时间分辨激光荧光光谱分析技术研究——Ⅱ.微秒级时间分辨激光荧光光谱测量

本文主要以进行稀土元素分析为目的,在已建立的激光荧光寿命测量装置的基础上,建立了时间分辨激光荧光光谱测量装置。结合在此装置上取得的初步实验结果,对装置的原理、特点、使用范围、工作条件进行了讨论。为进行稀土元素的时间分辩激光荧光光谱分析建立了必要的手段,也为某些发光材料的发光动力学研究提供了一定的方法。     

树枝化对聚芴类分子发光行为的影响

运用稳态吸收、稳态荧光光谱及皮秒时间分辨荧光光谱等手段, 研究了树枝化对聚芴分子的光谱动力学行为的影响. 在1×10-5 mol/L四氢呋喃溶液中, 非树枝化聚芴和不同代数的树枝化聚芴的稳态吸收和稳态荧光光谱基本一致, 表明树枝化不影响聚芴基团的本征电子性质; 在薄膜状态下, 紧密排列的聚芴分子表现出明显的链间聚集行为. 不同代数树枝化聚芴的时间分辨荧光动力学研究结果表明, 溶液状态下的发光为单指数衰减行为, 而薄膜状态下的发光为多指数衰减行为, 且其发光寿命随树枝化代数增加而增长, 表明树枝化基团抑制了邻近的聚芴分子之间能量传递所致的激发态能量耗散.     

基于荧光染料和牛血清白蛋白嵌合物对氧化还原状态的探测

为制备一种与生物分子兼容性好并且具有较大动态检测范围的新型氧化还原探针,将氨苯乙烯类荧光分子4-[4-(二甲氨基)苯乙烯基]-1-甲基吡啶碘(p-DASPMI)嵌合到BSA中形成p-DASPMI-BSA嵌合体探针,采用稳态荧光光谱和时间分辨荧光光谱技术研究其与还原剂和氧化剂反应的荧光性质及相互作用的机理。实验表明,BSA能够感受环境的氧化还原状态,并通过p-DASPMI-BSA嵌合体探针的荧光变化来反映。在不同的氧化还原状态下,还原剂能使得探针的荧光强度增强3倍左右,平均寿命从1. 47 ns增加到2. 12 ns。而氧化剂使整个样品的荧光淬灭,平均寿命从2. 15 ns减小到1. 47 ns。时间分辨荧光数据表明氧化剂和还原剂会引起BSA的结构变化,进而影响进入BSA的p-DASPMI分子的数量,并最终影响整个体系的荧光性质。这个探针对氧化还原的动态检测范围能达到45倍左右,在研究细胞内大动态范围的氧化还原成像方面具有较好的应用前景。     

激光诱导荧光光谱分析进展

本文对激光诱导荧光光谱分析的研究现状和发展趋势进行了综述。着重介绍了激光诱导原子荧光光谱、激光诱导分子荧光光谱、激光低温光谱,时间分辨光谱和激光诱导荧光光谱与其它分析技术的联用研究。     

飞秒时间分辨荧光非共线光参量放大光谱技术

时间分辨荧光光谱技术是研究激发态弛豫、能量传递以及电荷转移等光化学过程的重要且直接的工具．飞秒时间分辨荧光非共线光参量放大光谱技术是一种新发展的具有高时间分辨率、宽探测带宽、高增益的时间分辨光谱技术．本文对该技术的基本原理与工作特性、系统配置、荧光收集和会聚、数据采集模式、时问分辨光谱数据处理等进行了系统阐述．最后简单介绍了飞秒时间分辨荧光非共线光参量放大光谱技术在物理、生物和化学领域的3个典型应用,并以此展现该技术的高时间分辨率、宽光谱探测及高增益优势．     

寡聚酰胺PyPyPybDp与DNA相互作用的荧光动力学

通过稳态吸收光谱、荧光光谱和时间分辨荧光光谱对寡聚酰胺分子PyPyPybDp(简称PPP)的光物理性质进行了详细研究. 发现PPP的激发态性质受溶剂环境影响较大, 在TKMC缓冲液中, PPP有较弱的荧光, 其荧光寿命为16 ps; 随着溶剂极性逐渐降低, 荧光光谱蓝移, 荧光强度增加, 相应荧光寿命增长. 通过对PPP与DNA双螺旋分子相互作用的荧光动力学研究表明, PPP与DNA相互作用后, 荧光强度增强, 荧光寿命从16 ps增加到32 ps, 证实了存在PPP与双螺旋DNA的结合相互作用.     

