纳米银、金溶胶的电化学合成及其基本胶体性质——物理化学综合实验设计

电化学和胶体体系基础理论是大学本科物理化学学习的重要内容。通过综合化学实验设计,以直接电化学还原方法制备纳米银、金溶胶,利用紫外-可见光谱分析溶胶粒子的特征吸收光谱,并运用循环伏安法探讨表面活性剂的稳定作用和纳米金属溶胶的形成机理,从而提高学生的基础知识综合运用能力与综合实验技能,适合在大学化学及其相关专业的综合化学实验中推广。     

K2GeF6:Mn荧光粉的化学共沉淀合成、结构测定与发光性能研究——介绍一个研究型综合实验

介绍一个大学化学研究型综合实验——K2GeF6:Mn荧光粉的化学共沉淀合成、结构测定与发光性能研究。本实验结合氧化还原与化学共沉淀法制备K2GeF6:Mn荧光粉,借助XRD和SEM对粉体进行结构表征,并利用荧光光谱仪测试分析其发光性能,探究激活剂含量和反应温度对粉体结构与性能的影响,获得可应用于商业白光LED的红色荧光粉。通过该实验的设计与实施,使学生在掌握基本实验技能的同时,能够结合基础理论知识解释实验原理、分析实验现象,并进一步提升学生的科学研究思维和综合运用知识的能力。     

超分子组装体动态重构综合实验

为提高化学及相关专业本科生对超分子化学及耗散结构的认知并锻炼其大学化学综合实验技能，设计了基于鸟苷5’-单磷酸二钠盐与尿素-脲酶计时反应的超分子组装体动态重构综合实验。本实验主要包括基于计时反应的非平衡超分子组装体系构建方法、结构表征、组装体动态重构机制探究等内容。通过科教融合的形式提高学生对科学研究的兴趣，培养学生科学思维；通过本实验的实践，可提升学生综合技能。     

表面活性剂溶致液晶的表征及相图绘制

该实验以离子型表面活性剂C14TAB-水二元体系为研究对象,通过偏光显微镜和目视观察法详细研究体系的各向同(异)性、双折射、偏光织构等光学性质和相行为,利用小角X射线散射(SAXS)技术表征溶致液晶相的结构和参数,并绘制其二元相图。该实验在原有综合化学实验的基础上拓展研究体系,降低实验成本,提升实验准确性,可帮助学生在了解溶致液晶表观性质的基础上,进一步认识其微观结构,掌握表征技术的原理和方法,激发学生对物理化学实验的兴趣,有助于学生科学逻辑思维的拓展和实验技能的提高。     

电子废弃物中金元素的绿色溶解与提取

电子废弃物中含有Au、Pt、Pd、Ag等多种贵重金属,其处理处置的无害化、资源化成为目前一项重要课题。本文通过使用安全的试剂来溶解金,从而达到从含金废弃物中回收金的目的,说明利用配体与金形成配合物从而有效降低溶金电极电势的化学原理。普及科学原理,树立科学理念。介绍电子废弃物处置的常识,普及绿色化学的观念,避免新的污染与危险,树立环境保护的观念。     

芦丁的提取鉴定及不同剂型与体内释放相关性的研究——制药工程相关专业综合创新实验设计

国家大学生创新性实验计划是高等学校本科教学"质量工程"的重要组成部分。本文介绍了基于PBL法设计和开设的"芦丁的提取鉴定及不同剂型与体内释放相关性的研究"综合创新实验。通过本实验,学生体验了查阅文献、了解实验原理、确立研究思路和策略、制备产品、表征性能、处理数据、分析讨论、撰写实验报告等环节,掌握了天然产物的提取和精制、胶囊和片剂的制备、物质的化学反应性质、药物的体内释放性研究等相关知识。实践表明,本实验选题针对性强,有助于提高学生学习的积极性、主动性和综合实验技能,有利于培养学生的创新意识和科学精神。     

水参与制氢的Cu-P体系研究

研究了水参与的Cu-P氧化还原体系制氢过程。考察了Cu/P物质的量比、反应温度、酸度、外加Cu单质等对氢气产率的影响,设计了Cu的循环利用和P的转化利用过程,实现了Cu-P体系的绿色化过程。结果表明,通过调控Cu/P物质的量比和反应温度等因素可以控制反应过程中生成的氢原子转化为氢气的量,在以0.20 g五水硫酸铜为基准物的Cu2+/H2PO-2物质的量比为0.05和95℃反应条件下可获得大于反应计量比的18.6 mL氢气;酸性条件下H2O2氧化单质Cu可以实现Cu的10次循环利用;制氢过程生成的亚磷酸氢根可以用Ca(OH)2处理转化为新型防锈剂CaHPO3·H2O,该防锈剂用红外光谱(FT-IR)和X射线衍射(XRD)得到了表征。     

氮化物荧光粉Sr2Si5N8:Eu2 与纤维素复合农用转光材料制备与表征——化学相关专业研究性综合实验设计

结合新型生态农业应用功能材料和光学农业背景下化学相关专业的特点,开设“氮化物荧光粉Sr2Si5N8:Eu2 与纤维素复合农用转光材料制备与表征”研究性综合实验项目,通过实验原理阐述、研究思路和方法的确立、材料制备、测试表征、数据处理等环节,使学生充分掌握专业中与化学相关的多门课程内涉及的光学材料发光过程、纤维素溶解、复合材料制备、光谱表征及分析、力学性能分析等关键知识点。实践表明,该实验项目选题针对性强,有助于提高学生的综合实验技能,有利于培养学生的基本科研素养,从而达到了提高教育和教学质量的目的。     

Sr_2Si_5N_8∶Eu~(2+)与纤维素复合农用转光材料制备与表征——化学相关专业研究性综合实验设计

结合新型生态农业应用功能材料和光学农业背景下化学相关专业的特点,开设"氮化物荧光粉Sr2Si5N8∶Eu2+与纤维素复合农用转光材料制备与表征"研究性综合实验项目,通过实验原理阐述、研究思路和方法的确立、材料制备、测试表征、数据处理等环节,使学生充分掌握专业中与化学相关的多门课程内涉及的光学材料发光过程、纤维素溶解、复合材料制备、光谱表征及分析、力学性能分析等关键知识点。实践表明,该实验项目选题针对性强,有助于提高学生的综合实验技能,有利于培养学生的基本科研素养,从而达到提高教育和教学质量的目的。     

电沉积Bi2Te3基薄膜的电化学阻抗谱研究

以不锈钢为基底,利用电化学沉积方法制备Bi2Te3基薄膜材料,并采用X射线衍射技术、电子探针微观分析等方法对薄膜进行结构和成分表征,通过电化学阻抗谱技术对不锈钢表面Bi2Te3的电化学沉积机理进行了初步探讨.结果表明Bi-Te和Bi-Te-Se体系具有相似的电化学沉积机理,即Bi3+和2HTeO+或H2SeO3首先被还原为Bi单质和Te或Se单质,然后Bi单质与Te或Se单质反应生成Bi2Te3基化合物,而Bi-Sb-Te体系中,2HTeO+首先被还原为Te单质,生成的Te再与Bi3+和Sb(III)反应生成Bi2Te3基化合物,三种体系的沉积都受电化学极化控制.     

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%).     

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.     

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.