【作者】 杨清玲；

【导师】 刘绍璞；

【作者基本信息】 西南大学 ， 分析化学， 2008， 博士

【摘要】 共振瑞利散射（RRS）和共振非线性散射（RNLS）是20世纪90年代以后发展起来的新分析技术。由于它们的高灵敏度和简易性引起了人们的关注,研究和应用日益增多。其研究和应用已涉及蛋白质、核酸、多糖类等生物大分子、药物、有机物的分析和纳米微粒的研究。近年来此项技术在环境分析中的应用也受到重视,分析应用研究逐渐增多,表明RRS和RNLS法在环境分析中有广泛的应用潜力,成为扩展这一技术分析应用的新领域和发展环境分析的新途径。为此我们选择阴离子表面活性剂、氯化氢和氯化物及铝和汞等金属离子作为研究对象,研究和发展用RRS和RNLS法测定环境中上述物质的新体系和新方法。1、共振瑞利散射和共振非线性散射法测定阴离子表面活性剂的研究（1）盐酸氯丙嗪与阴离子表面活性剂的相互作用的RRS和RNLS光谱及其分析应用在pH 3.0～5.0的HAc-NaAc缓冲溶液中,盐酸氯丙嗪与十二烷基苯磺酸钠、十二烷基磺酸钠和十二烷基硫酸钠等阴离子表面活性剂反应形成离子缔合物时,仅能引起吸收光谱和荧光光谱的微小变化,但却能导致共振瑞利散射（RRS）的显著增强并产生新的RRS光谱,与此同时也观察到二级散射（SOS）和倍频散射（FDS）等共振非线性散射（RNLS）的增强。最大RRS峰分别位于277、369和278 nm处,而它们的SOS峰均在548 nm附近,最大FDS峰均在393 nm附近。其中RRS法灵敏度最高,它对十二烷基苯磺酸钠、十二烷基硫酸钠和十二烷基磺酸钠的检出限分别为0.018、0.046和0.200μg·mL^-1,而其线性范围分别为0.06～10.0、0.15～15.0和0.67～12.5μg·mL^-1。文中研究了反应产物的吸收、荧光、RRS、SOS和FDS光谱特征,适宜的反应条件及分析化学性质,据此发展了一种用RRS技术灵敏、简便、快速测定阴离子表面活性剂的新方法。（2）Co（Ⅱ）-5-Br-PADAP螯合物与十二烷基苯磺酸钠的相互作用的RRS光谱及其分析应用在pH 1.8～3.0的BR缓冲溶液中,钴（Ⅱ）与2-（5-溴-2-吡啶偶氮）-5-二乙氨基酚（5-Br-PADAP,HL）反应形成紫红色螯合阳离子,此时仅能引起吸收光谱的变化,不能导致共振瑞利散射（RRS）的增强。当钴（Ⅱ）-5-Br-PADAP螯合阳离子与阴离子表面活性剂十二烷基苯磺酸钠（SDBS）、十二烷基磺酸钠（SLS）和十二烷基硫酸钠（SDS）作用时,仅能与SDBS进一步反应形成三元离子缔合物并引起RRS的显著增强,而不与SDS和SLS产生类似反应。离子缔合物的RRS峰分别位于306nm、370nm和650nm处,在一定范围内RRS增强（ΔI）与SDBS浓度成正比,当用650nm处测量时,其检出限为0.043μg·mL^-1,线性范围为0.14～7.00μg·mL^-1。文中研究了反应产物的RRS光谱特征,适宜的反应条件及分析化学性质,据此发展了一种在一定量SDS和SLS等阴离子表面活性剂存在下选择性测定SDBS的新方法,方法灵敏、简便、快速,用于天然水和污水中SDBS的测定,能获得满意结果。文中还对反应机理进行了讨论。（3）Co（Ⅱ）-钴试剂螯合物与十二烷基苯磺酸钠的相互作用的RRS光谱及其分析应用在pH 1.8～3.0的BR缓冲溶液中,钴（Ⅱ）与钴试剂（5-Cl-PADAB,L）反应形成螯合物阳离子[CoL₂]²⁺,当它与十二烷基苯磺酸钠（SDBS）、十二烷基硫酸钠（SDS）及十二烷基磺酸钠（SLS）等阴离子表面活性剂作用时,仅能与SDBS反应形成三元离子缔合物{[CoL₂][SDBS]₂},疏水性的离子缔合物在水的挤压作用下和范德华力的作用下彼此靠近,进一步聚集形成纳米微粒{[CoL₂][SDBS]₂}_n（平均粒径为30nm）。此时将引起共振瑞利散射（RRS）的显著增强并产生新的RRS光谱,而SDS和SLS则不产生类似反应,也不导致RRS的明显变化,因此可用于在SDS和SLS等存在下选择性测定SDBS,当用516 nm作为检测波长测定SDBS时,其线性范围为0.05～6.00μg·mL^-1,检出限为0.015μg·mL^-1。文中研究了反应体系的RRS光谱特征,适宜的反应条件和影响因素,考察了共存物质的影响,表明方法有良好的选择性。因此,基于离子缔合物纳米微粒{[CoL₂][SDBS]₂}_n的形成发展了一种用RRS技术,灵敏、简便、快速测定环境水样中SDBS的新方法,文中还对反应机理进行了讨论。2、共振瑞利散射和共振非线性散射法测定氯化氢和氯化物的研究（1）Ag⁺-Cl^--荧光素体系的RRS和RNLS光谱及其分析应用在pH 3.5～4.4的醋酸盐缓冲溶液中,Ag⁺与Cl^-反应形成AgCl。当Ag⁺适当过量时,AgCl能与Ag⁺结合形成[AgCl·Ag]⁺阳离子,它能进一步借静电引力和疏水作用力与荧光素一价阴离子（HL^-）反应形成离子缔合物[（AgCl·Ag）HL],该疏水性的离子缔合物能在水相挤压作用和范德华力的作用下彼此靠近而进一步聚集,形成平均粒径约为20 nm的纳米微粒[（AgCl·Ag）HL]_n。此时仅能引起吸收光谱和荧光光谱的微小变化,但能导致共振瑞利散射（RRS）以及倍频散射（FDS）和二级散射（SOS）等共振非线性散射（RNLS）的显著增强,其最大RRS、FDS和SOS波长分别位于313nm、349nm和564nm处。三种散射增强(ΔI^RRS、ΔI^FDS和ΔI^SOS)在一定范围内均与氯离子浓度成正比,均可用于氯离子的测定。其中以RRS最灵敏,对于氯离子的检测,其线性范围是0.006～1.90μg·mL^-1,检出限为1.9 ng·mL^-1;在环境空气或无组织排放废气氯化氢（HCl）的检测中,当采气体积为60 L时,其线性范围是0.001～0.33 mg·m^-3,检出限为3.30×10^-4mg·m^-3;在有组织排放废气HCl的检测中,当采气体积为10 L时,其线性范围是0.008～2.00 mg·m^-3,检出限为2.00×10^-3mg·m^-3。本文研究了[AgCl.Ag.HL]_n纳米微粒对吸收、荧光、RRS和RLNS光谱的影响、反应的适宜条件及影响因素,考察了共存物质的影响,表明方法有良好的选择性,据此利用上述反应发展了一种用RRS、SOS和FDS技术高灵敏度、高选择性和简便、快速测定环境空气和废气中HCl及环境水样中氯化物的新方法。文中还对反应机理进行了讨论。（2）Ag⁺-Cl^--二卤代荧光素体系的RRS和RNLS光谱及其分析应用在pH 3.2～6.2的醋酸盐缓冲溶液中,Ag⁺与Cl^-离子反应形成AgCl。当Ag⁺适当过量时,AgCl能与Ag⁺形成[AgCl·Ag]⁺阳离子,它能进一步借静电引力和疏水作用力与二卤代荧光素（二氯荧光素、二溴荧光素和二碘荧光素）一价阴离子（HL^-）反应形成离子缔合物[（AgCl·Ag）HL],该疏水性的离子缔合物能在水相挤压作用和范德华力的作用下彼此靠近而进一步聚集,形成平均粒径约为20 nm的纳米微粒[（AgCl·Ag）HL]_n。此时仅能引起吸收光谱和荧光光谱的微小变化,但能导致共振瑞利散射（RRS）以及倍频散射（FDS）和二级散射（SOS）等共振非线性散射（RNLS）的显著增强,其中以二氯荧光素体系最灵敏。