激光诱导荧光辅助激光诱导击穿光谱检测有源发光玻璃中的微量元素

在有源发光玻璃的制备过程中,通常需要掺杂微量元素,用于改善玻璃的发光性能,因此在生产过程中进行快速检测非常重要.本实验针对激光诱导击穿光谱技术(LIBS)分析玻璃中微量元素灵敏度不足的问题,利用激光诱导荧光辅助激光诱导击穿光谱技术(LIBS-LIF)检测了玻璃中3种微量元素Yb,Al和P.使用波长可调谐激光激发等离子体中的Yb+离子、Al原子和P原子,并对这3种粒子在激光诱导荧光中的跃迁过程进行了分析.结果表明,通过激光诱导荧光辅助激光诱导击穿光谱技术,Yb+离子、Al原子和P原子的光谱强度分别增强了23,50和8倍,大幅度提高了LIBS分析的灵敏度.     

寡聚酰胺PyPyPyβDp与DNA相互作用的荧光动力学

通过稳态吸收光谱、荧光光谱和时间分辨荧光光谱对寡聚酰胺分子PyPyPy(Dp(简称PPP)的光物理性质进行了详细研究. 发现PPP的激发态性质受溶剂环境影响较大, 在TKMC缓冲液中, PPP有较弱的荧光, 其荧光寿命为16 ps; 随着溶剂极性逐渐降低, 荧光光谱蓝移, 荧光强度增加, 相应荧光寿命增长. 通过对PPP与DNA双螺旋分子相互作用的荧光动力学研究表明, PPP与DNA相互作用后, 荧光强度增强, 荧光寿命从16 ps增加到32 ps, 证实了存在PPP与双螺旋DNA的结合相互作用.     

邻苯二甲酸铽配合物与铕离子间能量传递

本文应用红外光谱、紫外吸收光谱、稳态和时间分辨荧光光谱研究了邻苯二甲酸铽及邻甲基苯甲酸铽配合物的发光性能,配位体结构以及铕离子对配合物发光的猝灭方式,并探讨了溶剂、pH值对发光强度和寿命的影响。     

激光诱导钡的原子与离子荧光光谱研究

许多作者报导了在 ICP 和火焰等原子化系统中钡的原子和离子荧光检测,并将其应用于光谱分析.但有关钡的荧光光谱特性研究报道较少.本工作以空心阴极灯作为原子化器,利用连续波染料激光器研究了钡的原子与离子荧光,观察了各种因素对钡荧光信号强度的影响,测量了不同类型的原子和离子荧光,研究了所观察到的反常信号产生的机理.实验中用全谱线的氩离子激光器(南京电子管厂,362型,约5W)泵浦 R6G 染料激光器。在570—815nm 范围产生可调谐激光.典型的光谱带宽约0.1GHz.激光束经调制后用透镜聚     

Spectral and photophysical properties of thioxanthone in protic and aprotic solvents: the role of hydrogen bonds in S1-thioxanthone deactivation.

Spectral and photophysical properties of thioxanthone (9H-thioxanthen-9-one, TX) were determined in a few protic solvents (H2O, D2O, hexafluoro-2-propanol) and compared with those in aprotic solvents. On the basis of the time-resolved and steady-state emission measurements and available literature data, it has been shown that the dominant S1-TX deactivation process in protic solvents is the formation of the S1-complex. The important modes of deactivation of the S1-complex are fluorescence (phiF approximately 0.4-0.5) and intersystem crossing to the T1 state. The S1-complex-->S0 internal conversion plays, at most, an insignificant role in S1-complex deactivation, which is evidenced by the absence of an isotope effect of protic solvents on the lifetime and quantum yield of fluorescence.     

