Fluorescence anisotropy of cyanobacterial phycobilisomes oriented in polyvinyl alcohol (PVA) films

Polarized absorption (at 296 and 85 K), fluorescence, and photoacoustic (at 296 and 85 K) spectra of antenna complexes—phycobilisomes isolated from cyanobacteriaTolypothrix tenuis andOscillatoria and embedded in isotropic and anisotropic polyvinyl alcohol films—were measured. From the sets of polarized components of emission, the anisotropy of fluorescence for the pools of differently oriented molecules was calculated. On the basis of polarized photoacoustic and emission spectra, the competition between the process of thermal deactivation of excitation and excitation energy transfer in a chain of excitation donor and acceptor chromophores of phycobilisomes is discussed.     

惰性离子(La3+,Y3+,Gd3+)对配合物苯乙酮酸邻菲咯啉铕荧光性能的影响

以苯乙酮酸和邻菲咯啉为配体,不同摩尔比铕和惰性离子(La3 ,Y3 ,Gd3 )为中心离子,合成了系列配合物EuxRE1-xL3phen(RE=La,Y,Gd),测定了其荧光激发光谱和荧光发射光谱,研究了惰性离子(La3 ,Y3 ,Gd3 )对Eu3 荧光性能的影响.结果表明,配合物激发光谱相似,均在350～360 nm范围内出现最大激发,属于配体的吸收峰,在398 nm附近出现弱的激发为Eu3 的吸收峰;系列配合物荧光发射光谱相似,均显示Eu3 离子的特征发射光谱,位于583,595,617,654,703 nm附近出现5组强度不同的发射峰,分别归属为Eu3 的5D0-7F0,5D0-7F1,5D0-7F2,5D0-7F3,5D0-7F4能级跃迁.发射光谱表明,系列配合物中La3 离子对Eu3 的荧光发射峰峰位影响最大,EuxLa1-xL3phen中La3 的摩尔分数为0.7时,Eu3 的5D0-7F2跃迁可改变5.2 nm,而Y3 和Gd3 对Eu3 的荧光发射峰峰位影响较弱,配合物EuxY1-xL3phen和EuxGd1-xL3phen中Eu3 的荧光发射峰位变化较小,最大时仅改变2 nm;发射光谱强度表明,La3 对Eu3 的荧光发射影响最大,EuxLa1-xL3phen中La3 含量为0.7时,可使其相对荧光强度增大2倍以上,对其具有很好的敏化作用.这对人们寻找发光性能好、价格便宜的发光材料提供了理论依据.     

Single molecule spectroscopy on photosynthetic pigment-protein complexes

Single molecule spectroscopy was applied to unravel the energy transfer pathway in photosynthetic pigment-protein complexes. Detailed analysis of excitation and fluorescence emission spectra has been made for peripheral plant antenna LHC II and Photosystem I from cyanobacterium Synechococcus elongatus. Optical transitions of individual pigments were resolved under nonselective excitation of antenna chlorophylls. High-resolution fluorescence spectroscopy of individual plant antenna LHC II indicates that at low temperatures, the excitation energy is localized on the red-most Chl a pool absorbing at 680 nm. More than one pigment molecule is responsible for the fluorescence emission of the LHC II trimer. The spectral lines of single Chl a molecules absorbing at 675 nm are broadened because of the Foerster energy transfer towards the red-most pigments. Low-temperature spectroscopy on single PS I trimers indicates that two subgroups of pigments, which are present in the red antenna pool, differ by the strength of the coupling with the protein environment and by the efficiency of the triplet state quenching. Based on single molecule and hole burning data, we envisage the dimeric nature of the strongly phonon coupled red-most Chl state.     

