高等植物光系统Ⅱ反应中心的亚纳秒时间分辨荧光光谱的测量

高等植物光系统Ⅱ是光合作用中的一个非常重要的单元,它是与裂解水放氧相关的功能结构,光系统Ⅱ反应中心是进行光化学反应的场所,在其内部发生的光能的吸收、激发态的传递、电荷的分离重组以及迁移等等过程,都是在非常短的时间里发生的,其时间尺度在10^-15～10^-7s之间,本文建立了亚纳秒时间分辨荧光光谱测量装置,并对菠菜光系统Ⅱ反应中心蛋白复合体D₁/D₂/cyt b─559,在不同波长激发下的时间分辨荧光光谱进行了测量,经过解卷积和多指数数据拟合,获得4个寿命组分,并对结果进行了分析讨论,指出在不同的激发波长激发下的荧光衰减曲线的差异可能源于被激发的组分不同和能量传递路径的不同.     

激光诱导荧光确定NiB自由基一个新的电子激发态：在19000-22100 cm -1的2II态

Ni针放电产生的Ni原子与B₂H₆反应产生NiB自由基,得到了在19000～22100 cm^-1的激光诱导荧光光谱. 通过对激光诱导荧光激发谱和色散谱的研究,发现了一个新的电子跃迁序列[20.77]²II-X²∑⁺,序列共包括11个振动谱带,光谱分析得到了这个新的电子激发态和基态的跃迁寿命. 在光谱常数和跃迁寿命等数据的基础上,讨论了新发现电子激发态的电子构型.     

若丹明B荧光增强二硫化碳高阶受激喇曼散射

 利用若丹明B乙醇溶液的荧光改变了二硫化碳的一至三阶Stokes喇曼谱线的强度分布,选择性地增强了三阶Stokes喇曼谱线。在泵浦功率密度为~560MW^.cm^-2时,对染料摩尔浓度分别为~10^-5、cm^-5散射池和~10^-4、1cm散射池进行实验,观察到二硫化碳的三阶Stokes喇曼谱线与染料激光形成的共振增强现象及、二阶Stokes喇曼谱线的部分或完全耗尽。     

掺铍GaAs量子阱的光致荧光

测量了掺铍的,阱宽约为10nm的GaAs量子阱在4.2K的光致荧光。掺杂浓度分别为1×10¹⁷和5×10¹⁸cm^-3。测量结果表明:对于无规掺杂,局域在阱中心的铍的状态密度与导带电子从n=1量子能级到阱中心中性铍的跃迁概率的乘积大于对应于介面铍的乘积。另外,实验结果也表明:当掺杂浓度升高时,由于带隙收缩的影响,阱中心铍的电离能减小。     

Yb:FAP晶体的光谱特性

研究了Yb:FAP晶体的光谱特性.用980nm的InGaAs激光二极管激发测量了Yb:FAP晶体的偏振发射光谱和荧光寿命,结合晶体的偏振吸收光谱,采用对易法计算了晶体的吸收截面和发射截面.讨论了Yb³⁺掺杂浓度对Yb:FAP的光谱参数的影响.在较低掺杂浓度下,Yb:FAP晶体π偏振方向在903nm处的吸收截面为10×10^-20cm²,在1.043μm处的发射截面为5.8×10^-20cm²,激光上能级的荧光寿命为1.1ms.比较了Yb:FAP晶体和Yb:YAG晶体的光谱性能参数.     

Ag+掺杂的立方相Y2O3:Eu纳米晶体粉末发光强度研究

采用化学自燃烧法制备了不同Ag⁺掺杂浓度的Y₂O₃:Eu纳米晶体粉末样品(［Y³⁺］∶［Eu³⁺］∶［Ag⁺］=99∶1∶X，X=0—3.5×10^-2)，以及通过退火处理得到了相应的体材料.根据X射线衍射谱确定所得纳米和体材料样品均为纯立方相.实验表明在纳米尺寸样品中随着Ag离子浓度的增加，荧光发射强度随之增加，当X=2×10^-2时达到最大值，其发光强度比X=0时提高了近50%.当Ag离子浓度继续增加，样品发光强度保持不变.在相应的体材料样品中则没有观察到此现象.通过对各样品的发射光谱，激发光谱，X射线衍射图谱，透射电镜(TEM)照片和荧光衰减曲线的研究，分析了引起纳米样品荧光强度变化的原因是由于Ag离子与表面悬键氧结合，从而使这一无辐射通道阻断，使发光中心Eu³⁺的量子效率提高；Ag⁺的引入所带来的另一个效应是使激发更为有效.这两方面原因使发光效率得到了提高.     

