【作者】 康彩艳；

【导师】 奚旦立； 蒋治良；

【作者基本信息】 东华大学 ， 环境工程， 2007， 博士

【摘要】 采用荧光分光光度计同步扫描技术建立的共振瑞利散射（RRS）光谱是一种高灵敏的简便的可获得较宽频率范围瑞利散射信号的光谱新技术,近年来,已引起分析工作者的广泛兴趣和关注,国内外研究和应用日益增多,已用于生物大分子和痕量无机、有机和药物分析研究等,它在环境分析领域的应用也很活跃,但对于水处理剂氯、二氧化氯及其副产物的分析研究尚未涉及。因此,建立一种灵敏度高、选择性好、简便快速测定饮用水中氯、二氧化氯及其副产物含量的方法具有重要的意义。本文利用共振瑞利散射光谱、荧光光谱、紫外-可见吸收光谱,并结合透射电子显微镜、激光散射技术等研究了氯、二氧化氯、亚氯酸根与I^-、罗丹明染料、阳离子表面活性剂、银纳米微粒等的相互作用过程和机理,考察了它们的光谱特征、适宜的反应条件、影响因素,讨论了共振散射增强的原因,RRS光谱与吸收光谱的关系,建立了简便、快速、灵敏测定氯、二氧化氯、亚氯酸根的共振瑞利散射新方法。说明这一技术在ClO₂、Cl₂、ClO₂^-的研究和测定中具有很好的应用前景,也是共振散射在无机物分析应用中的一个新发展。此外,本文综述了氯、二氧化氯及氯氧化物分析研究进展,阐述了共振瑞利散射的理论基础、发展过程及其在科学研究中的应用和发展方向。本文主要研究内容及成果如下:1.痕量二氧化氯的罗丹明染料共振散射光谱分析在酸性介质中,ClO₂能氧化I^-为I₂,过量的I^-与I₂形成I₃^-,它分别能与罗丹明B（RhB）、丁基罗丹明B（b-RhB）、罗丹明6G（RhG）及罗丹明S（RhS）反应形成缔合微粒,显示较强的共振散射效应,最强共振散射峰均位于420nm处。ClO₂浓度分别在0.0056～0.787μg/mL、0.0034～0.396μg/mL、0.0057～0.795μg/mL和0.0052～0.313μg/mL范围内与各体系的共振散射光强度成线性关系。RhB、b-RhB、RhG及RhS体系的检测限分别为0.0011μg/mL、0.006μg/mL、0.0054μg/mL和0.0023μg/mL ClO₂。据此建立了测定ClO₂的罗丹明B缔合微粒共振散射光谱分析新法,用于饮用水中ClO₂的测定,灵敏度高、选择性和精密度好、结果满意。2.痕量氯的罗丹明染料共振散射光谱分析及应用在Na₂HPO₄-柠檬酸缓冲液中,Cl₂能氧化I^-为I₂,过量的I^-与I₂形成I₃^-,罗丹明B（RhB）、丁基罗丹明B（b-RhB）、罗丹明6G（RhG）及罗丹明S（RhS）分别能与I₃^-发生缔合,发生共振散射效应,共振强峰均在420 nm处出现。Cl₂浓度分别在0.008～1.74μg/mL、0.019～1.33μg/mL、0.021～2.11μg/mL和0.019～2.04μg/mL范围内与RhB、b-RhB、RhG及RhS缔合微粒体系的共振散射光强度成线性关系。各体系的检测限分别为0.0020μg/mL、0.0048μg/mL、0.0063μg/mL和0.0017μg/mL Cl₂。据此建立了测定Cl₂的分析法。其中罗丹明B体系最稳定,且灵敏度也高。用于饮用水中Cl₂的测定,并与光度法对照,结果满意。3.痕量亚氯酸根的罗丹明染料共振散射光谱分析及应用在乙酸钠-盐酸缓冲液中,亚氯酸根能氧化I^-为I₂,过量的I^-与I₂形成I₃^-,罗丹明B（RhB）、丁基罗丹明B（b-RhB）、罗丹明6G（RhG）及罗丹明S（RhS）分别能与I₃^-发生缔合,在400nm处产生共振散射效应。ClO₂^-浓度分别在0.00726-0.218μg/mL、0.0102～0.292μg/mL、0.00726～0.145μg/mL和0.0290～0.174μg/mL范围内与RhB、b-RhB、RhG及RhS缔合微粒体系的共振散射光强度成线性关系。各体系的检测限分别为0.00436μg/mL、0.00652μg/mL、0.0058μg/mL和0.0145μg/mL ClO₂^-。据此建立了测定ClO₂^-的分析法。其中罗丹明B体系最稳定,且灵敏度也高。用于水中ClO₂^-的测定,结果满意。4.痕量亚氯酸根的罗丹明缔合微粒荧光光谱分析在有KI存在的乙酸钠-HCl酸性缓冲溶液中,罗丹明B（RhB）、丁基罗丹明（b-RhB）、罗丹明6G（RhG）及罗丹明S（RhS）分别在580nm、580nm、550nm和5500nm处有一个荧光峰。当有ClO₂^-存在时,罗丹明染料荧光峰发生猝灭。考察了荧光光谱特征,影响因素和适宜的反应条件。对于RhB、b-RhB、RhG及RhS体系,亚氯酸根浓度分别在0.0218～0.51、0.0218～0.304、0.0728～1.092、0.051～0.51μg/ml范围内与荧光猝灭强度成线性关系,建立了一个简便灵敏的亚氯酸根荧光分析新方法,用于测定合成水样中ClO₂^-的分析,结果满意。5.罗丹明染料缔合微粒荧光光谱法分别测定痕量二氧化氯和亚氯酸根在HCl-NaAc或NH₃-NE₄Cl缓冲溶液中,罗丹明S（RhS）、罗丹明6G（RhG）、罗丹明B（RhB）及丁基罗丹明B（b-RhB）分别在550nm、550nm、576nm、576nm处产生一荧光峰。ClO₂在酸性或碱性缓冲液中均能氧化罗丹明染料使其退色、荧光峰降低;亚氯酸根离子仅在酸性溶液中氧化罗丹明染料。在碱性条件下可通过测定ClO₂产生的荧光猝灭强度选择性地测定ClO₂的含量;在酸性条件下可测量ClO₂与ClO₂^-共同产生的荧光猝灭强度,利用差减法可求出ClO₂^-的含量。对于RhS、RhG、RhB及b-RhB四体系,ClO₂浓度分别在0.00840～0.53μg/mL、0.0930～3.15μg/mL、0.215～2.610μg/mL及0.0825～1.096μg/mL范围内与四体系的荧光猝灭强度成线性关系;亚氯算根浓度分别在0.00950～0.711μg/mL、0.0940～2.36μg/mL、0.473～4.73μg/mL及0.473～2.36μg/mL范围内与四体系的荧光猝灭强度成线性关系。在四体系中,罗丹明S具有好的灵敏度和稳定性,因此选择罗丹明S体系测定ClO₂与ClO₂^-。据此,建立了分别测定ClO₂与ClO₂^-的罗丹明S荧光猝灭分析法,用于饮用水中ClO₂及ClO₂的测定,获得了满意的结果。6.痕量二氧化氯和亚氯酸根的阳离子表面活性剂体系缔合微粒共振散射光谱及分析应用在乙酸钠-盐酸缓冲液中,二氧化氯及亚氯酸根离子能氧化I^-为I₂,过量的I^-与I₂形成I₃^-,阳离子表面活性剂（CS）十四烷基二甲基苄基氯化铵（TDMBA）、溴代十四烷基吡啶（TPB）、十六烷基三甲基溴化铵（CTMAB）、四丁基碘化铵（TBAI）等分别能与I₃^-形成缔合物微粒,在320 nm、467 nm、480nm、530nm处产生共振散射效应。激光散射法测得（TDMBA-I₃）_n缔合物微粒的平均粒径为347 nm。