氯金酸-罗丹明S缔合纳米微粒体系的共振散射增强与荧光猝灭研究

在0．2mol/L HCl介质中，罗丹明S(RDS)分别在520nm和550nm处有一个吸收峰和荧光峰。当有Au(Ⅲ）存在时，Au（Ⅲ）与Cl^-形成AuCl4^-，AuCl^-与RDS^ 借助于静电引力形成疏水性的AuCl4-RDS缔合物分子。AuCl4-RDS分子间存在较强的分子间作用力和疏水作用力而生成(AuCl4-RDS)。缔合纳米微粒，粒径为45nm。在360nm产生瑞利散射峰，在600nm产生共振散射峰。由于纳米微粒形成后，只有裹露在(AuCl4-RDS)n纳米微粒界面的RDS荧光分子才能吸收激发光子跃迁到激发态，进而返回基态产生荧光。而体相的RDS荧光分子无法与激发光作用产生荧光，即受激RDS分子数大为降低，故550nm荧光峰和520nm吸收峰的降低。当缔合纳米微粒体系加入乙醇后，体系的红紫色和共振散射峰消失，吸收峰和荧光峰恢复，由于乙醇致使(AuCl4-RDS)。纳米微粒分解为AuCl4-RDS分子。结果表明：红紫色(AuCl4-RDS)n纳米粒子的形成是其共振散射增强、荧光猝灭和产生共振散射峰的根本原因。     

西替利嗪-碘铂酸缔合微粒体系的吸收光谱研究及分析应用

Pt(IV)与I-形成[PtI6]2-,[PtI6]2-和盐酸西替利嗪(CTRZ)通过静电引力作用形成疏水性的(PtI6—CTRZ)缔合物分子.由于(PtI6-CTRZ)缔合物分子间存在较强的分子间作用力和疏水作用力而生成紫红色(CTRZ—PtI6)n缔合微粒,在310、400、610nm处产生3个共振散射峰;在350～740nm波长范围的吸光度值均增大.在选定条件下,CTRZ浓度在0～10μg/mL范围内与A580nm成正比,摩尔吸光系数ε580nm为1.30×104L/(mol·cm).实验结果表明,(CTRZ—PtI6)n缔合微粒的形成是导致同步散射信号增强的根本原因,而纳米纳米微粒的颜色是共振散射所致.     

小檗碱-Ⅰ3^-缔合微粒体系的光度分析应用

在稀HCl介质中,I-3在340 nm处有一吸收峰;当小檗碱(BB)与I-3共存时体系呈橙黄色,在580 nm处产生一共振散射峰.以试剂作参比,该缔合微粒体系在530 nm产生一吸收峰,BB浓度在0～7.0×10-5mol/L范围内与A530 nm呈线性,据此建立了一种测定小檗碱含量的分光光度新方法,并用于针剂样品中小檗碱测定,结果满意.同步散射光谱研究表明,BB+与I-3可通过静电引力作用形成疏水性的(I3-BB)缔合物分子,并进一步聚集形成稳定的(I3-BB)n缔合纳米微粒.由于该缔合纳米微粒在580 nm处产生共振散射效应,故体系呈橙黄色.     

四苯硼钠-甲苯胺蓝缔合物纳米微粒体系减色效应研究

在PH4.0醋酸-醋酸钠介质中，甲苯胺蓝在600nm处有一个吸收峰，随着四苯硼钠浓度的增大甲苯胺蓝在600nm处吸收峰降低，颜色减弱，这是由于甲苯胺蓝-四苯硼钠缔合物分子间存在较强的疏水作用及分子间作用力，聚集形成纳米微粒所致，甲苯胺蓝-四苯硼钠纳米微粒体系亦在600mm处有1个吸收峰，在400mm、470mm和580mm处产生3共振散射峰，其中400mm和580mm为甲苯胺蓝-四苯硼钠复合纳米微粒产生的特征共振散射峰，这也表明有纳米微粒存在，丙酮浓度的影响实验结果等表明，纳米微粒的形成是产生其减色效应的原因。     

