Enhancing the electrochemiluminescence of tris(2,2'-bipyridyl)ruthenium(II) by ionic surfactants

The dependence of the electrochemiluminescence of Ru(bpy)3(2+) (bpy = 2,2'-bipyridine) with tri-n-propylamine as co-reactant on the anionic surfactant SDS (sodium dodecyl sulfate) and the cationic surfactants CTAX (CTA = cetyltrimethylammonium cation, X = bromide, chloride and hydrogensulfate) was studied. Both SDS and CTAX, at low surfactant concentrations below the critical micelle concentrations, enhance the electrochemiluminescence at a platinum working electrode. A further enhancement of the light emission intensity by bromide ions was observed when CTAB (B = bromide) was used-an overall 30-fold increase in electrochemiluminescence efficiency was obtained at a CTAB concentration of 0.08 mM. Voltammetric data support adsorption of surfactant molecules on the electrode surface as the cause of the enhancement of electrochemiluminescence by ionic surfactants.     

Flow-injection chemiluminescence determination of enalapril maleate in pharmaceuticals and biological fluids using tris(2,2'-bipyridyl)ruthenium(II).

A chemiluminescence (CL) method using flow injection (FI) has been investigated for the rapid and sensitive determination of enalapril maleate. The method is based on the CL reaction of the drug with tris(2,2'-bipyridyl)ruthenium(II), Ru(bipy)3(2+) and acidic potassium permanganate. After selecting the best operating parameters, calibration graphs were obtained over concentration ranges of 0.005-0.2 microg/ml and 0.7-100 microg/ml with a detection limit (S/N=2) of 1.0 ng/ml. The average % found was 99.9 +/- 0.7 and 100.2 +/- 0.3 for the two concentration ranges respectively. %RSD (n=10) for 5.0 microg/ml was 0.44. The method was successfully applied to the determination of enalapril maleate in dosage forms and biological fluids without interferences.     

Tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence

This paper critically reviews analytical applications of the chemiluminescence from tris(2,2'-bipyridyl)ruthenium(II) and related compounds published in the open literature between mid-1998 and October 2005. Following the introduction, which summarises the reaction chemistry and reagent generation, the review divides into three major sections that focus on: (i) the techniques that utilise this type of detection chemistry, (ii) the range of analytes that can be determined, and (iii) analogues and derivatives of tris(2,2'-bipyridyl)ruthenium(II).     

Electrogenerated chemiluminescence: an oxidative-reductive mechanism between quinolone antibiotics and tris(2,2'-bipyridyl)ruthenium(II)

The cyclic voltammetry and electrogenerated chemiluminescent (ECL) reactions of a series of quinolone and fluoroquinolone antibiotics were investigated in a flow injection analysis (FIA) system. 7-Piperazinyl fluoroquinolone antibiotics were found to participate as a coreactant in an oxidative-reductive ECL mechanism with tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺) as the luminescent reagent. The reaction mechanism was investigated in order to understand and optimize the processes leading to light emission. The optimal conditions included a solution pH ∼7 at a flow rate of 3.0 mL min⁻¹ with no added organic modifier and application of 1.2 V vs. a Pt quasi-reference electrode (QRE). Fluoroquinolones containing a tertiary distal nitrogen on the piperazine ring, such as enrofloxacin and ofloxacin, reacted to produce more intense ECL than those with a secondary nitrogen, such as ciprofloxacin and norfloxacin. The method linear range, precision, detection limits, and sensitivity for the detection of enrofloxacin and ciprofloxacin were compared to that of tripropylamine. The method was applied to the determination of the ciprofloxacin content in a pharmaceutical preparation. The assay is discussed in terms of its analytical figures of merit, ease of use, speed, accuracy and application to pharmaceutical samples.     

