Einstein Relation in n-Channel Inversion Layers of Nonlinear Optical, Optoelectronic and Related Materials: Simplified Theory, Relative Comparison and Suggestion for an Experimental Determination

In this paper, we study the Einstein relation for the diffusivity to mobility ratio (DMR) in n-channel inversion layers of non-linear optical materials on the basis of a newly formulated electron dispersion relation by considering their special properties within the frame work of k.p formalism. The results for the n-channel inversion layers of III-V, ternary and quaternary materials form a special case of our generalized analysis. The DMR for n-channel inversion layers of II-VI, IV-VI and stressed materials has been investigated by formulating the respective 2D electron dispersion laws. It has been found, taking n-channel inversion layers of CdGeAs2, Cd(3)AS(2), InAs, InSb, Hg1-xCdxTe, In1-xGaxAsyP1-y lattice matched to InP, CdS, PbTe, PbSnTe, Pb1-xSnxSe and stressed InSb as examples, that the DMR increases with the increasing surface electric field with different numerical values and the nature of the variations are totally band structure dependent. The well-known expression of the DMR for wide gap materials has been obtained as a special case under certain limiting conditions and this compatibility is an indirect test for our generalized formalism. Besides, an experimental method of determining the 2D DMR for n-channel inversion layers having arbitrary dispersion laws has been suggested.

Self-assembly of indole-2-carboxylic acid at graphite and gold surfaces

Model systems are critical to our understanding of self-assembly processes. As such, we have studied the surface self-assembly of a small and simple molecule, indole-2-carboxylic acid (I2CA). We combine density functional theory gas-phase (DFT) calculations with scanning tunneling microscopy to reveal details of I2CA assembly in two different solvents at the solution/solid interface, and on Au(111) in ultrahigh vacuum (UHV). In UHV and at the trichlorobenzene/highly oriented pyrolytic graphite (HOPG) interface, I2CA forms epitaxial lamellar structures based on cyclic OH⋯O carboxylic dimers. The structure formed at the heptanoic acid/HOPG interface is different and can be interpreted in a model where heptanoic acid molecules co-adsorb on the substrate with the I2CA, forming a bicomponent commensurate unit cell. DFT calculations of dimer energetics elucidate the basic building blocks of these structures, whereas calculations of periodic two-dimensional assemblies reveal the epitaxial effects introduced by the different substrates.

The electronic properties of Si(001)–Bi(2 × n)

A Bi 2 × n surface net was grown on the Si(001) surface and studied with inverse photoemission, scanning tunnelling microscopy and ab initio and empirical pseudopotential calculations. The experiments demonstrated that Bi adsorption eliminates the dimer related π1* and π2* surface states, produced by correlated dimer buckling, leaving the bulk bandgap clear of unoccupied surface states. Ab initio calculations support this observation and demonstrate that the surface states derived from the formation of symmetric Bi dimers do not penetrate the fundamental bandgap of bulk Si. Since symmetric Bi dimers are an important structural component of the recently discovered Bi nanolines, that self-organize on Si(001) above the Bi desorption temperature, a connection will be made between our findings and the electronic structure of the nanolines.

Synthesis, crystal structure and DNA cleavage activity of (aqua)bis(dipyridophenazine)copper(II) complex

A copper(II) complex of dipyridophenazine, viz., [Cu(dppz)(2)(H2O)](ClO4)(2) (I), has been prepared and structurally characterized by X-ray crystallography. The crystal structure of the complex shows a five-coordinate structure in which two N,N-donor dipyridophenazine (dppz) and one aqua ligand bind to the copper(II) center giving Cu-O and Cu-N bond distances in the range of 1.981(6) to 2.043(6) angstrom. The ESI-MS spectrum of 1 in MeCN shows a peak at m/z value of 313 (100%) indicating the dissociation of the aqua ligand in the solution phase. The complex is one-electron paramagnetic (mu(eff), 1.86 mu(B)). It displays a quasi-reversible Cu(II)/Cu(I) redox process at 0.096 V. The complex is an avid binder to CT DNA giving a binding constant value of 3.5 x 10(5) M-1. It shows significant hydrolytic cleavage of supercoiled pUC19 DNA in dark ill the absence of any external agents. The complex exhibits chemical nuclease activity oil treatment with 3-mercaptopropionic acid as a reducing agent forming hydroxyl radicals. Complex 1 is a model synthetic nuclease and hydrolase showing both modes of DNA cleavage under different reaction conditions. The DNA cleavage activity of 1 is significantly better than its phen analogue but similar to that of the bis-dpq complex.