Fluorescence dynamics of interactions between polyamide PyPyPyβDp and DNA

The photophysical properties of the polyamide PyPyPyβDp (PPP) were investigated by means of steady-state absorption and fluorescence spectroscopies, as well as time-resolved fluorescence spectroscopy. It was found that the excited-state properties of PPP are very sensitive to solvents. In TKMC buffer PPP exhibited weak fluorescence with a decay time constant of 16 ps, while with the decrease of the solvent polarity PPP showed the blue-shifted peak position, increased intensity and lengthened life-time for its fluorescence behavior. In the presence of calf thymus DNA, it was observed that the fluorescence intensity was enhanced and the fluorescence lifetime increased from 16 to 32 ps for PPP, which verified that PPP bound into the minor groove of DNA duplex.     

Photophysical properties of core-modified expanded porphyrins: nature of aromaticity and enhancement of ring planarity

We have investigated the excited-state dynamics and nonlinear optical properties of representative core-modified expanded porphyrins, tetrathiarubyrin, tetraselenarubyrin, pentathiaheptaphyrin, tetrathiaoctaphyrin, and tetraselenaoctaphyrin, containing 26, 30, and 34 pi electrons using steady-state and time-resolved absorption and fluorescence spectroscopic measurements along with femtosecond Z-scan method, with a particular attention to the photophysical properties related to molecular planarity and aromaticity. Core-modification of macrocycles by sulfur and selenium leads to NIR-extended steady-state absorption and fluorescence spectra and short-lived excited-state due to the heavy-atom effect in time-resolved spectroscopic experiments. Large negative nucleus-independent chemical shift values ranging from -13 to -15 ppm indicate that all molecular systems are highly aromatic. The observed enhancement of two-photon absorption cross-section values over 10 (4) GM for core-modified hepta- and octaphyrins is mainly attributable to their rigid and planar structures as well as their aromaticity. Overall, the observed spectroscopic and theoretical results consistently demonstrate the enhanced molecular planarity of core-modified expanded porphyrins compared with their corresponding all-aza expanded porphyrins.     

Ground state isomerism and dual emission of the β-carboline anhydrobase (N2-methyl-9H-pyrido[3,4-b]indole) in aprotic solvents

The spectral and photophysical properties of the betacarboline anhydrobase, N₂-methyl-9H-pyrido[3,4-b]indole, BCA, have been studied in aprotic solvents. The influence of solvent polarity and hydrogen-bonding interactions on the absorption, steady-state and time-resolved fluorescence spectra provides founded proofs on the existence of two ground state BCA isomers whose equilibrium concentrations change with the medium polarity. We propose that the isomers possess quinonoid, Q, and dipolar zwitterionic, Z, structures, respectively. Upon excitation, each isomer gives rise to a double emission. To account for this phenomenon, photophysical diagrams based on the simultaneous emission from locally excited states, LE, and charge transfer excited states, CT, are proposed.     

Automated Phasor Segmentation of Fluorescence Lifetime Imaging Data for Discriminating Pigments and Binders Used in Artworks

The non-invasive analysis of fluorescence from binders and pigments employed in mixtures in artworks is a major challenge in cultural heritage science due to the broad overlapping emission of different fluorescent species causing difficulties in the data interpretation. To improve the specificity of fluorescence measurements, we went beyond steady-state fluorescence measurements by resolving the fluorescence decay dynamics of the emitting species through time-resolved fluorescence imaging (TRFI). In particular, we acquired the fluorescence decay features of different pigments and binders using a portable and compact fibre-based imaging setup. Fluorescence time-resolved data were analysed using the phasor method followed by a Gaussian mixture model (GMM) to automatically identify the populations of fluorescent species within the fluorescence decay maps. Our results demonstrate that this approach allows distinguishing different binders when mixed with the same pigment as well as discriminating different pigments dispersed in a common binder. The results obtained could establish a framework for the analysis of a broader range of pigments and binders to be then extended to several other materials used in art production. The obtained results, together with the compactness and portability of the instrument, pave the way for future in situ applications of the technology on paintings.     

