Fluorescence Characteristics of Schiff Bases Derived from Amino- and Aminoalkylpyridines

The fluorescence characteristics of the Schiff bases 2-(3-pyridylmethyliminornethyl)phenol (1), 2-(2 pyridyliminomethyl)phenol (2), N.N-bis(salicylidene)-2,3-pyridinediamine (3), N,N'-bis(salicylidene)-2,6-pyridinediamine (4) and 2-(2-amino-4-methoxymethyl-6-methyl-3-pyridylmethyliminomethyl)phenol (5) were studied in various solvents at different pH values. Corresponding quantum efficiencies were determined. Compound 1, which showed a tendency towards tautomeric mterconversion to ketoamine in polar protic solvents, was not fluorescent at pH < 8. The fluorescence of other compounds was very sensitive to solvent polarity and the pH of the medium. Compounds 2-4, preferably present as enolimines in all solvents, were not fluorescent in non-polar and moderately polar solvents, whereas weak emission was observed in polar solvents, like methanol, dimethylformamide and dioxane/water 1/1 (0.001 < Q < 0.072). A significant increase in Stokes shifts and in quantum efficiencies was noted as a result of increasing polarity of dioxane/water mixtures, indicating specific interactions with polar water molecules. The emission was promoted at acidic pH values where a pyridinium cation was formed (0.061 < Q < 0.519, in dioxane/water 1/1 at pH 3.4). Compound 5, which was a tautomeric mixture of enoiimine and cyclic diamine in all solvents, was fluorescent in polar as well as in non-polar media. The quantum efficiency varied dependent on the solvent and pH (0.023 <Q< 0.435). The cyclic diamine, i. e. the more rigid structure was supposed to be responsible for the fluorescence in non-polar and aprotic solvents as well as at neutral, and weakly basic pH values.     

两种有机磷农药的吸收光谱和荧光光谱研究

以常见的有机磷农药对硫磷和甲基对硫磷为对象,采用量子化学半经验方法AM1优化它们的基态构型,然后采用单激发组态相互作用CIS方法将基态构型优化为激发态构型。在此基础上,采用含时密度泛函TD-DTF,在B3LYP/6-31+G(d)水平下,分别计算了它们基态构型的吸收光谱和激发态构型的荧光发射光谱。优化完成后的基态构型经振动分析,均未出现虚频率,说明得到的构型基本合理。比较优化完成后的基态和激发态的构型推测了光谱产生的机理,光谱的理论值与使用英国Edinburgh FLS920P光谱仪测得的实验值基本吻合,说明了推测的合理性。以上研究为农药的光谱检测提供了一定的理论支持。     

Tm3+掺杂的MFT玻璃蓝色荧光动力学

测量了Tm^3 掺杂的MFT玻璃材料的吸收光谱，J－O计算给出了该材料的光学跃迁强度参数Ωt(t=2,4,6)。测量了355nm激发下该材料的发射光谱，通过测量不同掺杂浓度Tm^3 的^1D2→^3H4和^1G4→^3H6荧光衰减曲线讨论了这两个能级寿命及荧光量子效随浓度的变化关系，计算当Tm^3 浓度的4％时引起^1D2和^1G4荧光猝灭的能量传递效率。指出了^1D2→^3H4的荧光猝灭属于电偶极－电偶极相互作用的能量传递所导致。     

广范pH试纸的荧光pH传感特性及应用

对广范pH试纸在pH值2.2~12.5范围内的荧光特性及基于试纸荧光的pH传感系统进行了探索。检测了不同pH缓冲液中浸渍过并晾干的pH试纸的光致发光,并分析了试纸荧光光谱的谱峰频移以及谱带重心频移。实验结果表明,pH试纸的荧光在实验pH区间的变化有明确的规律性,其中在弱酸碱性的pH值（4.0~9.0）范围内,谱带重心λ_B随pH值近似线性变化,相应的经验传感方程为λ_B=603.8-4.09pH。以pH为7对应的荧光谱带重心作参考,其相对灵敏度为0.71%/pH,实验系统的pH分辨力约为0.4。用该实验系统实际测试了稀的尿素水溶液及自来水的pH值,与商用电化学式pH计的结果一致,验证了实验方法及传感系统的通用性、实用性。该实验为pH检测提供了一种较比色读数更加精确客观、成本低廉、数据可靠、样品可保存可追溯的传感方法及测试系统。该系统还可以弥补广范pH试纸不能准确测试弱酸弱碱的不足。     

Electronic Absorption and Fluorescence Spectra of Fluorescein in Aprotic Solvents

The absorption, excitation and fluorescence spectra of fluorescein in ethyl acetate and acetone were obtained. It was verified that the neutral lactonic form of fluorescein is present in dilute solutions of those organic solvents. However, in concentrated solutions it was observed a shift of the dissociation equilibrium to form the neutral zwitterionic form of the dye in both electronic ground and excited states.     

