痕量葡萄糖的双酶催化荧光分析

在HAc-NaAc缓冲溶液中,葡萄糖氧化酶(GOD)催化葡萄糖与溶解氧反应生成H₂O₂;辣根过氧化物酶(HRP)催化H₂O₂氧化过量的KI生成I-₃, I-₃分别与罗丹明S(RhS), 罗丹明6G(Rh6G), 丁基罗丹明B(b-RhB), 罗丹明B(RhB)结合形成缔合物微粒,使得4体系分别在556,556,584和584 nm处的荧光峰强度线性降低。在最佳条件下,葡萄糖的浓度分别在0.083～9.99,0.17～8.33,0. 33～8.33,0. 33～9.99 μmol·L-1范围内与RhS,Rh6G,b-RhB,RhB四体系的荧光猝灭强度呈良好的线性关系,其回归方程、相关系数、检出限分别为ΔF=40.0c+ 3.0,ΔF=23.9c+8.1,ΔF=25.6c+4.2,ΔF=18.4c+ 0.8;0.995 1,0.997 3,0.996 0,0.996 5;0.059,0.17,0.21,0.16 μmol·L-1。RhS催化体系最灵敏、稳定,将其用于人血清中葡萄糖的检测,结果满意。     

罗丹明6G缔合微粒光度法检测羟自由基及其在离体筛选抗氧化剂中的应用

在HCl-NaAc缓冲溶液中,Fenton反应产生的羟自由基被过量的KI捕获;生成的I-₃分别与罗丹明B(λ_max=554 nm)、罗丹明6G(λ_max=526 nm)、罗丹明S(λ_max=526 nm)和丁基罗丹明B(λ_max=556 nm)形成缔合微粒,导致其吸收峰降低。羟自由基浓度(以H₂O₂浓度计)分别在0.136～0.68 μg·mL-1,0.064～0.680 μg·mL-1,0.064～0.680 μg·mL-1和0.064～0.680 μg·mL-1范围内与罗丹明B、罗丹明6G、罗丹明S和丁基罗丹明B体系的吸光度降低值成正比。据此建立了一种测定抗氧化剂对羟自由基的清除率的新方法。测试了抗坏血酸等4种抗氧化剂以及6种茶叶提取液的抗氧化活性,所得到的结果较为满意。     

碘、碘离子和碘三离子的紫外吸收光谱

研究了碘I₂、碘离子I- 和碘三离子I-₃ 水溶液的紫外吸收光谱,测定了三种型体的摩尔吸光系数。I₂水溶液在203 nm呈现一吸收峰,摩尔吸光系数为1.96×104 L·mol-1·cm-1;I- 水溶液在193和226 nm呈现双吸收峰,摩尔吸光系数分别为1.42×104和1.34×104 L·mol-1·cm-1;当I₂水溶液与KI溶液混合时,在288和350 nm出现两个吸收峰,表明I-₃的形成。利用饱和法测得I-₃在288和350 nm处的摩尔吸光系数分别为3.52×104和2.32×104 L·mol-1·cm-1。     

罗丹明B荧光猝灭法测定水中痕量亚氯酸根

在有KI存在的乙酸钠-HCl酸性缓冲溶液中,用520 nm光激发罗丹明B(RhB),在580 nm处有一个荧光峰。当有亚氯酸根(ClO-2)存在时,罗丹明B荧光峰发生猝灭。亚氯酸根浓度在0.021 8～0.51 μg·mL-1范围内与荧光猝灭强度成线性关系,据此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(ClO-₂)的分析,结果令人满意。     

