不同润湿表面液体沸腾的分子动力学模拟

采用分子动力学方法研究纳米尺度下液氩在过热基板上的沸腾过程。通过调节固液间相互作用的方式改变壁面润湿性，模拟并分析了壁面润湿性对沸腾过程中能量传递和液体运动情况的影响。结果表明：不同润湿性表面均会发生固液分离的现象，但是固体表面附近吸附的氩原子数密度随润湿性增强而增大；润湿性较强时，液体的能量上升快，热通量高，液体内部温度梯度大，发生固液分离时间早，系统中氩的温度和能量低，上升过程中液氩密度、厚度变化小；润湿性较弱时，液体的能量上升慢，热通量小，液体内部温度梯度小，发生固液分离时间延后，系统中氩的温度、能量更高，上升过程中液氩密度、厚度变化较大。下部气体压力整体上大于上部气体压力，发生固液分离时润湿性越强的表面上液体上下压差越大，首次上升过程能达到的高度越高，所需时间越短。     

Precise Molecular Sieving Architectures with Janus Pathways for Both Polar and Nonpolar Molecules

Precise molecular sieving architectures with Janus superhighways are constructed via a molecularly engineered interfacial reaction between cyclodextrin (CD) and trimesoyl chloride (TMC). Interestingly, the CD/TMC nanofilms constructed with both hydrophobic inner cavities and hydrophilic channels exhibit exceptionally high permeances for both polar and nonpolar solvents. The precise molecular sieving functions are determined by the type of CD building blocks and the inner cavities of intrinsic 3D hollow bowls. Positron annihilation spectroscopy (PAS) confirms that a larger inner CD cavity tends to generate a larger free volume and higher microporosity. Based on the rejection ratio of various dyes, the estimated molecular weight cutoff of CD/TMC nanofilms follows the trend of α‐CD/TMC (320 Da) <β‐CD/TMC (400 Da) <γ‐CD/TMC (550 Da), which is in strict accordance with the orders of their free volumes measured by PAS and inner cavity sizes of α‐CD <β‐CD <γ‐CD. This kind of novel CD/TMC molecular sieving membrane with intrinsic microporosity containing tunable pore size and sharp pore‐size distribution can effectively discriminate molecules with different 3D sizes.     

Precipitation location of secondary phase and microstructural evolution during static recrystallization of as-cast Ti-25V-15Cr-0.3Si titanium alloy

The microstructural evolution and precipitation location of the secondary phase of an as-cast Ti-25V-15Cr-0.3Si titanium alloy were investigated via isothermal compression experiments and heat treatment. The average aspect (length-to-width) ratio, average area and size of the grains at different heat treatment temperatures and holding time were analyzed and the effects of deformation and annealing time on the grain area and size were considered. It was found that the grain size was strongly influenced by the height reduction and holding time. Grain growth was significant when annealing time increased from 10 min to 2 h at 950 °C and height reduction of 30%; however, grain growth was minimal at annealing time between 2 and 4 h. Many dispersion particles were observed to form in continuous chains; the precipitation location was confirmed to be along initial grain boundaries, and the dispersion particles were identified to be Ti₅Si₃ phase by TEM.     

Volatile organic compound profiles of yoghurt produced from cow's milk with different somatic cell counts

The present study aimed to investigate the effect of somatic cell count (SCC) of raw cow's milk on the volatile organic compound (VOC) profiles of yoghurt. Test yoghurt samples were produced from three batches of cow's milk with low, medium and high SCC, respectively. The VOCs were determined by gas chromatography–mass spectrometry (GC–MS) analysis. A lower diacetyl and acetoin content and a higher content of 2‐heptanone, and butanoic and hexanoic acids were established in the yoghurt samples from batches with high SCC of above 1 000 000 cells/cm³. The increased SCC of cow's milk had a negative effect on the volatile organic compound profiles of yoghurt.     

Predictive association of metal–organic systems in the solid-state: the molecular electrostatic potential based approach

Designing crystalline solids with improved properties or performances remains a challenging task, despite great strides that have been made within the field of crystal engineering since its birth several decades ago. Herein, we are bringing examples that illustrate recent successes in taking supramolecular synthetic guidelines from the organic crystal engineering and adjusting those to metal-containing systems, particularly to the lower-dimensional ones. The versatility of calculated molecular electrostatic potential (MEP) as a new crystal engineering tool is demonstrated.     

芳烃与烯烃烷基化反应的催化机理进展

芳烃与烯烃的反应在有机合成中应用广泛。随着环保要求的提高，用于芳烃烷基化反应的传统催化剂逐渐被新型绿色催化剂所替代。近年来研究发现离子液体和分子筛对该反应具有高效催化作用且环境友好。本文探讨了离子液体和分子筛的酸性，总结了相应的的催化机理，对有关实验和理论研究工作进行了分析。同时揭示了离子液体和分子筛的结构对其催化性能的影响，为烷基化反应进一步研究奠定了基础。分析表明离子液体既能作为B酸，也能作为L酸起催化作用；分子筛主要作为B酸起催化作用，同时其催化性能与孔道结构、孔径大小及反应物尺寸密切相关。离子液体的稳定性较差、成本较高，而分子筛失活较快，未来需围绕提高离子液体稳定性、改进其制备方法以降低成本及改善分子筛结构以延长使用周期等方面展开研究。     

