Investigation of Uranium(VI) Extraction Mechanisms from Phosphoric and Sulfuric Media by 31P-NMR

Uranium extraction using DEHCNPB (butyl-1-[N,N-bis(2-ethylhexyl)carbamoyl]nonyl phosphonic acid, a bifunctional cationic extractant) has been studied to better understand mechanism differences depending on the original acidic solution (phosphoric or sulfuric). Solvent extraction batch experiments were carried out and the organic phases were probed using ³¹P-NMR. This technique enabled to demonstrate that phosphoric acid is poorly extracted by DEHCNPB ([H₃PO₄]_org < 2mM), using direct quantification in the organic phase by ³¹P-NMR spectra integration. Moreover, in the presence of uranium in the initial phosphoric acid solution, uranyl extraction by DEHCNPB competes with H₃PO₄ extraction.Average stoichiometries of U(VI)-DEHCNPB complexes in organic phases were also determined using slope analysis on uranium distribution data. Uranium seems to be extracted from a phosphoric medium by two extractant molecules, whereas more than three DEHCNPB on average would be necessary to extract uranium from a sulfuric medium. Thus, uranium is extracted according to different mechanisms depending on the nature of the initial solution.     

Random forests for functional covariates

We propose a form of random forests that is especially suited for functional covariates. The method is based on partitioning the functions' domain in intervals and using the functions' mean values across those intervals as predictors in regression or classification trees. This approach appears to be more intuitive to applied researchers than usual methods for functional data, while also performing very well in terms of prediction accuracy. The intervals are obtained from randomly drawn, exponentially distributed waiting times. We apply our method to data from Raman spectra on boar meat as well as near‐infrared absorption spectra. The predictive performance of the proposed functional random forests is compared with commonly used parametric and nonparametric functional methods and with a nonfunctional random forest using the single measurements of the curve as covariates. Further, we present a functional variable importance measure, yielding information about the relevance of the different parts of the predictor curves. Our variable importance curve is much smoother and hence easier to interpret than the one obtained from nonfunctional random forests.     

Silver(I) complex with 2-amino-4,4α-dihydro-4α,7-dimethyl-3H-phenoxazin-3-one (Phx-1) ligand: crystal structure,vibrational spectra and biological studies

The first metal complex of Phx-1 ligand, bis(2-amino-4,4α-dihydro-4α,7-dimethyl-3H-phenoxazin-3-one)nitratosilver(I), [Ag(Phx-1)₂NO₃], has been obtained and investigated by single crystal X-ray diffraction and vibrational spectroscopy methods. The Ag⁺ is bonded to heterocyclic nitrogen atoms of two organic ligands and one oxygen atom of a nitrate anion. The Phx-1 ligand coordination mode is supported by IR and Raman spectra, interpreted with the help of theoretical DFT studies. The antibacterial activity of the ligand and its Ag(I) complex as well as some reference compounds were screened against Gram-positive and Gram-negative bacteria, applying microdilution procedures. High sensitivity to the studied complex was found for Rhodococcus erythropolis and Bacillus licheniformis strains. Modified Phx-1 ligand preparation procedures are also presented.     

Preparation and characterization of poly(m-xylylene oxamide) and its copolymer

New polyoxamides, poly(m-xylylene oxamide) (PMXD2) and its copolymer with 2-methyl-1,5- pentanediamine (P(MXD2/M52)) with relative viscosity up to 4.6 were synthesized via spray/solid state polymerization. The obtained polyoxamides were characterized by FTIR, NMR, WAXD, DSC and TGA. The T_m of the copolymers decreased with increasing percentage of poly(2-methyl-1,5- pentaneoxamide) (PM52) in the copolymer from 346°C for 100% poly(meta-xylyleneoxamide) (PMXD2) to 277°C for copolymers of PMXD/PM52 (60/40). TGA analysis revealed that the thermal stability of the copolymers compared well with commercial PA6 and XRD studies suggested the copolymers possessed high crystallinity. DMA profile of the PMXD/PM52 (70/30) copolymer showed better mechanical performance with a storage modulus of about 7.2 GPa as compared to 1.8 GPa of PA6 at 25°C.     

Research of Fluorination Process of Rutile Concentrate

The brief review of industrial technologies of titanium-containing concentrates processing has been carried out. Drawbacks of the existing titanium manufacture schemes are shown and the necessity of the essentially new fluoride technologies development has been proved. The reactions proceeding during the fluorination of rutile concentrate with element fluoride are described in the given work. The thermodynamic research of the process has been carried using ASTRA software. Dependence of mass concentration change of titanium tetrafluoride has been investigated in products of reaction on the temperature of the process, and the choice of optimum excess of fluoride has been proved.     

Protein environmental effects on iron‐sulfur clusters: A set of rules for constructing computational models for inner and outer coordination spheres

The structural properties and reactivity of iron‐sulfur proteins are greatly affected by interactions between the prosthetic groups and the surrounding amino acid residues. Thus, quantum chemical investigations of the structure and properties of protein‐bound iron‐sulfur clusters can be severely limited by truncation of computational models. The aim of this study was to identify, a priori, significant interactions that must be included in a quantum chemical model. Using the [2Fe‐2S] accessory cluster of the FeFe‐hydrogenase as a demonstrative example with rich electronic structural features, the electrostatic and covalent effects of the surrounding side chains, charged groups, and backbone moieties were systematically mapped through density functional theoretical calculations. Electron affinities, spin density differences, and delocalization indexes from the quantum theory of atoms in molecules were used to evaluate the importance of each interaction. Case studies for hydrogen bonding and charged side‐chain interactions were used to develop selection rules regarding the significance of a given protein environmental effect. A set of general rules is proposed for constructing quantum chemical models for iron‐sulfur active sites that capture all significant interactions from the protein environment. This methodology was applied to our previously used models in galactose oxidase and the 6Fe‐cluster of FeFe‐hydrogenase. © 2016 Wiley Periodicals, Inc.     

