高分子材料基因组——高分子研发的新方法

材料基因组旨在将计算工具、数据库和实验工具有机结合,缩短研发时间,提高材料研发效率.高分子材料因其结构独特性和复杂性阻碍了材料基因组在高分子材料领域的发展.目前,国内外学者在高通量筛选高分子化学结构策略和构建性能预测方法等方面开展了尝试,并取得了一些成果.本文总结和评述了当前利用代理量方法和机器学习预测模型实现高分子材料基因组的进展,利用可计算的量代理宏观性能的代理量法和利用机器学习模型预测材料性能的方法在一定程度上克服了高分子复杂性的影响.在此基础上,系统地介绍了数据挖掘或模型构建的方法以及运用这些模型筛选不同类型高分子的思路,着重探讨了方法构建和材料筛选背后的思想以及对各类问题的解决措施.最后,探讨了当前高分子材料基因组发展中所面临的主要挑战,并展望了高分子材料基因组的未来发展方向.     

材料基因工程技术在分子筛领域中的应用

材料基因工程是近年来材料领域兴起的前沿技术, 其基本理念是融合材料高通量计算、 高通量实验和数据技术加速新材料的设计和研发. 分子筛作为一种重要的化工材料, 因其良好的热稳定性、 较高的比表面积、 独特的孔道结构及可调变的元素组成和酸性, 在气体吸附、 分离、 异相催化和离子交换等工业领域应用广泛. 近年来, 融合高通量计算、 高通量实验和数据库技术的材料基因工程技术正逐步应用于分子筛研发等领域: 高通量计算能够从理论上预测并筛选出具有优异性能的分子筛合成目标、 高通量实验显著提升了分子筛材料合成与表征的效率、 数据库技术则为未来挖掘分子筛材料的合成规律与构效关系奠定了数据基础. 本文主要从这3个方面阐述材料基因工程技术在分子筛材料研发领域的应用及进展, 总结以功能为导向、 定向设计和构筑分子筛材料所面临的机遇与挑战, 并对材料基因工程技术在分子筛领域的前景进行了展望.     

机器学习在设计高性能锂电池正极材料与电解质中的应用

随着大数据和人工智能的发展以及机器学习(ML)与化学学科领域的交叉，ML技术与电池领域的结合激发了更有前途的电池开发方法，尤其在电池材料设计、性能预测、结构优化等方面的应用愈加广泛。应用ML可以有效地加速电池材料的筛选进程并预测锂电池(LBs)的性能，从而推动LBs的发展。本文简要介绍了ML的基本思想及其在LBs领域中几种重要的ML算法，之后讨论了传统模拟计算方法与ML方法各自的误差表现及分析，借此来提高LBs专家对ML方法的理解。其次，重点介绍了ML在电池材料实际开发中的应用，包括正极材料、电解质、材料多尺度模拟及高通量实验(HTE)等方面，借此介绍ML方法在电池领域应用的思想和手段。最后，总结了ML方法在锂电池领域中的研究现状并展望了其应用前景。本综述旨在阐明ML在LBs开发中的应用，并为先进LBs的研究提供借鉴。     

量子机器学习在催化化学研究中的应用

量子机器学习融合了量子化学与机器学习的优点,具有比传统密度泛函理论更快的计算速度和更高的准确性.量子机器学习可为复杂、多维、多尺度的催化化学提供更智能和有效的研究方式,通过训练可靠的数据及建立合理的模型和算法,快速、准确地预测最优的催化剂设计参数、最佳的催化剂材料的合成方法和反应条件、以及催化剂结构和性能之间的关系.作者就量子机器学习应用于催化材料的设计、催化反应性能和催化反应机理三方面的发展趋势进行了概述.     

基于机器学习势函数的熔盐体系分子动力学研究进展

熔盐是一类具有重要应用价值的熔融态材料,然而其微观结构与宏观性质之间的关系尚未完全探明,因此开展针对熔盐体系的分子动力学研究具有重要意义.针对高温熔盐体系的分子动力学研究以往主要依赖于传统分子动力学中力场的开发和第一性原理分子动力学的发展.近年来得益于机器学习和神经网络的加速发展,针对熔盐体系的机器学习势函数的开发工作取得了显著进展,其在探索熔盐配位化学和预测物理性质方面表现优异.本文首先梳理了熔盐领域内常用的分子动力学方法,重点介绍了机器学习势函数的发展现状;然后总结了机器学习势函数在熔盐研究方面的应用进展;最后展望了机器学习势函数在该领域的应用前景,并对可能存在的问题给出了建议.     

从催化导向性基础研究到工业应用的若干创新思路与实践——庆祝闵恩泽先生九十华诞

闵恩泽先生曾经指出:开展导向性基础研究对研发新技术及其实现工业应用至关重要.将高性能催化材料和化学工程技术的结合是石油化工技术创新的重要途径之一.在传统的石油化工领域引入和集成新材料、新工艺与新过程,可有力地推动石油化工技术的发展.本文对近年来在多孔催化新材料及若干石油化工关键催化技术的创新实践进行总结,包括多孔复合催化新材料与工业催化反应的结合、绿色反应工艺与催化剂、过程耦合与强化等几个方面,凝练了材料科学与化学工程结合与应用的创新思路.     

水滑石(LDHs)及其衍生物在生物医药领域的研究进展

生物医学涉及到人类健康相关的多个领域: 临床医疗、公共卫生、医药研发等多个方面. 其中在医药研发领域, 基于插层结构的纳米药物载体的研发已经成为重要发展方向之一. 水滑石(LDHs)及其衍生物具有成本低、合成简单、载药高效、细胞膜透过率高、生物相容性好、易降解等优点, 在生物医药领域得到了广泛关注. 本文主要介绍了LDHs及其衍生物的制备方法, 以及在抗菌治疗、生物成像和肿瘤治疗等方面的应用. 此外, 还简述了LDHs材料的规模化生产方法和现状, 进一步分析了LDHs的实际应用前景. 最后, 对LDHs材料在生物医药领域的未来发展方向进行了展望.     

机器学习结合密度泛函理论计算在材料科学中的研究进展

近年来,材料科学研究中密度泛函理论(DFT)计算与机器学习相结合的方法呈现爆炸式增长的趋势。本文综述了密度泛函理论(DFT)及其高通量方法产生的大量计算数据与机器学习相结合的原理和意义,从DFT计算的基本原理出发,重点介绍了机器学习(ML)方法的流程、常用的算法及其在催化材料预测热门研究方向中的应用,最后剖析了这个新兴领域目前存在的研究问题、挑战以及未来的发展前景。     

有机硼酸锂盐及亚硫酸酯类功能电解质材料

随着锂离子电池对高安全性、高容量、高功率等性能的技术需求,新型功能电解质材料的研究开发成为锂离子电池新材料领域研发工作的重点.本文对面向锂离子电池应用的功能电解质材料锂盐和添加剂的最新研究进展作了较为全面的阐述,其中重点介绍了本研究团队近年来在面向改善锂离子电池安全性能、提高其温度适应性、增强电解质与电极材料相容特性等...     

锂离子电池正极材料的第一性原理

锂离子电池的发展主要依赖于电极材料的突破,解决现有电极材料存在的问题和预测新型未知材料是提高锂离子电池性能的关键,而第一性原理计算的出现能够较好地满足这一需求.本文介绍了第一性原理计算在锂离子电池正极材料研究方面的原理和应用,对该原理在正极材料的平均嵌锂电压计算、嵌/脱锂机理、结构稳定性研究及新材料预测等方面的应用进行了详细论述,并指出了这一理论计算工具在电池材料设计过程中的重要性和局限性.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.