二氯荧光素体系的最大RRS、FDS和SOS波长分别位于314 nm、349 nm和564 nm处,三种散射增强(ΔI^RRS、ΔI^FDS和ΔI^SOS)在一定范围内均与氯离子浓度成正比,均可用于氯离子的测定。其中以RRS法最灵敏,FDS法次之。三种方法（RRS、FDS和SOS法）对于氯离子的检测,其线性范围分别是0.006～1.94μg·mL^-1、0.030～2.20μg·mL^-1和0.074～1.94μg·mL^-1;检出限分别为1.7 ng·mL^-1、8.9 ng·mL^-1和22.1 ng·mL^-1。在环境空气或无组织排放废气氯化氢（HCl）的检测中,当采气体积为60 L时,其线性范围分别是0.001～0.333mg·m^-3、0.005～0.375 mg·m^-3和0.012～0.333 mg·m^-3;检出限分别为3.0×10^-4mg·m^-3、1.5×10^-3mg·m^-3和3.8×10^-3 mg·m^-3。在有组织排放废气HCl的检测中,当采气体积为10 L时,其线性范围分别是0.006～2.00 mg·m^-3、0.031～2.25 mg·m^-3和0.074～2.00 mg·m^-3;检出限分别为1.8×10^-3mg·m^-3、9.2×10^-3mg·m^-3和2.2×10^-2mg·m^-3。本文研究了[AgCl.Ag.HL]_n纳米微粒对吸收、荧光、RRS和RLNS光谱的影响、反应的适宜条件及影响因素,考察了共存物质的影响,表明方法有良好的选择性,据此利用上述反应发展了一种用RRS、SOS和FDS技术高灵敏度、高选择性和简便、快速测定环境空气和废气中HCl及环境水样中氯化物的新方法。文中还对反应机理进行了讨论。（3）Ag⁺-Cl^-多取代荧光素体系的RRS和RNLS光谱及其分析应用在pH 3.2～5.7的醋酸盐缓冲溶液中,Ag⁺与Cl^-离子反应形成AgCl。当Ag⁺离子适当过量时,AgCl能与Ag⁺结合形成[AgCl·Ag]⁺阳离子,它能借静电引力和疏水作用力与多取代荧光素（曙红B、曙红Y、虎红、荧光桃红、乙基曙红）一价阴离子（HL^-）反应形成离子缔合物[（AgCl·Ag）HL],该疏水性的离子缔合物能在水相挤压作用和范德华力的作用下彼此靠近而进一步聚集,形成平均粒径约为20 nm的纳米微粒[（AgCl·Ag）HL]_n。此时虽仅引起吸收光谱和荧光光谱的微小变化,但能导致共振瑞利散射（RRS）以及倍频散射（FDS）和二级散射（SOS）等共振非线性散射（RNLS）的显著增强,其中以曙红B体系最灵敏。曙红B体系的最大RRS、FDS和SOS波长分别位于315 nm、349nm和564 nm处,三种散射增强(ΔI^RRS、ΔI^FDD和ΔI^SOS)在一定范围内均与氯离子浓度成正比,均可用于氯离子的测定。其中以FDS法最灵敏、RRS法次之。三种方法（RRS、FDS和SOS法）对于氯离子的检测,其线性范围分别是0.005～1.22μg·mL^-1、0.004～2.92μg·mL^-1和0.01～1.94μg·mL^-1;检出限分别为1.5 ng·mL^-1、1.2ng·mL^-1和3.9 ng·mL^-1。在环境空气或无组织排放废气氯化氢（HCl）的检测中,当采气体积为60 L时,其线性范围分别是0.0008～0.21mg·m^-3、0.0007～0.50 mg·m^-3和0.002～0.33 mg·m^-3;检出限分别为2.50×10^-4mg·m^-3、2.00×10^-4mg·m^-3和6.70×10^-4 mg·m^-3。在有组织排放废气HCl的检测中,当采气体积为10L时,其线性范围分别是0.005～1.25 mg·m^-3、0.004～3.00 mg·m^-3和0.01～2.00 mg·m^-3;检出限分别为1.50×10^-3mg·m^-3、1.20×10^-3mg·m^-3和4.00×10^-3mg·m^-3。本文研究了[AgCl.Ag.HL]_n纳米微粒对吸收、荧光、RRS和RLNS光谱的影响、反应的适宜条件及影响因素,考察了共存物质的影响,表明方法有良好的选择性,据此利用上述反应发展了一种用RRS、SOS和FDS技术高灵敏度、高选择性和简便、快速测定环境空气和废气中HCl及环境水样中氯化物的新方法。文中还对反应机理进行了讨论。3、铝（Ⅲ）-铬偶氮酚KS-溴化十六烷基吡啶体系的RRS和RNLS光谱及其分析应用在pH 5.8～6.5的HAc-NaAc缓冲介质中,铝（Ⅲ）离子与铬偶氮酚KS（CALKS,H₂L）形成螯合阴离子,能进一步与溴化十六烷基吡啶（CPB）反应形成疏水性的三元离子缔合物Al（OH）[H₂L（CP）₄]₂,此离子缔合物在水相的“挤压”作用和范德华力的作用下能进一步聚集形成平均粒径约50 nm的纳米微粒{Al（OH）[H₂L（CP）₄]}_n,此时将引起共振瑞利散射（RRS）、二级散射（SOS）和倍频散射（FDS）等共振非线性散射（RNLS）的显著增强,并出现新的散射光谱,其最大RRS、SOS和FDS光谱分别位于277 nm、550 nm和350 nm处。在一定范围内散射强度与铝（Ⅲ）的浓度均呈良好的线性关系。三种方法测定Al（Ⅲ）的线性范围和检出限分别为0.76～30.0 ng·mL^-1和0.23 ng·mL^-1（RRS）、0.73～35.0 ng·mL^-1和0.22 ng·mL^-1（SOS）以及1.03～35.0ng·mL^-1和0.31 ng·mL^-1（FDS）。本文研究了反应产物的RRS、SOS和FDS光谱特征、适当的反应条件和影响因素,试验了共存离子的影响,表明方法有较好的选择性。据此发展了用铬偶氮酚KS和溴代十六烷基吡啶的灵敏、简便、快速测定Al（Ⅲ）的新方法,应用于实际水样中Al（Ⅲ）的测定,取得了令人满意的结果。文中还对反应机理进行了讨论。4、汞（Ⅱ）-碘化物-溴化十四烷基吡啶体系的RRS和RNLS光谱及其分析应用在pH 1.8～6.0的Britton-Robinson（BR）的缓冲溶液中,Hg（Ⅱ）与适当过量的I^-生成[HgI₄]^2-配阴离子,此时仅能引起RRS光谱和RNLS光谱的微小变化;当加入溴化十四烷基吡啶（TPB）之后,[HgL₄]^2-配阴离子能与TPB反应形成离子缔合物,该疏水性的离子缔合物能在水相挤压作用和范德华力的作用下彼此靠近而进一步聚集,形成平均粒径约为10 nm的纳米微粒。此时仅能引起吸收光谱的微小变化,但能导致共振瑞利散射（RRS）以及倍频散射（FDS）和二级散射（SOS）等共振非线性散射（RNLS）的显著增强,其最大RRS、FDS和SOS波长分别位于366 nm、390 nm和570 nm处。三种散射增强(ΔI^RRS、ΔI^FDS和ΔI^SOS)在一定范围内均与Hg（Ⅱ）浓度成正比,均可用于Hg（Ⅱ）的测定。其中以RRS最灵敏,其线性范围分别是0.003～0.125μg·mL^-1（RRS）、0.003～0.100μg·mL^-1（FDS）和0.004～0.100μg·mL^-1（SOS）;检出限分别为0.8 ng·mL^-1（RRS）、0.9 ng·mL^-1（FDS）和1.2 ng·mL^-1（SOS）。本文还研究了反应产物的RRS、SOS和FDS光谱特征,适宜的反应条件及分析化学性质,还研究了共存物质的影响,讨论了反应机理。该方法用于地表水和污水及大气降水中汞的测定,结果满意。更多还原

