Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine

Fe(III), Cr(III), Fe(II), Co(II) and Ni(II) chloride complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine have been synthesized and characterized along with single crystal X-ray diffraction. These complexes, in combination with MAO, have been examined in butadiene polymerization. The catalytic activity and regioselectivity are strongly controlled by metal center and cocatalyst (MAO/Co ratio dependent in the case of Co(II) complex). The activity decreases in the order of Fe(III) > Co(II) > Cr(III) approximate to Ni (II) complexes, in consistent with the space around the metal center. Polybutadiene with different microstructure content, from high trans-1,4 units (88-95% for iron(III) and Cr(III)), medium trans-1,4 and cis-1,4 units (55% and 35%, respectively, for iron(II)) to high cis-1,4 units 79% for Co(II) and 97% for Ni(II) call be easily achieved by varying of the metal center.

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.

Electrochemiluminescence detection of NADH and ethanol based on partial sulfonation of sol-gel network with gold nanoparticles

We developed a stable, sensitive electrochemiluminescence (ECL) biosensor based on the synthesis of a new sol-gel material with the ion-exchange capacity sol-gel to coimmobilize the Ru(bpy)(3)(2+) and enzyme. The partial sulfonated (3-mercaptopropyl)-trimethoxysilane sol-gel (PSSG) film acted as both an ion exchanger for the immobilization of Ru(bpy)(3)(2+) and a matrix to immobilize gold nanoparticles (AuNPs). The AuNPs/PSSG/Ru(bpy)(3)(2+) film modified electrode allowed sensitive the ECL detection of NADH as low as 1 nM. Such an ability of AuNPs/PSSG/Ru(bpy)(3)(2+) film to promote the electron transfer between Ru(bpy)(3)(2+) and the electrode suggested a new, promising biocompatible platform for the development of dehydrogenase-based ECL biosensors. With alcohol dehydrogenase (ADH) as a model, we then constructed an ethanol biosensor, which had a linear range of 5 mu M to 5.2 mM with a detection limit of 12 nM.

Solid-state electrochemiluminescence sensor based on the Nafion/poly(sodium 4-styrene sulfonate) composite film

An effective electrochemiluminescence (ECL) sensor based on Nafion/poly(sodium 4-styrene sulfonate) (PSS) composite film-modified ITO electrode was developed. The Nafion/PSS/Ru composite film was characterized by atomic force microscopy, UV-vis absorbance spectroscopy and electrochemical experiments. The Nafion/PSS composite film could effectively immobilize tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) via ion-exchange and electrostatic interaction. The ECL behavior of Ru(bpy)(3)(2+) immobilized in Nafion/PSS composite film was investigated using tripropylamine (TPA) as an analyte. The detection limit (S/N = 3) for TPA at the Nafion/PSS/Ru composite-modified electrode was estimated to be 3.0 nM, which is 3 orders of magnitude lower than that obtained at the Nafion/Ru modified electrode. The Nafion/PSS/Ru composite film-modified indium tin oxide (ITO) electrode also exhibited good ECL stability. In addition, this kind of immobilization approach was simple, effective, and timesaving.

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.

Polyethyleneimine-Functionalized Platinum Nanoparticles with High Electrochemiluminescence Activity and Their Applications to Amplified Analysis of Biomolecules

Polyethyleneimine-functionalized platinum nanoparticles (PtNPs) with excellent electrochemiluminescence (ECL) properties were synthesized and applied to the amplified analysis of biomolecules. These particles were prepared at room temperature, with hyperbranched polyethyleneimine (HBPEI) as the stabilizer. The UV/Vis absorption spectra and transmission electron microscopy images clearly confirmed the formation of monodisperse PtNPs. Such particles proved to possess high stability against salt-induced aggregation, enabling them to be employed even under high-salt conditions. Owing to the existence of many tertiary amine groups, these particles exhibited excellent ECL behavior in the presence of tris(2.2'-bipyridyl)ruthenium(II). An HBPEI-coated particle possessed an ECL activity that was at least 60 times higher than that of a tripropylamine molecule. Furthermore, these particles could be immobilized on the 3-aminopropyltriethoxysilane-treated quartz substrates to amplify the binding sites for carboxyl groups. Through this approach, PtNPs were applied to the amplified analysis of the hemin/G-quadruplex DNAzyme by using the luminol/H2O2 chemiluminescence method.

