Complexation of pyrene and anthracene with human blood plasma

We have studied the interaction between polycyclic aromatic hydrocarbons (pyrene and anthracene) with human serum albumin (HSA) and human blood plasma. We have shown that the increase in the fluorescence intensity and the decrease in the polarity index of pyrene on going from an aqueous solution to a pH 7.4 buffer solution of HSA suggests that polycyclic aromatic hydrocarbons are localized in the hydrophobic microphase of the proteins. The increase in the fluorescence intensity for anthracene and pyrene, and also the decrease in the polarity index of pyrene on going from HSA to blood plasma is connected with the fact that polycyclic aromatic hydrocarbons can bind both to plasma proteins and to plasma lipids. When sodium dodecyl sulfate (SDS) is added to the blood plasma in a concentration greater than the critical micelle concentration, we observe an increase in the fluorescence intensity and the polarity index of pyrene. We hypothesize that this is connected with localization of pyrene near the interface between the hydrophobic and hydrophilic phases of the protein-SDS system. We have established that SDS leads to a change in the structure of blood plasma proteins and promotes escape of polycyclic aromatic hydrocarbons from the protein globules. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 379–382, May–June, 2008.     

Sonophotoluminescence from aqueous and non-aqueous solutions

The sonoluminescence generated in air-saturated aqueous and non-aqueous solutions using 515 kHz ultrasound has been used to vibronically excite several fluorescent solutes, namely fluorescein, eosin, pyranine and pyrene. Emission, referred to as 'sonophotoluminescence', was generated in situ with emission spectra that closely matched those obtained by direct photoexcitation of the solutes by an external light source. In the case of pyranine, experiments were also conducted in the presence of the surfactant, sodium dodecyl sulphate (SDS). The presence of 1 mM SDS enhances the sonoluminescence and sonophotoluminescence signals above that seen in pure water by a factor of about 2. Pyrene sonophotoluminescence was observed in ethylene glycol. The emission was quenched by the addition of I-, providing good evidence that emission was from pyrene in bulk solution and not within, or on the surface of cavitation bubbles.     

An improved self‐assembly gold colloid film as surface‐enhanced Raman substrate for detection of trace‐level polycyclic aromatic hydrocarbons in aqueous solution

To detect trace‐level polycyclic aromatic hydrocarbons, some investigations of an improved self‐assembly method are carried out using gold colloid films for the preparation of the surface‐enhanced Raman scattering (SERS)‐active substrate. Extinction spectra and scanning electron microscopy images reveal that controllable surface plasmonic metal substrates can be obtained by increasing the temperature of (3‐aminopropyl)trimethoxysilane solution up to 64.5 °C. The SERS‐active substrates have a high enhancement factor, and they can be both easily prepared and reproducible. With the use of these substrates, different concentrations of pyrene and anthracene in aqueous solutions were detected by SERS. A further enhancement can be supported by shifted excitation Raman difference spectroscopy. Raman signals of pyrene and anthracene adsorbed on gold colloid substrates up to limits of detection at 5 and 1 nmol/l, respectively, can be obtained. The quantitative analysis shows the possibility of in situ detection of polycyclic aromatic hydrocarbons while such gold colloid film serves as a SERS‐active substrate. Copyright © 2012 John Wiley & Sons, Ltd.     