【Abstract】 Resonance Rayleigh scattering（RRS） and resonance non-linear scattering（RNLS） are new technologies developed in 1990s.Due to their remarkable characteristics of high sensitivity and simple operation,RRS and RNLS have received much attention. They have been extensively and successfully unitized to study and determination of such biological macromolecules as proteins,nucleic acids and polysaccharides,as well as pharmaceuticals,organic compounds and nanoparticles.In recent years,they have been more and more applied in environmental analysis,which show that RRS and RNLS have broad application potential in field of environmental analysis.This would become a new field for extending the application of these two techniques and a new way for developing environmental analysis.Therefore,taking anion surfactants, hydrogen chloride,chloride,metal ions such as aluminum（Ⅲ） and mercury（Ⅱ） as examples,we have studied and developed new systems and methods for the determination of the above analytes in environment using RRS and RNLS techniques.1 The Study on the Determination of Some Anionic Surfactants by Resonance Rayleigh Scattering and Resonance Non-Linear Scattering Spectra（1） Resonance Rayleigh Scattering and Resonance Nonlinear Scattering of the Interaction of Chlorpromazine Hydrochloride with Anionic Surfactants and Its Analytical ApplicationIn pH 3.0-5.0 acetate（HAc-NaAc） buffer media,chlorpromazine hydrochloride can react with some anionic surfactants such as sodium dodecylbenzene sulfonate, sodium dodecyl sulfate or sodium lauryl sulfonate.As a result,the spectra of absorption and fluorescence changed a little,but the resonance Rayleigh scattering（RRS） was enhanced greatly,and a new RRS spectrum appeared.At the same time,their resonance non-linear scattering（RNLS） such as second-order scattering（SOS） and frequency doubling scattering（FDS） were also increased.The maximum RRS wavelengths of three anionic surfactants were located at 277,369 and 278 nm.Their maximum scattering peaks were at 548 nm for SOS and 393 nm for FDS,respectively.The sensitivity of RRS method was much higher than those of SOS and FDS.The detection limits for three anionic surfactants were 0.018μg·mL^-1 for sodium dodecylbenzene sulfonate,0.046μg·mL^-1 for sodium dodecyl sulfate and 0.200μg·mL^-1 for sodium lauryl sulfonate.There was a linear relationship between the RRS intensity and the drug concentration in the range of 0.06-10.0μg·mL^-1 for sodium dodecylbenzene sulfonate, 0.15-15.0μg·mL^-1 for sodium dodecyl sulfate and 0.67-12.5μg·mL^-1 for sodium lauryl sulfonate,respectively.In this work,the spectral characteristics of the absorption, fluorescence,RRS,SOS and FDS,the optimum conditions of the reaction and the properties of analytical chemistry were investigated.A sensitive,simple and new method for the determination of anionic surfactants based on RRS has been developed.