Synthesis, crystal structures and spectroscopic properties of copper(I) complexes containing beta-dialdiminato supporting ligands

Two mononuclear neutral copper(I) complexes, Cu(L-1)PPh3 (1), Cu(L-2)(PPh3)(2) (2) ([L-1](-) = [{N((C6H3Pr2)-Pr-i-2,6)C(H)}(2)CPh](-); [L-2](-) = [{N(C6H5)C(H)}(2)CPh](-)) have been synthesized and structurally characterized by X-ray crystallography. In complex 1, the copper(I) atom is in a distorted three-coordinate trigonal planar environment, whereas in complex 2 with the less sterically hindered beta-dialdiminato ligand, the copper(I) atom is the centre of a four-coordinate distorted tetrahedron. At room temperature complexes 1 and 2 in a film of PMMA exhibit green emission at 543 and 549 nm with lifetimes of 5.28 and 5.32 ns, respectively.

Novel luminescent iminephosphine complex of copper(I) with high photochemical and electrochemical stability

Luminescent heteroleptic Cu-I complexes based on asymmetrical iminephosphine ligands exhibit improved electrochemical and photochemical stability as compared to the analogous complexes based on traditional diimine or diphosphine ligands.

Turn-on fluorescent cyanide sensor based on copper ion-modified CdTe quantum dots

A new fluorescent sensor for the sensitive and selective detection of cyanide (CN-) in aqueous media was developed herein. The sensing approach is based on CN--modulated quenching behavior of Cu2+ toward the photoluminescence (PL) of CdTe quantum dots (QDs). In the presence of CN-, the PL of QDs that have been quenched by Cu2+ was found to be efficiently recovered, which then allows the detection of CN- in a very simple approach. Experimental results showed that the pH of the buffer solution, concentration of copper ions, and size of CdTe QDs all influenced the response of the sensor to CN-. Under the optimal conditions, a good linear relationship between the PL intensity and the concentration of CN- can be obtained in the range of 3.0 x 10(-7) to 1.2 x 10(-5) M, with a detection limit as low as 1.5 x 10(-7) M. In addition, the present fluorescent sensor possesses remarkable selectivity for cyanide over other anions, and negligible influences were observed on the cyanide detection by the coexistence of other anions or biological species (such as albumin and typical blood constituents).

Realization of negative differential resistance and switching devices based on copper phthalocyanine by the control of evaporation rate

We have observed, respectively, a negative differential resistance (NDR) and switching conduction in current-voltage (I-V) characteristics of organic diodes based on copper phthalocyanine (CuPc) film sandwiched between indium-tin-oxide (ITO) and aluminum (Al) by controlling the evaporation rate. The NDR effect is repeatable which can be well, controlled by sweep rate and start voltage, and the switching exhibits write-once-read-many-times (WORM) memory characteristics. The traps in the organic layer and interfacial dipole have been used to explain the NDR effect and switching conduction. This opens up potential applications for CuPc organic semiconductor in low power memory and logic circuits.

The structural composite effect of Au-WO3-Al interconnecting electrode on performance of each unit in stacked OLEDs

In this article, we report the effects of the thickness of metal and oxide layers of the Al/WO3/Au interconnecting structure on the electrical and optical characteristics of the and bottom units of the two-unit stacked organic-light-emitting-devices (OLEDs). It is found that light emission performance of the upper unit is sensitive to the transmittance of semitransparent Al/WO3/Au structure, which can be improved by changing the thickness of each layer of the Al/WO3/Au structure. It is important to note that the introduction WO3 between Al and Au significantly enhances the current efficiency of both the upper and bottom units with respect to that of the corresponding Al/Au structure without WO3. In addition, the emission spectra of both the upper and bottom units are narrower than that of the control device due to microcavity effect. Our results indicate that the All WO3/Au interconnecting structure is a good candidate for fabricating independently controllable high efficiency stacked OLEDs.

Double-template synthesis of platinum nanomaterials for oxygen reduction

Gas bubble dynamic template, a new green and promising template, can be used to prepare nanostructured materials with different shapes from electrochemical deposition processes. Different morphological platinum nanomaterials have been synthesized by the replacement reaction of the deposited copper nanomaterials which were obtained under negative potential along with H-2 evolution (dynamic template) at a glassy carbon electrode. Scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and electrochemical methods were adopted to characterize their structures and properties. The nanomaterials platinum exhibited excellent catalytic activity toward oxygen reduction. The results demonstrated that the strategy is a simple, cost-effective, and potent method to prepare platinum nanomaterials.

