Na0.33V2O5 center dot 1.5H(2)O nanorings/nanorods and Na0.33V2O5 center dot 1.5H(2)O/RGO composite fabricated by a facile one pot synthesis and its lithium storage behavior

In this work, Na0.33V2O5 center dot 1.5H(2)O nanorings/nanorods and Na0.33V2O5 center dot 1.5H(2)O/reduced graphene oxide (RGO) composites have been prepared through a facile hydrothermal route in acidic medium at 200 degrees C for 2 days. The hydrothermally derived products have been characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, UV-Visible spectroscopy, Thermogravimetric analysis (TGA), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM) and electrochemical discharge-charge cycling in lithium ion battery. XRD pattern exhibits the layered structure of Na0.33V2O5 center dot 1.5H(2)O and the composite shows the presence of RGO at 2 theta = 25.8 degrees. FTIR spectrum shows that the band at 760 cm(-1) could be assigned to a V-OH2 stretching mode due to coordinated water. Raman spectrum shows that the band at 264 cm(-1) is due to the presence of water molecules between the layers. FESEM/TEM micrographs reveal that the products consist of nanorings of inner diameter 5 mu m and thickness of the ring is found to be 200-300 nm. Addition of exfoliated graphene oxide (EGO) destroys the formation of rings. The reduction of EGO sheets into RGO is also evidenced by the red shift of the absorbance peak from 228 nm to 264 nm. In this composite Na0.33V2O5 center dot 1.5H(2)O nanorods may adhere to the surface of RGO and/or embedded in the RGO nanosheets. As a result, an effective three-dimensional conducting network was formed by bridging RGO nanosheets, which can facilitate electron transport effectively and thus improve the kinetics and rate performance of Na0.33V2O5 center dot 1.5H(2)O nanorings/nanorods. The Na0.33V2O5 center dot 1.5H(2)O/RGO composites exhibited a discharge capacity of 340 mAh g(-1) at a current density of 0.1 mA g(-1) and also an improved cyclic stability. RGO plays a `flexible confinement' function to enwrap Na0.33V2O5 center dot 1.5H(2)O nanorods, which can compensate for the volume change and prevent the detachment and agglomeration of pulverized Na0.33V2O5 center dot 1.5H(2)O, thus extending the cycling life of the electrode. A probable reaction mechanism for the formation of Na0.33V2O5 center dot 1.5H(2)O nanorings is also discussed. (C) 2012 Elsevier B.V. All rights reserved.

Layerwise decomposition of water dynamics in reverse micelles: A simulation study of two-dimensional infrared spectrum

We present computer simulation study of two-dimensional infrared spectroscopy (2D-IR) of water confined in reverse micelles (RMs) of various sizes. The present study is motivated by the need to understand the altered dynamics of confined water by performing layerwise decomposition of water, with an aim to quantify the relative contributions of different layers water molecules to the calculated 2D-IR spectrum. The 0-1 transition spectra clearly show substantial elongation, due to in-homogeneous broadening and incomplete spectral diffusion, along the diagonal in the surface water layer of different sized RMs. Fitting of the frequency fluctuation correlation functions reveal that the motion of the surface water molecules is sub-diffusive and indicate the constrained nature of their dynamics. This is further supported by two peak nature of the angular analogue of van Hove correlation function. With increasing system size, the water molecules become more diffusive in nature and spectral diffusion almost completes in the central layer of the larger size RMs. Comparisons between experiments and simulations establish the correspondence between the spectral decomposition available in experiments with the spatial decomposition available in simulations. Simulations also allow a quantitative exploration of the relative role of water, sodium ions, and sulfonate head groups in vibrational dephasing. Interestingly, the negative cross correlation between force on oxygen and hydrogen of O-H bond in bulk water significantly decreases in the surface layer of each RM. This negative cross correlation gradually increases in the central water pool with increasing RMs size and this is found to be partly responsible for the faster relaxation rate of water in the central pool. (C) 2013 AIP Publishing LLC.

Quantum chemical study on influence of intermolecular hydrogen bonding on the geometry, the atomic charges and the vibrational dynamics of 2,6-dichlorobenzonitrile