小檗碱-I－3缔合微粒体系的光度分析应用

在稀HCl介质中,I-3在340 nm处有一吸收峰;当小檗碱(BB)与I-3共存时体系呈橙黄色,在580 nm处产生一共振散射峰.以试剂作参比,该缔合微粒体系在530 nm产生一吸收峰,BB浓度在0～7.0×10-5mol/L范围内与A530 nm呈线性,据此建立了一种测定小檗碱含量的分光光度新方法,并用于针剂样品中小檗碱测定,结果满意.同步散射光谱研究表明,BB+与I-3可通过静电引力作用形成疏水性的(I3-BB)缔合物分子,并进一步聚集形成稳定的(I3-BB)n缔合纳米微粒.由于该缔合纳米微粒在580 nm处产生共振散射效应,故体系呈橙黄色.     

小檗碱-I_3~-缔合微粒体系的光度分析应用

在稀HCl介质中,I_3~-在340 nm处有一吸收峰;当小檗碱(BB)与I_3~-共存时体系呈橙黄色,在580 nm处产生一共振散射峰。以试剂作参比,该缔舍微粒体系在530 nm产生一吸收峰,BB浓度在0～7.0×10~(-5)mol/L范围内与A_(530nm)呈线性,据此建立了一种测定小檗碱含量的分光光度新方法,并用于针剂样品中小檗碱测定,结果满意。同步散射光谱研究表明,BB~+与I_3~-可通过静电引力作用形成疏水性的(I_3-BB)缔合物分子,并进一步聚集形成稳定的(I_3-BB)_n缔合纳米微粒。由于该缔合纳米微粒在580 nm处产生共振散射效应,故体系呈橙黄色。     

(阳离子表面活性剂-I3)n缔合微粒体系的光谱特性及分析应用

在0.01 mol/L HCl介质中,I-3在350 nm处有一吸收峰;当十六烷基三甲基溴化铵(CTMAB)与I-3共存时体系呈红紫色,在550 nm处产生一新的吸收峰.CTMAB浓度CCTMAB在0.0～7.0×10-5 mol/L范围内符合比耳定律,回归方程为A550 nm =0.989×104 CCTMAB+0.0138,相关系数R为0.999 5,摩尔吸光系数ε为1.06×104 L/(mol·cm),据此建立了一种测定阳离子表面活性剂含量的分光光度新方法,并用于合成样品和新洁尔净样品中阳离子表面活性剂测定.共振散射光谱研究表明,CTMAB+与I-3可通过静电引力作用形成疏水性的CTMA-I3缔合物分子,并进一步聚集形成稳定的 (CTMA-I3)n缔合微粒.由于该缔合微粒在580 nm处产生共振散射效应,故体系呈红紫色.     

罗丹明6G缔合微粒荧光猝灭法测定痕量碘酸根

研究发现在0.01mol/LHCl-8.0×10-4mol/LKI介质中,罗丹明6G(RhG)在550nm处有1个荧光峰.当有IO-3,I-3与RhG形成缔合微粒,550nm处荧光峰猝灭,在320、400、6103存在时,IO-3与过量的I-反应生成I-nm处有3个共振散射峰,在470nm处有1个同步散射峰.碘酸根浓度在2.0～100×10-7mol/L范围内与荧光猝灭强度成线性关系.据此建立了一个测定食盐中IO-3的荧光猝灭分析法.光谱研究结果表明,(RhG-I3)n缔合微粒和界面的形成是导致体系荧光猝灭的根本原因.     

