State-to-state dynamics of elementary chemical reactions using Rydberg H-atom translational spectroscopy

In this review, a few examples of state-to-state dynamics studies of both unimolecular and bimolecular reactions using the H-atom Rydberg tagging TOF technique were presented. From the H2O photodissociation at 157 nm, a direction dissociation example is provided, while photodissociation of H2O at 121.6 has provided an excellent dynamical case of complicated, yet direct dissociation process through conical intersections. The studies of the O(D-1) + H-2 --> OH+H reaction has also been reviewed here. A prototype example of state-to-state dynamics of pure insertion chemical reaction is provided. Effect of the reagent rotational excitation and the isotope effect on the dynamics of this reaction have also been investigated. The detailed mechanism for abstraction channel in this reaction has also been closely studied. The experimental investigations of the simplest chemical reaction, the H-3 system, have also been described here. Through extensive collaborations between theory and experiment, the mechanism for forward scattering product at high collision energies for the H+HD reaction was clarified, which is attributed to a slow down mechanism on the top of a quantized barrier transition state. Oscillations in the product quantum state resolved different cross sections have also been observed in the H+D-2 reaction, and were attributed to the interference of adiabatic transition state pathways from detailed theoretical analysis. The results reviewed here clearly show the significant advances we have made in the studies of the state-to-state molecular reaction dynamics.

Quantum dynamics study of isotope effect for H+CH4 reaction using the SVRT model

The semirigid vibrating rotor target model is applied to study the isotope effect in reaction H + CH4-->H-2 + CH3 using time-dependent wave-packet method. The reaction probabilities for producing H-2 and HD product channels are calculated. The energy dependence of the reaction probabilities shows oscillating structures for both reaction channels. At low temperature or collision energies, the H atom abstraction is favored due to tunnelling effect. In partially deuterated CHxDy (x + y = 4), the breaking of the C-H bond is favored over that of the C-D bond in the entire energy range studied. In H + CHD3 reaction at high energies, the HD product dominates simply due to statistical factor. (C) 2003 American Institute of Physics.

Tunable Photoluminescence and Cathodoluminescence Properties of Eu3+-Doped LaInO3 Nanocrystalline Phosphors

LaInO3:Eu3+ phosphors were prepared by a Pechini sol-gel process. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), diffuse reflectance, photoluminescence, cathodoluminescence spectra, as well as lifetimes were utilized to characterize the synthesized phosphors. XRD results reveal that the sample begins to crystallize at 600 degrees C and pure LaInO3 phase can be obtained at 800 degrees C. The crystallinity increases upon raising the annealing temperature. The FE-SEM images indicate that LaInO3:Eu3+ phosphors are composed of fine and spherical grains around 40-80 nm in size. Under the excitation of UV light and low-voltage electron-beams, LaInO3:Eu3+ phosphors show the characteristic emissions of the Eu3+ (D-5(J)-F-7(J) J,J(')=0,1,2,3 transitions). The luminescence colors can be tuned from yellowish warm white to red by changing the doping concentration of Eu3+ to some extent. The corresponding luminescence mechanisms have been proposed.

Synthesis and characterization of monodisperse spherical core-shell structured SiO2@Y3Al5O12 : Ce3+/Tb3+ phosphors for field emission displays

Nanocrystalline Y3Al5O12: Ce3+/Tb3+ ( average crystalline size 30 nm) phosphor layers were coated on non-aggregated, monodisperse and spherical SiO2 particles by the sol-gel method, resulting in the formation of core-shell structured SiO2@Y3Al5O12:Ce3+/Tb3+ particles. X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, photoluminescence, cathodoluminescence spectra, as well as lifetimes were utilized to characterize the core-shell structured SiO2@Y3Al5O12: Ce3+/Tb3+ phosphor particles. The obtained core-shell structured phosphors consist of well-dispersed submicron spherical particles with a narrow size distribution. The thickness of the Y3Al5O12:Ce3+/Tb3+ shells on the SiO2 cores ( average size about 500 nm, crystalline size about 30 nm) could be easily tailored by varying the number of deposition cycles (100 nm for four deposition cycles). Under the excitation of ultraviolet and low-voltage electron beams (1-3 kV), the core-shell SiO2@Y3Al5O12:Ce3+/ Tb3+ particles show strong yellow-green and green emission corresponding to the 5d-4f emission of Ce3+ and D-5(4)-F-7(J) ( J = 6, 5, 4, 3) emission of Tb3+, respectively.

