Metal-ion-mediated tuning of duplex DNA binding by bis(2-(2-pyridyl)-1H-benzimidazole)

Studies of double-stranded-DNA binding have been performed with three isomeric bis)2-(n-pyridyl)-1H-benzimidazole)s (n = 2, 3, 4). Like the well-known Hoechst 33258, which is a bisbenzimidazole compound, these three isomers bind to the minor groove of duplex DNA. DNA binding by the three isomers was investigated in the presence of the divalent metal ions Mg2+, Co2+, Ni2+, Cu2+, and Zn2+. Ligand-DNA interactions were probed with fluorscence and circular dichroism spectroscopy. These studies revealed that the binding of the 2-pyridyl derivative to DNA is dramatically reduced in the presence of Co2+, Ni2+, and Cu2+ ions and is abolished completely at a ligand/metal-cation ratio of 1:1. Control experiments done with the isomeric 3- and 4-pyridyl derivatives showed that their binding to DNA is unaffected by the aforementioned transition-metal ions. The ability of 2-(2-pyridyl)benzimidazole changes of the ligand associated with ion chelation probably ledto such unusual binding results for the ortho isomer. The addition of ethylenediaminetetraacetic acid (EDTA) reversed the effects completely.

Metal-spinel-corundum three phase equilibria in the system Ni-Cr-Al-O at 1373 K

The tie-lines representing the inter-crystalline ion exchange equilibria between the NiCr2O4-NiAl2O4 spinet solid solution and Cr2O3-Al2O3 corundum solid solution are determined by electron microprobe andEDAX pointcountanalysis of the oxide phases equilibrated with metallic Ni at 1373 K. The component activities in the spinet solid solution are derived from the tie-lines and thermodynamic data for Cr2O3-Al2O3 solid solution available in the literature. The Gibbs energy of mixing of the spinet solid solution calculated from the experimental data is discussed in relation to the values derived from the cation distribution models which assume random mixing of cations on both tetrahedral and octahedral sites. Positive deviation from the models is observed indicating significant positive enthalpy contribution arising form the size mismatch between Al+3 and Ni+2 ions on the tetrahedral site and Al+3, Ni+2 and Cr+3 on the octahedral site. Variation of the oxygen potential for threephase equilibrium involving metallic nickel, spinet solid solution and corundum solid solution is computed as a function of composition of the solid solutions at 1373 K. The oxygen potential exhibits a minimum at aluminum cationic fraction eta(Al)/(eta(Al) + eta(Cr)) = 0.524 in the oxide solid solutions.

A bile acid derived potassium ion sensor

A chenodeoxycholic acid based K+ ion sensor has been designed using a modular approach in which a fluorophore and a cation receptor are attached to the bile acid backbone. In the absence of K+ the fluorescence of the molecule is quenched because of through-space, photo-induced electron-transfer from the aza-crown unit. Fluorescence enhancement was observed upon titration with K+ (and other alkali metal ions too). In methanol, good selectivity towards the sensing of K+ has been observed.

Zervamicins, a structurally characterised peptide model for membrane ion channels

Voltage dependent membrane channels are formed by the zervamicins, a group of α-aminoisobutyric acid containing peptides. The role of polar residues like Thr, Gln and Hyp in promoting helical bundle formation is established by dramatically reduced channel lifetimes for a synthetic apolar analog. Crystal structures of Leu1-zervamicin reveal association of bent helices. Polar contacts between convex faces result in an ‘hour glass’ like arrangement of an aqueous channel with a central constriction. The structure suggests that gating mechanisms may involve movement of the Gln11 carboxamide group. Gln3 may play a role in modulating the size of the channel mouth.

Ion channel formation by zervamicin-IIB. A molecular modelling study.

Zervamicin-IIB (Zrv-IIB) is a 16 residue peptaibol which forms voltage-activated, multiple conductance level channels in planar lipid bilayers. A molecular model of Zrv-IIB channels is presented. The structure of monomeric Zrv-IIB is based upon the crystal structure of Zervamicin-Leu. The helical backbone is kinked by a hydroxyproline residue at position 10. Zrv-IIB channels are modelled as helix bundles of from 4 to 8 parallel helices surrounding a central pore. The monomers are packed with their C-terminal helical segments in close contact, and the bundles are stabilized by hydrogen bonds between glutamine 11 and hydroxyproline 10 of adjacent helices. Interaction energy profiles for movement of three different probes species (K+, Cl- and water) through the central pore are analyzed. The conformations of: (a) the sidechain of glutamine 3; (b) the hydroxyl group of hydroxyproline 10; and (c) the C-terminal hydroxyl group are "optimized" in order to maximize favourable interactions between the channel and the probes, resulting in favourable interaction energy profiles for all three. This suggests that conformational flexibility of polar sidechains enables the channel lining to mimic an aqueous environment.