FT-IR (4000-400 cm(-1)) and FT-Raman (4000-200 cm(-1)) spectral measurements on solid 2,6-dichlorobenzonitrile (2,6-DCBN) have been done. The molecular geometry, harmonic vibrational frequencies and bonding features in the ground state have been calculated by density functional theory at the B3LYP/6-311++G (d,p) level. A comparison between the calculated and the experimental results covering the molecular structure has been made. The assignments of the fundamental vibrational modes have been done on the basis of the potential energy distribution (PED). To investigate the influence of intermolecular hydrogen bonding on the geometry, the charge distribution and the vibrational spectrum of 2,6-DCBN; calculations have been done for the monomer as well as the tetramer. The intermolecular interaction energies corrected for basis set superposition error (BSSE) have been calculated using counterpoise method. Based on these results, the correlations between the vibrational modes and the structure of the tetramer have been discussed. Molecular electrostatic potential (MEP) contour map has been plotted in order to predict how different geometries could interact. The Natural Bond Orbital (NBO) analysis has been done for the chemical interpretation of hyperconjugative interactions and electron density transfer between occupied (bonding or lone pair) orbitals to unoccupied (antibonding or Rydberg) orbitals. UV spectrum was measured in methanol solution. The energies and oscillator strengths were calculated by Time Dependent Density Functional Theory (TD-DFT) and matched to the experimental findings. TD-DFT method has also been used for theoretically studying the hydrogen bonding dynamics by monitoring the spectral shifts of some characteristic vibrational modes involved in the formation of hydrogen bonds in the ground and the first excited state. The C-13 nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge independent atomic orbital (GIAO) method and compared with experimental results. Standard thermodynamic functions have been obtained and changes in thermodynamic properties on going from monomer to tetramer have been presented. (C) 2013 Elsevier B.V. All rights reserved.

Upconversion fluorescence property of Er3+/Yb3+-codoped novel bismuth-germanium glass

Infrared-to-visible upconversion fluorescence property of Er3+/Yb3+ codoped novel bismuth-germanium glass under 975 nm LD excitation has been studied. Intense green and red emissions centered at 525, 546 and 657 nm, corresponding to the transitions H-2(11/2) -> I-4(15/2), S-4(3/2) -> I-4(15/2), and F-4(9/2) -> I-4(15/2), respectively, were observed at room temperature. The quadratic dependence of the 525, 546 and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs. The structure of the bismuth-germanium glass has been investigated by peak-deconvolution of FT-Raman spectrum, and the structural information was obtained from the peak wavenumbers. This novel bismuth-germanium glass with low maximum phonon energy (similar to 750 cm(-1)) can be used as potential host material for upconversion lasers. (c) 2005 Elsevier Ltd. All rights reserved.

Optical transitions of Er3+ and Yb3+ ions in novel oxyfluoride bismuth-germanium glass: Observation of up-conversion

Er3+/Yb3+-codoped novel oxyfluoride bismuth-germanium glass was prepared and its up-conversion fluorescence property under 975 nm excitation has been studied. Intense green and weak red emissions centered at 525, 546, and 657 nm, corresponding to the transitions 2H(11/2) -> I-4(15/2), S-4(3/2) -> I-4(15/2), and F-4(9/2) -> I-4(15/2), respectively, were observed at room temperature. The possible up-conversion mechanism was also evaluated. The optimal Yb3+-Er3+ concentration ratio is found based on the direct lifetime measurements of excited levels for Er3+ ion. The structure of this novel oxyfluoride bismuth-germanium glass has been investigated by peak-deconvolution of FT-Raman spectrum, and the structural information was obtained from the peak wavenumbers. This novel oxyfluoride bismuth-germanium glass with relatively lower maximum phonon energy (similar to 731 cm(-1)) can be used as potential host material for up-conversion lasers. (c) 2005 Elsevier B.V. All rights reserved.

Structural and optical properties of YAG : Ce3+ phosphors by sol-gel combustion method

High-quality Ce3+-doped Y3Al5O12 (YAG:Ce3+) phosphors were synthesized by a facile sol-gel combustion method. In this sol-gel combustion process, citric acid acts as a fuel for combustion, traps the constituent cations and reduces the diffusion length of the precursors. The XRD and FT-IR results show that YAG phase can form through sintering at 900 degrees C for 2 h. This temperature is much lower than that required to synthesize YAG phase via the solid-state reaction method. There were no intermediate phases such as YAlO3 (YAP) and Y4Al2O9 (YAM) observed in the sintering process. The average grain size of the phosphors sintered at 900-1100 degrees C is about 40 nm. With the increasing of sintering temperature, the emission intensity increases due to the improved crystalline and homogeneous distribution of Ce3+ ions. A blue shift has been observed in the Ce3+ emission spectrum of YAG:Ce3+ phosphors with increasing sintering temperatures from 900 to 1200 degrees C. It can be explained that the decrease of lattice constant affects the crystal field around Ce3+ ions. The emission intensity of 0.06Ce-doped YAG phosphors is much higher than that of the 0.04Ce and 0.02Ce ones. The red-shift at higher Ce3+ concentrations may be Ce-Ce interactions or variations in the unit cell parameters between YAG:Ce3+ and YAG. It can be concluded that the sol-gel combustion synthesis method provides a good distribution of Ce3+ activators at the molecular level in YAG matrix. (c) 2005 Elsevier B.V. All rights reserved.

