Solvent Relaxation of Prodan and Patman: A Useful Tool for the Determination of Polarity and Rigidity Changes in Membranes

The time dependence of the solvent relaxation behavior of two polarity-sensitive dyes called Prodan and Patman has been investigated in detail in artificial membrane systems of different compositions. The works provides a comparison of the solvent relaxation behavior of the mentioned dyes, using steady-state and time-resolved fluorescence methods, and exemplifies their complementary use for membrane studies.     

Dynamics in Diether Lipid Bilayers and Interdigitated Bilayer Structures Studied by Time-Resolved Emission Spectra, Decay Time and Anisotropy Profiles

We present a comparative fluorescence spectroscopic investigation of diacyl and diether phosphatidylcholine vesicles using different probes with well-defined localization within either the hydrophilic headgroup region or the hydrophobic part of the bilayer. Time-resolved emission spectra have been used to characterize the solvent relaxation behavior in both symmetric and asymmetric diether and diacyl phosphatidylcholines. It is shown that time-resolved emission spectra of Prodan (6-propionyl-2-(dimethylamino)-naphthalene) and its long-alkyl chain derivative Patman (6-palmitoyl-2-[[trimethylammoniumethyl]methylamino]-naphthalene chloride) are a sensitive tool for the detection of differences in the micropolarities and viscosities at the hydrophobic/hydrophilic membrane interface of diether and diacyl lipids, respectively. Moreover, a new approach for the detection of interdigitated bilayers is discussed. It relies on the construction of anisotropy and decay time profiles for the set of n-anthroyloxy fatty acids and is compared with an older fluorescence assay based on intensity measurements only. The shape of plots of the fluorescence steady-state anisotropy versus the position of the chromophore (anthracene-9-carboxylic acid) combined with fluorescence lifetime measurements can be used to differentiate among non-fully, and mixed interdigitated gel phase structures and to predict structures for new lipid species.     

等离子体X射线吸收谱及发射谱研究

 报道计算高温高密等离子体吸收谱和发射谱（光学薄）的理论方法；该方法基于相对论原子理论，可以计算任何单元素以及多元素等离子体的谱分辨X射线吸收谱和发射谱（光学薄）；应用了量子亏损理论，可以减少计算量。利用该方法计算金等离子体LTE吸收谱，计算结果与实验符合良好。本文还对金等离子体LTE的光学薄发射谱进行了研究, 这将有利于对实验进行进一步的诊断分析。该理论计算方法还可提供等离子体内各电离度能级布居等重要物理参数。因此经“标准实验”检验的该理论计算方法将是提供ICF“精密”物理辐射参数的重要基础。     

等离子体X射线吸收谱及发射谱研究

报道计算高温高密等离子体吸收谱和发射谱（光学薄）的理论方法;该方法基于相对论原子理论,可以计算任何单元素以及多元素等离子体的谱分辨X射线吸收谱和发射谱（光学薄）;应用了量子亏损理论,可以减少计算量。利用该方法计算金等离子体LTE吸收谱,计算结果与实验符合良好。本文还对金等离子体LTE的光学薄发射谱进行了研究, 这将有利于对实验进行进一步的诊断分析。该理论计算方法还可提供等离子体内各电离度能级布居等重要物理参数。因此经“标准实验”检验的该理论计算方法将是提供ICF“精密”物理辐射参数的重要基础。     

Collision-induced light scattering spectra and pair-polarizability trace and anisotropy of gaseous neon

New empirical pair-polarizability trace and anisotropy parameters, consistent with the spectroscopic measurements of neon gas at room temperature are obtained by fitting the calculated lineshapes and their first few even moments to the measured polarized and depolarized light scattering spectra. Good agreement with ab initio results in the literature is obtained and profiles calculated with these models are in excellent agreement with experiments.     