Determination of diphenhydramine by capillary electrophoresis with tris(2,2'-bipyridyl)ruthenium(II) electrochemiluminescence detection

Tris(2,2′-bipyridyl)ruthenium(II) electrochemiluminescence detection in a capillary electrophoresis separation system was used for the determination of diphenhydramine. In this study, platinum disk electrode (300 μm in diameter) was used as a working electrode and the influence of applied potential and buffer conditions were investigated. Under optimal conditions: 1.2 V applied potential, pH 8.50, 15 kV separation voltage and 10 mmol l⁻¹ running buffer, the calibration curve of diphenhydramine was linear over the range of 4×10⁻⁸ to 1×10⁻⁵ mol l⁻¹. This technique gave satisfactory precision, and relative standard deviations of migration times and chemiluminescence peak intensities were less than 1 and 6%, respectively. The technique was applied to animal studies for determination of diphenhydramine extracted from rabbit plasma and urine samples, and the extraction efficiency were between 92 and 98.5%.     

Direct tris(2,2'-bipyridyl)ruthenium (II) electrochemiluminescence detection of polyamines separated by capillary electrophoresis

Capillary electrophoresis (CE) with tris(2,2'-bipyridyl) ruthenium (II) (Ru(bpy)3(2+)) electrochemiluminescence (ECL) detection technique was developed for the analysis of four polyamines (putrescine (Put), cadaverine (Cad), spermidine (Spd), and spermine (Spm)) analysis. The four polyamines contain different amine groups, which have different ECL activity. There are several parameters which influence the resolution and ECL peak intensities, including the buffer pH and concentrations, separation voltage, sample injection, electrode materials, and Ru(bpy)3(2+) concentrations. Polyamines are separated by capillary zone electrophoresis in an uncoated fused-silica capillary (50 cmx25 micro m (ID) filled with acidic phosphate buffer (200 mmol/L phosphate, pH 2.0) - 1mol/L phosphoric acid (9:1 v/v) and a separation voltage of 5 kV (25 micro A), with end-column Ru(bpy)3(2+) ECL detection. A 5 mmol/L Ru(bpy)3(2+) solution plus 200 mmol/L phosphate buffer (pH 11.0) is added into the reagent reservoir. The calibration curve is linear over a concentration range of two or three orders of magnitude for the polyamines. The analysis time is less than 25 min. Detection limits for Put and Cad are 1.9x10(-7) mol/L and 7.6x10(-9) mol/L for Spd and Spm, respectively. Intraday and interday relative standard deviations of ECL peak intensities are less than 8%. The main advantages of this CE-ECL detection technique for polyamines analysis presented herein are the omission of chemical derivatization of the analytes and the high selectivity.     

Solid-supported chemiluminescence and electrogenerated chemiluminescence based on a tris(2,2'-bipyridyl)ruthenium(II) derivative

We report a simple and efficient technique for the covalent immobilisation of a tris(2,2'-bipyridyl)ruthenium(II) derivative suitable for both chemiluminescence and electrochemiluminescence detection.     

Sensitive determination of heroin based on electrogenerated chemiluminescence of tris(2,2'-bipyridyl)ruthenium(II) immobilized in zeolite Y modified carbon paste electrode

A novel method for rapid, inexpensive, sensitive and selective determination of heroin was proposed by flow injection electrogenerated chemiluminescence (ECL). Zeolite Y sieves were used for the preparation of a ECL sensor by immobilizing tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)3(2+)) in their supercages, which was achieved through the ion exchange properties of the sieves. The electrochemical and ECL behaviors of Ru(bpy)3(2+) immobilized in zeolite Y modified carbon paste electrode was investigated. The immobilized Ru(bpy)3(2+) displayed a pair of surface-controlled redox peaks with an electron transfer rate constant of 1.2 +/- 0.1 s(-1) in 0.1 mol dm(-3) pH 6.3 phosphate buffer. The modified electrode showed an electrocatalytic response to the oxidation of heroin, producing a sensitized ECL signal. The ECL sensor showed a linear response to flow injection of heroin in the range of 2.0-80 micromol dm(-3) with a detection limit of 1.1 micromol dm(-3). This method for heroin determination possessed good sensitivity and reproducibility with a coefficient of variation of 1.99% (n = 15) at 50.0 micromol dm(-3). The ECL sensor showed good selectivity and long-term stability. Its surface could be renewed quickly and reproducibly by a simple polish step.     

