Determination of trace metallothioneins at nanogram levels with Eosin Y by resonance light scattering method

The interactions of metallothioneins with Eosin Y were studied by the absorption spectra and resonance light scattering (RLS) spectra methods. A direct RLS spectra method was applied for the determination of trace metallothioneins. The interaction of Eosin Y and metallothioneins enhanced the RLS intensity of system in Britton-Robinson buffer (pH 3.91), with the help of anionic surfactant (sodium dodecyl benzene sulphate). The mechanism was studied and discussed in terms of the RLS and UV-absorption spectra. Under optimal experimental conditions, at 366 nm, there was a linear relationship between the RLS intensity and the concentration of the metallothioneins in the range of 0.04–14.0 μg mL^?1, with a correlation coefficient of r = 0.9985 and detection limit of 11.9 ng mL^?1. The relative standard deviation was 3.1% (n = 11), and the average recovery was 95.2%. The method proposed was reliable, selective and sensitive in determining trace metallothioneins in human urine samples with the results in good agreement with those obtained by high-performance liquid chromatography.     

Sensitive Determination of Prulifloxacin by Its Fluorescence Enhancement on Terbium(III)–Sodium Dodecylbenzene Sulfonate System

Abstract

A terbium-sensitized fluorescence spectrophotometry method using an anionic surfactant, sodium dodecyl benzene sulphonate (SDBS), was developed for the determination of prulifloxacin (PUFX). It was found that SDBS significantly enhanced the fluorescence intensity of the PUFX–Tb³⁺ complex (about 13-fold). The optimal experimental conditions were determined as follows: excitation and emission wavelengths of 290 nm and 545 nm, pH 8.0, 4.0 × 10^?5 mol L^?1 terbium(III), and 4.0 × 10^?4 mol L^?1 SDBS. The enhanced fluorescence intensity of the system (ΔF) showed a good linear relationship with the concentration of PUFX over the range 6.0 × 10^?8 to 2.0 × 10^?6mol L^?1 with a correlation coefficient of 0.9991. The detection limit (S/N = 3) was determined as 8.5 × 10^?9 mol L^?1. This method has been successfully applied for the determination of PUFX in pharmaceuticals and human urine/serum samples. Compared with most other methods reported, the rapid and simple procedure proposed here offered higher sensitivity, wider linear range, and good stability. The luminescence mechanism of the system was also discussed in detail. In the fluorescence system of PUFX–Tb³⁺–SDBS, SDBS acted not only as the surfactant but also as the energy donor.     

DNA对Ru(bpy)_2(dppx)~(2+)-SDS体系共振光散射的猝灭作用及其应用

研究了Ru(bpy)2(dppx)2+-SDS-DNA(bpy=2,2′-联吡啶,dppx=7,8-二甲基-吡啶并[3,2-a:2′,3′-c]吩嗪)体系的共振光散射光谱。结果表明,在阴离子表面活性剂十二烷基硫酸钠(SDS)预胶束聚集体存在下,Ru(bpy)2(dppx)2+-SDS体系具有很强的共振光散射,DNA的加入使其共振散射光猝灭。探讨了反应机理。基于DNA对Ru(bpy)2(dppx)2+-SDS体系共振光散射的猝灭作用,建立了共振光散射法测定DNA的新方法。在最佳实验条件下,体系在393nm处的共振光散射猝灭程度与DNA的浓度呈线性关系,线性范围为0.01～1.2mg/L,检出限为1.5μg/L。     