内周天线CP43、CP47中β-Car到Chla分子间的能量传递

采用超快荧光光谱动力学对从菠菜中分离纯化的内周天线CP43、CP47进行研究,获取了它们的动力学三维荧光谱,CP43的荧光光谱范围为640～780nm,最大峰位于680nm处,在该峰值处的荧光寿命约为3.54ns;CP47的荧光光谱范围为630～775nm,最大峰位于691nm处,在该峰值处的荧光寿命约为3.22ns,在CP43和CP47中,Chla分子发射荧光的效率分别约为38.3%和40.6%.依据分子的退激发途径,我们分析认为在CP43、CP47中β-Car→Chla分子的能量传递速率常量分别为9.06×10¹¹s^-1,1.3×10¹²s^-1;能量传递效率分别为47.5%、66.5%;并估计β-Car分子与Chla分子外周之间的距离分别为0.110nm、0.085nm.     

香蕉叶片Chla荧光动力学参量对激发光强的反应

在蓝色激发光(λ_m＝660nm)作用下,香蕉叶片的叶绿素a(Chla)发出波长为720～740nm的荧光信号,荧光强度随时间呈现有规律的变化.随着激发光强的增加,荧光动力学参量F₀和F_VI/F_V呈上升趋势,F_V/F₀与F_V/F_M逐渐达到饱和,而CA和T_1/2呈下降趋势.研究结果表明,保证香蕉叶片光合机构高速有序运转的适宜光强在20～60μmol·m^-2·s^-1之间,过量的光强将造成叶片光合机构的损伤.讨论了香蕉叶片诸荧光动力学参量的生物学意义及其随激发光强度增加而变化的原因.     

Tm3+/Yb3 :LiYF4单晶的高效近红外量子剪裁及其在光伏电池中的应用

采用改进的坩埚下降法成功地生长了Tm/Yb共掺氟化钇锂单晶. 该单晶体具有每吸收一个蓝色光子并能发射出2个1000 nm近红外光子的下转换发光效应. 测定了样品的激发光谱、发射光谱和荧光衰减曲线. 在465 nm蓝光激发下观察到由Yb³⁺：²F_5/2→²F_7/2能级跃迁所致的960～1050 nm 波段的发射带,此发光带源于Tm³ 对Yb³ 离子的能量下转换过程. 应用Inokuti-Hirayama模型,研究了晶体的能量转换过程,结果表明Tm³ 向Yb³ 的能量传递是一个电偶极子相互作用机制过程. 当Tm³ 与Yb³ 离子的掺杂浓度为0.49mol%与5.99mol%时,单晶的量子剪裁效率达到最大值167.5%.     

掺Bi的GeO2-Al2O3-Na2O玻璃的热学和光学性质

 用高温熔融法制备了96GeO-(3-χ)Al₂O₃-χNa₂O-1NaBiO₃ （将χ分别为0，0.5，1.5的玻璃命名为A1，A2，A3）和 96GeO-(3.5-ψ)Al₂O₃-ψχNa₂O-0.5Bi₂O₃（将ψ分别为0，0.5，2的玻璃命名为B1，B2，B3）玻璃。观察到样品在1 220 nm处（800 nm 激光二极管激发）的超宽带发光特性（半高宽约250 nm）。结果表明，以NaBiO₃形式引入Bi⁵⁺到玻璃原料中比以Bi₂O₃形式引入Bi³⁺到原料中得到的玻璃在1 220 nm处的发光强度大4.6倍，且荧光寿命和荧光半高宽也分别从280 μs和195 nm增加到了434 μs和275 nm。从A3，A2和A1的吸收边带的红移可初步推断出A3，A2及A1玻璃中Bi5+的含量逐步增加。总结吸收光谱与发射光谱的变化规律，认为Bi离子近红外高发射强度和宽荧光半高宽是由Bi⁵⁺的发光引起的。在两组玻璃中，热稳定性以及荧光发射截面积与荧光寿命的乘积值和荧光发射截面积与荧光半高宽的乘积值随着Na₂O含量的增加而增加。     

苯并咪唑的三维荧光光谱与三维室温磷光光谱

测量了浓度为1×10^-4mol/L苯并咪唑水溶液的三维荧光光谱,三维室温磷光光谱和紫外/可见吸收光谱,还测量了苯并咪唑固体紫外/可见吸收光谱对化合物的荧光和室温磷光进行了分析、比较,发现苯并咪唑在290nm、580nm和870nm区域均有强而丰富的荧光谱线,而室温磷光谱线(RTP)单一地出现在290nm区域,且强度很小;同时还讨论了苯并咪唑的升频转换荧光现象.     

