共振瑞利散射法测定硫氰酸盐—碱性三苯甲烷染料体系中？…

研究了钼（Ｖ）与硫氰酸盐和结晶紫，乙基紫，孔雀石绿，亮绿及碘绿等５种碱性三苯甲烷染料形成离子缔合配合物的共振瑞利散射光谱，考察了它们的光谱特征，影响因素和适宜的反应条件，确定了共振瑞利散射强度与钼（Ｖ）浓度之间的关系，方法灵敏度高，不同体系对钼的检出限在２．１～１２．０μｇ／Ｌ之间，提出了用共振瑞利散射测定钼的新分析方法，将其用于钢铁中痕量钼的测定获得满意的结果。     

砷(Ⅴ)—钼酸铵—碘绿的共振瑞利散射光谱及其应用研究

研究了砷(Ⅴ)-钼酸铵-碘绿体系的共振瑞利散射光谱特性。在硫酸介质中,砷(Ⅴ)与钼酸反应生成砷钼杂多酸大阴离子,其与阳离子染料碘绿结合形成离子缔合配合物,导致体系共振瑞利散射光剧烈增强,据此建立了共振瑞利散射分析法测定砷(Ⅴ)的新方法。方法的线性范围为0.01~0.40μg/mL,检出限1.5μg/L。RSD为2.55%、1.86%,样品加标回收率为95.5%~104.3%。该法简便快速,用于测定化妆品中微量砷,结果满意。     

结晶紫-苯唑西林的共振瑞利散射光谱及应用

在pH 8.71的Tris-HCI缓冲介质中,结晶紫(CV)与苯唑西林(OXA)结合,使体系的共振瑞利散射(RRS)急剧增强并出现新的RRS光谱,最大共振瑞利散射峰位于380nm处,苯唑西林的浓度在0.08～0.8μg·mL-1范围内与散射强度(△1RRS)成良好的线性关系,据此建立了测定苯唑西林的共振瑞利散射法,检出...     

溴代十六烷基吡啶增敏共振瑞利散射法测定药物中的维生素B_1含量

在pH 6.38的三羟甲基氨基甲烷-盐酸缓冲溶液和溴代十六烷基吡啶存在下,维生素B_1与氯酚红结合生成的缔合物使共振瑞利散射显著增强并产生新的共振瑞利散射光谱,最大共振瑞利散射峰位于339nm处,维生素B_1的质量浓度在0.03~0.42mg·L~(-1)内与其对应的共振瑞利散射增强程度(ΔI/_(RRS))呈线性关系,检出限(3s/k)为0.004 2mg·L~(-1)。据此提出了溴代十六烷基吡啶增敏共振瑞利散射法测定药物中的维生素B_1的方法。应用此方法分析了维生素B_1药物,加标回收率在99.2%~102%之间,测定值的相对标准偏差(n=6)在2.1%~2.5%之间。     

双波长共振瑞利散射法测定皮蛋中的汞

建立了测定皮蛋中Hg的双波长共振瑞利散射新方法,研究了共振瑞利散射的光谱特征、共存物质的影响及反应机理。在pH 6.58的Tris-HCl缓冲介质中,Hg(Ⅱ)与快绿-溴代十六烷基吡啶结合生成三元络合物,使体系的双波长-共振瑞利散射(DWO-RRS)光谱显著增强,最大和次大的共振瑞利散射峰分别位于344 nm和470 nm波长处。当用双波长-共振瑞利散射(DWO-RRS)法测定时,Hg(Ⅱ)的质量浓度在0.005~0.50 mg/L范围内与体系的共振瑞利散射增强强度△I_(RRS)呈线性关系,检出限(3σ/S)为1.4 ng/mL,定量限为0.034 mg/kg。方法用于皮蛋中Hg的测定,回收率为98.2%~102%,相对标准偏差(n=5)为2.1%~2.7%。     

三元缔合-共振瑞利散射测定奶粉中的Ca

建立了快速、准确测定奶粉中Ca的共振瑞利散射方法。在弱酸性Tris-盐酸介质中,Ca(Ⅱ)和表面活性剂十六烷基三甲基溴化铵与刚果红反应生成一种红色的三元离子缔合物,使共振瑞利散射(RRS)信号明显增强,并产生新光谱。最大共振瑞利散射峰位于371 nm,Ca(Ⅱ)的质量浓度在0. 004~0. 80 mg·L~(-1)范围内与体系的共振瑞利散射增强强度ΔIRRS呈线性关系,检出限为3. 1 ng·mL~(-1)。方法用于奶粉中Ca的测定,结果满意。     

