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.     

新型纳米平板陶瓷膜在纸箱生产废水回用中的工程应用

采用混凝沉淀+水解酸化+MBR+活性炭吸附组合工艺来回用纸箱厂废水。MBR膜采用的是新型纳米平板陶瓷膜。介绍了各处理段的工艺特点、构筑物的设计尺寸、设备选型等,并对新型纳米平板陶瓷膜的清洗进行了介绍。系统运行一年,出水水质稳定,优于≤城市污水再生利用城市杂用水水质≥GB/T 18920-2002表1中的城市绿化排放标准,即BOD5≤20 g/L,浊度≤10 NTU,色度≤30,并分析了本工程的处理成本及所产生的经济效益。     

HF刻蚀工艺对AZ91D镁合金疏水膜性能的影响

为了改善AZ91D镁合金表面疏水膜的疏水性,对以HF和N^MoOq为主要成分的刻蚀液进行了研究。通过改变刻蚀温度、刻蚀时间、HF的浓度及Na2MoO4的质量浓度,确定了最佳的刻蚀工艺条件为:HF 0.10 mol/L,Na2MoO41.00 g/L,1525°C,90 so实验结果表明:使用HF刻蚀液可以在镁合金表面形成理想的微纳结构。通过刻蚀构建的微纳结构可以明显提高疏水膜的疏水性。     

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。     

高温车用燃料电池的发展及现状综述

燃料电池车以其能量转化效率高、绿色环保、噪音低等优点，被认为是替代传统化石能源汽车最有前景的新能源汽车。目前车用燃料电池的工作温度一般都低于80℃，低温的工作环境使其面临着诸多问题，如复杂的水管理和CO中毒等。通过提高质子交换膜燃料电池（PEMFC）的工作温度可以缓解这些问题，提高燃料电池的性能。然而，高温的工作环境也会对燃料电池带来诸多挑战，如膜脱水、催化剂团聚、冷启动速度缓慢等。要促进高温（90～120℃）车用燃料电池的快速发展，需要对其问题及解决方法进行分析。本文从电堆比功率、膜电极、双极板、进气方式、加湿方式等方面，介绍燃料电池的发展现状及存在的问题，包括Nafion膜和催化剂的热稳定问题、双极板的耐腐蚀问题、流道的气体分配问题、进气方式和加湿方式的优化以及冷启动问题。指出通过掺杂亲水性氧化物改善Nafion膜的高温性能；将Pt合金化及采用介孔炭提高催化剂的稳定性和电化学活性；镀层不锈钢金属双极板可以增强耐腐蚀性；3D流场等新型流场结构及提高进气温度、速度可以提高气体的均匀性；采用自增湿方式可以简化电堆结构等解决方法，以期对燃料电池车的进一步发展起到引导作用。     

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.     

Sequence-Dependent Nanofiber Structures of Phenylalanine and Isoleucine Tripeptides

The molecular design of short peptides to achieve a tailor-made functional architecture has attracted attention during the past decade but remains challenging as a result of insufficient understanding of the relationship between peptide sequence and assembled supramolecular structures. We report a hybrid-resolution model to computationally explore the sequence–structure relationship of self-assembly for tripeptides containing only phenylalanine and isoleucine. We found that all these tripeptides have a tendency to assemble into nanofibers composed of laterally associated filaments. Molecular arrangements within the assemblies are diverse and vary depending on the sequences. This structural diversity originates from (1) distinct conformations of peptide building blocks that lead to different surface geometries of the filaments and (2) unique sidechain arrangements at the filament interfaces for each sequence. Many conformations are available for tripeptides in solution, but only an extended β-strand and another resembling a right-handed turn are observed in assemblies. It was found that the sequence dependence of these conformations and the packing of resulting filaments are determined by multiple competing noncovalent forces, with hydrophobic interactions involving Phe being particularly important. The sequence pattern for each type of assembly conformation and packing has been identified. These results highlight the importance of the interplay between conformation, molecular packing, and sequences for determining detailed nanostructures of peptides and provide a detailed insight to support a more precise design of peptide-based nanomaterials.