Infrared vibrational spectra of l-histidinium dihydrogen orthophosphate orthophosphoric acid (LHP)

The entire vibrational spectrum of a single crystal of l-histidinium dihydrogen orthophosphate orthophosphoric acid (LHP) was studied by infrared (IR) spectroscopy from 10 up to 4000 cm⁻¹. The polarized infrared (IR) reflectivity spectra were measured between 7 and 250 K, in the frequency range 10–600 cm⁻¹. From the IR spectral analysis, the phonon modes were classified within their symmetry species, and their longitudinal (LO) and transversal (TO) optical frequencies were calculated. A tentative assignment of the various internal modes observed in the transmissivity spectrum of LHP, between 300 and 4000 cm⁻¹, is proposed. The present study did not reveal any low-temperature structural phase transition.     

Nanocomposites of poly(l-lactide) and surface modified magnesia nanoparticles: Fabrication, mechanical property and biodegradability

A novel nanocomposite based on biodegradable poly(l-lactide) (PLLA) was prepared by the incorporation of surface modified magnesia (g-MgO) nanoparticles using a solution casting method. The mechanical properties, biodegradable properties and protein adhesion behavior of the g-MgO/PLLA nanocomposites were investigated. Scanning electron microscopy (SEM) results showed that g-MgO nanoparticles could comparatively uniformly disperse in PLLA matrix. The addition of g-MgO nanoparticles to PLLA matrix improved the tensile strength and elastic modulus, whereas reduced the elongation at break. The mass loss results showed that the nanocomposites with higher g-MgO content had faster degradation rates. The in vitro pH value determination results indicated that the g-MgO nanoparticles could neutralize effectively the lactic acid resulting from the degradation of PLLA. The g-MgO/PLLA nanocomposites exhibited enhanced protein adsorption, i.e., with the increase of g-MgO content, the amount of protein adsorption increased. The (5 wt%)g-MgO/PLLA nanocomposites adsorbed 33% more protein than the pure PLLA.     

Specific heat measurements in pure and in (Cu, Mn, Fe, Ni)-doped single-crystals of l-arginine phosphate monohydrate

The influence of highly diluted impurities (Cu, Mn, Fe, Ni) on the temperature (T) dependence of the specific heat (c_p) of l-arginine phosphate monohydrate (LAP) was investigated in the temperature range 1.8-300 K. The doped samples yielded values for c_p in excess to those obtained for a pure LAP sample. The melting temperatures (T_m≈420 K) obtained by differential scanning calorimetry for pure and doped LAP samples were found not to be significantly affected by the impurities. The T-dependence of c_p was fully accounted for by taking into consideration the Debye contribution, an Einstein term and a contribution due to both Frenkel and Schottky defects. The model fit all c_p versus T data using a single value for both the Debye (θ_D=160 K) and the Einstein (T_E=376.8 K) temperatures, and for the energy (ε_d=157.9 meV) required to create the defects.     

Preparation and thermal decomposition studies of l-tyrosine intercalated MgAl, NiAl and ZnAl layered double hydroxides

l-Tyrosine (represented as l-Tyr) intercalated MgAl, NiAl and ZnAl layered double hydroxides (LDHs) have been obtained by the method of coprecipitation. In situ FT-IR, in situ HT-XRD and TG-DTA measurements allow a detailed understanding of the thermal decomposition process for the three intercalated composites. In situ HT-XRD reveals that the layered structure of l-Tyr/MgAl-LDH collapses completely at 450 °C with the first appearance of reflections of a cubic MgO phase, while the corresponding temperature for l-Tyr/NiAl-LDH is some 50 °C lower. In contrast, there is a major structural change in l-Tyr/ZnAl-LDH at 250 °C as shown by the disappearance of its (0 0 6) and (0 0 9) reflections at this temperature accompanied by the appearance of reflections of ZnO. In situ FT-IR experiments give information about the decomposition of the interlayer -Tyr ions. The decomposition temperature of l-Tyr in the ZnAl host is about 50 °C lower than the corresponding values for the MgAl and NiAl hosts. TG-DTA curves show a significant weight loss step (170-260 °C) in l-Tyr/ZnAl-LDH which is due to the dehydroxylation of the host layers, with a corresponding weak endothermic peak at 252 °C. This temperature range is much lower than that observed for MgAl and NiAl hosts, indicating that the ZnAl-LDH layers are relatively unstable. The data indicate that the order of thermal stability of the three intercalates is: l-Tyr/MgAl-LDH > l-Tyr/NiAl-LDH > l-Tyr/ZnAl-LDH.     