锑(Ⅲ)-碘化钾-若丹明B体系共振瑞利散射光谱法测定痕量锑

在稀硫酸和聚乙烯醇介质中,锑(Ⅲ)与碘离子的配阴离子和若丹明B染料形成的三元缔合物具有共振瑞利散射光谱,其最强共振瑞利散射峰位于623nm处。锑(Ⅲ)离子浓度在2.000×10-7mol/L~2.560×10-6mol/L范围内呈良好的线性关系,检测限为1.9×10-9mol/L。基于共振瑞利散射峰的增强,建立了测定痕量锑(Ⅲ)的共振瑞利散射方法,用于水样中锑的测定。     

锑(Ⅲ)-碘化钾-罗丹明B体系共振瑞利散射光谱法测定痕量锑

在稀硫酸和聚乙烯醇介质中,锑(Ⅲ)与碘离子的配阴离子和若丹明B染料形成的三元缔合物具有共振瑞利散射光谱,其最强共振瑞利散射峰位于623nm处。锑(Ⅲ)离子浓度在2.000×10-7mol/L~2.560×10-6mol/L范围内呈良好的线性关系,检测限为1.9×10-9mol/L。基于共振瑞利散射峰的增强,建立了测定痕量锑(Ⅲ)的共振瑞利散射方法,用于水样中锑的测定。     

盐酸吖啶黄-脱氧核糖核酸反应体系的共振瑞利散射及其应用

研究了盐酸吖啶黄与脱氧核糖核酸(DNA)之间的共振瑞利散射(RRS)增强作用,提出了共振瑞利散射技术测定核酸的方法。在pH 6.4的B-R缓冲溶液中,盐酸吖啶黄与脱氧核糖核酸结合使溶液共振瑞利散射强度增强,其最大散射峰位于505 nm处,而在330 nm波长处有一稍弱的散射峰。DNA质量浓度在0.04~0.80 mg.L-1范围内,与RRS强度呈线性关系,检出限(3S/N)为0.023 mg.L-1。应用于测定合成样品中DNA含量并测得回收率为98.0%~104.0%。初步探讨了反应机理,盐酸吖啶黄与DNA间的相互作用包含有静电引力、π-π堆积力。     

锌(Ⅱ)-硫氰酸盐-中性红体系共振瑞利散射法测定痕量锌

在pH 5.1的HAc-NaAc缓冲溶液中,聚乙烯醇存在下,Zn(Ⅱ)和硫氰酸盐形成的配阴离子[Zn(SCN)4]2-与中性红阳离子结合形成的离子缔合物具有共振瑞利散射光谱,其最强共振瑞利散射峰位于594.5 nm处。基于共振瑞利散射峰的增强,建立了测定痕量Zn(Ⅱ)的共振瑞利散射方法。Zn2+质量浓度在0~0.5μg/mL范围内呈良好的线性关系,检出限为1.9×10-5μg/mL。方法已用于水样中Zn2+的测定。     

Resonance Rayleigh scattering method for the determination of trace amounts of cadmium with iodide-basic triphenylmethane dye systems

In dilute phosphoric acid solution, cadmium (II) reacts with a large excess of I- to form [CdI4]2- which reacts further with basic triphenylmethane dyes such as crystal violet (CV), ethyl violet (EV), methyl violet (MV), brilliant green (BG) or malachite green (MG) to form an ion-association complex. This results in a significant enhancement of resonance Rayleigh scattering (RRS) intensity and the appearance of new RRS spectra. The characteristics of RRS spectra of the ion-association complexes, the influencing factors and the optimum conditions of these reactions have been investigated. The intensity of RRS is directly proportional to the concentration of cadmium from 0 to 60 ng mL(-1) for EV and MV systems, 0 to 80 ng mL(-1) for CV system, and 0 to 100 ng mL(-1) for BG and MG systems. The methods exhibit high sensitivities and the detection limits for cadmium are between 0.35 and 2.00 ng mL(-1) depending on the different reaction systems. The new RRS method was applied to the direct determination of traces of cadmium in pure zinc and synthetic water samples.     