Electrolummescence from (5)Do -> F-7(J) and D-5(1) -> F-7(J) (J=0-4) transitions with a europium complex as emitter

Electroluminescence (EL) devices with Eu(HTH)(3)phen [HTH: 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)-1,3-hexanedione, phen: I 10-phenanthroline] as an emissive centre were fabricated using vacuum evaporation. In addition to the Eu3+ 5D0 --> F-7(J) (J = 0-4) lines that were visible in the photoluminescence signal, the device also showed strong emission from the D-5(1) --> F-7(J) (J = 0-4) transitions. The enhanced emission from the D-5(1) F-7(J) (J = 0-4) transitions was attributed to the increased excitation intensity in the EL device. The luminescence lifetimes of the 5 D, and 5 Do levels were measured to be 0.6 mus and 866 mus, respectively.

Rapid self-assembly of oligo(o-phenylenediamine) into one-dimensional structures through a facile reprecipitation route

The self-assembly of oligo(o-phenylenediamine) (OPD) into 1-D nanostructures on a macroscopic length scale was found when they were transferred from N-methyl pyrrolidone to deionized water. Field emission scanning electron microscopy and confocal fluorescence microscopy were used to investigate the morphology of the precipitates. Results showed that large amounts of OPD 1-D supertructures could be obtained through the simple reprecipitation route, and the length of the fibers could be tuned from microscale to macroscale by adjusting the ratio of two solvents. X-ray diffraction patterns and UV-vis spectra revealed that pi-pi interactions between OPD molecules that facilitated the formation of 1-D structures became predominant when they were transferred from a good solvent to a bad one. Accordingly, a possible formation mechanism was proposed.

Preparation and luminescence properties of hybrid materials containing europium(III) complexes covalently bonded to a silica matrix

A new kind of luminescent organic-inorganic hybrid material (denoted Hybrid I) consisting of europium 1,10-phenanthroline complexes covalently attached to a silica-based network was prepared by a sol-gel process. 1,10-Phenanthroline grafted to 3-(triethoxysilyl)propyl isocyanate was used as one of the precursors for the preparation of an organic-inorganic hybrid materials. For comparison purposes, the hybrid material (denoted Hybrid II) in which phenanthroline was not grafted onto the silica backbone of the frameworks was also prepared. Elemental analysis; NMR, FT-IR, UV/vis absorption, and luminescence spectroscopies, and luminescence decay analysis were used to characterize the obtained hybrid materials. It is shown that the homogeneity of Hybrid I is superior to that of Hybrid II, and a higher concentration europium can be incorporated into Hybrid I than Hybrid II. Excitation at the ligand absorption wavelength (283 nm) resulted in the strong emission of the Eu3+ D-5(0)-F-7(J) (J = 0-4) transition lines as a result of the efficient energy transfer from the ligands to the EU3+ in Hybrid I. The number of water molecules coordinated to the europium ion was estimated, and the structure of the as-synthesized Hybrid I was predicted on the basis of the experimental results.

Microstructure analysis of nylon 66 by WAXD and SAXS

The analysis of the small angle X-ray scattering (SAXS) data was based upon particle characteristic function, one-dimensional electron-density correlation function and particle distribution function. The microstructure of nylon 66 with different degrees of crystallinity was studied by means of X-ray scattering method. The radius of gyration R-g, the Porod radius R-p, the thickness of crystalline region L-c the thickness of non-crystalline region L-n, the thickness of interphase region d(tr), the long period L, the semiaxises of particles (a, a, b), the distribution of the particle sizes and the scattering invariant were calculated. The results indicate that there was a significant interphase region between the crystalline region and the non-crystalline region. and its content (W-t,W-x) should not be neglected in comparison with that of crystalline region W-c,W-x. The morphology of nylon 66 prepared by isothermal crystallization at a high temperature was mainly a lamellar structure, while the spherical crystals dominated in the quenched sample. The size of the particles in the quenched sample was smaller than that of those in the isothermally crystallized sample. and the distribution of the particle sizes in the isothermally crystallized sample was wider.

A study of dimethylferrocene diffusion and electrode kinetics using microelectrode voltammetry in poly(ethylene glycol) solvent

The heterogeneous electron transfer rate constant (k(s)) of dimethylferrocene (DMFc) was estimated using cyclic voltammetric peak potential separations taken typically in a mixed diffusion geometry regime in a polyelectrolyte, and the diffusion coefficient (D) of DMFc was obtained using a steady-state voltammogram. The heterogeneous electron transfer rate constant and diffusion coefficient are both smaller by about 100-fold in the polymeric solvent than in the monomeric solvent. The results are in agreement with the difference of longitudinal dielectric relaxation time (tau(L)) in the two kinds of solvents, poly(ethylene glycol) (PEG) and CH3CN, indicating that k(s) varies inversely with tau(L); k(s), is proportional to D of DMFc. Both D and k(s) of DMFc in PEG containing different supporting electrolytes and at different temperatures have been estimated. These results show that D and k(s) of DMFc increase with increasing temperature in the polyelectrolyte, whereas they vary only slightly with changing the supporting electrolyte.