Pressure-induced phase transformations in l-alanine crystals

Raman scattering and synchrotron X-ray diffraction have been used to investigate the high-pressure behavior of l-alanine. This study has confirmed a structural phase transition observed by Raman scattering at 2.3 GPa and identified it as a change from orthorhombic to tetragonal structure. Another phase transformation from tetragonal to monoclinic structure has been observed at about 9 GPa. From the equation of state, the zero-pressure bulk modulus and its pressure derivative have been determined as (31.5±1.4) GPa and 4.4±0.4, respectively.     

Single crystal EPR and optical absorption study of Cr doped l-histidine hydrochloride monohydrate

EPR study of the Cr³⁺ ion doped l-histidine hydrochloride monohydrate single crystal is done at room temperature. Two magnetically inequivalent interstitial sites are observed. The hyperfine structure for Cr⁵³ isotope is also obtained. The zero field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular rotations and the parameters are: D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.9108±0.0002, g_y=1.9791±0.0002, g_z=2.0389±0.0002, A_x=(252±2)×10⁻⁴ cm⁻¹, A_y=(254±2)×10⁻⁴ cm⁻¹, A_z=(304±2)×10⁻⁴ cm⁻¹ for site I and D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.8543±0.0002, g_y=1.9897±0.0002, g_z=2.0793±0.0002, A_x=(251±2)×10⁻⁴ cm⁻¹, A_y=(257±2)×10⁻⁴ cm⁻¹, A_z=(309±2)×10⁻⁴ cm⁻¹ for site II, respectively. The optical absorption studies of single crystals are also carried out at room temperature in the wavelength range 195-925 nm. Using EPR and optical data, different bonding parameters are calculated and the nature of bonding in the crystal is discussed. The values of Racah parameters (B and C), crystal field parameter (Dq) and nephelauxetic parameters (h and k) are: B=636, C=3123, Dq=2039 cm⁻¹, h=1.46 and k=0.21, respectively.     

Polystyrene-co-maleic acid/CdS nanocomposites: Preparation and properties

Composites of CdS nanoparticles confined in a polystyrene-co-maleic acid (PS-co-MAc) matrix have been prepared and characterized. It was shown that the acid groups of the co-polymer could be successfully used to control the aggregation of the nanoparticles, because they act as coordinate sites for Cd ions. UV-VIS measurements showed a blue shift of the absorption threshold, proving the presence of nanoparticles. An average size of the nanoparticles of about 4 nm is estimated from the change in band gap energy. Although the FTIR spectrum of the nanocomposite showed the presence of C-S bonds, a broad emission originating from surface recombination sites are noticed. DSC and TGA measurements revealed changes in thermal properties upon incorporation of nanoparticles. No thermal transition was observed in the nanocomposite, while the pure co-polymer exhibits a glass transition at 190 °C. In the presence of nanoparticles the onset of the thermal decomposition of the matrix is also shifted by 50 °C towards a higher temperature.     

