The Reasons for Ligand-Dependent Quantum Yields and Absorption Spectrum of Four Polypyridylruthenium(II) Complexes with a Tetrazolate-Based Ligand: TDDFT Study

The quantum yield, lifetime, and absorption spectrum of four [Ru(bpy)(2)L](+) [where bpy is 2,2'-bipyridyl; L is represented by the deprotonated form of 2-(1H-tetrazol-5-yl)pyridine (L1) or 2-(1H-tetrazol-5-yl)pyrazine (L2)], as well as their methylated complexes [Ru(bpy)(2)LMe](2+) (RuL1Me and RuL2Me) are closely ligand dependent. In this paper, density functional theory (DFT) and time-dependent DFT (TDDFT) were performed to compare the above properties among these complexes. The calculated results reveal that the replacement of pyridine by pyrazine or the attachment of a CH3 group to the tetrazolate ring greatly increases the pi-accepting ability of the ancillary ligands.

Determination of isocyanates by capillary electrophoresis with tris(2,2 '-bipyridine) ruthenium(II) electrochemiluminescence

CE with tris(2,2'-bipyridyl) ruthenium(II) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL) detection for the quantitative determination of isocyanates was first reported. Hexamethylene diisocyanate (HDI) and hexyl isocyanate (HI) were used as the model analytes. Commercially available N,N-diethyl-N'-methylethylenediamine was used as the derivatization reagent. It has both a secondary amine group and a tertiary amine group. The secondary amine group can quantitatively react with isocyanate group, and the tertiary amine group can react with Ru(bpy)(3)(2+) to produce strong ECL signal for sensitive detection. The derivatization reaction was almost instantaneous and is much faster than other reported derivative reactions using other derivative reagents.

Electrochemiluminescence from tris(2,2 '-bipyridyl)ruthenium(II)-graphene-Nafion modified electrode

An electrochemiluminescence (ECL) sensor based on Ru(bpy)(3)(2+)-graphene-Nafion composite film was developed. The graphene sheet was produced by chemical conversion of graphite, and was characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), and Raman spectroscopy. The introduction of conductive graphene into Nafion not only greatly facilitates the electron transfer of Ru(bpy)(3)(2+), but also dramatically improves the long-term stability of the sensor by inhibiting the migration of Ru(bpy)(3)(2+) into the electrochemically inactive hydrophobic region of Nafion. The ECL sensor gives a good linear range over 1 x 10(-7) to 1 x 10(-4) M with a detection limit of 50 nM towards the determination of tripropylamine (TPA), comparable to that obtained by Nafion-CNT.

Progress in Ru (bpy)(3)(2+) Electrogenerated Chemiluminescence

Among various ECL systems, such as 9,10-diphenylanthracene, lucigenin, tris(2,2'-bipyridyl) ruthenium, peroxyoxalate, luminol, graphene, and nanocrystals, Ru(bpy)(3)(2+) ECL is one of the most widely studied ECL systems in recent years due to its broad applications in immunoassays, DNA probe assays, coreactants analysis, and aptasensors. In this review, the progress in Ru(bpy)(3)(2+) ECL has been summarized on the whole, and the future research trends have been proposed.

Effect of hydroxyl and amino groups on electrochemiluminescence activity of tertiary amines at low tris(2,2 '-bipyridyl)ruthenium(II) concentrations

ECL of several amines containing different numbers of hydroxyl and amino groups was investigated. N-butyldiethanolamine is found to be more effective than 2-(dibutylamino)ethanol at gold and platinum electrodes, and is the most effective coreactant reported until now. Surprisingly, ECL intensities of monoamines, such as 2-(dibutylamino)ethanol and N-butyldiethanolamine, are much stronger than that of diamines including N,N,N',N'-tetrakis-(2-hydroxyethyl)-ethylenediamine and N,N,N',N'-tetrakis-(2-hydroxypropyl)ethlenediamine. The striking contrast between ECL signals of the investigated monoamines and diamines may result from more significant side reactions of diamines, such as the intramolecular side reactions between oxidative amine cation radicals and reductive amine free radicals.

A novel tris(2,2 '-bipyridine)ruthenium(II)/tripropylamine cathodic electrochemiluminescence in acetonitrile for the indirect determination of hydrogen peroxide

A novel tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)3(2+)) cathodic electrochemiluminescence (ECL) was generated at -0.78V at the Pt electrode in acetonitrile (ACN), which suggested that the cathodic ECL differed from conventional cathodic ECL It was found that tripropylamine (TPrA) could enhance this cathodic ECL and the linear range (log-log plot) was 0.2 mu M-0.2 mM. In addition, hydrogen peroxide (H2O2) could inhibit the cathodic ECL and was indirectly detected with the linear range of 27-540 mu M. The RSD (n = 12) of the ECL intensity in the presence of 135 mu M H2O2 was 0.87%. This method was also demonstrated for the fast determination of H2O2 in disinfectant sample and satisfactory results were obtained.

