Zr4+ doping in Li4Ti5O12 anode for lithium-ion batteries: Open Li+ diffusion paths through structural imperfection

One-dimensional nanomaterials have short Li+ diffusion paths and promising structural stability, which results in a long cycle life during Li+ insertion and extraction processes in lithium rechargeable batteries. In this study, we fabricated one-dimensional spinel Li 4Ti5O12 (LTO) nanofibers using an electrospinning technique and studied the Zr4+ doping effect on the lattice, electronic structure, and resultant electrochemical properties of Li-ion batteries (LIBs). Accommodating a small fraction of Zr4+ ions in the Ti4+ sites of the LTO structure gave rise to enhanced LIB performance, which was due to structural distortion through an increase in the average lattice constant and thereby enlarged Li+ diffusion paths rather than changes to the electronic structure. Insulating ZrO2 nanoparticles present between the LTO grains due to the low Zr4+ solubility had a negative effect on the Li+ extraction capacity, however. These results could provide key design elements for LTO anodes based on atomic level insights that can pave the way to an optimal protocol to achieve particular functionalities. Distorted lattice: Zr4+ is doped into a 1 D spinel Li4Ti5O12 (LTO) nanostructure and the resulting electrochemical properties are explored through a combined theoretical and experimental investigation. The improved electrochemical performance resulting from incorporation of Zr4+ in the LTO is due to lattice distortion and, thereby, enlarged Li+ diffusion paths rather than to a change in the electronic structure.

Anomalous dynamical charges, phonons, and the origin of negative thermal expansion in Y2W3O12

We use a combination of classical model and first-principles density functional theory calculations to study lattice dynamics of Y2W3O12 and identify phonons responsible for its negative thermal expansion (NTE). Born dynamical charges of various atoms are found to deviate anomalously from their nominal values. We find that the phonons with energy from 4 to 10 meV are the primary contributors to its NTE. These phonons involve rotations of the YO6 octahedra and WO4 tetrahedra in mutually opposite sense and collective translational atomic displacements, reflecting a strong mixing between acoustic and optic modes.

Effect of the addition of B2O3 and BaO-B2O3-SiO2 glasses on the microstructure and dielectric properties of giant dielectric constant material CaCu3Ti4O12

The effect of the addition of glassy phases on the microstructure and dielectric properties of CaCu3Ti4O12 (CCTO) ceramics was investigated. Both single-component (B2O3) and multi-cornponent (30wt% BaO-60wt% B2O3-10wt% SiO2 (BBS)) glass systems were chosen to study their effect on the density, microstructure and dielectric properties of CCTO. Addition of an optimum amount of B2O3 glass facilitated grain growth and an increase in dielectric constant. However, further increase in the B2O3 content resulted in its segregation at the grain boundaries associated with a reduction in the grain size. In contrast, BBS glass addition resulted in well-faceted grains and increase in the dielectric constant and decrease in the dielectric loss. An internal barrier layer capacitance (IBLC) model was invoked to correlate the dielectric constant with the grain size in these samples. (c) 2007 Elsevier Inc. All rights reserved.

Manifolds with nonnegative isotropic curvature

We prove that if (M-n, g), n >= 4, is a compact, orientable, locally irreducible Riemannian manifold with nonnegative isotropic curvature,then one of the following possibilities hold: (i) M admits a metric with positive isotropic curvature. (ii) (M, g) is isometric to a locally symmetric space. (iii) (M, g) is Kahler and biholomorphic to CPn/2. (iv) (M, g) is quaternionic-Kahler. This is implied by the following result: Let (M-2n, g) be a compact, locally irreducible Kahler manifold with nonnegative isotropic curvature. Then either M is biholomorphic to CPn or isometric to a compact Hermitian symmetric space. This answers a question of Micallef and Wang in the affirmative. The proof is based on the recent work of Brendle and Schoen on the Ricci flow.

Vibrational phase relaxation of O–H stretch in bulk water: Role of large amplitude angular jumps and negative cross-correlations among the forces on the O–H bond

The ultrafast vibrational phase relaxation of O–H stretch in bulk water is investigated in molecular dynamics simulations. The dephasing time (T2) of the O–H stretch in bulk water calculated from the frequency fluctuation time correlation function (Cω(t)) is in the range of 70–80 femtosecond (fs), which is comparable to the characteristic timescale obtained from the vibrational echo peak shift measurements using infrared photon echo [W.P. de Boeij, M.S. Pshenichnikov, D.A. Wiersma, Ann. Rev. Phys. Chem. 49 (1998) 99]. The ultrafast decay of Cω(t) is found to be responsible for the ultrashort T2 in bulk water. Careful analysis reveals the following two interesting reasons for the ultrafast decay of Cω(t). (A) The large amplitude angular jumps of water molecules (within 30–40 fs time duration) provide a large scale contribution to the mean square vibrational frequency fluctuation and gives rise to the rapid spectral diffusion on 100 fs time scale. (B) The projected force, due to all the atoms of the solvent molecules on the oxygen (FO(t)) and hydrogen (FH(t)) atom of the O–H bond exhibit a large negative cross-correlation (NCC). We further find that this NCC is partly responsible for a weak, non-Arrhenius temperature dependence of the dephasing rate.