Diffusivity control in nanoporous membrane through organic-inorganic hybridization

Nanoporous inorganic materials have attracted great interest due to their potential application as nanofilters, drug delivery carriers and adsorbents. In order to control the molecular passage through nanopores, we have modified the pore channel of inorganic materials with organic moieties and investigated the diffusion pattern of small molecules. The surface was modified by octyltriethoxysilane (OTS) by refluxing in toluene for 12 h. The water contact angle of OTS modified zirconia membrane was observed ∼110° showing hydrophobic surface. Contact angles to various solvents were also examined to verify the self-assembled monolayer of octyl chains on the inorganic membrane. The molecular passage patterns of both pristine and modified nanoporous membrane were evaluated by means of the diffusivity of small dye molecule, azobenzene. The diffusion coefficients of azobenzene on both membranes were measured in various solvents on the basis of Fick’s diffusion law. The diffusivities in various solvents for pristine and its modified zirconia membrane were determined. The diffusivity was observed to be influenced by surface energy of both membrane and solvent as well as the polarity of solvents.     

FTIR, XRD, SEM and solid state NMR investigations of carbonate-containing hydroxyapatite nano-particles synthesized by hydroxide-gel technique

Nano-crystalline hydroxyapatite (HA), Ca₁₀(PO₄)₆(OH)₂ has been synthesized by a precipitate conversion technique using hydroxide gel at lower temperatures, e.g. 80 °C. HA crystallizes in hexagonal structure (space group: P6₃/m) having lattice parameters: and and around 17 nm in crystallite-size for the 80 °C-heated sample. SEM micrographs show hexagonal crystallites of average particle dimensions approximately 50×20 nm for 80 °C heated sample. The structure analysis by XRD, FTIR, ¹H and ³¹P MAS NMR show the existence of structural disorder at the particle surface that either does not form hydrogen bonding due to lack of adequate bonding parameters or forms a very weak dipolar bonding. The structural disorder has been explained as a result of chemical interactions between the phosphate groups either with the surface adsorbed water or the hydroxyl groups at the surface of the nano-particles.     

Copper reduction and hydroxyl formation by hydrogen process in alumino-silicate glasses

The process of nanometric copper (Cu⁰) precipitation by hydrogen in alumino-silicate glasses was studied regarding the simultaneous formation of hydroxyl bonding. Firstly, copper-ion-doped alumino-silicate glasses were melt-quenched and then heat-treated in the presence of hydrogen gas, which allowed copper ions to be reduced into nanometric metal particles. Along with the metallic copper formation, there was also formed the hydroxyl groups as a byproduct of the reaction. From spectroscopic studies, it was revealed that the reduction process was kinetically controlled by the hydrogen diffusion into the glasses. After the Cu⁰ precipitation, in particular, at temperatures higher than 700 °C or for reduction times longer than 5 h the copper metal was found to move towards the surface, creating a copper metal rich surface. Moreover, an increase in hydrogen permeation with the treatment time was also observed and this tendency was more intense for the matrix, which allowed higher copper reduction.     

Magnetic transitions and magnetoresistance of -type () compounds

Magnetic transitions and magnetotransport properties of polycrystalline Tb_1−xGd_xMn₆Ge₆ (x=0.2–1.0) compounds have been investigated by magnetic property and resistivity measurements in an applied magnetic field up to 50 kOe. The cell parameter a,c and cell volume V of compounds (x=0.2–1.0) increase with an increasing Gd content. The compounds (x=0.2–1.0) show a rich variety of magnetic behavior, such as antiferromagnetic, ferrimagnetic and paramagnetic state with increasing temperature. Their Curie temperatures increase almost linearly with an increasing Gd content from 460 K for x=0.2 to 484 K for x=1.0. The compounds (x=0.2–1.0) display the field induced metamagnetic transitions, and the threshold fields first increase and then decrease with an increasing Gd content. The magnetoresistance curves of the Tb_0.4Gd_0.6Mn₆Ge₆ compounds in an applied magnetic field up to 50 kOe are presented and the magnetoresistance effects are related to the metamagnetic transitions.     