Elastic properties of fast ion conducting lithium based borate glasses

Elastic properties of Li2O-PbO-B2O3 glasses have been investigated using sound velocity measurements at 10 MHz. Four series of glasses have been investigated with different concentrations of Li2O, PbO and B2O3. The variations of molar volume have been examined for the influences of Li2O and PbO. The elastic moduli reveal trends in their compositional dependence. The bulk and shear modulus increases monotonically with increase in the concentration of tetrahedral boron which increases network dimensionality. The variation of bulk moduli has also been correlated to the variation in energy densities. The Poisson's ratio found to be insensitive to the concentration of tetrahedral boron in the structure. The experimental Debye temperatures are in good agreement with the expected theoretical values. Experimental observations have been examined in view, the presence of borate network and the possibility of non-negligible participation of lead in network formation. (c) 2005 Elsevier B.V. All rights reserved.

Conformation of the flexible bent helix of Leu1-zervamicin in crystal C and a possible gating action for ion passage

The membrane channel-forming polypeptide, Leu(1)-zervamicin, Ac-Leu-Ile-Gln-Iva-Ile(5)-Thr-Aib-Leu-Aib-Hyp(10) -Gln-Aib-Hyp-Aib-Pro(15)-Phol (Aib: alpha-aminoisobutyric acid; Iva: isovaline; Hyp: 4-hydroxyproline; Phol: phenylalininol) has been analyzed by x-ray diffraction in a third crystal form. Although the bent helix is quite similar to the conformations found in crystals A and B, the amount of bending is more severe with a bending angle approximate to 47 degrees, The water channel formed by the convex polar faces of neighboring helices is larger at the mouth than in crystals A and B, and the water sites have become disordered. The channel is interrupted in the middle by a hydrogen bond between the OH of Hyp(10) and the NH2 of the Gln(11) of a neighboring molecule. The side chain of Gln(11) is wrapped around the helix backbone in an unusual fashion in order that it can augment the polar side of the helix. In the present crystal C there appears to be an additional conformation for the Gln(11) side chain (with approximate to 20% occupancy) that opens the channel for possible ion passage. Structure parameters for C85H140N18O22.xH(2)O.C2H5OH are space group P2(1)2(1)2(1), a = 10.337 (2) Angstrom, b = 28.387 (7) Angstrom, c = 39.864 (11) Angstrom, Z = 4, agreement factor R = 12.99% for 3250 data observed > 3 sigma(F), resolution = 1.2 Angstrom. (C) 1994 John Wiley & Sons, Inc.

Characterization of Alkali Induced Formation of Lanthionine, Trisulfides, and Tetrasulfides from Peptide Disulfides using Negative Ion Mass Spectrometry

Peptide disulfides are unstable under alkaline conditions, resulting in the formation of products containing lanthionine and polysulfied linkages. Electrospray ionization mass spectrometry has been used to characterize major species obtained when cyclic and acyclic peptide disulfides are exposed to alkaline media. Studies on a model cyclic peptide disulfide (Boc - Cys - Pro - Leu - Cys - NHMe) and an acyclic peptide, oxidized glutathione, bis ((gamma)Glu Cys - Gly - COOH), are described. Disulfide cleavage reactions are initiated by the abstraction of (CH)-H-alpha or (CH)-H-beta protons of Cys residues, with Subsequent elimination of H2S or H2S2. The buildup of reactive thiol species which act on intermediates containing dehydroalanine residues, rationalizes the formation of lanthionine and polysulfide products. In the case of the cyclic peptide disulfide, the formation of cyclic products is facilitated by the intramolecular nature of the Michael addition reaction of thiols to the dehydroalanine residue. Mass spectral evidence for the intermediate species is presented by using alkylation of thiol groups as a trapping method. Mass spectral fragmentation in the negative ion mode of the peptides derived from trisulfides and tetrasulfides results in elimination of S-2. (J Am Soc Mass Spectrom 2009, 20, 783-791) (C) 2009 American Society for Mass Spectrometry.