The interaction between furosemide-palladium (II) chelate and basic triphenylmethane dyes by resonance Rayleigh scattering spectra and resonance non-linear scattering spectra and their analytical applications

In pH 4.5–7.0 Britton-Robinson buffer solution, furosemide (FUR) reacted with Pd (II) to form a 1:1 anionic chelate. This chelate could further react with such basic triphenylmethane dyes (BTPMD) as ethyl violet (EV), crystal violet (CV), methyl violet (MV), methyl green (MeG) and brilliant green (BG) to form 1:1 ion-association complexes. This not only resulted in the change of absorption spectra, but also led to the significant enhancement of resonance Rayleigh scattering (RRS), second-order scattering (SOS) and frequency doubling scattering (FDS). The maximum RRS wavelengths were located at 324 nm for the EV, CV and MV system, and 340 nm for the BG and MeG system. The maximum SOS wavelengths were located at 550 nm for the EV, CV, BG and MeG system, and 530 nm for the MV system. The maximum scattering peaks of all the systems were at 392 nm for FDS. The enhanced RRS, SOS and FDS intensities were directly proportional to the concentration of FUR. The detection limits for the different dye systems were 0.3–4.9 ng mL^?1 for the RRS method, 3.2–33.1 ng mL^?1 for the SOS method and 9.0–85.7 ng mL^?1 for the FDS method. These methods could be used for the determination of trace amounts of FUR. The effects of the formation of ternary ion-association complexes on the spectral characteristics and intensities of absorption, RRS, SOS and FDS have been investigated. The optimum conditions of these reactions, the influencing factors and the analytical properties have been tested. The influences of coexisting substances were tested by RRS method and the results showed that this method exhibited a high sensitivity. Based on the aforementioned research, the highly sensitive, simple and rapid methods for the determination of trace amounts of FUR by resonance light scattering technique have been established, which could be applied to the determination of FUR in tablet, injection, human serum and urine samples. The composition and structure of the ternary ion-association complex and the reaction mechanism were discussed.     

Resonance Rayleigh scattering method for the determination of trace amounts of cadmium with iodide-basic triphenylmethane dye systems

In dilute phosphoric acid solution, cadmium (II) reacts with a large excess of I^– to form [CdI₄]^2– which reacts further with basic triphenylmethane dyes such as crystal violet (CV), ethyl violet (EV), methyl violet (MV), brilliant green (BG) or malachite green (MG) to form an ion-association complex. This results in a significant enhancement of resonance Rayleigh scattering (RRS) intensity and the appearance of new RRS spectra. The characteristics of RRS spectra of the ion-association complexes, the influencing factors and the optimum conditions of these reactions have been investigated. The intensity of RRS is directly proportional to the concentration of cadmium from ¶0 to 60 ng mL^–1 for EV and MV systems, 0 to 80 ng mL^–1 for CV system, and 0 to 100 ng mL^–1 for BG and MG systems. The methods exhibit high sensitivities and the detection limits for cadmium are between 0.35 and 2.00 ng mL^–1 depending on the different reaction systems. The new RRS method was applied to the direct determination of traces of cadmium in pure zinc and synthetic water samples.     

HgCl2-头孢噻肟螯合阴离子与碱性三苯甲烷类染料相互作用的共振瑞利散射光谱及其分析应用

在pH为5.3～6.8的Britton-Robinson(BR) 缓冲溶液中, 头孢噻肟钠(CFTM)与HgCl2形成摩尔比为1∶1的螯合阴离子, 它能进一步与结晶紫、甲基紫、乙基紫、亮绿、碘绿、甲基绿和孔雀石绿等碱性三苯甲烷类染料反应形成三元离子缔合物, 导致共振瑞利散射(RRS)的显著增强. 最大RRS峰分别位于367, 367, 340, 367, 340, 340和340 nm附近, 在一定的CFFM质量浓度范围内散射强度与头孢噻肟钠的浓度均呈良好的线性关系. 用结晶紫、甲基紫、乙基紫、亮绿、碘绿、甲基绿和孔雀石绿体系测定头孢噻肟钠的线性范围和检出限(3σ) 分别为0.0090～3.5 μg/mL和2.7 ng/mL, 0.0092～3.5 μg/mL和2.8 ng/mL, 0.013～3.5 μg/mL和4.0 ng/mL, 0.010～3.5 μg/mL和3.1 ng/mL, 0.011～3.5 μg/mL和3.4 ng/mL, 0.012～4.0 μg/mL和3.5 ng/mL以及0.016～3.5 μg/mL和4.7 ng/mL, 其中以结晶紫体系灵敏度最高. 研究了适宜的反应条件和影响因素, 对离子缔合物的组成和离子缔合反应机理进行了探讨, 考察了共存物质的影响, 表明方法有良好的选择性, 据此发展了用HgCl2和碱性三苯甲烷类染料的灵敏、简便、快速测定痕量头孢噻肟钠的新方法.     