碱性添加剂在钛硅分子筛/H2O2催化丙烯环氧化反应中的作用

考察了反应溶液中碱性添加剂{氨水（NH₄OH）、氢氧化钠（NaOH）、碳酸钠（Na₂CO₃）、碳酸铵[(NH₄)₂CO₃]和四甲基氢氧化铵（TMAOH）}及其浓度对钛硅分子筛（TS-1）催化丙烯环氧化反应性能的影响，并采用紫外拉曼光谱（UV-Raman）与气相色谱（GC）联用原位分析（Raman-GC）碱性添加剂的作用机理。结果表明：反应体系中添加碱性添加剂可有效改善TS-1催化丙烯环氧化反应的选择性。不同碱性添加剂对TS-1催化丙烯环氧化活性和稳定性影响不同，NaOH、Na₂CO₃和TMAOH的添加造成催化活性和稳定性降低。NH₄OH或(NH₄)₂CO₃作为添加剂改善环氧化反应选择性的同时提高了反应稳定性，其中以(NH₄)₂CO₃效果最佳。添加(NH₄)₂CO₃浓度为8.0×10^-4mol/L时，TS-1催化丙烯环氧化在固定床反应器上连续运行336h时，X(H₂O₂)仍保持在90%以上。原位Raman-GC分析发现，反应体系中NH₄OH和(NH₄)₂CO₃添加可加快反应活性中间体Ti-OOH(η²)基团的生成，促进反应产物从活性中心快速扩散，从而提高丙烯环氧化反应选择性和稳定性。     

高分子絮凝剂处理高浓度化妆品原料生产废水研究

化妆品原料生产过程中产生的废水水质成分复杂、有机物含量高、难降解，利用混凝工艺处理该废水能够减缓生化处理单元的负担，提高污水处理效率。为揭示无机高分子混凝剂混凝过程中污染物的去除机制和污泥性质的变化，考察了不同的絮凝剂聚合氯化铝（PAC）、聚合硫酸铁（PFS）、聚合氯化铝铁（PAFC）和助凝剂聚丙烯酰胺（PAM）投加浓度对污染物去除率和污泥性质的影响。采用傅里叶变换红外光谱（FTIR）、X射线能谱（EDX）、扫描电镜（SEM）、热重分析仪（TGA）分析污泥絮体官能团、表面形貌、元素组成和热稳定性的变化，采用三维荧光光谱（3D-EEM）和超滤技术分析出水中有机物分子量的分布规律和有机物成分的变化，优化最佳混凝工艺运行条件。结果表明：进水中的天然有机物（NOM）荧光强度高，有机物分子量主要分布在>100×10³和<3×10³区间，其所占比例分别为22.89%和50.57%。当进水COD为6700~7500 mg/L时，在助凝剂PAM投加浓度为0.03 g/L，PAC、PFS和PAFC投加浓度分别为2.8 g/L、2.8 g/L和3.0 g/L的条件下，COD去除率分别为87.20%、79.89%和83.74%，出水浊度分别为2.54 NTU、9.3 NTU和5.51 NTU，NOM荧光强度大大减弱。其中，PAC+PAM对废水中有机物去除效果最好，出水有机物分子量主要分布在(10~30)×10³和<3×10³范围内，其所占比例分别为31.84%和25.92%，形成的混凝污泥具有较好的热稳定性，污泥表面蓬松,呈多孔网状结构。混凝工艺可吸附脂类大分子物质，提高了高浓度化妆品原料生产废水的可生化性。     

Genes Identification,Molecular Docking and Dynamics Simulation Analysis of Laccases from Amylostereum areolatum Provides Molecular Basis of Laccase Bound to Lignin

An obligate mutualistic relationship exists between the fungus Amylostereum areolatum and woodwasp Sirex noctilio. The fungus digests lignin in the host pine, providing essential nutrients for the growing woodwasp larvae. However, the functional properties of this symbiosis are poorly described. In this study, we identified, cloned, and characterized 14 laccase genes from A. areolatum. These genes encoded proteins of 508 to 529 amino acids and contained three typical copper-oxidase domains, necessary to confer laccase activity. Besides, we performed molecular docking and dynamics simulation of the laccase proteins in complex with lignin compounds (monomers, dimers, trimers, and tetramers). AaLac2, AaLac3, AaLac6, AaLac8, and AaLac10 were found that had low binding energies with all lignin model compounds tested and three of them could maintain stability when binding to these compounds. Among these complexes, amino acid residues ALA, GLN, LEU, PHE, PRO, and SER were commonly present. Our study reveals the molecular basis of A. areolatum laccases interacting with lignin, which is essential for understanding how the fungus provides nutrients to S. noctilio. These findings might also provide guidance for the control of S. noctilio by informing the design of enzyme mutants that could reduce the efficiency of lignin degradation.     

GCr15轴承钢成品套圈热处理后点线状缺陷原因分析

在热处理后的GCr15成品轴承套圈表面发现疑似裂纹的点线状缺陷。通过无损检测、光学显微镜、扫描电镜、能谱分析等手段对缺陷进行分析,发现缺陷处存在较大尺寸的氧化铝和硅酸盐复合夹杂物。通过采取“高拉碳”、“白渣操作”、“软吹”“保护浇铸”等措施后,钢水纯净度得到进一步提高,避免了点线状缺陷的再次发生。