Electrochemiluminescence sensor based on partial sulfonation of polystyrene with carbon nanotubes

Herein, homogenously partial sulfonation of polystyrene (PSP) was performed. An effective electrochemiluminescence (ECL) sensor based on PSP with carbon nanotube (CNTs) composite film was developed. Cyclic voltammetry and electrochemical impendence spectroscopy were applied to characterize this composite film. The PSP was used as an immobilization matrix to entrap the ECL reagent Ru(bpy)(3)(2+) due to the electrostatic interactions between sulfonic acid groups and Ru(bpy)(3)(2+) cations. The introduction of CNTs into PSP acted not only as a conducting pathway to accelerate the electron transfer but also as a proper matrix to immobilize Ru(bpy)(3)(2+) on the electrode by hydrophobic interaction. Furthermore, the results indicated the ECL intensity produced at this composite film was over 3-fold compared with that of the pure PSP film due to the electrocatalytic activity of the CNTs. Such a sensor was verified by the sensitive determinations of 2-(dibutylamino)ethanol and tripropylamine.

Characterization of procaine metabolism as probe for the butyrylcholinesterase enzyme investigation by simultaneous determination of procaine and its metabolite using capillary electrophoresis with electrochemiluminescence detection

Capillary electrophoresis with electrochemiluminescene detection was used to characterize procaine hydrolysis as a probe for butyrylcholinesterase by in vitro procaine metabolism in plasma with butyrylcholinesterase acting as bioscavenger. Procaine and its metabolite N,N-diethylethanolamine were separated at 16 kV and then detected at 1.25 V in the presence of 5.0 mM Ru(bpy)(3)(2+), with the detection limits of 2.4 x 10(-7) and 2.0 x 10(-8) mol/L (S/N=3), respectively. The Michaelis constant K-m value was 1.73 x 10(-4) mol/L and the maximum velocity V-max was 1.62 x 10(-6) mol/L/min. Acetylcholine bromide and choline chloride presented inhibition effects on the enzymatic cleavage of procaine, with the 50% inhibition concentration (IC50) of 6.24 x 10(-3) and 2.94 x 10(-4) mol/L.

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.

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.

Luminescent supramolecular polymers: Cd2+-directed polymerization and properties

A family of supramolecular polymers was prepared via Cd2+-directed self-assembly polymerization of his (2,2':6',2 ''-terpyridine)-based ligand monomers, using oligofluorenes and triphenylamine as bridges under mild conditions. The polymers were fully characterized using thermogravimetric analysis, inherent viscosity, electrochemical measurements, UV-visible spectroscopy, photoluminescence (PL) and electroluminescence (EL). Polymers with oligofluorenes as spacers exhibited blue emission (434-442 nm) in dimethyl acetamide (DMAc) solution, while polymers with triphenylamine as spacer presented an emission peak at 494 nn in DMAc solution. Complexation polymerization of bis(2,2':6',2 ''-terpyridine)-based ligand monomers with cadmium(II) improved fluorescence quantum yields dramatically, and the film PL quantum yields of these polymers were about 0.38-0.54. Single-layer light-emitting diodes were fabricated with the configuration indium tin oxide (ITO)/polymer/Ca/Al; the EL showed green emission and the onset voltages of the devices were 8-11 V.

Drug-human serum albumin binding studied by capillary electrophoresis with electrochemiluminescence detection

A new technique for investigating drug-protein binding was developed employing capillary electrophoresis (CE) coupled with tris(2,2'-bipyridyl) ruthenium(II) [Ru(bPY)(3)(2+)] electrochemiluminescence (ECL) (CE-ECL) detection after equilibrium dialysis. Three basic drugs, namely pridinol, procyclidine and its analogue trihexyphenidyl, were successfully separated by capillary zone electrophoresis with end-column Ru(bPY)(3)(2+) ECL detection. The relative drug binding to human serum albumin (HSA) for each single drug as well'as for the three drugs binding simultaneously was calculated. It was found that the three antiparkinsonian drugs compete for the same binding site on HSA. This work demonstrated that Ru(bPY)(3)(2+) CE-ECL can be a suitable technique for studying drug-protein binding.

