Structurally Modelling the 2-His-1-Carboxylate Facial Triad with a Bulky N,N,O Phenolate Ligand

We present the synthesis and coordination chemistry of a bulky, tripodal N,N,O ligand, Im^Ph2NNO ^{t Bu} ( L ), designed to model the 2-His-1-carboxylate facial triad (2H1C) by means of two imidazole groups and an anionic 2,4-di-tert-butyl-subtituted phenolate. Reacting K-L with MCl₂ (M = Fe, Zn) affords the isostructural, tetrahedral non-heme complexes [Fe(L)(Cl)] ( 1 ) and [Zn(L)(Cl)] ( 2 ) in high yield. The tridentate N,N,O ligand coordination observed in their X-ray crystal structures remains intact and well-defined in MeCN and CH₂Cl₂ solution. Reacting 2 with NaSPh affords a tetrahedral zinc thiolate complex, [Zn(L)(SPh)] ( 4 ), that is relevant to isopenicillin N synthase (IPNS) biomimicry. Cyclic voltammetry studies demonstrate the ligand's redox non-innocence, where phenolate oxidation is the first electrochemical response observed in K-L , 2 and 4 . However, the first electrochemical oxidation in 1 is iron-centred, the assignment of which is supported by DFT calculations. Overall, Im^Ph2NNO ^{t Bu} provides access to well-defined mononuclear, monoligated, N,N,O-bound metal complexes, enabling more accurate structural modelling of the 2H1C to be achieved.     

Stability of AgIII towards Halides in Organosilver(III) Complexes

The involvement of silver in two-electron Ag^I/Ag^III processes is currently emerging. However, the range of stability of the required and uncommon Ag^III species is virtually unknown. Here, the stability of Ag^III towards the whole set of halide ligands in the organosilver(III) complex frame [(CF₃)₃AgX]⁻ (X=F, Cl, Br, I, At) is theoretically analyzed. The results obtained depend on a single factor: the nature of X. Even the softest and least electronegative halides (I and At) are found to form reasonably stable Ag^III−X bonds. Our estimates were confirmed by experiment. The whole series of nonradiative halide complexes [PPh₄][(CF₃)₃AgX] (X=F, Cl, Br, I) has been experimentally prepared and all its constituents have been isolated in pure form. The pseudohalides [PPh₄][(CF₃)₃AgCN] and [PPh₄][(CF₃)₃Ag(N₃)] have also been isolated, the latter being the first silver(III) azido complex. Except for the iodo compound, all the crystal and molecular structures have been established by single-crystal X-ray diffraction methods. The decomposition paths of the [(CF₃)₃AgX]⁻ entities at the unimolecular level have been examined in the gas phase by multistage mass spectrometry (MSⁿ). The experimental detection of the two series of mixed complexes [CF₃AgX]⁻ and [FAgX]⁻ arising from the corresponding parent species [(CF₃)₃AgX]⁻ demonstrate that the Ag−X bond is particularly robust. Our experimental observations are rationalized with the aid of theoretical methods. Smooth variation with the electronegativity of X is also observed in the thermolyses of bulk samples. The thermal stability in the solid state gradually decreases from X=F (145 °C, dec.) to X=I (78 °C, dec.) The experimentally established compatibility of Ag^III with the heaviest halides is of particular relevance to silver-mediated or silver-catalyzed processes.     

Monodentate AIEgen Anchored on Metal‐Organic Framework for Fast Fluorescence Sensing of Phosphate

Herein, a novel sensor (TPE‐UiO‐66) was designed via anchoring monodentate tetraphenylethylene (TPE) onto UiO‐66 framework. The combination of the distinct aggregation‐induced emission (AIE) of TPE and the easy replacement of monodentate linker by guest phosphate, makes TPE‐UiO‐66 an ideal platform for sensing HPO₄^2–. Experimental results indicate that TPE‐UiO‐66 can selectively sense HPO₄^2– from other common anions. The limit of detection (LOD) can reach to 5.56 μmol·L^–1 and more importantly, TPE‐UiO‐66 also exhibits an ultra‐fast equilibrium response of 2 min, far faster than those of other sensors especially for UiO‐66‐NH₂. The combination of experimental analysis and density functional theory (DFT) calculations demonstrates that the high selectivity, high sensitivity and fast response of HPO₄^2– detection by TPE‐UiO‐66 can be attributed to the stronger coordination interactions of HPO₄^2– with Zr‐O cluster of UiO‐66 than that of TPE molecule. This study not only provides a potential probe for phosphate, but also represents a novel strategy to design stimuli‐responsive fluorescent MOF‐based sensors via using monodentate AIEgens.     

Organocatalytic asymmetric [3 + 3] annulation of isatin N,N'-cyclic azomethine imines with enals: Efficient approach to functionalized spiro N-heterocyclic oxindoles

An unprecedented chiral secondary amine-catalyzed [3 + 3] annulation of isatin N,N'-cyclic azomethine imines with α,β-unsaturated aldehydes was developed. This strategy allowed the construction of structurally novel spiro N-heterocyclic oxindole derivatives in good yields (up to 91%) and good to excellent enantioselectivities (up to >99% ee), albeit with modest diastereoselectivities (up to 3.1:1 dr).     

Enantioselective Diels–Alder reactions with left-handed G-quadruplex DNA-based catalysts

Since the discovery of left-handed G-quadruplex (L-G4) structure formed by natural DNA, there has been a growing interest in its potential functions. This study utilised it to catalyse enantioselective Diels-Alder reactions, considering its different optical rotation compared to an ordinary G4. It was determined that when L-G4 was used with a combination of copper(II) ions, there was a good enantioselectivity (?52% ee) without further addition of ligands. When further consideration was given by adding G4 ligands, G4 was further stabilised, even obtaining a better enantioselectivity (up to ?80% ee). Moreover, when using ligands that have regulatory effects on G4, the ee value can be adjusted. In this work, a minimal left-handed G4 was reported. A follow-up study was also conducted, which recovers that the minimal left-handed G4 remains its catalytic effect and enantioselectivity, but is not so effective as the former case. This indicates that a complete G4 structure is relatively conducive to chiral catalysis.     

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。     

In Silico Analysis of P450s and Their Role in Secondary Metabolism in the Bacterial Class Gammaproteobacteria

The impact of lifestyle on shaping the genome content of an organism is a well-known phenomenon and cytochrome P450 enzymes (CYPs/P450s), heme-thiolate proteins that are ubiquitously present in organisms, are no exception. Recent studies focusing on a few bacterial species such as Streptomyces, Mycobacterium, Cyanobacteria and Firmicutes revealed that the impact of lifestyle affected the P450 repertoire in these species. However, this phenomenon needs to be understood in other bacterial species. We therefore performed genome data mining, annotation, phylogenetic analysis of P450s and their role in secondary metabolism in the bacterial class Gammaproteobacteria. Genome-wide data mining for P450s in 1261 Gammaproteobacterial species belonging to 161 genera revealed that only 169 species belonging to 41 genera have P450s. A total of 277 P450s found in 169 species grouped into 84 P450 families and 105 P450 subfamilies, where 38 new P450 families were found. Only 18% of P450s were found to be involved in secondary metabolism in Gammaproteobacterial species, as observed in Firmicutes as well. The pathogenic or commensal lifestyle of Gammaproteobacterial species influences them to such an extent that they have the lowest number of P450s compared to other bacterial species, indicating the impact of lifestyle on shaping the P450 repertoire. This study is the first report on comprehensive analysis of P450s in Gammaproteobacteria.     

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。