Ion channel behavior of amphotericin B in sterol-free and cholesterol- or ergosterol-containing supported phosphatidylcholine bilayer model membranes investigated by electrochemistry and spectroscopy

Amphotericin B (AmB) is a popular drug frequently applied in the treatment of systemic fungal infections. In the presence of ruthenium (II) as the maker ion, the behavior of AmB to form ion channels in sterol-free and cholesterol- or ergosterol-containing supported phosphatidylcholine bilayer model membranes were studied by cyclic votammetry, AC impedance spectroscopy, and UV/visible absorbance spectroscopy. Different concentrations of AmB ranging from a molecularly dispersed to a highly aggregated state of the drug were investigated. In a fixed cholesterol or ergosterol content (5 mol %) in glassy carbon electrode-supported model membranes, our results showed that no matter what form of AmB, monomeric or aggregated, AmB could form ion channels in supported ergosterol-containing phosphatidylcholine bilayer model membranes. However, AmB could not form ion channels in its monomeric form in sterol-free and cholesterol-containing supported model membranes. On the one hand, when AmB is present as an aggregated state, it can form ion channels in cholesterol-containing supported model membranes; on the other hand, only when AmB is present as a relatively highly aggregated state can it form ion channels in sterol-free supported phosphatidylcholine bilayer model membranes. The results showed that the state of AmB played an important role in forming ion channels in sterol-free and cholesterol-containing supported phosphatidylcholine bilayer model membranes.

Study of the interaction between lanthanide ions and a supported bilayer lipid membrane by cyclic voltammetry and ac impedance

The interaction of lanthanide ions with a supported bilayer lipid (1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine) membrane (sBLM) was investigated by cyclic voltammetry and ac impedance spectroscopy in this paper, Lanthanide can affect the conformation of the supported bilayer lipid membrane and cause pore formation. Through the pores, Fe(CN)(6)(3) (4) can reach the electrode surface and show its redox behaviour. Furthermore the redox currents or Fe(CN)(6)(3) (4) increased with increasing concentration of lanthanides and leveled off at 1.2 muM for Eu3+. The interaction ability of three lanthanides with sBLM follows the sequence: Eu3+ > Tb3+ > La3+.

Grafting of diaminoalkane on glassy carbon surface and its functionalization

Diaminoalkanes (NH2(CH2)(n)NH2, n = 7,10,12) were grafted onto a glassy carbon electrode (GCE) surface by amino cation radical formed during electrooxidation of amino group. The presence of diamine grafted layer at the GCE is demonstrated by X-ray photoelectron spectroscopy. The effect of the grafted layer at the GCE surface on the redox responses of Ru(NH3)(6)(3+) and Fe(CN)(6)(3-) redox probes has been investigated. Electrochemical impedance experiments indicate that the kinetics of electron transfer are slowed down when the scan rate taken to modify the GCE is low, and that diaminoalkane with longer alkyl-chain used has higher blocking characteristics. The amine-functionalized GCE is versatile not only to further covalently immobilize ferrocene acetic acid via carbodiimide coupling, but also as a charge-rich substrate to successfully adsorb heteropolyanion P2W18 in acidic solution by electrostatic interaction. (C) 2000 Elsevier Science S.A. All rights reserved.

Covalent modification of a glassy carbon surface by 4-aminobenzoic acid and its application in fabrication of a polyoxometalates-consisting monolayer and multilayer films

