Semiclassical Trajectory Studies of Reactive and Nonreactive Scattering of OH(A 2Σ+) by H2 Based on an Improved Full-Dimensional Ab Initio Diabatic Potential Energy Matrix

We present a new full-dimensional diabatic potential energy matrix (DPEM) for electronically nonadiabatic collisions of OH(A ²Σ⁺) with H₂, and we calculate the probabilities of electronically adiabatic inelastic collisions, nonreactive quenching, and reactive quenching to form H₂O+H. The DPEM was fitted using a many-body expansion with permutationally invariant polynomials in bond-order functions to represent the many-body part. The dynamics calculations were carried out with the fewest-switches with time uncertainty and stochastic decoherence (FSTU/SD) semiclassical trajectory method. We present results both for head-on collisions (impact parameter b equal to zero) and for a full range of impact parameters. The results are compared to experiment and to earlier FSTU/SD and quantum dynamics calculations with a previously published DPEM. The various theoretical results all agree that nonreactive quenching dominates reactive quenching, but there are quantitative differences between the two DPEMs and between the b=0 results and the all-b results, especially for the probability of reactive quenching.     

Facile Fabrication of PBS/CNTs Nanocomposite Foam for Electromagnetic Interference Shielding

In order to reduce the pollutants of environment and electromagnetic waves, environment friendly polymer foams with outstanding electromagnetic interference shielding are imminently required. In this paper, a kind of electromagnetic shielding, biodegradable nanocomposite foam was fabricated by blending poly (butylene succinate) (PBS) with carbon nanotubes (CNTs) followed by foaming with supercritical CO₂. The crystallization temperature and melting temperature of PBS/CNTs nanocomposites with 4 wt % of CNTs increased remarkably by 6 °C and 3.1 °C compared with that of pure PBS and a double crystal melting peak of various PBS samples appeared in DSC curves. Increasing the CNT content from 0 to 4 wt % leads to an increase of approximately 3 orders of magnitude in storage modulus and nearly 9 orders of magnitude in enhancement of electrical properties. Furthermore, CNTs endowed PBS nanocomposite foam with adjustable electromagnetic interference (EMI) shielding property, giving a specific EMI shielding effectiveness of 28.5 dB cm³/g. This study provides a promising methodology for preparing biodegradable, lightweight PBS/CNTs foam with outstanding electromagnetic shielding properties.     

DCE-MRI参数联合IFIT1基因对腰椎间盘突出患者椎间盘退变程度的评估价值

探讨DCE-MRI参数及IFIT1基因对腰椎间盘突出症(LDH)患者椎间盘退变(IDD)程度的评估价值。随机选取确诊的66例LDH患者作为研究对象,根据改良Pfirrmann分级法将患者分为2组:轻中度IDD(Ⅰ~Ⅲ级)组(46例)和重度IDD(Ⅳ~Ⅴ级)组20例。通过DCE-MRI检查考察患者的K-trans值,采用日本骨科学会评分(JOA)评估腰椎功能,采用视觉模拟评分法(VAS)评估腰部疼痛,采用RT-PCR检测外周血单个核细胞(PBMC)中IFIT1的mRNA表达。轻中度IDD组的K-trans值显著低于重度IDD组。轻中度IDD组患者PBMC中的IFIT1 mRNA相对表达量显著低于重度IDD组。K-trans值与PBMC中的IFIT1 mRNA水平和VAS评分正相关,与JOA评分负相关(P<0.05)。PBMC中的IFIT1 mRNA水平与VAS评分正相关,与JOA评分负相关(P<0.05)。K-trans值和PBMC中的IFIT1 mRNA水平联合诊断重度IDD的AUC值、敏感性和特异性分别为0.991、91.3%和100.0%,AUC值和特异性均高于单独诊断。DCE-MRI检查中的K-trans值联合PBMC中的IFIT1 mRNA水平可用于LDH患者IDD程度的诊断。     

Mixed Quantum Classical Reaction Rates based on the Phase Space Formulation of the Hierarchical Equations of Motion

In a previous work [J. Chem. Phys. 140 , 174105 (2014)], we have shown that a mixed quantum classical (MQC) rate theory can be derived to investigate the quantum tunneling effects in the proton transfer reactions. However, the method is based on the high temperature approximation of the hierarchical equation of motion (HEOM) with the Debye-Drude spectral density, and results in a multi-state Zusman type of equation. We now extend this theory to include quantum effects of the bath degrees of freedom. By writing the full HEOM into a multidimensional partial differential equation in phase space, we can define a new reaction coordinate, and the previous method can be generalized to the full quantum regime. The validity of the new method is demonstrated by using numerical examples, including the spin-Boson model, and the double well model for proton transfer reaction. The new method is found to resolve some key problems of the previous theory based on high temperature approximation, including possible numerical instability in long time simulation and wrong rate constant at low temperatures.     

