Tunable and reversible surface wettability transition of vertically aligned ZnO nanorod arrays

Vertically aligned zinc oxide (ZnO) nanorods (NRs) with different surface morphology were grown by metal organic chemical vapor deposition (MOCVD) on sapphire substrate. To study the effect of surface morphology on wettability, the contact angle (CA) of water was measured. It was demonstrated that the CA of the deposited ZnO NRs varied between 104° and 135° depending upon the surface morphology. The ZnO NRs became super-hydrophilic after ultraviolet (UV) illumination. However, the NR arrays were reconverted to their previous hydrophobic state after low temperature annealing (50 °C) in open atmosphere. Structural effect and preferential adsorption of water molecules on the defective sites of UV illuminated surface was used to explain the transition mechanism. Under the alternations of heat treatment and UV illumination, a reversible transition between hydrophobicity and super-hydrophilicity were observed.     

Study on the interaction of tropisetron hydrochloride and l-tryptophan by spectrofluorimetry and its analytical application

A new method to determine tropisetron hydrochloride with l-tryptophan in the medium with pH=9.0 was studied, which is based on the fluorescence quenching effect of tropisetron hydrochloride on l-tryptophan. The fluorescence quenching mechanism and various factors influencing fluorescence quenching were discussed. Under the optimum conditions, the linear range and detection limit were 0.03-12.0 and 0.01 μg/mL (correlation coefficient r=0.9970), respectively. The calibration curve equation was ΔF=6.17+12.56 C (μg/mL). RSD was 3.4% (c=4.0 μg/mL, n=5); the detection limit estimated (S/N=3) was 0.01 μg/mL. The proposed method had been successfully applied to determine tropisetron hydrochloride in real samples and the obtained results were in good agreement with the results of the official method.     

Both experimental and theoretical investigations of solid-state 17O NMR for L-valine and L-isoleucine

We have presented an experimental investigation of the carboxyl oxygen NMR parameters for four distinct sites in l-valine and l-isoleucine. The carboxyl (17)O quadrupolar coupling constant, C(Q), and isotropic chemical shift, delta(iso), for these compounds are obtained by analyzing two-dimensional (17)O multiple-quantum magic-angle spinning (MQMAS) and/or 1D MAS spectra. The values of C(Q) and delta(iso) found to be in the range of 7.00-7.85 MHz, and 264-314 ppm, respectively. Extensive quantum chemical calculations at the density functional levels have been performed for a full cluster of l-valine molecules and a few theoretical models. The calculated results indicated that there was a correlation between the (17)O NMR parameters and C-O bond lengths, which was helpful for the spectral assignment. They also demonstrated that the torsion angle of l-valine plays an important role in determining the magnitudes of (17)O NMR parameters.     

Coupled radiation and natural convection: Different approaches of the slw model for a non-gray gas mixture

The coupling between non-gray radiation heat transfer and convection-conduction heat transfer is studied. The spectral line weighted sum of gray gases model (slw) is used to account for non-gray radiation properties. The aim of this work is to analyze the influence of the different approaches used when calculating the parameters of the slw model. Such strategies include the use of optimized model coefficients to reduce the number of operations, and the interpolation of the distribution function instead of the use of mathematical correlations. Non-gray calculations are also compared to gray solutions using the Planck mean absorption coefficient, which can be also calculated with the slw model. The radiative transfer equation (rte) is solved by means of the discrete ordinates method (dom). A natural convection driven cavity is chosen to couple radiation and conduction-convection energy transfer. Several cases, with a significant variation of the ratio between radiation to convection heat transfer, as well as the ratio between radiation to conduction heat transfer, are discussed.     

Molecular dynamics of poly(L-lactide) biopolymer studied by wide-line solid-state 1H and 2H NMR spectroscopy

The molecular dynamics of poly(L-lactide) (PLLA) biopolymer was characterized through analyses of 1H and 2H NMR line-shapes and spin-lattice relaxation times at different temperatures. At low temperatures (e.g. 90 K), the methyl group rotation is dominant leading to a significant reduction in the proton second moment. Fast methyl group reorientation occurs at ca. 130 K. In additional to the fast methyl group rotation, hydroxyl groups start to reorient as the temperature increases further, eventually leading to the breakdown of the segments of the biopolymer chains above its glass transition temperature Tg of 323 K. The analyses of the 2H NMR line-shapes indicate that both the methyl and hydroxyl reorientations can be described by the so-called cone model, in which the former has three equilibrium positions with theta(C-D) = 70.5 degrees and phi = 120 degrees while the latter one exhibits two equilibrium positions with theta(O-D) = 78 degrees and phi = 180 degrees .     