Chemical reactivity of solid [PtnC60] towards carbon monoxide

Evidence of chemical reactivity of solid platinum-fullerene [Pt_nC₆₀] compounds towards carbon monoxide is presented. The interaction was systematically studied by means of infrared spectroscopy, X-ray powder diffraction and thermogravimetric analysis. The interaction of carbon monoxide, even under low pressure, is confirmed by the appearance of infrared absorption bands in the CO stretching region at 2064, 2014 and 1991 cm⁻¹ for the carbonylation products. The exceptions were those products with low Pt:C₆₀ ratios, which also displayed bands at 1870 and 1830 cm⁻¹. The data suggest that the CO coordination depends on the specific morphology of the solids, the original Pt:C₆₀ ratio, and the carbon monoxide nominal pressure. Therefore, these results indicate the formation of [(CO)_xPt]_m species supported in a fullerene matrix mixed with [Pt_n−mC₆₀] compounds. As there is a competition between carbon monoxide and fullerene molecules for the electronic density at the platinum centers, the nature of the CO interaction with [Pt_nC₆₀] was found to be destructive, leading to the displacement of the latter. Nevertheless, the platinum-carbonyl species formed presents relatively high stability, as shown by desorption tests.     

Growth and characterization of two new NLO materials from the amino acid family: l-Histidine nitrate and l-Cysteine tartrate monohydrate

Single crystals of organic nonlinear optical (NLO) materials l-Histidine nitrate (C₆H₁₀N₃O₂)⁺ · (NO₃)⁻ and l-Cysteine tartrate monohydrate (C₃H₈NO₂S)⁺ · (C₄H₅O₆)⁻ · H₂O were grown by submerged seed solution method. Characterization of the crystals was made using single crystal X-ray diffraction. Fourier transform infrared (FTIR) spectroscopic studies, optical behaviour such as UV-visible-NIR absorption spectra and second harmonic generation (SHG) conversion efficiency were investigated to explore the NLO characteristics of the above materials. Microhardness measurements and dielectric studies of the compounds were also carried out.     

Synergistic effect of efficient adsorption g-C3N4/ZnO composite for photocatalytic property

Novel g-C₃N₄/ZnO composite photocatalyst was synthesized from an oxygen-containing precursor by direct thermal decomposition urea in air without any other templates assistance. Different percentages of g-C₃N₄ were hybridized with ZnO via the monolayer-dispersed method. The prepared g-C₃N₄/ZnO composites were characterized by XRD, SEM, UV–vis diffuse reflectance spectra (DRS), FT-IR, TEM and XPS. The composites showed much higher efficiency for degradation of Rhodamine B (RhB) than ZnO under UV and visible light irradiation. Especially, the photocatalytic efficiency was the highest under UV light irradiation when the percentage of g-C₃N₄ was 6%. The improved photocatalytic activity may be due to synergistic effect of photon acquisition and direct contact between organic dyestuff and photocatalyst. Then, effective separation of photogenerated electron–hole pairs at the interface of g-C₃N₄ is an important factor for improvement of photocatalytic activity. This work indicates that g-C₃N₄ hybrid semiconductors photocatalyst is a promising material in pollutants degradation.     

The luminescence and structural characteristics of Eu- doped NaSrB5O9 phosphor

A red-emitting phosphor NaSrB₅O₉:Eu³⁺ was synthesized by employing a solid-state reaction (SSR) method. The structures of the phosphors were analyzed by X-ray diffraction (XRD), Fourier-transform infrared (FTIR) and Raman studies. The band at ~282 nm in the excitation spectra indicated the charge transfer band (CTB) of B-O in the host, whereas the CTB of Eu-O was observed at ~275 nm for the NaSrB₅O₉:Eu³⁺ (Eu³⁺=1 at.%) phosphor, which was supported by diffuse reflectance spectroscopy (DRS) measurements. The photoluminescence (PL) measurements exhibited a strong red emission band centered at about 616 nm (⁵D₀→⁷F₂) under an excitation wavelength of 394 nm (⁷F₀→⁵L₆). Upon host excitation at 282 nm, the pristine NaSrB₅O₉ exhibited a broad UV emission centered at ~362 nm. The energy transfer from host to Eu³⁺ ions was confirmed from luminescence spectra, excited with a 355 nm Nd:YAG laser. In addition, the asymmetric ratios indicate a higher local symmetry around the Eu³⁺ ion in the host. The calculated CIE (Commission International de l′Eclairage) coordinates displayed excellent color purity efficiencies (around 99.7%) compared to other luminescent materials.     