Pressure effect on emission spectra and crystal field for La OBr : Eu

Abstract

The emission spectra for LaOBr : Eu were measured at pressures up to 13 GPa and room temperature. The pressure dependences of levels of ⁷F_0,1,2,3,4 and ⁵D_0,1,2 are given. The crystal field parameters B^k _q were computed by fitting the experimental levels. The strength of crystal field decreases with increasing pressure. A brief discussion on the observed phenomena is presented.     

Plasma emission spectra of working media of KrC1 and XeC1 electric-discharge lasers

Results of investigations of survey spectra of plasma emission of the working media of inert-gas-chloride electric-discharge lasers in the 200–600 nm range are reported. In the UV spectra, FeI lines, which are of interest for lasing with optical pumping of iron vapors by excimer molecules, were observed. In the visible spectrum, a number of HeI, KrI, and XeII lines are suggested for determination of electron density and investigation of the discharge instability on XeCl^* and KrCl^* molecules. Uzhgorod State University, 46, Pidgirna St., Uzhgorod, 294000, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 523–527, July–August, 1997.     

Effects of light quenching on the emission spectra and intensity decays of fluorophore mixtures

We examined a series of fluorophore mixtures to determine the wavelength selectivity of light quenching and the effects of light quenching on the emission spectra and intensity decays. Light quenching can be accomplished using a single excitation pulse train and quenching wavelength (one-beam) or with longer-wavelength quenching pulses time-delayed relative to the excitation pulses (two-beam). Both one-beam and two-beam light quenching were found to alter the intensity decays of the mixtures. The frequency-domain intensity decay data were analyzed to reveal the fractional intensity of each fluorophore in the mixture and the effects of light quenching on the fractional contribution of each fluorophore to the total intensity. Fluorophores were selected to provide a range of decay times and emission wavelengths. The extent of quenching in the mixtures was dependent on which fluorophore had the higher radiative decay rate and emission intensity at the quenching wavelength. A general theory is presented which describes the intensity decays in terms of the extent of quenching of each fluorophore and the time delay between excitation and quenching pulses. The effects of light quenching on the fractional intensities of each fluorophore in the mixture, recovered from the intensity decay analysis, were found to be in quantitative agreement with that predicted from steady-state measurements of light quenching and from the spectral properties of the fluorophores. The data on light quenching of mixtures demonstrate that light quenching may be used for selective quenching of fluorophores and thus of potential value for studies of multichromophoric systems.     

Time-resolved spectral wing emission kinetics and optical imaging of human cancerous and normal prostate tissues

Time-resolved polarization-dependent kinetics of near infrared (NIR) spectral wing (SW) emission from human cancerous and normal prostate tissues was investigated. The differences between the temporal profiles, intensities and polarization properties of SW emission from cancerous and normal prostate tissues were observed. The intensity of SW emission from cancerous prostate tissue at peak position was found ∼2 times stronger than the normal prostate tissue indicating changes of fluorophores contained in the cancerous tissue compared with normal tissue. The decay time of anisotropy of SW emission from cancerous tissue was found ∼1.4 times longer than that of normal tissue reflecting changes of the micro-environment of fluorophores in the cancerous tissue as compared with the normal tissue. The stronger intensity of SW emission from cancerous tissue was used to image and identify cancerous areas surrounded by normal tissue.     

Understanding the absorption and emission spectra of borondipyrromethene dye and its substituted analogues

Borondipyrromethene (BODIPY) dye possesses a bright and long wavelength emitting fluorescent character with a wide spectral range from visible to near infrared region. In the present work, the spectral properties of BODIPY dyes were analyzed using ab intio and density functional theory methods. The ground and excited state geometries of BODIPY and its substituted analogues in chloroform medium, were optimized using the density functional theory (DFT) and singly excited configuration interaction (CIS) methods. Based on the ground and excited state geometries, the absorption and emission spectra have been calculated using time-dependent density functional theory (TDDFT) method. The TDDFT calculations have been performed using hybrid exchange correlation functionals B3LYP and M06-HF and long-range separated functionals LC-BLYP, LC-BOP, LC-PBE, LC-PBE0 and CAM-B3LYP. The solvent phase calculations were carried out using polarizable continuum model (PCM). The TDDFT investigation reveals that the substitution of acceptor, donor–donor, donor–acceptor–donor and phenyl group in BODIPY dye influence the absorption and emission spectra significantly.     