（2） Resonance Rayleigh Scattering Spectra of the Interaction of Co（Ⅱ）-2-（5-Bromo-2-Pyridylaro）-5-Diethylaminophenol with Sodium Dodecylbenzene Sulfonate and Its Analytical ApplicationIn pH 1.8-3.0 Britton-Robinson（BR） buffer medium,Co（Ⅱ） reacts with 5-Br-PADAP（2-（5-bromo-2-pyridylaro）-5-diethylaminophenol,HL） to form a cationic chelate Co[（HL）₂]²⁺.In this case,only the characteristics of the absorption spectra changed,but the intensity of the resonance Rayleigh scattering（RRS） didn’t increase. When the cationic chelate reacts further with some anionic surfactants such as sodium dodecylbenzene sulfonate（SDBS）,sodium dodecyl sulfate（SDS） and sodium lauryl sulfonate（SLS）,only SDBS can form a ternary ion-association complex and result in the enhancement of the resonance Rayleigh scattering（RRS） enhanced greatly.But, both of SDS and SLS do not have the similar reaction.The RRS peaks for the ion-association complex are located at 306,370 and 650 nm,respectively.There was a linear relationship between the RRS intensity（A/RRs） and the SDBS concentration in a certain range,the detection limits was 0.043μg·mL^-1 and the linear range was 0.14-7.00μg·mL^-1 at 650 nm.In this work,the characteristics of the RRS spectrum,the optimum conditions of the reaction and the properties of analytical chemistry were investigated.A new method for selective determination of SDBS in the presence of some other anionic surfactants such as SDS and SLS has been developed.The method is sensitive,simple and fast,which can be applied to the determination of SDBS in natural water and waste water samples with satisfactory results.In this work,the reaction mechanism was also discussed.（3） Resonance Rayleigh Scattering Spectra of the Interaction of Co（Ⅱ）-4-[（5-Chloro-2-pyridyl） azo]-1,3-diaminobenzene with Sodium Dodecylbenzene Sulfonate and Its Analytical ApplicationIn pH 1.8-3.0 Britton-Robinson（BR） buffer solution,cobalt（Ⅱ） reacts with 4-[（5-Chloro-2-pyridyl） azo]-1,3-diaminobenzene（5-Cl-PADAB,L） to form a cationic chelate[COL₂]²⁺.When interacting with anionic surfactants such as sodium dodecyl benzene sulfonate（SDBS）,sodium dodecyl sulfate（SDS） or sodium dodecyl sulfonate （SLS）,the chelate can only react with SDBS to form ternary ion-association complexes （[CoL₂][SDBS]₂）.By virtue of the extrusion action of water and Van der Waals force, the hydrophobic ion-association complexes draw close to each other and further aggregate to form {[CoL₂][SDBS]₂}_n nanoparticles with an average diameter of 30 nm. As a result,resonance Rayleigh scattering（RRS） is enhanced greatly and new RRS spectra appear.Under the same conditions,both SDS and SLS exhibit no similar reactions and do not result in obvious change of RRS.Therefore,SDBS can be determined selectively by RRS method in the presence of SDS or SLS.When 516 nm was chosen as a detection wavelength,the linear range and the detection limit（3σ） are 0.05-6.00μg mL^-1 and 0.015μg mL^-1 for the determination of SDBS,respectively.The characteristics of RRS spectra of the[CoL₂]²⁺-SDBS system,the optimum conditions of the reaction and the influencing factors have been investigated.The effects of coexisting substances were examined too,which indicated a good selectivity of the method for the determination of SDBS.The method can be used for the determination of SDBS in waste water and fiver water samples,and the results