Controlled Dissolution of Phenytoin by Hybridizing with Silica Nanoparticles

A sparingly soluble model drug, phenytoin (5,5-diphenyl-hydantoin, denoted as PT), was incorporated during or after hydrolysis and polycondensation of tetra orthoethyl silicate (TEOS) to obtain silica–drug hybrids. We also compare the hybrids obtained by sol–gel process with those obtained by simple adsorption on nonporous silica particles. The initial rate of dissolution in water increases by a factor of 40 with respect to the intact PT by aging silica before drug addition. The IR results show that C=O in the position 2 of PT and N–H shift toward the higher wavenumber, showing that intermolecular hydrogen bonds between C=O and N–H are loosened or broken to form new hydrogen bonds between C=O in PT and Si–OH in silica. The dissolution rate of PT is determined by the degree of the breakage of hydrogen bonds between PT molecules and the intensity of the interaction between silica and PT.     

Hydrogen-related defect creation at the Si(100)–SiO2interface of metal-oxide-semiconductor field effect transistors during hot electron stress

We explore the hydrogen-related microstructures involved in hot electron defect creation at the Si(100)–SiO₂interface of metal-oxide-semiconductor field effect transistors. Based on the energetics of hydrogen desorption from the interface between silicon and silicon-dioxide, we argue that the hard threshold for hydrogen-related degradation may be considerably lower than the previously assumed value of 3.6 eV. Also, hydrogen atoms released from Si–H bonds at the interface by hot electron stress are trapped in bulk silicon near the interface.     

Effect of annealing in N2 atmosphere on net acceptor concentration in ZnSe:N grown by MOCVD

Annealing effect on net acceptor concentration in ZnSe:N is investigated. ZnSe:N homo-epitaxial layer was grown at 823 K by MOCVD using ammonia (NH₃) as a dopant source. Photoluminescence (PL) spectra measured on as-grown layer exhibited the strong deep donor–acceptor pair (D^dAP) emission and the weak I₁^N emission line. In order to enhance the activation of nitrogen in ZnSe epitaxial layer, sample was annealed at the 823 K in nitrogen (N₂) and hydrogen (H₂) atmosphere. Only the annealing in nitrogen atmosphere increased I₁^N emission intensity indicate the activation of nitrogen acceptor. And net acceptor concentration was estimated to be 3 × 10¹⁷cm⁻³ by C–V measurements. This activation mechanism is interpreted as hydrogen is released from N–H bonds during annealing in nitrogen atmosphere.     

<Superscript>2</Superscript>H and <Superscript>13</Superscript>C NMR investigation of deuterofullerites C<Subscript>60</Subscript>D<Subscript>x</Subscript>

Deuterofullerites C₆₀D_x have been studied by ²H and ¹³C NMR. These fullerites have two types of carbon–deuterium bonds: C–D terminal bonds, characterized by the quadrupole coupling constant (QCC) of 171 kHz, and –C ··· D ··· C– bridging bonds with a QCC of 56 kHz. The latter is responsible for the rigid lattice found in these fullerites, which is untypical of fullerenes. PACS 81.05.Tp; 82.56.Fk; 61.48.+c; 61.18.Fs; 61.10.Nz     

Catalytic effect of 3d transition metals on hydrogen storage properties in mechanically milled graphite

In this paper, we examined the catalytic effect of 3d transition metals on hydrogen storage properties in nanostructural graphite prepared by ball milling under hydrogen atmosphere. The Fe-doped nanostructured graphite shows the most marked hydrogen storage properties among the Fe-, Co-, Ni- and Cu-catalyzed graphite systems. The absorbed hydrogen concentration reaches up to ∼4 wt% by mechanically milling for 32 h (∼7 wt% for 80 h), and two peaks of hydrogen (mass number=2) around 730 and 1050 K were observed in the thermal desorption mass spectra (TDS). The starting temperature for hydrogen desorption was ∼600 K. On the other hand, the Co-doped graphite indicates that absorbed hydrogen concentrations reaches up to ∼2 wt% by mechanically milling for 32 h. The TDS spectrum showed only a broad peak around 1100 K, but the starting point for hydrogen desorption lowered down to ∼500 K. The Ni- and Cu-doped graphites did not show any significant improvement for hydrogen storage. These results suggest that the catalytic effect on hydrogen storage properties strongly depends on the affinity of graphite and doped metals.     