某些碱性三苯甲烷染料共振瑞利散射法测苯唑西林

在NaOH 溶液中,苯唑西林（OXA）能与某些碱性三苯甲烷染料如甲基紫（MV）、乙基紫（EV）和孔雀石绿（MG）结合,使体系的共振瑞利散射（RRS）急剧增强并产生新的RRS光谱,最大共振光散射峰分别位于333 nm(MV体系)、342 nm(EV体系)和343 nm（MG体系）,苯唑西林的质量浓度在0.080～0.60 mg/L(MV体系)、0.040～0.40 mg/L(EV体系和MG体系)时与散射强度呈良好的线性关系,检出限（3σ）分别为0.064 mg/L(MV体系)、0.024 mg/L(EV体系)和0.013 mg/L(MG体系),其中以孔雀石绿体系最灵敏,以其为例考察了共存物质的影响。 结果表明,方法具有较高的选择性,用于人血清、人尿及市售药物中苯唑西林的测定,结果满意。     

呋塞米-Pd(Ⅱ)螯合物与某些碱性三苯甲烷类染料相互作用的共振瑞利散射和共振非线性散射光谱及其分析应用

在pH4.5～7.0的Britton-Robinson(BR)缓冲溶液中,呋塞米(FUR)与Pd(Ⅱ)形成1:1的螯合阴离子,它能进一步与乙基紫(EV)、结晶紫(CV)、甲基绿(MeG)、亮绿(BG)、甲基紫(MV)等碱性三苯甲烷染料(BTPMD)阳离子通过静电引力和疏水作用形成FUR:Pd(II):BTPMD为1:1:1的离子缔合物.此时,该离子缔合反应不仅能引起吸收光谱的变化,而且更能导致共振瑞利散射(RRS)、二级散射(SOS)和倍频散射(FDS)的显著增强,其最大RRS波长分别位于324nm(EV,CV和MV体系)和340nm(BG和MeG体系),最大SOS波长分别位于550nm(EV,CV,BG和MeG体系)和530nm(MV体系),而最大FDS波长均位于392nm附近.在一定条件下三种散射增强(ΔIRRS,ΔISOS和ΔIFDS)均与呋塞米(FUR)的浓度成正比.对不同染料体系,三种方法对FUR的检出限分别在0.3～4.9ng/mL(RRS),3.2～33.1ng/mL(SOS)和9.0～85.7ng/mL(FDS)之间,均可用于痕量FUR的测定.本文研究了三元离子缔合物的形成对吸收,RRS,SOS和FDS光谱特征和强度的影响,考察了适宜的反应条件、影响因素和分析化学性质,并以RRS法为例考察了共存物质的影响.据此提出了一种高灵敏度、简便、快速测定FUR的共振光散射新方法,将其用于片剂、注射液、人血清和尿样中FUR的测定,结果满意.文中还对三元离子缔合物的组成、结构和反应机理进行了讨论.     