Fabrication, characterization, and application in surface-enhanced Raman spectrum of assembled type-I collagen-silver nanoparticle multilayered films

In this paper, we report a facile method for the fabrication of type-I collagen-silver nanoparticles (Ag NPs) multilayered films by utilizing type-I collagen as a medium. These samples were characterized by UV-vis spectra photometer, atomic force microscopy, scanning electron microscopy, and Fourier transform IR spectrum. Experimental results show that collagen molecules serve as effective templates to assemble Ag NPs into multilayer films. These samples exhibit high surface-enhanced Raman scattering (SERS) enhancement abilities.

Preparation and luminescence properties of Mn2+-doped ZnGa2O4 nanofibers via electrospinning process

One-dimensional Mn2+-doped ZnGa2O4 nanofibers were prepared by a simple and cost-effective electrospinning process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), scanning electron microscopy (SEM), energy-dispersive X-ray spectrum (EDS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL) and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. SEM results indicated that the as-formed precursor fibers and those annealed at 700 degrees C are uniform with length of several tens to hundred micrometers, and the diameters of the fibers decrease greatly after being heated at 700 degrees C. Under ultraviolet excitation (246 nm) and low-voltage electron beams (1-3 kV) excitation, the ZnGa2O4:Mn2+ nanofibers presents the blue emission band of the ZnGa2O4 host lattice and the strong green emission with a peak at 505 nm corresponding to the T-4(1)-(6)A(1) transition of Mn2+ ion.

Electrospinning Synthesis and Luminescence Properties of One-Dimensional Zn2SiO4:Mn2+ Microtibers and Microbelts

One-dimensional Mn2+-doped Zn2SiO4 rnicrobelts and microfibers were prepared by a simple and cost-effective electrospinning process. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), scanning electron microscopy (SEM), energy-dispersive X-ray spectrum (EDS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL), and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The XRD and DTA results show that the Zn2SiO4 phase begins to crystallize at 800 degrees C and crystallizes completely around 1000 degrees C. SEM results indicate that the as-prepared microbelts/fibers are smooth, whose diameters decrease with increasing the annealing temperature. The average diameter of the Zn2SiO4:Mn2+ microfibers annealed at 1000 degrees C is 0.32 mu m, and their lengths reach up to several millimeters. The average width and thickness of the Zn2SiO4:Mn2+ microbelts fired at 1000 degrees C are around 0.48 and 0.24 mu m, respectively.

Grafting polymerization of L-lactide on the surface of hydroxyapatite nano-crystals

A novel method of grafting ring-opening polymerization of L-lactide (LLA) onto the surface of hydroxyapatite nano-particles (n-HAP) was developed. PLLA was directly connected onto the HAP surface through a chemical linkage. The PLLA-g-HAP particles could be stably dispersed in organic solvent such as chloroform for several weeks. The n-HAP particles still retained the original dimension and shape after the grafting of PLLA. Compared with the P-31 MAS-NMR spectrum of pure HAP powders, there appeared a downfield displacement of 1.2 ppm in the spectrum of PLLA-g-HAP. Fourier transformation infrared (FT-IR) spectra further confirmed the existence of PLLA on the surface of PLLA-g-HAP. The amount of grafted polymer determined by thermal gravimetric analysis (TGA) was about 6% in weight. The tensile strength and elongation at break of the PLLA/PLLA-g-HAP composite containing 8 wt% of PLLA-g-HAP were 55 MPa and about 10-13%, respectively, while those of the PLLA/n-HAP composites were 40 MPa and 3-5%, respectively.

IR/Raman spectroscopy and DFT calculations of cyclic di-amino acid peptides. Part III: comparison of solid state and solution structures of cyclo(L-Ser-L-Ser)

B3-LYP/cc-pVDZ calculations of the gas-phase structure and vibrational spectra of the isolated molecule cyclo(L-Ser-L-Ser), a cyclic di-amino acid peptide (CDAP), were carried out by assuming C-2 symmetry. It is predicted that the minimum-energy structure is a boat conformation for the diketopiperazine (DKP) ring with both L-Beryl side chains being folded slightly above the ring. An additional structure of higher energy (15.16 kJ mol(-1)) has been calculated for a DKP ring with a planar geometry, although in this case two fundamental vibrations have been calculated with imaginary wavenumbers. The reported X-ray crystallographic structure of cyclo(L-Ser-L-Ser), shows that the DKP ring displays a near-planar conformation, with both the two L-Beryl side chains being folded above the ring. It is hypothesized that the crystal packing forces constrain the DKP ring in a planar conformation and it is probable that the lower energy boat conformation may prevail in the aqueous environment. Raman scattering and Fourier-transform infrared (FT-IR) spectra of solid state and aqueous solution samples of cyclo(L-Ser-L-Ser) are reported and discussed. Vibrational band assignments have been made on the basis of comparisons with the calculated vibrational spectra and band wavenumber shifts upon deuteration of labile protons. The experimental Raman and IR results for solid-state samples show characteristic amide I vibrations which are split (Raman:1661 and 1687 cm(-1), IR:1666 and 1680 cm(-1)), possibly due to interactions between molecules in a crystallographic unit cell. The cis amide I band is differentiated by its deuterium shift of ~ 30 cm(-1), which is larger than that previously reported for trans amide I deuterium shifts. A cis amide II mode has been assigned to a Raman band located at 1520 cm(-1). The occurrence of this cis amide II mode at a wavenumber above 1500 cm(-1) concurs with results of previously examined CDAP molecules with low molecular weight substituents on the C-alpha atoms, and is also indicative of a relatively unstrained DKP ring.