One- and two-dimensional C–H/N–H dipolar correlation experiments under fast magic-angle spinning for determining the peptide dihedral angle φ

A recently proposed ¹³C–¹H recoupling sequence operative under fast magic-angle spinning (MAS) [K. Takegoshi, T. Terao, Solid State Nucl. Magn. Reson. 13 (1999) 203–212.] is applied to observe ¹³C–¹H and ¹⁵N–¹H dipolar powder patterns in the ¹H–¹⁵N–¹³C–¹H system of a peptide bond. Both patterns are correlated by ¹⁵N-to-¹³C cross polarization to observe one- or two-dimensional (1D or 2D) correlation spectra, which can be simulated by using a simple analytical expression to determine the H–N–C–H dihedral angle. The 1D and 2D experiments were applied to N-acetyl[1,2-¹³C,¹⁵N] -valine, and the peptide φ angle was determined with high precision by the 2D experiment to be ±155.0°±1.2°. The positive one is in good agreement with the X-ray value of 154°±5°. The 1D experiment provided the value of φ=±156.0°±0.8°.     

A multinuclear magnetic resonance study of intramolecular hydrogen bonding in some Schiff and Schiff-Mannich bases in solution and in the solid state

Two Schiff bases; N, N′-bis(5-bromosalicylidene)-1,2-diaminoethane, BS, and 7-[(1-{5-bromo-2-hydroxyphenyl} methylidene)amino]-4-methylcoumarin, Sc, and two appropriate Schiff–Mannich bases, N, N′-bis{5-bromo-3-[(diethylamino)methyl]salicylidene}-1,2-diaminoethane, BSM, and 7-[(1-{5-bromo-3-[(diethylamino)methyl]-2-hydroxyphenyl} methylidene)amino]-4-methylcoumarin, SMc, capable of intramolecular hydrogen bonding have been investigated by multinuclear magnetic resonance methods in both solid and liquid phases. In all of the compounds under investigation tautomeric equilibrium involving an intramolecular hydrogen bond has been found. The Schiff–Mannich bases, which can form two different kinds of H bonds at room temperature, form relatively weak H bonds with the imino nitrogen atoms. At low temperatures the tautomeric proton exchange becomes slow on the NMR time scale and both hydrogen-bonded forms can be observed by ¹H, ¹³C, and ¹⁵N NMR methods. In the solid state the tautomeric process is frozen and only one H-bonded form is present. On the basis of 13C and ¹⁵N CPMAS NMR spectra this is identified as the form with hydrogen bonds involving the imino groups. This conclusion is in good agreement with previous results obtained by X-ray diffraction methods.

The investigated Schiff bases (BS and Sc) form relatively weak H bonds. The proton position in the hydrogen bridge, estimated from ¹⁵N and ¹³C chemical shifts, is very similar in both the solution and solid phases. In chloroform solution the observed tautomeric equilibria are almost insensitive to a temperature change within the range 223 to 303 K.     

Mössbauer effect study of antiferromagnetic Fe–Mn–Si alloys

Antiferromagnetic Fe–30Mn–Si alloys containing 2.0–8.7 at.% Si are known to exhibit several attractive physical properties at Néel temperatures which render them candidate materials for functional alloys applications. The Néel transitions and anomalous transport phenomena have been studied extensively in a wide temperature range. In the present work, the hyperfine interactions are studied by Mössbauer spectroscopy measured at temperatures 95–623 K. It is found that the Mössbauer spectra are singlets at temperatures above the Néel temperature and doublets below the Néel temperature. The alloys have a small hyperfine field around the Fe nuclei below the Néel temperature and the hyperfine field increases linearly with increasing silicon concentration. This can be explained by the presence of a localised net magnetic moment on the Fe nuclei which is induced by the silicon atoms. A decrease in isomer shift with increasing silicon concentration is observed and this can be accounted for by the change in the occupation of the Fe 3d shell. There is a small quadrupole splitting, it increases with increasing silicon concentration, and is consistent with the lattice shrinking and magnetostriction.     