Enhanced electrochemiluminescence sensor from tris(2,2'-bipyridyl)ruthenium(II) incorporated into MCM-41 and an ionic liquid-based carbon paste electrode

The electrochemiluminescence (ECL) of tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)(3)(2+)] ion-exchanged in the sulfonic-functionalized MCM-41 silicas was developed with tripropylamine (TPrA) as a co-reactant in a carbon paste electrode (CPE) using a room temperature ionic liquid (IL) as a binder. The sulfonic-functionalized silicas MCM-41 were used for preparing an ECL sensor by the electrostatic interactions between Ru(bpy)(3)(2+) cations and sulfonic acid groups. We used the IL as a binder to construct the CPE (IL-CPE) to replace the traditional binder of the CPE (T-CPE)--silicone oil. The results indicated that the MCM-41-modified IL-CPE had more open structures to allow faster diffusion of Ru(bpy)(3)(2+) and that the ionic liquid also acted as a conducting bridge to connect TPrA with Ru(bpy)(3)(2+) sites immobilized in the electrode, resulting in a higher ECL intensity compared with the MCM-41-modified T-CPE. Herein, the detection limit for TPrA of the MCM-41-modified IL-CPE was 7.2 nM, which was two orders of magnitude lower than that observed at the T-CPE. When this new sensor was used in flow injection analysis (FIA), the MCM-41-modified IL-CPE ECL sensor also showed good reproducibility. Furthermore, the sensor could also be renewed easily by mechanical polishing whenever needed.     

Using stannous ion as an excellent inorganic ECL coreactant for tris(2,2'-bipyridyl) ruthenium(II)

It was found that stannous chloride (SnCl(2)), as a popular inorganic reducing reagent, could obviously enhance the electrochemiluminescence (ECL) of tris(2,2'-bipyridyl) ruthenium(II) (Ru(bpy)(3)(2+)) in aqueous solution. Some factors affecting the ECL reactions between Ru(bpy)(3)(2+) and Sn(2+), including pH, concentrations of coreactant, and electrode materials, were investigated by comparison with a classic ECL coreactant tripropylamine (TPA). The Ru(bpy)(3)(2+)-Sn(2+) ECL coreactant system produces stronger and more stable ECL signals, can keep its excellent ECL activity over a wider pH range and has more choices in using electrode materials than the Ru(bpy)(3)(2+)-TPA ECL coreactant system. The ECL mechanism of the Ru(bpy)(3)(2+)-Sn(2+) coreactant system was also studied in detail.     

Diffusivities of tris(2,2'-bipyridyl)ruthenium inside silica-nanochannels modified with alkylsilanes.

The apparent diffusion coefficients of tris(2,2'-bipyridyl)ruthenium ([Ru(bpy(3))](2+)) are estimated in silica-nanochannels which are assembled inside columnar alumina pores in an anodic alumina membrane, and are modified with alkylsilanes such as trimethylchlorosilane (C1), butyldimethylchlorosilane (C4), and dodecyldimethylchlorosilane (C12). The estimation is performed by observing the lag-time, which is defined as the time required for [Ru(bpy)(3)](2+) to diffuse through alkylsilane-modified silica-nanochannels in the alumina membrane. When ethanol is used as a solvent, the apparent diffusion coefficients of [Ru(bpy)(3)](2+) are estimated as 2.1 x 10(-10) and 3.2 x 10(-10) cm(2) s(-1) in the C1- and C4-modified silica-nanochannels, respectively. These values are about 10(4) times smaller than that obtained in bulk ethanol. Based on the experimental results on the solvent dependency of the lag-time, the hydrogen-bonding interaction between ethanol molecules is considered to be stronger in the C1- and C4-modified silica-nanochannels than in bulk ethanol, and the hydrogen-bonding interaction plays a critical role for the slow diffusivity in those nanochannels. In contrast, the apparent diffusion coefficient in the C12-modified silica-nanochannel is at least two orders of magnitude larger than those in the C1- and C4-modified silica-nanochannels. This relatively fast diffusion is most likely explained by the presence of a long alkyl chain of C12, which reduces a hindrance effect that is originates in the hydrogen-bonding interaction.     