染料分子对硫纳米微粒共振散射光谱的影响

在聚丙烯酰胺存在下液相硫纳米微粒在 470nm处产生 1个强共振散射峰 ;在可见光范围内无吸收峰且吸收值较小。硫微粒质量浓度在 0 0 5～ 1 0mg/L范围内与I4 70nm间有良好线性关系。研究了乙醇、丙酮 ,以及溴酚蓝、溴甲基紫、结晶紫、亮绿等有机染料对硫纳米微粒共振散射的影响。结果发现 ,染料分子吸收是产生共振散射峰的一个重要原因 ;随着染料分子非辐射吸收值的增大 ,硫纳米微粒共振散射光强度降低。实验证明 ,溴酚蓝浓度在 0～ 1 0× 10 -5mol/L范围内 ,在溴酚蓝最大吸收波长 5 90nm处的ΔI590nm与溴酚蓝浓度呈线性关系。     

液相卤化银纳米微粒的界面荧光和共振散射光谱特性

液相卤化银纳米微粒的共振散射光谱和发射光谱表明,AgCl和AgBr纳米微粒均在330,400,470和680nm处产生4个共振散射峰,在340,400和470nm处产生三个荧光峰．Ad纳米微粒在340,400,437,470和680nm处产生5个共振散射峰;除在340,400和470nm处产生3个荧光峰外,在434nm处有一最强的荧光峰．卤化银纳米微粒体系的浓度对共振散射信号的影响与浓度对荧光强度的影响一致,Aga,AgBr和AgI体系的共振散射光信号强度分别约为荧光信号的110,130和80倍,即荧光与共振散射之间存在相关性．提出了液相AgX纳米微粒荧光产生机理,解释了荧光与共振散射之间存在相关性的原因．     

Spectral properties of the association nanoparticle system of ciprofloxacin-phloxine and its application to fluorescence analysis.

There is a fluorescence peak at 570 nm, and a maximum absorption peak at 560 nm for phloxine (PHLO) in a pH 7 water solution. Under these conditions, the ciprofloxacin cation (CPFX+) and PHLO- combine into hydrophobic CPFX-PHLO association molecule by means of static gravitation. There are stronger van der Waals forces and hydrophobic forces among the CPFX-PHLO molecules. Thus, they aggregate automatically to the (CPFX-PHLO)n association nanoparticle in red-violet color. That was characterized by scan electron microscopy (SEM), hyperfiltration and dialysis tests. In 0.04 M HCl, the red-violet nanoparticles exhibited a Rayleigh scattering peak at 470 nm, a resonance scattering peak at 580 nm, a maximum absorption wavelength at 565 nm, and a fluorescence peak at 450 nm. The fluorescence analytical conditions of CPFX have been considered. The CPFX concentration in the range of 1.0 x 10(-6)-4.0 x 10(-5) M is linear to the fluorescence intensity, F450nm. The detection limit was achieved at 4.0 x 10(-7) M CPFX. The CPFX in real samples was determined with satisfactory results.     

罗丹明B-PdI2-4缔合纳米粒子体系的极谱猝灭效应

缔合纳米微粒;共振散射;罗丹明B-PdI2-4缔合纳米粒子体系的极谱猝灭效应     

Change Color Effect and Spectral Properties of Gold Nanoparticle-cationic Surfactants System

The change color effect of gold nanoparticle solutions was studied by means of resonance scattering and absorption spectrometry and scan electron microscopy. The red Au nanoparticles with a size of 10 nm exhibit a resonance absorption peak and a resonance scattering peak all at 525 nm. After some inorganic electrolyte was added to a red Au nanoparticles solution, the color of the solution became blue and the absorbance at 600-700 nm was significantly increased. The ratio of the concentration of rnonovalent cations, at which the resonance scattering of the system at 525 nm is maximal to that of divalent cations, is in the range of 100 : 1--100 ; 1. 8. It is in good agreement with the Schulze-Hardy rule of the coagulation value of electrolyte. After adding some cationic surfactants to the above solution, the color of the solution is in deep blue, with two resonance absorption peaks at 550 and 680 nm, and a greatly enhanced resonance scattering peak at 525 nm. The experiments demonstrate that the stronger the hydrophobicity of the cationic surfactant is, the stronger the change color effect of the Au nanoparticle solution promoted by cationic surfactant is. The change color effect of Au nanoparticle solution is resulted from the increased diameter of Au nanoparticles, and the changes of resonance absorotion DeaR and resonance scattering.     

