Fast Evaluation Peanut Oil Quality by Synchronous Fluorescence Spectroscopy and Statistical Analysis

Peanut oil oxidation was to monitor and quantify combining synchronous fluorescence spectroscopy and chemometrics. Peanut oil was subjected to an accelerated oxidation testing. The spectral and related chemical indicators were caught during oxidation induce testing. Fluorescence spectra were gained for each sample with simultaneous excitation from 200 to 800 nm and the offsets (Δλ) of 10 to 180 nm during the oxidation process. The results showed the induce period (IP) of the peanut oil was 16.45 h. Parallel factor analysis (PARAFAC) was performed to select the best Δλ interval of 70 nm, which spectral data was the most suitable for interval partial least square (iPLS) and synergy interval PLS (siPLS) modeling and forecast. The study presented all interval selection methods had the better results than the global spectrum modelling. iPLS reached the best into 10 intervals with a ratio of prediction to deviation (RPD) of 2.10. siPLS that separated the whole spectrum into 15 intervals and combined the third intervals (282 to 320 nm, 362 to 400 nm, and 761 to 800 nm) had a ratio of RPD of 2.26. The results showed the optimal siPLS model performed a little better than iPLS. The established model lying on interval selection could improve the prediction accuracy. It could provide a quick, accurate method to monitor oil oxidation process.

THE RAPID DETERMINATION FOR BENZO(a)PYRENE WITH SYNCHRONOUS FLUORESCENCE SPECTROSCOPY SCANNING IN DEFINED RANGE OF DUAL—WAVELENGTHS

A rapid method of determination of BaP in various environmental samples,using synchronous fluorescence spectroscopy scanning in defined range of dual-wavelengths(SFDW)is described in this paper.

Characterization of Anabaena cylindrica Solution System Using Synchronous-Scan Fluorescence Spectroscopy

The characterization of the algae Anabaena cylindrical solution with Fe (III)was investigated using fluorescence emission and synchronous-scan spectroscopy. The ranges ofconcentrations of algae and Fe (III) in aqueous solutions were 5.0 X 10~7-2.5 X10^8 cell/L and 10-60mu mol/L, respectively. The effective characterization method used was synchronous-scanfluorescence spectroscopy (SFS). The wavelength difference (triangle open lambda) of 90 nm wasmaintained between excitation wavelength (lambda_(ex)) and emissionwavelength(lambda_(em)). The peakwas observed at about lambda_(ex) 236 nm / lambda_(em) 326 nm for synchronous-scan fluorescencespectroscopy. The fluorescence quenching in system of algae-Fe( III )-HA was studied usingsynchronous-scan spectroscopy forthe first time, Fe(III) was clearly the effective quencher. Therelationship between I_0/I (quenching efficiency) and c (concentration of Fe (III). added) was alinear correlation for the algae solution with Fe(III). Also, Aldrich humic acid (HA) was found tobe an effective quencher.

Qualitative Characterization and Differentiation of Digestates from Different Biowastes Using FTIR and Fluorescence Spectroscopies

Anaerobic digestion of biomasses originates different products, the most abundant of which are methane and carbon dioxide. During this process, a 60-70% organic matter reduction occurs and the final product, the digestate, is charac- terized by high biological stability and high contents of recalcitrant organic molecules and nutrients. In the present work digestates obtained by different mixture of biomasses in a full-scale co-digestion plant operating in Italy were characterized as whole samples without any pre-treatment or extraction by means of Fourier transform infrared spec- troscopy and fluorescence spectroscopy in the synchronous-scan mode and results were compared to those obtained on the single fresh substrates. Biomasses considered were: beef cattle slurry, maize or sorghum silage, agro-industrial residues, olive residues and olive mill wastewater. These substrates exhibited typical spectra related to their different chemical composition. Results obtained on digestates provided evidence of distinctive characteristic of the final product as a function of the different composition of the biomasses loaded into the digestion plant. We concluded that FTIR and fluorescence spectra of digestates produced in a real co-digestion plant “inherit” the main spectroscopic features of the organic wastes from which they are produced. Spectroscopic techniques used in this work succeeded in qualitatively characterizing and differentiating digestates obtained from biomasses of different chemical composition.

