Structure and kinetic studies of U(VI)-benzamidoxime complex in non-aqueous solutions by H- and C-NMR

The structural and kinetic studies of U(VI) complex with benzamidoxime(Hba) as ligand in CD₃COCD₃ have been studied by means of ¹H and ¹³C NMR. The Hba molecule was found to coordinate to UO₂²⁺ in the form of anionic benzamidoximate (ba), and the number of ba coordinated to UO₂²⁺ was determined to be 3 by analyzing the chemical shift of ¹³C NMR signal for Hba in the presence of UO₂²⁺. The exchange rate constants(k_ex) of ba in [UO₂(ba)₃] were determined by the NMR line-broadening method. The kinetic parameters were obtained as follows: k_ex(25°C) = 3.1 × 10³s⁻¹, ΔH^≠ = 35.8 ± 3.5 KJ mol⁻¹, and ΔS^≠ = −65 ± 13.7 J K⁻¹ mol⁻¹. The UV-visible absorption spectra of solutions containing UO₂²⁺ and Hba were also measured. The molar extinction coefficient of the complex was found to be extremely large compared with those of UO₂(L)₅²⁺ (L = unidentate oxygen donor ligands) complexes. This is due to the strong electron withdrawing of UO₂²⁺ from Hba and suggests that an interaction between UO₂²⁺ and Hba is very strong. Such a high affinity of monomeric amidoxime to UO₂²⁺ reasonably explains the high adsorptibility of amidoxime resin to U(VI) species, and is considered to result in the high recovery of U(VI) species from sea water using amidoxime resin.     

Structural evaluation of thermal stratification for PWR surge line

Recent observations at operating plants and subsequent US NRC requirements have identified flow stratification in surge lines as a phenomenon that must be considered in the design basis of surge lines. To address these concerns, the stratified loading conditions were included in the design of YGN 3 and 4 surge line as a design basis transient and pipe temperature and displacement measurement were taken during YGN 3 pre-core hot functional testing to determine the degree of surge line flow stratification. The measured displacements and temperatures were extensively reviewed and evaluated in detail: (1) to verify the validity of the thermal hydraulic model used to predict the pipe top-to-bottom temperature differentials; (2) to analytically correlate measured surge line temperatures and displacements; and (3) to confirm the validity of the stratified flow analysis procedure. This paper shows that the stratified flow phenomenon is generic and therefore generic loadings can be developed and evaluated for the surge line analyses.     

Bioleaching of trace elements and rare earth elements from coal fly ash

International Journal of Coal Science & Technology - Coal fly ash originated from coal combustion has high concentrations of metals. If suitable leaching techniques are identified, then coal...     

Sn self-doped α-Fe2O3 nanobranch arrays supported on a transparent,conductive SnO2 trunk to improve photoelectrochemical water oxidation

We produced hierarchically branched Fe₂O₃ nanorods on a Sb:SnO₂ transparent conducting oxide (TCO) nanobelt structure as photoanodes for photoelectrochemical water splitting. Single-crystalline SnO₂ nanobelts (NBs) surrounded by Fe₂O₃ nanorods (NRs) were synthesized by thermal evaporation, then underwent chemical bath deposition and annealing. When Fe₂O₃ was crystallized by annealing, Sn was diffused from SnO₂ NBs and incorporated to Fe₂O₃ NRs, which was confirmed through Energy dispersive spectroscopy. Unlike previous high temperature sintering (∼800 °C), Sn doped hematite NRs were obtained at a low temperature (∼650 °C). This occurred since SnO₂ NBs directly connected to Fe₂O₃ NRs are an abundant source of Sn dopant. The 3D hematite NRs on SnO₂ NBs annealed at 650 °C produce a photocurrent density of 0.88 mA/cm² at 1.23 V vs. RHE, which is 3 times higher than that of hematite NRs on a fluorine doped tin oxide (FTO) glass substrate annealed at the same temperature. The enhanced photocurrent is attributed to the improved electrical conductivity of Fe₂O₃ NRs by Sn doping, the efficient electron transport pathway by TCO nanowire and the increased surface area by hierarchically branched structure.     

Synthesis and nonlinear optical properties of PMMA copolymers having novel benzoxazole chromophores attached with various electron-withdrawing groups

For improvements of thermal stability and nonlinear optical (NLO) activity of chromophores, we newly synthesized a series of NLO chromophores incorporating aromatic benzoxazole unit as a π-conjugated bridge with various electron-withdrawing groups, such as nitrophenyl, nitrothiophene, nitrofuran, dicyanovinylphenyl, and nitrophenylethenyl group. Polymethylmethacrylate copolymers (PMBz) containing these benzoxazole chromophores were synthesized and their properties were investigated by thermogravimetry and ultraviolet-visible spectroscopy. The PMBz copolymers exhibited better thermal and ultraviolet stabilities than the corresponding copolymer with general stilbene chromophores (PMSt). Moreover, temporal stability of nonlinear optical coefficient (d₃₃) of PMBz copolymer increased in comparison with that of PMSt. The copolymer with benzoxazole–nitrothiophene chromophores had the largest d₃₃ value of 153 pm/V (at 1.064 mm) and nonresonant d₃₃ calculated by the two-level model was 21.3 pm/V.     

Identification of Novel Pepper Genes Involved in Bax- or INF1-Mediated Cell Death Responses by High-Throughput Virus-Induced Gene Silencing

Hot pepper is one of the economically important crops in Asia. A large number of gene sequences, including expressed sequence tag (EST) and genomic sequences are publicly available. However, it is still a daunting task to determine gene function due to difficulties in genetic modification of a pepper plants. Here, we show the application of the virus-induced gene silencing (VIGS) repression for the study of 459 pepper ESTs selected as non-host pathogen-induced cell death responsive genes from pepper microarray experiments in Nicotiana benthamiana. Developmental abnormalities in N. benthamiana plants are observed in the 32 (7%) pepper ESTs-silenced plants. Aberrant morphological phenotypes largely comprised of three groups: stunted, abnormal leaf, and dead. In addition, by employing the combination of VIGS and Agrobacterium-mediated transient assays, we identified novel pepper ESTs that involved in Bax or INF1-mediated cell death responses. Silencing of seven pepper ESTs homologs suppressed Bax or INF1-induced cell death, five of which suppressed both cell death responses in N. benthamiana. The genes represented by these five ESTs encode putative proteins with functions in endoplasmic reticulum (ER) stress and lipid signaling. The genes represented by the other two pepper ESTs showing only Bax-mediated cell death inhibition encode a CCCH-type zinc finger protein containing an ankyrin-repeat domain and a probable calcium-binding protein, CML30-like. Taken together, we effectively isolated novel pepper clones that are involved in hypersensitive response (HR)-like cell death using VIGS, and identified silenced clones that have different responses to Bax and INF1 exposure, indicating separate signaling pathways for Bax- and INF1-mediated cell death.