离子缔合物二级散射光谱的分析应用: 硒(IV)-碘化物-罗丹明B体系

从硒(IV)-碘化物-罗丹明B反应体系的研究中, 发现了离子缔合物水溶液的两种二级散射光谱现象。研究了它们的光谱特征、影响因素和适宜条件, 确定了二级散射强度与溶液中离子缔合物浓度的关系, 提出了利用二级散射光谱测定痕量硒的高灵敏分析方法。对反应机理和二级散射变化的原因也进行了初步的探讨。     

离子缔合物二级散射光谱的分析应用——Ⅰ.硒(Ⅳ)-碘化物-罗丹明B体系

从硒(Ⅳ)-碘化物-罗丹明B反应体系的研究中,发现了离子缔合物水溶液的两种二级散射光谱现象.研究了它们的光谱特征、影响因素和适宜条件,确定了二级散射强度与溶液中离子缔合物浓度的关系,提出了利用二级散射光谱测定痕量硒的高灵敏分析方法.对反应机理和二级散射变化的原因也进行了初步的探讨     

离子缔合物二级散射光谱的分析应用2: 汞(II)-硫氰酸盐-感性三芳基甲烷染料体系

研究了[Hg(SCN)4]^2^1与结晶紫、孔雀石绿、亮绿或碘绿等碱性三芳基甲烷染料的离子缔合配合物的二级散射(DS)和"反二级散射"(ADS)光谱, 以及这类散射光谱的特征、影响因素和反应的适宜条件。确定了散射光强度与溶液中汞(II)浓度的关系。提出了用二级散射光谱测定痕量汞的新的高灵敏分析方法, 并对反应机理和两种二级散射发生变化的原因作了初步的讨论。     

离子缔合物二级散射光谱的分析应用——Ⅱ.汞(Ⅱ)-硫氰酸盐-碱性三芳基甲烷染料体系

研究了[Hg(SCN)_4]~(2-)与结晶紫、孔雀石绿、亮绿或碘绿等碱性三芳基甲烷染料的离子缔合配合物的二级散射(DS)和“反二级散射”(ADS)光谱,以及这类散射光谱的特征、影响因素和反应的适宜条件.确定了散射光强度与溶液中汞(Ⅱ)浓度的关系.提出了用二级散射光谱测定痕量汞的新的高灵敏分析方法,并对反应机理和两种二级散射发生变化的原因作了初步的讨论.     

阳离子表面活性剂-曙红Y体系的二级散射光谱及其在分析化学上的应用

本文研究了阳离子表面活性剂（C－sf）与曙红Y离子缔合物的二级散射和“反二级散射”光谱．考察了它们的光谱特征,影响因素和适宜条件,提出用二级散射光谱法测定痕量c－sf的新的高灵敏度分析方法。     

阴离子表面活性剂-健那绿体系的二级散射光谱及其分析应用

建立了二级散射光谱法测定阴离子表面活性剂的新方法。研究了阴离子表面活性剂SDBS与健那绿离子缔合物的二级散射和"反二级散射"光谱。结果表明:当λem=340nm,λex=680nm时,在0～50μg mL质量浓度范围内,ΔIFDS与溶液中物质的质量浓度成正比,线性相关系数为0.9988,检出限为17.4ng mL。     

硒(Ⅳ)-硫氰酸钾-甲基紫萃取光度法测定痕量硒

研究了硒(Ⅳ)与硫氰酸钾和甲基紫(MV)的显色反应,发现在pH=1.85的HCl介质中,[Se(SCN)_6)~(2-)与MV形成不溶解于水的三元离子缔合物,该缔合物可溶解于苯等有机溶剂,在苯溶液中,该缔合物的最大吸收峰位于600nm处,其摩尔吸光系数为1.18×10~5L/(mol·cm),硒(Ⅳ)浓度在0.0～6.0μg/25mL范围内符合比耳定律。该方法应用于合成水样和环境水样中硒的测定,结果准确、可靠。     

烟碱-磷钼杂多酸缔合微粒体系的光谱研究及分析应用

采用分光光度法和共振散射光谱法研究了小烟碱一磷钼杂多酸缔合微粒体系．在波长300～800nm范围内,波长愈短缔合微粒体系的吸光度值愈大,在400nm处的吸光度与烟碱浓度在0．50-50．0μg／mL范围成良好线性关系,检出限(3σ)为0．1μg／mL．据此建立了一个测定烟草中烟碱含量的分光光度法．该法灵敏、简便、快速、准确、重复性好,平均回收率为99％～103％,相对标准偏差RSD为0．9％～1．3％．共振散射光谱研究结果表明,该体系存在烟碱-磷钼杂多酸缔合微粒,该微粒在420nm处存在共振散射效应．     

小檗碱-Ⅰ3^-缔合微粒体系的光度分析应用

在稀HCl介质中,I-3在340 nm处有一吸收峰;当小檗碱(BB)与I-3共存时体系呈橙黄色,在580 nm处产生一共振散射峰.以试剂作参比,该缔合微粒体系在530 nm产生一吸收峰,BB浓度在0～7.0×10-5mol/L范围内与A530 nm呈线性,据此建立了一种测定小檗碱含量的分光光度新方法,并用于针剂样品中小檗碱测定,结果满意.同步散射光谱研究表明,BB+与I-3可通过静电引力作用形成疏水性的(I3-BB)缔合物分子,并进一步聚集形成稳定的(I3-BB)n缔合纳米微粒.由于该缔合纳米微粒在580 nm处产生共振散射效应,故体系呈橙黄色.     