Ultrasensitive Detection of Polycyclic Aromatic Hydrocarbons(PAHs) in Water Using Three-Dimensional SERS Substrate Based on Porous Material and pH 13 Gold Nanoparticles

Sensitivity is crucially important for surface-enhanced Raman spectroscopy(SERS)application to detect trace-level polycyclic aromatic hydrocarbons(PAHs)in the seawater.In this study,a high sensitivity three-dimensional(3-D)SERS substrate composed with syringe filter,glycidyl methacrylate-ethylene dimethacrylate(GMA-EDMA)porous material and optimal parameters(57 nm,pH 13)gold nanoparticles(Au NPs)was developed for the detection of PAHs in water.The enhancement effect and repeatability of this 3-D substrate were also explored.The Raman intensity of pyrene using 3-D SERS substrate is about 8 times higher than that of substrate only using p H 13 gold colloid solution and about 12 times higher than that of substrate using natural Au NPs and GMA-EDMA porous material,which means both the pH 13 AuN Ps and the GMA-EDMA porous material are important factors for the sensitivity of this 3-D SERS substrate.Good repeatability of this optimal 3-D substrate was obtained.The relative standard deviation(RSD)is less than 8.66% on the same substrate and less than 3.69% on other different substrates.Four kinds of PAHs,i.e.,phenanthrene,pyrene,benzo(a)pyrene,benzo(k)fluoranthene and their mixture,were detected at the different concentrations.Their limits of detection(LODs)are 8.3×10^-10(phenanthrene),2.1×10^-10(pyrene),3.8×10^-10(benzo(a)pyrene)and 1.7×10^-10 mol L^-1(benzo(k)fluoranthene),respectively.In addition,these four PAHs were also detected by fluorescence spectroscopy to evaluate the sensitivity of SERS technology using this optimal 3-D SERS substrate.The results showed that the sensitivity of SERS based on the 3-D SERS substrate even using the portable Raman system was closed to that of fluorescence spectroscopy.Therefore,the SERS technology using this optimal 3-D substrate is expected to be an in-situ method for the detection of environmental PAHs.

Determination of Luzhou-flavor liquor ages by three-dimensional fluorescence spectroscopy combined with NMF

The determination of Luzhou-flavor liquor ages is carried out by three-dimensional fluorescence spectroscopy combined with non-negative matrix factorization(NMF). 37 samples of aged liquors with weighted ages of 15, 20 and 25 years were prepared by blending three Luzhou-flavor original base liquors with storage ages of 10, 20 and 30 years in different proportions. The fluorescence spectra of the samples were measured, and then factorized into basis matrix and coefficients matrix by multiplicative iterative NMF. The fluorescence spectra, reconstructed from the basis matrix, are similar to the original spectra. The coefficients matrix is taken as the input of support vector machine(SVM) to establish a prediction model for the determination of liquor ages. Compared with the principal component analysis, the prediction model based on SVM has a predicted accuracy better than 91.7%. This method can provide helps for the market supervision on the aged liquors.

应用同步荧光光谱对比研究天麻粉与伪品

精加工后的天麻粉与伪品难以肉眼区分,应用同步荧光光谱技术有助于对比研究天麻粉与伪品。使用爱丁堡公司FLS920荧光光谱仪获得天麻粉、伪品天花粉和紫茉莉粉的3维同步荧光光谱及等高线图谱,发现不同种类物质的光谱图像具有显著差异。通过进一步分析天麻粉中分别掺入不同伪品时的同步荧光光谱和等高线图谱,发现纯天麻粉溶液与掺入伪品的天麻粉溶液光谱图像有明显区别,有助于研究者轻松分辨天麻粉中是否掺入伪品。该方法操作简单,无需繁杂预处理与提纯,可实现实时在线检测。同时,3维同步荧光光谱从中药材的整体特征、全局视角研究荧光特性,降低了光谱分析难度,其等高线图谱具有指纹图谱特征,可完善我国中药材指纹图谱库信息,并为多组分的中药材鉴定提供参考依据。

