Voltammetric sensing of triclosan in the presence of cetyltrimethylammonium bromide using a cathodically pretreated boron-doped diamond electrode

ABSTRACT

In the present study, a simple, cheap and sensitive electrochemical method based on a cathodically pretreated boron-doped diamond (CPT-BDD) electrode is described for the detection of triclosan with the cationic surfactant (cetyltrimethylammonium bromide, CTAB) media. The oxidation of triclosan was irreversible and exhibited an adsorption controlled process. The sensitivity of the adsorptive stripping voltammetric measurements was significantly improved with addition of CTAB. Using square-wave stripping mode, a linear response was obtained for triclosan determination in Britton-Robinson buffer solution at pH 9.0 containing 2.5 × 10^?4 M CTAB at around + 0.67 V (vs. Ag/AgCl) (after 30 s accumulation at open-circuit condition). The method could be used in the range of 0.01–1.0 μg mL^?1 (3.5 × 10^?8–3.5 × 10^?6 M), with a detection limit of 0.0023 μg mL^?1 (7.9 × 10^?9 M). The feasibility of the proposed method for the determination of triclosan in water samples was checked in spiked tap water.     

Anodic stripping voltammetric determination of titanium(IV) using a carbon paste electrode modified with cetyltrimethylammonium bromide

A method is described for the voltammetric determination of titanium(IV) using a carbon paste electrode modified in situ with cetyltrimethylammonium bromide. The cationic micellar surfactant adsorbs onto the electrode particularly at negative potentials, simultaneously preconcentrating titanium(IV) as the oxalate complex with reduction to titanium(III). Anodic stripping voltammetry exploiting reoxidation can be used for the determination of trace levels of titanium(IV). Linearity between current and concentration exists between 5 and 160 mug l(-1) Ti(IV) (preconcentration time 2 min). The limit of detection (calculated as 3sigma) is 0.1 mug l(-1), with a preconcentration time of 10 min.     

Influence of the fluoride ion on the aggregation and catalytic properties of micellar solutions of cetyltrimethylammonium bromide

The influence of the fluoride ion on the aggregation behavior and catalytic properties of neutral and alkaline aqueous solutions of cetyltrimethylammonium bromide in nucleophilic substitution reactions of phosphorus acid esters was studied by tensiometry, small-angle neutron scattering, and UV spectrophotometry. The critical micelle concentrations and the radii, aggregation numbers, and shape of micelles forming in these systems, as well as the kinetic parameters of the nucleophilic substitution reactions of phosphorus acid esters, were determined.     

Simultaneous electrochemical determination of three sunscreens using cetyltrimethylammonium bromide

This paper proposes a methodology based on electrochemical reduction for the simultaneous determination of three sunscreen agents, namely 4-methylbenzylidene camphor (MBC), benzophenone-3 (BENZO) and 2-ethylhexyl-4-methoxycinnamate (EHMC) by differential-pulse polarography (DPP). The highest peak currents and optimal separation of reduction peaks were obtained by using a supporting electrolyte consisted of Britton-Robinson buffer-methanol (8:2) solution at pH 4.0 and cationic surfactant 3.0 x 10(-4)mol L(-1) cetyltrimethylammonium bromide (CTAB). The methodology was validated using four commercial sunscreen preparation as a sample and the results showed high recovery rates. The efficiency of the proposed methodology was demonstrated by comparing the results obtained by DPP with those obtained by the high-performance liquid chromatography (HPLC) method.     

Isotachophoretic separation of cetyltrimethylammonium bromide

Capillary isotachophoresis (ITP), equipped with the conductivity detection, was tested for the separation of cetyltrimethylamonium (CTMA) bromide. To prevent adsorption of CTMA to the capillary walls, several neutral polymers and ethanol were added into the leading electrolytes. Unlike polymer additives, the CTMA free monomers and micelles, created as a result of the isotachophoretic concentration effect, were recognised in the presence of ethanol from 10 to 25% (v/v). At 30% of ethanol, only a single zone of CTMA monomer was registered because the micellization process did not take place under this condition.Employing an ITP apparatus in the column-coupling configuration, the operational system with 30% of ethanol was tested for the determination of CTMA in hair conditioners. The achieved detection limits were about 0.02 mM. Both model solutions and real samples of hair conditioners were analysed with the precision about R.S.D. = 3%. One analysis in the column-coupled system takes circa 15 min.     