十二烷基硫酸钠自组装过程中分子间相互作用力的垂直偏振拉曼光谱研究

Molecular self-assembly is extremely important in many fields, but the characterization of their corresponding intermolecular interactions is still lacking. The C-H stretching Raman band can reflect the hydrophobic interactions during the self-assembly process of sodium dodecyl sulfate (SDS) in aqueous solutions. However, the Raman spectra in this region are seriously overlapped by the OH stretching band of water. In this work, vertically polarized Raman spectra were used to improve the detection sensitivity of spectra of C-H region for the first time. The spectral results showed that the first critical micelle concentration and the second critical micelle concentration of SDS in water were 8.5 and 69 mmol/L, respectively, which were consistent with the results given by surface tension measurements. Because of the high sensitivity of vertically polarized Raman spectra, the critical micelle concentration of SDS in a relatively high concentration of salt solution could be obtained in our experiment. The two critical concentrations of SDS in 100 mmol/L NaCl solution were recorded to be 1.8 and 16.5 mmol/L, respectively. Through comparing the spectra and surface tension of SDS in water and in NaCl solution, the self-assembly process in bulk phase and at interface were discussed. The interactions among salt ions, SDS and water molecules were also analyzed. These results demonstrated the vertically polarized Raman spectra could be employed to study the self-assembly process of SDS in water.     

标准芳烃及其混合溶液的同步荧光光谱分析

为了提供区分标准芳烃的实验依据,并为环境中芳烃污染检测提供参考.对10个标准芳烃样品(萘、芴、蒽、菲、荧蒽、苊、芘、1,2-苯并[A]蒽、苯并[k]荧蒽、苯并菲)及其混合溶液(蒽、萘、芴混合溶液,苊、荧蒽、菲混合溶液和芘、1,2-苯并[A]蒽、苯并[k]荧蒽、苯并菲混合溶液)的同步荧光特性进行了分析,获得10种标准芳烃标志峰最好时对应的Δλ值及其标志峰位.在此基础上,通过同步荧光光谱分析区分了三种标准芳烃混合溶液的组分,实验发现对蒽、萘、芴混合溶液,Δλ=3 nm时最易区分三种组分|对苊、荧蒽、菲混合溶液,Δλ=3 nm或Δλ=10 nm均可区分三种组分,相对而言,Δλ=10 nm更简便些|对芘、1,2-苯并[A]蒽、苯并[k]荧蒽、苯并菲混合溶液,Δλ=5 nm时是最好的,但也仅能区分芘、1,2-苯并[A]蒽、苯并[k]荧蒽三种组分,苯并菲不确定.     

SDS胶束溶液在石油类污染物荧光光谱测量中的应用

提出了一种以十二烷基硫酸钠(SDS)胶束溶液为溶剂增溶、增敏、增稳石油类物质的新方法。研究了石油类物质的荧光强度随SDS胶束溶液浓度的变化规律,确定了其溶剂SDS胶束溶液的最佳浓度为0.1 mol·L-1。使用FLS920荧光光谱仪测量得到不同稀释浓度的汽油、柴油、煤油SDS胶束溶液的三维荧光光谱矩阵(EEMs),分析了瑞利(Rayleigh)散射、拉曼(Raman)散射以及仪器光谱特性对测量光谱的影响,经过光谱校正,建立了三种油的SDS胶束溶液在激发波长为250～400 nm、发射波长为260～500 nm范围内的三维荧光光谱图,并确定了在一定浓度范围内荧光强度与浓度具有良好的线性关系。在相同条件下,用同样的方法配制各种浓度汽油、柴油、煤油水溶液作对比,验证了SDS胶束溶液作为石油类物质的溶剂可以使水中石油类物质的溶解度增加、荧光强度增大、稳定性更好,实现了石油类物质可以不依赖于某些有毒溶剂萃取,又解决了其水中溶解度低不宜定量的问题。     

Fluorescence Study of Intermolecular Interactions in Diluted Aqueous Solutions of Some Cationic Amphiphilic Polysaccharides

The intermolecular hydrophobic association in diluted aqueous solutions of some cationic amphiphilic polysaccharides was investigated using fluorescence techniques. Dextran and dextran carrying N-alkyl-N,N-dimethyl-N(2-hydroxypropylene) ammonium chloride groups as side chains were single labeled with pyrene or naphthalene. The intensity of the pyrene excimer peak and the ratio I₃/I₁ determined from the fluorescence emission spectra of pyrene-labeled amphiphilic polymer increased with increasing polymer concentration and were higher than in the solution containing pyrene-labeled dextran. Emission spectra of diluted solution (0.008–0.2 g/dl) containing mixtures of pyrene and naphthalene single-labeled amphiphilic polymers proved the occurrence of a nonradiative energy transfer between labels at very a low polymer concentration (<10^?2 g/dl). The energy transfer was not observed in mixtures of single-labeled unmodified dextran. All these results suggest that the intermolecular hydrophobic association of alkyl substituents takes place at a very low concentration of amphiphilic polymers.     