ClO₂浓度分别在0.00992～0.546μg/mL、0.0102～1.024μg/mL、0.0269～0.538μg/mL和0.0178～1.095μg/mL范围内与TDMBA、TPB、CTMAB及TBAI缔合微粒体系在467nm处共振强度成线性关系,各体系的检测限分别为0.00593μg/mL、0.00600μg/mL、0.0198μg/mL和0.0645μg/mL ClO₂;ClO₂^-浓度分别在0.00948～0.664μg/mL、0.0170～1.706μg/mL、0.0474～0.855μg/mL和0.0237～1.138μg/mL范围内与TDMBA、TPB、CTMAB及TBAI缔合微粒体系的共振强度成线性关系。各体系的检测限分别为0.00610μg/mL、0.00819μg/mL、0.0378μg/mL和0.00949μg/mL ClO₂^-。其中TDMBA体系最稳定,且灵敏度较高,用于样品中ClO₂及ClO₂^-的测定。提供了一个新的研究方法,拓展了共振散射的应用。讨论了体系稳定性与分子结构的关系。7.银纳米微粒的等离子体共振散射（PRLS）及其在痕量二氧化氯分析中的应用在pH 9.1的NH₄NO₃^-NH₃·H₂O缓冲溶液中,银纳米微粒显示强的PRLS信号,特征峰位于470 nm,ClO₂能氧化银纳米微粒,导致PRLS发生猝灭。猝灭强度与ClO₂浓度在0.0011～0.185μg/mL范围内成线性关系,检测限（3σ）为0.00050μg/mL,相关系数0.9995,该法被应用于饮用水中ClO₂的测定,获得了满意的结果。利用激光散射、透射电镜技术、原子吸收光度法及显色剂对银纳米微粒及其与ClO₂的反应进行了表征,阐释了PRLS信号猝灭的原因,讨论了紫外-可见吸收光谱与PRLS光谱之间的关系,该法简便、快速、灵敏,是利用共振散射技术将金属纳米微粒探针应用于无机物分析的新尝试。8.银纳米微粒荧光猝灭法测定水中痕量二氧化氯在pH=9.1的NH₄Cl-NH₃·H₂O缓冲溶液中,银纳米微粒在470nm处产生一个荧光峰;它能被ClO₂氧化导致体系的荧光发生猝灭。ClO₂浓度在0.0011～0.185μg/mL范围内与荧光猝灭强度成良好的线性关系,检测限为0.0047μg/mL ClO₂。据此建立了测定ClO₂的荧光分析新方法,用于饮用水中ClO₂的测定,结果满意。更多还原

【Abstract】 Resonance Rayleigh scattering（RRS）spectrum is a new,sensitive and simple spectral technique.It can be obtained by the synchronous scanning technique on a fluorescence spectrophotometer.It brings to extensive attention and interesting in recent years and has been applied to determination of some biomacromolecules,trace inorganic,organic substances and pharmaceutical analysis,and also to the field of environmental analysis.However,up to now it is seldom applied to the study of water treatment chemical,Cl₂,ClO₂ and its by-products.It is very important to establish a simple,rapid,sensitive,selective method for determination of trace Cl₂, ClO₂ and its by-products.Therefore,in the dissertation,the reaction of ClO₂,Cl₂ and ClO₂^- with I^--rodamine dyes,sufactants and silver nanoparticles have been studied by resonance scattering spectra,fluorescence spectra,UV-Vis absorption spectra coupling with scanning electron microscope and laser scattering technology.Their spectral optimum reaction conditions, influencing factors and analytical applications have been examined.Furthermore,the reasons of RRS enhancement,the relationship between RRS spectra and absorption spectra are discussed. Some new,simple,convenient,rapid and sensitive RRS methods are proposed for the determination of ClO₂,Cl₂ and ClO₂^-.This is new development of the RRS technology used in the analytical application of the inorganics.In addition,the analytical methods of chlorine dioxide,chlorine and chlorite,the theory of resonance Rayleigh scattering and their applications were reviewed.The main contents and some conclusions of the dissertation are as follows:1.A Novel and Selective Resonance Scattering Spectral Method for the Determination of Trace ClO₂ Using Rhodamine DyeIn HCl-NaAc buffer solutions,ClO₂ oxidize I^- to form I₂ and then the excess I^- reacts with I₂ to form I₃^-.The I₃^- combine respectively