硫氰酸盐-乙基紫-阿拉伯树胶体系吸光光度法测定痕量硒

在0.50～0.58mol·L~(-1)硫酸溶液中,在阿拉伯树胶存在下,Se(Ⅳ)与硫氰酸盐,乙基紫形成可溶性离子缔合物。此缔合物在波长620nm处有最大吸收,表观摩尔吸光系数(?)为4×10~(?),硒含量在0～4.0μg/25ml范围内服从比耳定律。研究了形成离子缔合物的最佳条件和共存离子的影响,方法用于水样和人发样中痕量硒的测定,结果满意     

绿色银纳米粒子的共振散射光谱研究

以柠檬酸钠作光还原剂,采用紫外光-可见光二步光化学法制备了绿色银纳米离子,在399.4nm和691.5nm处有二个紫外-可见吸收峰;在340nm,470nm和520nm处有三个共振散射峰,从超分子和纳米粒子这一整体出发,探讨了共振散射光谱产生的原因及银超分子光反应机理。     

Spectrophotometric determination of trace amounts of selenium with catalytic reduction of bromate by hydrazine in hydrochloric acid media

A method is presented for the determination of selenium, based on the catalytic effect of selenium(IV) on the reduction reaction of BrO(-)(3) by N(2)H(4).2HCl. The decolourization of Methyl Orange by the reaction products was used to monitor the reaction spectrophotometrically at 525 nm. This method is precise, highly sensitive, simple, rapid, widely applicable and selective for the determination of selenium(IV) and total selenium. The variables which affected the reaction rate were fully investigated and the optimum conditions were established. Selenium, as low as 1 ng/ml, can be determined by this method. The relative standard deviation of 20 ng of selenium was 0.94% (N = 10). The method was applied to the determination of Se(IV) in a health-care product.     

Frequency doubling scattering and second-order scattering spectra of phosphato-molybdate heteropoly acid-protein system and their analytical application

In the sulfuric acid medium, the reaction of heteropoly compounds with proteins could result in the enhancement of frequency doubling scattering (FDS) and second-order scattering (SOS). Based on the characteristic, a novel method for the determination of trace amounts of protein by using the FDS and SOS method has been developed. Their maximum scattering wavelengths, lambda(ex)/lambda(em), appear at 940/470 nm for FDS and 350/700 nm for SOS, respectively. In a certain range, the concentration of proteins is directly proportional to the enhanced intensity of FDS and SOS. The suitable reaction conditions, affecting factors as well as the influence of some coexisiting substances were investigated. The methods exhibited high sensitivity, and the detection limits were in the range of 8.6-39.3 ng ml(-1) depending on different methods. The method had good selectivity, and was applied to the determination of protein in synthetic samples and practical samples with satisfactory results.     

降解裙带菜多糖对纳米硒的形成与稳定作用

在常温下的降解裙带菜多糖(Degraded Undaria Pinnatifida Charv. Suringer polysaccharide, DUP)水溶液中, 由适当过量的抗坏血酸(Vc)与二氧化硒(SeO2)反应制备纳米单质硒(Se0). 通过共振瑞利散射、激光散射和透射电镜(TEM)研究了DUP对Se0粒径的调控和在液相中的稳定作用. 结果表明, DUP通过控制还原速度和表面修饰而把Se0粒子调节在较窄的粒径分布范围内当Se0浓度为0.0507—3.245 mmol/L时, DUP表面修饰的球状纳米硒的平均粒径稳定地保持在24—65 nm范围内, 4 ℃时可在水溶液中稳定保存1个月.     

Anion-exchange resin modified with bismuthiol-II, as a new functional resin for the selective collection of selenium(IV)

A functional resin for the collection of selenium(IV) has been prepared simply by the conversion of a common ion-exchange resin with bismuthiol-II which has three functional properties, namely the capabilities of selective reaction with selenium(IV), ion-exchange reaction with ion-exchange resin and strong physical sorption to the ion-exchange resin matrix. The binding ratio of selenium(IV) to bismuthiol-II on the resin was confirmed to be 1:4. The reaction was represented as follows: 4RSH + H(2)SeO(3)--> R-S-Se-S-R + R-S-S-R + 3H(2)O. Highly selective sorption of selenium(IV) was achieved, based on the formation of stable selenotrisulphide on the resin. Selenium(IV) sorbed on bismuthiol-II resin was eluted effectively with 8-13M nitric acid or some thiols, such as cysteine and penicillamine. In the cases of thiols, the elution of selenium was found to be also based on the formation of selenotrisulphide, and the bismuthiol-II resin was regenerated. Satisfactory results were obtained when this resin was applied to the determination of selenium(IV) in river, estuarine or sea water samples.     