荧光光谱法检测非水体系中蒽和芘

用荧光光谱法检测建立了非水体系中蒽和芘的测试方法,蒽和芘的检测线性范围分别为5.6×10^-9—2.8×10^-6mol/L和4.9×10^-8—1.47×10^-6mol/L,相关系数为0.99959和0.99822,检出限分别为0.356ng/mL,5.230ng/mL,回收率分别为86.61%—98.66%和96.60%—115.80%。考察了常见离子、时间以及温度对荧光强度的影响,结果表明,常见离子对分析检测干扰均不大,可忽略,在2h、5—55℃温度范围内,对荧光强度影响较弱,故此分析检测方法对温度的适应范围较宽。方法可直接用于食品、饮料、酒产品等非水体系中的蒽和芘的测定。     

Lifetime of negative molecular ions of tetracene and pentacene with respect to the autodetachment of an electron

The processes of nondissociative resonant attachment and autodetachment of electrons in a number of poly-cyclic aromatic hydrocarbon molecules have been investigated by mass spectrometry. Long-lived negative molecular ions of phenanthrene and triphenylene have not been observed. Such ions have been detected for anthracene, pyrene, and benzo[e]pyrene capturing thermal electrons. Negative molecular ions of tetracene and pentacene have also been observed up to 2.5–3 eV. The lifetimes of these ions with respect to the auto-detachment of an electron have been measured throughout the energy range where they are observed. This lifetime for tetracene and pentacene is more than 10 ms, which is two or three orders of magnitude larger than that for remaining compounds. Correlation between the lifetime of ions and the electron affinity of the molecules has been revealed.     

十二烷基硫酸钠(SDS)增强若丹明6G水溶液激光激发荧光谱研究

报道了若丹明6G水溶液添加不同浓度的表面活性剂十二烷基硫酸钠(SDS)时激光激发染料的变化,发现较低的掺入量导致R6G荧光减弱,适量SDS的加入使荧光增强,在5×10-5 mol·L-1的R6G水溶液中,加入6×10-2 mol·L-1 SDS,荧光增强因子达到3.1。当R6G浓度为1×10-4 mol·L-1时,加入2×10-2 mol·L-1,染料激光阈值显著降低。测量了不同浓度的R6G溶液的吸收光谱及加入不同浓度SDS后的荧光谱,分析了不同SDS加入量下R6G荧光减弱及增强的物理机制。     

The Amplified Resonance Light Scattering Signal Detection of DNA Hybridization Using Polycyclic Aromatic Hydrocarbons as a Probe

A simple and rapid method has been developed to detect the nucleic acid–based polycyclic aromatic hydrocarbons as a probe by the amplified resonance light scattering signals of DNA hybridization. Five polycyclic aromatic hydrocarbons including naphthalene, pyrene, fluoranthene, anthracene, and phenanthrene, particularly naphthalene, with double-stranded DNA and single-stranded DNA in aqueous solution were investigated. Through amplified resonance light scattering signals, the complementary and mismatched sequences of DNA can be both detected and identified easily. Mechanism investigations by multiple spectra have shown that groove binding occurs between PAHs and double-stranded DNA.

Supplemental materials are available for this article. Go to the publisher's online edition of Spectroscopy Letters to view the supplemental file.     