with rhodamine dyes,including rhodamine B（RhB）,butyl rhodamine B（b-RhB）,rhodamine 6G（RhG）and rhodamine S（RhS）to form association particles which exhibit stronger resonance scattering effect at 420nm.The resonance scattering intensity for the system of RhB,bRhB,RhG and RhS at 420nm is proportional to chlorine dioxide concentrations in the range of 0.0056-0.787μg/mL,0.0034-0.396μg/mL,0.0057-0.795μg/mL and 0.0052- 0.313μg/mL,respectively.The detection limits of the systems were 0.0011μg/mL,0.006μg/mL, 0.0054μg/mL and 0.0023μg/mL ClO₂,respectively.A novel resonance scattering spectral（RSS） method for determination of chlorine dioxide has been proposed,based on the formation of association complex particles of RhB-I₃.This method has high sensitivity,good selectivity and precision,and has been used for the determination of ClO₂ in drinking water with satisfactory results.2.Resonance Rayleigh scattering spectral study of Cl₂ -KI- rodamine dyes and its analytical applicationsIn Na₂HPO₄-citric acid buffer solution,Cl₂ can oxidize I^- to form I₂ and then it reacts with excess I^- to form I₃^-.The I₃^- combines respectively with rhodamine dyes,including rhodamine B （RhB）,butyl rhodamine B（b-RhB）,rhodamine 6G（RhG）and rhodamine S（RhS）,to form association particles which give stronger resonance scattering（RS）effect at 400 nm.The RS intensity of the RhB,b-RhB,RhG and RhS systems is proportional to chlorine concentrations in the range of 0.008-1.74,0.019-1.33,0.021-2.11 and 0.019-2.04μg/mL Cl₂,respectively.The detection limits of the systems were 0.0020,0.0048,0.0063 and 0.0017μg/mL,respectively.In them,the RhB system has good stability and high sensitivity,and has been applied to the analysis of chlorine in drinking water,with satisfactory results which is in agreement with that of the methyl orange（MO）spectrophotometry.3.Resonance Rayleigh scattering spectrum of KI- ClO₂^- - rodamine dyes and its analytical applicationsIn acidic sodium acetate-HCl buffer solution containing KI,chlorite may oxidize I^- to form I₂,and then I₂ reacts with excess I^- to I₃^-,which combines with RhB,b-RhB,RhG and RhS, respectively,to form association particles,which give resonance scattering（RS）effect at 400 nm. The RS intensity at 400 nm of the RhB,b-RhB,RhG and RhS association particles systems is linear to chlorite concentration in the range of 0.00726-0.218μg/mL,0.0102-0.292μg/mL, 0.00726-0.145μg/mL and 0.0290-0.174μg/mL ClO₂^-.The detection limits of the systems were 0.00436μg /mL,0.00652μg /mL,0.0058μg /mL and 0.0145μg /mL ClO₂^-,respectively. Based on this,a new,simple and sensitive analysis method for the determination of chlorite in water was developed.In the four systems,the RhB system possess good stability and high sensitivity.The proposed method has been applied to the analysis of chlorite in water,with satisfactory results.4.Fluorescence analysis of trace ClO₂^- based on formation of