Effect of urea on synchronous fluorescence spectra and electrochemical behaviour of cytochrome

The changes of the synchronous fluorescence spectra and the electrochemical behaviour of cytochrome c with the urea concentration are studied. It has been found that with the increase of urea concentration, there occur sequentially the deaggregation of cytochrome c molecules, the increase of exposure extent of the heme group to the solvent, the disruption of Fe-S bond of the heme group and the change in the electrochemical behaviour of cytochrome c. It is suggested that the reason why the electrochemical reaction of cytochrome c is irreversible is that cytochrome c molecules exist in the concentrated solution as oligomers which are electrochemically inactive.

基于导数-恒基体同步荧光的纺织品中萘胺同分异构体快速定量检测

2-萘胺是纺织品中禁用的一种致癌芳香胺,其与同分异构体1-萘胺(非禁用)的结构、性质相似,传统检测方法在检测纺织品实际样品时可能会造成阳性结果的误判,因此相关检测标准要求采用多种方法对阳性结果进行复查确认。目前常规的复查方法为气相色谱-质谱联用法和高效液相色谱法,存在操作复杂、耗时长等弊端,因此开发一种简单、快速的方法用于鉴别和定量纺织品中的致癌芳香胺及其异构体具有重要意义。导数-恒基体同步荧光法具有灵敏度高、选择性好、可消除背景干扰等特点,已广泛地应用于复杂基质中物质的测定。为了实现纺织品中1-萘胺(1-NA)和2-萘胺(2-NA)的快速鉴别定量,建立了一种导数-恒基体同步荧光分析法。研究确立了一条合适的恒基体同步荧光扫描路径,提高1-NA和2-NA的光谱分辨率;结合一阶导数技术消除背景干扰,得到1-NA和2-NA的净信号。以上两种技术的结合,能够保持较高的灵敏度和选择性,同时避免了耗时的物理分离过程且无需多次扫描。整个光谱的扫描过程可在2分钟内完成。实验结果表明,1-NA和2-NA的检出限分别为0.001 mg/L(相当于纺织品中的0.1 mg/kg)和0.006 mg/L(相当于纺织品中的0.6 mg/kg),远远低于国家标准中规定的限量(20 mg/kg);1-NA的加标回收率在89.1~122.1%之间,2-NA的加标回收率在88.5~111.0%之间,相对标准偏差均小于9.3%;将所提出的方法与HPLC法作统计比较,得到的测试结果之间无显著差异。因此,所提出的方法具有较高的选择性、灵敏度,能够准确、可靠地鉴别和定量2-NA及其同分异构体1-NA,可应用于纺织品中禁用芳香胺的实际检测。

柚皮素、柚皮苷与牛血清白蛋白相互作用的机理分析

采用荧光光谱法对柚皮素(naringenin,NG)、柚皮苷(柚皮素-7-新橙皮苷,naringin,NA)猝灭牛血清白蛋白(bovine serum albumin,BSA)荧光发射的机理进行了研究,并使用分子对接技术获得了NG,NA同BSA之间的结合模型。优化了水浴时间和溶液pH等实验条件,荧光测试结果显示NG,NA浓度与BSA的荧光发射强度呈负相关,并且NG猝灭BSA的程度强于NA。通过分析不同浓度NG,NA猝灭BSA的荧光发射可知,NG与NA猝灭BSA的机理都是静态猝灭,即与BSA形成1∶1型非共价复合物。同步荧光光谱实验结果表明,NG与NA对BSA的Trp残基的影响强于对Tyr残基的影响。分子对接结果表明,在BSA的Trp213残基附近存在一个疏水性口袋,NG可以进入其中并与BSA形成复合物,而NA则结合在BSA表面,无论NA还是NG都与BSA的多个氨基酸残基存在氢键或疏水作用。