The power of line-narrowing techniques: Applications to photosynthetic chromoprotein complexes and autofluorescent proteins

Laser spectroscopic techniques at low temperature, such as fluorescence line-narrowing and hole burning, enable an increase of spectral resolution by a factor of 10³–10⁵ compared to conventional spectroscopy at room temperature. With these methods, it is possible to retrieve a fingerprint of the species involved and to measure the rates of dynamic processes that normally remain hidden in the broad absorption bands. A few applications carried out in our laboratory will be discussed: (1) the determination of energy transfer rates in the peripheral LH2 complex of purple bacteria; (2) the study of spectral diffusion and its implications in three types of systems: (a) the B820 and B777 subunits of the LH1 complex of purple bacteria, (b) the photosystem II reaction center (PSII RC) and CP47 antenna complex of green plants, and (c) an organic glass doped with bacteriochlorophyll a; (3) the unraveling of 0-0 transitions and the pathways of photoconversion between a number of conformations of the green fluorescent protein mutant S65T; (4) the measuring of electron-phonon coupling strengths in PSII RC and the red fluorescent protein DsRed; and (5) the determination and comparison of the homogeneous linewidths and optical dephasing in photosynthetic chromoprotein complexes and autofluorescent proteins.     

Luminescence and energy transfer processes in Lu2SiO5:Ce scintillator

The energy transfer processes in Lu₂SiO₅:Ce³⁺ luminescence was investigated through the temperature dependent luminescence under excitation with VUV-UV. Ce1 center emission peaking at 393 and 422 nm and Ce2 center emission peaking at 462 nm were observed. Ce2 center emission is enhanced with the temperature, which can be explained by the rate of energy transfer from Ce1 center increases when the temperature rises. The Ce1 emission shows the thermal quenching effect under the direct excitation of Ce³⁺ at 262 nm. However, under the interband excitation of 183 nm, the Ce1 center emission exhibits undulating temperature dependence. This is because the emission is governed by thermal quenching and possible thermal enhancement of the transport of free carriers with the rising temperature.     

Spectral Properties of Bacteriochlorophyll c in Organisms and in Model Systems

Polarized absorption and fluorescence spectra of bacteriochlorophyll c and green photosynthetic bacterium Prostheecochloris aestuarii cells and cell fragments embedded in stretched polymer film were measured. In pigment samples the artificial oligomers of bacteriochlorophyll c (with absorption about 750 nm) and other forms of this pigment and bacteriopheophytin (with absorption at 670 nm) were present. In bacteria samples, embedded in polymer, oligomers were in high degree disaggregated and as a result the absorption about 670 nm was observed. Previously for similar sets of samples the decay of fluorescence excited only at one wavelength was analyzed on three exponential components, but exact lifetime values of these components for various samples were different. The aim of present paper was to check if these differences occur because of various contributions to decay from three well defined forms or if they were related to the existence of several pigment forms with slightly different lifetimes. The global analysis of data obtained for various excitation and observation wavelengths of fluorescence were done. From this analysis it follows that the second situation occurs. For a model system containing artificial oligomers the largest component of decay has a ⁴ of about 0.183 ns or 0.136 ns depending on observation wavelength. For the bacteria sample, in which the emission at 680 nm is the superposition from various pigments, global analysis done for various excitation wavelengths shows also that the values differ depending on the regions of fluorescence observation. From polarized spectra, it follows that in the model system the pigments absorbing at 670 nm are randomly distributed whereas oligomers are highly oriented. In bacteria fragments absorbing at 670 nm pigment molecules can be divided into two groups: one oriented along the axis of film stretching and the second practically randomly distributed. In living organisms, under some conditions, small amount of 670 nm pigments can be present and can work as excitation energy traps or as antenna transferring the excitation. Present results show that the role of various pools of 670 nm absorbing pigments can be different because of their differing orientation.     

Anomalous wavelength dependent effects in photoacoustic measurements of Nd3+ luminescence quantum efficiency in various laser materials

Values for the luminescence quantum efficiency of Nd³⁺ in phosphate glass, silicate glass and YAG have been obtained from measurement of the photoacoustic and optical absorption spectra. For the phosphate glass a quantum efficiency value of 0.31 ±0.10 was obtained for excitation in the wavelength range 350–750 nm, silicate glass gave a value of 0.72 ±0.10 for the range 350–600 nm. In both cases, anomalously high photoacoustic signals were obtained in the IR, around 800 nm, suggesting lower quantum efficiencies in this region. YAG gave a value of 0.95 ±0.10 for the excitation range 450–800 nm with smaller than expected PA signals in the UV (355 and 334 nm bands) suggesting the existence of an alternative decay mechanism following excitation in this region.     

