超分子组合流体室温磷光现象（Ⅱ）—醇对环糊精／碘代乙基联 …

在外部重原子微拢剂溴代环己烷存在下，β－ＣＤ／碘代乙基联苯体系可发射一定强度的室温磷光信号，若丁醇作为第四组分存在，则能显著提高体系的室温磷光发射强度。研究了该体系室温磷光发射的适宜条件和多种醇、不同环糊精及其衍生物的影响。认为β－ＣＤ／碘代乙基联苯／溴代环乙烷／丁醇体系属于一种超分子组合的发光体系，醇的作用属典型的分子调控作用。β－ＣＤ／碘代乙基联苯／溴代环乙烷形成主、客三元包结物，可醇则利用其     

超分子组合流体室温磷光现象(Ⅱ)——醇对环糊精/碘代乙基联苯/溴代环己烷体系室温磷光的影响

在外部重原子微拢剂溴代环己烷存在下，β－ＣＤ／碘代乙基联苯体系可发射一定强度的室温磷光信号，若丁醇作为第四组分存在，则能显著提高体系的室温磷光发射强度。研究了该体系室温磷光发射的适宜条件和多种醇、不同环糊精及其衍生物的影响。认为β－ＣＤ／碘代乙基联苯／溴代环己烷／丁醇体系属于一种超分子组合的发光体系，醇的作用属典型的分子调控作用。β－ＣＤ／碘代乙基联苯／溴代环己烷形成主、客三元包结物，而醇则利用其羟基与ＣＤ端口羟基形成氢键，其烷基键借助于疏水相互作用力，覆盖在ＣＤ上、下端口，对外部氧向ＣＤ腔内的扩散起着隔离作用，减少了三线态氧对发光体激发三线态的猝灭，从而显著提高了体系室温磷光发射强度     

磷光光度法在药物分析中的应用

本文评述了固体基质室温磷光，流体介质室温磷光，低温磷光和室温磷光传感器在药物分析中的应用，涉及到的药物有生物碱，中草药有效成分，四环素类，喹喏酮类，维生素B2，抗癌药物，萘唑啉，萘普生和血管扩张剂潘生丁双嘧哌胺醇等，在药物分析中，固体基质室温磷光取样量只有微升级，操作快，成本低，流体室温磷光结合流动注射和化学传感技术，在药物的快速连续在线监测方面优势明显，而经过改善的低温磷体室温磷光结合流动注射和化学传感技术，在药物的快速连续在线监测方面优势明显，而经过改善的低温磷光方法，除了克服操作方面的某些弱点外，仍然保持高灵敏度的特点，随着敏化和猝死发光，能量转移，衍生发光和免疫发光等技术的发展，磷光方法在药物分析中的应用将会更加广泛。     

蛋白质的室温磷光法研究

提出了牛血清蛋白(BSA)和人血清蛋白(HSA)的室温磷光法,蛋白质的磷光主要来自于包埋于其中的色氨酸残基,并对影响其室温磷光强度的的各种因素:如重原子浓度,酸度,除氧剂浓度等进行了详细研究,建立了测定痕量HSA和BSA的室温磷光法.该法是以KI为重原子微扰剂,在水溶液中用Na2SO3化学除氧后,以287nm为激发波长,BSA和HSA在443nm左右的磷光具有较好的重复性和稳定性.在此条件下它们的线性范围分别为:1×10-6-8.6×10-5mol/L和3×10-6-13×10-5mol/L,检出限分别为:2.20×10-7mol/L和4.10×10-7mol/L.同时,还对它们的光谱性质如荧光、磷光寿命,偏振等进行了测量.结果显示BSA中色氨酸残基有两种荧光衰减形式,HSA则只有一种衰减形式,它们的磷光属于长寿命磷光,都能引起光的偏振.     

菲的无保护性介质流体室温磷光性质研究

在无任何保护性介质存在下,以Na2SO3作化学除氧剂,KI为重原子微扰剂,菲即能产生强而稳定的流体室温磷光发射.激光和发射波长λex/λem为283/482,504nm,不同有机溶剂存在对其磷光发射的性质有不同影响.1%乙腈存在时,菲浓度在8.0×10-7～6.0×10-6mol*L-1和6.0×10-6～4.0×10-5mol*L-1范围内分别与磷光发射强度呈良好的线性关系,检出限为2.6×10-8mol*L-1.     