Magnetic Coupling between Copper(II) Ions Mediated by Hydrogen-Bonded (Neutral) Water Molecules

A new hydrogen-bonded dinuclear copper(II) coordination compound has been synthesized from the Schiff-base ligand 6-(pyridine-2-ylhydrazonomethyl)phenol (Hphp). The molecular structure of [Cu-2(php)(2)(H2O2)(2)(ClO4)](ClO4)- (H2O) (1), determined by single-crystal X-ray diffraction, reveals the presence of two copper(II) centers held together by means of two strong hydrogen bonds, with O center dot O contacts of only 2.60-2.68 angstrom. Temperature-dependent magnetic susceptibility measurements down to 3 K show that the two metal ions are antiferromagnetically coupled (J = -19.8(2) cm(-1)). This exchange is most likely through two hydrogen-bonding pathways, where a coordinated water on the first Cu, donates a H bond to the O atoms of the coordinated php at the other Cu. This strong O center dot H (water) bonding interaction has been clearly evidenced by theoretical calculations. In the relatively few related cases from the literature, this exchange path, mediated by a (neutral) coordinated water molecule, was not recognized.

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.

Electrochemical impedance detection of DNA hybridization based on dendrimer modified electrode

Bioactive ultrathin films with the incorporation of amino-terminated G4 PAMAM dendrimers have been prepared via layer-by-layer self-assembly methods on a gold electrode and used for the DNA hybridization analysis. Surface plasmon resonance (SPR), X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy (EIS) are used to characterize the successful construction of the multicomponent film on the gold substrate. The dendrimer-modified surfaces improve the immobilization capacity of the probe DNA greatly, compared to the AET (2aminoethanethiol) SAM sensor surfaces without dendrimer molecules. DNA hybridization analysis is monitored by EIS. The dendrimer-based electrochemical impedance DNA biosensor shows high sensitivity and selectivity for DNA hybridization assay. The multicomponent films also display a high stability during repeated regeneration and hybridization cycles.

Electrochemiluminescence-based DNA detection using guanine oxidation at electrostatic self-assembly of Ru(bpy)(3)(2+)-doped silica nanoparticles on indium tin oxide electrode

A Ru(bpy)(3)(2+)-doped silica nanoparticle-[Ru@Silica] modified indium tin oxide electrode was prepared by simple electrostatic self-assembly technique, and one-electron catalytic oxidation of guanine bases in double-strand and denatured DNA was realized using the electrochemiluminescence detection means.

Tris(2,2 '-bipyridyl) ruthenium(II) doped silica film modified indium tin oxide electrode and its electrochemiluminescent properties

An approach was reported to synthesize silica hybridized ruthenium bipyridyl complex through amidation reaction by covalent attachment of bis(bipyridyl)-4,4'-dicarboxy-2,2'-bipyridyl-ruthenium to (3-aminopropyl)-triethoxysilane. The hybrid complex then was gelatinized through acid catalytic hydrolysis method and a sol-gel modified indium, tin oxide electrode was prepared via spin coating technique. As prepared indium tin oxide electrode possesses good stability therein with excellent electrochemiluminescence behavior.

Electrochemical catalysis and thermal stability characterization of laccase-carbon nanotubes-ionic liquid nanocomposite modified graphite electrode

The hydrophobic carbon nanotubes-ionic liquid (CNTs-IL) get forms a stable modified film on hydrophobic graphite electrode surface. Laccase immobilized on the CNTs-IL gel film modified electrode shows good thermal stability and enhanced electrochemical catalytic ability. The optimal bioactivity occurs with increasing temperature and this optimum is 20 degrees C higher in comparison to free laccase. The improvement of laccase thermal stability may be due to the microenvironment of hydrophobic CNTs-IL gel on graphite electrode surface. On the other hand, the sensitive detection of oxygen has been achieved due to the feasibility of oxygen reduction by both of laccase and nanocomposite of CNTs-IL gel. Furthermore, the laccase hybrid nanocomposite also shows the fast electrochemical response and high sensitivity to the inhibitors of halide ions with the approximate IC50 of 0.01, 4.2 and 87.5 mM for the fluoride, chloride and bromide ions, respectively. It implies the feasibility of laccase modified electrode as an inhibition biosensor to detect the modulators of laccase.

Assembly of polyoxometalates on carbon nanotubes paste electrode and its catalytic behaviors

Carbon nanotubes paste (CNTP) electrode was prepared with multi-walled carbon nanotubes and methyl silicone oil. Polyoxometalates (POMs) were assembled on the electrode surface with different methods, and investigated by cyclic voltammetry and Raman spectroscopy. Experiments showed that POMs/CNTP electrode prepared by direct method had better performance. K6P2Mo18O62 center dot 14H(2)O (P2Mo18) assembled CNTP electrode (P2Mo18/CNTP) electrode possessed good reversibility and could catalyze the reduction of bromate and iodate in 0.1 M H2SO4 Solution. Further, the multilayer films of P2Mo18 assembled CNTP electrodes were fabricated by layer-by-layer technique, which showed higher electrocatalytic activities. All these POMs assembled CNTP electrodes prepared exhibited good stability.