4-Aminobenzoic acid (4-ABA) was covalently grafted on a glassy carbon electrode (GCE) by amine cation radical formation in the electrooxidation process of the amino-containing compound. X-ray photoelectron spectroscopy measurement proves the presence of 4-carboxylphenylamine monolayer on the GCE. The redox responses of various electroactive probes were investigated on the 4-ABA-modified GCE. Electron transfer to Fe(CN)(6)(3-) in solutions of various pHs was studied by both cyclic voltammetry and electrochemical impedance analysis on the modified electrode. Changes in the solution pH value result in the variation of the terminal group charge state, based on which surface pK(a) values are estimated. The 4-ABA-modified GCE was used as a suitable charged substrate to fabricate polyoxometalates-consisting (POM-consisting) monolayer and multilayer films through layer-by-layer assembly based on electrostatic attraction. Cyclic voltammetry shows the uniform growth of these three-dimensional multilayer films. Taking K10H3[Pr-(SiMo7W4O39)(2)]. H2O (abbreviated as Pr(SiMo7W4)(2)), for example, the preparation and electrochemical behavior of its monolayer and multilayer film had been investigated in detail. This modification strategy is proven to be a general one suitable for anchoring many kinds of POMs on the 4-ABA-modified GCE.

Formation of a self-assembled monolayer of 2-mercapto-3-n-octylthiophene on gold

Monolayer assembly of 2-mercapto-3-n-octylthiophene (MOT) having a relatively large headgroup onto gold surface from its dilute ethanolic solutions has been investigated by electrochemistry. An electrochemical capacitance measurement on the permeability of the monolayer to aqueous ions, as compared with its alkanethiol counterpart [CH3(CH2)(9)SH (DT)] with a similar molecular length, shows that the self-assembled monolayers (SAMs) of MOT can be penetrated by aqueous ions to some extent. Furthermore, organic molecular probes, such as dopamine, can sufficiently diffuse into the monolayer because a diffusion-limited current peak is observed when the dopamine oxidation reaction takes place, showing that the monolayer is loosely packed or dominated by defects. But the results of electron transfer to aqueous redox probes (including voltammetry in Fe(CN)(6)(3-/4-) solutions and electrochemical ac impedance spectrum) confirm that the monolayer can passivate the gold electrode surface effectively for its very low ratio of pinhole defects. Moreover, a heterogeneous patching process involving addition of the surfactants into the SAMs provides a mixed or hybrid membrane that has superior passivating properties. These studies show that the MOT monolayer on the electrode can provide an excellent barrier for hydrated ionic probe penetration but cannot resist the organic species penetration effectively. The unusual properties of the SAMs are attributed to the entity of the relatively large thiophene moiety between the carbon chain and the thiol group.

The transfer of chloride ion across an anion exchange membrane

The transfer of chloride ions into a low resistance anion exchange membrane (AEM) was investigated by cyclic voltammetry (CV) and electrochemical impedance spectra. In all cases, concentration polarization of Cl- ions is exterior to the membrane. It controls the flux and produces the limiting currents: either steady state or transient (peak type) current. In CV experiments, when the size of the holes in the membrane was much smaller than the distance between membrane holes, the Cl- anion transfer showed steady state voltammetric behavior. Each hole in the membrane can be regarded as a microelectrode and the membrane was equivalent to a microelectrode array in this condition. When the hole in the membrane was large or the distance between membrane holes was small, the CV curve of the Cl- anion transfer across the membrane showed a peak shape, which was attributed to linear diffusion. In AC impedance measurement, the impedance spectrum of the membrane system was composed of two semicircles at low DC bias, corresponding to the bulk characteristics of the membrane and the kinetic process of ion transfer, respectively. The bulk membrane resistance increases with increasing DC bias and only one semicircle was observed at higher DC bias. The parameters related to kinetic and membrane properties were discussed.

2,3,5-triphenyl-2H-tetrazolium chloride and 2,4,6-tri(2-pyridyl)-s-triazine on the corrosion of mild steel in HCl

Electrochemical measurement, quantum chemical method, and scanning electron microscopy (SEM) were performed to investigate the inhibitive effect of 2,3,5-triphenyl-2H-tetrazolium chloride (TTC) and 2,4,6-tri(2-pyridyl)-s-triazine(TPT) on the corrosion of mild steel in 1mol.L-1 HCl at room temperature. Impedance spectroscopy measurement showed that the polarization resistance increased and that double layer capacitance decreased with the increase in the inhibitive concentration, and the results of potentiodynamic polarization showed that the inhibitors suppressed both cathodic and anodic processes of steel corrosion without change in the mechanism. Higher the orbital density distribution strength of the lowest unoccupied molecular orbital, higher is the molecule dipole, and lower energy gap between the energy of the highest occupied molecular orbital and the energy of the lowest unoccupied molecular orbital resulted in higher inhibitory efficiency. The results of SEM analysis showed that the metal was protected from aggressive corrosion by the addition of TTC and TPT.