are satisfactory compared with those of standard samples of SDBS.Based on the formation of {[CoL₂][SDBS]₂}_n nanoparticles,a sensitive,simple and rapid method has been developed for the determination of SDBS in environmental water samples using a RRS technique. Moreover,the reaction mechanism was discussed.2 The Study on the Determination of Hydrochloride and Chloride by Resonance Rayleigh Scattering and Resonance Non-Linear Scattering Spectra（1） Resonance Rayleigh Scattering and Resonance Non-linear Scattering Spectra of Ag⁺-Cl^--Fluorescein Dye System and Their Analytical ApplicationIn pH 3.5-4.4 acetate（HAc-NaAc） buffer solution,AgCl formed by the reaction of Ag⁺ with Cl^- can bind with excessive Ag⁺ to form a[AgCl·Ag]⁺ cation.The cation further reacts with fluorescein anion（HL） to form ion-association complexes [（AgCl·Ag）HL]by virtue of electrostatic attraction and hydrophobic force.Then the complexes draw close to each other and further aggregate to produce[（AgCl·Ag）HL]_n nanoparticles with an average diameter of 20 nm due to the extrusion action of water and Van der Waals force.As a result,the spectra of absorption and fluorescence were changed a little,but resonance Rayleigh scattering（RRS） and resonance non-linear scattering（RNLS） such as frequency doubling scattering（FDS） and second-order scattering（SOS） were enhanced greatly.The maximum wavelengths of RRS,FDS and SOS were located at 313,349 and 564 nm,respectively.The increments of three scattering intensity(△I^RRS,△I^FDS and△I^SOS) were directly proportional to the concentration of Cl^- in certain ranges,and three scattering methods could be applied to the determination of Cl^-.The sensitivity of RRS method was the highest among the three scattering methods.The linear range and the detection limit for Cl^- using RRS method were 0.006-1.90μg·mL^-1 and 1.9 ng·mL^-1.In analysis of hydrochloride（HC1） in environmental air or inorganization discharge of waste gas samples,the linear range and the detection limit were 0.001-0.33 mg·m^-3 and 3.30×10^-4 mg·m^-3 when the sampling volume of air was 60 L;In organization discharge of waste gas samples,the linear range and the detection limit were 0.008-2.00 mg·m^-3 and 2.00×10^-3 mg·m^-3 for HCl when the sampling volume of air was 10 L.In this work,the influences of[（AgCl·Ag）HL]_n nanoparticles on the spectra of absorption,fluorescence,RRS and RNLS,the optimum conditions and the influencing factors have been investigated.Meanwhile,the effects of coexisting substances have been discussed and the results show that the method has good selectivity.Based on the above researches,a highly sensitive,selective,simple and fast method for the determination of HC1 in environmental air and waste gas samples and chloride in environmental water samples by RRS,SOS and FDS techniques has been developed.In addition,the reaction mechanism was discussed.