基于交叉优势特色学科的大学化学创新实验教学体系构建与实践*

以大学化学与农林优势学科交叉融合为教学改革任务,构建“基础+模块”的大学化学实验创新教学体系,分别开展“项目式”教学、“科教融合”教学、“产学研”教学、“混合式”教学、“虚实结合”教学等五位一体的实验教学实践,并建立化学创新实验课程评价新体系。本化学创新实验教学体系改革明显提高了学生的实践动手能力与综合素质,为深入开展化学基础学科与农林优势学科交叉融合教学奠定一定基础。     

本科化学专业实验教学模式的改革与实践

以培养学生的创新思维和实践能力为目标,对本科化学专业实验课程体系与内容进行了全面改革。将化学学科中传统的无机化学实验、有机化学实验、分析化学实验、物理化学实验4大实验的内容设计优化成基础实验、综合设计实验、研究创新实验3个实验模块,搭建了基础型、提高型、创新型3个能力训练层次和1条毕业设计/专业实习能力训练主线,构建了具有地方本科院校特色的化学专业 “331”实验课程新体系,实现了课程结构的模块化,实验内容的层次化和教学科研的一体化。实践证明,通过改革与实践激发了学生的学习兴趣和主动性,动手能力、分析问题和解决问题的能力都有一定程度的提高。     

基于创新能力培养的化学专业本科实验教学新体系的构建与实践

课程体系是人才培养的载体。为了更好地培养拔尖创新人才,南京大学化学国家级实验教学示范中心依据化学学科的特点和发展趋势,以科学内容的内在联系和研究规律为主线构建了“化学实验基础?化学合成与表征+化学原理与测量?化学功能分子实验+化学生物学综合实验+基于项目的研究实验”实验课程新体系,按照一流课程建设要求(高阶性、创新性和挑战度)对实验教学内容进行了优化,并建立起与之相适应的实验教学平台。新课程体系综合考虑了化学一级学科的整体性和关联学科的交叉性,在南京大学化学化工学院“拔尖计划”和“强基计划”学生中实施,教学效果显著。     

化学课程结构的横向衔接性与创新思维

化学课程结构的横向衔接性包括化学教科书内容的横向衔接性和化学课程设置类型的横向衔接性。从化学教科书内容的横向衔接性分析,化学学科在培养学生的创新思维、提高学生的实践能力上发挥着重要的作用;从化学课程类型的横向衔接性分析,化学学科有利于增强学生探索未知世界的兴趣和能力等。在义务教育阶段的理科综合不能普及的情况下,化学课程结构的横向衔接性对于培养学生的创新思维和实践能力具有独特的作用。     

化学生物学实验课程体系的建立

将化学学科教师的学术研究与本科生的化学生物学实验课程建设紧密结合,建立化学生物学创新实验课程体系。     

跨学科项目教学案例*——魔力沙

以魔术表演用的沙子为素材,开发了适用于高中选修课程“发展中的化学学科”的具有跨学科性的项目教学案例,该项目弱化理论分析环节后也可以用于初中科学实践活动课程。项目引导学生在更宽广的学科背景下认识物质及其变化的规律,帮助学生拓展视野和思路,综合运用化学、物理等学科的知识分析解决有关问题,发展“宏观辨识与微观探析”“科学探究与创新意识”“科学态度与社会责任”等化学学科核心素养。     

介绍一个针对非化学专业的化学科普实验——头发中微量元素的测定

结合中国科学技术大学的学期改制,在夏季学期面向全校非化学专业的低年级本科生开设了“生活中的化学科普实验”公选课程,课程内容多为与生活密切相关的热点问题。“头发中微量元素的测定”是其实验项目之一。该实验将学生自己的头发作为分析对象,合理地设计教学内容和实验步骤,以期激发学生对化学实验的兴趣,提高学生对化学学科的认识。     

发展学生化学学科核心素养离不开化学实验

化学实验是化学教学的重要组成部分,不仅具有教育教学功能,而且具有发展学生化学学科核心素养的功能。从认识层面、实践层面和价值追求层面来看,化学实验在发展学生科学本质观、科学实践观和科学价值观方面均发挥着不可替代的功能。教师可以利用化学实验史实呈现真实的科学发现过程,发展学生的科学本质观;可以通过引导学生对化学实验现象的观察和基于实验事实证据的推理发展学生“宏观辨识与微观探析”“证据推理和模型认知”素养;可以通过开展化学实验探究,引导学生拓宽认识视角和认识思路,发展学生“科学探究与创新意识”素养;可以通过化学实验评价发展学生的“科学态度和社会责任”素养。     

高师无机化学实验教学的改革与学生综合能力的培养

化学是一门实验科学,无机化学实验又是高师化学系学生学习的第一门专业实验课程,它关系到学生能否掌握无机化学知识和有关技能,能否有效地掌握科学思维方法、养成科学精神和品质,因此有必要加强和改进无机化学实验课程的教学。根据学科的特点和师范性的要求,高师化学教育改革必须以进取和创新为主导,因材施教,教书育人,重视发掘人的潜能,重视素质教育。     

基于香港高中化学学科校本评核的教、学、评活动设计*

化学实验评价对于培养学生的创新意识和化学学科实践能力具有重要意义,尝试借鉴香港高中化学学科校本评核方法设计“教、学、评”活动促进学生化学学习和实验能力发展。介绍了香港高中化学学科校本评核框架及准则,以人教版《化学1》(2003年课标本)“铁盐和亚铁盐”为例,结合2017年课标设计实验评价量表,通过实验活动串联教学任务,以期实现教、学、评目标。通过评价反馈,促使更加科学、全面地评估学生的实验能力表现,为教师的化学教学实践提供改进依据。     

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%.     

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.     

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.