rodanmine dyes association complex particlesIn acidic sodium acetate-HCl buffer solution containing KI,rhodamine B（RhB）,butyl rhodamine B（BRhB）,rhodamine 6G（RhG）and rhodamine S（RhS）has a fluorescence peak at 580 nm,580nm,550nm,550nm,respectively.When ClO₂^- exists fluorescence quenching occur. The fluorescence spectral characteristics,the influencing factors and the optimum conditions of these reactions have been investigated.For RhB,b-RhB,RhG and RhS systems,fluorescence quenching intensity is linear to the concentration of ClO₂^- in the range of 0.0218-0.51, 0.0218-0.304,0.0728-1.092 and 0.051-0.51μg/ml,respectively.The new,simple,sentisive fluorescence method has been applied to the determination of ClO₂^- in water,with satisfactory results.5.Fluorescence spectral study of rodamine dyes association particles and their application to respective determination of trace ClO₂ and ClO₂^-A fluorescence quenching method has been proposed for respective determination of chlorine dioxide and chlorite by using rhodamine dyes.In HCl-NaAc or NH₃-NH₄Cl buffer solution,rhodamine S（RhS）,rhodamine 6G（RhG）,rhodamine B（RhB）and butyl rhodanmine B（b-RhB）respectively exhibit a maximal fluorescence peak at 550nm,550nm,576nm and 576nm.Chlorine dioxide oxidizes rhodamine dyes in acidic or alkaline solution and chlorite oxidize them only in acidic solution,which results in the decolorization of rhodamine dyes and the quenching of fluorescence peak.Under alkaline condition,concentration of ClO₂ can be selectively determined by measuring the fluorescence quenching intensity.Concentration of ClO₂^- can be obtained by measuring the fluorescence quenching intensity that is produced by the reaction of chlorine dioxide and chlorite and by differential method.For RhS,RhG,RhB and b-RhB systems,the linear range for chlorine dioxide is 0.00840-0.53μg/mL,0.0930-3.15μg/mL, 0.215-2.610μg/mL and 0.0825-1.096μg/mL,respectively;the linear range for chlorite is 0.00950-0.711μg/mL,0.0940-2.36μg/mL,0.473-4.73μg/mL and 0.473-2.36μg/mL, respectively.In the four systems,the RhS system have good stability and high sensitivity and was chosen to determine chlorine dioxide and chlorite.It has been applied to the analysis of chlorine dioxide and chlorite in water,with satisfactory results.6.Resonance Rayleigh scattering spectral determination of trace ClO₂ and ClO₂^- with cationic sursfactsClO₂ and ClO₂^- oxidize I^- to form I₂ and it reacts with the excess I^- to form I₃^-,which combine with a cationic surfactant such as tetrdecyldimethyl benzylammonium chloride（TDMBA）,tetradecane pyridinium bromide（TPB）,cetyltrimethylammonium bromide（CTMAB）,tetrabutyl-ammonium iodie（TBAI）to form association particles in acidic sodium acetate-HCl buffer solution,which exhibit stronger resonance scattering effect at 320 nm,467 nm,480nm,530nm.The laser scattering indicates that the average diameter of （TDMBA-I₃）_n association particles was