β-二亚胺配体支持的铝胺化合物的制备及其催化ε-己内酯开环聚合的高效性能

成功合成了由β-二亚胺配体(L)支持的铝胺化合物(L)AlH(NMe2)2(L=HC(C(Me)NAr)2,Ar=2,6-iPr2C6H3)(1)。该化合物采用分步合成法进行制备,以n-BuLi与HNMe2反应生成的锂盐LiNMe2作为前驱体,进一步与(L)AlH2溶液共混通过消除LiH得到目标产物。通过核磁共振谱、元素分析、红外漫反射光谱和X射线单晶衍射确定了铝胺化合物(L)AlH(NMe2)2的组成与结构。该铝胺化合物中,金属Al中心同时形成Al-H和Al-NMe2基团,在催化ε-己内酯的开环聚合的反应中展现出了优异的催化活性。通过高效凝胶渗透色谱测定了所得聚合物的分子量和分子量分布。     

基于类salen配体的二苯基锡配合物的合成、抗肿瘤活性及其与DNA相互作用

利用类salen配体二苯乙二酮苯甲酰腙或二苯乙二酮水杨酰腙与二苯基二氯化锡反应,合成了2个二苯基锡配合物[(C_6H_5(O)C=N—N=C(Ph)—(Ph)C=N—N=C(O)—C_6H_5)_2SnPh_2(CH_3OH)]·3CH_3OH (1)和 [(o-OH—C_6H_4(O)C=N—N=C(Ph)—(Ph)C=N—N=C(O)—(o-OH—C_6H_4))_2SnPh_2(CH_3OH)]·CH_3OH (2),通过IR、~1H NMR、~(13)C NMR、~(119)Sn NMR、元素分析、HRMS 以及X射线单晶衍射等表征了配合物结构。测试了配合物1、2的热稳定性及其对癌细胞的体外抑制活性,发现配合物2对癌细胞NCIH460、HepG2、MCF7表现出略优的抑制活性。利用紫外可见吸收光谱、荧光猝灭光谱研究了配合物2与ct-DNA之间的相互作用,结果表明配合物以嵌入模式与DNA结合。     

大学基础化学教学中的知其所以然*

针对大学本科一年级基础化学如“化学概论”等课程教学中,学生对于不断出现的专业名词及物理化学含义的理解问题,以“焓”“熵”等外来词汇以及角动量l、能级分裂单位“Dq”等缩写为例,从专业名词来源开始讲解,使学生在学习过程中既知其然又知其所以然,更好地理解化学专业词汇,尤其是外来词汇的内涵与物理化学意义。     

N-(2-吡咯甲基)-1-苯基乙亚胺·二甲基铝的合成、结构及其催化丙交酯的活性

通过席夫碱配体N-（2-吡咯甲基）-1-苯基乙亚胺与三乙基铝按物质的量之比为1：1在无氧无水的条件下反应,合成了席夫碱铝的有机金属化合物N-（2-吡咯甲基）-1-苯基乙亚胺·二甲基铝。其结构分别用核磁氢谱、碳谱,元素分析和X射线单晶衍射技术进行了表征。铝化合物在催化外消旋丙交酯开环聚合反应中表现出了中等的活性并得到了以等规聚合为主的高聚物。     

A New Class of Amide Ligands Enable Cu‐Catalyzed Coupling of Sodium Methanesulfinate with (Hetero)aryl Chlorides

((2S ,4R )‐4‐Hydroxy‐N ‐(2‐methylnaphthalen‐1‐yl)pyrrolidine‐2‐carboxamide (HMNPC), an amide derived from 4‐hydroxy‐L ‐proline and 2‐methyl naphthalen‐1‐amine, is a powerful ligand for Cu‐catalyzed coupling of (hetero)aryl halides with sulfinic acid salts, allowing for first time the metal‐catalyzed coupling of (hetero)aryl chlorides and NaSO₂Me. A considerable number of (hetero)aryl chlorides worked well, providing the pharmaceutically important (hetero)aryl methylsulfones in good to excellent yields.     

Novel chiral multidentate P3N4-type ligand for asymmetric transfer hydrogenation of aromatic ketones

Novel chiral multidentate P₃N₄-type ligand has been synthesized and characterized by NMR and HRMS. Using i-PrOH as solvent and hydrogen source, asymmetric transfer hydrogenation of various ketones was investigated. The catalyst generated in situ from chiral multidentate aminophosphine ligand (R,R,R,R)-3 and IrCl(CO)(PPh₃)₂ exhibited highly catalytic activity and excellent enantioselectivity under mild conditions, achieving the corresponding chiral alcohols with up to 99% yield and 99% ee.     