（2） Resonance Rayleigh Scattering and Resonance Non-linear Scattering Spectra of Ag⁺-Cl^--Dihalogenated Fluorescein Dyes Systems and Their Analytical ApplicationIn pH 3.2-6.2 acetate（HAc-NaAc） buffer solution,AgCl formed by the reaction of Ag⁺ with Cl^- can bind with excessive Ag⁺ to form a[AgCl·Ag]⁺ cation.The cation further reacts with dihalogenated fluorescein dyes（dichlorofluorescein, dibromofluorescein,diiodofluorescein） anion（HL-） to form ion-association complexes [（AgCl·Ag）HL]by virtue of electrostatic attraction and hydrophobic force.Then the hydrophobic complexes draw close to each other and further aggregate to form [（AgCl·Ag）HL]_n nanoparticles with an average diameter of 20 nm due to the extrusion action of water and Van der Waals force.As a result,the spectra of absorption and fluorescence were changed a little,but resonance Rayleigh scattering（RRS） and resonance non-linear scattering（RNLS） such as frequency doubling scattering（FDS） and second-order scattering（SOS） were enhanced greatly.The sensitivity of Ag⁺ -Cl^--dichlorofluorescein system was the highest among three systems.Its maximum wavelengths of RRS,FDS and SOS were located at 314,349 and 564nm,respectively. The increments of three scattering intensity(△I^RRS,△I^FDS and△I^SOS) were directly proportional to the concentration of Cl^- in certain ranges,and three scattering methods could be applied to the determination of Cl^-.Among them,the RRS method has the highest sensitivity,and followed by the FDS method.The linear ranges and the detection limits for Cl^- of the three methods（RRS,FDS and SOS） were 0.006-1.94μg·mL^-1,0.030-2.20μg·mL^-1,0.074-1.94μg·mL^-1 and 1.7 ng·mL^-1,8.9 ng·mL^-1,22.1 ng·mL^-1,respectively.In analysis of hydrogen chloride（HC1） in environmental air or inorganization discharge of waste gas samples,the linear ranges and the detection limits were 0.001-0.333 mg·m^-3,0.005-0.375 mg·m^-3,0.012-0.333 mg·m^-3 and 3.0×10^-4 mg·m^-3, 1.5×10^-3 mg·m^-3,3.8×10^-3 mg·m^-3 when the sampling volume of air was 60 L;In organization discharge of waste gas samples,the linear ranges and the detection limits were 0.006-2.00 mg·m^-3,0.031-2.25 mg·m^-3,0.074-2.00 mg·m^-3 and 1.8×10^-3 mg·m^-3, 9.2×10^-3 mg·m^-3,2.2×10^-2 mg·m^-3 for HCl when the sampling volume of air was 10 L.In this paper,the influences of[（AgCl·Ag）HL]_n nanoparticles on the spectra of absorption, fluorescence,RRS and RNLS,the optimum conditions and the influencing factors have been investigated.Meanwhile,the effects of coexisting substances have been discussed and the results show that the method has good selectivity.Based on the above researches,a highly sensitive,selective,simple and fast method for the determination of HCl in environmental air and waste gas samples and chloride in environmental water samples by RRS,SOS and FDS techniques has been developed.In addition,the reaction mechanism was discussed.