Synthesis, Characterization, Luminescence and Defect Centres in CaYAl(3)O(7):Eu(3+) Red Phosphor

CaYAl(3)O(7):Eu(3+) phosphor was prepared at furnace temperatures as low as 550A degrees C by a solution combustion method. The formation of crystalline CaYAl(3)O(7):Eu(3+) was confirmed by powder X-Ray diffraction pattern. The prepared phosphor was characterized by SEM, FT-IR and photoluminescence techniques. Photoluminescence measurements indicated that emission spectrum is dominated by the red peak located at 618 nm due to the (5)D(0)-(7)F(2) electric dipole transition of Eu(3+) ions. Electron Spin Resonance (ESR) studies were carried out to identify the centres responsible for the thermoluminescence (TL) peaks. Room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0126 is identified as an O(-) ion while centre II with an isotropic g-factor 2.0060 is assigned to an F(+) centre (singly ionized oxygen vacancy). An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F(+) centre) seems to originate from an F centre (oxygen vacancy with two electrons). The F(+) centre appears to correlate with the observed high temperature TL peak in CaYAl(3)O(7):Eu(3+) phosphor.

Thermal and structural properties of commercial dental resins light-cured with blue emitting diodes (LEDs)

We have investigated the thermal and structural properties of different commercial dental resins: Filtek(TM) Z-350, Grandio(A (R)), Tetric Ceram(A (R)), and TPH Spectrum(A (R)). The purpose of the present study was to evaluate quantitatively the photo-polymerization behavior and the effect of filler contents on the kinetic cures of the dental resins by using Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FT-IR) techniques. We have successfully obtained the low and high glass transition T (g) values of the dental composite resins from DSC curves. It was also observed a good agreement between the both T (g) values, activation energies from thermal degradation, and the degree of conversion obtained for all samples. The results have shown that Tetric Ceram(A (R)) dental resin presented the higher T (g) values, activation energy of 215 +/- A 6 KJ mol(-1), and the higher degree of conversion (63%) when compared to the other resins studied herein.

Influence of ceria addition on thermal properties and local structure of bismuth germanate glasses

Bismuth germanate glasses are interesting materials due to their physical properties and their unique structural characteristics caused by the coordination changes of bismuth and germanium atoms. Glasses of the bismuth germanate system were prepared by melting/molding method and were investigated concerning their thermal and structural properties. The structural analysis of the samples was carried out by micro-Raman and Fourier transform infrared spectroscopes. It was observed that the glass structure is formed basically by GeO(4) tetrahedral units also having the formation of the GeO(6) octahedral units. BiO(2) was considered a network former by observing the presence of octahedral BiO(6) and pyramidal BiO(3) groups in the local structure of the samples. An absorption band observed at 1103 cm(-1) in the IR spectrum of the undoped glass was attributed to the Bi-O-Ge and/or Bi-O-Bi linkage vibration. The said band shifted to lower wavenumbers after the CeO(2) addition thus reflecting changes in the glass network. Cerium oxide was an efficient oxidant agent to prevent the darkening of the glasses which was probably associated to the reduction of Bi ions. However, CeO(2) was incorporated as a local network modifier in the glass structure even at concentrations of 0.2 mol%. (C) 2010 Elsevier B.V. All rights reserved.

Systematic analysis of the Fourier transform spectrum of (CH3OH)-C-13 between 400 and 950 cm(-1)

We have investigated a high-resolution Fourier transform (FT) absorption spectrum of the (CH3OH)-C-13 isotopomer of methanol from 400 to 950 cm(-1) with the Ritz program. We present the assignments of 7160 transitions, 3021 of which belong to Asymmetry, and 4139 to E-symmetry. These transitions occur between states labeled by K quantum numbers up to 14, and by torsional quantum numbers n up to 4. The Ritz program evaluated the energies of the 4684 involved levels with an accuracy of the order of 10(-4) cm(-1). All of the assigned lines correspond to transitions involving torsionally excited levels within the ground small-amplitude vibrational state. (c) 2005 Elsevier B.V. All rights reserved.