Oligoaniline-Functionalized terpyridine ligands and their ruthenium(II) complexes: synthesis, spectroscopic property and redox behaviors

A series of oligoaniline-functionalized mono- and bis-topic terpyridine ligands, i.e. C6H5[N(R)C6H4](n)TPY (R = H, butyl, tert-butyloxycarbonyl; n = 1-4; TPY = 2,2':6',2"-terpyridyl) and TPYC6H4[N(R)C6H4](m)TPY (R = H, tert-butyloxycarbonyl; m = 2, 4), and the corresponding monoand bis-nuclear ruthenium(II) complexes have been synthesized and verified. The spectroscopic results indicate that two kinds of pi-pi* transitions from TPY and oligoaniline fragments of ligands strongly shift to lower energy, and the metal-to-ligand charge-transfer transition ((MLCT)-M-1) bands of all obtained complexes are considerably red-shifted (Delta lambda(max) = 22-64 nm) and their intensities become much more intense (approximately 4-6 times), compared with those of the reported complex [Ru(TPY)(2)](2+). Moreover, the spectroscopic properties of the ligands and complexes with longer oligoaniline units (n = 3, 4) are markedly influenced by the external stimulus, such as the oxidation and proton acid doping.

Formation of [Ru(bpy)(3)](2+)-containing microstructures induced by electrostatic assembly and their application in solid-state detection of electrochemiluminescence

Tris(2,2'-bipyridine)ruthenium(II) ((Ru(bpy)(3)](2+)) is one of the most extensively studied and used electrochemiluminescent (ECL) compounds owing to its superior properties, which include high sensitivity and stability under moderate conditions in aqueous solution. In this paper we present a simple method for the preparation of [Ru(bpy)(3)](2+)-containing microstructures based on electrostatic assembly The formation of such micro-structures occurs in a single process by direct mixing of aqueous solutions of [Ru(bpy)(3)]Cl-2 and K-3[Fe(CN)(6)] at room temperature. The electrostatic interactions between [Ru(bpy)(3)]Cl-2 cations and [Fe(CN)(6)](3-) anions cause them to assemble into the resulting microstructures. Both the molar ratio and concentration of reactants were found to have strong influences on the formation of these microstructures. Most importantly, the resulting [Ru(bpy)(3)](2+)- containing microstructures exhibit excellent ECL behavior and, therefore, hold great promise for solid-state ECL detection in capillary electrophoresis (CE) or CE microchips.

Label free electrochemiluminescence protocol for sensitive DNA detection with a tris(2,2'-bipyridyl)ruthenium(II) modified electrode based on nucleic acid oxidation

Label free electrochemiluminescence (ECL) DNA detection based on catalytic guanine and adenine bases oxidation using tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)(3)(2+)] modified glassy carbon (GC) electrode was demonstrated in this work. The modified GC electrode was prepared by casting carbon nanotubes (CNT)/Nafion/Ru(bpy)(3)(2+) composite film on the electrode surface. ECL signals of doublestranded DNA and their thermally denatured counterparts can be distinctly discriminated using cyclic voltammetry (CV) with a low concentration (3.04 x 10(-8) mol/L for Salmon Testes-DNA). Most importantly, sensitive single-base mismatch detection of p53 gene sequence segment was realized with 3.93 x 10(-10) mol/L employing CV stimulation (ECL signal of C/A mismatched DNA oligonucleotides was 1.5-fold higher than that of fully base-paired DNA oligonucleotides). Label free, high sensitivity and simplicity for single-base mismatch discrimination were the main advantages of the present ECL technique for DNA detection over the traditional DNA sensors.

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(2,29-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.

One-step synthesis of Ru(2,2 '-bipyridine)(3)Cl-2-immobilized silica nanoparticles for use in electrogenerated chemiluminescence detection

One-step synthesis of Ru (bpy)(3) Cl-2-immobilized (bpy = 2,2'-bipyridine) silica nanoparticles (Ru-silica nanoparticles) for use in electrogenerated-chemiluminescence (ECL) detection is reported. Ru-silica nanoparticles are prepared by using the Stober method. Compared with free Ru(bpy)(3)Cl-2, Ru-silica nanoparticles are seen to exhibit a red-shift of the UV-vis absorbance peak and a longer fluorescence lifetime, which are attributed to the electrostatic interaction of Ru(bpy)(3)(2+) and silica. Because silica nanoparticles are used as immobilization matrices, the surfaces of Ru-silica nanoparticles are easily modified or functionalized via the assembly of other nanoparticles, such as Au. For ECL detection, Au-colloid-modified Ru-silica nanoparticles are immobilized on a 3-mercaptopropyl-trimethoxysilane-modified indium tin oxide electrode surface by Au-S interaction; the surface concentration of electroactive Ru(bpy)(3)Cl-2 is obviously higher than that in silica films.

