Fluorescence Properties of Twenty Fluorescein Derivatives: Lifetime,Quantum Yield,Absorption and Emission Spectra

The fluorescence lifetime (τ_f), emission quantum yield (Φ_f), absorption and emission spectral data of 20 fluorescein derivatives were measured under the same conditions by using time-correlated single photon counting, steady state fluorescence and absorption methods to get comparable data. Based on the results, the factors and mechanism that control the fluorescence properties of the fluorescein dyes are discussed. Both Φ_f and τ_f are remarkably dependent on the substitution on either xanthene or phenyl rings, but their ratio (Φ_f/τ_f), i.e. rate constant of radiation process, is a constant value (0.20?×?10⁹ s^?1). The rate constant of nonradiation process, on the other hand, is varied with both the structure and the solvent used.     

Microquantification of Proteins by Spectrophotometry. Part II : Application Procedure for Complex Mixture Containing Interfering Substances

In a previous paper we have shown that it was possible to quantify protein solutions at very weak concentrations directly by UV-visible spectroscopy. Nevertheless the protein quantification could not be possible if there is any trace of interferents left in the solution. So it is necessary to eliminate all the interferents to make the measure at 190 and/or 277 nm possible. We have developped a method based on the use of Microcon membranes and centrifugation. Interferents could be eliminated from protein solutions after four centrifugations at 13000 g during 5 min. This procedure allowed the recovering of proteins, with 80 to 99 % yield, and thus making microquantification possible.

This method is particularly interesting for enzymatic solutions after a purification procedure by HPLC where very tiny quantities of protein are recovered. This protocol has been tested on three enzymes; enzymatic activity recovered after four centrifugations was quite high for PEPcase and malic enzyme (71 and 64 % respectively).     

Practical Use of Corrected Fluorescence Excitation and Emission Spectra of Fluorescent Proteins in Förster Resonance Energy Transfer (FRET) Studies

Corrected fluorescence excitation and emission spectra have been obtained from several enhanced variants of the green fluorescent protein (EGFP) isolated from the jellyfish Aequorea victoria, blue fluorescence protein (EBFP), cyan fluorescent protein (ECFP), EGFP and yellow fluorescent protein (EYFP–citrine) and from the red fluorescent protein (DsRed) isolated from the coral species Discosoma. The spectra are stored in a database. This report describes how the spectra can be used as templates to derive the critical transfer distance for any pair of fluorescent proteins.     

量化计算在二芳基二硫代膦酸结构和光谱分析中的应用

在拉曼和红外光谱分析中，谱峰的归属直接关系到对分子结构的判定。本工作以量子化学理论计算为基础，探索对二芳基二硫代磷酸实验拉曼谱图进行谱峰归属的可行性。结果表明：二芳基二硫代膦酸理论计算谱图与实验谱图具有相关性，理论计算谱图可以指导实验谱图谱峰的归属分析。     

Features of the Emission Spectra of Ni-Like Ions. Application to Calculating the Wavelengths of Self-Photo-Pumped X-Ray Lasers

The energy levels and probabilities of radiative transitions to the ground state of Ni-like ions with Z = 36–51 are calculated. The energies of the upper working level 3d_3/24f_5/2 [J = 1] and the lower working level 3d_3/24d_3/2 [J = 1] of self-photo-pumped X-ray lasers along the sequence of Ni-like ions are studied. It is shown that, at the points of intersection of levels of the same parity, a strong interaction of these levels takes place, which leads to a redistribution of the oscillator strengths of the radiative transitions from these levels. Near the intersection points, the emission spectra change abruptly with variation in the nuclear charge Z.     

三维荧光光谱结合组合算法在环境污染监测中的应用:油种鉴别与定量分析

针对油类污染物成分复杂,光谱重叠难以识别的问题,提出采用三维荧光光谱结合组合算法对油类污染物进行了定性和定量分析。荧光光谱中存在的瑞利散射对三维荧光光谱检测有较大影响,提出了缺损数据修复-主成分分析（MDR-PCA）方法对矿物油三维荧光光谱的瑞利散射进行处理,原理是单个荧光光谱激发发射矩阵符合双线性,可用主成分分析（PCA）法来解析。MDR-PCA法首先将荧光数据中的散射干扰数据全部扣除,之后利用主成分分析（PCA）迭代过程对扣除数据进行重构修复后补全数据。该方法在消除散射干扰的同时充分利用了荧光物质光谱矩阵中的有效信息。利用不同浓度的矿物油的激发-发射荧光光谱构建了三维数据。样品数据来源于柴油、汽油和煤油三种溶质的四氯化碳溶液。常用于三维荧光光谱数据分析的三线性分解算法有平行因子分析（PARAFAC）、交替三线性分解（ATLD）和自加权交替三线性分解算法（SWATLD）等。PARAFAC基于严格意义上的最小二乘原则,具有抗噪声强、模型稳定、微小预期误差等优点,可以实现三维数据阵列的最佳拟合,但该算法收敛速度较慢,对组分数敏感。ATLD算法通过提取对角主元和切尾奇异值求解广义逆,极大提高了收敛速度并降低了对组分数的敏感度,从而实现三线性分解。然而,取对角元时易使ATLD方法对噪声敏感。SWATLD算法既继承了对组分数不敏感、收敛速度快等优点,又降低了噪声水平的影响。但是在抗共线程度方面,SWATLD算法在抵抗共线性程度方面的能力较ATLD略有降低。基于此,论文根据三线性分解算法迭代过程中损失函数的变化,对迭代过程进行划分,提出了三线性迭代方法的组合算法（algorithm combination methodology, ACM）—将ATLD, SWATLD与PARAFAC组合在一起,充分发挥各算法的优点,实现二阶校正算法的优势互补。采用ACM算法对两组分及三组分矿物油样品的三维荧光光谱数据进行解析,并对三种矿物油的回收率进行了计算。柴油的回收率为97.08%,汽油的回收率为97.34%,煤油的回收率为97.25%。解析光谱和回收率表明,ACM算法能够实现油类污染物的种类识别及浓度测量。     