Ultrafiltration of cetyltrimethylammonium bromide solutions

Permeation data of cetyltrimethylammonium bromide (CTABr) in water by ultrafiltration (UF) through zircon membranes are reported as a first step in the knowledge of micellar enhanced ultrafiltration of heavy metals by cationic surfactants [1]. The experimental results are analysed using a model of diffusion in the membrane matrix based on the thermodynamics of irreversible processes (TIP). A comparison with the classical model of resistances in series indicates that these two approaches are consistent and that the TIP method leads to new insights into the observed resistances. The major insight relates to the understanding of the membrane resistance in terms of interactions membrane-permeants and permeants-permeants.     

Micellization and catalytic activity of the cetyltrimethylammonium bromide-Brij 97-water mixed micellar system

Surface tension measurements and the kinetic study of the basic hydrolysis of ethyl p-nitrophenyl chloromethyl phosphonate were used to examine the structural behavior and catalytic activity of the cethyltrimethylammonium bromide (CTAB)-polyoxyethylene (10) oleyl ether, C(18)H(35)(OCH(2)CH(2))(10)OH (Brij 97)-water mixed micellar system. Application of the regular solution model to the experimental data yields the value of the interaction parameter beta as -4.6, which indicates an attractive interaction of the surfactants in the mixed micelle and reflects synergistic solution behavior of the mixture. The mixed micellar composition is found to be enriched in the surfactant with the lower critical micelle concentration (cmc). In the kinetic study a nonmonotonic change in the pseudo-first-order rate constant of basic hydrolysis of the substrate is observed with increasing mole fraction of nonionic surfactant. The pseudophase micellar model reveals that the concentration factor mainly contributes to the catalytic effect, while the microenvironmental factor plays a negative role.     

Surfactant ion electrode measurements of sodium alkylsulfate and alkyltrimethylammonium bromide micellar solutions

EMF measurements in water at 25°C have been made using surfactant ion and counterion electrodes on two homologous series of long chain surfactants, the sodium alkylsulfates (R=n-C₈H₁₇ to n-C₁₄H₂₉) and the alkyltrimethylammonium bromides (R=C₁₀H₂₁ to C₁₆H₃₃). The data show evidence of association below the critical micelle concentration (CMC) but not of micelle ordering due to coulombic repulsion above this concentration.     

银纳米粒子共振光散射光谱法测定痕量CTMAB

利用十六烷基三甲基溴化铵(CTMAB)与银纳米粒子作用生成的聚集体,使体系的共振光散射(RLS)强度明显增强,建立了一种快速、简便的测定痕量CTMAB的RLS光谱法。考察了p H值,反应最佳时间,试剂加入顺序等因素对测定CTMAB的影响。实验结果表明,在p H值为10.88,作用时间为10 min,银纳米粒子浓度(以银原子计算)为2.5×10-3mol·L-1,按CTMAB、BR、银纳米粒子为添加顺序的条件下,测定CTMAB的线性范围为:5.0×10-9~5.0×10-7mol·L-1,检出限为3.8×10-9mol·L-1。该法用于合成样品中CTMAB的测定,灵敏度高,重现性好,结果准确。     

Adsorption of cetyltrimethylammonium bromide and cetyldimethylbenzylammonium chloride on a hanging mercury electrode studied by adsorptive transfer stripping voltammetry

The adsorption of cetyltrimethylammonium bromide (CTAB) and cetyldimethylbenzylammonium chloride (CDBACl) on a hanging mercury electrode is studied using adsorptive transfer stripping voltammetry. The surfactants are adsorbed on mercury and are then transferred in KBr or KCl under various conditions, including temperatures from 1 to 40°C, open or closed circuits with different initial potentials, and repeated scans, etc. The results are compared with previously published results on the adsorption of CTAB or CDBACl on mercury, where condensed films were formed and are quite different than those obtained by adsorptive stripping voltammetry. In this case, an absence of condensed film is observed for CTAB. A condensed film with low capacitance value is formed in the case of CDBACl after transfer at low temperatures, or after repeated scans, resulting in reorientation of the molecules to more compact states. Capacity time curves at the potentials where the film is formed show in a few cases a nucleation and growth mechanism, with induction time and studied by the Avrami formulation, while an observed increase of the capacitance with time is attributed to the formation of hemimicelles. The results also indicate the importance of interactions between the hydrophobic chains.     

Voltammetric behavior and determination of estrogens at Nafion-modified glassy carbon electrode in the presence of cetyltrimethylammonium bromide

A method is described for the determination of estrogens (estradiol, estrone and estriol) by stripping voltammetry. These estrogens yield one well-defined oxidation peak at the Nafion-modified glassy carbon electrode in the presence of cetyltrimethylammonium bromide (CTAB). The peak current is proportional to the concentration of estradiol in the range from 2.5×10⁻⁸ to 1.5×10⁻⁶ mol/l, and the detection limit is 1×10⁻⁹ mol/l after accumulation of 6 min. The total amounts of estrogens in the blood serums were determined using the voltammetric method, and the average recovery was 106.04%. The mechanism of the oxidation of estradiol was investigated by electrochemical techniques and UV spectra.     