First donor-acceptor interaction promoted gelation of organic fluids

In recent years there has been considerable interest in developing new types of gelators of organic solvents.1 Despite the recent advances, a priori design of a gelator for gelling a given solvent has remained a challenging task. Various noncovalent interactions like hydrogen-bonding,2 metal coordination3 etc. have been used as the driving force for the gelation process. A special class of cholesterol-based gelators were reported by Weiss,4 and by Shinkai.5 Gels derived from these molecules have been used for chiral recognition/sensing,6 for studying photo- and metal-responsive functions,7 and as templates to make hollow fiber silica.8 Other types of organogels have been used for designing polymerized 9 and reverse aerogels,10 and in molecular imprinting.11 Hanabusa’s group has recently reported organogels with a bile acid derivative.12 This has prompted us to disclose our results on a novel electron donor–acceptor (EDA) interaction mediated two-component13 gelator system based on the bile acid14 backbone.

Formal total synthesis of 2-pupukeanone via radical mediated cyclisation of an enyne

Diels-Alder reaction of the dienone 12, obtained by C-alkylation of sodium 2,6-dimethylphenoxide, with acrylonitrile and phenyl vinyl sulfones generate the enynes 14 and 17. Tributyltin radical addition to the terminal acetylene in 14 and 17 lead to the vinylstannanes 15 and 18 via 5-exo trig cyclisation of the resulting vinyl radical, which on oxidative cleavage furnishes the isotwistane-diones 16 and 19. Reductive desulfonylation of the diketosulfone 19 furnishes the dione 11, constituting a formal total synthesis of 2-pupukeanone 5 and 2-isocyanopupukeanone 3.

Studies on the target conditioning for deposition of $LiCoO_{2}$ films

Deposition of good quality thin films of Lithium Cobalt Oxide (LiCoO2), by sputtering is preceded by target conditioning, which dictates the surface composition, morphology and electrochemical performance of the deposited film. Sputtering from a Virgin target surface, results in films with excess of the more reactive elements. The concentration of these reactive elements in the films decreases until the system reaches a steady state after sufficient sputtering from the target. This paper discusses the deposition kinetics in terms of target conditioning of LiCoO2. The composition, morphology and texturing of deposited film during various hours of sputtering were analyzed using X-ray photoelectron Spectroscopy (XPS) and Field Emission Scanning electron microscopy (FESEM). The compositional stability is not observed in the films formed during the initial hours or Sputtering from the fresh target, which becomes stable after several hours of sputtering. The Li and Co concentration in the Films deposited subsequently is found to be varying and possible causes are discussed. After the compositional stability is reached, electrochemical analysis of LiCoO2 thin films was performed, which shows a discharge capacity of 129 mu Ah/cm(2).

Colossal dielectric behavior of semiconducting $Sr_{2}TiMnO_{6}$ ceramics

Manganitelike double perovskite Sr2TiMnO6 (STMO) ceramics fabricated from the powders synthesized via the solid-state reaction route, exhibited dielectric constants as high as similar to 10(5) in the low frequency range (100 Hz-10 kHz) at room temperature. The Maxwell-Wagner type of relaxation mechanism was found to be more appropriate to rationalize such high dielectric constant values akin to that observed in materials such as KxTiyNi(1-x-y)O and CaCu3Ti4O12. The dielectric measurements carried out on the samples with different thicknesses and electrode materials reflected the influence of extrinsic effects. The impedance studies (100 Hz-10 MHz) in the 180-300 K temperature range revealed the presence of two dielectric relaxations corresponding to the grain boundary and the electrode. The dielectric response of the grain boundary was found to be weakly dependent on the dc bias field (up to 11 V/cm). However, owing to the electrode polarization, the applied ac/dc field had significant effect on the low frequency dielectric response. At low temperatures (100-180 K), the dc conductivity of STMO followed a variable range hopping behavior. Above 180 K, it followed the Arrhenius behavior because of the thermally activated conduction process. The bulk conductivity relaxation owing to the localized hopping of charge carriers obeyed the typical universal dielectric response.

Structure and magnetotransport properties of the layered manganites REl.2Srl.8Mn,07(R E = La, Pr, Nd)

We have examined the magnetotransport properties and the structure, by Rietveld refinement of powder X-ray data, of the phases RE(1.2)Sr(1.8)Mn(2)O(7) (RE = La, Pr, Nd). We find that on cooling, La1.2Sr1.8Mn2O7 undergoes a transition to a nearly perfect ferromagnet with 90% magnetization at 1.45 T, as reported by earlier workers, but the Pr and Nd phases show only a small magnetization that grows gradually as the temperature is decreased. There seems to be significant correlation between electrical transport and the Jahn-Teller elongation of the apical Mn-O bonds in these systems. The elongation of the apical Mn-O bonds forces the nine-coordinate rock-salt site to be occupied preferentially by the smaller rare-earth-metal cations. This preferential occupation is reliably obtained from the X-ray refinement. All three title phases show a magnetoresistance ratio of about 4(corresponding to a magnetoresistance, [R(0)-R(H)]/R(0), of about 75%) at a field of 7 T and temperatures around 100 K.