EPR and optical absorption studies of VO doped l-alanine (C3H7NO2) single crystals

VO²⁺ doped l-alanine (C₃H₇NO₂) single crystals and powders are examined by electron paramagnetic resonance (EPR) and optical absorption spectroscopy. Three magnetically different sites are resolved from angular variations of l-alanine single crystal EPR spectra. In some specific orientations each VO²⁺ line splits into three superhyperfine lines with intensities of 1:2:1 and maximum splitting value of 2.23 mT. The local symmetries of VO²⁺ complex sites are nearly axial. The optical absorption spectra show three bands. Spin Hamiltonian parameters are measured and molecular orbital coefficients are calculated by correlating EPR and optical absorption data for the central vanadyl ion.     

Monoatomic and cluster beam effect on ToF-SIMS spectra of self-assembled monolayers on gold

Self-assembled monolayers represent well-defined systems that is a good model surface to study the effect of primary ion beams used in secondary ion mass spectrometry. The effect of polyatomic primary beams on both aliphatic and aromatic self-assembled monolayers has been studied. In particular, we analysed the variation of the relative secondary ion yield of both substrate metal-cluster (Au_n⁻) in comparison with the molecular ions (M⁻) and clusters (M_xAu_y⁻) by using Bi⁺, Bi₃⁺, Bi₅⁺ beams. Moreover, the differences in the secondary ion generation efficiency are discussed. The main effect of the cluster beams is related to an increased formation of low-mass fragments and to the enhancement of the substrate related gold-clusters. The results show that, at variance of many other cases, the static SIMS of self-assembled monolayers does not benefit of the use of polyatomic primary ions.     

Sphere-like CuGaS2 nanoparticles synthesized by a simple biomolecule-assisted solvothermal route

Sphere-like CuGaS₂ nanoparticles were successfully synthesized by a simple biomolecule-assisted solvothermal route using a mixed solution compose of ethylenediamine and distilled water (1:1, v/v), in which l-cystine was used as the sulfide source and complexing molecule. Phase analysis was carried out by X-ray diffraction (XRD) and the results confirmed the as-prepared CuGaS₂ as a single-phase tetragonal structure. Field-emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) showed that the morphologies of CuGaS₂ were sphere-like nanoparticles in shape, and the average diameters was about 600 nm. X-ray photoelectron spectrum (XPS) was used to analyze the composition of CuGaS₂ and the ratio of Cu/Ga/S is 1:0.97:1.98. Raman spectrum of the obtained CuGaS₂ exhibit a high-intensity peak of the A1 mode at 305 cm⁻¹. The influence of reaction temperature, time and solvent was initially investigated. The possible formation mechanism was also discussed.     

Influence of microscopic parameters of chiral molecules on the first-order hyperpolarizability

One-electron model is chosen to analyze the second harmonic response of an organic inclusion complex - urea l-malic acid (ULMA). ULMA has broad transparent region and large nonlinear optical coefficient and damage threshold. Based on the ULMA crystal structure, the model parameters are determined using the unit cell parameters. Numerical results show that the contribution of electric-field to the first-order hyperpolarizability β is larger than that of magnetic-field but the contribution of magnetic-field is important and cannot be neglected. Modeling parameters pitch ξ and radius ρ are found to be involved in the position of peak of β. The peak position of β undergoes red-shift with increasing of ρ and blue-shift with the increasing of ξ. It suggests that the expected nonlinear optical response of a chiral molecule can be obtained through molecular modification to adjust ξ and ρ. Therefore, a chiral molecule may be a favorable host to afford organic inclusion complex with superb nonlinear optical properties.     