量子点腔系统中抽运诱导受激辐射与非谐振腔量子电动力学特性的研究

从量子点和腔相互作用的哈密顿量出发,利用包括非相干抽运,退相干项主方程,并结合量子回归定理,考虑相关初始条件,理论推导和数值计算相结合得出量子点多光子发射光谱精确数值结果.分析多光子发射光谱(费米子统计)和相应单光子情况(玻色子统计)时,得到依据费米子统计,退相干和热浴模型的多光子发射光谱同最近文献[22]量子点——微柱腔实验结果符合得非常好.结合理论和当前实验,显示了量子点腔系统中抽运诱导受激辐射和非谐振腔量子电动力学. 关键词： 量子点 微腔 受激辐射 发射光谱     

Dynamics ofLens culinaris agglutinin studied by red-edge excitation spectra and anisotropy measurements of 2-p-toluidinylnaphthalene-6-sulfonate (TNS) and of tryptophan residues

The fluorescence of 2-p-toluidinylnaphthalene-6-sulfonate bound toLens culinaris agglutinin and of the Trp residues of the protein was investigated. Red-edge excitation spectra and steady-state anisotropy as a function of temperature indicate that the TNS is bound rigidly. Red-edge excitation spectra, steady-state anisotropy as a function of sucrose and anisotropy decay experiments performed on Trp residues fluorescence prove that the internal fluorophore presents residual motion independent of the global rotation of the protein. Fluorescence anisotropy decay allows to calculate the rotational correlation time (351 ps) of this local motion. Quenching resolved emission anisotropy with iodide gives values equal to 0.257 and 0.112 for the anisotropies of the buried and the surface Trp residues, respectively. This result indicates that the Trp residues present at the surface of the protein have important local motions compared to those embedded in the protein matrix. The results obtained from TNS and Trp residues indicate that the agglutinin has different dynamic domains.     

Fluorescence intensity and anisotropy decays of the intrinsic tryptophan emission of hemoglobin measured with a 10-GHz fluorometer using front-face geometry on a free liquid surface

We measured the intensity and anisotropy decays of the intrinsic tryptophan emission from hemoglobin solutions obtained using a 10-GHz frequency-domain fluorometer and a specially designed cuvette which allows front-face excitation on a free liquid surface. The cuvette eliminates reflections and stray emissions, which become significant for low-intensity fluorescence such as in hemoglobin. Three lifetimes are detectable in the subnanosecond range. The average lifetime of hemoglobin emission is ligand dependent. The measured values of average lifetimes are 91, 174, and 184 ps for deoxy-, oxy-, and carboxyhemoglobin, respectively. Fluorescence anisotropy decays of oxy-, deoxy-, and carbonmonoxyhemoglobin can be fitted with up to three correlation times. When three components are used, the floating initial anisotropyr _o is, in each case, higher than the steady-state anisotropy of tryptophan in vitrified solution. For deoxy hemoglobin it is close to 0.4. The data are consistent with an initial loss of anisotropy from 0.4 to about 0.3 occurring in the first 2 ps.     