Voltammetric determination of trace doxorubicin at a nano-titania/nafion composite film modified electrode in the presence of cetyltrimethylammonium bromide

A sensitive electrochemical method was developed for the determination of doxorubicin at a glassy carbon electrode (GCE) modified with a nano-titania (nano-TiO₂)/nafion composite film. Nano-TiO₂ was dispersed into nafion to give a homogeneous suspension. After solvent evaporation, a uniform film of nano-TiO₂/nafion composite was obtained on the GCE surface. The nano-TiO₂/nafion composite film modified GCE exhibited excellent electrochemical behavior toward the reduction of doxorubicin. Compared to the reduction of doxorubicin at the bare GCE, the reduction current of doxorubicin at the nano-TiO₂/nafion composite film modified GCE was greatly enhanced. Based on this, a novel voltammetric method was applied to the determination of doxorubicin. The experimental parameters that influence the reduction current of doxorubicin, were optimized. Under optimal conditions, a linear response of doxorubicin was obtained in the range from 5.0?×?10^?9 to 2.0?×?10^?6 mol L^?1 (R?=?0.998) and with a limit of detection (LOD) of 1.0?×?10^?9 mol L^?1(S/N?=?3). The RSD of the measurement is 4.7%, and the RSD of the inter-electrode is of 5.1% which indicate the reproducibility of this method. The current response decreased only by around 3.8% of its initial response after 2 weeks exposing the electrode in air. The procedure was applied to assay doxorubicin in human plasma samples with the recoveries of 94.9–104.4%.     

Flow injection determination of bromide ion in a developer using bromide ion-selective electrode detector

A potentiometric flow injection determination method for bromide ion in a developer was proposed, by utilizing a flow-through type bromide ion-selective electrode detector. The sensing membrane of the electrode was Ag(2)S-AgBr membrane. The response of the electrode detector as a peak-shape signal was obtained for injected bromide ion in a developer. A linear relationship was found to exist between peak height and the concentration of the bromide ion in a developer in a concentration range from 1.0x10(-3) to 1.0x10(-2) mol l(-1). The relative standard deviation for 10 injections of a 6x10(-3) mol l(-1) bromide ion in a developer was 1.3% and the sampling rate was ca 17-20 samples h(-1). The present method was free from the interference of an organic reducing reagent, an organic substance in a developer sample solution for the determination of bromide ion in a developer.     

Influence of cetyltrimethylammonium bromide on phosphatidylcholine-coated capillaries

Large unilamellar vesicles of egg-phosphatidylcholine (eggPC), a naturally occurring phospholipid, were used in capillary electrophoresis (CE) for semi-permanent coating of fused silica capillaries. The stability of the phospholipid coating was tested at different cetyltrimethylammonium bromide (CTAB) concentrations with and without CaCl₂ present in the coating solution. The effect of physical factors influencing the coating stability (e.g. duration of the coating time, storage temperature of the coating solution) were also studied. Standing overnight in background electrolyte (BGE) solution did not alter the eggPC phospholipid coating noticeably. The performance of the coating was tested with a mixture of basic proteins (lysozyme, ribonuclease A and -chymotrypsinogen A). Highest efficiencies (over 200,000 plates m^–1) were achieved when the capillary was filled for 15 h with a liposome solution containing both CTAB and CaCl₂.Electronic Supplementary Material Supplementary material is available for this article at     

Substoichiometric determination of mercury with cetyltrimethylammonium bromide

A radiometric method based on substoichiometric isotope dilution analysis has been developed for the determination of mercury using cetyltrimethylammonium bromide (CTAB) as the substoichiometric reagent. The method is based on the extraction of mercury as an ionassociation complex of tetraiodomercurate(II) ion with a substoichiometric amount of CTAB in benzene. The calibration graph was found to be linear in the range 0–10 μg Hg (II) in the aqueous phase of 10 ml volume. A detection limit of 0.06 μg·ml⁻¹ could be achieved by the proposed method. The relative standard deviation of the method was found to be 3.0% and the method has been successfully applied to study the determination of mercury in various synthetic mixtures.     