Confirmation of the classic tris(2,2'-bipyridyl)ruthenium(II) and oxalate electrochemiluminescence mechanism using EPR spectroscopy

A chemically initiated adaptation of the classic [Ru(bipy)(3)](2+)/oxalate electrochemiluminescence coreactant system has revealed the elusive radical intermediates of the light-producing pathway. Oxalyl (HC(2)O(4)˙) and hydroxyformyl (HCO(2)˙) radicals have been captured on a quartz surface and characterised using EPR spectroscopy.     

One-step immobilization of tris(2,2'-bipyridyl)ruthenium(II) via vapor-surface sol-gel deposition towards solid-state electrochemiluminescence detection

A novel method for immobilization of tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)₃Cl₂) on electrode surfaces based on the vapor-surface sol-gel deposition strategy is first demonstrated in this paper. Ru(bpy)₃Cl₂ immobilized sol-gel (Ru(bpy)₃Cl₂/sol-gel) films were characterized by UV-vis spectroscopy and field-emitted scanning electron microscopy (FE-SEM). These results showed that Ru(bpy)₃Cl₂ was successfully incorporated into the silica sol-gel film. It was found that many irregular Ru(bpy)₃Cl₂/sol-gel clusters were formed on surfaces through one deposition and thick sol-gel films were observed after further deposition. Electrochemical properties and electrochemiluminescence (ECL) behaviors of Ru(bpy)₃Cl₂/sol-gel films could be easily adjusted by deposition numbers and time. At last, the Ru(bpy)₃Cl₂/sol-gel film modified electrode was used for solid-state ECL detection of tripropylamine. The linear range was from 5.8 × 10⁻⁸ to 2.4 × 10⁻⁴ M with the detection limit of 5 nM, which was three orders of magnitude lower than that from pure Nafion-modified electrodes. The ECL sensor also exhibited high stability, and still remained 92% response after being stored in air for 35 days. This method for immobilization of Ru(bpy)₃Cl₂ is simple, convenient and low-cost relative to others, so it shows promising applications in solid-state ECL detection.     

DNA mismatch detection by resonance energy transfer between ruthenium(II) and osmium(II) tris(2,2'-bipyridyl) chromophores

Octahedral tris-chelate complexes [M(II)(bpy)(3)](2+) (M = Ru or Os, bpy = 2,2'-bipyridyl), covalently attached to the 3'- and 5'-phosphates of two oligonucleotides, are juxtaposed when hybridized contiguously to a fully complementary DNA target. Visible metal-to-ligand charge-transfer (MLCT) excitation of the [Ru(II)(bpy)(3)](2+) unit leads to resonance energy transfer to the MLCT state of the [Os(II)(bpy)(3)](2+) moiety, with the energy transfer efficiency depending on the degree of hybridization. The extent of attenuation of the intense red luminescence from the Ru(II) chromophore hence allows highly sensitive structural probing of the assembly and constitutes a novel approach to DNA sensing which is capable of detecting mutations.     

Determination of proline in wine using flow injection analysis with tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence detection

Flow injection methodology is described for the determination of proline in red and white wines using tris(2,2′-bipyridyl)ruthenium(II) chemiluminescence detection. Selective conditions were achieved for proline at pH 10, while other amino acids and wine components did not interfere. The precision of the method was less than 1.00% (R.S.D.) for five replicates of a standard (4 × 10⁻⁶ M) and the detection limit was 1 × 10⁻⁸ M. The level of proline in white and sparkling wines using the developed methodology was equivalent to those achieved using HPLC-FMOC amino acid analysis. SPE removal of phenolic material was required for red wines to minimize Ru(bipy)₃³⁺ consumption and its associated effect on accuracy.     

Tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence enhanced by silver nanoparticles

Mixtures of silver(I) and citrate that are used to produce silver nanoparticles evoke intense chemiluminescence with tris(2,2'-bipyridyl)ruthenium(II) and cerium(IV), which can be exploited for the determination of citrate ions and other analytes over a wide concentration range.     

Flow injection fluorimetric determination of chromium(VI) in electroplating baths by luminescence quenching of tris(2,2'-bipyridyl) ruthenium(II)

A sensitive and selective luminescence quenching method is developed and used for manual and flow injection analysis (FIA) of chromium(VI) by reaction with [Ru(bpy)₃]²⁺. The emission peak of ruthenium(II) at 595 nm is linearly decreased as a function of Cr(VI) concentration. This permits determination of chromium(VI) ion over the concentration range 0.1-20 μg ml⁻¹ with a detection limit of 33 ng ml⁻¹. The quenching process is due to an electron transfer from the luminescent [Ru(bpy)₃]²⁺ complex ion to Cr(VI) resulting in the formation of the non-luminescent [Ru(bpy)₃]³⁺ complex ion. Selectivity for Cr(VI) over many anions and transition, alkali and alkaline earth metal cations is demonstrated. High concentration levels of sulphate, chloride, borate, acetate, phosphate, nitrate, cyanide, Pb²⁺, Zn²⁺, Hg²⁺, Cu²⁺, Cd²⁺, Ni²⁺ and Mn²⁺ ions are tolerated. The effects of solution pH and [Ru(bpy)₃]²⁺ reagent concentration are examined and the reaction conditions are optimized. Validation of the method according to the quality assurance standards show suitability of the proposed method for use in the quality control assessment of Cr(VI) in complex matrices without prior treatment. The method is successfully applied to determine chromium(VI) in electroplating baths using flow injection analysis. Results with a mean standard deviation of ±0.6% are obtained which compare fairly well with data obtained using atomic absorption spectrometry.     

Emission of tris(2,2'-bipyridine)ruthenium(II) by coreactant electrogenerated chemiluminescence: from O2-insensitive to highly O2-sensitive

We describe the influence of dissolved oxygen on the emission of Ru(bpy)3(2+) (bpy = 2,2'-bipyridine) by electrogenerated chemiluminescence (ECL) with tertiary amine as coreactant in aqueous solutions. The significance of the reactions between molecular oxygen and the ECL intermediate reducing radicals has been demonstrated for the first time. By varying the experimental conditions, the oxygen effect on different ECL routes of the Ru(bpy)3(2+)/tri-n-propylamine (TPrA) system was examined. When coreactant direct oxidation played a predominant role in producing ECL, the maximum emission intensity, especially that of the low-oxidation-potential (LOP) ECL, could change from O2-insensitive to highly O2-sensitive with decreasing TPrA concentration. This behavior can be interpreted as follows: A large excess of intermediate reducing radicals was produced at high [TPrA], and the dissolved oxygen within the ECL reaction layer was completely reduced by these radicals and exerted no quenching effect on the emission. At low [TPrA], however, coreactant oxidation generated a relatively small amount of reducing intermediates, and molecular oxygen acted as an interceptor, destroying the intermediates before they participated in the ECL pathways, which led to the obvious reduction of the emission intensity. In the latter case, the less efficient LOP ECL route was more remarkably affected. When ECL was generated primarily via the catalytic route at high [Ru(bpy)3(2+)], the reactions consuming the intermediate radicals by O2 became insignificant, and he drop of emission intensity in the presence of oxygen could mainly be ascribed to the excited-state quenching. A similar oxygen effect was also observed for the Ru(bpy)3(2+)/triethylamine (TEA) system.