阴离子表面活性剂作为添加剂种子生长法制备尺寸可调的单分散金纳米棒

以不同阴离子表面活性剂作为添加剂种子生长法制备金纳米棒, 并考察阴离子表面活性剂种类对金纳米棒形貌及光学性质的影响。在十二烷基苯基磺酸钠(SDBS)存在下, 金纳米棒的产率明显高于使用十二烷基磺酸钠的反应体系。对添加SDBS的种子生长法制备金纳米棒的反应条件进行优化, 得到十六烷基三甲基溴化铵、SDBS、抗坏血酸和硝酸银的最佳浓度分别为0.04 mol·L^-1、2.4 mmol·L^-1、1.2 mmol·L^-1和0.08 mmol·L^-1。在此条件下, 金纳米棒的生长在30 min内完成, 所制备的金纳米棒表面等离子共振吸收峰位于823 nm, 其横纵比为(5±0.03)。当改变生长液中硝酸银浓度时, 金纳米棒的尺寸也随之发生改变。此外, 我们还探讨了SDBS的作用机理。相对于经典种子生长法, 新方法制备纳米金棒在尺寸可调性、单分散性和生物毒性方面明显改善, 可广泛应用于各种光学及生物分析。     

Study on the Interaction between a Novel Ionic Liquid Probe and Anionic Surfactants Using Resonance Light Scattering Spectra and Its Analytical Application

The interaction between anionic surfactants (AS) and 1‐hexadecyl‐3‐methylimidazolium bromide [C₁₆mim]Br was studied by using resonance light scattering (RLS) technique, UV‐Vis spectrophotometry and fluorometric methods. In Britton Robinson (BR) buffer (pH 6.0), [C₁₆mim]Br reacted with AS to form supermolecular complex which resulted in enhancement in RLS intensity. Their maximum RLS wavelengths were all at 390 nm. Some important interacting experimental variables, such as the solution acidity, [C₁₆mim]Br concentration, salt effect and addition order of the reagents, were investigated and optimized. Under the optimum conditions, quantitative determination ranges were 0.001–7 μg·mL^?1 for dodecyl sodium sulfate (SDS), 0.001–6 μg·mL^?1 for sodium dodecylbenzene sulfonate (SDBS) and 0.005–7 μg·mL^?1 for sodium lauryl sulfonate (SLS), respectively, while the detection limits were 1.3 ng·mL^?1 for SDS, 1.0 ng·mL^?1 for SDBS and 5.1 ng·mL^?1 for SLS, respectively. Based on the ion‐association reaction, a highly sensitive, simple and rapid method has been established for the determination of AS.     

Determination of bovine serum albumin using resonance light scattering technique with sodium dodecylbenzene sulphonate-cetyltrimethylammonium bromide probe

In this paper, the anionic surfactant sodium dodecylbenzene sulphonate (SDBS) and cationic surfactant cetyltrimethylammonium bromide (CTMAB) were used as resonance light scattering (RLS) probe to determine bovine serum albumin (BSA). Based on the weak RLS intensity of SDBS-CTMAB probe and the enhancement of RLS intensity of BSA in the presence of the probe, a simple assay for BSA was developed. The experimental results showed that the formation of three component complex BSA-SDBS-CTMAB is the main reason for the enhancement of RLS intensity of BSA, in which SDBS as a bridge can interact with both BSA and CTMAB. The effects of pH value, incubation time, concentrations of SDBS and CTMAB on the enhanced RLS intensity of BSA were investigated. Under the optimum conditions, the enhanced RLS intensity is proportional to the concentration of BSA in the range from 2.5 x 10(-8) to 2.0 x 10(-6)mol L(-1). The detection limit is 9.7 x 10(-9) mol L(-1) for BSA. The study of foreign substance effect on the determination of BSA indicated that most of metal ions have little effect on the determination of BSA. The results of assay for BSA in synthetic samples were satisfactory.     

阴离子表面活性剂作为添加剂种子生长法制备尺寸可调的单分散金纳米棒

以不同阴离子表面活性剂作为添加剂种子生长法制备金纳米棒,并考察阴离子表面活性剂种类对金纳米棒形貌及光学性质的影响。在十二烷基苯基磺酸钠(SDBS)存在下,金纳米棒的产率明显高于使用十二烷基磺酸钠的反应体系。对添加SDBS的种子生长法制备金纳米棒的反应条件进行优化,得到十六烷基三甲基溴化铵、SDBS、抗坏血酸和硝酸银的最佳浓度分别为0.04 mol.L-1、2.4 mmol.L-1、1.2 mmol.L-1和0.08 mmol.L-1。在此条件下,金纳米棒的生长在30 min内完成,所制备的金纳米棒表面等离子共振吸收峰位于823 nm,其横纵比为(5±0.03)。当改变生长液中硝酸银浓度时,金纳米棒的尺寸也随之发生改变。此外,我们还探讨了SDBS的作用机理。相对于经典种子生长法,新方法制备纳米金棒在尺寸可调性、单分散性和生物毒性方面明显改善,可广泛应用于各种光学及生物分析。     

