Form selection of concomitant polymorphs: A case study informed by crystallization kinetics modeling

Molecular mechanisms and process kinetics of crystallizing concomitant polymorphs remain poorly understood. Solvent-mediated phase transformation and concomitant crystallization are difficult to be distinguished in practice, as multiple forms can be detected at the same time. Herein, we developed a population balance model to simulate a concomitant crystallization process of two polymorphs of tolfenamic acid. Our kinetic modeling aims to understand concomitant crystallization and help guide form selection of such a molecular system. Crystallization kinetics of ethanolic solutions were uncovered from induction time measurements, as well as seeded and unseeded crystallization experiments. Experimental and simulation results demonstrate that the stable form I crystallizes concomitantly with the metastable form II. The faster growing form II results in an intermediate decline in the composition of form I in crystallized samples, a characteristic feature of the concomitantly crystallized system. A four-quadrant scheme of attainable polymorph outcome was simulated under various crystallization conditions.     

Suppressed Lattice Disorder for Large Emission Enhancement and Structural Robustness in Hybrid Lead Iodide Perovskite Discovered by High-Pressure Isotope Effect

The soft nature of organic–inorganic halide perovskites renders their lattice particularly tunable to external stimuli such as pressure, undoubtedly offering an effective way to modify their structure for extraordinary optoelectronic properties. Here, using the methylammonium lead iodide as a representative exploratory platform, it is observed that the pressure-driven lattice disorder can be significantly suppressed via hydrogen isotope effect, which is crucial for better optical and mechanical properties previously unattainable. By a comprehensive in situ neutron/synchrotron-based analysis and optical characterizations, a remarkable photoluminescence (PL) enhancement by threefold is convinced in deuterated CD₃ND₃PbI₃, which also shows much greater structural robustness with retainable PL after high peak-pressure compression–decompression cycle. With the first-principles calculations, an atomic level understanding of the strong correlation among the organic sublattice and lead iodide octahedral framework and structural photonics is proposed, where the less dynamic CD₃ND₃⁺ cations are vital to maintain the long-range crystalline order through steric and Coulombic interactions. These results also show that CD₃ND₃PbI₃-based solar cell has comparable photovoltaic performance as CH₃NH₃PbI₃-based device but exhibits considerably slower degradation behavior, thus representing a paradigm by suggesting isotope-functionalized perovskite materials for better materials-by-design and more stable photovoltaic application.     

Enhanced electromagnetic microwave absorption of Fe/C/SiCN composite ceramics targeting in integrated structure and function

The Fe/C/SiCN composite ceramics were synthesized by polymer-derived method to obtain the integration of structure and functions. The electromagnetic waves (EMW) absorption properties at X and Ku bands were investigated. The addition of nano-sized Fe particles improved the magnetic loss and impedance matching, and the carbon nanotubes generated by the iron in-situ catalysis increased the internal relaxation polarization and interfacial polarization, which together improved the EMW absorption properties significantly. In particular, the Fe/C/SiCN-9 showed the optimum reflection loss (RL) of ?31.06 dB at 10.03 GHz with an effective absorption bandwidth (EAB, RL < ?10 dB) of 3.03 GHz at 2.51 mm, indicating the excellent EMW absorption properties of Fe/C/SiCN composite ceramics.     

Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics

In this work, we developed a novel system of isovalent Zr⁴⁺ and donor Nb⁵⁺ co-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics to enhance dielectric response. The influences of Zr⁴⁺ and Nb⁵⁺ co-substituting on the colossal dielectric response and relaxation behavior of the CCTO ceramics fabricated by a conventional solid-phase synthesis method were investigated methodically. Co-doping of Zr⁴⁺ and Nb⁵⁺ ions leads to a significant reduction in grain size for the CCTO ceramics sintered at 1060 °C for 10 h. XRD and Raman results of the CaCu₃Ti_3.8-xZr_xNb_0.2O₁₂ (CCTZNO) ceramics show a cubic perovskite structure with space group Im-3. The first principle calculation result exhibits a better thermodynamic stability of the CCTO structure co-doped with Zr⁴⁺ and Nb⁵⁺ ions than that of single-doped with Zr⁴⁺ or Nb⁵⁺ ion. Interestingly, the CCTZNO ceramics exhibit greatly improved dielectric constant (~10⁵) at a frequency range of 10²–10⁵ Hz and at a temperature range of 20–210 °C, indicating a giant dielectric response within broader frequency and temperature ranges. The dielectric properties of CCTZNO ceramics were analyzed from the viewpoints of defect-dipole effect and internal barrier layer capacitance (IBLC) model. Accordingly, the immensely enhanced dielectric response is primarily ascribed to the complex defect dipoles associated with oxygen vacancies by co-doping Zr⁴⁺ and Nb⁵⁺ ions into CCTO structure. In addition, the obvious dielectric relaxation behavior has been found in CCTZNO ceramics, and the relaxation process in middle frequency regions is attributed to the grain boundary response confirmed by complex impedance spectroscopy and electric modulus.     