Drying of PAAm Hydrogels at Various Temperatures: A Fluorescence Study

The steady‐state fluorescence (SSF) technique was employed for studying the drying of polyacrylamide (PAAm) hydrogels. Disc‐shaped hydrogels were prepared by free‐radical crosslinking copolymerization of acrylamide (AAm) with N,N′‐methylene bisacrylamide (BIS) as crosslinker in the presence of ammonium persulfate (APS) as an initiator. Pyranine (P) was introduced as a fluorescence probe and the intensity of pyranine was monitored during in situ drying at various temperatures. It was observed that the fluorescence intensity of pyranine increased during the drying process. A supporting, gravimetrical experiment was also performed. A phenomenological equation was introduced to determine the desorption coefficient, D, of water molecules from the drying hydrogels at various temperatures. The desorption activation energy, ΔE _d, values were measured for the drying processes and found to be 91.08 and 36.82 kJ mol^–1 by fluorescence and gravimetrical methods, respectively. This difference most probably originates from the origin of the techniques; the fluorescence technique measures the parameters at a molecular level, whereas the gravimetrical technique measures a parameter in the bulk.     

基于谷胱甘肽配体的ZnSe量子点对pH响应的时间分辨荧光光谱特性

当前,有关量子点pH响应方面的研究主要集中在含Cd(镉)类量子点,且都是研究其稳态荧光光谱对p H值的响应.然而,C d类量子点对生物体系具有一定的毒性,且稳态荧光光谱法由于受浓度等因素的影响具有一定的不稳定性,因此应用于生物体系中作为pH探针具有明显的缺点.基于以上分析,通过水相合成法,我们制备出了基于谷胱甘肽配体的...     

不同生境条件下藻蓝蛋白活体荧光光谱特性研究

蓝藻生物量检测技术发展是应对目前频繁发生的水华事件的重要环节。藻蓝蛋白作为蓝藻的特异性蛋白,在一定程度上比叶绿素更能准确反应自然水体中的蓝藻生物量,因而成为蓝藻生物量检测技术的重要指标。本文利用三维荧光光谱技术,以不同光照、不同生长期的铜绿微囊藻、鱼腥藻活体为研究对象,比较了单点法和包络法两种光谱解析方法的可靠性,探究了不同生境条件下的藻蓝蛋白活体荧光光谱特性。结果表明：(1)荧光光谱强度随生长期延长而增大;(2)采用包络法解析藻蓝蛋白特征荧光光谱的方法比单点法更为可靠;(3)在不同生境条件下,铜绿微囊藻藻蓝蛋白活体荧光激发波长基本保持614 nm、发射波长基本保持654 nm不变,鱼腥藻藻蓝蛋白活体荧光激发波长随生长期在610和620 nm之间波动减小,发射波长随生长期在650和660 nm之间波动增大。这种波动与藻种样品颗粒度大小和光谱扫描模式有关。该研究结果为发展蓝藻生物量活体荧光监测技术发展提供了实验基础。     

Absorption,fluorescence, and SERS spectra of sanguinarine at different pH values

We have studied the absorption, fluorescence, and surface-enhanced Raman scattering (SERS) spectra of sanguinarine using a silver hydrosol and an electrochemical cell with a silver working electrode for different pH values in the medium. We carried out quantum chemical calculations in order to interpret the electronic and vibrational spectra and to establish their correlations with the structure of the molecules. We optimized the structure and determined the spectral characteristics of the cationic and neutral forms of the sanguinarine molecules in solution and adsorbed on the surface of an anodized Ag electrode for different potentials. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 604–609, September–October, 2007.     

维生素C在不同PH值下的拉曼光谱和表面增强拉曼光谱

报道了维生素C(VC)的FT-拉曼光谱和在银胶基底上的表面增强拉曼光谱(SERS),并对它的拉曼特征谱带进行了初步的指认和归属.结合pH值的变化探讨了吸附作用的特点和规律.实验结果表明,1748、1651、1372、1256、562、446cm-1、和149cm-1处都能看到表面增强,VC的内酯环是以倾斜的方向吸附于银胶表面,并且VC分子是通过O-H键吸附在银胶表面上的,并在吸附过程中与银发生了电荷转移而形成负离子自由基,碳氧双键打开.     