黄嘌呤甲基衍生物滤纸基质室温磷光光谱研究

以滤纸为基质,详细讨论了3种黄嘌呤甲基衍生物可可碱、咖啡因、茶碱的固体基质温磷光光谱特性,研究表明：它们的滤纸基质室温磷光（PS－RTP）光谱基本相近,其最大激发波长λem分别为435、432、427nm。40余种无机盐类重原子微扰剂对这3种化合物诱发室温磷光的研究结果为：KI、NaI,Zn(NO3)2,SrCl2对可可碱、咖啡因、茶碱发射PS－RTP都有一定的重原子效应,其中I^-对它们诱发PS－RTP重原子效应最大,酸度实验表明,酸度对可可碱的影响在于咖啡因和茶碱,3种化合物在pH-2-8范围内都有PS－RTP,而且在强酸和强碱笥条件下它们的PS－RTP均发生猝灭,此外,本文也对影响PS－RTP的温度、干燥时间等条件进行了考察。     

不除氧条件下环糊精诱导室温磷光法测定喹啉

在不除氧条件下，１０ｍＬ含喹啉／β－ＣＤ溶液中只需加入１５μＬ１，２－二溴丙烷（ＤＢＰ）作重原子微扰剂，就能产生强而稳定的室温磷光信号。最大λｅｘ／λｅｍ＝２７３／４９６ｎｍ。喹啉浓度在５．０×１０＾－７￣５．０×１０＾－５ｍｏｌ／Ｌ，５．０×１０＾－４ｍｏｌ／Ｌ，两段三个数量级范围与室温磷光信号有良好的线性关系，最低检测限７．４×１０＾－８ｍｏｌ／Ｌ。本体系的特点是ＤＢＰ用量少，从而减少了因过量     

八元瓜环诱导菲、芴的室温磷光研究

以八元瓜环为诱导剂、碘化钾作重原子微扰剂,在亚硫酸钠除氧下,实现了菲、芴的室温磷光发射。在该体系中菲、芴的最大激发和发射波长分别为282和509 nm,276和518 nm,磷光寿命分别为1.82和3.68 ms。在最佳实验条件下,菲在1.0×10-7~1.5×10-6mol.L-1,1.5×10-6~1.0×10-5mol.L-1和芴在8.0×10-7~8.0×10-6mol.L-1的浓度范围内分别与其磷光强度呈良好的线性关系,检出限分别为4.8×10-9和8.0×10-9mol.L-1。     

异硫氰酸荧光素标记抗体的固体基质室温磷光性质研究

研究了异硫氰酸荧光素（FITC）标记的羊抗人抗体（GAHAb-FITC)和兔抗羊抗体9RAGAb-FITC)，及其以三种免疫方式与人免疫球蛋白（IgG)反应所得免疫复合物在多种固体薄膜基质上发射室温磷光（RTP）的适宜条件及其光谱，强度和寿命等性质。研究发现，标记抗体及其免疫复合物保留了FITC优良的固体基质室温磷光性质，λ m0643em^(max)=525/650nm，其RTP强度与其浓度线性相关，并有很高的灵敏度，更为重要的是，免疫反应及其RTP检测能结合于同一基质，方便地相继完成，在聚酰胺膜（PM）上，以Pb(Ac)2为重原子微扰剂，稀释比为1：10（ψ）的GAHAb-FITC,RAGAb-FITC及其与人IgG形成的免疫复合物均能发射较强制 RTP信号并有较长的RTP寿命，本结果为建立相应的固体基质室温磷光免疫分析（SS-RTP-IA）新方法奠定了相应的实验基础。     

6-巯基嘌呤滤纸基质室温磷光光谱研究

本文建立了 6 -巯基嘌呤 (6 - MP)的滤纸基质室温磷光 (PS- RTP)检测法 ,实验条件已经最佳化。研究表明 ,6 - MP的 PS- RTP光谱的最大激发波长 λex与最大发射波长 λem分别为 312 nm和 4 5 5 nm。30多种无机盐类重原子微扰剂对 6 - MP的 RTP影响的研究结果表明 ,Cd盐可增强 RTP,其中 Cd(OAc) 2 重原子效应最为显著。酸度条件对 6 - MP的 PS- RTP有较大影响 ,在 p H为 7— 8时 RTP发射较强。此外 ,本文也对影响 6 - MP的 PS- RTP的固体基质类型、重原子浓度、干燥条件等进行了详细的研究。实验表明 ,方法的线性范围为 4 .2 6— 10 6 6 ng/spot,检出限为 3.31ng/spot,相关系数为 0 .997,相对标准偏差为 4 .0 7% ,回收率为 99.6 %— 10 0 .5 %。该方法简便、快速、灵敏 ,应用于商业药片的分析 ,结果令人满意。     

吲哚-3-丁酸无保护流体室温燐光和胶束增稳室温燐光性质的比较

仔细研究了吲哚-3-丁酸(IBA)的无保护流体室温燐光(NP—RTP)及以高分子分散剂聚乙二醇-200,聚乙二醇-400和非离子表面活性剂Tween-20,Tween-40,Tween-80,Tween-85,Brij35和乳化剂OP为介质的流体室温燐光性质。表面活性剂和高分子分散剂能抑制IBA燐光猝灭,使其具有更低的检出限,同时也使燐光强度-激发光照射时间曲线发生改变,但不影响IBA燐光光谱特性。无论是否存在表面活性剂或高分子分散剂,TINO3都不能诱导IBA产生燐光,KI却能诱导其产生强烈燐光。用于强化水样和土壤样品中IBA的测定,回收率95．2％～104％,相对标准偏差2．4％～4．0％。     

External heavy atom effect on the emission of carbazole

External heavy atom induced quenching of luminescence emission of carbazole in n-hexane and methylcyclohexane in the presence of chloro- and bromoacetic acids at 300 K and 77 K is described. A straight line relation between fluorescence quenching rate constant and the acid dissociation constant of chloroacetic acids, which is related to electron affinity, is observed. Different photophysical parameters at 77 K of unperturbed and perturbed fluorescent carbazole in ternary solutions have been determined and suitable reaction mechanism for quenching has been proposed. Inference has been drawn about complex formation in the triplet state of carbazole from the biexponential nature of the phosphorescence decay curve.     

