Disorder in cellulosic fibers

Ruland's concept of an isotropic disorder function is applied to estimate the disorder parameter and the degree of crystallinity in a few cellulosic fibers: two cottons, native ramie, and a high-tenacity rayon. The results indicate an increase in disorder without any change in crystallinity on mercerization of native celluloses. On hydrolysis, with or without a pretreatment of mercerization, the samples exhibit a higher crystallinity, disorder remaining the same as for native celluloses. A ball-milled sample of “amorphous” cellulose is still found to be fairly crystalline with the lowest disorder. On being wetted in water and oven-dried, a distorted form of cellulose II with higher crystallinity and disorder was obtained. The polynosic fiber, Tufcel, has low values for the degree of crystallinity, disorder parameter, as well as crystallite dimension. A strong dependence of the degree of crystallinity on the crystallite size, particularly the lateral, is observed.     

Photoluminescence,Judd–Ofelt analysis and photometric characterization of Eu<Superscript>3+</Superscript> activated Ca<Subscript>0.5</Subscript>Gd(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> red phosphor

The red emitting Ca_0.5Gd(WO₄)₂:Eu³⁺ was synthesized by a solid-state reaction method. X-ray diffraction patterns were used to characterize crystal structure as well as phase purity. The results suggest that the as synthesized powder phosphor possess scheelite crystal structure with tetragonal symmetry along with the space group of I4₁/a. SEM studies reveal that the as synthesized sample show polyhedral morphology with particle size of 5.5 µm. Photoluminescence excitation spectrum depicts that a broad band (from 200 to 300 nm) centered at 242 nm is attributed to the ligand to metal charge transfer transition of WO₄ ^2? and three intense with sharp absorption bands (observed at 394, 464 and 535 nm) are designated as f–f electronic transitions of Eu³⁺. Photoluminescence emission studies indicate that, under 394 nm UV excitation, a hypersensitive red emission was observed at 617 nm due to the transition from upper ⁵D₀ level to the ⁷F₂ lower level of Eu³⁺ ion. The spectroscopic behaviour of the as synthesized phosphor Ca_0.5Gd(WO₄)₂:Eu³⁺ was determined using Judd–Ofelt theory. The CIE color coordinates, colour correlated temperature and luminous efficacies of radiation were estimated. The as obtained results indicating that the Ca_0.5Gd(WO₄)₂:Eu³⁺ red phosphor is most suitable for solid state lighting applications.     

Preparation and characterization of sputtered Cu films containing insoluble Nb

Copper films containing various amounts of insoluble Nb (up to 24.7 at.%) were prepared by r.f. magnetron sputtering. The crystallography and microstructure of the films were investigated for as-deposited and annealed Cu(Nb) thin films. Cu(Nb) thin films are found to consist of non-equilibrium supersaturated solid solution of Nb in Cu with a nanocrystalline microstructure. X-ray diffraction and scanning electron microscope analyses revealed a reduction in the grain sizes of the films with increasing Nb content in the films leading to a grain refinement. The electrical resistivity of as-deposited and annealed Cu(Nb) thin films is found to be low for an Nb content 2.7 at.%. Significant drops in the resistivity were observed for the high Nb contents after annealing at 530 °C which may be due to grain growth and formation of Nb-bearing phase in the film. Microhardness of the films was found to increase with the Nb concentration due to the combined effects of grain refinement and the solute strengthening of Nb.     

Relative quantities of catalytically active CYP 2C9 and 2C19 in human liver microsomes: application of the relative activity factor approach

The relative catalytic activities of CYP2C9 and CYP2C19 in human liver microsomes has been determined using the approach of relative activity factors (RAFs). Tolbutamide methylhydroxylation and S-mephenytoin 4'-hydroxylation were used as measures of CYP2C9 and CYP2C19 activity, respectively. The kinetics of these reactions were studied in human liver microsomes, in microsomes from human lymphoblastoid cells, and in insect cells expressing CYP2C9 and CYP2C19. RAFs were calculated as the ratio of Vmax (reaction velocity at saturating substrate concentrations) in human liver microsomes of the isoform-specific index reaction divided by the Vmax of the reaction catalyzed by the cDNA expressed isoform. RAFs were also determined for SUPERMIX, a commercially available mixture of cDNA expressed human drug metabolizing CYPs formulated to achieve a balance of enzyme activities similar to that found in human liver microsomes. Lymphoblast RAF2C9 in human liver microsomes ranged from 54 to 145 pmol CYP/mg protein (mean value: 87), while a value of 251 pmol CYP/mg protein was obtained for SUPERMIX. Insect cell RAF2C9 in human liver microsomes ranged from 1.6 to 143 pmol CYP/mg protein (mean value: 49), while a value of 201 pmol CYP/mg protein was obtained for SUPERMIX. Both lymphoblast and insect cell RAF2C19 in human liver microsomes ranged from 4 to 45 pmol CYP/mg protein (mean values: 29 and 28, respectively), while a value of 29 pmol CYP/mg protein was obtained for SUPERMIX. The nature of the cDNA expression system used had no effect on the kinetic parameters of CYP2C9 as a tolbutamide methylhydroxylase, or of CYP2C19 as a S-mephenytoin hydroxylase. However insect cell expressed CYP2C19 (which includes oxidoreductase) had substantially greater activity as a tolbutamide methylhydroxylase when compared to lymphoblast expressed CYP2C19. The ratio of mean lymphoblast-determined RAF2C9 to RAF2C19 in human livers was 3.0 (range 1.6-17.9; n = 10), while this ratio for SUPERMIX was 8.6. The ratio of mean insect cell-determined RAF2C9 to RAF2C19 in human livers was 1.7 (range 0.04-16.2; n = 10), while this ratio for SUPERMIX was 7.0. Neither ratio is in agreement with the 20:1 ratio of immunoquantified levels of CYP2C9 and 2C19 in human liver microsomes reported in previous studies. SUPERMIX may contain catalytically active CYP2C9 in levels higher than those in human liver microsomes.     