Catalytic resonance scattering spectral method for the determination of trace amounts of Se

A new catalytic kinetic method has been proposed for the determination of Se from 8.0x10(-9) to 8.0x10(-8) M, using the fact that Se(IV) can catalyze the slow reaction between KClO(3) and phenylhydrazine sulfate (PH) in 0.1 M H(2)SO(4) solution at 100 degrees C. The reduction product of ClO(3)(-), Cl(-), reacts with Ag(+) to form (AgCl)(n) nanoparticles. The nanoparticles exhibit a maximum resonance scattering spectral peak at 470 nm. The intensity of resonance scattering light at 470 nm is linear with respect to the Se concentration, using the fixed-reaction time procedure. The factors influencing the determination of Se were examined. This catalytic resonance scattering spectral method has been applied to the analysis of Se in real samples, with satisfactory results.     

Resonance Rayleigh scattering spectra, non-linear scattering spectra of tetracaine hydrochloride-erythrosin system and its analytical application

The interaction between erythrosine (ET) and tetracaine hydrochloride (TA) was studied by resonance Rayleigh scattering (RRS), frequency doubling scattering (FDS) and second-order scattering (SOS) combining with absorption spectrum. In a weak acidic medium of Britton-Robinson (BR) buffer solution of pH 4.5, erythrosine reacted with tetracaine hydrochloride to form 1:1 ion-association complex. As a result, the new spectra of RRS, SOS and FDS appeared and their intensities enhanced greatly. The maximum peaks of RRS, SOS and FDS were at 342 nm, 680 nm and 380 nm, respectively. The intensities of the three scattering were directly proportional to the concentration of TA in the range of 0.008-4.2 microg mL(-1) for RRS, 0.027-4.2 microg mL(-1) for SOS and 0.041-4.2 microg mL(-1) for FDS. The methods had very high sensitivities and good selectivities, and the detection limits were 0.003 microg mL(-1) for RRS, 0.008 microg mL(-1) for SOS and 0.012 microg mL(-1) for FDS, respectively. Therefore, a new method was developed to determinate trace amounts of TA. The recovery for the determination of TA in blood serum and urine samples was between 97.0% and 103.8%. In this study, mean polarizability was calculated by AM1 quantum chemistry method. In addition, the reasons for the enhancement of scattering spectra and the energy transfer between absorption, fluorescence and RRS were discussed.     

Absorption and Rayleigh scattering and resonance Rayleigh scattering spectra of [HgX<Subscript>2</Subscript>]<Subscript>n</Subscript> nanoparticles

The composition and existing species ot the reaction production ot Hg ana X (X= Cl, Br and I) under different conditions, and their absorption, Rayleigh scattering (RS) and resonance Rayleigh scattering (RRS) spectra have been studied. The results show that the products exist in the form of nanoparticles as [HgX2]n aggregates under suitable conditions, and their average diameters increase with the increase of X- diameters. The diameters of [HgCI2]n, [HgBr2]n and [Hgl2]n are less than 4 nm, equal to 9 nm and 70 nm respectively. There are bathchromic shifts gradually with the increase of X- diameters in their absorption spectra. The absorption bands of [HgCI2]n and [HgBr2]n locate at ultraviolet region. However, the absorption band of [Hgl2]n is obvious in visible light region. Among three particles, only [Hgl2]n exhibits a strong RRS and its scattering peak is at 580 nm. The main reasons leading to the enhancement of resonance scattering are the large size of nanoparticle, the formation of the interface     

A combined spectroscopic and light scattering study of hydrolysis of uranium(VI) leading to colloid formation in aqueous solutions

This study mainly focuses hydrolysis reactions of uranium(VI) under an ambient atmosphere leading to colloid formation in near neutral solution using light scattering, UV–Vis and FTIR-ATR studies. UV–Vis and IR spectrum was recorded for uranyl solution at different pH range. U(VI) hydrolyzed colloids were detected and it was confirmed by the appearance of a band at 941 cm^?1 in the IR spectra. Light scattering measurements were performed on colloidal U(VI) solutions formed at pH range of 7–8. The average particle diameter was determined as 32–36 nm using dynamic light scattering. Well defined colloidal species are formed with no considerable change in particle size with increasing U(VI) concentration. The weight average molecular weight of colloidal species was predicted as 763 Da by Debye plot. The second virial coefficient (A₂) was found to be ?0.1139 ml g^?1 Da. The present study confirms that behaviour of U(VI) contradicts conventional Zr(IV), Th(IV) and Pu(IV) solution chemistry. U(VI) polymerization is less extensive and in neutral solutions it forms only oligomers with 2–3 uranyl units.