Electroporative Adjustment of pH in Living Yeast Cells: Ratiometric Fluorescence pH Imaging

A number of vital cell functions including modulation of signaling pathways and regulation of the cellular transport critically depends on the cytoplasmic pH. Many pathological cellular changes are related to the abnormal cytosolic pH as well. Reliable and well-calibrated methods for quantification of the cytosolic pH are therefore of high importance. The pH calibration is particularly difficult in walled cells since standard methods fail. In this report we evaluated the new electroporative calibration method of the cytosolic pH in yeasts by the fluorescence microscopy. The calibration was done on living cells using pyranine as a ratiometric pH-sensitive probe. The probe was electroporatively delivered to the cytosol. We have shown that unlike the measurements in suspension the fluorescence microscopy reveals cell subpopulations with different sensitivity to the pH calibration. While the majority of the cells were well calibrated, there was found subpopulation of uncalibrated cell as well as singular cells exhibiting anomalous pH calibration due to the staining of acidic organelles. Resolution of cell subpopulations helps to achieve better pH calibration compared to the calibration in cuvette on a cell suspension.     

不同环境条件杂环农药三维荧光光谱发射特性研究

掌握不同环境因素下的光谱发射特性是农药准确测量的前提。以多菌灵、西维因、麦穗宁三种杂环农药为研究对象,研究了农药在不同pH值和常见阴、阳离子条件下的三维荧光光谱发射特性,并初步分析了Fe3+和Cu2+对三种农药的荧光猝灭机制。结果表明,多菌灵和麦穗宁均具有两个荧光峰,西维因仅有一个荧光区域,三种农药的主要荧光峰分别位于λ_ex/λ_em=280/300,310/340和280/335 nm,多菌灵和麦穗宁的次荧光峰Peak B分别位于λ_ex/λ_em=245/305 nm,λ_ex/λ_em=250/340 nm;多菌灵与麦穗宁随pH值变化表现为相似的荧光发射特征,在酸性/碱性降低时,荧光强度增大;酸性条件下西维因的荧光发射强度无明显变化,但在碱性条件下,随pH值的减小荧光强度不断增强;三种农药在pH值6.16～7.4范围内均可获得较好的荧光发射特征。水中CO2-₃,SO2-₄,NO-₃,Cl-,HPO2-₄,HCO-₃,Mg2+,Zn2+,NH+₄,Na+,Ca2+和K+等12种常见离子对多菌灵,西维因和麦穗宁的荧光发射特性无明显影响。Fe3+与Cu2+离子通过静态荧光猝灭反应, 影响三种农药的荧光发射强度。随着离子浓度的增加荧光强度不断降低,在实际测量中,需重点考虑Fe3+和Cu2+对测量结果的影响。该研究结果为水体杂环农药的准确测量提供了基础数据。     

Comparison of Detection Limits in Atomic Fluorescence and Absorption Spectroscopy

Dagnall, Taylor, and West have recently compared detection limits for a number of metals in atomic fluorescence and absorption spectroscopy and have concluded that “atomic fluorescence measurements using an electrodeless discharge tube are inherently more sensitive than those obtainable by atomic absorption measurements”. Likewise West and Williams have compared the two techniques for magnesium²and silver³, using high-intensity hollow-cathode lamps as sources, and have found much lower detection limits in fluorescence than in absorption.     

叶绿体不同浓度下光诱导延迟荧光光谱研究

针对《光子学报》文献［1］中实验结果与已有报道相关光谱特征的显著差异,利用多种光谱学手段对不同浓度下叶绿体延迟荧光行进了研究.实验结果表明：PSⅠ反应中心叶绿素P700对PSⅡ所发685 nm成份的吸收随叶绿体浓度的增加而增强,从而导致PSⅠ发出的730 nm成份增强,而使得延迟荧光光谱中730 nm成为主峰,甚至685 nm成份的消失.该研究结果表明：叶绿体延迟荧光光谱中730 nm成份,是由PSⅠ作用中心叶绿素P700对PSⅡ中所发685 nm成份延迟荧光的重吸收,产生激发态所发出的荧光.该结论有助于延迟荧光光谱中各成份产生机理的进一步研究.     

Fluorescence and Time-Resolved Delayed Luminescence of Porphyrins in Organic Solvents and Polymer Matrices

Porphyrin dyes fulfill an essential function in photosynthesis and are important in photodynamic therapy and in a range of electronic devices. Their spectroscopic characteristics may play a crucial role in these processes. The spectral properties of two porphyrin dyes: tetraphenylporphyrin and tetraphenysulfporphyrin in organic solvents (acetone, chloroform, methyl alcohol, and dimethyl-sulfoxide) and in polyvinyl alcohol and poly(methylmethacrylate) films have been investigated. Absorption, fluorescence, and microsecond time-resolved delayed luminescence spectra have been measured at room temperature. The existence of different aggregated dye forms in the ground and excited states has been demonstrated. The manifold of dye species depends on the solvent/polymer. In the case of the polymers, it also depends on the solvent used to coat the polymer film. Delayed luminescence spectra and decay times of the two porphyrins in the different solutions and in polymeric matrices suggest that different mechanisms of deexcitation of the singlet excited states may be responsible for their generation in these and other porphyrin dyes.     