Highly efficient electrochemiluminescence of functionalized tris(2,2 '-bipyridyl)ruthenium(II) enrichment of its co-reactants

An enhanced electrochemiluminescence (ECL) efficiency is obtained from the ruthenium complex tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) by introduction of an ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF(4)). Upon addition of 1% (v/v) BMImBF(4) to 0.1 mm Ru(bpy)(3)(2+) solution, a maximum increase in ECL intensity is obtained both at an indium tin oxide (ITO) electrode (15-fold) and at a glassy carbon (GC) electrode (5- to 64old). Furthermore, upon addition of 1% (v/v) BMImBF4 to 5 pm Ru(bpy)(3)(2+)/100 mm co-reactant systems at a GC electrode, IL adsorption occurs at the electrode surface, which results in a change of the polarity of the electrode surface. Such functionalization greatly improves the functions of both Ru(bpy)(3)(2+) and ionic liquids, as is demonstrated in the sensitive and selective concentration enrichment of the Ru(bpy)(3)(2+) co-reactants.

Silver(I) ions-enhanced electrochemiluminescence of tris(2,2-bipyridyl)ruthenium(II)

In this paper. we demonstrate an clectrochemiluminescence (ECL) enhancement of tris(2,2-bipyridyl)rutheniuin(II) (Ru(bpy)(3)(2+)) by the addition of silver(l) ions. The maximum enhancement factor of about 5 was obtained on a glassy carbon electrode in the absence of co-reactant. The enhancement of ECL intensity was possibly attributed to the unique catalytic activity of Ag+ for reactions between Ru(bpy)(3)(3+) with OR The higher enhancement was observed in phosphate buffer solutions compared with that from borate buffer solutions. This resulted from the fact that formation of nanoparticles with large surface area in the phosphate buffer solution exhibited high catalytic activity. The amount of Ag+, solution pH and working electrode materials played important roles for the ECL enhancement. We also studied the effects of Ag+ on Ru(bpy)(3)(2+)/tripropylamine and Ru(bpy)(3)(2+)/C2O42- ECL systems.

A novel alcohol dehydrogenase biosensor based on solid-state electrogenerated chemiluminescence by assembling dehydrogenase to Ru(bpy)(3)(2+)-Au nanoparticles aggregates

Based on electrogenerated chemiluminescence (ECL), a novel method for fabrication of alcohol dehydrogenase (ADH) biosensor by self-assembling ADH to Ru(bpy)(3)(2+) -AuNPs aggregates (Ru-AuNPs) on indium tin oxide (ITO) electrode surface has been developed. Positively charged Ru(bpy)(3)(2+) could be immobilized stably on the electrode surface with negatively charged AuNPs in the form of aggregate via electrostatic interaction. On the other hand, AuNPs are favourable candidates for the immobilization of enzymes because amine groups and cysteine residues in the enzymes are known to bind strongly with AuNPs. Moreover, AuNPs can act as tiny conduction centers to facilitate the transfer of electrons. Such biosensor combined enzymatic selectivity with the sensitivity of ECL detection for quantification of enzyme substrate, and it displayed wide linear range, high sensitivity and good stability.

Tris(2,2 '-bipyridyl)ruthenium(II) electrochemiluminescent detection of coreactants containing aromatic diol group by the interaction between diol and borate anion

Previous studies show that aromatic diols inhibited Ru(bpy)(3)(2+) electrochemiluminescence (ECL), and all reported Ru(bpy)(3)(2+) ECL methods for the determination of aromatic diols-containing coreactants are based on inhibition of Ru(bpy)(3)(2+)/tripropylamine ECL. In this study, the interaction between diol and borate anion was exploited for Ru(bpy)(3)(2+) ECL detection of coreactants containing aromatic diol group using epinephrine as a model analyte. The interaction prevented from the inhibition of Ru(bpy)(3)(2+) ECL by aromatic diol group of epinephrine. As a result, epinephrine was successfully detected in the absence of tripropylamine simply by using borate buffer solution as the supporting electrolyte. Under the optimum conditions, the log of the ECL intensity increases linearly with the log of epinephrine concentrations over the concentration range of 1.0x10(-9)-1.0x10(-4) M. The detection limit is 5.0x10(-10) M at a signal-to-noise ratio of three. The proposed method exhibit wider dynamic range and better detection limit than that by inhibited Ru(bpy)(3)(2+) ECL method. The relative standard deviation for 14 consecutive determinations of 5 mu M epinephrine was 3.5%. The strategy by interaction with borate anion or boronate derivatives is promising for the determination of coreactants containing aromatic diol group or aromatic hydroxyl acid group. Such interaction can also be used to avoid interference from aromatic diols or aromatic hydroxyl acids.