荧光光谱对自组装多肽作为药物载体的初步研究

为解决疏水性药物普遍存在的因水中溶解度低而给药困难、生物利用度低的问题,采用了新型两亲性自组装多肽RGA16(Ac-RADAGAGARADAGAGS-NH₂)作为载体包裹和释放疏水性模型药物。以芘为模型疏水性药物,以鸡蛋卵磷脂脂质体模拟细胞膜,通过稳态荧光光谱表征和测定芘的存在形式和浓度。两亲性自组装多肽RGA16能够在水溶液中稳定模型疏水性药物芘的晶体。扫描电镜图像显示多肽RGA16与芘晶体相互吸引,两者形成10 μm以上大小的复合体。在机械搅拌下多肽RGA16与水溶液中的芘相互作用5 d左右形成稳定的胶体混悬液(多肽-芘复合体)。被多肽包裹时,芘以晶体的形式存在。而当与EPC脂质体溶液混合时,芘可从多肽的包裹中以分子形式释放到EPC的双层膜中。芘从自组装多肽所稳定的胶态晶体向EPC脂质体释放的过程采用连续时间扫描稳态荧光光谱加以观察。通过将释放过程中芘单体的荧光强度与标准曲线相比较,确定了特定时间点EPC脂质体中芘的转移量。以上结果表明：该两亲性自组装多肽RGA16具有作为小分子量疏水性药物载体的潜力。     

Aromatic Chromophore-Tethered Schiff Base Ligands and Their Iron(III)/Chromium(III) Salen and Saloph Capped Complexes

Aromatic chromophores; pyrene, phenanthrene, anthracene, naphtalene and benzene-tethered Schiff base ligands and their iron(III)/chromium(III) Salen and Saloph capped complexes have been synthesized. Compounds have been characterized by means of FT-IR Spectroscopy, (1)H-NMR Spectroscopy, Magnetic Susceptibility, Elementel Analsis, TG/DTA measurements. Their fluorescence and absorbance properties have been investigated by Luminescence Spectroscopy and UV-vis Spectroscopy. Generally, ligands show an intense excimer fluorescence emissions in acetonitrile-methanol medium while iron(III) and chromium(III) complexes exhibit low fluorescence's. Intensity compared to ligands iron and chromium centers act as an extra chromophore that quench the pyrene, phenanthrene, anthracene, naphtalene and benzene molecules' singlet state. The mechanism of quenching is attributed to a iron (or chromium)-to-pyrene (or phenanthrene, anthracene, naphtalene and benzene) electronic energy transfer process.     

Determining Eigenfrequencies and Homogeneous Widths of Lines of Intermolecular Vibrations in Water and in Aqueous Solutions of Hydrogen Peroxide Using Raman Spectroscopy

We have examined low-frequency Raman spectra of intermolecular vibrations of weak aqueous solutions of hydrogen peroxide and water. The differences between the observed Raman frequencies and the data from the literature on the IR-absorption frequencies of the same vibrations, as well as the interrelations between the frequencies and the widths of Lorentzian contours that approximate the vibrational spectra of the dynamic susceptibility, have been discussed. Based on a model of free damped vibrations of a classical oscillator with an inhomogeneous broadening, we have explained these effects for the first time. The homogeneous line widths and the damping times of the observed intermolecular vibrations have been determined. The eigenfrequencies of these vibrations have been calculated, and they have been shown to agree well with the data from the literature on the frequencies of IR absorption of water. We have shown that these parameters of intermolecular vibrations for water and for aqueous solutions of hydrogen peroxide differ from each other.     

Steady state and time-resolved studies of pyrene in solution and in single microcrystals

Single microcrystals of pyrene have been studied by steady state and time resolved fluorescence microscopy. The fluorescence spectra of microcrystals exhibit vibrational structure unlike the broad spectrum observed in pyrene excimer. A risetime is observed in the decay curves of the concentrated solutions, indicating the excimer formation. In contrast, the fluorescence decay profiles of the single microcrystals are nonexponential in nature and the decay times vary with their size and the wavelength of emission. This behaviour has been explained mainly by considering the pyrene dimer stabilized in the ground state.     

