Electrochemiluminescence of tris(2,2 '-bipyridyl)ruthenium (II) ion-exchanged in polyelectrolyte-silica composite thin-films

The organic-inorganic hybrid, PSS-silica composite material was developed for the immobilization of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) on glassy carbon electrode via ion-exchange (PSS stands for poly(sodium 4-styrene-sulfonate)). The electrochemiluminescence (ECL) and electrochemistry of Ru(bpy)(3)(2-) immobilized in the composite thin films have been investigated with tripropylamine (TPA) as the coreactant. The immobilized Ru(bpy)(3)(2-) underwent a surface process. The modified electrode was used for the ECL detection of TPA and showed high sensitivity. Detection limit was 0,1 mumol L-1 for TPA (S/N = 3) with a linear range from 0.5 mumol L-1 to 5 mmol L-1 (R = 0.998), Moreover, the resulting modified electrode was stable over six months and the good stability may be due to the strong interaction between Ru(bpy)(3)(2-) and the high ion-exchange able PSS-silica composite films on GCE. Compared with other materials. the PSS-silica composite films containing incorporated Ru(bpy)(3)(2-) showed improved sensitivity and long-term stability, Thus, such composite thin film can be a promising material for the construction of ECL sensor.

Electrochemical study of ion channel behavior in incorporated poly L-glutamate bilayer lipid membranes

The lipid layer membranes were fabricated on the glassy carbon electrode (GC) and demonstrated to be bilayer lipid membranes by impedance spectroscopy. The formation of incorporated poly L-glutamate bilayer lipid membrane was achieved. The ion channel behavior of the incorporated poly L-glutamate membrane was determined. When the stimulus calcium cations were added into the electrolyte, the ion channel was opened immediately and exhibited distinct channel current. Otherwise, the ion channel was closed. The cyclic voltammogram at the GC electrode coated with incorporated poly L-glutamate DMPC film response to calcium ion is very fast compared with that at the GC electrode coated only with DMPC film. Ion channel current is not dependent on the time but on the concentration of calcium. The mechanism of the ion channel formation was investigated.

Preparation of rare earth ion induced conformation-specific anti-calmodulin monoclonal antibody

Monoclonal antibody technique was employed to detect the conformational change of calmodulin induced by metal ions. Bovine calmodulin was firstly modified by 2,4-dinitrofluorobenzene to improve its immunogenicity, then, the derived protein was saturated with trivalent europium ions and injected to Balb/c mice as antigen. After four times of immunization, a corresponding antibody was detected and its titer in serum was determined as 1 : 12 000. By fusing of the spleen cells with hybridoma cells, a europium induced conformation-specific anti-calmodulin monoclonal antibody cell strain named as 2C3 was produced successfully. The molecular recognition ability of antibody to apocalmodulin and holocalmodulin showed a significant difference, indicating that this antibody could be applied to the studies of different effects of metal ions on the conformational change of calmodulin and its interaction with target molecules.

Investigation of ion transfer across the micro-water/nitrobenzene interface facilitated by a fullerene derivative

A functionalized fullerene derivative containing a monoaza-18-crown-6 moiety was investigated by facilitated ion (such as Li+, Na+, K+, NH4+, Mg2+, and Ca2+) transfer across the micro-water/nitrobenzene interface supported at the tip of a micropipet. The current responses were detected by cyclic voltammetry and Osteryoung square wave voltammetry, which demonstrated that the facilitated ion transfer does occur by an interfacial complexation-dissociation process. The diffusion coefficient of this compound in nitrobenzene was approximately (5.90 +/- 0.04) x 10(-7) cm(2) s(-1), which is 1 order of magnitude less than other common ionophores due to the large size of the molecule. The selectivity of this molecule toward the metal ions followed the sequence Na+ > Li+ > K+ > NH4+ > Ca2+ similar to Mg2+. In addition, this compound was also easy to form film at the water/nitrobenzene interface to inhibit the simple ion transfer of tetramethylammonium ion. However, the adsorption of this ionophore has less influence on the facilitated metal ion transfer.

Application of resonance raman spectroscopy to study the effect of rare-earth ion Er3+ on myoglobin

The effect of rare-earth ion Er3+ On myoglobin(Mb) was studied by using Resonance Raman spectroscopy. The results show that with the variation of Er3+ concentrations, both the oxidation state and spin state of Mb are sensitive to the perturbation of Er3+. Er3+ added to Mb affects the oxidation and spin state synchronously. The structure-sensitive groups of Mb are more accessible to the Er3+ than other groups. According to the fluorometry and CD spectra studied and our results as mentioned above, we considered that Er3+ does not interact with heme directly, and Er3+ probably leads to the conformational changes of Mb due to the change of oxidation and spin state of Heme.