Corrosion of carbon steel influenced by anaerobic biofilm in natural seawater

The bacteria in the anaerobic biofilm on rusted carbon steel immersed in natural seawater were characterized by culturing and molecular biology techniques. Two types of anaerobic bacterium, sulfate-reducing bacteria (SRB) Desulfovibrio caledoniensis and iron-reducing bacteria Clostridium sp. uncultured were found. The compositions of the rust layer were also analyzed and we found that iron oxide and sulfate green rust were the major components. To investigate the corrosion mechanisms, electrochemical impedance spectra was obtained based on the isolated sulfate-reducing bacteria and mixed bacteria cultured from rust layer in laboratory culture conditions. We found that single species produced iron sulfide and accelerated corrosion, but mixed species produced sulfate green rust and inhibited corrosion. The anaerobic corrosion mechanism of steel was proposed and its environmental significance was discussed. (c) 2008 Elsevier Ltd. All rights reserved.

Studies of polysaccharides from three edible species of Nostoc (cyanobacteria) with different colony morphologies: Structural characterization and effect on the complement system of polysaccharides from Nostoc commune

The cyanobacterium Nostoc commune Vaucher produces quite complex extracellular polysaccharides. The cyanobacterium is nitrogen fixing, and on growing the cyanobacterium in media with and without nitrogen, different types of extracellular polysaccharides were obtained. These were also different from the polysaccharides present in N. commune collected in the field. High pH anion exchange chromatography (HPAEC) of weak acid hydrolysates of the culture-grown material demonstrated that, in this case, HPAEC was useful for comparison of the different polymers. The main differences between the polymers from the field group and the culture-grown samples were the presence of substantial amounts of arabinose, 2-O-methylglucose, and glucuronic acid in the latter. Methylation studies also revealed a difference in the branching points on the glucose units between the field and cultured samples, being 1,4,6 for the first and 1,3,6 for the latter. The field acidic fraction gave, on weak acid hydrolysis and separation on BioGel P2 and HPAEC, 12 oligosaccharide fractions that were isolated and studied by different mass spectroscopy techniques. The structures of the oligosaccharides were determined, and two different series that can originate from two repeating pentamers were identified: GlcAl-4/6GlcM1-4Ga11-4Glc1-4Xyl and GlcAl-4/6Glc1-4Ga11-4Glc1-4Xyl. The difference between these oligosaccharides lies in the methyl substituent on carbon 2 of the glucose unit next to the nonreducing glucuronic acid unit. The polysaccharides from field material were shown to have a strong effect on the complement system.

Optical and electrical characterizations of ZnSe self-organized quantum dots grown by molecular beam epitaxy

Optical and electrical properties of ZnSe self-organized quantum dots were investigated using photoluminescence, capacitance-voltage, and deep level transient Fourier spectroscopy techniques. The temperature dependence of photoluminescence was employed to clarify the mechanism of photoluminescence thermal quenching processes in ZnSe quantum dots. A theoretic fit on considering a two-step quenching processes well explained the experimental data. The apparent carrier concentration profile obtained from capacitance-voltage measurements exhibits an accumulation peak at the depth of about 100nm below the sample surface, which is in good agreement with the location of the quantum dot layer. The electronic ground state of ZnSe quantum dots is determined to be about 0.11 eV below the conduction band of ZnS, which is similar to that obtained by simulating the thermal quenching of ZnSe photoluminescence.