Absorption,fluorescence, and fluorescence excitation spectra of free molecules of indole and its derivatives

We have obtained and analyzed the absorption, fluorescence, and fluorescence excitation spectra of indole vapor, N-acetyl-L-tryptophan vapor, and 3-indole aldehyde vapor. From analysis of the dependence of the fluorescence spectrum of the free indole molecules on the wavelength of the exciting radiation λ_ex, it follows that emission of fluorescence occurs when the molecules undergo a transition from the one electronically excited state ¹L_b. The fluorescence spectra of the studied compounds are insignificantly different, suggesting a major role for the indole chromophore in formation of the compounds. The absorption spectrum of N-acetyl-L-tryptophan, in which the group of atoms is added to the indole ring through a-C-C bond, is similar to the spectrum of indole, while the spectrum of 3-indole aldehyde is significantly different from the indole spectrum due to the effect of the C=O group conjugated with the indole ring. The fluorescence excitation spectra are considerably different from the absorption spectra. This is associated with the strong dependence of the quantum yield for the free molecules on λ_ex. Qualitatively, they are mirror-symmetric to the fluorescence spectra of the stodied compounds. Analysis of the data obtained provides a basis for assuming that in the case of free molecules of indole and its derivatives, the ¹L_a absorption in the extreme long-wavelength region of the spectrum does not overlap ¹L_b absorption. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 218–222, March–April, 2007.     

一种新的芴类衍生物的三光子吸收诱导荧光和光限幅效应研究

通过对新合成的芴的一种具有对称性衍生物4-2-(7-(4-氨基苯乙烯基)-9，9-二(2-乙基己基)-9H-芴-2-)乙烯基)苯胺(BASF)的DMF溶液的研究，发现其具有很强三光子吸收频率上转换荧光发射特性，实验测出上转换荧光的波长范围是456—775nm，在510nm处的荧光强度与入射光强的三次方成正比.在0.03mol/L的浓度下就有明显的三光子吸收诱导的光限幅效应.非线性吸收系数和吸收截面分别为γ=4.34×10^-20cm³/W²和σ₃＝2.4×10^-39cm⁶/W². 关键词： 三光子吸收 光限幅 上转换荧光 吸收截面     

Inflection point of the fluorescence excitation spectra induced by secondary inner filter effect

Abstract

The secondary inner filter effect on the fluorescence excitation spectra of rhodamine 6G aqueous solutions with concentration was demonstrated in this paper. The peak of fluorescence excitation spectrum stays at 525?nm at low concentrations, while it breaks up and turns into valley at high concentrations. The threshold concentration was determined to be 3.16?mg/L by the second derivative spectroscopy. A mathematical model was proposed to explain the inflection point of fluorescence excitation spectrum caused by the secondary inner filter effect. On the basis of it, the threshold concentration was calculated to be 2.86?mg/L, approaching to the experimental result.     

Dual fluorescence and laser emissions from fluorescein-Na and eosin-B

Dual laser emissions were observed from fluorescein-Na and eosin-B in ethanolic solutions individually in the concentration range from 10⁻² to 10⁻³ mol dm⁻³ under N₂ laser excitation. The first compound was found to lase at two distinct regions with wavelength maxima around 540, 550 nm, while the second one around 558, 574 nm. Steady-state absorption, fluorescence excitation, fluorescence polarization, fluorescence emission and decays of the dyes in various solvents under varying conditions of excitation and detection systems were carried out to identify the nature of the emitting species responsible for laser emissions in two distinct regions. Both the dyes exhibited concentration and excitation wavelength dependence of fluorescence and the effects were found to be more pronounced in binary solution. The fluorescence decays of dyes were monoexponential in ethanol, while in some other solvents used, the decays showed biexponential behavior. The absorption and excitation studies using thin layers of solutions revealed the formation of dimers with the dye concentration around 1×10⁻³ mol dm⁻³. Fluorescence polarization and decay studies confirmed the presence of dimers. The two laser bands observed in the shorter and longer wavelengths were respectively ascribed to monomeric and dimeric species.     

Spectrophotometric Study of Luminol in Dimethyl Sulfoxide–Potassium Hydroxide

The spectrophotometric study of luminol (LH₂) in dimethyl sulfoxide (DMSO), DMSO-water solutions, and alkaline DMSO and DMSO-water solutions has been done, focusing on the effect of the KOH additon on LH₂ absorption and fluorescence properties. The absorption spectra indicate an acid-base equilibrium, and the luminol dianion (L^2–) formation at 3 × 10^–4 – 2.4 × 10^–3 M KOH. The decrease of the fluorescence intensity and the variation of the excitation spectra of LH₂-DMSO-KOH solutions with KOH concentration have been similarly explained. The acid-base process is reversible. The addition of HCl to the solution with 3.0 × 10^–3 M KOH leads to an increase of the fluorescence intensity to its highest value, observed in pure DMSO. The addition of HCl to the LH₂-DMSO solution leads to the decrease of the fluorescence intensity as a result of the LH⁺ ₃ cation formation. In LH₂-DMSO-water, the fluorescence band is shifted from 405 nm to 424 nm and increased in the intensity. In the presence of KOH (in LH₂-DMSO-water-KOH solution) a new band appears, with the maximum at 485 nm and the band at 405 nm decreased. The changes in fluorescence lifetimes also evidence the different chemical species formed.     