组合肽配体库技术富集蛋白研究进展

低丰度蛋白是生物体中重要的活性物质,参与新陈代谢、转录和翻译等多种生理及病理过程,因此对低丰度蛋白的研究具有重要意义。组合肽配体库技术(CPLL)是富集低丰度蛋白的一种有效方法,通过CPLL富集作用可以实现低丰度蛋白的检测与鉴定。该文总结了CPLL应用于不同领域中(包括人体、动物源、植物源等蛋白研究方面)低丰度蛋白样品的富集研究,可为CPLL的进一步应用提供参考。     

Crown ether complexes of sodium and potassium 2-(benzotriazol-2-yl)phenolates: Synthesis and catalysis towards the ring-opening polymerization of rac-lactide

Crown ether complexes of sodium and potassium 2-(benzotriazol-2-yl)phenolates were synthesized and characterized. In the presence of BnOH these complexes are highly active catalysts for the controlled ring-opening polymerization of rac-lactide. The polymerizations are iso-selective and the P_m of polylactide reached 0.77 when the polymerization was performed in toluene at ?60°C; whereas heterorich-polylactide was obtained when the polymerization was carried out in CH₂Cl₂ or THF.     

The Quest for Mononuclear Gold(II) and Its Potential Role in Photocatalysis and Drug Action

The chemistry of gold strongly focuses on the ubiquitous oxidation states +I and +III. The intermediate oxidation state +II is generally avoided in mononuclear gold species. In recent years, gold(II) has been increasingly suggested as a key intermediate in artificial photosynthesis systems, with gold(III) moieties acting as electron acceptors, as well as in gold‐catalyzed photoredox catalysis and radical chemistry. This Minireview provides a concise summary of confirmed and characterized mononuclear open‐shell gold(II) complexes. Recent findings on structural motifs and reactivity patterns will be discussed. Exciting developments in the fields of photosynthesis, photocatalysis, and potential roles in medicinal chemistry will be outlined.     

3‐(Pyridin‐4‐yl)acetylacetone: CdII and HgII compete for nitrogen coordination

3‐(Pyridin‐4‐yl)acetylacetone (HacacPy) acts as a pyridine‐type ligand towards Cd^II and Hg^II halides. With CdBr₂, the one‐dimensional polymer [Cd(μ‐Br)₂(HacacPy)Cd(μ‐Br)₂(HacacPy)₂]_∞ is obtained in which five‐ and six‐coordinated Cd^II cations alternate in the chain direction. Reaction of HacacPy with HgBr₂ results in [Hg(μ‐Br)Br(HacacPy)]_∞, a polymer in which each Hg^II centre is tetracoordinated. In both compounds, each metal(II) cation is N‐coordinated by at least one HacacPy ligand. Equimolar reaction between these Cd^II and Hg^II derivatives, either conducted in ethanol as solvent or via grinding in the solid state, leads to ligand redistribution and the formation of the well‐ordered bimetallic polymer catena‐poly[[bromidomercury(II)]‐μ‐bromido‐[aquabis[4‐hydroxy‐3‐(pyridin‐4‐yl)pent‐3‐en‐2‐one]cadmium(II)]‐di‐μ‐bromido], [CdHgBr₄(C₁₀H₁₁NO₂)₂(H₂O)]_n or [{HgBr}(μ‐Br){(HacacPy)₂Cd(H₂O)}(μ‐Br)₂]_∞. Hg^II and Cd^II cations alternate in the [100] direction. The HacacPy ligands do not bind to the Hg^II cations, which are tetracoordinated by three bridging and one terminal bromide ligand. The Cd^II centres adopt an only slightly distorted octahedral coordination. Three bromide ligands link them in a (2 + 1) pattern to neighbouring Hg^II atoms; two HacacPy ligands in a cis configuration, acting as N‐atom donors, and a terminal aqua ligand complete the coordination sphere. Classical O—H…Br hydrogen bonds stabilize the polymeric chain. O—H…O hydrogen bonds between aqua H atoms and the uncoordinated carbonyl group of an HacacPy ligand in a neighbouring strand in the c direction link the chains into layers in the (010) plane.