不同气体氛围下硅量子点的结构及其发光机理

纳秒脉冲激光在氮气、氧气和空气等不同氛围中加工出的硅量子点都有光致荧光(PL)的发光增强效应,并且在700 nm波长附近观察到了受激辐射.在不同氛围下生成的样品有几乎相同的PL光谱分布,其原因是不同氛围下加工出的样品带隙中有相同的电子态分布.计算结果显示:当硅量子点表面被氮或氧钝化后,在带隙中能够形成几乎相同的局域电子态,这种局域电子态可以俘获来自导带的电子,从而形成亚稳态,这是PL发光增强乃至产生受激辐射的关键因素. 关键词： 硅量子点 PL光谱 发光增强 电子局域态     

Prompt neutron emission spectra and multiplicities in the thermal neutron induced fission of235U

The emission spectra of prompt fission neutrons from mass and kinetic energy selected fission fragments have been measured in²³⁵U(n _th,f). Neutron energies were determined from the measurement of the neutron time of flight using a NE213 scintillation detector. The fragment energies were measured by a pair of surface barrier detectors in one set of measurements and by a back-to-back gridded ionization chamber in the second set of measurements. The data were analysed event by event to deduce neutron energy in the rest frame of the emitting fragment for the determination of neutron emission spectra and multiplicities as a function of the fragment mass and total kinetic energy. The results are compared with statistical model calculations using shell and excitation energy dependent level density formulations to deduce the level density parameters of the neutron rich fragment nuclei over a large range of fragment masses.     

Comparison of intrinsic zero-energy loss and Shirley-type background corrected profiles of XPS spectra for quantitative surface analysis: Study of Cr, Mn and Fe oxides

The intrinsic zero-energy loss profiles of transition metal 2p and 3p XPS spectra for Cr, Mn, and Fe oxides are obtained by spectral deconvolution and compared with Shirley-type background corrected profiles. The metal core level spectra are deconvoluted by O 1s spectra as the response function of each oxide. As the O 1s spectra include intrinsic and extrinsic energy loss parts, the background corrected core level spectra are zero-energy loss spectra. The good agreement of the deconvoluted spectra with the reported spectra obtained by the many body effect theory indicates that the background subtraction method is accurate. A comparison of the deconvoluted with the background corrected spectra of the Shirely-type subtraction reveals that almost all the spectra coincide with each other except for Fe 3p with -Fe₂O₃. The good coincidence of the Shirley-type corrected spectra with the deconvoluted and calculated spectra indicates that Shirley-type background correction can be used for daily quantitative surface analysis.     

Lβ2 satellites in the X‐ray emission spectra of elements 72Hf, 73Ta, 74W, 81Tl, 83Bi and 92U

The satellite spectra arising due to the L₃M_x–M_xN_4,5 (x = 1–5) transition array in the X‐ray emission spectra of ₇₂Hf, ₇₃Ta, ₇₄W, ₈₁Tl, ₈₃Bi and ₉₂U have been calculated using available HFS data on K–LM and L–MN Auger transition energies. The agreement between the calculated and measured energies, that between calculated and measured separations in energies and the consideration of the relative probabilities of all the L₃M_x–M_xN_4,5 transitions have been used as the basis for deciding the origin of the satellites. It has been established that two satellites observed in the Lβ₂ region of the X‐ray spectra of various elements, named β₂^I and β₂^II in the order of increasing energy, are mainly emitted by the L₃M_4,5–M_4,5N_4,5 transitions. It is observed that satellite β₂^I in the spectra of elements with ₇₂Hf to ₇₄W has been assigned to the superposition of the ³F₄–³G₅ and ³F₄–³D₃ transitions and must be the most intense one among all these satellites. The same transition has been proved to be the main origin of satellite β₂^II, reported in the element with ₈₁Tl, ₈₃Bi and ₉₂U. Further, satellite β₂^I, reported in the spectra of elements with ₈₁Tl and ₉₂U, has been associated with the transitions ³D₃–³F₄ and ¹D₂–¹F₃. Finally, line β₂^II, reported in the spectra of elements with Z = 72–74, has been assigned to the ¹F₃–¹G₄ and ³P₀–³D₁ transitions. The possible contributions of other transitions of the L₃M_x–M_xN_4,5 (x = 1–5) array having intensities comparable with those of the above transitions, as well as the corresponding lines that have not yet been observed, have also been discussed. Copyright © 2011 John Wiley & Sons, Ltd.