Thermal Performance of a Blend System Based on Poly(l-lactic acid) and an Aliphatic Multiamide Derivative of 1H-Benzotriazole

An aliphatic multiamide derivative derived from 1H-benzotriazole, N, N'-bis(1H-benzotriazole) sebacic acid acethydrazide (SA), was synthesized to evaluate its effect on the thermal performance, including non-isothermal crystallization and melting behavior as well as thermal stability, of poly(l-lactic acid) (PLLA). The comparative study, by means of DSC measurements, showed that the incorporation of SA caused a non-isothermal crystallization peak to appear and become sharp, showing its advanced crystallization promoting effect for PLLA. The non-isothermal crystallization results further indicated that 2 wt% SA was the saturation concentration for PLLA crystallization, and that the cooling rate was also a crucial determinant for PLLA crystallization. Considering the melting behavior, the difference between the virgin PLLA and PLLA/2%SA further confirmed the crystallization accelerative effect of SA for PLLA, with the increase of crystallization temperature in the temperature zone from 90 to 130°C being beneficial to the crystallization of PLLA during processing. Compared to the virgin PLLA, the trends of thermal decomposition curves were similar, suggesting that the introduction of SA of 0.5–3 wt% did not significantly change the thermal decomposition behavior of PLLA.     

Propagation of cylindrical shock waves in a rotating atmosphere under the action of monochromatic radiation

Summary  A model of cylindrical shock waves is discussed in a non-uniform rotating atmosphere under the action of monochromatic radiation. We have assumed that the radiation flux moves through a rotating gas with constant intensity and the energy is absorbed only behind the shock wave which moves in opposite direction to the radiation flux.     

Interaction of water-soluble CdTe quantum dots with octacarboxy metallophthalocyanines: A photophysical and photochemical study

Water-soluble CdTe quantum dots capped with l-cysteine (QD-CYS) were found to improve the photophysical and photochemical properties of octacarboxy metallophthalocyanine (MOCPc, M=Zn(II), Al(III)(OH), Ge(IV)(OH)₂ and Si(IV)(OH)₂) complexes. Increased diffusional interactions between the molecules and the ground-state molecular oxygen were established resulting from the increase in the triplet-state quantum yield and lifetimes of the MOCPcs in the presence of QD-CYS. Energy transfer occurred from QD-CYS to the MOCPcs upon excitation of QD-CYS. It was found that an efficient energy transfer process, which is not directly related to the amount of spectral overlap between the donor (QD-CYS) and the acceptor (MOCPc) can occur. Singlet oxygen via fluorescence resonance energy transfer (FRET) mechanism was produced in the QD-MPc mixture.     

Preparation and purification of l-cysteine capped CdTe quantum dots and its self-recovery of degenerate fluorescence

l-cysteine capped CdTe quantum dots (QDs) were prepared in aqueous solution by a simple and efficient method, showing many advantages such as short synthesis period, the broaden range of starting pH value and the wide fluorescence emission wavelength range. A novel purification process was designed to remove excess Cd²⁺ which has potential cytotoxicity for bio-analysis. Three-dimensional fluorescence charts of pre- and post-purification showed that the purified QDs were of better luminescent performance. The prepared QDs were of cubic crystal structure with an average size of 2-6 nm, which were characterized by XRD and HRTEM. It is confirmed by IR spectra that the l-cysteine ligands were conjugated with CdTe cores via covalent bond. The degenerate fluorescence of QDs can be self-recovered in the presence of l-cysteine without other processing steps.     

Probing the chemical reactivity of free titanium clusters by x-ray absorption spectroscopy

Synchrotron radiation-based experimental techniques are largely employed for the characterization of the reactivity of finite size systems; in particular, x-ray absorption spectroscopy (XAS) is a suitable tool to shed light on the local electronic structure and chemical status of atoms in nano-objects, as it is very sensitive to the local bonding environment of the probed site. In supported clusters intrinsic properties and reactivity are largely distorted and obscured by the changes imposed by the growth procedure and by the influence of the substrate, so the attainability of experiments on free clusters reacting with species in the gas phase is a primary goal in the development of cluster science. In this paper we report a proof of principle of the applicability of gas phase XAS technique to titanium and titanium oxide, hydride and hydrate systems. Experiments are performed by coupling a pulsed microplasma cluster source (PMCS) with a third generation synchrotron light source, and measuring the intensity of the electron yield coming from the interaction of VUV photons with the clusters seeded in a supersonic beam.     