Influence of annealing on structure of poly(aryl ether ether ketone ketone) revealed by SAXS

Structural studies of poly(aryl ether ether ketone ketone) (PEEKK) using small-angle X-ray scattering and one-dimensional electron density correlation function methods revealed that its aggregated state structure was significantly influenced by the annealing temperature. The long period L, the average thickness of the lamellae d, the electron density difference between the crystalline and amorphous regions eta(c) - eta(a), and the invariant Q increased with increasing annealing temperature, but it was opposite to the case of the specific inner surfaces O-s. A transition zone existed between the traditional "two phases" with a dimension about 0.5 nm for semicrystalline PEEKK. (C) 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1829-1835, 1998.

The origin of nonlinearities in K[B5O6(OH)(4)]center dot 2H(2)O crystal

In this paper the origin of nonlinearities of the K[B5O6(OH)(4)].2H(2)O(KB5) crystal has been investigated from a comprehensive view-point by using the bond-valence theory of complex crystals. The results of the calculation (d(31) = -1.18 X 10(-10) esu, d(32) = 0.20 X 10(-10) and d(33) = -1.03 X 10(-9) esu) are in good agreement with experimental data. For the first time we pointed out that its nonlinearities come from the H(2)-O(2) bonds and the [B5O6(OH)(4)](-) group, and estimated its larger nonlinear optical (NLO) coefficient d(33).

Charge transport of indigo-carmine doped polypyrrole

Charge transport in polypyrrole doped with indigo-carmine was investigated by the method of electrochemical alternating current impedance. By the nonlinear least square fitting, the equivalent circuit and parameter of each component are obtained. The apparent diffusion coefficients and heterogeneous electron transfer constants are given. It is found that, along with the increasing of film thickness, D-app and k(0) increase also.

The influence of heat treatment on structures of the aggregated state of polyamide-1010

The structural parameters of the aggregated state of polyamide (PA)-1010 annealed at various temperatures were computed by means of the desmearing intensity from Smalt Angle X-ray Scattering (SAXS) measurements and by using the concept of the distance distribution function. The results indicated that the structural parameters of the aggregated state were strongly dependent upon heat treatment conditions and the maximum values of the structural parameters were obtained for the samples annealed at T = 175 degrees C. The particle size Z annealed at different temperature was ranged between 8.1-12.8nm, and the values of the distance distribution function P-max(Z) were obtained when Z = 4.0-6.8 nm. Using one dimension electron density correlation function (1D EDCF) method long period (L) and thickness of the lamellar (d(0)) were estimated and were found to increase with the increase of the degree of crystallinity.

ISOLATION AND CHARACTERIZATION OF CHLORELLA SOROKINIANA GXNN01 (CHLOROPHYTA) WITH THE PROPERTIES OF HETEROTROPHIC AND MICROAEROBIC GROWTH

Heterotrophic and anaerobic microalgae are of significance in both basic research and industrial application. A microalga strain was isolated from a wastewater treatment pond and identified as Chlorella sorokiniana Shihira et W. R. Krauss GXNN01 in terms of morphology, physiology, and phylogeny. The strain grows rapidly in heterotrophic or mixotrophic conditions with addition of various carbon sources, and even in anaerobic conditions. The maximum growth rate reached 0.28 d(-1) when using D,L-malate as the carbon source, and the protein content of the microalgae was 75.32% in cell dry weight. The strain was shown to be capable of (1) utilizing D, L-malate only with light, (2) inhibiting photosynthesis in mixotrophic growth, and (3) growing in anaerobic conditions with regular photosynthesis and producing oxygen internally. This study demonstrates the influence of oxygen (aerobic vs. anaerobic) and metabolic regime (autotrophy, mixotrophy, heterotrophy) on the physiological state of the cell.

Establishment of a micro-particle bombardment transformation system for Dunaliella saliva

In this study, we chronicle the establishment of a novel transformation system for the unicellular marine green alga, Dunaliella salina. We introduced the CaMV35S promoter-GUS construct into D. saliva with a PDS1000/He micro-particle bombardment system. Forty eight h after transformation, via histochemical staining, we observed the transient expression of GUS in D. salina cells which had been bombarded under rupture-disc pressures of 450 psi and 900 psi. We observed no GUS activity in either the negative or the blank controls. Our findings indicated that the micro-particle bombardment method constituted a feasible approach to the genetic transformation of D. salina. We also conducted tests of the cells' sensitivity to seven antibiotics and one herbicide, and our results suggested that 20 mu g/ ml of Basta could inhibit cell growth completely. The bar gene, which encodes for phosphinothricin acetyltransferase and confers herbicide tolerance, was introduced into the cells via the above established method. The results of PCR and PCR-Southern blot analyses indicated that the gene was successfully integrated into the genome of the transformants.