烟碱与牛血清白蛋白相互作用的光谱研究

在0.1mol·L-1的磷酸氢二钠-柠檬酸体系中,采用荧光光谱、紫外吸收光谱研究了牛血清白蛋白(BSA)与烟碱的相互作用。荧光滴定表明这种相互作用使BSA的内源荧光猝灭,尼古丁和BSA形成1∶1稳定复合物。不同温度和酸度下的猝灭作用证实其静态猝灭行为和疏水作用机制。紫外吸收光谱和同步荧光光谱表明,相互作用引起BSA构象变化,而同步荧光光谱提示结合位点更接近于色氨酸。

荧光光谱在蛋白质分子构象研究中的应用

荧光光谱法是研究蛋白质在水溶液中分子构象的一种有效方法。文章综述了常见的蛋白质荧光光谱的研究方法 。

杂多酸盐K_7[PTi_2W_(10)O_(40)]·6H_2O与牛血清白蛋白相互作用的研究

20世纪70年代初期。法国科学家报道了杂多阴离子[SiW12O40]^4-的抗病毒活性，以后相继发现了[BW12O40]^5-[P2W12O40]^6-等在体外也表现出抗病毒活性。80年代后期。具有抑制艾滋病病毒作用的（NH4）17Na[NaSb9W21O86]·14H2O（HPA-23）被应用于临床试验回。虽然其治疗效果不够理想．但却激发了人们对多金属氧酸盐的研究兴趣。90年代以来．Yamase等研究了十几种多金属氧酸盐的抗肿瘤、抗爱滋病毒活性，发现K7[PTi2W10O40]·6H2O（PM-19）具有较强的抗HIV病毒能力和较低的毒性。此后多金属氧酸盐的药物化学迅速发展起来。

铱(IV)离子与人血丙种球蛋白的作用研究

在 0.1 mol?L-1醋酸-醋酸钠(pH 5.0)体系中, 采用紫外吸收光谱、荧光光谱及同步荧光光谱法研究了人血丙种球蛋白(gamma seroglobulinum humanum, 简称 GSH)与铱(IV)离子的相互作用. 结果表明, Ir(IV)离子使人血丙种球蛋白的构象发生了改变, α-螺旋含量减少, 并且用同步荧光光谱发现 Ir(IV)离子与人血丙种球蛋白的作用位点更接近于色氨酸,从而使色氨酸残基的疏水性略有减小. 荧光光谱结果表明Ir(IV)对人血丙种球蛋白内源荧光(342 nm)产生了较强的荧光猝灭作用, 根据不同温度下 Ir(IV)对人血丙种球蛋白的荧光猝灭作用, 证明了这种荧光猝灭为静态猝灭机制, 计算了其结合常数和结合位点数, 从而得出了静电作用力为其主要的作用力.

环丙沙星与牛血清白蛋白的相互作用

AIM To study the interaction between ciprofloxacin and BSA in physiological condition by fluorescence spectroscopy. METHODS The affection of drug to the protein conformation was investigated. The binding constant between drug and BSA from a double reciprocal Lineweaver Burk plot was determined and the main sort of binding force was found according to the thermodynamic parameters. RESULTS The binding constants between BSA and ciprofloxacin at 26℃and 45℃ are about 10 4. At 26℃, the thermodynamic parameters of reaction between BSA and ciprofloxacin are Δ H = -49 13 kJ·mol -1 , Δ G = -26 45 kJ·mol -1 , Δ S = -75 kJ·mol -1 . The maximum wavelength of the synchronous fluorescence spectra of BSA moved from 279 nm to 289nm with the incresing of the amount of ciprofloxacin. CONCLUSION There exists fluorescence energy transfer between BSA and ciprofloxacin. The main sort of binding force between BSA and ciprofloxacin is Van der Waals′ interaction. Ciprofloxacin can be deposited and be transported by serum protein in vivo . Ciprofloxacin affects the protein conformation.