Effective biosorption of arsenic from water using La(III) loaded carboxyl functionalized watermelon rind

Arsenic is highly toxic and carcinogenic element that mainly enters into our body through drinking water and caused adverse effect even at low concentration. A new type of cation exchanger is developed from waste biomass of watermelon rind after increasing the carboxyl functional groups by saponification. Saponified Watermelon Rind (SWR) was further loaded with La(III) to attenuate the contamination of As(III) from water. Characterization of biosorbent was performed using Fourier Transform Infra-Red (FTIR) spectroscopy, Field emission Scanning Electron Microscopy (Fe-SEM,) Energy Dispersive X-ray (EDX) spectroscopy and zeta potential analysis. Arsenic speciation of sorption product through X-ray photoelectron spectroscopic (XPS) analysis revealed that As(III) is partially converted into As(V) during biosorption process. The biosorption tests for As(III) were explored under different operating conditions. La(III)-SWR towards As(III) biosorption was best described by Langmuir biosorption isotherm and pseudo second order kinetic model. At a pH of 12.08, the optimum biosorption capacity was found to be 37.73 ± 0.12, 48.78 ± 0.09, 62.50 ± 0.11 mg/g, respectively at temperatures 298 K, 303 K and 308 K. The existance of chloride and nitrate showed negligible interference whereas sulphate and phosphate significantly inhibits As(III) biosorption. Thermodynamic study showed spontaneous and endothermic nature As(III) biosorption onto La(III)-SWR. The sorbed As(III) was eluted almost completely using 2 M NaOH. The findings of this study insinuated that La(III)-SWR biosorbent investigated in this study can be a low cost, environmentally benign and eco-friendly material for the treatment of aqueous solution polluted with arsenic ions.     

Highly efficient photocatalytic degradation for antibiotics and mechanism insight for Bi2S3/g-C3N4 with fast interfacial charges transfer and excellent stability

Bi₂S₃/g-C₃N₄ (BSCN) samples with different mass ratios of CN to BS were prepared by a facile and practicable hydrothermal method with 2D g-C₃N₄ nanosheets (CN). The microscopic morphology and structure of pure CN, BS and BSCN were measured by multiple testing methods. Analysis results show that the BSCN was prepared successfully, and the Bi₂S₃ nanoparticles closely and uniformly adhered to the surface of CN with sheet-like structure. The introduction of Bi₂S₃ did not change the structure of the CN. The results of the ultraviolet–visible spectroscopic analysis, photoluminescence spectra and electrochemical performance indicated that BSCN showed superior visible-light response compared with CN, and the separation and transfer efficiency of photogenerated carriers was significantly improved. With the decrease of mass ratio of CN/BS, the photocatalytic activity of BSCN initially increased and then decreased for 20 ppm of Rhodamine B solution (RhB), and the Bi₂S₃/g-C₃N₄-B with a mass ratio of 8:1 for CN to BS showed optimal photocatalytic performance (98.98%). Furthermore, the Bi₂S₃/g-C₃N₄-B exhibited apparent degradation effects (1.021 x10^-2, 0.879 x10^-2 and 0.793 x10^-2 min^?1) to three kinds of antibiotics (tetracycline, ciprofloxacin, and oxytetracycline). The BSCN samples still maintained higher degradation efficiency after five cycles of degradation to tetracycline. The capture experiments and the electron spin resonance (ESR) spectra analysis indicated that the h⁺ and ·O₂^? played a major role, and ·OH played secondary role during the photocatalytic reaction.     

Development and validation of high-performance liquid chromatography method for analysis of β-CCT and its related substances

Compound 2β-carbomethoxy-3β-(4-chlorophenyl)tropane (β-CCT) is a key intermediate for the synthesis of some clinical dopamine transporter (DAT) imaging agents. Potential impurities from synthesis process of β-CCT and degradation during storage might have detrimental effect on the final imaging agents. Thus, it is necessary to guarantee the quality of β-CCT. In this study, a rapid, sensitive and accurate high-performance liquid chromatography (HPLC) method was developed and validated for the analysis of β-CCT and its related substances. The chromatographic separation was achieved on a reverse-phase phenomenex? Gemini C18 column with an isocratic mobile phase consisted of methanol, water and TFA (30:70:0.1 v/v/v). The flow rate was 1.0 mL/min at 30 °C and samples were monitored at 220 nm. The method was validated concerning system suitability, linearity, accuracy, precision, specificity, robustness and stability. The limit of detection (LOD) and the limit of quantification (LOQ) of β-CCT were 0.5 and 1.5 μg/mL, respectively. The linearity range of β-CCT was 1.5–450 μg/mL with a good linear correlation coefficient (R² = 0.9999) between the peak response and concentration. Specificity investigation through forced degradation experiments displayed that β-CCT was stable in acidic, thermal and photolytic degradation conditions, but significantly unstable in alkaline and oxidative conditions. With the developed chromatographic method, possible impurity α-CCT from synthetic process and potential degradation products could be well separated from β-CCT. Good recovery and precision were manifested in the assay method. These results indicated that the present method would be suitable for not only the quality assurance of β-CCT in regular production sample assays but also the monitoring and determination of its related substances.     