Characterization of MHz pulse repetition rate femtosecond laser-irradiated gold-coated silicon surfaces

In this study, MHz pulse repetition rate femtosecond laser-irradiated gold-coated silicon surfaces under ambient condition were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), and X-ray photoelectron spectroscopy (XPS). The radiation fluence used was 0.5 J/cm² at a pulse repetition rate of 25 MHz with 1 ms interaction time. SEM analysis of the irradiated surfaces showed self-assembled intermingled weblike nanofibrous structure in and around the laser-irradiated spots. Further TEM investigation on this nanostructure revealed that the nanofibrous structure is formed due to aggregation of Au-Si/Si nanoparticles. The XRD peaks at 32.2°, 39.7°, and 62.5° were identified as (200), (211), and (321) reflections, respectively, corresponding to gold silicide. In addition, the observed chemical shift of Au 4f and Si 2p lines in XPS spectrum of the irradiated surface illustrated the presence of gold silicide at the irradiated surface. The generation of Si/Au-Si alloy fibrous nanoparticles aggregate is explained by the nucleation and subsequent condensation of vapor in the plasma plume during irradiation and expulsion of molten material due to high plasma pressure.     

Cyclic voltammetric study of zinc and zinc oxide electrodes in 5.3 M KOH

The behaviour of zinc and zinc oxide in 5.3 M KOH in the presence of alkaline earth oxides, SnO, Ni(OH)₂ and Co(OH)₂ was examined by cyclic voltammetry. The influence of the alkaline earth oxides was compared with additives of established effects (Bi₂O₃, LiOH, Na₂CO₃ and CdO). The alkaline earth oxide each exhibits a distinct behaviour towards zincate. Whereas, a single process of interaction with zincate was shown by CaO; two modes of reaction were obtained with SrO and BaO. Solid solution formation was noticed with BeO and MgO. The other additives forming solid solution with ZnO were CdO, SnO. The ionic sizes of Ni(OH)₂ and Co(OH)₂ allow solid solution formation with Zn(OH)₂. Both Bi₂O₃ and Na₂CO₃ enter into complexation with zincate. LiOH forms two distinct zincates, of which one is an oxo zincate leaching the `hydroxyl' functionality. Cyclic voltammetry revealed the deposition of the oxide/hydroxide additives as metal prior to the onset of zinc deposition and the potential range for this additive metal deposition is almost the same for different additives (SnO, CdO, Ni(OH)₂). The beneficial action of these additives to zinc alkaline cells is associated with a substrate effect. The implication of this electrocatalytic deposition of metals on a zinc oxide electrode is also discussed.     

Synthesis of 3D nanostructured metal alloy of immiscible materials induced by megahertz-repetition femtosecond laser pulses

In this work, we have proposed a concept for the generation of three-dimensional (3D) nanostructured metal alloys of immiscible materials induced by megahertz-frequency ultrafast laser pulses. A mixture of two microparticle materials (aluminum and nickel oxide) and nickel oxide microparticles coated onto an aluminum foil have been used in this study. After laser irradiation, three different types of nanostructure composites have been observed: aluminum embedded in nickel nuclei, agglomerated chain of aluminum and nickel nanoparticles, and finally, aluminum nanoparticles grown on nickel microparticles. In comparison with current nanofabrication methods which are used only for one-dimensional nanofabrication, this technique enables us to fabricate 3D nanostructured metal alloys of two or more nanoparticle materials with varied composite concentrations under various predetermined conditions. This technique can lead to promising solutions for the fabrication of 3D nanostructured metal alloys in applications such as fuel-cell energy generation and development of custom-designed, functionally graded biomaterials and biocomposites.