Steady‐State and Time‐Resolved Emission Studies of 6‐Methoxy Quinoline

Abstract

Steady‐state absorption, fluorescence excitation, and emission spectra of 6‐methoxy quinoline (6‐MQ) were measured at room temperature in cyclohexane, dioxane, ethanol, acetonitrile, water, and water–dioxane solvents. Absorption spectra of cyclohexane, n‐hexane, and isopentane solutions show resolved vibronic structure at room temperature. However, the excitation spectrum of cyclohexane solution is structureless and is found to be emission wavelength dependent, indicating the formation of at least two distinct species in the ground state. Similar behavior was observed in dioxane and water–dioxane solutions. For all other solutions, the fluorescence excitation spectrum of 6‐MQ was found to be the same for different emissions. Emission of 6‐MQ in all solvents consisted of two bands with their maxima around 355 nm (I) and 430 nm (II), the actual positions and the relative intensities being dependent on the solvent used. The bands I and II were respectively attributed to normal and protonated/H‐bonded species of either ¹L_a or ¹L_b states or mixed (¹L_a/¹L_b) state of ππ* character. Fluorescence decay of this dye in all solvents monitored over each emission maximum showed biexponential behavior, and the analysis yielded two different lifetime components for each emission band. The short and long fluorescence decay components were respectively in the range of 0.30–3.00 ns and 18–20 ns. The observed emission characteristics coupled with the nature of the fluorescence polarization spectra and two different decay components for each emission suggest the existence of two different conformers having two different excited electronic states.     

Concentration dependence of steady-state fluorescence behavior of a liquid crystal molecule E7 in ethanol

The fluorescence excitation and emission spectra of a liquid crystal E7 in ethanol have been explored at a variety of concentrations from very dilute solutions (<1.0×10⁻⁷ mol/L) to concentrated solutions (>1.0×10⁻² mol/L) and also for neat E7. The result showed a strong dependence of the steady-state fluorescence behavior on E7 concentration in ethanol. The photophysical behavior has been interpreted in terms of short-range and long-range intermolecular interactions and ground-state molecular association as well as spectral changes of the fluorescence excitation and emission. The short-range intermolecular interaction characterized by the fluorescence emission band with the maximum between 376 and 385 nm gradually increases with increasing E7 concentration. On the other hand, the long-range intermolecular interaction characterized by the emission band with the maximum between 347 and 362 nm gradually decreases with increasing E7 concentration. Consequently, with increasing E7 concentration in ethanol the long-range interaction effect is reduced, whereas the short-range effect is enhanced and the monomer emission completely disappears at concentrations greater than 2.83×10⁻⁵ mol/L.     

Nd∶GGG晶体荧光寿命的测试及受激发射截面的计算

介绍了荧光寿命的测试原理。设计了荧光寿命测试系统。利用脉冲取样技术测试了Nd∶GGG晶体的荧光寿命,约为250μs。采用英国的荧光光谱仪,在室温条件下,用波长为488nm的Ar离子激光器激发Nd:GGG晶体,获得了Nd:GGG晶体的荧光光谱,计算出的Nd∶GGG晶体的受激发射截面σ(λ)为21.57×10-20cm2。     

Synthesis and Analytical Application of a Novel Fluorescent Hg2+ Probe 3′, 6′-Bis(Diethylamino)-2-((2,4-Dimethoxybenzylidene)Amino)Spiro[Isoindoline-1,9′-Xanthene]-3-Thione

A novel probe, 3′,6′ - bis(diethylamino) -2- ((2,4-dimethoxybenzylidene)amino) spiro [isoindoline-1,9′-xanthene]-3-thione (RBS), was designed and synthesized. Its structure was characterized with elemental analysis, IR spectra and ¹H NMR. The probe displayed highly selective and sensitive recognition of Hg²⁺. Reacting with mercury ions in aqueous solution, its fluorescence intensity was enhanced significantly, while its color was changed from colorless to pink. So, a new fluorescence method of detection of Hg²⁺ was proposed. Its dynamic response concentration range and detection limit for Hg²⁺ were 5.00?×?10^?9 M to 1.00?×?10^?6 M detected and 1.83?×?10^?9 M, respectively. Satisfying results were obtained when the probe was applied to detect spiked Hg²⁺ in samples.