Modeling vibrational spectra of indole in water

Vibrational spectra of indole in the isolated state and in aqueous solution have been calculated using a B3LYP/6-311++G(d, p) method. The influence of water as a solvent on vibrational spectra of indole was examined with due regard for intermolecular interactions (SCRF method) and explicit consideration of the effect of hydrogen bonds (1:1 indole:water complex).     

荧光光谱数据解析中的信息冗余初步研究

提出了光谱数据解析中的信息冗余系数的问题,从光谱数据处理过程中波段优化选择的方法入手,考察了多环芳烃(polycyclic aromatic hydrocarbons,PAHs)中的蒽、芘和菲三组分混合体系的荧光光谱数据,采用化学计量学中的主成分回归分析和波段变量选择的窗口移动法,通过理论分析和实验论证得到结论:(1)荧光光谱信号中存在信息冗余;(2)经冗余优化后的荧光光谱数据可以反演出更真实的样本的定量信息,对光谱重叠严重的多组分混合体系,采用冗余优化分析过的数据可以增加预测模型的灵敏度和稳定性。     

A thermodynamic and photophysical study of the effects of thiourea on the micellar properties of aqueous sodium dodecyl sulphate solution

The micellar properties of sodium dodecyl sulphate (SDS) in aqueous thiourea solutions were investigated with the aim of studying the effect of thiourea on these properties. The critical micelle concentrations (cmc) and the degree of dissociation of the micelle were determined by the conductometric method over the temperature range 298–323 K for different concentrations of thiourea. The cmc values of the surfactant in the presence of thiourea were obtained by following the change in the relative intensities of vibrational fine structure of the pyrene fluorescence spectra. The aggregation numbers were determined by employing the static quenching fluorescence method. The cmc values in the presence of varying electrolyte concentrations (NaCl) were obtained with 8-anilinonaphthalene 1-sulphonate (ANS) as a fluorescence probe, and from these values the degree of dissociation was calculated. The mass action model was applied in the present study to obtain various thermodynamic parameters of micellization. All these properties were compared with the micellar properties of an aqueous urea/SDS system, and it was found that thiourea is a better demicellization agent.     

Fluorescence and absorption spectra of Rose-Bengal dye in the presence of surfactants

The fluorescence and absorption spectra of Rose Bengal dye in aqueous solution have been studied in the presence of various nonionic, anionic and cationic surfactants. With cationic and nonionic surfactants, shifts occur in the absorption and emission peaks of the dye solution, with a large enhancement in the absorption and fluorescence intensity at the shifted λ_max. No appreciable change in the absorption and fluorescence spectra of the dye has been observed on the addition of anionic surfactants.All the changes observed in the absorption and fluorescence spectra of the dye solution with surfactants may be attributed, to binding of the surfactant with dye molecules and the disaggregation of the dye multimer forms into the monomeric form.     

消除溶剂水吸收峰干扰的红外光谱测量新方法

水在中红外波段的强吸收有时会遮蔽水溶液中溶质的特征峰,从而干扰溶质的红外谱带归属和分析。提出了一种新方法,控制水峰的吸收强度逐渐变化(强→弱→消失),从而得到高质量的红外光谱。利用单次ATR附件,通过先扫描空ATR晶体N次,经短暂暂停后,再继续扫描载有纯水(或参比溶液)的ATR晶体M次,这样累加得到的背景单光束谱(N+M次扫描)中水的吸收强度就直接与扫描次数N和M相关。选择足够大的扫描次数N和合适的扫描次数M,就可以彻底扣除水峰的干扰。利用该方法,成功获得了K₂CO₃溶液和牛血清白蛋白(BSA)溶液的消除了水吸收峰的高质量红外光谱。实验结果证实新方法具有快速、高效等优点。文中也讨论了该方法的局限性。