Electrochemiluminescence of SDBS‐Ru(bpy)32+‐CPM System and Its Application

When the concentration of dodecyl benzene sulfonic acid sodium salt (SDBS) is 0.7 mmol·L^?1, the electrochemical and electrochemiluminescence (ECL) intensity of Ru(bpy)₃²⁺‐chlorpheniramine maleate (CPM) system at the Au electrode were studied. The results showed that compared with the absence of SDBS, enhancement of the ECL intensity was 14‐fold at Au electrode. Base on this, an ECL method was established for efficient and simple determination of CPM at Au electrode. Under the optimum experimental condition, the enhanced ECL intensities had good linear relationship with the concentration of CPM in the range of 1.0×10^?4–1.0×10^?7 mol·L^?1, and a linear regression equation was obtained as follows: I (counts)=48.805×10⁶c+394.03 (r=0.9975), the detection limit for CPM was 1.4×10^?8 mol·L^?1. The RSD for 5 times determinations of 1.0×10^?5 mol·L^?1 CPM was 3.2%. The results of recovery test were between 96.3%–102.5%, and the RSD of recovery test (n=5) was 2.7%. In addition, eleven kinds of tertiary amines‐Ru(bpy)₃²⁺ systems were investigated in the absence and presence of SDBS. The results showed that the enhancement of SDBS on ECL intensity of tertiary amines‐Ru(bpy)₃²⁺ systems was universal.     

Micro-pumping flow system for spectrophotometric determination of anionic surfactants in water

A novel procedure has been developed for spectrophotometric determination of anionic surfactants in water using a solenoid micro-pump as fluid-propulsion device. The proposed method is based on substitution of methyl orange (MO) by anionic surfactants in the formation of an ion-pair with the cetyl pyridine ion (CPC⁺) at pH 5.0. The flow network comprised four solenoid micro-pumps which, under microcomputer control, enabled sample and reagent introduction, and homogenisation in the reaction zone. The system is flexible and simple to operate and control, and sensitive and precise. The analytical plot for the anionic surfactant was linear between 1.43×10^–6 and 1.43×10^–5 mol L^–1 (0.5 to 5.0 mg L^–1; R=0.997, n=5). The relative standard deviation was 0.8% (n=11) for a sample containing 5.74×10^–6 mol L^–1 (2 mg L^–1) surfactant. The limit of detection was 9.76×10^–8 mol L^–1 (0.034 mg L^–1) and the sampling throughput was 60 determinations per hour. The results obtained for washing-water samples were comparable with those obtained by use of the reference method, and no significant differences at the 95% confidence level were observed.     

Resonance light-scattering method for the determination of BSA and HSA with sodium dodecyl benzene sulfonate or sodium lauryl sulfate

A new resonance light-scattering (RLS) assay of proteins such as bovine serum albumin (BSA) and human serum albumin (HSA) is presented. In the medium of phosphoric acid (pH=2.6), the weak RLS of sodium dodecyl benzene sulfonate (SDBS) or sodium lauryl sulfate (SLS) can be greatly enhanced by proteins, owing to interaction between the protein and the anionic surfactant and formation of an associate. The RLS intensity of the SDBS–protein system is stronger than that of the SLS–protein system under same experimental conditions. It is considered that the synergistic resonance caused by the absorption of both protein and SDBS could produce strong RLS, while absorption of protein only in the SLS system could cause relatively weak RLS. The enhanced intensity of RLS is proportional to the concentration of the protein. If SDBS is used as the probe the linear range is 7.5×10^–9–1.5×10^–5 g mL^–1 for BSA and 1.0×10^–8–1.0×10^–5 g mL^–1 for HSA. The detection limits are 1.8 and 2.8 ng mL^–1, respectively. When SLS is used as the probe the linear range is 2.0×10^–8–1.0×10^–5 g mL^–1 and 2.5×10^–8–1.0×10^–5 g mL^–1 for BSA and HSA, respectively, and the detection limits are 12.8 and 21.6 ng mL^–1, respectively. The biological mimics samples are synthetic concoctions of BSA and HSA with some interferents. In these samples, the concentration of interferents is higher than the concentration normally existing in organisms. The samples were determined satisfactorily.     

