β-溴代萘的无保护流体室温磷光性质及介质效应

无任何保护性介质存在下,β－溴代萘（β－ＢｒＮ）水溶液仅以Ｎａ２ＳＯ３作化学除氧剂,经仪器光源适当照射,即能很快产生强而稳定的室温磷光（ＲＴＰ）信号．不同种类和用量的有机溶剂存在时,ＲＴＰ强度和获得稳定ＲＴＰ信号所需光诱导的时间显著不同．含２．５％乙腈的β－ＢｒＮ水溶液仅需极短的光诱导时间就能产生很强的ＲＴＰ发射,β－ＢｒＮ浓度在８．０×１０－８～１．６×１０－５ｍｏｌ／Ｌ范围内与其ＲＴＰ强度呈良好线性关系,检出限４．７×１０－８ｍｏｌ／Ｌ     

β—溴代萘瓣无保护流体室温磷光性质及介质效应

无任何保护性介质存在下,β－溴代奈（β－ＢｒＮ）水溶液仅以Ｎａ２ＳＯ３作化学除氧剂,经仪器光源适当照射,即能很快产生强而稳定的室温磷光（ＲＴＰ）信号,不同种类和用量的有机溶剂存在时,ＲＴＰ强度和获得稳定ＲＴＰ信号所需光诱导的时间显著不同,含２．５％乙腈的β－ＢｒＮ水溶液仅需极短的光诱导时间就能产生很强的ＲＴＰ发射,β－ＢｒＮ浓度在８．０×１０＾－８－１．６×１０＾－５ｍｏｌ／Ｌ范围内与其ＲＴＰ强度     

α- 萘氧乙酸无保护流体室温磷光的重原子效应及有机溶剂的影响

萘氧乙酸（ＮＯＡ）是一类植物生长调节剂．对ＮＯＡ在β－环糊精（β－ＣＤ）保护下的室温磷光（ＲＴＰ）性质［１］和荧光性质［２］研究已有报道,但无保护性介质存在下的ＲＴＰ性质研究尚未见报道．我们在研究丹磺酰氯及其衍生物的无保护流体室温磷光（ＮＰ－ＲＴＰ）...     

多环芳烃芴、苊的无保护流体室温磷光性质研究

我们[1,2 ]曾报道丹磺酰氯及其衍生物在无保护性介质亦无有机溶剂存在的水溶液中能诱导出强而稳定的室温磷光 (ＲＴＰ) ,并命名为ＮＰ ＲＴＰ[37].此后 ,Ｃａｒｒｅｔｅｒｏ等[810 ]亦发现了萘唑啉、萘氧乙酸和苊溶液在无任何有序介质时的ＲＴＰ发射现象 .在已有的研究中至少有两个问题需进一步探索 :其一 ,除苊外 ,已实现ＮＰ ＲＴＰ发射的化合物都仅具双环结构 ,即萘系化合物 ,对于多环化合物是否有类似的发射特性和随环的增多是否会出现新的特性 ;其二 ,对于无水溶性取代基的多环芳烃 ,因其在水中的溶解度很小 ,所引入的有机溶剂的种类和…     

香豆素衍生物在数种薄层基质上的室温磷光发射特性

考查了二十多种香豆素衍生物在国产ＭＮ－Ｐ型和ＭＮ－Ｃ型微晶纤维素膜，ＤＥＡＥ离子交换膜上的室温磷光发射特性，并与用滤纸作基质时的结果作了比较。在这些基质上，多数衍生物都能发射不同强度的ＲＴＰ信号，且在其ＲＴＰ特性间呈现，某些取代基效应。从发光稳定性和信背比考虑，ＭＮ－Ｃ型比ＭＮ－Ｐ型膜更适合于这些衍生物的ＲＴＰ发射。     

胺类对α—溴代萘／β—环糊精体系流体室温磷光的影响

首次研究了不同的胺对α－溴代萘（α－ＢｒＮｐ）／β－环糊精（β－ＣＤ）体系ＲＴＰ发射的影响,发现胺能显著增强α－ＢｒＮｐ／β－ＣＤ体系的ＲＴＰ发射,ＲＴＰ强度 随着胺的烷基链的增长和支锭的增加而增加,且当胺的用量是β－ＣＤ用量的一倍时,ＲＴＰ强度最大。由此认为,胺的影响主要应归因地胺分别从β－ＣＤ的二端接近,胺的－ＮＨ２基与β－ＣＤ的－ＯＨ基形成氢键,而其烷基从ＣＤ二端折向空腔,封住了ＣＤ的上、下     

