Dual-high-frequency from single-piezoelectric crystal for ACE degradation by hybrid advanced oxidation UV-sonochemistry process

This study investigates the combination of two waves emitted from a single-piezoelectric crystal by use of a dual-frequency generator in a sonochemical reactor. The dual-frequency configurations analyzed were the double-modulated fundamental frequency (376–376 kHz), resonant and second harmonic, termed 376D, 376R and 376H respectively. The effect of the phase shift (Φ) and the percentage of modulation between added waves were described by the total acoustic power distribution (P_t) measured inside the sonoreactor. Moreover, optimal angle alignment and modulation between dual-frequency waves for 376D, 376R and 376H cases were selected in order to evaluate the ultrasonic synergy by sonochemical reactivity in production of H₂O₂, in degradation rate of a model emerging pollutant ACE, and in the TOC and biodegradability evolution in the treated effluent. Phase shift and percentage of modulation had strong effect on the resulted waveform and on the sonochemical efficiency for all, harmonic and non-harmonic, dual-frequency combinations created. In the 376D case, the best reinforcement conditions are founded at 0° and 360°. In the 376H the maximum power distribution presents a 90° period. Shift phase does not determines any cyclic pattern in the total power distribution for the 376R case. The highest H₂O₂ production rate was observed for the 376H case followed for 376D and 376R configurations with 1.61, 1.12 and 0.58 μM/min by angle alignment in 105, 0 and 110° respectively. The highest initial degradation rate of ACE was observed for the 376D case followed for 376H and 376R with 0.56, 0.42 and 0.33 μM/min at 100% modulation. Reduced mineralization was observed in all dual-frequency configurations (8.54% for 376D and approximately 4.5% for 376R and 3756H modes). Contrasting results are observed regard to biodegradability ratio following the next sequence 376D < 376H≈376R with 0.9, 2.30 and 2.33 respectively. Relevant intensification in hydroxyl radicals production is observed by the UV-US system increasing up three folds the ACE removal and mineralization and two folds higher biodegradability of effluent in particular for 376R and 376H cases at optimal operation condition of dual-frequency signal.     

线型脲醛树脂的半结晶模板化作用

酸性条件下硅溶胶体系中尿素和甲醛聚合反应会产生脲醛树脂-氧化硅杂化沉淀. 沉淀的质量随有机组分比例的增加而增加, 当尿素和甲醛物质的量比≥1.0时生成沉淀的量为恒定最大值. 红外分析表明杂化材料在3348, 1635, 1572和784 cm^－1处产生了可被归结为线型结构(—[NHCONHCH₂]_n—)的特征吸收. XRD分析表明这种线型分子可形成氢键(C＝O…H—N)导向型的半结晶. 微分热重和XRD结果证明结晶物种在290 ℃完全分解. SEM表征显示半结晶杂化沉淀以三维网络结构为特征, 具有层状结晶的各向异性, 其初级粒子即使在室温下干燥也容易开裂. 随着反应时间的延长、酸性的增加或无机组分量的相对增加杂化粒子变得更加致密. 液氮吸附结果证明沉淀焙烧后所得氧化硅材料的结构具有层状孔结构性质, 其比表面积、孔尺寸和孔体积可以达到510 m²/g, 14.3 nm和1.68 cm³/g. 改变反应体系的酸性和反应组分配比等条件可以方便地控制杂化材料的结构.     

Bayesian Variable Selection and Estimation in Semiparametric Simplex Mixed-Effects Models with Longitudinal Proportional Data

In the development of simplex mixed-effects models, random effects in these mixed-effects models are generally distributed in normal distribution. The normality assumption may be violated in an analysis of skewed and multimodal longitudinal data. In this paper, we adopt the centered Dirichlet process mixture model (CDPMM) to specify the random effects in the simplex mixed-effects models. Combining the block Gibbs sampler and the Metropolis–Hastings algorithm, we extend a Bayesian Lasso (BLasso) to simultaneously estimate unknown parameters of interest and select important covariates with nonzero effects in semiparametric simplex mixed-effects models. Several simulation studies and a real example are employed to illustrate the proposed methodologies.     

An Efficient Method of Birch Ethanol Lignin Sulfation with a Sulfaic Acid-Urea Mixture

For the first time, the process of birch ethanol lignin sulfation with a sulfamic acid-urea mixture in a 1,4-dioxane medium was optimized experimentally and numerically. The high yield of the sulfated ethanol lignin (more than 96%) and containing 7.1 and 7.9 wt % of sulfur was produced at process temperatures of 80 and 90 °C for 3 h. The sample with the highest sulfur content (8.1 wt %) was obtained at a temperature of 100 °C for 2 h. The structure and molecular weight distribution of the sulfated birch ethanol lignin was established by FTIR, 2D ¹H and ¹³C NMR spectroscopy, and gel permeation chromatography. The introduction of sulfate groups into the lignin structure was confirmed by FTIR by the appearance of absorption bands characteristic of the vibrations of sulfate group bonds. According to 2D NMR spectroscopy data, both the alcohol and phenolic hydroxyl groups of the ethanol lignin were subjected to sulfation. The sulfated birch ethanol lignin with a weight average molecular weight of 7.6 kDa and a polydispersity index of 1.81 was obtained under the optimum process conditions. Differences in the structure of the phenylpropane units of birch ethanol lignin (syringyl-type predominates) and abies ethanol lignin (guaiacyl-type predominates) was manifested in the fact that the sulfation of the former proceeds more completely at moderate temperatures than the latter. In contrast to sulfated abies ethanol lignin, the sulfated birch ethanol lignin had a bimodal and wider molecular weight distribution, as well as less thermal stability. The introduction of sulfate groups into ethanol lignin reduced its thermal stability.     

