Synthesis, Crystal Structure and Biological Activity of Novel Dichloroacetyl Oxazolidine Herbicide Safeners

A series of novel N-dichloroacetyl oxazolidine herbicide safeners was synthesized and characterized by IR, 1H NMR, 13C NMR, elemental analysis and X-ray diffraction. The preliminary biological test shows that the compounds could protect maize against injury caused by chlorsulfuron to a certain extent.     

Packed-Fiber Solid Phase-Extraction Coupled with HPLC-MS/MS for Rapid Determination of Lipid Oxidative Damage Biomarker 8-Iso-Prostaglandin F2α in Urine

The 8-iso-prostaglandin F_2α (8-iso-PGF_2α) biomarker is used as the gold standard for tracing lipid oxidative stress in vivo. The analysis of urinary 8-iso-PGF_2α is challenging when dealing with trace amounts of 8-iso-PGF_2α and the complexity of urine matrixes. A packed-fiber solid-phase extraction (PFSPE)–coupled with HPLC-MS/MS–method, based on polystyrene (PS)-electrospun nanofibers, was developed for the specific determination of 8-iso-PGF_2α in urine and compared with other newly developed LC-MS/MS methods. The method, which simultaneously processed 12 samples within 5 min on a self-made semi-automatic array solid-phase extraction processor, was the first to introduce PS-electrospun nanofibers as an adsorbent for the extraction of 8-iso-PGF_2α and was successfully applied to real urine samples. After optimizing the PFSPE conditions, good linearity in the range of 0.05–5 ng/mL with R² > 0.9996 and a satisfactory limit of detection of 0.015 ng/mL were obtained, with good intraday and interday precision (RSD < 10%) and recoveries of 95.3–103.8%. This feasible method is expected to be used for the batch quantitative analysis of urinary 8-iso-PGF_2α.     

Cloning,Expression, Purification,and Characterization of β-Galactosidase from Bifidobacterium longum and Bifidobacterium pseudocatenulatum

Expression and purification of β-galactosidases derived from Bifidobacterium provide a new resource for efficient lactose hydrolysis and lactose intolerance alleviation. Here, we cloned and expressed two β-galactosidases derived from Bifidobacterium. The optimal pH for BLGLB1 was 5.5, and the optimal temperature was 45 °C, at which the enzyme activity of BLGLB1 was higher than that of commercial enzyme E (300 ± 3.6 U/mg) under its optimal conditions, reaching 2200 ± 15 U/mg. The optimal pH and temperature for BPGLB1 were 6.0 and 45 °C, respectively, and the enzyme activity (0.58 ± 0.03 U/mg) under optimum conditions was significantly lower than that of BLGLB1. The structures of the two β-galactosidase were similar, with all known key sites conserved. When o-nitrophenyl-β-D-galactoside (oNPG) was used as an enzyme reaction substrate, the maximum reaction velocity (V_max) for BLGLB1 and BPGLB1 was 3700 ± 100 U/mg and 1.1 ± 0.1 U/mg, respectively. The kinetic constant (K_m) of BLGLB1 and BPGLB1 was 1.9 ± 0.1 and 1.3 ± 0.3 mmol/L, respectively. The respective catalytic constant (k_cat) of BLGLB1 and BPGLB1 was 1700 ± 40 s⁻¹ and 0.5 ± 0.02 s⁻¹, respectively; the respective k_cat/K_m value of BLGLB1 and BPGLB1 was 870 L/(mmol∙s) and 0.36 L/(mmol∙s), respectively. The K_m, k_cat and V_max values of BLGLB1 were superior to those of earlier reported β-galactosidase derived from Bifidobacterium. Overall, BLGLB1 has potential application in the food industry.     

Analytical performance study of solar blind non-line-of-sight ultraviolet short-range communication links

Motivated by recent advances in solid-state incoherent ultraviolet sources and solar blind detectors, we study communication link performance over a range of less than 1 km with a bit error rate (BER) below 10(-3) in solar blind non-line-of-sight situation. The widely adopted yet complex single scattering channel model is significantly simplified by means of a closed-form expression for tractable analysis. Path loss is given as a function of transceiver geometry as well as atmospheric scattering and attenuation and is compared with experimental data for model validation. The BER performance of a shot-noise-limited receiver under this channel model is demonstrated.     

Palladium-catalyzed chemoselective direct α-arylation of carbonyl compounds with chloroaryl triflates at the C–Cl site

This study described palladium-catalyzed chemoselective direct α-arylation of carbonyl compounds with chloroaryl triflates in the Ar–Cl bond. The Pd/SelectPhos system showed excellent chemoselectivity toward the Ar–Cl bond in the presence of the Ar–OTf bond with a broad substrate scope and excellent product yields. The electronic and steric hindrance offered by the –PR₂ group of the ligand with the C2-alkyl group was found to be the key factor affecting the reactivity and chemoselectivity of the α-arylation reaction. The chemodivergent approach was also successfully employed in the synthesis of flurbiprofen and its derivatives (e.g., –OMe and –F).

Palladium-catalyzed chemoselective direct α-arylation of carbonyl compounds with chloroaryl triflates in the Ar–Cl bond is reported. The effects of –PR₂ and C2-alkyl groups of the ligands are investigated using experimental and computational methods.     

