VESTA软件在晶体结构教学中的应用

以晶体结构教学为例,引导学生利用VESTA软件搭建典型晶体的晶胞模型可大大激发学习兴趣,降低认知难度。通过金刚石、金属镁、金属铜、氯化钠、萤石等晶胞模型的搭建,空间充填模型的旋转与观察,晶面及配位多面体的插入,帮助学生突破原子分数坐标、空间利用率计算、晶体空隙的洞察等难点,是VESTA支撑下的具体教学策略。学生在体验真实建模的过程中加深了对认识原型的理解,收获了知识与快乐,发展了证据推理与模型认知这一化学学科核心素养。     

基于Unity3D交互软件辅助金属晶体结构教学

基于中学晶体教学特点和教学实际的疑难,开发了基于Unity 3D的晶体教学的交互软件,该软件具有三维模型展示、晶体交互操作等功能,实现对金属晶体的堆积方式、晶胞结构、晶胞参数、晶胞的配位数以及空间利用率等知识点的可视化三维教学。软件可在手机、平板、电脑上应用,方便课内外学习。教学实践表明,该软件能改善教学情况。     

利用三维虚拟技术突破物质结构教学*——从演示型工具到探索型工具的转变

针对物质结构教学的抽象性,开发了一套基于三维虚拟技术的物质结构教学软件,可对结构模型进行旋转、平移、缩放、切割、镜像、插入或删除原子(团)及启停预先设置的动画等操作,强大的交互功能不仅能对分子或晶体结构如构造异构、立体异构、晶体的堆积方式、晶胞的划分、配位数、晶体结构中的空隙及空间利用率等问题进行效果极佳的可视化教学,另一方面,通过对B₁₂与C₆₀分子空间构型转变的探究揭示数学构型的重要性,通过对六方晶胞占有原子个数的探究修正晶胞模型,通过对金属晶体的4种基本堆积方式成因的探究提出“半密置层”概念来完善紧密堆积规律等案例,展示出三维虚拟技术在微观结构探索发现方面的巨大潜力。     

“多角度欣赏面心立方晶胞”教学设计*

尝试利用“火花学院”App等在线交互资源,引导学生从立体几何及密置层堆积模型视角,观察、描述、绘制面心立方晶胞的正四面体填隙、正八面体填隙、三视图和沿体对角线投影图像,加深学生对以面心立方晶胞结构为基础的CaF₂→金刚石晶胞、NaCl→钙钛矿晶胞结构的理解;再结合新型材料透明镁铝尖晶石晶体结构的探讨,了解晶体制备中的掺杂改性等常用方法,发展学生的微观探析能力和科学创新意识。     

交互3D技术在物质结构教学中的应用

介绍了交互3D技术在物质结构教学中的设计与应用,采用3d max制作三维模型和Virtools Dev中应用行为模块控制三维模型构成交互3D相结合,详细地描述了动态控制三维模型的方法,从而形成灵活、交互的三维作品。在化学多媒体教学中,可形象地模拟物质结构中的分子空间结构、晶胞堆积、晶体结构、原子杂化等相关微观知识,有利于物质结构的教学,提高教学效率。     

“发现”密堆积:基于3ds MAX软件的金属晶体教学设计

利用3ds MAX软件对金属晶体进行实时三维建模,在课堂上引导学生从简单立方晶胞开始,采用“修改-试错-验证”模式,逐步构建出立方晶系的所有晶胞。使学生在好奇心驱动下逐步理解并自主“发现”知识,探究密堆积的特点与条件,最终建立晶胞结构与堆积的关系。通过学生的主体参与,将知识传授与能力培育相融合,提升学生化学学科核心素养。     

Materials Studio软件辅助中学化学教学*——以晶体结构为例

引入一种新的化学软件--Material Studio(MS),利用其晶体结构数据库和立体演示功能辅助晶体结构教学,并设计了典型化合物晶胞结构以及金属晶体晶胞堆积的演示实例和教学过程。MS软件的晶体结构演示功能简单易学,能帮助学生更好地掌握晶体结构知识点,实现个性化教学和学生自主学习,提高课堂教学效率。     

“素养为本”的化学课堂教学*——以“原子晶体”为例

基于“素养为本”视角,以“原子晶体”的教学为例,对教学主题内容、教学现状及学情进行分析;以发展学生化学学科核心素养为主旨确定教学目标;以“微粒-微粒间的相互作用-物质的聚集状态-物质性质”的认识思路为主线,以“模型认知,建构概念-证据推理,归纳性质-微观探析,探究结构-科学史实,揭示价值”的任务型教学流程,达到落实并发展学生化学学科核心素养的目的。     

“电离与离子反应”的单元教学设计与实施*——食盐精制:从微观角度看粗盐中可溶性杂质的去除

在“食盐精制:从微观角度看粗盐中可溶性杂质的去除”的单元教学中,通过初识粗盐中的杂质、微观角度看氯化钠、微观角度看粗盐溶液、微观角度认识除杂方法、设计除杂方案并实施等活动,促进学生理解与应用电离、离子反应等核心概念,引领学生解决真实问题,形成解决除杂实验问题的基本思路,实现能力素养的发展。经过多轮次教学改进,结合教学实践及其教学效果抽提出“聚焦核心概念和学生必做实验,实现认识能力的进阶与实际问题解决过程高度融合”“通过学科实践及实验探究,建立宏观、微观、符号关联,突出证据推理,构建思维模型”“通过持续性评价活动,外显学生的前概念,促进概念转变,形成化学学科思维方式”等教学策略。     

基于化学学科核心素养的初高中衔接教学——初三化学“金属的化学性质”

“金属的化学性质”是初高中化学学习的重要内容,该部分内容涉及到重要的化学观念和化学学科核心素养,如元素观、转化观、微粒观、STS观,以及宏观辨识与微观探析、证据推理与模型认知素养。但是初三学生认知水平受限,在教学中不能深入电子转移的微观角度,不能充分认知模型、应用模型。为弥补这一问题,本研究基于化学学科核心素养,进行“金属的化学性质”的初高中衔接教学研究。     

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.     

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%).     

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.     

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.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.