（3） Resonance Rayleigh Scattering and Resonance Non-linear Scattering Spectra of Ag⁺-Cl^--Polysubstituted Fluorescein Dyes Systems and Their Analytical ApplicationIn pH 3.2-5.7 acetate（HAc-NaAc） buffer solution,AgCl formed by the reaction of Ag⁺ with Cl^- can bind with excessive Ag⁺ to form a[AgCl·Ag]⁺ cation.The cation further reacts with Polysubstituted fluorescein dyes（eosin B,eosin Y,tiger red,phloxine and ethyl eosin） anion（HL^-） to form ion-association complexes[（AgCl·Ag）HL]by virtue of electrostatic attraction and hydrophobic force.Then the complexes draw close to each other and further aggregate to produce[（AgCl·Ag）HL]_n nanoparticles with an average diameter of 20 nm due to the extrusion action of water and Van der Waals force. As a result,the spectra of absorption and fluorescence were changed a little,but resonance Rayleigh scattering（RRS） and resonance non-linear scattering（RNLS） such as frequency doubling scattering（FDS） and second-order scattering（SOS） were enhanced greatly.The sensitivity of Ag⁺-Cl^--eosin B system was the highest among six systems.Its maximum wavelengths ofRRS,FDS and SOS were located at 315,349 and 564 nm,respectively.The increments of three scattering intensity(△I^RRS,△I^FDS and△I^SOS) were directly proportional to the concentration of Cl^- in certain ranges,and three scattering methods could be applied to the determination of Cl^-.Among them,the FDS method has the highest sensitivity,and followed by the RRS method.The linear ranges and the detection limits for Cl^- of the three methods（RRS,FDS and SOS） were 0.005-1.22μg·mL^-1,0.004-2.92μg·mL^-1,0.01-1.94μg·mL^-1 and 1.5 ng·mL^-1,1.2ng·mL^-1, 3.9 ng·mL^-1,respectively.In analysis of hydrochloride（HCl） in environmental air or inorganization discharge of waste gas samples,the linear ranges and the detection limits were 0.0008-0.21mg·m^-3,0.0007-0.50 mg·m^-3,0.002-0.33 mg·m^-3 and 2.50×10^-4 mg·m^-3, 2.00×10^-4 mg·m^-3,6.70×10^-4 mg·m^-3 when the sampling volume of air was 60 L;In organization discharge of waste gas samples,the linear ranges and the detection limits were 0.005-1.25 mg·m^-3,0.004-3.00 mg·m^-3,0.01-2.00 mg·m^-3 and 1.50×10^-3 mg·m^-3, 1.20×10^-3 mg·m^-3,4.00×10^-3 mg·m^-3 for HCl when the sampling volume of air was 10 L. In this paper,the influences of[（AgCl·Ag）HL]_n nanoparticles on the spectra of absorption,fluorescence,RRS and RNLS,the optimum conditions and the influencing factors have been investigated.Meanwhile,the effects of coexisting substances have been discussed and the results show that the method has good selectivity.Based on the above researches,a highly sensitive,selective,simple and fast method for the determination of HC1 in environmental air and waste gas samples and chloride in environmental water samples by RRS,SOS and FDS techniques has been developed.In addition,the reaction mechanism was discussed.3 Resonance Rayleigh Scattering and Resonance Non-linear Scattering Spectra of Aluminum（Ⅲ）-Chromazol KS-Cetyipyridinium Bromide System and Their Analytical ApplicationIn the pH 5.8-6.5 acetate（HAc-NaAc） buffer medium,Al（Ⅲ） can react with chromazol KS to form an chelated anion which can further react with cetylpyridinium bromide（CPB） to form hydrophobic ion-association complexes Al（OH）[H₂L（CP）₄]₂. Then the complexes can draw close to each other and further aggregate to form {Al（OH）[H₂L（CP）₄]}_n nanoparticles with an average diameter of 50 nm due to the extrusion action of water and Van der Waals force.As a result,resonance Rayleigh scattering（RRS） and resonance non-linear scattering（RNLS） such as