不除氧条件下喹啉的环糊精诱导室温燐光性质

不除氧条件下，在含２０μＬ二溴烷（ＤＢＥ）的１０ｍＬ体系中，喹啉就能产生强而稳定的环糊精诱导室温燐光（ＣＤ－ＲＴＰ）信号，最大λｅｘ／λｅｍ＝２７６／４９６ｎｍ，喹啉浓度在２．０×１０－６～４．０×０１０－４ｍｏｌ／Ｌ范围内与ＲＴＰ信号呈良好的线性关系，检测限２．０×１０－７ｍｏｌ／Ｌ。由于所用重原子微扰剂ＤＢＥ的量很少，本发光体系仅均匀地呈轻微的雾状，而无明显沉淀，使测量精度明显改善。实验还发现，Ｎａ２ＳＯ３化学除氧可使体系ＲＴＰ强度稍有增加，而通氮除氧反而因ＤＢＥ的挥发损失使体系的ＲＴＰ强度明显降低。     

有机小分子对两种萘酚三元包络物室温燐光的影响

详细研究了９种有机小分子对两种萘酚三元包络物β－环糊精（ＣＤ）／萘酚／１，２－二溴乙烷（ＤＢＥ）室温■光（ＲＴＰ）强度及■光寿命的影响。对比了各种有机小分子对包络于β－ＣＤ中两种萘酚ＲＴＰ的增敏、增稳作用及分析特性。     

α-溴代萘的无保护性介质流体室温燐光特性

含α－溴代萘（ａ－ＢｒＮｐ）的水溶液仅以Ｎａ２ＳＯ３作化学除氧剂，在仪器光源的照射下，即能很快触发α－ＢｒＮｐ强而稳定的室温光（ＲＴＰ）信号。体系ＲＴＰ性质和所需光诱导的时间对有机试剂的存在及其种类和用量极为敏感。０．５％（Ｖ／Ｖ）乙腈或丙酮的存在所需光照时间短，ＲＴＰ强度高。α－ＢｒＮｐ浓度分别在 １．０ × １０－６～ ２． ４ × １０－５ ｍｏｌ／Ｌ和 ４． ０ × １０－７～ ２． ０ × １０－５ｍｏｌ／Ｌ范围内与 ＲＴＰ强度呈良好线性关系，检出限分别为 ３，８ × １０－８ ｍｏｌ／Ｌ和 ６．５ × １０－８ ｍｏｌ／Ｌ。     

环氧溴丙烷作重原子微扰剂环糊精诱导室温燐光法测定7种痕量多环芳烃化合物

１引言环糊精诱导室温燐光法（ＣＤ－ＲＴＰ）测定痕量多环芳烃化合物的研究，我们曾做过大量的工作。在此基础上，本文研究ＴＮａ２ＳＯ３化学除氧技术用于环氧溴丙烷作重原子微扰剂β－ＣＤ－ＲＴＰ法测定痕量菲（Ｐｈｅｎ．），苊（Ａｃｅ．），芴（Ｆｌｕ．），７，８－苯并喹啉（７，８－ＢＱ），７－甲基喹啉（７－ＭｅＱ），α－４嗅代萘（α－ＢｒＮ），β－溴代茶（β－ＢｒＮ）中，均取得了成功。说明化学除氧技术在ＣＤ－ＲＴＰ法中具有普遍的意义。２实验部分２．１仪器和试剂ＬＳ－５０Ｂ型发光分析仪；菲、芴、苊（高效液相色…     

Room-temperature phosphorimetry studies of some addictive drugs following dansyl chloride labelling

A room-temperature phosphorimetric (RTP) method for the analysis of barbital, codeine, morphine and practolol after labelling with dansyl chloride (DNS-Cl) is described. The drug-DNS derivatives were obtained by refluxing with drug-ethyl acetate solutions and solid DNS-Cl in the presence of anhydrous potassium carbonate. The reaction conditions were investigated in detail. The fluorescence emission of drug-DNS derivatives shifted to longer wavelengths compared with that of DNS-Cl. The RTP phenomena observed for these derivatives by using a micellar stabilized room-temperature phosphorescence technique were examined and optimum conditions for their RTP emission were studied using an orthogonal array design. Derivative RTP spectra were obtained and successfully used to determine practolol by the established method without further separation.     

