Ag^+-Cl^--荧光素体系的离子缔合纳米微粒的共振非线性散射光谱及其在环境分析中的应用  

Study on the New Application of Resonance Non-linear Scattering Spectra of [( AgCl·Ag) HL]_n Nanoparticle in Environmental Analysis

作　　者：杨清玲[1,2] 刘健[2,3] 陈刚才[1] 傅生会[2,4] 王剑[2] 宋威威[2] 张筑元[1] 

机构地区：[1]重庆市环境科学研究院,重庆401147 [2]西南大学化学化工学院,重庆400715 [3]重庆市九龙坡区环境监测站,重庆400050 [4]重庆市巴南区环境监测站,重庆401342

出　　处：《中国环境监测》2013年第6期151-162,共12页Environmental Monitoring in China

基　　金：国家自然科学基金(批准号:20475045);重庆市自然科学基金(No.CSTC2006BB7267;No.CSTC2006BA7026);重庆市环科院环保基金(No.200706);重庆市重点科技攻关项目(CSTC;2011GGB-20001);国家水体污染控制与治理科技重大专项(2012ZX07104-001)

摘　　要：在pH 3.5~4.4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20nm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FDS和SOS波长分别位于350和560 nm处。两种散射增强(ΔIFDS和ΔISOS)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最灵敏,对于氯离子的检测,其线性范围是0.04~1.22μg/mL,检出限为10.9 ng/mL;在环境空气或无组织排放废气HCl的检测中,当采气体积为60L时,其线性范围是0.007~0.21 mg/m3,检出限为1.9×10-3mg/m3;在有组织排放废气样品中,当采气体积为10 L时,其线性范围是0.04~1.25 mg/m3,检出限为1.1×10-2mg/m3。该文研究了纳米微粒对吸收、RNLS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。In pH 3.5-4.4acetate buffer,Ag＋ reacted with Cl-to form AgCl.When the Ag＋ was at a opportune high concentration,AgCl formed could interacted with Ag ＋ remained to form [AgCl· Ag] ＋,which could combine with monovalence fluorescein anion （HL-） to form a compound,[（AgCl· Ag） HL],because of the electrostatic interaction and hydrophobic effect.Furthermore,the compound [（AgCl· Ag） HL] could form nanoparticles,[（AgCl· Ag） HL] n,with the average diameter of 20 nm in the effect of VDW force and squeezing action of water,which could enhance the resonance non-linear scattering （RNLS）,for example second-order scattering （SOS） and frequency-doubling scattering （FDS）,intensity strongly,while there had little changes of fluorescence and absorbance intensities.The maximal wavelength of FDS and SOS were appeared 350 nm and 560nm,respectively.Under the optimum conditions,,the enhancement of FDS and SOS intensities （△IFDS和 △ISOS） were both in proportion to the concentrations of Cl-,however,the FDS method was more sensitive with the range of 0.04 to 1.22 μg/ml and the limit of 10.9 ng/ml.For the detection of HCl,in air and fugitive emission waste gas,the range of concentration was 0.007 to 0.21 mg/m^3 with a limit of 1.9 × 10^-3 mg/m^3 in the volume of gathering gas 60 L,while in stationary source emission waste gas samples with a range of 0.04 to 1.25 mg/m^3 and a limit of 1.1 × 10^-2 mg/m^3.In this work,the spectral characteristics,optimum conditions of the reaction,influencing factors and the effects of coexisting substances have been investigated.The reaction mechanism and binding mode are discussed.The method can be applied to the determination of HCl and chloride with satisfactory results.

关 键 词：共振非线性散射(RNLS) 荧光素钠 氯化氢 氯化物 

分 类 号：X830.2[环境科学与工程—环境工程]