基于银纳米三角片与罗丹明6G的荧光共振能量转移法检测钴离子

以罗丹明6G和牛血清白蛋白的复合物为荧光探针,银纳米三角片为猝灭剂,研究了银纳米三角片与荧光复合物的荧光共振能量转移现象,建立了测定钴离子的荧光分析法。研究发现,一定浓度的荧光复合物与银纳米三角片混合后,由于荧光复合物在银纳米三角片上吸附而发生荧光共振能量转移,荧光猝灭达到80%左右。当钴离子存在时,银纳米三角片与罗丹明6G荧光共振能量转移被破坏,荧光逐渐恢复。随着钴离子浓度的增加,体系荧光值的恢复率(I/I₀)与钴离子的浓度(c_Co2+)有良好的线性关系,线性回归方程为I/I₀=1.054+21.72 c_Co2+,相关系数r2为0.996 2。通过对自然水样进行加标回收检测,实现了钴离子的定量检测,回收率在90.4%～115.1%之间。建立了一种可靠的选择性检测钴离子的荧光分析方法。     

1 520 nm激光激发的Er(0.5):FOG材料的上转换发光与立体显示研究

立体显示为现代重要的科学前沿。上转换三维立体显示为一种新颖的自体视三维立体显示,在1996年被评为十大科技创新成就之一,现正向应用快速发展。研究了1 520 nm半导体激光激发的Er(0.5):FOG材料的上转换发光,发现了(407.43, 411.20 nm), (522.51m, 528.57 nm), (540.53m, 543.70,549.00 nm), (654.75m, 665.50 nm), 和802.10m nm的上转换发光(m代表主峰),依次为(2G4F2H)_9/2→4I_15/2, 4H_11/2→4I_15/2, 4S_3/2→4I_15/2, 4F_9/2→4I_15/2和4I_9/2→4I_15/2的跃迁。值得注意的是上转换发光强度随激光功率变化的双对数曲线的斜率有各种各样的值。通过详细研究发现(407.43, 411.20 nm)的(2G4F2H)_9/2→4I_15/2上转换发光是四光子荧光;(522.51m, 528.57 nm)的2H_11/2→4I_15/2,(540.53m, 543.70,549.00 nm)的4S_3/2→4I_15/2和(654.75m, 665.50 nm)的4F_9/2→4I_15/2的上转换发光为三光子荧光;而802.10m nm的4I_9/2→4I_15/2上转换发光为双光子荧光。很明显从基态4I_15/2到第一激发态的吸收很大,因为它的振子强度f和与1 520 nm激光的匹配都很好,随后的起源于第一激发态的能量传递和相继吸收都很易于发生,这导致了1 520 nm激光激发下的Er(0.5): FOG材料的丰富和有意义的上转换发光现象。     

吖啶橙-罗丹明B荧光共振能量转移猝灭法测定砷

研究了利用吖啶橙(AO)-罗丹明B(RB)共振能量转移荧光猝灭法测定痕量砷的方法。在λ_ex/λ_em=470/580 nm,0.016 mol·L-1 H₂SO₄溶液中,十二烷基苯磺酸钠(DBS)存在下,吖啶橙-罗丹明B能够发生有效的能量转移,使罗丹明B的荧光强度大大增强;在酸性条件下,砷与钼酸铵生成砷钼杂多酸使能量转移体系罗丹明B的荧光猝灭。利用吖啶橙-罗丹明B能量转移荧光猝灭法测定痕量砷,砷在0.01～0.25 mg·L-1范围内与罗丹明B荧光猝灭程度呈良好的线形关系,方法检出限为2.56 μg·L-1。该方法用于茶叶中痕量砷的测定,相对标准偏差为0.48%～0.64%,回收率为98%～103%,结果满意。     

催化分光光度法测定辣根过氧化物酶新方法研究

本文基于微量辣根过氧化物酶 (HRP)对过氧化氢氧化还原型罗丹明B这一显色反应的催化作用 ,建立了一个高灵敏度测定HRP及其酶标记结合物的催化光度新方法 ,探讨了该催化反应体系的反应条件及干扰情况 ,实验表明 β CD能显著增强还原型罗丹明B的稳定性 ,邻苯二胺对该催化反应有催化诱导作用。应用于测定痕量辣根过氧化物酶 ,其检出限为 12pg·mL-1,其线性范围为 15～ 2 5 0pg·10mL-1,RSD为4 2 5 % (n =10 )。     

