苯基桥联双咔咯镓配合物的合成与发光性质

合成了苯基桥联双咔咯(1)及其镓配合物(2),利用紫外-可见光谱(UV-Vis),核磁共振波谱(1H NMR,19F NMR)及质谱(MS)对它们进行了表征.采用稳态和时间分辨荧光光谱对化合物1和2的发光性质进行了研究.实验结果表明,双咔咯1及其镓配合物2的荧光量子产率分别为0.142和0.473,荧光寿命相应为5.2与3.2 ns,且配合物2的荧光光谱显著蓝移.瞬态吸收光谱显示,在无氧条件下双咔咯1和配合物2的三重激发态(T1)寿命分别为58与34μs,其T1态的量子产率则分别为0.47和0.63.     

[Tris(2‐amino­ethyl)­amine‐κ4N]chloro­(dimethyl sulfoxide‐O)­cobalt(III) diper­chlorate

The title compound, [CoCl(tren)(dmso)](ClO₄)₂ [tren is tris‐(2‐amino­ethyl)­amine, C₆H₁₈N₄; dmso is di­methyl sulfoxide, C₂H₆OS], is the first crystal structure reported with dmso coordinated to Co^III. It crystallizes with two independent mol­ecules in the asymmetric unit. A localized non‐crystallographic inversion centre is observed between the two cations.     

Polyethylene glycol radical-initiated aerobic propargylic oxidation in dense carbon dioxide

The selective aerobic oxidation of alkynes to correspondingα,β-acetylenic ketones was achieved in polyethylene glycol/dense CO₂/O₂ biphasic system without any catalyst or additive.The effects of reaction parameters,e.g.temperature,CO₂ pressure,PEG molecular weight and loading on the reaction were carefully examined.Moreover,various substrates worked well in the presence of PEG 1000 under 5 MPa of CO₂ and 2 MPa of O₂ at 100℃for 12 to 24 h and acceptable yield and selectivity could be obtained in most cases.Preliminary mechanistic investigations were also discussed.     

金属配合物用于细胞内动态实时荧光示踪研究

近年来金属配合物因其优异的光物理性质,如大的斯托克位移、好的光稳定性、长的荧光寿命以及双光子荧光性质等,在生物成像领域中引起了广泛关注,并被应用于细胞内动态变化的实时示踪研究。本文综述了近年来金属配合物对线粒体、溶酶体、脂滴、乏氧、pH、黏度、温度、极性等细胞内动态行为和演化过程的实时示踪研究。总结了金属配合物应用于细胞内动态实时示踪所需的条件,包括特异性、好的光稳定性和低细胞毒;同时结合金属配合物的光物理性质,对实时示踪过程中不同成像模式（单光子成像、多光子成像、荧光寿命成像）的优缺点进行了比较;最后,针对目前金属配合物荧光示踪应用中存在的一些问题,进行了分析和探讨。     

5，10，15，20-四(2-甲氧基苯基)卟啉合钴的晶体和分子结构

用X-射线测定了5，10，15，20-四(2-甲氧基苯基)卟啉合钴［TMOPCo(Ⅱ)］的晶体结构，实验表明，晶体属正交晶系，空间群Pbca, a=11.544(2), b=14.294(2), c=23.984(2)?，V=3957?³,Z=4, d_c=1.329 g/cm³, μ(CuKα)=39.45 cm^-1, <     

1—甲苯磺酰基—3—芳基—4—苯基—1,4,2—二氮磷杂环戊—5—酮的合成及除草…

通过１－苯基－３－对甲苯磺酰基脲与亚磷酸三苯酯和取代苯甲苯在甲苯中进行的类Ｍａｎｎｉｃｈ反应合成１－对甲苯磺酰基－２－苯氧基－２－氧代－３－芳基－４－苯基－１，４，２－二氮磷杂环戊－５－酮。生物测定实验表明，某些产物具有良好的选择性除草活性。     

Cyclometalated Ruthenium(II) Anthraquinone Complexes Exhibit Strong Anticancer Activity in Hypoxic Tumor Cells

Hypoxia is the critical feature of the tumor microenvironment that is known to lead to resistance to many chemotherapeutic drugs. Six novel ruthenium(II) anthraquinone complexes were designed and synthesized; they exhibit similar or superior cytotoxicity compared to cisplatin in hypoxic HeLa, A549, and multidrug‐resistant (A549R) tumor cell lines. Their anticancer activities are related to their lipophilicity and cellular uptake; therefore, these physicochemical properties of the complexes can be changed by modifying the ligands to obtain better anticancer candidates. Complex 1 , the most potent member of the series, is highly active against hypoxic HeLa cancer cells (IC₅₀=0.53 μM ). This complex likely has 46‐fold better activity than cisplatin (IC₅₀=24.62 μM ) in HeLa cells. This complex tends to accumulate in the mitochondria and the nucleus of hypoxic HeLa cells. Further mechanistic studies show that complex 1 induced cell apoptosis during hypoxia through multiple pathways, including those of DNA damage, mitochondrial dysfunction, and the inhibition of DNA replication and HIF‐1α expression, making it an outstanding candidate for further in vivo studies.     

具有生物活性的磷杂环化合物研究: XIV. Lawesson试剂与 含活泼氢的双官能团 化合物的环化反应

研究Lawesson试剂与含活泼氢的双官能团化合物的环化反应,合成了O-P-O,N-P-O,N-P-N型五元、六元及七元磷杂环。探讨了其成环可能性及其环化机理。初步的生物活性测定结果表明,应用Lawesson试剂所合成的磷杂环具有较好的选择性除草活性。     

The ternary metal mixed ligand complexes formed by benzimidazole and N, N-bis(2-hydroxyethyl) glycine

The stability constants of the ternary M(Bic)(Bzim)~ complexes, where M~(2 )=Cu~(2 ), Ni~(2 ) or Zn~(2 ), Bic~-=the anion of N, N-bis(2-hydroxyethyl) glycine and Bzim = benzimidazole, were determined by potentiometric pH titration in aqueous solution. One of them (M~(2 ) = Cu~(2 )) was also separately determined by spectrophotometry. The results show that these ternary complexes are stabler than expected on statistical grounds. The enhanced stability of the ternary M(Bic) (Bzim)~ complexes is attributed to the π_A-π_B cooperative effect between Bic~- and benzimidazole. Besides, compared with Cu(Bic) (Bzim)~ and Ni(Bic) (Bzim)~ , the ternary Zn(Bic)(Bzim)~ complex has relatively high stability. The crystal structure of [Cu(Bic)(Bzim)]ClO_4 was determined by single crystal X-ray diffraction techniques. The copper atom has a trigonal-bipyramidal geometry, the basal plane is formed by an oxygen atom of the carboxylato group and two hydroxyl oxygen atoms, the apical position is occupied by a nitrogen a     

关于我国生物无机化学发展战略的一点思考

本文简要地回顾了国际生物无机化学发展的历史过程、当前的研究热点以及我国生物无机化学研究已取得的成就.在此基础上,探讨了我国生物无机化学的进一步发展策略和方向.