Ion channel behavior of supported bilayer lipid membranes on a glassy carbon electrode

A new kind of solid substrate, a glassy carbon (GC) electrode, was selected to support lipid layer membranes. On the surface of the GC electrode, we made layers of didodecyldimethylammonium bromide (a synthetic lipid). From electrochemical impedance experiments, we demonstrated that the lipid layers on the GC electrode were bilayer lipid membranes. We studied the ion channel behavior of the supported bilayer lipid membrane. In the presence of perchlorate anions as the stimulus and ruthenium(II) complex cations as the marker ions, the lipid membrane channel was open and exhibited distinct channel current. The channel was in a closed state in the absence of perchlorate anions.

Europium ion labeling anti-HBs

A microsecond time-resolved laser fluorescence spectroscopic analysis set was developed, A chelate-cyclic anhydride of diethylenetrimin pentaacetic acid anhydride (DTPAA) was synthesized. An anti-HBs antibody was purified, A EU3+ -DTPAA-anti-HBs label was prepared by two step procedure. We described the optimal condtion with EU3+ as marker and DTPAA as chelate bounding to antibody molecule. Labeling parameters such as solvent pH, protein and chelate molar ratio, reaction time, separation method were discussed in detail.

Studies on the adduct reaction of disubstituted benzenes with ion system of acetone in gas phase

Ion - molecule reactions of disubstituted benzene with ion system of acetone and deuterium - labelled acetone under chemical ionization conditions were examined and the fragmentation reactions of the adduct ions formed by the ion - molecule reactions were studied using collision - induced dissociation (CID) technique. It was found that the electron - releasing groups favored the adduct reactions, whereas the electron - withdrawing groups did not. The position and properties of substituted groups affected the relative abundance of the adduct ions. The fragmentation reaction of the adduct ion formed by ortho - phenylenediamine with acetyl ion was similar to the reductive alkylation reaction of amine in condensed phase.

Concentration effects of Er3+ ion in YAG : Er laser crystals

Laser crystals of (Y1-xErx)(3)Al5O12, (YAG:Er) have been grown by the Czochralski method and the spectral properties have been studied for different Er3+ concentrations. The effects of various Er3+ concentrations on the structural distortions, luminescence quenching Of F-4(9/2), H-2(11/2), S-4(3/2) and red shift in laser wavelength have been discussed for the YAG:Er laser crystals. By using absorption spectra and Judd-Ofelt theory the experimental oscillator strengths, Omega(lambda), parameters and the excited state integrated absorption cross sections of Er3+ ion are reported and some variation regularities of these parameters have been observed. (C) 2000 Published by Elsevier Science S.A. All rights reserved.

Gas-phase ion-molecule reactions of C-60 with the plasma of methyl acrylate

The gas-phase ion-molecule reactions of C-60 with the plasma generated from methyl acrylate under self-chemical ionization conditions were studied by use of a triple-quadrupole mass spectrometer. The adduct cation [C60C3H3O](+) and protonated molecular ion [C60H](+) were observed as the major product ions. The former adduct ion is formed by electrophilic reaction of C-60 with the ion [CH2=CHCO](+), a main fragment ion resulting from the methyl acrylate molecular ion [CH2=CHCOOCH3](+) through alpha cleavage. The latter ion is generated by proton transfer from protonated methyl acrylate to C-60. Semi-empirical quantum chemical calculations have been performed for the eight possible isomers of [C60C3H3O](+) at the Hartree-Fock level by use of the AMI method. The results show three types of cycloadducts as the most stable structures among the possible isomers.