交换纤维柱分离ICP-AES测定高纯氧化镱中La、Nd、Eu和Gd

以强酸型离子交换纤维柱分离富集高纯Yb₂O₃中La,Nd,Eu和Gd等痕量杂质元素,并用Optima 5300 DV ICP-AES测定分离富集后的这4种元素。供试纤维对Yb的动态吸附容量为134 mg·g-1,4.0 g纤维柱的分离条件为：pH 3.00的试液以1.0 mL·min-1流速上柱后,分离柱先以流速为1.5 mL·min-1的pH 3.00 HNO₃溶液80 mL预淋洗,再以同样流速pH 5.00的0.01 mol·L-1 EDTA铵溶液淋洗。结果表明：10 mg Yb与各为0.100 μg的La,Nd,Eu和Gd能达到基线分离;分离含100 mg Yb的试液后,在杂质富集液中Yb的残留浓度仅为0.017 1 μg·mL-1。 研究显示,当待测试液中Yb₂O₃的浓度小于100 μg·mL-1(如Yb 87.8 μg·mL-1)时,它对测定La,Nd,Eu和Gd等杂质元素的基体干扰可以忽略不计。富集倍数分别为La₂O₃ 3.68×105,Nd₂O₃ 4.20×105,Eu₂O₃ 3.82×105,Gd₂O₃ 4.01×105。方法检出限分别为La₂O₃ 0.005 0 pg·mL-1,Nd₂O₃ 0.014 pg·mL-1,Eu₂O₃ 0.001 8 pg·mL-1,Gd₂O₃ 0.008 2 pg·mL-1。本方法已用于99.99% Yb₂O₃样品中4种稀土杂质的测定,标准加入的平均回收率分别为La₂O₃ 94.2%,Nd₂O₃ 107%,Eu₂O₃ 97.8%,Gd₂O₃ 102%,RSD (%, n=5)分别为La₂O₃ 6.2,Nd₂O₃ 5.9,Eu₂O₃ 7.3,Gd₂O₃ 2.5,校正曲线不需进行Yb的基体匹配,分析周期为4 h。     

氢化物发生-催化共振瑞利散射光谱法测定痕量砷

在硫酸介质中,以硼氢化钠(NaBH₄)为还原剂,可将As(Ⅲ)还原为砷化氢(AsH₃)气体使其逸出,用Ce(SO₄)₂-H₂SO₄-KI混合液做吸收液,在催化剂KI存在下四价铈与AsH₃气体反应生成具有共振瑞利散射(RRS)的砷微粒和具有荧光的三价铈,导致体系在370 nm处的RRS信号和在351 nm处的荧光强度增大。在选定条件下,As(Ⅲ)浓度分别在0.006～0.76 mg·L-1和0.006～0.28 mg·L-1范围内与RRS增加值ΔI和荧光强度增大值ΔF₃₅₁呈线性关系,检出限均为3.0 μg·L-1。据此可建立新的检测As(Ⅲ)的催化RRS和荧光光谱法。     

罗丹明6G缔合微粒共振散射光谱法测定过氧化氢

在0.020mol.L-1HCl-4.0×10-4mol.L-1KI-1.6×10-5mol.L-1Mo(Ⅵ)介质中,罗丹明6G(RhG)在540nm处有1个荧光峰,在540nm处有1个同步荧光峰。当有H2O2存在时,H2O2与过量的I-反应生成I3-,I3-与RhG形成缔合微粒,在320,400,595nm处产生3个共振散射(RS)峰;而在540nm处荧光峰猝灭。H2O2浓度在0.068~34μg.mL-1范围内与400nm波长处的共振散射光强度呈线性关系。据此建立了一个测定水中H2O2的共振散射光谱分析法。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RS增强和荧光猝灭的根本原因。     

