“铁盐+空气”催化氧化体系在绿色交叉偶联反应中的应用——推荐一个本科生科研训练项目

为深入开展创新创业教育与实践,培养学生创新创业能力,提高本科生人才培养质量,进一步推动创新创业教育改革,南开大学开展了“国家级大学生创新创业训练计划”项目。化学学院结合学科自身特点,践行科教融合、理论联系实际的培养方法,不仅能够引导本科生积极参加科研训练,还能将本科生的创新结果应用于实际生产中。实现“科研反哺教学”与“教学支撑科研”这样一个相互补充、相互促进的统一体。本文介绍了一组比较典型的本科生参与“国创”项目的例子,从项目准备入手介绍了该“国创”项目的具体实施过程、同学们所遇困难及收获心得等,希望将我们积累的一些经验与化学相关专业的同学分享,助力他们更好地完成创新项目。     

国家大学生创新性实验项目:新型F-N-P环三磷腈阻燃剂的合成及阻燃聚碳酸酯的应用*

南开大学化学学院为了提高本科生培养质量,通过开展“国创项目”创新综合实验,引导学生积极参加科研创新实践教学环节。介绍了在本科生有机化学综合实验中开设的新型F-N-P环三磷腈阻燃剂的合成及阻燃聚碳酸酯的应用实验,同时介绍了实验具体实施过程和教学效果。     

本科生创新实践能力的全过程培养探索——以北京科技大学化学与化学工程系为例

为了培养学生的创新实践能力,制订具有创新实践能力培养特色的本科生培养计划;搭建多种形式的创新实践平台;利用本科生导师制根据学生特点进行个性化培养;鼓励科研成果进课堂、进教材,发挥科研反哺教学的作用;建设一支具有创新实践能力和创新实践指导能力的师资队伍;采用在传授知识的同时培养学生创新意识和实践能力的教学方法;建立了能够考查学生创造性地分析问题、解决问题能力的考核模式。     

中国科学院成都有机化学研究所1847有机（药物）合成技术创新实验室

我实验室拥有近40余名研发专家与10余名在读研究生及其他科研人员,是“不对称合成与手性技术中心”的核心组成部分,是完全依靠市场机制与企业合作求得生存和发展的科研团体之一。先后负责承担了中科院“西部行动”计划、发改委重大项目、科技部“支撑计划”、中科院知识创新工程重要方向项目等多项国家级项目及几十项企业重大技术合作项目;     

高分子专业创新创业教育实践及实践基地建设研究

以我们学校高分子工程领域的人才培养模式为样本进行研究,探讨适合工科本科生及研究生培养的创新创业基地建设。通过对比分析国内创新创业实践教学基地建设研究,找出国内实践教学基地建设存在的问题,确定了解决这些问题的方法,从而使工科学生在理论知识和动手能力及创新思维积累方面得到一定的提高。培养出的本科生及研究生就业渠道拓宽。为企业培养了"留得住,用得上"的高分子材料工程实践和创新能力强的应用型高级人才。     

关于本科生科研能力培养的思考

在高等教育人才培养中对本科生进行科研能力的培养不仅是时代的要求,而且也是确保更高层次人才培养质量的基本保障。本文介绍与分析了我国现阶段高等教育开展本科生科研的意义与作用,并针对如何在研究型大学和地方综合性大学两类不同层次的大学中做好本科生科研提出了一些自己的认识,包括如何在本科生科研培养过程中树立端正的学风;应当将教学与科研相结合;如何处理好本科生外语能力的培养与科学研究的关系;建立本科生科研中的合作式学习模式;积极开展课外科技活动的意义和具体实践,合作式学习并探讨了其他国家本科生科研能力培养中值得借鉴的一些经验。     

中国科学院成都有机化学研究所1847有机（药物）合成技术创新实验室

我实验室拥有40余名研发专家与10余名在读研究生及其他科研人员,是“不对称合成与手性技术中心”的核心组成部分,是完全依靠市场机制与企业合作求得生存和发展的科研团体之一。先后负责承担了中科院“西部行动”计划、发改委重大项目、新科技部“支撑计划”、中科院知识创新工程重要方向项目等多项国家级项目及几十项企业重大技术合作项目;通过在市场上近20多年的艰苦创业及与国内众多医药化工企业通力合作,有数十个具有重大创新（专利）知识产权的医药产品已经或即将陆续进入生产和市场,已建立起自己的特点与品牌。     

基于“大学化学”的科创培育模式探索

“大学化学”注重基础理论也注重实验教学。在重视创造力和革新的“新工科”背景下，对基础知识进行拓展，与本科生科技活动关联，形成“课堂-微课题-竞赛”的科创培育模式，并将获得的创新实验案例反哺课堂。实践表明，此模式激发了学生的学习兴趣，达到了知识活学活用的目的，同时也培养了学生的科研创新能力。     

不对称合成与手性技术四川省重点实验室

中国科学院成都有机化学研究所1847有机（药物）合成技术创新实验室 我实验室拥有40余名研发专家与10余名在读研究生及其他科研人员,是“不对称合成与手性技术中心”的核心组成部分,是完全依靠市场机制与企业合作求得生存和发展的科研团体之一。先后负责承担了中科院“西部行动”计划、发改委重大项目、新科技部“支撑计划”、中科院知识创新工程重要方向项目等多项国家级项目及几十项企业重大技术合作项目：通过在市场上近20多年的艰苦创业及与国内众多医药化工企业通力合作,     

如何实现从高校基础化学课程到本科科研创新的跨越式发展——从学生角度分享高校科研创新成长经历

化学学科在高等教育阶段对人才的培养涉及多个方面,包括专业基础知识的掌握、研究理论的了解和各项实验技能的训练实践。其中,一个良好的科研训练环境非常重要,它不仅能让学生对专业知识进行实践、熟练掌握各种实验技能,还能对科学研究思维的培养起到作用。以2019级本科生参与科研实践和科创竞赛为主线,详细介绍了从大学初期进入课题组了解参与科学研究到成功申请“国家级大学生创新创业训练计划”的过程,以及期间参加科创竞赛的经历,通过分享经验与做法为即将参与本科科研创新训练的同学提供参考。     

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.     

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.     

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.     

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.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

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%).