Resonance scattering spectral analysis of chlorides based on the formation of (AgCl)n(Ag)s nanoparticle

A novel resonance scattering spectral method has been proposed for the determination of trace amounts of chlorides in the range of 2 x 10(-7)-8 x 10(-6) mol/l. It was based on the photochemical reaction system of AgNO3-NaCl-sodium oxalic to form the (AgCl)nucleus (n)(Ag)shell (s) nanoparticle. There is a strongest resonance scattering peak at 470 nm and a maximum absorption peak at 425 nm. The concentration of chlorides is proportional to the intensity of resonance scattering at 470 nm. The nonlinear resonance scattering peaks of the nanoparticle system have been also considered, according to the theory of the interaction between the surface electron of nanoparticle and the incidence photon.     

曙红Y-Triton X-100疏水性氢键纳米微粒的吸收、荧光及共振瑞利散射光谱及其分析应用

在pH2.4～2.8的酸性介质中,曙红Y分子(H2L)取代水分子而与Triton X-100形成氢键缔合物.该疏水性的氢键缔合物,在水相的"挤压"作用和范德华力的作用下,能进一步聚集形成纳米微粒.此时将引起吸收光谱的变化和荧光猝灭,并导致共振瑞利散射(RRS)显著增强,为建立褪色分光光度法、荧光猝灭法和共振瑞利散射法测定Triton X-100创造了条件.三种方法均有较高的灵敏度.其中以RRS法灵敏度最高,对于Triton X-100的检出限为20.6ng/mL.本文研究了曙红Y与Triton X-100相互作用的适宜条件和对吸收、荧光和RRS光谱的影响.考察了共存物质的影响,表明方法有良好的选择性.发展和建立了灵敏、简便、快速测定Triton X-100的分光光度、荧光猝灭法和RRS新方法.文中还结合红外光谱、透射电子显微镜技术和量子化学方法对曙红Y-Triton X-100氢键缔合物及纳米微粒的形成以及对相应的光谱特性的影响进行了讨论,并研究了方法在环境分析中的应用.     

A study on the sizes and concentrations of gold nanoparticles by spectra of absorption, resonance Rayleigh scattering and resonance non-linear scattering

Liquid phase gold nanoparticles with different diameters and colors can be prepared using sodium citrate reduction method by controlling the amounts of sodium citrate. The mean diameters of gold nanoparticles are measured by transmission electron microscope (TEM). Gold nanoparticles with different sizes have specific absorption spectra. When the diameters of nanoparticles is between 12 and 41 nm, the maximum absorption peaks locate at 520-530 nm and there are red shifts gradually with the increase of diameters of gold nanoparticles. And when the size of gold nanoparticle is constant, the absorbance is proportional to the concentration of gold. Obvious resonance Rayleigh scattering (RRS) and the resonance non-linear scattering such as second-order scattering (SOS) and frequency-doubling scattering (FDS) appear at the same time as well, and the maximum scattering peaks are located at 286 nm (RRS), 480 nm (SOS) and 310 nm (FDS), respectively. When the concentration of gold is constant, absorbance and the intensities of RRS, SOS and FDS (I(RRS), I(SOS) and I(FDS)) have linear relationships with the diameters of gold nanoparticles. When the diameter of gold nanoparticle is constant, the absorbance and I(RRS), I(SOS), I(FDS) are directly proportional to the concentrations of gold nanoparticles. Therefore, it is very useful for studying the liquid phase gold nanoparticles by investigating the absorption, RRS, SOS and FDS spectra.