High-Temperature Mössbauer Spectroscopy of Mechanically Milled NiFe2O4

Oxide spinels, in particular those containing iron, often exhibit technically important electrical- and magnetic-properties. We report here on X-ray powder diffraction and Mössbauer studies of nanostructured NiFe₂O₄ particles prepared by high-energy ball milling from bulk NiFe₂O₄, which is an inverse spinel. The Mössbauer spectra were recorded in situ at different temperatures in the range of 300–850 K. The Mössbauer spectra of the milled samples show a broad distribution of magnetic hyperfine fields together with a paramagnetic state at room temperature. Initially, at 700 K the spectrum is mainly paramagnetic, but during the process of annealing, magnetic sextets emerge. The treatment results in a significant change in the B/A area ratio of the ferrite. The Neél temperature of the samples is estimated from the B(T) relation to be in the range of 800–850 K.     

Storage of hydrogen on single-walled carbon nanotubes and other carbon structures

The sorption of hydrogen on carbon structures and nanostructures offers a way to reduce the storage pressure of hydrogen with respect to compression storage while achieving interesting gravimetric storage densities. The most readily available carbon structures, activated carbons, can achieve reproducible, high gravimetric storage densities under cryogenic operating conditions: 5–6% at 35 bar and 77 K, in excess of the normal density that would be present in the pore volume under compression at the same temperature and pressure. We discuss and compare the adsorption of hydrogen on high specific surface activated carbons, nanofibres and nanotubes from experimental and theoretical considerations. In particular, we present gravimetric and volumetric hydrogen sorption measurements on single-walled carbon nanotubes (SWNTs) at (1 bar, 77 K) and (1 bar, 295 K) within the context of our ongoing work on the storage of hydrogen on activated carbon and carbon nanostructures. BET surface area and XRD characterization results on SWNTs are also presented. The experiments were performed on as received, chemically treated and metal-incorporated SWNT samples. Hydrogen sorption capacities measured on treated samples ranged from 0 to about 1 wt.% at 1 bar and 295 K and reached about 4 wt.% at 1 bar and 77 K. Our results show that under certain conditions, SWNTs have better hydrogen uptake performance than large surface area activated carbons. PACS 81.07.de; 81.05.Uw; 68.43.h     

Hydrogen adsorption and desorption in carbon nanotube systems and its mechanisms

The hydrogen physisorption properties in single-walled carbon nanotube (SWNT) based materials were characterized. The SWNTs were highly purified and three useful pores for hydrogen physisorption were activated. Hydrogen was physisorbed in intra-tube pores at room temperature and the capacity was estimated to be about 0.3–0.4 wt.% at room temperature. The adsorption capacity can be explained by the Langmuir model. The intra-tube pores have large adsorption potential and this induces hydrogen physisorption at comparatively higher temperatures. This fact indicates the importance of fabricating sub-nanometer ordered pores for this phenomena. PACS 51.30.+i; 51.90.+r; 81.05.Tp; 81.07.De     

Competition of N-passivation and Te-passivation in hydrogenation of Te-doped (Ga,In)(N,As)

(Ga,In)(N,As) lattice matched to GaAs with a band gap of 1 eV is employed as active material in high-efficiency III–V solar cells. Te-doped Ga_0.934In_0.066N_0.023As_0.977 layers were grown by metal-organic vapor-phase epitaxy on (1 0 0) GaAs. The samples were highly doped n-type with carrier concentrations ranging from about 10¹⁷–10¹⁹ cm⁻³. Pieces of the samples were hydrogenated with H-doses of 10¹⁸ ion/cm². The optical and electrical properties of the samples before and after hydrogenation were studied by low-temperature photoluminescence and magnetotransport. In undoped samples hydrogen is known to form N–H complexes which strongly reduce the local perturbation of the lattice due to nitrogen and thus reverse the N-induced global changes of the band structure. Combined analysis of photoluminescence and transport measurements on Te-doped samples, however, indicates a competition between N–H formation and passivation of the Te donor favoring the latter. Hardly any band structure changes due to hydrogenation are observed in these Te-doped samples, instead a strong reduction of the free-carrier concentration is observed after hydrogenation.     