放顶煤液压支架在土耳其IMABT煤矿现场的应用

通过对土耳其IMBAT煤矿地质条件的分析研究，结合多种选型计算方法的验证，最终选择了合适的设备，使该矿的开采效率得到较大提升。同时也扩大了我国的煤炭开采装备应用范围。根据在土耳其IMBAT煤矿现场多年的服务经验，将理论与实践相结合，就综采放顶煤液压支架在土耳其IMABT煤矿现场的应用进行了论述。     

镜铁山矿倾斜矿体上盘边角矿回采方案研究

镜铁山矿Ⅰ#矿体向下延伸时倾角由急倾斜变为倾斜，若继续按照急倾斜矿体的回采方式布置采切工程，将会在矿体上盘或者下盘处残留三角形边角矿，进而导致矿石损失率增大。为有效解决因矿体倾角缓化出现的三角区域矿体难以回收的问题，首先提出了脉内布置分段沿脉巷和沿矿岩边界布置分段沿脉巷两类回采方案，其中脉内布置分段沿脉巷回采方案设计了15°、30°、45° 3种不同中深孔边孔角布置方案；然后分别从中深孔施孔精度要求、中深孔施工适应性、对矿体条件适应性、生产效率等4个方面定性分析了不同回采方案的优劣性；最后整合生产效率、施工适应性、通风效果、井巷工程量、工期和成本等12个指标组成优选评价体系，采用层次分析法（Analytic Hierarchy Process，AHP）构建了倾斜矿体上盘边角矿回采方案层次分析优选模型。计算得到3种脉内布置分段沿脉巷与沿矿岩边界布置回采方案的最终评价值分别为0.213、0.201、0.198和0.388，结果表明：沿矿岩边界布置分段沿脉巷为最优回采方案。实践表明：优选出的方案在实践中取得了理想效果，经济效益显著，可满足该矿倾斜矿体上盘边角矿回采需求。研究结果可为类似开采条件矿山的边角矿回采提供有益参考。     

地表移动带范围内建构筑物安全可靠性分析

地表建构筑物位于在生产矿山地表开采移动范围内，如果按照一般圈定地表移动范围原则判断建构筑物的安全可靠性，结果是不安全或者预留保安矿柱可保证安全。为分析地表移动带范围内建构筑物安全可靠性，采用FLAC3D软件建立数值模拟模型，对矿区地表移动进行分析研究，并结合建构筑物的破坏等级评判标准，可以更加合理地判断地表移动范围内建构筑物的安全可靠性，对存在相似条件的矿山具有一定的借鉴意义。     

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.     

Measurement of chemical emission rates from cigarette butts into air

This study examined airborne emissions from cigarette butts for styrene, 2-methyl-2-cyclopenten-1-one, naphthalene, triacetin, and nicotine. Ten experiments were conducted by placing butts in a stainless steel chamber and measuring the chemical concentrations in chamber air. Emission rates were determined from the concentrations. Triacetin and nicotine concentrations were roughly 50% of initial concentrations after 100 hours, while concentrations of other chemicals decayed to less than 10% of initial concentrations within 24 hours. Initial emission rates per cigarette butt ranged from 200 to 3500 ng h⁻¹. Triacetin and nicotine emission rates at 25°C were 1.6 to 2.2 times higher than the rates at 20°C, while the emission rates of other chemicals at 25°C were 1.1 to 1.3 times higher than the rates at 20°C only during the first sampling period. The chemical concentrations and emission rates at 30°C were comparable or lower than the values at 25°C, possibly due to different batches of cigarettes used. The 24-hours emitted mass of nicotine from a cigarette butt at 25°C could be up to 14% of the literature reported nicotine masses emitted from a burning cigarette.