若干香豆素衍生物在滤纸基质上的RTP和RTF特性

详细考察了各种基质、重原子微扰剂和实验条件的影响之后,成功地实现了多种香豆素衍生物的室温磷光(RTP)发射。在滤纸基质上,以1mol/L的Pb(Ac)_2作重原子微扰剂时,近20种香豆素衍生物大都能产生较强的RTP发射。而且某些衍生物的RTP强度和λ_(ex)/λ_(em)等特性间呈现出明显的取代基效应。本文还对这些衍生物在滤纸基质上的室温荧光(RTF)和其混和光谱(在重原子微扰剂存在下以荧光方式测得的光谱)等特性作了对比测定,发现其间亦呈现类似的取代基效应。有关香豆素衍生物的RTP特性,迄今尚未报道。这类衍生物RTP发射的实现,预示着它们用作RTP标记物的可能性。     

Study of the heavy atom-induced room temperature phosphorescence properties of melatonin and its analytical application

Liquid phase room temperature phosphorescence (RTP) properties of melatonin were studied using heavy atom induced-room temperature phosphorescence (HAI-RTP) technique. 1.2 M potassium iodide was used as a heavy atom reagent together with 0.002 M sodium sulphite as deoxygenating agent to produce the RTP signal. The maximum phosphorescence emission and excitation wavelengths of melatonin were 290 and 457 nm, respectively. The effect of potassium iodide concentration on the RTP lifetime of melatonin was also investigated and based on the results, the rate constants for phosphorescence decay (k(p)) and radiationless deactivation through reaction with heavy atom (k(h)) were determined. Based on the obtained results, a simple and sensitive room temperature phosphorimetric method was developed for the determination of melatonin. The method allowed the determination of 10.0-200 ng ml(-1) melatonin in aqueous solution with the limits of detection and quantification of 3.6 and 12 ng ml(-1), respectively. The proposed method was satisfactorily applied to the determination of melatonin in commercial pharmaceutical formulations.     

Study of the substituent groups effect on the room-temperature phosphorescent emission of fluorene derivatives in solution

We present here the first study of the effect of substituent groups and the chemical structure of fluorene derivatives on phosphorescent emission. A group of fluorene derivatives have been studied with a new methodology of room-temperature phosphorescence emission called heavy atom induced room-temperature phosphorescence (HAI-RTP). This methodology makes use of RTP emission directly from the compound in fluid solution, without a protective medium but only with the presence of high concentrations of heavy atom perturbers and an oxygen scavenger. These experimental conditions permit sufficient interaction between the perturbers and the phosphors to produce effective population of the triplet states of the latter and, consequently, intense phosphorescent emission. Good deoxygenation conditions are obtained using sodium sulfite as the oxygen scavenger. We show here that it is possible that many fluorene derivatives can exhibit RTP emission in aqueous solutions in the absence of a protective medium. Phosphorescence spectral characteristics of these compounds (excitation and emission wavelengths and lifetime) and the optimization of the chemical variables involved in the phosphorescence phenomenon are reported. Under optimal experimental conditions, calibration graphs and detection and quantification limits in the ng ml⁻¹ level have been established.     

Investigation on the Luminescence Performance of Four Quinolones

Abstract

In this paper we report on the low temperature phosphorescence (LTP), the low temperature fluorescence (LTF), the paper substrate room temperature phosphorescence (PS‐RTP), and the room fluorescence (RTF) properties of ciprofloxacin (CPFX), lomefloxacin (LMX), fleroxacin (FLX), and ofloxacin (OFLX), which were investigated and compared. Some rules were discovered: their maximal excitation wavelength and emission wavelength are in the range of 280–295 nm and 428–500 nm, respectively, except OFLX, and the difference in molecular structure may be responsible for it. The pH experiments show that all their emissions are strongest in acid, followed by neutral, and weakest in alkali medium. The PS‐RTP characters of lifetime and polarization were also investigated and compared. It was found that the lifetimes of PS‐RTP were all in the level of 0.1 s. These quinolones belong to long‐life phosphorescence and their PS‐RTP spectra are incompletely polarized.     