Opto-acoustic study of tinuvin-P and rhodamine 6G in solid polymeric matrices

Laser-induced opto-acoustic calorimetry has been used to examine the thermo-elastic properties of two polymer matrices doped with tinuvin-P and the radiation-less decay processes of rhodamine 6G (Rh6G) in them. The matrices assayed were methyl methacrylate (MMA) homopolymers P(MMA), and methyl methacrylate and 2-hydroxyethyl methacrylate (HEMA) copolymers P(MMA:HEMA). A slight difference in the thermo-elastic properties of the polymers, namely their adiabatic expansion coefficients, has been detected and found to correlate with the long-term stability of the laser material. This suggests a key role of the heat-dissipation processes in the photostability of these polymeric materials. On the other hand, the fluorescence quantum yield of Rh6G is shown to vary with the polymer-matrix composition in a way consistent with its lasing efficiency. The Rh6G absorption and fluorescence quantum yield also change dramatically upon increasing its concentration, which suggests the co-existence of different Rh6G forms with different photophysical properties. Received: 10 February 2000 / Revised version: 12 June 2000 / Published online: 10 January 2001     

Diffusion Coefficients of Several Rhodamine Derivatives as Determined by Pulsed Field Gradient–Nuclear Magnetic Resonance and Fluorescence Correlation Spectroscopy

Rhodamine derivatives are popular, photostable fluorophores that are used in a number of fluorescent based techniques, including fluorescence correlation spectroscopy (FCS). Indeed, in FCS, both rhodamine 6G (R6G) and rhodamine 110 (R110) are used as calibration standards to determine the dimensions of the instrument confocal volume. In spite of a requirement for precise values of the diffusion coefficients, literature values are scarce and vary over an order of magnitude. In this paper, the diffusion coefficients of four rhodamine fluorophores (rhodamine 6G (R6G), rhodamine B (RB), rhodamine 123 (R123), rhodamine 110 (R110)) were determined by pulsed field gradient nuclear magnetic resonance (PFG-NMR) spectrometry and then validated by comparison with fluorescence correlation spectroscopy. With the objective of validating the FCS calibration, diffusion coefficients of several dextrans and a polystyrene nanoparticle were also determined and compared with literature values or theoretical values that were based upon the Stoke–Einstein equation. The work presented here lead us to conclude that the diffusion coefficients for R6G and R110 have generally been underestimated in the literature. We propose revised values of 4.4 × 10⁻¹⁰ m² s⁻¹ for R110 and 4.0 × 10⁻¹⁰ m² s⁻¹ for R6G. Using the revised D value for R110 to calibrate the FCS instrument, diffusion coefficients have then been systematically determined for different conditions of pH, ionic strength and concentration. To correct for differences due to solvent effects (D₂O vs. H₂O), an isotopic correction factor, of 1.23, was determined from both FCS and from the solvent auto-diffusion coefficients obtained by NMR.     

Fluorescence quantum yields of some rhodamine dyes

Fluorescence quantum yields of seven rhodamine dyes were measured relative to quinine sulfate dihydrate (QSH) in 1.0 N H₂SO₄. The values obtained were rhodamine 6G (0.95), B (0.65), 3B (0.45), 19 (0.95), 101 (0.96), 110 (0.92), 123 (0.90) at 25.0°C. Effects of temperature on the quantum yields of rhodamine B and QSH show a large temperature coefficient for rhodamine B and a significant one for QSH. Dye concentration was found to be critical in reporting observed fluorescence wavelength maxima.     

一个灵敏测定过氧化氢的吖啶红共振散射光谱新方法

在pH为5.0的HAc-NaAc缓冲液中,Fe2 催化H2O2产生·OH,·OH氧化I-为I2.过量I-与I2反应生成的I-3,与吖啶红(AR)形成AR-I3缔合物分子.在疏水作用和分子间力作用下,AR-I3缔合物分子自动聚集形成(AR-I3)n缔合物微粒.该缔合物微粒在320,400,595 nm处产生3个共振散射峰.H2O2的浓度在0.50～16.0×10-6 mol·L-1范围内与400 nm波长的共振散射光强度成线性关系,方法的检出限为2.0×10-7 mol·L-1 H2O2,用于废水中H2O2的测定,结果满意,回收率在97.9%～101.2%之间.     