IDENTIFICATION OF THE ENERGY-LEVELS OF SI-RH

Two thermostable levels E(0.31) and E(0.58) related to Rh in Si were observed using deep level transient spectroscopy and double correlation deep level transient spectroscopy techniques. By means of thermal annealing and electron irradiation, the microscopic natures of these levels were identified for the first time. The levels E(0.31) and E(0.58) arise from by the same impurity center but have different charge states. Their microstructures are not related to a pure substitutional Rh atom, but correspond to a complex. This result is compared to our self-consistent theoretical calculation.

Deep electron states in n-type Al-doped ZnS1-xTex grown by molecular beam epitaxy

Capacitance-voltage, photoluminescence (PL), and deep level transient spectroscopy techniques were used to investigate deep electron states in n-type Al-doped ZnS1-xTex epilayers grown by molecular beam epitaxy. The integrated intensity of the PL spectra obtained from Al-doped ZnS0.977Te0.023 is lower than that of undoped ZnS0.977Te0.023, indicating that some of the Al atoms form nonradiative deep traps. Deep level transient Fourier spectroscopy (DLTFS) spectra of the Al-doped ZnS1-xTex (x=0, 0.017, 0.04, and 0.046, respectively) epilayers reveal that Al doping leads to the formation of two electron traps 0.21 and 0.39 eV below the conduction band. DLTFS results suggest that in addition to the roles of Te as a component of the alloy as well as isoelectronic centers, Te is also involved in the formation of an electron trap, whose energy level with respect to the conduction band decreases as Te composition increases. Our results show that only a small fraction of Al atoms forms nonradiative deep defects, indicating clearly that Al is indeed a very good donor impurity for ZnS1-xTex epilayers in the range of Te composition being studied in this work. (C) 1997 American Institute of Physics. [S0021-8979(97)08421-1].

Search for signature inversion in the pi i(13/2) circle times upsilon i1(3/2) bands in Au-182,Au-184,Au-186

Search for low-spin signature inversion in the pi i(13/2) circle times nu i(13/2) bands in odd-odd Au-182,Au-184,Au-186 has been conducted through the standard in-beam gamma-spectroscopy techniques. The experiments for Au-182 and 186Au have been performed in the Japan Atomic Energy Agency (JAEA) via the Sm-152(Cl-35,5n)Au-182 and Yb-172(F-19,5n)Au-186 reactions, respectively. A study of Au-184 has been made using a multi-detector array GASP in LNL, Italy, via the Tb-159(Si-29,4n)Au-184 reaction. The pi i(13/2) circle times nu i(13/2) bands in these three nuclei have been identified and extended up to high-spin states. In particular, the inter-band connection between the pi i(13/2) nu i(13/2) band and the ground-state band in 184 Au has been established, leading to a firm spin-and-parity assignment for the pi i(13/2) circle times nu i(13/2) band. The low-spin signature inversion is found in the pi i(13/2) circle times nu i(13/2) bands in Au-182,Au-184,Au-186 according to our spin-assignment and the signature crossing observed at high-spin states.

Observation of negative-parity high spin states of Cs-126

The nucleus Cs-126 was investigated by means of in-beam gamma-ray spectroscopy techniques using the Nordball detector system at the Niels Bohr Institute. Excited states of Cs-126 were populated via the Cd-116(N-14, 4n)Cs-126 reaction at a beam energy of 65 MeV. The Cs-126 level scheme was considerably extended, especially at negative parity and about 40 new levels and 70 new transitions were added into the level scheme. The previously reported negative-parity rotational bands, built on pi g(7/2)circle times nu h(11/2),pi d(5/2)circle times nu h(11/2),pi h(11/2)circle times nu g(7/2), and pi h(11/2)circle times nu d(5/2) configurations, have been extended and evolve into bands involving rotationally aligned (pi h(11/2))(2) and (nu h(11/2))(2) quasiparticles. Two new rotational bands have been tentatively assigned the pi h(11/2)circle times nu s(1/2) and pi g(9/2)circle times nu h(11/2) configurations, respectively