Non-segmented negative sense RNA viruses as vectors for vaccine development

This article intends to cover two aspects of non-segmented negative sense RNA viruses. In the initial section, the strategy employed by these viruses to replicate their genomes is discussed. This would help in understanding the later section in which the use of these viruses as vaccine vectors has been discussed. For the description of the replication strategy which encompasses virus genome transcription and genome replication carried out by the same RNA dependent RNA polymerase complex, a member of the prototype rhabdovirus family - Chandipura virus has been chosen as an example to illustrate the complex nature of the two processes and their regulation. In the discussion on these viruses serving as vectors for carrying vaccine antigen genes, emphasis has been laid on describing the progress made in using the attenuated viruses as vectors and a description of the systems in which the efficiency of immune responses has been tested.

Formation of structure in dark energy cosmologies

Acceleration of the universe has been established but not explained. During the past few years precise cosmological experiments have confirmed the standard big bang scenario of a flat universe undergoing an inflationary expansion in its earliest stages, where the perturbations are generated that eventually form into galaxies and other structure in matter, most of which is non-baryonic dark matter. Curiously, the universe has presently entered into another period of acceleration. Such a result is inferred from observations of extra-galactic supernovae and is independently supported by the cosmic microwave background radiation and large scale structure data. It seems there is a positive cosmological constant speeding up the universal expansion of space. Then the vacuum energy density the constant describes should be about a dozen times the present energy density in visible matter, but particle physics scales are enormously larger than that. This is the cosmological constant problem, perhaps the greatest mystery of contemporary cosmology. In this thesis we will explore alternative agents of the acceleration. Generically, such are called dark energy. If some symmetry turns off vacuum energy, its value is not a problem but one needs some dark energy. Such could be a scalar field dynamically evolving in its potential, or some other exotic constituent exhibiting negative pressure. Another option is to assume that gravity at cosmological scales is not well described by general relativity. In a modified theory of gravity one might find the expansion rate increasing in a universe filled by just dark matter and baryons. Such possibilities are taken here under investigation. The main goal is to uncover observational consequences of different models of dark energy, the emphasis being on their implications for the formation of large-scale structure of the universe. Possible properties of dark energy are investigated using phenomenological paramaterizations, but several specific models are also considered in detail. Difficulties in unifying dark matter and dark energy into a single concept are pointed out. Considerable attention is on modifications of gravity resulting in second order field equations. It is shown that in a general class of such models the viable ones represent effectively the cosmological constant, while from another class one might find interesting modifications of the standard cosmological scenario yet allowed by observations. The thesis consists of seven research papers preceded by an introductory discussion.

Negative nuclear Overhauser effects as probes of macromolecular structure

Nuclear Overhauser effects (NOE) and circular dichroism (CD) techniques have been used to probe @-turn conformations in acyclic and cyclic peptides containingPro-Xsequences. The model peptides studied are of the type Piv-Pro-X-NHMe (X = Aib, D-Ala, Gly, Val, and Leu) and Boc-Cys-Pro-X-C s NHMe (X = Aib, L-Ala, D-Ala, Gly, and Leu). In the acyclic series, observation of NOES between Pro C"H and X-NH, together with solvent and temperature dependence of NH chemical shifts, establishes a 4 - 1 hydrogen bond stabilized type I1 @-turn in the Gly, D-Ala, and Aib peptides, in CDC13 and (CD3)2S0. A positive n-r* CD band at -225-230 nm appears to be characteristic of this structure. For the acyclic Pro-Leu peptide the observation of NOE's for both Pro and Leu C"H resonances on saturation of Leu NH is compatible with a type V bend or consecutive y-turn conformation. In the cyclic disulfide series the Pro-Aib and Pro-D-Ala peptides favor type I1 @-turns, whereas all other peptides adopt type I (111) conformations. All the cyclic disulfides exhibit an intense negative CD band at -228-230 nm. The results suggest thatgeneralcorrelations between CD spectral type and specific 0-turn conformations may not be obtained. Evidence for solvent-dependent structural changes in the Pro-Aib sequence in both cyclic and acyclic peptides is presented.

Simultaneous observation of positive and negative nuclear Overhauser effects in oligopeptides due to segmental motio

Nuclear Overhauser effect (NOE) studies of the symmetrical cystine peptides (Formula: see text) (n = 1-3) in dimethylsulfoxide, have resulted in the simultaneous observation of both positive and negative NOEs. Positive NOEs are observed on the Trp C2H and C4H protons of the indole ring upon irradiation of Trp C alpha H and C beta H2 resonances in the peptides where n = 1 and 2. Negative NOEs are observed between backbone NH and C alpha H protons. The magnitudes of the observed NOEs are sensitive to changes in molecular size and solvent viscosity. The results demonstrate that NOEs may be a useful probe of sidechain segmental motion in oligopeptides.

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.

Studies in bubble formation—II bubble formation under constant pressure conditions

Bubble formation under constant pressure conditions has been investigated for wide range of variation of liquid properties.Air bubbles were formed from single horizontal orifices submerged in liquids whose viscosity varied from 1·0 to 600 cPs and surface tension from 37 to 72 dyn/cm. Air flow rate was varied from 2 to 250 cm3/sec and the orifice diameter from 0·0515 to 0·4050 cm.

Studies in bubble formation—I bubble formation under constant flow conditions

A model based on two step mechanism of bubble formation is proposed. The resulting equations are used to explain the discrepancies existing in the literature. Data have been collected over a wide range of variables to test the model.

Stress concentration and load diffusion in rectangular panels with constant stress flanges

The stress concentration that occurs when load is diffused from a constant stress member into thin sheet is an important problem in the design of light weight structures. By using solutions in biharmonic polar-trigonometric series, the stress concentration can be effectively isolated so that highly accurate information necessary for design can be obtained. A method of analysis yielding high accuracy with limited effort is presented for rectangular panels with transverse edges free or supported by inextensional end ribs. Numerical data are given for panels with length twice the width.