Determination of benzhexol hydrochloride by capillary zone electrophoresis with an end-column electrochemiluminescence detection

A capillary zone electrophoresis with end-column electrochemiluminescence (ECL) detector was described for the determination of benzhexol hydrochloride. The detection was based on the tris(2,2'-bypyridine)ruthenium(II) [Ru(bpy)(3)(2+)] ECL reaction with the analyte. Electrophoresis was performed using a 25 mum i.d. uncoated capillary. 10 mM sodium phosphate buffer (pH=8.0) was used as the running buffer. The solution in the detection cell was 80 mM sodium phosphate (pH=8.0) and 5 mM)21 Ru(bpy)(3)(2+). A linear calibration curve of three-orders of magnitude was obtained (with a correlation coefficient of > 0.999) from 1.0X10(-8) to 1.0X10(-5) M and the limit of detection was 6.7 X 10(-9) M (S/N= 3). This just provides an easy and sensitive method to determine the active ingredient in pharmaceutical formulations.

Electrogenerated chemi luminescence from Ru(BPY)(3)(2+) ion-exchanged in carbon nanotube/perfluorosulfonated ionomer composite films

The electrochemistry and electrogenerated chemiluminescence (ECL) of ruthenium(II) tris(bipyridine) (Ru(bpy)(3)(2+)) ion-exchanged in carbon nanotube (CNT)/Nafion composite films were investigated with tripropylamine (TPA) as a coreactant at a glassy carbon (GC) electrode. The major goal of this work was to investigate and develop new materials and immobilization approaches for the fabrication of ECL-based sensors with improved sensitivity, reactivity, and long-term stability. Ru(bpy)(3)(2+) could be strongly incorporated into Nafion film, but the rate of charge transfer was relative slow and its stability was also problematic. The interfusion of CNT in Nafion resulted in a high peak current of Ru(bpy)(3)(2+) and high ECL intensity. The results indicated that the composite film had more open structures and a larger surface area allowing faster diffusion of Ru(bpy)(3)(2+) and that the CNT could adsorb Ru(bpy)(3)(2+) and also acted as conducting pathways to connect Ru(bpy)(3)(2+) sites to the electrode. In the present work, the sensitivity of the ECL system at the CNT/Nafion film-modified electrodes was more than 2 orders of magnitude higher than that observed at a silica/Nafion composite film-modified electrode and 3 orders of magnitude higher than that at pure Nafion films.

Electrochemical and electrogenerated chemiluminescence of clay nanoparticles/Ru(bpy)(3)(2+) multilayer films on ITO electrodes

The electrochemical and electrogenerated chemiluminescence of Ru(bpy)(3)(2+) immobilized in {clay/Ru(bpy)(3)(2+)}(n) multilayer films by layer-by-layer assembly were investigated. The stable multilayer films of clay and Ru(bpy)(3)(2+) were assembled by alternate adsorption of negatively charged clay platelets and positively charged Ru(bpy)(3)(2+) from their aqueous dispersions. UV-vis spectroscopy, quartz crystal microbalance (QCM), cyclic voltammetry, and electrogenerated chemiluminescence (ECL) were used to monitor the immobilization of Ru( bpy)(3)(2+) and the regular growth of the {clay/Ru( bpy)(3)(2+)}(n) multilayer films. The multilayer films modified electrode was used for the ECL detection of tripropylamine ( TPA) and oxalate. The proposed novel immobilized method exhibited good stability, reproducibility and high sensitivity for the determination of TPA and oxalate, which mainly resulted from the contributing of clay nanoparticles with appreciable surface area, special structural features and unusual intercalation properties.