds of the 9-H of anthracene moieties in hosts 1 and 2 with fluoride and pyrophosphate ions were observed on the basis of the (1)H NMR experiments. Furthermore, hosts 1 and 2 act as a colorimetric sensor and a fluorescent chemosensor for the recognition of fluoride ion, respectively.     

A water-soluble fluorescent fluoride ion probe based on Alizarin Red S-Al(III) complex

A new water-soluble fluorescent fluoride ion signaling system has been developed based on the ligand exchange mechanism in aqueous medium. This procedure is based on the exchange of two Alizarin Red S (ARS) molecules coordinated to Al(III) by fluoride ion without interference from other common anions. The binary complex of ARS with Al(III) provides a sensitive signaling system for fluoride ion in the concentration range from 5x10(-6) to 3x10(-4) M. The ligand exchange reaction of ARS-Al(III) complex with fluoride ion has been investigated by UV-vis and fluorescence spectroscopies combined with the AM1 semi-empirical quantum chemical calculations. The pale orange fluorescence (lambdamax=575 nm) exhibited by the complex upon excitation at 435 nm decreases in intensity with fluoride addition with a detection limit of 0.1 mg L-1.