若干多钒硼酸盐簇合物的光谱研究

合成了具有[(VO)₁₂O₆B₁₈O₄₂]簇骼的4种新颖的多钒硼酸盐簇合物：(enH₂)₆H₃[(VO)₁₂O₆B₁₈O₄₂]·13H₂O(1),[Ni(en)₂]₆H₃[(VO)₁₂O₆B₁₈O₄₂]·8H₂O(2),[Cu(en)₂]₅H₃[(VO)₁₂O₆B₁₈O₄₂][B(OH)₃]₂·16H₂O(3)和(enH₂)₄Na₄H₃[(VO)₁₂O₆B₁₈O₄₂]·8H₂O(4)。通过FTIR, UV-Vis DRS和荧光光谱等手段对其进行了研究,探讨了结构和性能的关系。其中,化合物(1)含有[(VO)₁₂O₆B₁₈O₄₂]的分立结构,环状B₁₈O₄₂通过8个B—(μ₃—O)—V键被两个V₆O₁₈簇夹在中间;而化合物(2)是在(1)的基础上,由6个[Ni(en)₂]各自通过两个Ni—(μ₃—O)—B与B₁₈O₄₂的桥氧配位形成另一类新的分立型结构;化合物(3)和(4)的[(VO)₁₂O₆B₁₈O₄₂]构筑单元间分别通过[Cu(en)₂]2+和无机Na+离子桥联形成二维层状结构。多钒硼酸盐簇合物的特征振动频率和这些化合物的结构相关;UV-Vis DRS表明,在205和260 nm附近出现金属氧簇化合物的荷移跃迁;用310 nm光激发, 在约415 nm处能引起由O_μ→Mo的荧光发射, 同时还研究了其荧光寿命。     

Charge‐dependent adsorption of rhodamine 6G on gold nanoparticle surfaces: fluorescence and Raman study

We study the adsorption behaviors of rhodamine dyes on gold nanoparticles (Au NPs) depending on their surface charges. Rhodamine 6G (Rh6G) dye is tested comparatively for positively and negatively charged Au NPs prepared by the reduction of chitosan and citric acid, respectively. The adsorption of Rh6G is found to be weaker on the positively charged Au NPs, whereas more substantial aggregation is found on negatively charged Au NPs. An increase in the concentration of Au NPs enhances the surface‐enhanced Raman scattering (SERS) intensities only for the Au(−) NPs, whereas the Au(+) NPs do not exhibit any strong SERS signals. Our findings suggest that SERS and reciprocal fluorescence measurements of Rh6G can be used to estimate the surface charges and atomic percentages of Au NPs less than ∼5 ppm. Copyright © 2011 John Wiley & Sons, Ltd.     

纳米氧化铁/膨润土催化剂的制备、表征及复相光降解罗丹明B的研究

钠基膨润土与羟基铁溶液反应,经过焙烧,制得性能良好的纳米复合型催化剂,结合比表面孔隙分析(BET)、X射线衍射谱(XRD)和高分辨扫描电镜(HRTEM)对催化剂的比表面积、晶相和粒度进行表征。用光度法对该催化剂降解染料罗丹明B进行了研究,详细考察了溶液起始pH值、H₂O₂浓度、催化剂用量和起始浓度对降解的影响以及催化剂的可重复使用性,紫外-可见光谱对降解过程进行跟踪检测,并对复相光助Fenton过程与均相光助Fenton过程进行了比较。结果表明,复合型催化剂具有很高的比表面积,铁以高催化活性的α-Fe₂O₃存在于复合催化剂中;在pH 3.0,催化剂浓度为0.3 g·L-1,H₂O₂浓度为10 mmol·L-1实验条件下,100 mL 2.5×10-5 mol·L-1罗丹明B,紫外光照射4 h后,紫外-可见光谱显示罗丹明B的特征峰消失,其脱色率和COD_Cr去除率分别为97%和71%,对该催化剂进行处理后,可以重复使用,复相光降解率要远大于均相光降解率。