水介质钯卟啉室温磷光探针与小牛胸腺DNA作用的光谱特性

研究水溶性卟啉及其金属配合物与生物大分子 ,特别是核酸的相互作用方式对获得 DNA的碱基序列和识别 DNA的结构进而设计新型药物尤其是抗癌药物具有重要意义 [1] .近年来 ,采用电子吸收光谱、荧光光谱法和电化学技术研究卟啉与 DNA的相互作用多有报道 [2～ 4 ] ,磷光探针 [5]已成为探索有机介质中微环境性质或生物大分子如核酸和蛋白质的构型变化以及它们与药物作用机理的有力工具 .由于磷光具有更高的选择性 ,且与体系氧浓度密切相关 ,而生物分子在接近红外的长波长区几乎没有室温磷光发射 ,因此 ,寻找或合成一种在这一波段具有室温磷…     

两种水溶性钯卟啉磷光探针的在位合成及其发光光谱特性研究

本文探索了合成水溶性钯卟啉(Pd—TAPP和Pd—TSPP)的最佳实验条件,通过紫外可见光谱、荧光光谱和室温磷光光谱研究了合成情况,并考察了其在不同有序介质中的室温磷光特性。     

金属钯/铂卟啉室温燐光探针在生物医学领域的应用研究

钯 铂 卟啉络合物在室温下发射长寿命 (ms)、长波长的光 ,这些特点使其在生物分析方面成为有用的探针。本文综述了该探针在光免疫标记、肿瘤诊断、DNA测定、生物传感器及其它方面的研究进展。引用文献 4 3篇     

钯卟啉室温燐光氧传感器的研究

以Dowex 5 0× 2 1 0 0树脂为载体固定四 (三甲氨基苯基 )钯卟啉 (Pd TAPP) ,利用其光被氧猝灭的特性 ,采用流动注射分析 (FIA)技术 ,制成氧传感器。该方法响应快 (响应时间从氮气到氧气为 1 8s,反之为86s) ,灵敏度高 (I0 I1 0 0 值为 5 .6) ,检测限可达 0 .0 9% (V V)。     

室温磷光分析法的进展与应用

本文对近5年来国内外室温磷光法的研究进展进行了综述,包括固体基质室温磷光、表面活性剂有序介质增稳室温磷光、环糊精诱导室温磷光、敏化和猝灭室温磷光、无保护流体室温磷光、室温磷光化学传感器、生物大分子的室温磷光研究与应用,引用文献158篇.     

室温磷光凝胶研究进展

室温磷光(RTP)材料因其独特的发光性质和在光电、传感、生物成像及信息加密等领域广阔的应用前景吸引了研究者的兴趣。近年来,科学家探索了各种方法调控有机分子的室温磷光,并通过磷光分子结构设计以及磷光保护基质的构建成功构筑了长寿命和高量子效率的有机室温磷光材料。超分子凝胶作为诱导室温磷光的新基质,具有三维网络结构、热可逆性质及刺激响应性等优势而引起关注。本综述围绕无金属室温磷光凝胶材料和含金属室温磷光凝胶材料,总结了近年来关于室温磷光凝胶材料的研究现状,并在此基础上,简要展望了室温磷光凝胶材料研究的发展趋势。     

金属钯／铂卟啉室温Lin光探针在生物医学领域的应用研究

钯（Ⅱ）／铂（Ⅱ）卟啉络合物在室温下发射长寿命（ms)、长波长的Lin光，这些特点使其在生物分析方面成为有用的探针。本文综述了该探针在Lin光免疫标记、肿瘤诊断、DNA测定、生物传感器及其它方面的研究进展。引用文献43篇。     

室温磷光分析法在我国的发展

室温磷光分析法是测定痕量有机化合物和生化物的高灵敏度和高选择性的一种新的测试手段，近２０年来在国外发展迅速，是当前分析化学研究中的热点和前沿。我国的研究工作虽赳不较晚，然而速度较快，现就室温磷光分析法在我国的发展作一回顾。     

Study on aggregation of palladium-porphyrins using room temperature phosphorescence

This paper reported room temperature phosphorescence (RTP) behaviors of meso-tetra-(4-sulfonatophenyl) porphyrin palladium (Pd-TSPP) and meso-tetra-(4-trimethylaminophenyl) porphyrin palladium (Pd-TAPP) in bovine serum albumin (BSA) medium. It was found that Pd-TSPP self-aggregated with its increasing concentration and hetero-aggregated with Pd-TAPP when they were mixed together. The self-aggregation of Pd-TSPP resulted in the remarkably splitting of excitation spectra because of the strongly excitonic coupling and phosphorescence quenching excited by Soret band, while Q band always kept the increase in intensity. The hetero-aggregation was out of the ground-state interaction stronger than the former one owing to its electrostatic-interaction nature. It was also indicated that inorganic salts like KCl would be an aid to hetero-aggregation. The equilibrium constants of both kinds of aggregation were estimated, namely, K(hom)=1.9 x 10(5) l/mol (homo-aggregation), and K(het)=1.06 x 10(7) l/mol (hetero-aggregation).     