Growth and characterization of $SrBi_{2}Nb_{2}O_{9}$ thin films by pulsed-laser ablation

Polycrystalline films of SrBi2Nb2O9 were grown using pulsed-laser ablation. The ferroelectric properties were achieved by low-temperature deposition followed by a subsequent annealing process. The lower switching voltage was obtained by lowering the thickness, which did not affect the insulating nature of the films. The hysteresis results showed an excellent square-shaped loop with results (P-r=6 mu C/cm(2), E-c=100 kV/cm) in good agreement with earlier reports. The films also exhibited a dielectric constant of 250 and a dissipation factor of 0.02. The transport studies indicated an ohmic behavior, while higher voltages induced a bulk space charge.

Bridged systems via radical cyclization reactions. Stereospecific synthesis of chiral tricyclo[6.2.1.0(1,5)]undecanes

The application of radical-mediated cyclizations and annulations in organic synthesis has grown in importance steadily over the years to reach the present status where they are now routinely used in the strategy-level planning.2 The presence of a quaternary carbon atom is frequently encountered in terpenoid natural products, and it often creates a synthetic challenge when two or more quaternary carbon atoms are present in a contiguous manner.3 Even though creation of a quaternary carbon atom by employing a tertiary radical is very facile, creation of a quaternary carbon atom (or a spiro carbon atom) via radical addition onto a fully substituted olefinic carbon atom is not that common but of synthetic importance. For example, the primary radical derived from the bromide 1 failed to cyclize to generate the two vicinal quaternary carbon atoms and resulted in only the reduced product 2.4 The tricyclic carbon framework tricyclo[6.2.1.01,5]undecane (3) is present in a number of sesquiterpenoids e.g. zizzanes, prelacinanes, etc.5

DC-SIGN and alpha 2,6-sialylated IgG Fc interaction is dispensable for the anti-inflammatory activity of IVIg on human dendritic cells

Intravenous immunoglobulin (IVIg) is widely used to treat autoimmune diseases. Several mutually nonexclusive mechanisms are proposed to explain the beneficial effects of IVIg in patients (1, 2). Lately, Ravetch and colleagues (3) demonstrate that anti-inflammatory activity of IVIg is mediated mainly by antibodies that contain terminal _2,6-sialic acid linkages at the Asn297-linked glycan of Fc region.

Transglutaminase-2 Regulation by Arecoline in Gingival Fibroblasts

Transglutaminase-2 (TGM-2) stabilizes extracellular matrix (ECM) proteins by cross-linking and has been implicated in several fibrotic disorders. Arecoline present in betel quid has been proposed as one of the causative factors for oral submucous fibrosis (OSMF). Hence, we hypothesize that arecoline may regulate TGM-2 and may have a role in the pathogenesis of OSMF. The expression of TGM-2 was studied in OSMF tissues by real-time RT-PCR analysis, and significant overexpression was observed in most OSMF tissues (P = 0.0112) compared with normal tissues. Arecoline induced TGM-2 mRNA and protein expression as well as TGM-2 activity in human gingival fibroblast cells. The addition of methocramine hemihydrate (M-2 muscarinic acetylcholine receptor selective antagonist) or 8'-bromo-cAMP abolished arecoline-mediated TGM-2 induction, suggesting a role for M-2 muscarinic acid receptor and a repressor role for cAMP. Our study provides evidence for TGM-2 overexpression in OSMF and its regulation by arecoline in oral fibroblasts.

Hydrogel-polymer electrolytes for electrochemical capacitors: an overview

Electrochemical capacitors are electrochemical devices with fast and highly reversible charge-storage and discharge capabilities. The devices are attractive for energy storage particularly in applications involving high-power requirements. Electrochemical capacitors employ two electrodes and an aqueous or a non-aqueous electrolyte, either in liquid or solid form; the latter provides the advantages of compactness, reliability, freedom from leakage of any liquid component and a large operating potential-window. One of the classes of solid electrolytes used in capacitors is polymer-based and they generally consist of dry solid-polymer electrolytes or gel-polymer electrolyte or composite-polymer electrolytes. Dry solid-polymer electrolytes suffer from poor ionic-conductivity values, between 10(-8) and 10(-7) S cm(-1) under ambient conditions, but are safer than gel-polymer electrolytes that exhibit high conductivity of ca. 10(-3) S cm(-1) under ambient conditions. The aforesaid polymer-based electrolytes have the advantages of a wide potential window of ca. 4 V and hence can provide high energy-density. Gel-polymer electrolytes are generally prepared using organic solvents that are environmentally malignant. Hence, replacement of organic solvents with water in gel-polymer electrolytes is desirable which also minimizes the device cost substantially. The water containing gel-polymer electrolytes, called hydrogel-polymer electrolytes, are, however, limited by a low operating potential-window of only about 1.23 V. This article reviews salient features of electrochemical capacitors employing hydrogel-polymer electrolytes.