Synthesis and characterization of CuO nanoparticles utilizing waste fish scale and exploitation of XRD peak profile analysis for approximating the structural parameters

In this research, we strived to utilize waste fish scale (labeo rohita) for synthesizing CuO nano-particles (CuO NPs), which gained much attention due to its distinctive properties and versatile applications. Upon the heat treatment, the collagen content of the fish scale got transformed into gelatin which in turn converted the precursor material into CuO NPs. The X-Ray diffraction (XRD) analysis confirmed the formation of CuO NPs and revealed the structure to be of monoclinic lattice. The structural parameters i.e. crystallite size, lattice parameters, microstrain, dislocation density was evaluated for the synthesized CuO NPs using the XRD data. Scherrer’s Method (SM), Scherrer Equation Average Method (SEAM), Linear Straight Line Method (LSLM), Straight Line Passing the Origin Method (SLPOM), Monshi Scherrer Method (MSM), Williamson-Hall Method (WHM), Size-Strain Plot Method (SSPM), Halder-Wagner Method (HWM) was exploited for the estimation of crystallite size. According to the calculations, the crystallite size was found to be 87 nm, 41 nm, 1980 nm, 62 nm, 66 nm, 28 nm, 13 nm, 13 nm respectively and the dislocation density was found to be 1.32 × 10^-4, 5.95 × 10^-4, 0.002 × 10^-4, 2.60 × 10^-4, 2.29 × 10^-4, 12.75 × 10^-4, 59.17 × 10^-4 and 59.17 × 10^-4 respectively. UV–Vis absorption analysis also confirmed the formation of CuO NPs based on the absorption peak at 262 nm (λ_max) and Tauc Plot method was used to calculate the optical band gap which was 3.84 eV. Functional group, especially the Cu-O bonding was confirmed by the Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) data. Field Emission Scanning Electron Microscopy (FESEM) showed three different shapes of CuO NPs which was also confirmed by Transmission Electron Microscopy (TEM). Particle size was determined based on FESEM and TEM image using imageJ software and also by the Dynamic Light Scattering (DLS) technique. Thermal analysis showed a four stage weight loss in case of Thermogravimetric (TGA) analysis and three conversion steps was observed in Differential Scanning Calorimetric (DSC) analysis. Such synthesis pathway is evidently green and facile for synthesizing CuO NPs with potentiality of various applications and also utilization of waste fish scale is a perquisite.     

Preparation,characterization and antioxidant activity of a novel polysaccharide-iron (III) from Flammulina velutipes scraps

In the present study, a novel polysaccharide from Flammulina velutipes scraps (FVSP) was extracted and purified from Flammulina velutipes scraps. FVSP was chemically chelated to synthesize FVSP-iron (III) complex. Based on single factor experiments, preparation process of FVSP- iron (III) was optimized by response surface methodology. The characterization and antioxidant activity of FVSP-iron (III) were investigated. The results showed that the optimal preparation process of FVSP-iron (III) was reaction temperature of 50 °C, reaction time of 4.7 h and the mass ratio of FVSP/sodium citrate - of 2:1. The relative molecular weight of FVSP-iron (III) was 36.25 kDa. FVSP-Iron (III) was composed of glucose, galactose, mannose and xylose in a molar ratio of 65.1:20.5:5.2:9.2.The results of UV–vis absorption spectrum, FI-IR spectrum and X-ray diffraction showed that both hydroxyl and carboxyl groups in FVSP participated in the coordination reaction and the iron core of FVSP-Iron(III) was a polymerized β-FeOOH structure. FVSP-iron (III) had better thermal stability and stronger antioxidant activities than FVSP. The results indicated that FVSP-iron (III) could be potentially used in food industry as a new food additive and iron supplement.     

An innovative SiO2-pyrazole nanocomposite for Zn(II) and Cr(III) ions effective adsorption and anti-sulfate-reducing bacteria from the produced oilfield water

Novel SiO₂-pyrazole (SiO₂-PYZ) nanocomposite was introduced for the elimination of Zn(II) and Cr(III) from oil reservoir water. Characterization analysis of prepared SiO₂-PYZ nanocomposite was investigated using SEM, FTIR, TGA, XRD, TEM, and BET. Studying the effects and optimization of the parameters such as retention time, pH, initial Cr(III) and Zn(II) ions concentrations, adsorbent dosage, and temperature were examined. For kinetics investigation, the pseudo-second-order (PSO) model matches the adsorption process effectively under different operating conditions. After applying two other isotherm models (Langmuir and Freundlich), the experimental data was adequately equipped with Langmuir, R² = 1. The thermodynamic results pointed that the adsorption of Zn(II) and Cr(III) ions was spontaneous, endothermic, and physisorption reaction. At pH 12, the influence of more than one ion, such as Ca(II) and Na(I), was checked, and the results revealed that this conjugate substance was highly selective to Cr(III). After washing with water in multiple cycles, the adsorbed material was regenerated with 0.1 M HCl and subsequently reused without deterioration in its case cavities. Interestingly, SiO₂-PYZ was highly effective against sulfate-reducing bacteria (SRB) in the petroleum field.