甲基紫硫酸软骨素共振瑞利散射光谱及其应用

在Britton-Robinson缓冲介质(pH9.37)中硫酸软骨素与甲基紫反应形成离子缔合物时,共振瑞利散射(RRS)强度会明显增强,其最大RRS峰位于505和661 nm处。本文对反应的最佳条件、影响因素、硫酸软骨素浓度与RRS强度的关系进行了研究,建立起一种快速、简便、灵敏的测定硫酸软骨素的方法。本法在661和505 nm测定波长处的线性范围均为:0.15~0.90 mg/L,其检出限分别为0.019 mg/L(505 nm)和0.043mg/L(661 nm)。该法应用于针剂中硫酸软骨素的测定,结果满意。     

A novel and sensitive method for recognition and indirect determination of Al(III) in biological fluid based on the quenching of resonance Rayleigh scattering intensities of "Al(III)-EV-DNA" complexing system

A novel method for recognition and indirect determination of Al(III) by using biological molecules has been established based on the quenching of RRS intensity. In the weak acidic medium, the reaction of ethyl violet (EV) and DNA would result in great enhancement of RRS intensity. However, the presence of Al(III) would lead to the decrease of the RRS intensity owing to the competition coordination of Al with DNA. The decreased intensity of RRS is directly proportional to the concentration of Al(III) in the range of (0.1-2.5)x10(-6) and (0.30-4.5)x10(-5)M, respectively. The method has high sensitivity and its detection limit (3sigma) is 3.6x10(-8)M. The characteristics of RRS spectra of the system, the optimum conditions of the reaction, and the reaction mechanism have been investigated. The method can recognize Al(III) selectively owing to its strong binding to the phosphate backbone of DNA, and has been applied to the determination of Al(III) concentration in synthetic biological samples with satisfactory results. Therefore, the proposed method is promising as an effective means for selective recognition and sensitive determination in situ of Al(III). Furthermore, this study would contribute to further understanding of the biological significance of Al neurotoxicity.     

6-苄氨基腺嘌呤-Cu(Ⅱ) -三苯甲烷类染料体系的吸收和共振瑞利散射光谱及其分析应用

在pH值为5.37～5.58的HAc-NaAc缓冲溶液中,6-苄氨基嘌呤(6-BA)能与Cu(Ⅱ)反应生成螯合物[6-BA·Cu]2+,可再与三苯甲烷类染料形成三元离子缔合物,其摩尔比分别为2∶1(里斯沙明绿)、3∶1(固绿)和2.5∶1(水溶性苯胺蓝).反应体系的吸收光谱发生变化,其共振瑞利散射光谱(RRS)和倍频散射(FDS)显著增强,3个体系的最大RRS峰均位于372 nm附近,6-BA浓度在一定范围内的增加与相应的RRS强度( △IRRs)、FDS( △IFDS)强度和吸光度(△A)均呈线性关系.其RRS检出限分别为5.48 μg/L(里斯沙明绿)、18.43 μg/L(固绿)和9.34 μg/L(水溶性苯胺蓝).据此建立6-BA-Cu(Ⅱ)-里斯沙明绿染料体系测定痕量6-BA的RRS法,并用于豆芽中6-BA的快速测定,结果令人满意.此外,还应用计算化学软件Gaussview3.07和Gaussian03W,采用密度泛函法,在B3 LYP/6 -31G基组水平上计算6-BA的电荷分布,并对里斯沙明绿体系的反应机理及RRS增强的主要原因进行了初步探讨.     

秋水仙碱水解产物与某些酸性磺酞类染料相互作用的 共振瑞利散射光谱及其分析应用

在pH 2.9～4.6 Britton-Robinson (BR)缓冲溶液中, 秋水仙碱的水解产物(H-COL)能与溴酚蓝(BPB)、溴甲酚绿(BCG)、溴百里酚蓝(BTB)和百里酚蓝(TB)等酸性磺酞类染料(ASPD)反应形成1∶1的离子缔合物, 此时将引起共振瑞利散射(RRS)的急剧增强, 并产生新的RRS光谱. 秋水仙碱水解产物与溴酚蓝、溴甲酚绿、溴百里酚蓝和百里酚蓝形成离子缔合物的最大散射波长分别位于327, 311, 305和306 nm处. 散射增强(ΔI)与秋水仙碱浓度在一定范围内成正比, 不同体系对于秋水仙碱的检出限(3σ)分别为12.3, 15.1, 16.4和20.0 ng•mL－1 (TB). 研究了适宜的反应条件, 考察了共存物质的影响, 表明方法有较好的选择性. 基于秋水仙碱水解产物与酸性磺酞类染料离子缔合物的反应, 发展了一种较灵敏, 且简便、快捷测定秋水仙碱的新方法. 方法用于片剂、黄花、血清和尿样中秋水仙碱的测定, 获得了满意的结果.