Spectroscopic studies on the luminescence properties of ternary europium complexes with different ligands

In this paper, ligand effect of several bi-dental oxygen (O) and nitrogen (N) ligands on the red luminescence properties of europium ion (Eu³⁺) was studied comprehensively. Absorption, emission, and excitation spectral properties of ternary europium complexes with different combinations of ligands including thenoyl trifluoroacetone (TTA), naphthyl trifluoroacetone (NTA), 2,2′-bipyridyl (bpy) and phenanthroline (Phen) were investigated. Efficient Eu³⁺ red emission was observed with all the combinations of the above mentioned ligands. The most intense emission was found with the all nitrogen coordinated complex Eu(bpy)₂(Phen)₂ while the longest wavelength excitation band was recorded with oxygen-nitrogen mixed NTA-bpy complex Eu(NTA)₁(bpy)₃. With change of the ligands combination and ratio, the Eu³⁺ emission peak changes slightly from 612 to 618 nm. The absorption and excitation spectra of the europium complexes were compared and analyzed referring to the individual absorption spectral properties of the ligands. The relation between ligand-to-metal charge transfer states and luminescence intensities for different complexes was studied.     

Multiphoton Ligand-Enhanced Excitation of Lanthanides

We describe multiphoton excitation of the lanthanides europium (Eu³⁺) and terbium (Tb³⁺) when these ions are complexed with nucleic acids, proteins, and fluorescent chelators. In all cases excitation occurs by multiphoton absorption of the sensitizers. For the nucleotide GDP and an oligonucleotide with several guanines, the sensitized emission of Tb³⁺ excited at 776 nm indicated a three-photon process. For Tb³⁺ bound to the wild-type troponin C and a single tryptophan mutant (26W), excitation at 794 nm was also close to a three-photon process. For lanthanide chelators containing various sensitizers, we observed three-photon excitation in the case of methyl anthranilate, a mixuture of two- and three-photon excitation for carbostyril 124, and a two-photon process with a coumarin derivative. In the case of coumarin-sensitized emission of Eu³⁺ varied from a two- to a three-photon process at wavelengths ranging from 780 to 880 nm. The sensitized luminescence also shows significantly higher photostability compared to the fluorescence from the organic fluorophores alone. These results suggest the use of multiphoton-induced sensitized lanthanide fluorescence in biochemistry and cellular imaging.On leave from the Institute of Experimental Physics     

Photoluminescence of a silver-doped glass

The absorption, emission and excitation spectra of Ag⁺ ions in a soda lime glass doped with two different concentration of silver are investigated. Absorption spectra exhibit a main broad band peaked at about 260 nm (4.77 eV) with a shoulder at about 227 nm (5.46 eV). The relative height of the shoulder depends on silver concentration in the glass. Emission spectra of Ag⁺ are dominated by an ultraviolet broad band at about 330 nm (3.76 eV). The excitation spectra for this emission show a preponderant broad band peaked at about 227 nm (5.46 eV) which coincides with peak position of the shoulder displayed in the optical absorption spectra. A weak broad featureless emission band centred at about 550 nm (2.25 eV) with an excitation peak at about 242 nm (5.12 eV) is tentatively related to an impurity from the host silica glass rather than originated in silver-type centres. Comparison of the luminescence decay curves for both emissions show substantial differences between them. Consequently, the emissions in the time-resolved spectra can easily be discriminated.     

稀土氟碳酸盐矿物的光致发光谱和吸收谱研究

测定并讨论了产自四川冕宁矿区的氟碳铈矿和产自内蒙白云鄂博稀土矿区的黄河矿、氟碳钙铈矿、氟碳铈钡矿的光致发光谱。结果表明,稀土氟碳酸盐矿物在488.0nm和514.5nm激光激发下的光致发光中心是Nd3+,发光谱中的所有谱带均出自Nd3+的辐射跃迁。在488.0nm激光激发下,稀土氟碳酸盐矿物在495nm到733nm谱区的发光谱带强而尖锐,但在514.5nm激光激发下,这个谱区的谱带明显变弱或消失,转而出现783nm到907nm谱区的强发光谱带。可见光吸收谱表明稀土氟碳酸盐矿物对可见光的吸收也与矿物中的Nd3+有关。     