Studies on the Toluidine Blue Dimer as a Fluorescence Probe for Protein Assays

Abstract

A spectrofluorometric method was developed for the determination of total serum protein by exploring toluidine blue (TB) as the fluorescence probe. The fluorescence intensity of TB at 648 nm was significantly quenched in the presence of sodium dodecylbenzene sulfonate (SDBS) by forming a dimer of the dye, which can afterwards reconvert to monomer when proteins were added accompanied by the recovery of the fluorescence. This might be attributed to the modulated transferring of the dimer‐monomer equilibrium of TB in the anionic surfactant caused by the addition of protein. A linear calibration graph was obtained in the range of 0.5–50 mg/l BSA, with a detection limit of 0.15 mg/l and a RSD of 1.3% (n=11, 5.0 mg/l BSA). Total proteins in human serums were analyzed by using the present procedure and the results agreed well with those obtained by the Biuret method.     

Polychlorinated Biphenyls-contaminated Soil Washing with Mixed Surfactants Enhanced by Electrokinetics

On the basis of comparing the adsorption loss of different surfactants[single nonionic surfactant sorbitanmonooleatepolyoxyethylene ether(Tween 80), anionic surfactant sodium dodecyl benzene sulfonate(SDBS), and mixed surfactants Tween 80/SDBS(3:2), Tween 80/SDBS(4:1)] and their performance in the enhancement of polychlorinated biphenyls(PCBs) desorption from soil, the impact of electric field intensity on the desorption of PCBs and the transport of surfactants in washing resulted solution were investigated in this study. With regard to the remediation cost, 1000 mg/L mixed Tween 80/SDBS(3:2) was recognized as an optimum concentration in the remediation of PCBs-contaminated soil, because Tween 80/SDBS(3:2) had the highest washing capacity and relatively low adsorption loss onto soil. Electrokinetics can enhance the washing efficiency of PCBs-contaminated soil by Tween 80/SDBS(3:2) effectively and safely at an electric field intensity of 1.5 V/cm for 10 d, for the desorption of PCBs was 1.57 times more than that without electrokinetics, and the most of organic residue in washing resulted solution was removed in an electrical field to avoid the possible secondary contamination risk.     

Effect of Cyclodextrins on the Interaction Between BSA and Sodium Dodecyl Benzene Sulfonate

Cyclodextrins offer the potential of modulating protein–surfactant interactions. In our work, the effect of cyclodextrin (CD) on the interaction between bovine serum albumin (BSA) and the anionic surfactant sodium dodecyl benzene sulfonate (SDBS) has been studied by isothermal titration calorimetry (ITC), fluorescence spectra and circular dichroism measurements. The presences of cyclodextrin can slightly hinder the strong interactions between BSA and SDBS by the combination of electrostatic and hydrophobic interactions between BSA and SDBS. Furthermore, the effectiveness of α-CD is lower than that of β-CD, due to the lower association constant between α-CD and surfactant. The presence of both α- and β-CD totally hinders the nonspecific interactions between BSA and SDBS, because the hydrophobic interaction between cyclodextrin and surfactant is stronger than that between BSA and surfactant.     