Synthesis and crystal structure of [3,5-(CH3)2C6H3NH3]4P4O12·3H2O

Chemical preparation and crystal structure are given for a new cyclotetraphosphate: [3,5-(CH₃)₂C₆H₃NH₃]₄P₄O₁₂·3H₂O. This compound is triclinic P with the following unit-cell parameters: a=8.298(3), b=8.299(3), c=17.242(7)Å, α=97.13(3), β=102.72(3), γ=64.55(3)°, Z=1 and V=1045.2(8)ų. The crystal structure has been solved and refined to R=0.040 using 6086 independent reflections. The atomic arrangement can be described as layers organization. Layers built by P₄O₁₂ ring anions, ammonium groups and water molecules parallel to the plan (001), between which the organic groups are located. Characterization by X-ray diffraction, IR absorption, and thermal analysis are described.     

Synthesis of earth-abundant Cu2SnS3 powder using solid state reaction

Cu₂SnS₃ (CTS) powder has been synthesized at 200 °C by solid state reaction of pastes consisting of Cu and Sn salts and different sulphur compounds in air. The compositions of the products is elucidated from XRD and only thiourea is found to yield CTS without any unwanted CuS_x or SnS_y. Rietveld analysis of Cu₂SnS₃ is carried out to determine the structure parameters. XPS shows that Cu and Sn are in oxidation states +1 and +4, respectively. Morphology of powder as revealed by SEM shows the powder to be polycrystalline with porous structure. The band gap of CTS powder is found to be 1.1 eV from diffuse reflectance spectroscopy. Cu₂SnS₃ pellets are p-type with electrical conductivity of 10⁻² S/cm. The thermal degradation and metal–ligand coordination in CTS precursor are studied with TGA/DSC and FT-IR, respectively, and a probable mechanism of formation of CTS has been suggested.     

The effect of zinc concentration on vacancies jump rate, diffusion coefficient and jump length in Cu-Zn ferrite

Samples with the chemical formula Cu_1−xZn_xFe₂O₄ (x=0.2, 0.4, 0.6, 0.8 and 1) were prepared by the standard ceramic method. The dielectric constant and dielectric loss tangent were studied as a function of vacancy jump rate. The results show that the dielectric constant and dielectric loss tangent decrease with increasing vacancy jump rate. In addition, the electron jump length in the octahedral sites was studied as a function of zinc concentration. The increase in jump length with Zn concentration has been attributed to the substitution of Fe⁺³ for Zn²⁺ at the A-sites, which increases the B-B interaction. The increase of diffusion coefficient with increasing Zn concentration was reinforced by the increase of jump rate.     

High-rate characteristic of F-substitution cathode materials for Li–ion batteries

The effect of fluorine substitution on the electrochemical properties of Li₃V ₂(PO₄)₃ cathode materials was studied. Samples with stoichiometric proportions of Li₃V ₂(PO₄)_3−xF_x (x=0,0.05,0.10,0.15) were prepared by adding LiF in the starting materials of Li₃V ₂(PO₄)₃. XRD studies showed that the F-substituted Li₃V ₂(PO₄)₃ had the same monoclinic structure as the un-substituted Li₃V ₂(PO₄)₃. SEM images showed that F-substitution Li₃V ₂(PO₄)₃ had a regular and uniform particles. The results of electrochemical measurement showed that F-substitution can improve the rate capability of these cathode materials. The Li₃V ₂(PO₄)_2.90F_0.10 sample showed the best high rate performance. Its discharge capacity at 10 C rate was 117 mA h g⁻¹ with 30th capacity retention of about 90.60%. The electrode reaction reversibility and electronic conductivity was enhanced, and the charge transfer resistance was decreased through F-substitution. The improved electrochemical performance of F-substitution Li₃V ₂(PO₄)₃ cathode materials were attributed to the above factors.