Scattering of a spherical wave from the coupling of two half-planes

Summary  The diffraction of a spherical acoustic wave from the juncture of pressure release (soft) and locally reacting (absorbing) half-planes in a fluid moving at subsonic velocity is examined. This consideration is important because the point sources are regarded as better substitutes for real sources than line sources/plane waves. The integral representation of the field is obtained using integral transforms and the Wiener-Hopf technique. The factorization of the kernel function in the Wiener-Hopf functional equation is accomplished. The analytic solution of the integrals is obtained by employing asymptotic methods and the far field is presented. The effect of the Mach number is shown explicitly on the diffracted field.     

Compressibility of hadrons from operator sum rules

Monopole sum rules for ar ² transition operator are discussed for baryons and mesons. From these, the energy of the compression modes can be directly related to the hadronic compressibility. From the systematics of excited hadrons the compressibility of baryons is found to be in the order of 1.3 GeV, quite close to that of mesons in the light and strange quark sector. Experiments will be very important to study the compression modes in different hadron systems.The author is indepted to the Institute of Nuclear Theory (INT Seattle) for the invitation to the program N ^* Excitations and the Structure of the Nucleon where basic ideas of the paper have been discussed. In particular, discussion with O. Bohigas, B.K. Jennings, and J. Wambach is gratefully acknowledged.     

Remote filament-induced fluorescence spectroscopy from thin clouds of smoke

Remote filament-induced fluorescence spectroscopy is used to probe a cloud of smoke, produced from burning mosquito coils, located at a distance of 25 m from the laser source and LIDAR detector. CN, CH and C₂ molecular fragments were identified in the sample. We demonstrate that temporally gated measurement is an efficient technique to easily suppress spectral contaminations, such as white light and atmospheric N₂ fluorescence.     

Sum-frequency spectroscopy of physisorbed and chemisorbed molecules at liquid and solid surfaces using band-width-limited picosecond pulses

We studied the vibrational Sum-Frequency (SF) spectra of long chain fatty alcohols and amines physisorbed at liquid/air interfaces and of OctadecylTrichlorSilan (OTS) chemisorbed on glass/air interfaces in situ, i. e., in normal laboratory environment. The intense, band-width-limited IR pulses generated by our laser system are tunable from 2600 to 4000 cm^–1 with a constant pulse duration of 3 ps and a band width of 5 cm^–1 (FWHM) over the entire tuning range, thus covering the CH-, NH-, and OH-stretching regions.Using suitable polarization geometries, information on the molecular orientation is obtained from the amplitudes of the symmetric and degenerate methyl-stretching modes. Opposite phase of adjacent vibrational modes can lead to destructive interference in the SF signal, as analyzed theoretically. This interference effect is observed experimentally for the first time, due to the superior spectral resolution and signal-to-noise ratio of our spectra.     

On the role of secondary interactions in the production of bremsstrahlung spectra from a thick target

Bremsstrahlung emission, or radiation loss, is the dominant mechanism of energy dissipation of electrons at relativistic energies greater than a few MeV when it is subjected to acceleration in the field of the nucleus or of the electrons. In this study, the Monte Carlo calculations for bremsstrahlung spectra have been described for the case of a thick tungsten target with incident electron beams from 10 to 50 MeV, where secondary interactions induced by the electrons and photons in the target, such as energy loss, absorption, scattering, and (e ⁺, e ⁻)-pair production effects, were taken into account. The text was submitted by the authors in English.     

Formation of Ring-Banded Spherulites of Poly (L-lactide) in its Miscible Mixture with an Ionic Liquid

Incorporation of an ionic liquid, nonvolatile and thermally stable, promoted formation of ring-banded spherulites in poly (l-lactide) (PLLA) during its sol–gel transition. Their formation is correlated with low viscosity and insignificant chain entanglements in the mixtures induced by the ionic liquid. In addition to a driving force for lamellar twisting that depended on the crystallization temperatures, it is believed that reduced lamellar twisting resistance caused by the ionic liquid plays a vital role in the formation of the ring-banded spherulites of PLLA from the mixtures. This study gives further insights into the structural formation of PLLA during a sol–gel transition, which could open new opportunities to tailor the properties of ion gels based on PLLA.