Spectroscopic properties of ethyl 5-(4-aminophenyl)-3-amino-2,4-dicyanobenzoate

The luminescence properties of ethyl 5-(4-aminophenyl)-3-amino-2,4-dicyanobenzoate (EAADCy) have been studied using steady-state, time-resolved spectroscopic techniques, electrochemical measurements and semiempirical calculations. A series of photophysical measurements and quantum-chemical calculations were carried out with EAADCy in search of an evidence of the occurrence of the aniline group rotation. Studies in different solvents, as well as semiempirical calculations, indicate that conformations with donor and acceptor groups coplanar absorb and emit at wavelengths that are longer than those observed for donor–acceptor groups oriented orthogonally. The values of the dipole moments of planar and perpendicular form of molecule under study were estimated from solvatochromic shifts of absorption and fluorescence spectra as a function of the solvent dielectric constant and refractive index. Experimentally calculated changes of the dipole moment values are in fair agreement with semiempirical computational predictions.     

Eosin y triplet state as a probe of spatial heterogeneity in microcrystalline cellulose

The photophysical behavior of eosin Y adsorbed onto microcrystalline cellulose was evaluated by reflectance spectroscopy, steady-state fluorescence spectroscopy and laser induced time-resolved luminescence. On increasing the concentration of the dye, small changes in absorption spectra, fluorescence redshifts and fluorescence quenching are observed. Changes in absorption spectra point to the occurrence of weak exciton interactions among close-lying dye molecules, whereas fluorescence is affected by reabsorption and excitation energy trapping. Phosphorescence decays are concentration independent as a result of the negligible exciton interaction of dye pairs in the triplet state. Lifetime distribution and bilinear regression analyses of time-resolved phosphorescence and delayed fluorescence spectra reveal the existence of two different environments: long-lived, more energetic triplet states arise from dyes tightly entrapped within the cellulose chains, while short-lived, less-energetic states result from dyes in more flexible environments. Stronger hydrogen bond interactions between the dye and cellulose hydroxyl groups lead in the latter case to a lower triplet energy and faster radiationless decay. These effects, observed also at low temperatures, are similar to those encountered in several amorphous systems, but rather than being originated in changes in the environment during the triplet lifetime, they are ascribed in this case to spatial heterogeneity.     

Photophysical properties of BODIPY-derived hydroxyaryl fluorescent pH probes in solution.

The photophysical properties of five fluorescent pH probes derived from 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene with phenolic or naphtholic subunits at position 8 and with substituents having different electron driving forces at positions 3 and 5 have been investigated in several organic solvents, by means of absorption, steady-state, and time-resolved fluorimetry. For each compound, the fluorescence quantum yield and lifetime are lower in solvents with higher polarity, owing to an increase in the rate of nonradiative deactivation. The rate constants for radiative deactivation, k(f), are nearly constant for all dyes in all solvents studied [k(f)=(1.7+/-0.2)x10(8) s(-1)]. In aqueous solution, these probes undergo a reversible protonation-deprotonation in the near-neutral to basic pH range, producing intensity increases with lower pH. The pK(a) values of the indicators are between 7.5 and 9.3, depending on the substitution pattern on positions 3, 5, and 8. The difference between the absorption and excitation spectra as a function of pH is indicative of the presence of two species in aqueous solution: the phenol- or naphthol-based indicator and its conjugate base.     

A novel time-resolved laser fluorescence spectroscopy system for research on complexation of uranium(IV)

To date only a small number of studies have investigated the chemical speciation of complexes and the fluorescence properties of metal ions whose emitted fluorescence lifetime is in the range of only few nanoseconds. This is due to a lack of advanced methods which allow the conduction of these measurements. In the current study we set up a new time-resolved laser fluorescence spectroscopy system with which the fluorescence properties of metal ions with very short fluorescence lifetimes such as uranium(IV) and its compounds can be investigated. By studying the fluorescence properties of uranium(IV) in perchloric acid, we showed uranium(IV) to have a detection limit of 5 × 10⁻⁷ M and a fluorescence decay time of 2.74 ± 0.36 ns. We further investigated the fluorescence properties of uranium(IV) during the reaction with fluoride and applied our novel laser system to study the complexation of uranium(IV) with fluoride.Our data revealed the formation of a 1:1 complex of uranium(IV) and fluoride. The corresponding complex formation constant of uranium(IV) fluoride UF³⁺ was found to be log β⁰ = 9.43 ± 1.94. Our results demonstrate that our novel time-resolved laser fluorescence spectroscopy system can successfully conduct speciation measurements of metal ions and their compounds with very short-lived fluorescence lifetimes. Using this laser system, it is possible to analytically investigate such elements and compounds in environmentally relevant concentration ranges.