Second-Order Data Obtained by Time-Resolved Room Temperature Phosphorescence. A New Approach for PARAFAC Multicomponent Analysis

A second-order multivariate calibration approach, based on a combination of PARAFAC with time-resolved room temperature phosphorescence (RTP), has been applied to resolve a binary mixture of Phenanthrene and 1,10-Phenanthroline, as model compounds. The RTP signals were obtained in aqueous β-cyclodextrin solutions, in the presence of several heavy atom containing compounds. No deoxygenation was necessary to obtain the phosphorescence signals, which adds simplicity to the method. The resolution of the model compounds was possible in base to the differences in the delay-time of the RTP signals of the investigated analytes, opening a new approach for second-order data generation and subsequent second order multivariate calibration.     

Room‐Temperature Phosphorescence in Metal‐Free Organic Materials

Purely organic materials with room‐temperature phosphorescence (RTP) have attracted a growing interest for their potential applications in biological imaging, digital encryption, optoelectronic devices, and so on. To date, many strategies have succeeded in designing efficient organic RTP materials by overcoming the spin‐forbidden transition between singlet and triplet states. However, the underlying mechanisms of RTP still remain ambiguous. Such spin prohibition in phosphorescence are clarified, herein, from the perspective of perturbation theory, helping to understand the intrinsic relationship among various phosphorescence parameters, like phosphorescence efficiency, lifetime, intersystem crossing rate, as well as radiative and nonradiative rates. Taking into consideration the recent progress in organic RTP materials, these factors are further illustrated by a selection of the most relevant molecules. In addition, some novel RTP phenomena are also reviewed, thus providing an excellent guideline to constructing efficient RTP materials.     

Determination of Bioactive Matter by Affinity Adsorption Solid Substrate–Room Temperature Phosphorimetry Based on Lectin Labeled with Self-ordered Ring of Eosin Y

A new phosphorescent labeling reagent named self-ordered ring (ESOR) of eosin Y (E) was developed. And the application of the determination of bioactive matter by affinity adsorption solid substrate–room temperature phosphorimetry (AA-SS-RTP) based on ESOR labeling lectin was studied. Results showed that pink and homogeneous ESOR could be formed by E on polyamide membrane (PAM) in the presence of cetyltrimethylammonium bromide (CTAB) and ammonia water. ESOR could emit strong and stable room temperature phosphorescence (RTP) signal of E in the presence of heavy atom perturber. Specific affinity adsorption (AA) reactions could be carried out between the products of concanavalin agglutinin (Con A), triticum vulgaris lectin (WGA) labeled with ESOR and alpha-fetoprotein variant (AFP-V), alkaline phosphatase (ALP), glucose (G), respectively. Not only did the products of the affinity adsorption reactions preserve good RTP characteristic of E, but also the ΔI _p (ΔI _p = I _p2 − I _p1, I _p1 is the RTP intensity of blank reagent, I _p2 is the RTP intensity of sample) of these products was proportional to the content of AFP-V, ALP and G, respectively. According to the facts above, a new method of AA-SS-RTP for the determination of AFP-V, ALP and G was established, based on ESOR labeling lectin. Detection limits (LD) of this method were 0.040 fg spot⁻¹ for AFP-V, 0.045 fg spot⁻¹ for ALP and 0.090 fg spot⁻¹ for G. And it has been successfully applied to the determination of AFP-V in human serum as well as the survey and forecast of human diseases. This method had high sensitivity, good repeatability, long RTP lifetime and little background interference with at the long wavelength area. Meanwhile, the mechanism for the determination of trace AFP-V by AA-SS-RTP based on Con A labeled with ESOR was also discussed.     

Investigation of the Heavy-Atom Effect on the Spectral-Luminescent Properties of Dichloroanilines

The influence of the chlorine atom position on the spectral, geometric, and photophysical characteristics of free molecules of dichloroaniline is studied by electron spectroscopy, fluorescence, and quantum chemistry. A chlorine atom included in the aniline aromatic ring is shown to exhibit properties inherent in a heavy atom, that is, the radiation is dominated by phosphorescence. According to quantum-chemical calculations, the quenching of fluorescence is due to the fact that the efficiency of the intersystem crossing conversion proves to be much higher than the radiative decay rate of the S ₁ state.