Interactions with ATP, DNA Cleavage and Anti-tumor Activities of Complexes with Anions [Mo（V）O2（O2CeH4）2]^3-, [Mo（Ⅴ）0.5W（Ⅵ）0.5O2（O2C6H4）2]^2.5- and [W（Ⅵ）O2（O2C6H4）2]^2-

(NH3CH2CH2NH2)3[Mo(Ⅴ)O2(O2C6H4)2] (1), (NH3CH2CH2NH2)2.5[Mo(Ⅴ)o.sW(Ⅵ)o.502(O2C6H4)2] (2) and(NH3CH2CH2NH2)2[VC(Ⅵ)O2(O2C6H4)2] (3) were synthesized, structurally characterized by X-ray diffraction analysis, and studied on their interactions with ATP, their DNA cleavage activities and antitumor properties. The redox state of molybdenum was not changed on going from crystal to aqueous solutions in complexes 1 and 2, while tungsten underwent reduction from W(VI) to W(V) in complexes 2 and 3. ATP promoted the oxidation of both molybdenum and tungsten from M(Ⅴ) to M(Ⅵ) and the hydrolysis of catecholate ligands in solution consisting of ATP and the complexes. Complex 1 possesses fairly good activity to DNA cleavage and against tumor S180 in mice, and is more effective than the control drug cyclophosphamide under the identical conditions. However, complexes 2 and 3 exhibited marginal effectiveness. The effectiveness of anti-tumor of the complexes was related positively to their DNA cleavage activities and their hydrolysis of catecholate ligands.     

Synthesis,Crystal Structure of Cis—dioxo—catecholatotungsten（VI） Complex and Its NMR Studies on the Interaction with ATP

Cis-dioxo-catecholatotungsten(VI) complex anion[W^(VI)O2-(OC6H4O)2]^2- was obtained with discrete protonated ethylenediamine (NH2CH2CH2NH3)^ cations by the reaction of tetrabutyl ammonium decatungstate with catechol in the mixed solvent of CH3OH,CH3CN and ethylenediamine,and compared with its molybdenum anaogue [Mo^(V) O2(OC6H4O)2]^3- by crystal structure,UV,EPR,The results of the UV and EPR spectra show that tungsten is less redox active than molybdenum since the molybdenum is reduced from Mo(VI) to Mo(V) but tungsten stays in the original highest oxidized state Mo(VI) when they are crystallized from the solution above.It is worthy to note that [W^(VI)O2(OC6H4O)]^2- shows the same coordination structure as its molybdenum analogue in which the metal center exhibits distorted octahedral coordination geometry with two cis-dioxocatecholate ligands and might have the related coordination structure feature with the cofactor of flavoenzyme because [Mo^(V)O2(OC6H4O)2]^3- presented essentially the same EPR spectra as flavoenzyme.The NMR studies on the interaction of the title complex with ATP reveal that the reduction of W(VI) to W(V) occurs when the title complex is dissolved in D2O and the W(V) is oxidized again when ATP solution is mixed with original solution and the hydrolysis of the catecholato ligand take places at mean time being monitored by ^1H NMR and ^13C NMR spectra.     

波谱学及其在我国三十年

波谱学是研究辐射和物质共振相互作用的科学.通过观测和研究这种相互作用的各种现象及其机理,人们可以得到物质的内部结构及其运动规律的知识.波谱学所涉及的辐射主要处在射频、微波、毫米波直至远红外波段,大体上是频率在10 13Hz以下(波长在30μm以上)的区域;它所处理的主要的是能级之间的受激跃迁.波谱学可以看成是光谱学的延长和发展,历史上,它由物理学的三个领域汇聚融合而来,这就是:远红外,毫米波,微波的分子光谱;原子束分子束共振及其对原子分子基本常数的测定;物质磁性,尤其是弛豫的研究(这和绝热去磁有关).因此,波谱学的内容远超过…