Characterization of Alkali Induced Formation of Lanthionine, Trisulfides, and Tetrasulfides from Peptide Disulfides using Negative Ion Mass Spectrometry

Peptide disulfides are unstable under alkaline conditions, resulting in the formation of products containing lanthionine and polysulfied linkages. Electrospray ionization mass spectrometry has been used to characterize major species obtained when cyclic and acyclic peptide disulfides are exposed to alkaline media. Studies on a model cyclic peptide disulfide (Boc - Cys - Pro - Leu - Cys - NHMe) and an acyclic peptide, oxidized glutathione, bis ((gamma)Glu Cys - Gly - COOH), are described. Disulfide cleavage reactions are initiated by the abstraction of (CH)-H-alpha or (CH)-H-beta protons of Cys residues, with Subsequent elimination of H2S or H2S2. The buildup of reactive thiol species which act on intermediates containing dehydroalanine residues, rationalizes the formation of lanthionine and polysulfide products. In the case of the cyclic peptide disulfide, the formation of cyclic products is facilitated by the intramolecular nature of the Michael addition reaction of thiols to the dehydroalanine residue. Mass spectral evidence for the intermediate species is presented by using alkylation of thiol groups as a trapping method. Mass spectral fragmentation in the negative ion mode of the peptides derived from trisulfides and tetrasulfides results in elimination of S-2. (J Am Soc Mass Spectrom 2009, 20, 783-791) (C) 2009 American Society for Mass Spectrometry.

Physicochemical, spectroscopic and electrochemical characterization of magnesium ion-conducting, room temperature, ternary molten electrolytes

Room temperature, magnesium ion-conducting molten electrolytes are prepared using a combination of acetamide, urea and magnesium triflate or magnesium perchlorate. The molten liquids show high ionic conductivity, of the order of mS cm(-1) at 298 K. Vibrational spectroscopic studies based on triflate/perchlorate bands reveal that the free ion concentration is higher than that of ion-pairs and aggregates in the melt. Electrochemical reversibility of magnesium deposition and dissolution is demonstrated using cyclic voltammetry and impedance studies. The transport number of Mg2+ ion determined by means of a combination of d.c. and ac. techniques is similar to 0.40. Preliminary studies on the battery characteristics reveal good capacity for the magnesium rechargeable cell and open up the possibility of using this unique class of acetamide-based room temperature molten electrolytes in secondary magnesium batteries. (C) 2010 Elsevier B.V. All rights reserved.

Hall thruster sequencer using Intel-8051 microcontroller for ion thrust measurement

Hall thrusters, such as Stationary Plasma Thruster (SPT), have been widely used on board modern satellites placed in geo-synchronows orbits for reasons such as orbit maintenance, repositioning and attitude control. In order to study the performance of the stationary plasma thruster, the thrust produced by it has been measured, using a thrust balance with strain gauge sensors under vacuum conditions, by activating the thruster. This activation of thruster has been carried out by switching ON and switching OFF of the necessary power supplies and control of other feed system such as the propellant flow in a particular sequence. Hitherto, these operations were done manually in the required sequence. This paper reports the attempt made to automate the sequential operation of the power supplies and the necessary control valves of the feed system using Intel 8051 microcontroller. This automation has made thrust measurements easier and more sophisticated.

Ion Transport in a Polymer-Plastic Solid Soft Matter Electrolyte in the Light of Solvent Dynamics and Ion Association

Ion transport in a recently demonstrated promising soft matter solid plastic-polymer electrolyte is discussed here in the context of solvent dynamics and ion association. The plastic-polymer composite electrolytes display liquid-like ionic conductivity in the solid state,compliable mechanical strength (similar to 1 MPa), and wide electrochemical voltage stability (>= 5 V). Polyacrylonitrile (PAN) dispersed in lithium perchlorate (LiClO4)-succinonitrile (SN) was chosen as the model system for the study (abbreviated LiClO4-SN:PAN). Systematic observation of various mid-infrared isomer and ion association bands as a function of temperature and polyme concentration shows an effective increase in trans conformer concentration along with free Li+ ion concentration. This strongly supports the view that enhancement in LiClO4-SN:PAN ionic conductivity over the neat plastic electrolyte (LiClO4-SN) is due to both increase in charge mobility and concentration. The ionic conductivity and infrared spectroscopy studies are supported by Brillouin light scattering. For the LiClO4-SN:PAN composites, a peak at 17 GHz was observed in addition to the normal trans-gauche isomerism (as in neat SN) at 12 GHz. The fast process is attributed to increased dynamics of those SN molecules whose energy barrier of transition from gauche to trans has reduced under influences induced by the changes in temperature and polymer concentration. The observations from ionic conductivity, spectroscopy, and light scattering studies were further supplemented by temperature dependent nuclear magnetic resonance H-1 and Li-7 line width measurements.