掺杂Y3+和Gd3+的 Phen-Eu(Ⅲ)二元固体配合物的红外及荧光光谱研究

合成了掺杂Y^3 和Gd^3 的Phen-Eu(Ⅲ）二元固体配合物，确定了它们的组成，测定了固体配合物的红外光谱和荧光光谱，并首次探讨了掺杂Y^3 和Gd^3 的Phen-Eu(Ⅲ）二元固体配合物荧光强度的影响。     

Biphasic Dielectrophoresis of Isotropic Pocket Carriers Containing Quantum Dots (QDs) in Nematic Medium and Fabrication of QD Cluster Array with Matrix Emission of Point Light Sources

Unusual physical properties of an anisotropic liquid crystal (LC) medium, such as topological defects, elastic interaction with particles, and nonlinear electrophoresis, are ingeniously utilized to handle nanoparticles. Here, a new approach to manipulate quantum dots (QDs) using volume‐tunable and electrically movable isotropic pocket carriers in a nematic medium is demonstrated. This method is based on multiple mechanisms: spontaneous formation of QD flocs in LCs, sharp solubility contrast of QDs in nematic and isotropic phases, and biphasic dielectrophoresis in isotropic–nematic mixture. By thermally and electrically controlling the isotropic pockets containing QDs, an array of hierarchical QD clusters with the arbitrarily controllable size and location is fabricated. The phase boundary pressure squeezes the QD flocs to adhere to each other and on the substrate. The QD cluster array can be transferred to a flexible substrate, and can serve as a point light source array for display and image acquisition applications.     

Semiphenomenological Model of the Nucleus and its Application to Description of the Rotational Spectra. I

The general structure of the semiphenomenological model as a unified nuclear model describing the rotational, charge oscillation and configurational states is considered. The basic HAMILTONIAN of the model including the average field and short -range “residual” interactions is given.     

Determination of Conjugation Efficiency of Antibodies and Proteins to the Superparamagnetic Iron Oxide Nanoparticles by Capillary Electrophoresis with Laser-Induced Fluorescence Detection

The method based on capillary electrophoresis with laser-induced fluorescence detection (CE/LIF) was developed for determination of magnetic iron oxide nanoparticles (hydrodynamic diameters of 100 nm) functionalized with molecules containing primary amino groups. The magnetic nanoparticles with carboxylic or aminopropyl-trimethoxysilane groups at their surface were conjugated to the model proteins (bovine serum albumin, BSA; streptavidin or goat anti-rabbit immunoglobulin G, IgG) using carbodiimide as a zero-length cross-linker.The nanoparticle–protein conjugates (hydrodynamic diameter 163–194 nm) were derivatized with naphthalene-2,3-dicarboxaldehyde reagent and separated by CE/LIF with a helium–cadmium laser (excitation at 442 nm, emission at 488 nm). The separations were carried out by using a fused-silica capillary (effective length 48 cm, inner diameter 75 um) and 100 mM sodium borate buffer (pH 9.2), the potential was 30 kV. The detection limit for BSA-conjugate was 1.3 pg/10 nl, i.e. about 20 amol. The present method provides an efficient and fast tool for sensitive determination of the efficacy of biomolecular functionalization of magnetic nanoparticles. The CE/LIF technique requires only negligible sample volumes for analysis, which is especially suitable for controlling the process of preparation of functionalized nanoparticles with unique properties aimed to be used for diagnostic or therapeutic purposes.     