Voltammetric study of the sodium ion transfer across micro-water/1,2-dichloroethane interface facilitated by terminal-vinyl liquid crystal crown ether

Sodium ion transfer across micro-water/1,2-dichloroethane (DCE) interface facilitated by a novel ionophore, terminal-vinyl liquid crystal crown ether (LCCE) was studied by cyclic voltammetry. LCCEs have potential applications because of their physicochemical properties and the utilization of crown ethers as selective ionophoric units in other functionalized compounds are interesting. Host-guest-type behavior for such compounds in the liquid-crystalline state is studied. The experimental results suggest that the transfer of the sodium ion facilitated by LCCE was controlled by diffusion of LCCE from bulk solution of DCE to the interface. The diffusion coefficient of LCCE in DCE was calculated to be equal to (3.62 +/- 0.20) x 10(-6) cm(2)/s. Steady-state voltammograms are due to sodium ion transfer facilitated by the formation of 1: 1 metal (M)-LCCE complex at the interface and the mechanism tends to be transfer by interfacial complexation or dissociation (TIC or TID). The stability constant of the complex formed was determined to be log beta(o) = 5.5 in DCE phase. The influence of parameters such as concentration of sodium ion and concentration of LCCE on the sodium ion transfer was investigated.

Metal ion and anion coordination in the thiamine-[Pt-II(NO2)(4)](2-) system. Structures of a metal complex, Pt(thiamine)(NO2)(3), and two salts, (H-thiamine)[Pt(NO2)(4)]center dot 2H(2)O and (thiamine monophosphate)(2)[Pt(NO2)(4)]center dot 2H(2)O

Reaction of thiamine or thiamine monophosphate (TMP) with K2Pt(NO2)(4) afforded a metal complex, Pt(thiamine)(NO2)(3) (1), and two salt-type compounds, (H-thiamine)[Pt(NO2)(4)]. 2H(2)O (2) and (TMP)(2)[Pt(NO2)(4)]. 2H(2)O (3), which were structurally characterized by X-ray diffraction. In 1, the square-planar Pt2+ ion is coordinated to the pyrimidine N(1'), a usual metal-binding site, and three NO2- groups. The thiamine molecule exists as a monovalent cation in 1 and a divalent cation in 2 while the TMP molecule is a monovalent cation in 3. In each compound, thiamine or TMP adopts the usual F conformation and forms two types of host-guest-like interactions with anions, which are of the bridging forms, C(2)-H . . . anion . . . pyrimidine-ring and N(4'1)-H(...)anion(...)thiazolium-ring. In 3, there is an additional anion-bridging interaction between the pyrimidine and thiazolium rings of TMP, being of the form C(6')-H . . . anion . . . thiazolium-ring. The salts 2 and 3 show similar hydrogen-bonded cyclic dimers of thiamine or TMP between which the anions are held. Results are compared with those of the other thiamine-platinum complexes. (C) 2001 Elsevier Science B.V. All rights reserved.

A study of tetraethylammonium ion transfer across a micro liquid/liquid interface

Tetraethylammonium (TEA(+)) ion transfer across micro-liquid/liquid interface has been studied with cyclic voltammetric measurements. The results showed that voltammetric responses of the currents obtained were peak and steady-state for TEA(+) transfer from inside and outside of the micropipette when the radius was bigger than 3 mum. However, the currents were pseudo-steady-state when the micropipette diameters were less than 3 mum. The values of i(p) decreased with decreasing concentration of TEA(+). Peak current was proportional to the square root of the scan rate and it obeyed a Randles-Sevcik type relationship. The mechanism of mass transport across a liquid/ liquid microinterface for TEA(+) system was aslo discussed.

Sodium ion transfer across micro water/1,2-DCE interface facilitated by liquid crystal crown ether

The sodium ion transfer across the micro-water/1,2-dichloroethane interface facilitated by a novel ionophore, liquid crystal crown ether was studied systematically. The sodium ion transfer facilitated by LCCE is controlled by diffusion studied by cyclic voltammetry. The diffusion coefficient of LCCE in 1,2-dichloroethane was calculated to be equal to (2.61 +/- 0.12) X 10(-6) cm(2)/s and the stability constant of the complex between Na+ and LCCE was determined as lg beta (o) = 5.7 in 1,2-dichloroethane.

Ion-channel sensing of ferricyanide anion based on a supported bilayer lipid membrane

Ferricyanide anion has usually been used as a marker of ion-channel sensors. In this work we first found that ferricyanide, itself, can act as a stimulus to regulate the permeability of sBLM prepared from didodecyldimethylammonium bromide (a kind of synthetic lipid) on a GC electrode. We used cyclic voltammetry and a.c. impedance to investigate this phenomenon. The interaction between sBLM and ferricyanide concerns time. Furthermore, we developed a sensor for ferricyanide anion. The ion-channel sensor is highly sensitive. It can detect ferricyanide concentration as low as 5 muM.