闪烁晶体的发光研究进展

概述了近年来闪烁体发光研究的进展,主要介绍用于未来高能物理实验的新型闪烁体发光机理研究,选取我们在研BaF₂,BaF₂:RE,CeF₃以及PbWO₄中的一些新进展。重点谈及三点:(1)在BaF₂的“价带^→芯带”跃迁发光研究基础上进行稀土(Gd³⁺-Eu³⁺)掺杂时观察到的量子剪裁以及对多光子发光的新思考;(2)CeF₃晶体发光的级联能量传递中,Ce³⁺(290nm发射带)与缺陷发光中心(340nm发射带)间能量传递及其传递效率的温度依赖;(3)PbWO₄晶体的发光中心研究中,提出以“WO₄^-2+O_i”绿光中心替代“WO³+F”中心观点的依据。同时也简介了医用闪烁体的最新进展。     

The special features of the luminescence and light resistance of europium complexes and their mixtures with lanthanum complexes in polymethyl methacrylate

The kinetics of luminescence and transformation of short-lived products of the photolysis of europium and lanthanum complexes with thenoyltrifluoroacetone and 1,10-phenanthroline and their mixtures in polymethyl methacrylate films was studied by the nanosecond laser photolysis method with recording both light emission and absorption. Fast (535 and 585 nm, ⁵ D ₁ → ⁷ F ₀, ⁷ F ₃, decay time 0.7 μs) and slow (613 nm, ⁵ D ₀ → ⁷ F ₂, luminescence rise and decay times 0.7 μs and 0.5 ms, respectively) luminescence was studied. Induced absorption with a maximum at 600 nm and decay time ∼3 ms was observed; this absorption was assigned to triplet states of the deprotonated form of thenoyltrifluoroacetone. The dependences of luminescence intensity on the concentration of the components in a mixture of complexes were analyzed, and synergistic effects of luminescence strengthening were estimated. The kinetics of a decrease in luminescence intensity during photolysis was studied. Possible mechanisms of a decrease in the relative initial process rate and an increase in the quasi-stationary value of relative luminescence intensity as the concentration of complexes in the polymer increased were discussed.     

La（Ⅲ）,Gd（Ⅲ）,Tb（Ⅲ）8—羟基喹啉固体配合物的光声光谱与 …

本文合成Ｌａ（Ⅲ）、Ｇｄ（Ⅲ）、Ｔｂ（Ⅲ）８－羟基喹啉固体配合物，通过对其光声光谱的分析，研究了８－羟基喹啉稀土配合物的荧光性质和驰豫过程。     

Luminescence quantum efficiency of Mn2+ states in ZnS as studied by photoacoustic spectroscopy

Photoacoustic spectroscopy is employed to determine the luminescence quantum efficiency of Mn²⁺ in ZnS. Three spectra, photoacoustic spectrum, luminescence excitation spectrum and absorption spectrum, are compared. It is observed that the photoacoustic spectrum and the excitation spectrum behave complementarily. Radiative quantum efficiencies of the five excited states for Mn²⁺ have been determined.     

一种具有应用潜力的等离子体用绿色荧光粉(英文)

研究了绿色荧光粉Ca2GeO4∶Tb3+的真空紫外光谱性质,用172 nm激发荧光粉,其发射峰在549 nm,此绿色发光峰归属于Tb3+的5D4→7F5磁偶极跃迁,Tb3+离子的最佳摩尔分数x=0.05。激发光谱中147 nm和172 nm的激发强度分别是218 nm的1.5和1.7倍。因为在等离子体显示中激发光波长是147 nm和172nm,因此荧光粉在这两个波长的激发强度对荧光粉在等离子体显示中的应用至关重要。Al3+的共掺杂可使荧光粉的发光强度增强2倍,因此,Ca2GeO4∶Tb3+是一种具有应用潜力的等离子体显示用绿色荧光粉。     