Simulation of Electrical and Thermal Behavior of Poly(propylene) / Carbon Filler Conductive Polymer Composites

PP-carbon CPC show interesting thermo-electrical properties, smooth resistivity increase with temperature up to 150°C and consequently high power dissipation on a wide temperature range. The addition of short carbon fibers to PP already formulated with carbon black increases sharply the electrical conductivity of the CPC but does not have much influence on thermal conductivity as it could have been expected from the favorable aspect ratio of the fibers. The simulations of the thermo-electrical behavior of the CPC under tension put into evidence a temperature gradient at high heat flux due to the low thermal conductivity, which may damage the material itself.     

亲水性聚硅氧烷改性天然乳胶的性能

以亲水性聚硅氧烷KGF-903共混改性天然乳胶,通过拉力试验、老化试验、接触角测量和扫描电子显微镜等研究了聚硅氧烷的添加量对天然乳胶力学性能、抗老化性能、亲水性能和表面形貌的影响。结果表明,KGF-903含量在1.5%时拉伸强度有最佳的改性效果;KGF-903添加量约为3%时断裂伸长率达到最大,老化前后的断裂伸长率比改性前分别提高57%和50%。随着KGF-903含量的增加,改性天然乳胶片的水接触角逐渐减小;扫描电子显微镜观察的结果表明,添加聚硅氧烷能改变乳胶的分散状态。利用小试的最佳配方(即KGF-903的添加量为1.5%)生产了2批次医用导尿管,其表面光洁度、导尿管球囊的成品率、管身硬度、连接器与导尿管排泄锥形接口所承受的拉力和充气漏斗与引流漏斗连接处所承受的拉力等均有显著的提高,有效改善了产品的质量。     

Shape‐Selective Alkylation of Naphthalene over Zeolites: Steric Interaction of Reagents with Zeolites

Steric interaction of reagents with zeolites was studied in isopropylation, sec‐butylation, and tert‐butylation of naphthalene (NP) over several large‐pore zeolites to elucidate the mechanism of selective catalysis. Selectivities for dialkylnaphthalene (DAN) isomers were influenced by the type of zeolite and bulkiness of alkylating agent. Selective formation of β,β‐ and 2,6‐diisopropylnaphthalene (DIPN) occurred only over H‐mordenite (MOR) in the isopropylation of NP using propene; bulky transition states of α,α‐ and α,β‐DIPN are excluded because of steric restriction by the channels, resulting in selective formation of β,β‐ and 2,6‐DIPN. However, low selectivities for β,β‐ and 2,6‐DIPN were observed over the zeolites, SSZ‐24 (AFI), SSZ‐55 (ATS), and SSZ‐42 (IFR) with 12‐membered‐ring (12‐MR) pore entrances of one‐dimensional channels, CIT‐5 (CFI), UTD‐1 (DON), and SSZ‐53 (SFH) with 14‐membered‐ring (14‐MR) pore entrances of one‐dimensional channels, and Y‐zeolite (FAU), zeolite β (BEA), and CIT‐1 (CON) with 12‐MR pore entrances of three‐dimensional channels, because their channels are too large for the exclusion of bulky isomers. Catalysis over these zeolites occurs under kinetic and/or thermodynamic control, resulting in predominant formation of α,α‐ and α,β‐DIPN at lower temperatures and an increase of the stable isomer β,β‐DIPN at higher temperatures. The selectivities for β,β‐ and 2,6‐DAN were enhanced with the increase in bulkiness of alkylating agents: 1‐butene for sec‐butylation and 2‐methylpropene for tert‐butylation. In particular, β,β‐di‐tert‐butylnaphthalene (DTBN) was selectively formed in the tert‐butylation. The selectivities for β,β‐ and 2,6‐DAN were enhanced even in large channels: the transition states of the least bulky isomers only fit the channels because other bulky isomers are excluded by steric restriction of the channels. However, tert‐butylation over FAU, BEA, and CON had selectivities for 2,6‐DTBN of around 50–60%, although selectivities for β,β‐DTBN were almost 100% selectivity; these zeolites can hardly recognize the differences between 2,6‐ and 2,7‐DTBN. The results indicate that the fitting of the least bulky isomers to zeolite channels, leading to the exclusion of other bulky isomers, is essential for highly shape‐selective catalysis.     

Antibacterial Constituents from Isodon Excisoides

Two new ent‐kaurane diterpenoids, taihangexcisoidesin C (1) and its acetonide, taihangexcisoidesin D (2), along with 9 known compounds were isolated from the leaves of Isodon excisoides. The structures of the new compounds were elucidated using 1D and 2D NMR spectroscopy analysis. Compounds 3‐6 and 8‐9 were tested for their antibacterial activity against Escherichia coli, Staphylococcus aureus, S. epidermidis and S. saprophyticus. Compound 6 showed inhibitory effects on Staphylococcus aureus, S. epidermidis and S. saprophyticus MIC values 32, 16 and 16 μg/mL, respectively. All of the compounds didn't show effects on Escherichia coli (MIC > 10 mg/mL).