Visible photoluminescence of co-sputtered Ge–Si duplex nanocrystals

The photoluminescence (PL) characteristics of co-sputtered Ge–Si duplex nanocrystal films were examined under excitation by a 325-nm HeCd laser, combined with Raman and Fourier-transform infrared reflection spectra analysis. A broad visible PL spectrum from the as-deposited Ge–Si nanocrystal films was observed in the wavelength range 350–700 nm. Basically, the PL spectrum can be considered to consist of two distinct parts originating from different emission mechanisms: (i) the spectrum in the range 350–520 nm, consisting of characteristic double peaks at 410 and 440 nm with PL intensities decreasing after vacuum annealing, probably due to vacancy defects in Si nanocrystals; and (ii) the spectrum in the range 520–700 nm, consisting of a characteristic peak at 550 nm with a PL intensity not affected by vacuum annealing, probably due to Ge-related interfacial defects. No size dependence of PL peak energy expected from quantum confinement effects was observed in the wavelength range investigated. However, with an increase of crystal size, the PL peak intensity in the blue zone decreased. The PL intensity is found to be strongly affected by silicon concentration. A film heated in air has a different PL mechanism from the as-deposited and vacuum-annealed films. PACS 78.67.Bf; 81.05.Cy; 81.15.Cd     

Mössbauer characterization of biotites from zoned pegmatites

We have measured total cross sections for 5–302 eV positrons and 31–302 eV electrons scattered by atomic hydrogen using a beam-transmission technique. Atomic hydrogen obtained from a radio frequency (rf) discharge source flows into an aluminium scattering cell maintained at about 150 K to minimize recombination. Absolute total cross sections are obtained by making relative measurements for positrons and electrons scattering from H₂ and a known mixture of H and H₂, and then normalizing the measurements for positron-H₂ scattering to prior absolute measurements. Our total cross section measurements for positrons and electrons scattering from H are found to be merged to within 5% for energies from 31 to 302 eV.     

Review of hydrogen storage in inorganic fullerene-like nanotubes

Following the discovery of carbon nanotubes, inorganic fullerene-like nanotubes such as WS₂–MoS₂, NbS₂, TiS₂, and BN were reported. Inorganic (non-carbon) nanotubes constitute an important class of nanomaterials with interesting properties and potential applications. As known, efficient hydrogen storage is one key problem in the development of a hydrogen energy system. Hydrogen storage using carbon nanostructures is scientifically interesting and challenging. It thus would be worthwhile to look into hydrogen storage in inorganic nanotubes because the van der Waals gaps between the nanotube layers are potential candidates for hydrogen uptake. Furthermore, the inorganic nanotubes combine two elements, which is different from the pure carbon nanotubes. These may show a novel hydrogen adsorption–desorption mechanism. The present review provides a brief study of hydrogen adsorption on MoS₂, TiS₂, and BN nanotubes. PACS 81.07.De; 81.07.-b; 81.05.Tp; 68.43.-h     

Effect of attrition milling on dispersion of onion like carbon in aqueous medium

Nanodiamond powders, synthesized by the detonation of explosives, can be transformed into onion like carbon (OLC) by means of thermal treatment in inert environments. OLC aggregates could not be reduced to nanometer sizes by conventional milling. The effect of milling with micron sized ceramic beads in water with polyacrylic acid on the dispersion of onion like carbon was investigated. The zeta potential of the OLC slurry with added surfactant was measured, in order to examine the electrostatic repulsion as a means of dispersing the OLC. The size of the OLC particles in water was measured using a particle size analyzer. Fourier transform infra-red spectroscopy, Raman spectroscopy, X-ray diffraction, and high-resolution transmission electron microscopy were used to observe the differences between the milled and non-milled OLC. The particle size of the OLC decreased steadily with increasing surfactant concentration in the water and milling time. By milling with a PAA concentration over 8.0×10^-4 m/L, the size of the OLC particles decreased to less than 100 nm. The effect of attritional milling with micron sized beads and the addition of surfactant on the dispersion of OLC was confirmed. It was observed that the defects on the dispersed OLC increased with increasing milling time. PACS 81.07.-b; 81.05.Tp; 81.05Uw; 83.80.Hj     