Influence of a Solvent on the Quantum Yield and Duration of the Fluorescence of Tetraazoporphin

In view of the discrepancies between the values available in the literature for the photophysical parameters of tetraazaporphin in solutions, we measured its quantum yield and duration of fluorescence in a number of solvents. It has been found that alcohols (isobutanol and isopropanol) quench the fluorescence appreciably. For a solution in toluene — a stable chemically inactive and low-polar solvent — the measured quantum yield of the fluorescence of tetraazaporphin is equal to 0.180 ± 0.015 and its duration is 3.4 ± 0.1 nsec. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 5, pp. 697–699, September–October, 2005.     

不同年代的纸颜料的拉曼光谱和荧光光谱分析

本文研究了不同年代的纸(记事本(1921年),信纸(1934年),英语字典封面(2001年)以及标签纸(2008年))上红色颜料的显微激光拉曼光谱和荧光光谱。结果表明:不同年代的纸的颜料结构和光学性能也不同,其生产工艺也不一样。     

醋酸N-正辛基吡啶离子液体在不同溶剂中的荧光光谱分析

离子液体具有熔点低、可忽略的蒸气压、电化学窗口宽、热稳定性高和良好的导电性等独特性能,引起了化学工业和相关领域的广泛关注。离子液体具有低蒸气压,不会造成空气污染,但这并不意味着它们对环境完全无害。大多数离子液体易溶于水,可能会因为意外泄漏或通过污水进入水生环境。常用离子液体[BMIM][PF₆]和[BMIM][BF₄]的水溶液中,很容易形成氢氟酸,磷酸,具有一定的腐蚀性。将离子液体列为绿色溶剂,也需要提供其关于代谢和降解的毒性、生态毒性研究数据,或者其对环境影响的数据,离子液体在不同溶剂中的检测方法是非常重要的。离子液体的光谱分析法用量较少、方法简单、结果准确。离子液体和许多有机溶剂互溶,可形成均一、稳定的溶液。荧光检测法具有灵敏度高,选择性好,线性范围宽和受外界干扰少等优点。本工作研究了醋酸N-正辛基吡啶（OP-OAc）离子液体在水、乙醇、乙腈、乙酸等4种溶剂中的荧光光谱。研究结果表明,OP-OAc离子液体在不同溶剂中的荧光强度：I_乙酸＞I_乙腈＞I_乙醇＞I_水;最大发射波长的大小顺序：λ_{em, 水}＞λ_{em, 乙醇}＞λ_{em, 乙腈}＞λ_{em, 乙酸};它们的最大发射波长相对于激发波长发生红移;水中OP-OAc的荧光强度与浓度存在较高的相关性;当加入的甲醇、乙醇、乙腈溶剂不断增加时,OP-OAc离子液体的荧光强度增加,溶剂与水的比例为8∶2时,OP-OAc离子液体的荧光强度最强,溶剂的比例超过80%时,荧光强度突然降低;水中OP-OAc离子液体在pH 10时,荧光强度最高,在pH 14时,荧光强度最低。     

秸秆-牛粪发酵过程中溶解性有机质的荧光光谱特征

溶解性有机质(DOM)在自然生态系统有机物向无机物的转换过程中起重要作用.DOM在发酵过程中为微生物提供营养和能量,同时对腐殖质的迁移和转化具有重要的指示作用.牛粪有助于提高玉米秸秆腐殖化效率,使农业废弃物得以更好的利用.为探讨玉米秸秆-牛粪体积比2:8(T1)、4:6(T2)、6:4(T3)和8:2(T4)处理发酵过...     

常用农药荧光特性的理论与实验

报道了一些有机农药的分子结构与荧光产生的关系,分析了西维因、克百威、啶虫脒等几种常用农药的分子结构和化学特性,揭示了它们产生荧光的机理特征。利用稳态荧光光谱仪,对西维因等农药分别在纯甲醇、80％水与20％甲醇混合液和呈碱性(pH=13)的甲醇混合液等溶剂中进行了荧光光谱测量,并分析了它们的荧光光谱特性和其分子结构的关系。实验结果表明,分子结构中具有平面刚性结构或共轭体系的一些芳香环、杂环等基团的农药,如西维因、克百威、啶虫脒,在一定的溶剂或酸碱条件下是能够被激发而产生荧光的,可以通过荧光分析方法对它们进行直接或间接地分析检测。为进一步研究和开发用于农药的荧光检测仪器提供了可行性的理论依据。