Anti-oxygen-quenching room temperature phosphorescence stabilized by deoxycholate aggregate

Oxygen is the most effective dynamic quencher in liquid room temperature phosphorimetry (LRTP). Using oxygen scavenger to achieve significant or more sensitive RTP signals may bring about kinds of trouble in many cases and is apparently not very convenient in procedures. To date a few examples on LRTP without deoxygenation have been reported. Herein, we present a new named anti-oxygen-quenching RTP system using deoxycholate as a rigid medium. It can induce both lipophilic alpha-bromonaphthalene or 1-bromo-2-methylnaphthalene (BrMeN) and strongly water-soluble meso-tetrakis-(4-trimethylaminophenyl)porphyrin palladium (Pd-TAPP) to produce strong RTP emission under sodium deoxycholate of 4 mmol l(-1) and incubation time of half an hour. The maximum excitation and emission wavelengths respectively lie at 408 and 680 nm, with phosphorescence lifetime of 0.39 ms for Pd-TAPP, and at 285 and 515 nm, with lifetime of 4.9 ms for BrMeN. It is supposed that the hydrophobic and oxyphobic sandwich structure formed by two deoxycholate molecules with a phosphor in the case of deoxycholate or the interdiction fully of oxygen molecule diffusion into the microenvironment where the phosphor exists in the case of cyclodextrin is a key factor in inducing anti-oxygen-quenching RTP.     

Enantioselective room temperature phosphorescence detection of non-phosphorescent analytes based on interaction with beta-cyclodextrin/1-bromonaphthalene complexes

Menthol (MT) induces strong room temperature phosphorescence (RTP) of 1-bromonaphthalene (1BrN) in aqueous β-cyclodextrin (β-CD) suspensions, even under non-deoxygenated conditions. Interestingly, (−)-MT and (+)-MT enantiomers give rise to different phosphorescence intensities, the difference being 19 ± 3%. It is argued that the signal can be mainly ascribed to the formation of ternary complexes β-CD/1BrN/MT which show different RTP lifetimes, i.e. 4.28 ± 0.06 and 3.71 ± 0.06 ms for (−)-MT and (+)-MT, respectively. Most probably, the stereochemical structure of (−)-MT provides a better protection of 1BrN against quenching by oxygen than (+)-MT. This interpretation is in line with the observation that under deoxygenated conditions the phosphorescence intensity difference for the two complexes becomes very small, i.e. only about 4%.The lifetime difference under aerated conditions enables the direct determination of the MT stereochemistry. For mixtures, in view of the 0.06 ms uncertainty in the lifetime, enantiomeric purity can be determined down to 10%. Furthermore, in the case of MT the concentration of the least abundant enantiomer should be at least 3 × 10⁻⁴ M, since otherwise complex dissociation would obscure the lifetime difference.     

Crystallization-induced phosphorescence of benzils at room temperature

Efficient room temperature phosphorescence (RTP) is rarely observed in pure organic luminogens. However, we have newly observed that benzil and its derivatives are nonluminescent in solvents and thin layer chromatography (TLC) plates, but become highly phosphorescent in crystal state at room temperature, exhibiting typical crystallization-induced phosphorescence (CIP) characteristics. The CIP phenomenon is ascribed to the restriction of intramolecular rotations in crystals owing to effective intermolecular interactions. Such intermolecular interactions greatly rigidify the molecular conformation and significantly decrease the nonradiative deactivation channels of the triplet excitons, thus giving boosted phosphorescent emission at room temperature.     

Direct determination of naftopidil by non-protected fluid room temperature phosphorescence

A selective and sensitive room temperature phosphorimetric method for the direct determination of naftopidil in biological fluids is described. The method is based on obtaining a phosphorescence signal from this antihypertensive drug using TlNO3 as a heavy atom perturber and Na2SO3 as a deoxygenator agent without a protective medium. This technique is named non-protected room temperature phosphorescence (NP-RTP), and enables us to determine analytes in complex matrices without the need for a tedious prior separation process. The optimization of Na2SO3 (8.5 x 10(-3) M) and the accurate value of pH (9.0) were determined using a simplex as a method of optimization. Sodium carbonate-hydrogencarbonate buffer solution (5.0 x 10(-2) M) was used to adjust the suitable pH. The optimum concentration of Tl+ (8.5 x 10(-2) M) was also determined. The delay time, gate time and time between flashes selected were 200 microseconds, 200 microseconds and 5 ms, respectively. Under the above conditions we propose a method to determine naftopidil by direct measurement of phosphorescence intensity with an emission wavelength of 526 nm and an excitation wavelength of 296 nm in the concentration range 0.05-1.00 mg L-1. Under these conditions the phosphorescence signal appears in 3 min once the sample has been prepared. Optimization of the various conditions permitted the establishment of an NP-RTP method for the determination with a detection limit, according to the error propagation theory, of 21.0 ng mL-1. The repeatability was studied using 10 solutions of 0.20 mg L-1 of naftopidil; if error propagation is assumed, the relative error is 1.39%. The standard deviation for replicate samples was 1.1 x 10(-2) mg L-1. This method was successfully applied to the determination of naftopidil, in human urine with recoveries between 106 and 112%.     