Metal‐Free Facile Synthesis of Multisubstituted 1‐Aminoisoquinoline Derivatives with Dual‐State Emissions

Although isoquinoline is a good traditional fluorescent structural unit, most of its derivatives emit fluorescence in solution and a few of them can emit solid‐state fluorescence as well. Herein, a series of multisubstituted 1‐aminoisoquinoline derivatives were synthesized by a simple reaction of a readily available 4H‐pyran derivative and secondary amines. The reaction had advantages of metal‐free, mild conditions, simple operation, and good yields, which was realized by a ring‐opening and sequential ring‐closing mechanism. These 1‐aminoisoquinoline derivatives were found to exhibit interesting dual‐state emissions. In the solution, they emitted strong blue fluorescence at about 458 nm. In the solid state, they emitted solid‐state blue fluorescence at 444–468 nm with high fluorescence quantum yields of 40.3–98.1%. Crystal structural analyses indicated that solid‐state emissions of these compounds originated from twisted molecular conformations and the resultant loose stacking arrangements. Furthermore, their solid‐state fluorescence wavelengths were demonstrated to depend on molecular conformations rather than stacking arrangements. The discovery of these 1‐aminoisoquinolines with multiple reaction sites provides new possibilities for the development of solid‐state fluorescent materials based on the traditional isoquinoline skeleton.     

Achieving room temperature phosphorescence from organic small molecules on amino acid skeleton

Room temperature phosphorescence (RTP) generated by small molecules has attracted great attention due to their unique potentials for biosensor, bioimaging and security protection. While, the design of RTP materials is extremely challenging for organic small molecules in non-crystalline solid state. Herein, we report a new strategy for achieving non-crystalline organic small molecules with RTP emission by modifying different phosphors onto diphenylalanine or phenylalanine derivatives. Benefiting from the skeletal structure of the amino acid derivatives, there are intermolecular hydrogen bond formation and rigidification effect, thereby minimizing the intermolecular motions and enhancing their RTP performance     

Achieving room temperature phosphorescence from organic small molecules on amino acid skeleton

Room temperature phosphorescence (RTP) generated by small molecules has attracted great attention due to their unique potentials for biosensor, bioimaging and security protection. While, the design of RTP materials is extremely challenging for organic small molecules in non-crystalline solid state. Herein, we report a new strategy for achieving non-crystalline organic small molecules with RTP emission by modifying different phosphors onto diphenylalanine or phenylalanine derivatives. Benefiting from the skeletal structure of the amino acid derivatives, there are intermolecular hydrogen bond formation and rigidification effect, thereby minimizing the intermolecular motions and enhancing their RTP performance     

Determination of photophysical rate constants for the non-protected fluid room temperature phosphorescence of several naphthalene derivatives.

The determination of kinetic parameters for luminescence processes is very important in understanding the phosphorescence process and the mechanisms of the heavy atom effect (HAE). In our previous work, we reported that room temperature phosphorescence (RTP) emission of many naphthalene derivatives can be induced directly from their aqueous solution without using any kind of protective medium, and the name Non-Protected Fluid Room Temperature Phosphorescence (NP-RTP) is suggested for this new type of RTP emission. In order to further understand this kind of luminescence phenomenon, the influence of heavy atom perturber (HAP) concentration on RTP lifetime of several naphthalene derivatives was studied in detail in this paper. The possibility of determination of photophysical parameters for emission of NP-RTP was explored based on the definition on the phosphorescence lifetime and the relation with the concentration of HAP in this paper. A static Stern-Volmer equation for phosphorescence was derived and the luminescence kinetic parameters were calculated. The results obtained by two different ways proved that photophysical parameters for RTP emission can be determined based on the changes of the RTP lifetime.