近紫外荧光粉SrAl_2Si_2O_8∶Ce~(3+)的光致发光特性

采用高温固相反应法制备了xCe~(3+)(x=0.01%,0.05%,0.10%和0.30%)激活的Sr_(1-x)Al_2Si_2O_8近紫外荧光粉,利用X射线衍射(XRD)和扫描电镜(SEM)检测出荧光粉的物相结构,通过光致发光谱(PL)和激发光谱(PLE)表征了荧光粉的发光性质。结果显示,在中波紫外光激发下,发射峰位于长波紫外区,归属于Ce~(3+)的5d→2 F5/2和5d→2 F7/2跃迁。激发波长308nm时,观察到近紫外SrAl_2Si_2O_8荧光粉的发光强度随Ce~(3+)掺杂量增加而先增大后减小,同时发射峰位置红移。280和325nm波长选择性激发条件下的差异性发射行为表明SrAl_2Si_2O_8∶Ce~(3+)具有两种性质不同的发光中心,该结论由监测320和390nm发射时获得的形状具有明显区别的激发光谱亦可得以验证。离子半径的匹配性支持Ce~(3+)优先取代Sr~(2+),同时Van Uitert的经验公式估算结果推断出低浓度的Ce~(3+)生成九配位的Ce(Ⅰ)发光中心,高浓度掺杂情况下部分相互近邻的Ce~(3+)有效配位数减小,形成八配位的Ce(Ⅱ)发光中心。紫外280nm激发下峰位348nm的发射谱带源于Ce(Ⅰ)和Ce(Ⅱ)发光中心共同贡献,紫外325nm激发下发射峰位于378nm的发射带则主要对应于Ce(Ⅱ)发光中心。紫外光激发下Ce~(3+)发射出较强的近紫外光,表明SrAl_2Si_2O_8∶Ce~(3+)是一种适用于研发紫外荧光光源的荧光粉体材料。     

温度梯度法生长的Ce: YAlOZr3高温闪烁晶体的光谱分析

采用温度梯度法生长了熔体掺杂Ce浓度为1at%的YAlO3晶体，对于其吸收光谱、荧光光谱和x射线激发发射谱进行了表征分析.根据吸收光谱提出了一个色心模型，从而成功的解释了为什么刚生长出的晶体为粉红色，而分别经氢气和空气在1400℃退火后均能变为无色的现象和退火以后吸收光谱发生的显著变化.温度梯度法生长的Ce:YAP在330nm处存在着一定程度的自吸收和自激发.光致激发发射谱的发射主峰在368nm，而x射线激发发射谱的主发射峰红移至391nm，这表明在x射线激发下，晶体对发射光的自吸收将会减少.另外在x射线 关键词： 温度梯度法 Ce: YAP 色心 光谱     

Photoluminescence and Photoacoustic Spectroscopies of Fe3+ in the LiGa5O8–LiGaSiO4–Li5GaSi2O8 System

This report is devoted to the study of the low and room temperature photoluminescence and photoacoustic spectroscopy of the Fe³⁺ impurity ion in the LiGa₅O₈–LiGaSiO₄–Li₅GaSi₂O₈ system. The sample was obtained by solid-state reaction between β-Ga₂O₃, Li₂CO₃, SiO₂ and appropriated quantities of Fe₂O₃. It was investigated by X-ray diffraction to determine the formed phases and through photoluminescence, excitation and photoacoustic spectroscopy measurements. The broad absorption and emission bands in the visible and near-infrared spectral regions presented by that system constitute the motivation for this study. More specifically, the luminescence occurs over a large interval of wavelengths, between 400 nm and 800 nm.     

紫细菌Rb.Sphaeroides 601外周捕光天线(LH2) B800吸收带的超快动力学研究

利用从紫细菌Rb.sphaeroides 601 所提取出的外周捕光天线LH2以及其不同pH值酸化样品(部分和全部去除B800分子LH2)并采用不同波长下的飞秒单色抽运探测技术详细研究了LH2中B800吸收带内的激发态动力学过程.通过对野生型与部分/完全去B800分子LH2的比较研究，分析了B800吸收带激发后所表现出的丰富变化的动力学过程，研究结果表明激发B800带的动力学过程中包含着B850上激子带的直接激发而产生的对激发态动力学的贡献. 关键词： 紫细菌外周捕光天线LH2 部分和全部去除B800分子LH2 激发态动力学的演变 飞秒抽运探测