about 347 nm.The resonance scattering intensity at 467nm for TDMBA、TPB、CTMAB and TBAI systems is proportional to chlorine dioxide concentrations in the range of 0.00992-0.546μg/mL,0.0102-1.024μg/mL,0.0269-0.538μg/mL and 0.0178-1.095μg/mL,respectively.The detection limits of the systems were 0.00593μg /mL,0.00600μg/mL,0.0198μg/mL and 0.0645μg /mL ClO₂,respectively.The RS intensity at 467 nm for the TDMBA,TPB,CTMAB and TBAI association particles systems is linear to chlorite concentration over the range of 0.00948-0.664μg/mL,0.0170-1.706μg/mL, 0.0474-0.855μg/mL and 0.0237-1.138μg/mL ClO₂^-,respectively,with detection limits of 0.00610μg /mL,0.00819μg /mL,0.0378μg/mL and 0.00949μg /mL ClO₂^-,respectively. Among the systems,the stability and sensitivity of TDMBA system is the best and has been used for the determination of ClO₂ and ClO₂^- in sample.Novel resonance scattering spectral（RSS） methods for determination of chlorine dioxide and chlorite have been respectively proposed with TDMBA and the application field of the RS technology has been developed.The relationship between stability of systems and molecular structure has been primarily discussed.7.Plasmon resonance light scattering of silver nanoparticles and its analytical application to trace ClO₂A plasmon resonance light scattering（PRLS）detection method of chlorine dioxide is reported based on the oxidization of silver nanoparticles（NPs）by it,in pH 9.1 ammonia-ammonium chloride buffer solutions.Silver NPs exhibit strong PRLS signals characterized at 470 nm,and can be oxidized by ClO₂,which results in PRLS quenching at 470 nm.It was found that the PRLS quenching intensity is proportional to the concentration of chlorine dioxide over the range of 0.0011-0.185μg/mL,with the corresponding detection limit（3σ）of 0.00050μg/mL and the correlation coefficient of 0.9995.The method is was applied to the determination of chlorine dioxide in drinking water,with satisfactory results.The laser scattering,TEM,AAS and colored reagents were used to Characterize silver NPs and the reaction of it with ClO₂.The reason of PRLS signal quenching is explained,and the relationship between UV-Vis absorption spectra and PRLS spectra is dicussed.The method is simple,convenient,cost effective,rapid and sensitive and is a innovation that RS technology is applied to the analysis of inorganics with metal nanoparticls.8.Fluorescence quenching method for the determination of trace ClO₂ in water by silver nanoparticlsIn pH=9.1 NH₄Cl-NH₃·H₂O buffuer solutions,there is a fluorescence peak at 470nm for silver nanoparticles.A fluorescence quenching take places when it was oxidized by ClO₂.The intensity of fluorescence quenching is linear to the concentration of ClO₂ in the range of 0.0011-0.185μg/mL.The detection limit is 0.0047μg/mL ClO₂.A new fluorescence method has been proposed for the determination of ClO2 in water samples,with satisfactory results更多还原