Simple Enzyme Immobilization for Flow Chemistry? An Assessment of Available Strategies for an Acetaldehyde-Dependent Aldolase

Enzyme immobilization is a technology that enables (bio-)catalysts to be applied in continuous-flow systems. However, there is a plethora of immobilization methods available with individual advantages and disadvantages. Here, we assessed the influence of simple and readily available methods with respect to the performance of 2-deoxy-d-ribose-5-phosphate aldolase (DERA) in continuous-flow conditions. The investigated immobilization strategies cover the unspecific attachment to carriers via epoxides, affinity-based attachment via metal ion affinity, StrepTag™-StrepTactin™ interaction as well as the covalent affinity attachment of an enzyme to a matrix tethered by the HaloTag^®. The metal-ion-affinity-based approach outperformed the other methods in terms of immobilized activity and stability under applied conditions. As most enzymes examined today already have a HisTag for purification purposes, effective immobilization may be applied, as simple as a standard purification, if needed.     

Cold Sintering of Li6.4La3Zr1.4Ta0.6O12/PEO Composite Solid Electrolytes

Ceramic/polymer composite solid electrolytes integrate the high ionic conductivity of in ceramics and the flexibility of organic polymers. In practice, ceramic/polymer composite solid electrolytes are generally made into thin films rather than sintered into bulk due to processing temperature limitations. In this work, Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO)/polyethylene-oxide (PEO) electrolyte containing bis(trifluoromethanesulfonyl)imide (LiTFSI) as the lithium salt was successfully fabricated into bulk pellets via the cold sintering process (CSP). Using CSP, above 80% dense composite electrolyte pellets were obtained, and a high Li-ion conductivity of 2.4 × 10⁻⁴ S cm^–1 was achieved at room temperature. This work focuses on the conductivity contributions and microstructural development within the CSP process of composite solid electrolytes. Cold sintering provides an approach for bridging the gap in processing temperatures of ceramics and polymers, thereby enabling high-performance composites for electrochemical systems.     

Enhanced Degradation of Antibiotic by Peroxydisulfate Catalysis with CuO@CNT: Simultaneous 1O2 Oxidation and Electron-Transfer Regime

The nonradical process in the peroxydisulfate (PDS) oxidation system is a promising method for antibiotic removal in water. In this study, CuO@CNT was successfully synthesized by a facile approach to catalyze PDS. The removal efficiency of the antibiotic sulfamethoxazole (SMX) was 90.6% in 50 min, and the stoichiometric efficiency (ΔSMX/ΔPDS) was 0.402. The very different degradation efficiency of common organic contaminants revealed the selective oxidation of the surveyed system. The process of ¹O₂ oxidation and the electron-transfer regime was exhibited by chemical quenching tests, electron paramagnetic resonance (EPR) determination, a UV–vis spectrophotometer, X-ray photoelectron spectroscopy (XPS) detection, and cyclic voltammetry (CV) measurements. Sustainable catalysis was promoted by the circulation between the surface electron-rich centers of Cu(II) and Cu(III). Dissolved oxygen (DO) and a metastable Cu(III) intermediate contributed to the generation of ¹O₂. Still, a portion of SMX was removed by the mildly activated PDS. Moreover, the influence factors (pH, dosage, water matrix) were examined, and suppressions were acceptable by common anions and real water. Distinguished from the radical process, unique intermediate products were ascertained via the theoretical calculation and liquid chromatography–mass spectrometry (LC-MS) detection. Furthermore, CuO@CNT showed a satisfactory activation ability in the cycling experiments. Overall, this study developed CNT to be a supporter of CuO, unveiled the mechanism of catalysis, and evaluated the application potential of the nonradical process.     

辐射在CH泡沫中传输的数值模拟

利用一维多群辐射输运程序对辐射在CH泡沫中的传输过程进行了数值模拟,给出一些细致的物理图像和定量结果。在一定的入射辐射流条件下,密度变化对辐射传输特征、辐射加热介质的热力学平衡弛豫过程有重要影响。随着密度下降,辐射由亚声速传输转变为超声速传输,辐射在传输过程中的能谱形状也不同。     

高功率激光诱导光学元件损伤阈值测量的不确定度分析

激光诱导损伤阈值作为一实验参量,对其结果作不确定度分析有利于激光工作者在某个精度范围内获知该参量的信息。从激光损伤和损伤阈值定义出发,分析了基于ISO11254的损伤几率测试法测试激光诱导损伤阈值的不确定度来源,包括激光能量测量、激光光斑有效面积测量、各能量密度处损伤几率的计算以及对损伤几率点进行直线拟合这4个方面。并利用统计学原理和线性拟合等理论对这4个方面引起的不确定度分量及最终测试结果的相对合成不确定度进行了计算。以1 064 nm高反薄膜样品为例,分析表明：损伤几率点的计算和几率图中损伤几率的直线拟合是损伤阈值测试结果不确定度的主要来源,当样品的损伤阈值为7.79 J/cm2时,这两种因素引起的相对不确定度可分别在4%和18%左右,损伤阈值的相对合成不确定度达18.72%。     

ZnSe多晶化学机械抛光研究

本文针对ZnSe多晶的性能,在试验的基础上,研究出一套实用的、行之有效的ZnSe多晶加工工艺,并重点讨论了化学机械抛光工艺.同时对加工后零件的工艺参数、表面质量及透过率的测试,结果表明所采用的化学机械加工法可取得非常好的抛光效果.