土壤重金属迁移转化实验应用于环境化学实验教学的探索——以室内土柱淋滤模拟实验为例

设计了一套土壤淋滤模拟实验装置,并将其引入一个典型的环境化学实验中。在淋滤装置的上端加入一定浓度的重金属溶液,重金属在土柱中进行不同层位的迁移,从淋滤柱下端滤出,实现其在土壤中的迁移与转化。然后应用X射线衍射（XRD）光谱仪和电感耦合等离子体发射光谱仪（ICP-OES）分别测定土柱中不同深度处土壤矿物组成和重金属元素含量,并结合重金属元素含量测试结果分析探讨重金属元素的纵向迁移转化规律。该实验可引导学生进一步理解环境化学中关于土壤的基本理论知识,了解重金属在土壤中的迁移转化机制及相关测试仪器的基本操作方法与原理,提高学生的综合实验操作技能,激发学生科学研究的潜在能力,培养学生的科研创新能力。     

EDTA作为螯合剂应用于棕地修复的研究综述

乙二胺四乙酸(Ethylenediaminetetraacetic acid,简称EDTA)是一种高效的螯合剂,可以应用于棕地修复中,具体体现在棕地空间(土壤、水体和空气)中重金属污染物含量的测定、清除,促进环境中的微生物反应等方面。首先介绍棕地相关的概念,重点从以EDTA为螯合剂制备的化学淋洗制剂、电化学絮凝剂、络合纳滤剂及EDTA分析滴定法2个角度阐述了EDTA对于棕地修复的应用。结合一个棕地治理工作的成功案例,总结螯合剂EDTA和配位反应的使用在棕地修复中的效果和我国棕地治理的现状,可以为EDTA与其相关反应在棕地修复中的实践应用提供一些参考。     

以实际问题解决吸引学生主动选修化学——校本课程“化学与考古”的案例分析

提升化学对学生的吸引力是促使学生选修化学、落实化学核心素养的前提。以校本选修课程“化学与考古”为例,从现代技术、物质性质、实验装备、反应原理、工艺、生物化学等多角度用化学知识解决考古与文保疑难,将抽象的化学知识落实到考古事例中探讨,主动创设情境帮助学生体验化学的魅力,为普高教学中化学知识的实用化提供新的视角。     

化学钝化法修复重金属污染土壤研究进展

化学钝化修复是通过往土壤中加入钝化剂,以调节和改变重金属在土壤中的物理化学性质,使其发生氧化还原、沉淀、吸附、螯合、抑制或拮抗等一系列反应,降低其在土壤环境中的生物有效性和可迁移性,从而减少这些重金属元素对动植物的毒性.这种方法因投入低、效率高、修复快速、操作简单等优点,对大面积污染土壤的修复具有较好的应用前景.文中系统地综述了土壤重金属污染现状、危害、来源、特点及化学钝化修复技术的类型、作用机理、影响因素、修复实例,并分析了化学钝化技术的研究现状、存在的问题及未来的发展方向.     

中级化学实验课的设立与建设

1　开设的原因与思路　　随着教学改革的深入开展 ,我校化学系取消了原有的专业方向 ,化学专业的学生不再分专业方向 ,专业方向实验课自然也应统一。中级化学实验正是在这种背景下 ,将原设的无机、分析、有机、物化专门化实验课取消 ,而用中级化学实验代替 ,当然这种代替决不能是简单的加合 ,而应是组合成一个有机的整体。　　实验在化学学科中占有重要地位 ,开设专业化学实验的目的是为了培养学生应用基础理论的能力、提高学生的实验技能和培养学生解决实际问题的能力。与过去专门化实验相比 ,中级化学实验取消了那些验证性的实验 ,应该更…     

浅谈重金属元素在土壤中的迁移及黏土矿物对其修复作用

重金属元素在土壤中的存在形式有多种,且迁移能力各不相同,而影响重金属元素形态的因素是土壤p H、土壤植物根际环境,重金属元素迁移的过程还受到土壤类型、含水量以及土壤中有机和无机配体的影响。黏土矿物具有良好的吸附作用,它主要是通过离子交换、配合反应和共沉淀反应来修复土壤中的重金属污染。     

污染土壤重金属稳定化修复的综合性实验

添加不同种类改良剂对污染农田土壤进行有毒重金属的稳定化修复,内容包括土壤样品制备与培养、pH测定、重金属离子总浓度及有效态浓度测定。首先,学生需要在实验过程中熟练掌握电子天平、pH计、微波消解仪和电感耦合等离子体质谱的操作规程。其次,学生能够在课后利用固化率公式处理数据和评价不同改良剂对重金属的稳定化修复效果,并进行机理解析。本实验不仅可以加强学生对相关专业理论知识的理解和精密化学仪器的使用,还能够培养学生综合运用所学专业知识解决实际应用问题的能力,并进一步激发学生探索化学前沿新知,从而达到拓展创新的培养目标。     

蒽与马来酸酐Diels-Alder反应的量化计算研究——介绍一个计算化学实验

蒽与马来酸酐的Diels-Alder反应是基础有机化学实验课程中普遍开展的一个经典实验。本文推荐蒽与马来酸酐Diels-Alder反应的计算化学实验,该实验采用Gaussian 16程序中的密度泛函方法对蒽和马来酸酐Diels-Alder反应的反应机理进行了研究。旨在通过本实验激发学生对有机化学和计算化学的兴趣,加深学生对化学学科的理解,提升学生在科研工作中学以致用的能力。     

涡旋提取-改进BCR法测定土壤中重金属的化学形态

土壤中重金属的化学形态更能表明其迁移性和生物毒性。传统的重金属化学形态检测方法BCR法由于其提取时间长,影响检测效率。采用涡旋提取对传统BCR法进行方法优化,对土壤中Cu、Zn、Pb、Cd、Ni、Cr等6种重金属元素化学形态进行了实验分析。研究了涡旋转速、涡旋时间以及涡旋提取的方法精密度与准确度。结果表明,当涡旋转速为2500rpm,酸可交换态涡旋10min,可还原态涡旋10min,可氧化态涡旋5min时,涡旋提取效果良好。采用土壤标准物质对方法的适用性进行了验证,6种元素的检出限在0.4?32μg/kg,测定值均在标准值范围内,相对标准偏差在0.3%?5.5%之间。涡旋提取-改进BCR法分析速度快,灵敏度高,能满足同时测定土壤中多种金属元素化学形态的检测要求。     

基于绿色化学理念的苯甲醛与安息香的相互转化

为了在基础教学实验中引入绿色化学理念以及强化氧化还原反应操作,本文设计了苯甲醛和安息香的相互转化实验:以苯甲醛为原料经维生素B1催化得到安息香,再用硼氢化钠还原安息香得到二苯乙二醇,二苯乙二醇用新型绿色催化剂NaMnOx氧化回到苯甲醛。通过氢核磁共振(1H NMR)对氧化还原反应的产物结构进行了鉴定,液相色谱分析结果表明氧化反应转化率达到90%以上。通过这一循环转化反应的实现,一方面树立了学生的绿色化学理念,另一方面加强了氧化及还原反应的操作训练,在进一步锻炼学生实验能力的同时,使其对化学反应的认知与评价更加完整。     

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.     

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.