Potentiometric microtitration of anions with cetyltrimethylammonium bromide

Summary A new titrant, cetyltrimethylammonium bromide, has been evaluated for the potentiometric precipitation titration of small amounts of some large inorganic anions. Emf's were monitored with a fluoroborate ion-selective electrode and a double-junction reference electrode. The perchlorate, nitrate, and calcium electrodes also respond to the various anions. Sharp endpoint breaks were obtained for permanganate, hexafluoroarsenate, hexafluorophosphate, persulfate, tetrachloroplatinite, hexachloroplatinate, tetrachlorostannite, tetrachloroaurate, ferricyanide, tetrachloromercurate, tetrachlorothallate, hexachloroosmiate, and bismuth(III) in hydrochloric acid. Medium breaks were obtained for perrhenate, perchlorate, tetrafluoroborate, dichromate, hexafluoroantimonate, ferrocyanide, hexachlorostannate, and hexachloroiridate. Shallow breaks were obtained for iodide, periodate, and tetrachloropalladate. Because of the limited solubility of the titrant in water it cannot be used at concentrations higher than 0.01 N.

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Potentiometrische Mikrotitration von Anionen mit Cetyltrimethyl-ammoniumbromid. I

Zusammenfassung Cetyltrimethylammoniumbromid wurde als neues Titrationsmittel für die potentiometrische Fällungstitration kleiner Mengen großer anorganischer Anionen eingesetzt. Die EMK wurde mit einer ionenspezifischen Fluorboratelektrode und einer doppelt verbundenen Bezugselektrode gemessen. Perchlorat-, Nitrat- und Calciumelektroden eignen sich ebenfalls für die entsprechenden Anionen. Scharfe Endpunkte wurden erhalten für Permanganat, Hexafluoroarseniat, Hexafluorophosphat, Persulfat, Tetrachloroplatinit, Hexachloroplatinat, Tetrachlorostannit, Tetrachloroaurat, Eisen(Ill)cyanid, Tetrachloromercurat, Tetrachlorothallat, Hexachloroosmiat und Wismuth(III) in Salzsäure. Mittelscharfe Umschlagpunkte erhielt man für Perrhenat, Perchlorat, Tetrafluoroborat, Dichromat, Hexafluoroantimonat, Eisen(II)cyanid, Hexachlorostannat und Hexachloroiridat. Unscharfe Umschlagpunkte ergaben Jodid, Perjodat und Tetrachloropalladat. Wegen der begrenzten Löslichkeit des Titrationsmittels in Wasser kann es maximal in 0,01 N Lösung angewendet werden.

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Work performed under the auspices of the U. S. Department of Energy by the Lawrence Livermore Laboratory under contract number W-7405-ENG-48.

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This paper is dedicated to the memory of my mother, Flora Selig, who died in June 1979.     

Pt/十六烷基三甲基溴化铵纳米聚集体修饰玻碳电极促进析氢(英文)

A novel, cost‐effective, and simple electrocatalyst based on a Pt‐modified glassy carbon electrode (GCE), using cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, is reported. Am‐phiphilic CTAB molecules were adsorbed on GCE by immersion in a CTAB solution. The positively charged hydrophilic layer, which consisted of small aggregates of average size less than 100 nm, was used for accumulation and complexation of [PtCl6]2? anions by immersing the electrode in K2PtCl6 solution. The modified electrode was characterized using scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, impedance spectroscopy, and electrochemical methods. The electrocatalytic activity of the Pt particles in the hydrogen evolution reaction (HER) was investigat‐ed. The results show that the CTAB surfactant enhances the electrocatalytic activity of the Pt parti‐cles in the HER in acidic solution.     

Improved hydrogen evolution on glassy carbon electrode modified with novel Pt/cetyltrimethylammonium bromide nanoscale aggregates

A novel, cost‐effective, and simple electrocatalyst based on a Pt‐modified glassy carbon electrode (GCE), using cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, is reported. Am‐phiphilic...     

Enhanced reduction and determination of trace thyroxine at carbon paste electrode in the presence of trace cetyltrimethylammonium bromide.

The electrochemical response of thyroxine (T4) at a carbon paste electrode (CPE) in the presence of cetyltrimethylammonium bromide (CTAB) was investigated. It gave a well-defined oxidation peak at 0.80 V and a sensitive reduction peak at 0.40 V. Compared with the indiscernible signal in the absence of CTAB, the reduction current of T4 at CPE was greatly enhanced in the presence of CTAB, due to the interactions between T4, CTAB and the hydrophobic electrode surface. The electrode process of T4 was explored by cyclic voltammetry and chronocoulometry. The effect of surfactants on the reduction reaction proved that bromide ions (Br(-)) in CTAB might form special ion complexes with T4 via a special interaction with the iodine atoms on T4, which would activate the reduction of T4. The sensitive and selective reduction of T4 in this system was applied to the determination of T4 in drugs; a detection limit of 6.5 x 10(-9) M was obtained (sigma= 3).