second-order scattering（SOS） and frequency doubling scattering（FDS） were enhanced greatly.Its maximum wavelengths of RRS,SOS and FDS were located at 277,550 and 350 nm, respectively.The increments of three scattering intensity(△I^RRS,△I^SOS and△I^FDS) were directly proportional to the concentration of Al（Ⅲ） in certain ranges,and three scattering methods could be applied to the determination of Al（Ⅲ）.The linear ranges and the detection limits for Al（Ⅲ）by the three methods（RRS,SOS and FDS） were 0.76-30.0 ng·mL^-1,0.73-35.0 ng·mL^-1,1.03-35.0 ng·mL^-1 and 0.23 ng·mL^-1,0.22 ng·mL^-1,0.31 ng·mL^-1,respectively.In the paper,the spectral characteristics of the RRS, SOS and FDS,the optimum conditions and the influencing factors have been investigated.These shows the method have a good selectivity.Based on the reaction,we develop a new method which is sensitive,simple and rapid to determinate Al（Ⅲ）.The method can be applied to the determination of Al（Ⅲ） in the real water samples,and the result is satisfactory.In addition,the reaction mechanism was discussed.4 Resonance Rayleigh Scattering and Resonance Non-linear Scattering Spectra of Mercury（Ⅱ）-Iodide-Tetradecyl Pyridinium Bromide System and Their Analytical ApplicationIn pH 1.8-6.0 Britton-Robinson（BR） buffer medium,Hg（Ⅱ） can react with I^- to form a complex anion([HgI₄]^2-),which can only lead to the small changes of resonance Rayleigh scattering（RRS） and resonance non-linear scattering（RNLS）.The complex anion can further react with tetradecyl pyridinium bromide（TPB） to form hydrophobic ion-association complex.Then the complexes can draw close to each other and further aggregate to form nanoparticles with an average diameter of 10 nm due to the extrusion action of water and Van der Waals force.As a result,resonance Rayleigh scattering （RRS） and resonance non-linear scattering（RNLS） such as frequency doubling scattering（FDS） and second-order scattering（SOS） were enhanced greatly.The maximum RRS,FDS and SOS wavelengths of the ion-association complex were located at 366,390 and 570 nm,respectively.The increments of three scattering intensity(△I^RRS,△I^FDS and△I^SOS) were directly proportional to the concentration of Hg（Ⅱ） in certain ranges,and three scattering methods could be applied to the determination of Hg（Ⅱ）.The linear ranges and the detection limits for Hg（Ⅱ） were 0.003-0.125μg·mL^-1 and 0.8 ng·mL^-1（RRS）,0.003-0.100μg·mL^-1 and 0.9 ng·mL^-1 （FDS）,and 0.004-0.100μg.mL^-1 and 1.2 ng·mL^-1（SOS）,separately.The sensitivity of RRS method was higher than those of SOS and FDS methods.In the paper,the RRS and RNLS spectral characteristics of ion-association complexes,the optimum conditions and the quality of analytical chemistry,the influencing factors have been investigated.In addition,the reaction mechanism and the size of ion-association complexes were discussed.Based on the ion-association reaction,we developed new methods which are sensitive,simple and rapid to determinate Hg（Ⅱ）.The methods can be applied to the determination of Hg（Ⅱ） in the surface water,sewage and wet precipitation samples with satisfactory results.更多还原