Use of Gemini surfactant in a one-step ellagic acid assay by resonance light scattering technique

Ellagic acid (EA) reacted with Gemini zwitterionic surfactant, phosphodiesters quaternary ammonium salt (PQAS), and formed fine particles which produced strong enhancement in intensity of resonance light scattering (RLS). The effects of several factors on the RLS signal, such as pH, ionic strength, PQAS concentration and so on, were optimized. The relationship between enhanced RLS intensity and EA concentration was constructed. A novel and rapid method for the determination of EA was built. The linear range of this method was 0.016-4.0 μg mL⁻¹ and the detection limit was 13.9 ng mL⁻¹. Under the optimum conditions, the proposed method was applied to determine EA in body fluids with the results of quantitative recoveries between 98.4-101.4% in human serum samples and 99.1-102% in human urine samples. This method characterized by low limit detection is very sensitive and the cost is low, and constitutes a fast one-step procedure which requires only measuring the RLS intensities. The mechanism of the reaction was also studied. This investigation could contribute to the research on the delivery and release of bioactive molecules by Gemini surfactants.     

The Effect of Sodium Dodecylbenzenesulfonate (SDBS) Micelles on a BelousovZhabotinsky Oscillating System Catalyzed with a Tetraazamacrocyclic Copper(II) Complex

This article deals with the influence of micelles of the anionic surfactant sodium dodecyl benzene sulfonate (SDBS) on the Belousov? Zhabotinsky (B? Z) oscillating reaction catalyzed by a tetraazamacrocyclic copper(II) complex [CuL](ClO₄)₂, an enzyme‐like catalyst (L=5,7,7,12,14,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradeca‐4,11‐diene). Unlike the classical B? Z oscillator in which malonic acid is usually used as a substrate, malic acid (an intermediate in the Krebs cycle) is involved in this oscillating system. Experiments reveal that formation of the SDBS micelles markedly affects the behavior of the oscillating reaction. It is found that there is a linear relationship between the change in the oscillation amplitude (ΔA) and the concentration of SDBS, whereas the change in the oscillation period (ΔT) is linearly proportional to the SDBS concentration. The most likely mechanism that involves the formation of the SDBS micelles and the effects of the micelles on the oscillating chemical system can be rationalized by assuming that the SDBS micelles are so negatively charged that they attract more [CuL]³⁺ than [CuL]²⁺. This hypothesis was confirmed by UV/VIS spectrophotometric measurements of a constant concentration of [CuL](ClO₄)₂ in different concentrations of SDBS; as the SDBS concentration increased, the absorbance of [CuL](ClO₄)₂ increased, while the maximum absorption wavelength for [CuL](ClO₄)₂ remained at 502 nm.     

Synergistic interactions between zwitterionic surfactants derived from olive oil and an anionic surfactant

Abstract

The surface properties of the mixtures of zwitterionic surfactants derived from olive oil (carboxylbetaine-OCB and sulfobetaine-OSB) and anionic surfactant-sodium dodecylbenzene sulfonate (SDBS) at different mole fractions were investigated by surface tension measurement. The influences of the addition of inorganic salts (NaCl, MgCl₂) on the surface activities in OCB/SDBS and OSB/SDBS systems were also studied. The result shows that the two mixed systems possess lower CMC values and higher surface activities over all mole fractions studied than their individual components. Meanwhile, the noticeable synergistic interactions of OCB/SDBS and OSB/SDBS were determined by the micelle interaction parameter (β^m) according to regular solution theory. It is observed that the mixed OCB/SDBS system at α_OCB?=?0.6 and the mixed OSB/SDBS system at α_OSB?=?0.6 exhibit the strongest synergism. In addition, the binary surfactant mixtures performed better surface activities upon addition of inorganic salts and the different valence state of mental ions of the inorganic salts had different surface ability effect on the mixed system: Mg²⁺?>?Na⁺.     

