钯(Ⅱ)与法莫替丁和卤代荧光素染料三元离子缔合物纳米微粒的共振瑞利散射光谱及其分析应用

Study on the ternary ion-association complex nanoparticles of palladium(Ⅱ)-famotidine and halogen-fluorescein dyes by the resonance Rayleigh scattering and their application

在pH3.5～4.7NaAc-HAc的缓冲溶液中,法莫替丁(FMTD)与Pd(Ⅱ)形成五元环螯合阳离子([Pd(FMTD)]2+),再与二氯荧光素(DCF)、二溴荧光素(DBF)、二碘荧光素(DIF)、赤鲜红(ER)、曙红Y(EY)、乙基曙红(EE)等卤代荧光素(HF)反应形成1:1:2的三元离子缔合物([Pd(FMTD)]·(HF)2).[Pd(FMTD)]·(HF)2在疏水作用和范德华力的作用下进一步聚集形成平均粒径为9nm左右的纳米微粒,此时将引起体系吸收光谱变化、荧光猝灭和共振瑞利散射(RRS)急剧增强.[Pd(FMTD)]·(HF)2的最大吸收峰位于476nm(DCF体系)、540nm(DBF体系)、553nm(DIF体系)、560nm(ER体系)、547nm(EY体系)和549nm(EE体系),最大RRS散射波长位于302～361nm,散射增强程度(ΔI)在一定的范围内与FMTD的浓度成良好的线性关系,检出限为1.0～2.6ng/mL.据此提出了灵敏度高、选择性好、快速准确测定FMTD的分子光谱新方法.适用于片剂、胶囊和注射液等药物制剂的测定.研究了反应的适宜条件、影响因素和分析化学特性,并结合吸收、荧光光谱的变化和纳米微粒的形成,讨论了反应机理和散射增强的原因.

In pH 3.5-4.7 NaAc-HAc buffer medium,famotidine（FMTD）reacted with palladium（Ⅱ）（Pd（Ⅱ））to form chelate cation,which further reacted with halogen-fluorescein dyes（HF）such as dichlorofluorescein（DCF）,dibromofluorescein（DBF）,diiodofluorescein（DIF）,Erythrosine（ER）,eosine（EY）and eosin（EE）to form ternary ion-association complexes[Pd（FMTD）]·（HF）2.It further aggregated to form average diameter of about 9 nm nanoparticles by hydrophobic forces and Van der Waals forces.As a result,the absorption bands of DCF,DBF,DIF,ER,EY,EE were shifted,the fluorescences of them were quenched and the resonance Rayleigh scattering（RRS） were enhanced greatly.The maximum absorption wavelengths of[Pd（FMTD）·（HF）2]were located at 476 nm（DCF system）,540 nm（DBF system）,553 nm（DIF system）,560 nm（ER system）,547 nm（EY system）,549 nm（EE system）and the maximum RRS wavelengths of those were located at 302-361 nm.The ΔI was proportional to the FMTD concentration in a certain range and the detection limit was 1.0-2.6 ng/L.Based on it,a high sensitive,good selective,rapid and new molecular spectrum method had been proposed to determine FMTD.It could be applied to determine FMTD in pharmaceutical preparation such as tablets,gelatin capsule and injection.In this work,the optimum reaction conditions,the influences of coexisting substances and the properties of analytical chemistry were investigated.Moreover,the mechanism of ion-association reaction and the reasons of enhancement for RRS were also discussed by the change of absorption,fluorescence and the formation of nanoparticles.