Determination of the pesticide carbaryl by chemical deoxygenation micellar-stabilized room temperature phosphorescence

This paper presents a convenient determination method for carbaryl in polluted water by micellar-stabilized room temperature phosphorescence with Na(2)SO(3) as oxygen scavenger. The effect of various experimental conditions on the determination of carbaryl is discussed in detail. The analytical curve of carbaryl gives a linear dynamic range of 2 x 10(-7)-6 x 10(-5) mol/l., and a detection limit of 2 x 10(-7) mol/l. A recovery of 90-100% was obtained for 0.05-0.1 ppm carbaryl.     

硫鸟嘌呤修饰的Mn:ZnS QDs磷光探针检测铂(Ⅲ)

通过水相合成法制备了硫鸟嘌呤(TG)修饰的锰掺杂硫化锌量子点(TG-Mn:ZnS QDs)。加入Pt⁴⁺后,Pt⁴⁺会与硫鸟嘌呤上的氮原子结合形成N-Pt⁴⁺配位结构附着在TG-Mn:ZnS QDs的表面,随着Pt⁴⁺浓度的增加,TG-Mn:ZnS QDs-Pt⁴⁺体系发生电子转移而导致磷光逐渐被猝灭,基于此构建了检测Pt⁴⁺的磷光探针。实验中考察了p H、时间对Pt⁴⁺猝灭TG-Mn:ZnS QDs磷光强度的影响。在最佳实验条件下,Pt⁴⁺浓度在0.06～2.4μg/mL范围内与TG-Mn:ZnS QDs的磷光强度呈良好的线性关系y=0.0884x+0.2319,R²=0.991,方法检出限(3σ/n)为1.3μg/mL。该磷光探针适用于实际样品中Pt⁴⁺含量的测定。     

Direct determination of biacetyl in fats by sensitized room temperature phosphorescence

A direct method for the determination of biacetyl in butter and margarine by sensitized room temperature phosphorescence (SRTP) is described. After dissolution of the sample in hexane, biacetyl is isolated by distillation, and its native phosphorescence is sensitized by a non-polar linear furocoumarin, 4′5′-dihydro-3-carbethoxypsoralen. The limit of detection is 0.05 ng ml^?1 biacetyl, with a linear response from 1 × 10^?4 to 1 μg ml^?1 (r = 0.999). The RSD is 3.5% at 100 ng ml^?1.     

Determination of the plant growth regulator beta-naphthoxyacetic acid by micellar-stabilized room temperature phosphorescence

This paper presents a method for the determination of the plant growth regulator beta-naphthoxyacetic acid (NOA) by micellar-stabilized room temperature phosphorescence with the surfactant Triton X-100 (TX-100) as the micellar medium, thallium nitrate as the heavy atom and sodium sulphite as the oxygen scavenger. A multivariate optimization approach using the blocked cube star design of central composite was carried out. The analytical curve of NOA gives a linear dynamic range of 0.4-3.0 mug ml(-1) and a detection limit of 0.13 mug ml(-1). A recovery of 93.6% was obtained for 1 mug ml(-1) NOA in spiked apple samples.     

Molecular probe for a fluorous medium: long-lived phosphorescence of alpha-diketones in perfluoromethylcyclohexane at room temperature.

We found that alpha-diketones (2,3-butanedione (BD) and 1-phenyl-1,2-propanedione (PPD)) were very suitable luminescence probes for studying the properties of a perfluorinated solvent (i.e., fluorous solvent; perfluoromethylcyclohexane (PFMC)), since these compounds were soluble in PFMC and showed long-lived phosphorescence even at room temperature. The phosphorescence lifetime (tau(p)) of BD in PFMC (650 micros) was much longer than that in cyclohexane (CH, 270 micros). The longer tau(p) value of BD in PFMC was ascribed to the variation of the intersystem crossing rate constant (k(isc)) from the excited triplet state (T1) to the ground state (S0) with the solvent. Some possible reasons for the change in k(isc) were discussed in terms of solute-solvent interactions. Furthermore, by utilizing phosphorescence quenching of BD by pyrene, we, determined a rate constant of the diffusion-controlled reaction in PFMC. Characteristic behaviors of mixing/separation processes between PFMC and a common organic solvent observed by Schlieren photographs were also reported.