基于酞菁铜衍生物为载体的电极对水杨酸根的选择性电位响应

本文以2,9,16,23-四硝基酞菁铜(II) (Cu(II)TNPc) 和2,9,16,23-四氨基酞菁铜(II) (Cu(II)TAPc) 为载体制备PVC聚合膜,构建了水杨酸根选择性电极,并探讨了该电极的选择性响应性能。研究了增塑剂的性质、载体的含量及阴、阳离子添加剂对电极电位响应的影响。结果表明,基于Cu(II)TNPc为载体的PVC膜电极对水杨酸根 (Sal－) 呈现出优先选择性电位响应。具有最佳电位响应的电极的膜组成是：(w/w) 3.0% Cu(II)TNPc,67.0% o-NPOE,29.5% PVC和0.5% NaTPB。基于该组成的电极的线性响应范围为1.0×10－1－9.0×10－7 mol·L－1,检测下限为7.2×10－7 mol·L-1,斜率为－59.8±0.5 mV/decade;其响应快速,稳定性好,适宜的pH范围是3.0－7.0。并成功运用于了实际样品中水杨酸含量的测定,获得令人满意的结果。     

Determination of carbofuran by the quenching effect on resonance light scattering and its application to water and vegetable samples

A new method for the determination of carbofuran (CF) with DNA by a resonance light scattering (RLS) technique was developed. The intensity of RLS (I _RLS) of DNA–HCl system was significantly quenched in presence of CF. A RLS peak at 315.6 nm was found, and the quenched intensity of RLS was proportional to the concentration of CF. The linear range of the calibration curve was ≈0.02–2.0 µg mL^?1 and the detection limit (S/N = 3) 7 ng mL^?1. The CF in river water, cucumbers and rice samples was determined. The recovery rates were in the range of 90.0–111.1, 95.0–106, 93.0–111.0%, respectively. The mechanism of the reaction between CF and DNA is also discussed.     

Carbofuran: analytical methods and its determination in natural water samples by flow injection DPA(III)–H2SO4 chemiluminescence

This study proposes, a simple, rapid and sensitive chemiluminescent (CL) method for determination of carbofuran based on diperiodatoargentate(III) (DPA)-sulfuric acid (H₂SO₄) reaction coupled with flow injection (FI) methodology. Under optimum conditions, a linear standard curve is achieved in the range of 0.001–8.0 mg L^–1 (R²= 0.9994 (n = 11) with relative standard deviation (RSD) of 1.4–3.7% (n = 4)), a limit of detection (LOD) 5.0 × 10^–4 mg L^–1 (S/N = 3) and injection throughput 180 h^–1. The proposed method was applied satisfactorily for the analysis of carbofuran in freshwater samples using solid phase extraction (SPE) technique with the recoveries of 94–110% (% RSD = 1.7–3.8, n = 4). A possible CL reaction mechanism has also been discussed briefly.     

Effect of self‐assemblies of various surfactants in their single and mixed states on the BZ oscillatory reaction

Micelles of different surfactants are well known to affect chemical equilibria and reactivities by selectively sequestering the reagent substrates through electrostatic and hydrophobic interactions. In this article, the effects of micelles of various surfactants on different parameters of the Ce(IV)‐catalyzed Belousov–Zhabotinsky (BZ) oscillatory reaction at 35°C in nonstirred closed conditions are studied by employing spectrophotometry and tensiometry. Surfactants used in this study are the cationics hexadecyltrimethylammonium bromide (CTAB) and pentamethylene‐1,5‐bis(N‐hexadecyl‐N,N‐dimethylammonium)bromide gemini (Gemini), anionic sodium dodecylbenzene sulfonate (SDBS), and nonionic Brij58, whereas the binary surfactant systems used are cationic–nonionic CTAB+Brij58 and anionic–nonionic SDBS+Brij58. The results revealed that the induction period shows a definite variation with increasing concentration of different surfactants above their critical micelle concentration (cmc). The amplitudes of oscillation and absorbance maxima and minima are enhanced in the presence of micelles of CTAB and Gemini surfactants, whereas micelles of SDBS and Brij58 have almost no effect on the nature of the oscillations. However, mixed micelles of CTAB+Brij58 and SDBS+Brij58 binary mixtures show a quite different effect on the overall behavior of the oscillations. The enhanced effect of CTAB and Gemini surfactants on the overall nature of oscillations has been attributed to the positive charge on the surface of their micelles and to some extent on the presence of nitrogen in their head group. The effect of mixed binary micelles may be attributed to their synergistic nature. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 659–668, 2010