Responses of Issatchenkia terricola WJL-G4 upon Citric Acid Stress

This study aimed to elucidate the responses of a novel characterized Issatchenkia terricola WJL-G4 against citric acid stress by performing physiological analysis, morphology observation, and structural and membrane fatty acid composition analysis. The results showed that under citric acid stress, the cell vitality of I. terricola WJL-G4 was reduced. The cell morphology changed with the unclear, uncompleted and thinner cell wall, and degraded the cell structure. When the citric acid concentration was 20 g/L, I. terricola WJL-G4 could tolerate citric acid and maintain the cell structure by increasing the intracellular pH, superoxide dismutase activity, and contents of unsaturated fatty acids. As the citric acid concentration was ≥80 g/L, the stress has exceeded the cellular anti-stress ability, causing substantial cell damage. The cell membrane permeability, the content of membrane lipids, malondialdehyde and superoxide anion increased, but the intracellular pH and superoxide dismutase activities decreased, accompanying the increase of citric acid concentrations. The findings of this work provided a theoretical basis for the responsive mechanism of I. terricola WJL-G4 under high concentrations of citric acid, and can serve as a reference for biological acid reduction in fruit processing.     

Computational Insight into Biotransformation Profiles of Organophosphorus Flame Retardants to Their Diester Metabolites by Cytochrome P450

Biotransformation of organophosphorus flame retardants (OPFRs) mediated by cytochrome P450 enzymes (CYPs) has a potential correlation with their toxicological effects on humans. In this work, we employed five typical OPFRs including tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), tris(1-chloro-2-propyl) phosphate (TCIPP), tri(2-chloroethyl) phosphate (TCEP), triethyl phosphate (TEP), and 2-ethylhexyl diphenyl phosphate (EHDPHP), and performed density functional theory (DFT) calculations to clarify the CYP-catalyzed biotransformation of five OPFRs to their diester metabolites. The DFT results show that the reaction mechanism consists of Cα-hydroxylation and O-dealkylation steps, and the biotransformation activities of five OPFRs may follow the order of TCEP ≈ TEP ≈ EHDPHP > TCIPP > TDCIPP. We further performed molecular dynamics (MD) simulations to unravel the binding interactions of five OPFRs in the CYP3A4 isoform. Binding mode analyses demonstrate that CYP3A4-mediated metabolism of TDCIPP, TCIPP, TCEP, and TEP can produce the diester metabolites, while EHDPHP metabolism may generate para-hydroxyEHDPHP as the primary metabolite. Moreover, the EHDPHP and TDCIPP have higher binding potential to CYP3A4 than TCIPP, TCEP, and TEP. This work reports the biotransformation profiles and binding features of five OPFRs in CYP, which can provide meaningful clues for the further studies of the metabolic fates of OPFRs and toxicological effects associated with the relevant metabolites.     

一种电流引线的热力学计算方法

从超导磁体气冷电流引线的热平衡方程出发,对电流引线进行分段,提出了一种较为精确计算电流引线长横比及由电流引线末端流入低温容器热量的计算方法;电流引线中氦气流阻是设计电流引线时一个很重要的参数,由于电流引线片形状很复杂,计算其中氦气流阻比较好的方法是采用CFD软件Fluent。氦气模型单元数很庞大,因此对氦气模型进行了简化和分段,相邻两段模型间采用流量和压力边界条件进行耦合。     

声光栅正弦结构光投射器的光学系统设计

针对一种新型的声光波干涉测量技术,对声光栅正弦结构光投射器的三维测量工作原理进行了系统的分析,讨论了影响投射器光学系统结构的因素和影响接收屏上的光照度的因素,并进行了光学系统设计。在优化设计过程中,采用了限制光线最大入射角的方法,达到控制投射系统的球差和保证接收屏上照明均匀的要求。所设计的声光栅正弦光投射器具有很好的成像质量。应用该系统对在500mm处的石膏像上投射干涉条纹,可以得到能量比较均匀、变形量很小的干涉条纹图,利用该条纹图和相关的算法可以对具有复杂几何形状的物体进行有效的三维测量。     

DFT Investigations of Aun Nano-Clusters Supported on TiO2 Nanotubes: Structures and Electronic Properties

TiO₂ nanotubes (TiO₂NTs) are beneficial for photogenerated electron separation in photocatalysis. In order to improve the utilization rate of TiO₂NTs in the visible light region, an effective method is to use Au_n cluster deposition-modified TiO₂NTs. It is of great significance to investigate the mechanism of Au_n clusters supported on TiO₂NTs to strengthen its visible-light response. In this work, the structures, electronic properties, Mulliken atomic charge, density of states, band structure, and deformation density of Au_n (n = 1, 8, 13) clusters supported on TiO₂NTs were investigated by DMOL3. Based on published research results, the most stable adsorption configurations of Au_n (n = 1, 8, 13) clusters supported with TiO₂NTs were obtained. The adsorption energy increased as the number of Au adatoms increased linearly. The Au_n clusters supported on TiO₂NTs carry a negative charge. The band gaps of the three most stable structures of each adsorption system decreased compared to TiO₂NTs; the valence top and the conduction bottom of the Fermi level come mainly from the contribution of 5d and 6s-Au. The electronic properties of the 5d and 6s impurity orbitals cause valence widening and band gap narrowing.