The changes in the electronic structure of B2 FeAl alloy with a Fe antisite and absorbed hydrogen

The electronic structure and bonding in a B2 FeAl alloy with and without hydrogen interaction with a Fe antisite were computed using a density functional theoretical method. The hydrogen absorption turns out to be a favorable process. The hydrogen was found close to an octahedral site where one of its Al capped is replaced by a Fe antisite. The Fe–H distance is of 1.45 Å same as the Al–H distance.The density of states (DOS) curves show several peaks below the d metal band which is made up mostly of hydrogen based states (>50% H_1s) while the metal contribution in this region includes mainly s and p orbitals.An electron transfer of nearby 0.21e⁻ comes from the metal to the H. The overlap population values reveal metal–metal bond breaking, the intermetallic bond being the most affected. The H bond mainly with the Al atom and the reported Fe–H overlap population is much lower than that corresponding to FePd alloys and BCC Fe. The changes in the overlap population show the Fe–Al bond is weakened nearly 41.5% after H absorption, while the Fe–Fe bond is only weakened 34.5%. H also develops a stronger bond with the Al atoms. The main bond is developed with Al being twice stronger than Fe–H.     

Adsorption of D(H) atoms on Ar ion bombarded (0 0 0 1) graphite surfaces

Adsorption of thermal (2000 K) D (H) atoms on HOPG surfaces prior to and after bombardment with 500 eV Ar ions was studied with thermal desorption and vibrational spectroscopies. Ion bombardment of HOPG generates vacancy (VD, displaced surface C atoms) and interstitial (ID, Ar captured between 1st and 2nd C plane) defects. These defects remove the ability of the surface to adsorb D like on virgin HOPG surfaces and to form C_gr–D bonds. After a dose of 0.1 Ar per C surface atom, D adsorption is markedly suppressed. Annealing of bombarded surfaces at 1350 K, connected with desorption of trapped Ar and removal of ID, recovers a large fraction of the adsorption capacity for D. Therefore, the long range stress in the surface plane introduced by ID must be responsible for a significant fraction of D adsorption blocking. It is suggested that ID prevent reconstruction of the C surface which is required for the formation of C_gr–D bonds. For ion doses above 0.5 Ar/C, adsorption of D on the surface is negligible. After annealing at 1350 K, D can be adsorbed in quantities comparable to the virgin HOPG surface, however forming C–D bonds which are similar to those observed in hydrogenated amorphous carbon instead of those which are normally formed on HOPG. Instationary etching via release of deuterocarbon species occurs primarily in the C₁ and C₂ channels. It is only observed at bombarded HOPG prior to annealing and probably due to the presence of isolated C₁ and C₂ species on the surface generated upon VD formation.     

First principle study of a bimolecular thin film on Ag(1 1 1) surface

The formation of melamine–PTCDI bimolecular networks deposited on Ag(1 1 1) is studied by means of first principle calculations. Emphasis is placed on the interplay of the inter-molecular hydrogen bonds and the molecule–substrate contacts. Our simulations show rather strong distortions of the adsorbed molecules near the contact points due to the influence the hydrogen bonds. Despite this, the charge transfer from the substrate to a PTCDI molecule remains almost the same (0.9 e⁻) as obtained for an isolated PTCDI molecule. A detailed analysis of the topological features of the electronic density reveals that the charge transfer modifies the two types of hydrogen bonds in opposite ways, weakening the central bond and strengthening the two lateral ones, while roughly keeping a constant binding energy. Altogether, the influence of the substrate on the molecular network is proved to be weak.     

Large-scale fast production of amorphous Si-Al-O nanowires under ambient conditions

A novel approach to the large-scale and fast production of free-standing nanowires and microwires under ambient conditions is reported. The method is based on the interaction of a high power laser beam with a commercial ceramic substrate under a high-pressure gas jet under ambient conditions. Large quantities of amorphous Si-Al oxide nanowires were produced and characterized. An explanation for the growth of the nanowires based in the vapor–liquid–solid (VLS) mechanism is proposed . PACS 81.05.Je; 81.07.b