光谱法研究欧前胡素及同分异构体与牛血清白蛋白的相互作用

采用紫外光谱法、荧光光谱法和同步荧光光谱法研究了欧前胡素及其同分异构体异欧前胡素与牛血清白蛋白(BSA)的相互作用。荧光光谱表明,欧前胡素和异欧前胡素对BSA的内源荧光均有显著的猝灭作用,且猝灭机制主要为静态猝灭和非辐射能量转移。308K下欧前胡素和异欧前胡素与BSA的结合常数K分别为1.48×104、1.04×104L·mol-1,结合位点数n分别为0.915、0.742。由热力学数据确定其作用力主要为氢键和范德华力。同步荧光光谱表明,欧前胡素和异欧前胡素与BSA的结合位点更靠近BSA中的色氨酸,引起色氨酸残基附近的疏水性环境减弱,从而使得BSA的构象发生改变。研究表明,香豆素母核上3-甲基-2-丁烯氧基的位置对它们的结合有重要影响,欧前胡素与BSA的作用强于异欧前胡素。

基于不同光谱技术的原油样品的荧光分析

应用同步扫描、三维发射以及目前石油荧光仪所采用的二维发射荧光分析技术对胜利油田15个井区25种原油样品在10^-4g·L^-1～10g·L^-1浓度范围内进行了光谱采集，对比分析了不同光谱技术所获取的光谱信息与浓度之间的相应关系。结果表明，对于原油这种多组分样品，二维发射光谱难以满足分析要求；三维光谱信息丰富但数据采集与提取困难。同步扫描光谱具有简单快捷、光谱特征丰富明显、干扰小等特点，选择出为40nm获得的原油同步扫描光谱可反映三维光谱的主要信息。与二维发射光谱和三维光谱相比，同步荧光法在原油样品分析中显现出较大优势和发展空间，可望发展成为石油录井中对岩屑岩芯样品含油量的定量分析的新方法。

硝基羟乙唑与溶菌酶反应机制的荧光光谱研究

分别在298,310,318 K温度下,利用荧光光谱法研究了p H=7.40生理条件下硝基羟乙唑(TRI)与溶菌酶(LYSO)的相互作用机理。结果表明,TRI与LYSO间通过静态猝灭方式相互作用。测定了LYSO与TRI反应的结合常数、结合位点数。利用反应过程的热力学参数,确定了LYSO-TRI体系的作用力类型;由Hill系数得出了LYSO或TRI的协同性;根据非辐射能量转移理论,确定了TRI到LYSO的结合距离,同时采用同步光谱法考察了TRI对LYSO构象的影响。

烟碱与人血清蛋白相互作用的光谱研究

在0·1mol/L的磷酸氢二钠-柠檬酸体系中,采用荧光光谱、紫外吸收光谱研究了人血清蛋白与烟碱的相互作用。荧光滴定表明这种相互作用使HSA的内源荧光猝灭。通过猝灭常数、结合常数和结合位点数的计算,证明了这种猝灭为静态猝灭机制。尼古丁和HSA形成1∶1稳定复合物;考察不同温度和酸度下的猝灭作用,进一步证实其静态猝灭行为和疏水作用机制。紫外吸收光谱和同步荧光光谱表明,相互作用引起HSA构象变化,而同步荧光光谱提示结合位点更接近于色氨酸。

三种查尔酮类化合物与人血清白蛋白相互作用及其构效关系研究

在模拟人体生理条件下,采用紫外光谱法、荧光光谱法和同步荧光光谱法研究查尔酮、4′-甲氧基查尔酮和4′-氯查尔酮与人血清白蛋白(HSA)的相互作用及其构效关系。实验表明:三种查尔酮类化合物对HSA的荧光猝灭机制主要为静态猝灭,与HSA均形成1∶1复合物,结合常数K分别为2.50×104、0.697×104和0.277×104 L.moL-1,结合距离r分别为3.78、3.93和4.25nm,其作用力均以氢键和范德华力为主。查尔酮类化合物中取代基的不同对其与HSA的结合产生影响,其作用力大小依次为查尔酮>4′-甲氧基查尔酮>4′-氯查尔酮。