Spectrofluorimetric Determination of 3-hidroxy-2-naphthoic Acid by Use of Its Ternary Complex with Zirconium (IV) and Beta-Cyclodextrin: Application to Determination in River Water

A spectrofluorimetric method has been developed for the determination of 3-hydroxy-2-naphthoic acid (3H2NA) by formation of a ternary complex with zirconium (IV) and β-cyclodextrin (β-CD). It has been observed that the fluorescence intensity of 3H2NA is greatly enhanced when the ternary complex is formed and is accompanied with shifts in the excitation and emission wavelengths. The conditions for the formation of the ternary complex have been optimized and the stoichiometry has been calculated, resulting a 1:2:1 complex (3H2NA:Zr: β-CD). The linear range was 20–2000 ng mL⁻¹ and the detection and quantification limits calculated were 17 and 58 ng mL⁻¹, respectively. The proposed method was applied to the determination of 3H2NA in river water. To eliminate interferences an off-line solid phase extraction (SPE) procedure using C18 cartridges was used. The extraction procedure was optimized and good recoveries were obtained (around 100%) with relative standard deviations (RSDs) of less than 5%.     

Augmented Lagrangian and penalty methods for the simulation of two-phase flows interacting with moving solids. Application to hydroplaning flows interacting with real tire tread patterns

The numerical simulation of the interaction between a free surface flow and a moving obstacle is considered for the analysis of hydroplaning flows. A new augmented Lagrangian method, coupled to fictitious domains and penalty methods, is proposed for the simulation of multi-phase flows. The augmented Lagrangian parameter is estimated by an automatic analysis of the discretization matrix resulting from the approximation of the momentum equations. The algebraic automatic augmented Lagrangian 3AL approach is validated on the natural convection in a differentially heated cavity, a two-dimensional collapse of a water column, the three-dimensional settling of a particle in a tank and the falling of a dense cylinder in air. Finally, the 3AL method is utilized to simulate the hydroplaning of a tire under various pattern shape conditions.     

Application of magnetic resonance imaging to the measurement of neurodegeneration in rat brain: MRI data correlate strongly with histology and enzymatic analysis.

Focal brain ischemia was induced by middle cerebral artery occlusion in the rat. The volume of cerebral damage was determined 2 days later by MRI in vivo and in the same animals histologically. The edema volume as measured by MRI and the histologically determined infarction was highly correlated. As a consequence, the neuroprotective effect of the N-methyl-D-aspartate (NMDA) receptor antagonists CGP 40116 and MK 801 were similar with both methods. Excitotoxic neurodegeneration in the rat striatum was induced by direct injection of quinolinic acid. The degree of damage was evaluated in vivo 1 day later by quantitative MRI, and 7 days later by measuring the activities of neuronal marker enzymes choline acetyltransferase and glutamic acid decarboxylase. Striatal damage assessed using the three approaches was highly correlated. Cerebroprotective efficacy of the NMDA receptor antagonist CGP 40116 was indistinguishable based on all methods. MRI was more reproducible than the enzymatic methods and was faster and simpler than histologic examination for routine analysis of excitotoxic damage and cerebroprotection in vivo in a pharmaceutical research environment.     

Selective Spectrofluorimetric Method with Enhanced Sensitivity for Determination of Silodosine in Dosage Form and Human Plasma. Application to Stability Studies and Content Uniformity Testing

A novel, sensitive and selective spectrofluorimetric method has been developed and validated for determination of silodosine (SLD) in its dosage form and human plasma. The method is based on nucleophilic substitution reaction of SLD with 5-(dimethylamino) naphthalene-1-sulfonyl chloride (dansyl chloride) in presence of 5.0 × 10^?4 M sodium carbonate (pH 10.50) to yield a highly fluorescent derivative that was measured at 435 nm after excitation at 347 nm. The different experimental parameters affecting the development and stability of the reaction product were carefully studied and optimized. The fluorescence-concentration plot was rectilinear over the range 30.0–200.0 ng ml^?1, with a correlation coefficient of 0.9979. The limits of detection (LOD) and quantification (LOQ) were found to be 5.44 and 16.47 ng ml^?1, respectively. The proposed method was validated according to ICH guidelines, and successfully applied to the assay of commercial capsules as well as content uniformity testing. The high sensitivity of the proposed method allowed its successful application to the analysis of SLD in spiked human plasma with % recovery of 92.88 ± 1.05–100.73 ± 0.75%, (n = 6). The application of the proposed method was further extended to stability studies of SLD after exposure to different forced degradation conditions, such as acidic, alkaline and oxidative conditions, according to ICH guidelines, where this work describe the first attempt for selective spectrofluorimetric determination of silodosine in plasma and in the presence of its oxidative degradation.     

Investigation of the interaction of some astrobiological molecules with the surface of a graphite (0 0 0 1) substrate. Application to the CO, HCN, H2O and H2CO molecules

Detailed interaction potential energy calculations are performed to determine the potential energy surface experienced by the molecules CO, HCN, H₂O and H₂CO, when adsorbed on the basal plane (0 0 0 1) of graphite at low temperatures. The potential energy surface is used to find the equilibrium site and configuration of a molecule on the surface and its corresponding adsorption energy. The diffusion constant associated with molecular surface diffusion is calculated for each molecule.