Binding sites of nitrogenase: kinetic and theoretical studies of cyanide binding to extracted FeMo-cofactor derivatives

The first kinetic study of a substrate (CN(-)) binding to the isolated active site (extracted FeMo-cofactor) of nitrogenase is described. The kinetics of the reactions between CN(-) and various derivatives of extracted FeMo-cofactor [FeMoco-L; where L is bound to Mo, and is NMF, Bu(t)NC, or imidazole (ImH)] have been followed using a stopped-flow, sequential-mix method in which the course of the reaction is followed indirectly, by monitoring the change in the rate of the reaction of the cofactor with PhS(-). The kinetic results, together with DFT calculations, indicate that the initial site of CN(-) binding to FeMoco-L is controlled by a combination of the electron-richness of the cluster core and lability of the Mo-L bond. Ultimately, the reactions between FeMoco-L and CN(-) involve displacement of L and binding of CN(-) to Mo. These reactions occur with a variety of rates and rate laws dependent on the nature of L. For FeMoco-NMF, the reaction with CN(-) is complete within the dead-time of the apparatus (ca. 4 ms), while with FeMoco-CNBu(t) the reaction is much slower and exhibits first order dependences on the concentrations of both FeMoco-CNBu(t) and CN(-) (k = 2.5 +/- 0.5 x 10(4) dm(3) mol(-1) s(-1)). The reaction of FeMoco-ImH with CN(-) occurs at a rate which exhibits a first order dependence on FeMoco-ImH but is independent of the concentration of CN(-) (k = 50 +/- 10 s(-1)). The results are interpreted in terms of CN(-) binding directly to the Mo site for FeMoco-NMF and FeMoco-ImH, but with FeMoco-CNBu(t) initial binding at an Fe site is followed by movement of CN(-) to Mo. Complementary DFT calculations are consistent with this interpretation, indicating that, in FeMoco-L, the Mo-L bond is stronger for L = ImH than for L = CNBu(t) and the binding of CN(-) to Mo is stronger than to any Fe atom in the cofactor.     

An indium(III)–water chain based on an unusual acyclic water pentamer

An in situ reaction under hydro­thermal conditions leads to the formation of the title compound, diaqua­(pyridine‐2‐carboxyl­ato)­(pyridine‐2,6‐dicarboxyl­ato)indium(II) trihydrate, [In(C₆H₄NO₂)(C₇H₃NO₄)(H₂O)₂]·3H₂O, in which the central In^III atom is seven‐coordinated by one pyridine‐2,6‐di­carboxyl­ate ligand, one pyridine‐2‐carboxyl­ate ligand and two water mol­ecules in a penta­gonal–bipyramidal coordination environment. An indium(III)–water chain based on an unusual water pentamer is observed.     

Assembly of azido- or cyano-bridged binuclear complexes containing the bulky [Mn(phen)2]2+ building block: syntheses, crystal structures, and magnetic properties

Two new cyano-bridged heterobinuclear complexes, [Mn(II)(phen)2Cl][Fe(III)(bpb)(CN)2] x 0.5CH3CH2OH x 1.5H2O (1) and [Mn(II)(phen)2Cl][Cr(III)(bpb)(CN)2] x 2H2O (2) [phen = 1,10-phenanthroline; bpb(2-) = 1,2-bis(pyridine-2-carboxamido)benzenate], and four novel azido-bridged Mn(II) dimeric complexes, [Mn2(phen)4(mu(1,1)-N3)2][M(III)(bpb)(CN)2]2 x H2O [M = Fe (3), Cr (4), Co (5)] and [Mn2(phen)4(mu(1,3)-N3)(N3)2]BPh4 x 0.5H2O (6), have been synthesized and characterized by single-crystal X-ray diffraction analysis and magnetic studies. Complexes 1 and 2 comprise [Mn(phen)2Cl]+ and [M(bpb)(CN)2]- units connected by one cyano ligand of [M(bpb)(CN)2]-. Complexes 3-5 are doubly end-on (EO) azido-bridged Mn(II) binuclear complexes with two [M(bpb)(CN)2]- molecules acting as charge-compensating anions. However, the Mn(II) ions in complex 6 are linked by a single end-to-end (EE) azido bridging ligand with one large free BPh4(-) group as the charge-balancing anion. The magnetic coupling between Mn(II) and Fe(III) or Cr(III) in complexes 1 and 2 was found to be antiferromagnetic with J(MnFe) = -2.68(3) cm(-1) and J(MnCr) = -4.55(1) cm(-1) on the basis of the Hamiltonian H = -JS(Mn)S(M) (M = Fe or Cr). The magnetic interactions between two Mn(II) ions in 3-5 are ferromagnetic in nature with the magnetic coupling constants of 1.15(3), 1.05(2), and 1.27(2) cm(-1) (H = -JS(Mn1)S(Mn2)), respectively. The single EE azido-bridged dimeric complex 6 manifests antiferromagnetic interaction with J = -2.29(4) cm(-1) (H = -JS(Mn1)S(Mn2)). Magneto-structural correlationship on the EO azido-bridged Mn(II) dimers has been investigated.     

LC-ESI-MS Determination of Bilobalide and Ginkgolides in Canine Plasma

A sensitive and selective method using liquid chromatography with electrospray ionization mass spectrometric detection was developed for the quantification of bilobalide and ginkgolides in canine plasma. The analytes were extracted with diethyl ether-dichloromethane-isopropanol (6:3:1, v/v) after spiking the samples with daidzein (internal standard). The lower limit of quantification (LLOQ) of the method was 2.5 μg L⁻¹ for ginkgolide B and 10.0 μg L⁻¹ for bilabolide, ginkgolide A and ginkgolide C. The accuracy of the method was within 15% of the actual values over a wide range of plasma concentrations. The intra-day and inter-day precision was better than 15% (R.S.D.). Finally, the LC-ESI-MS method was successfully applied to study the pharmacokinetics of ginkgolides and bilabolide after administration of Ginkgo biloba extracts to dogs.     

Reactivity of Ar'GeGeAr' (Ar' = C6H3-2,6-Dipp2, Dipp = C6H3-2,6-iPr2) toward alkynes: isolation of a stable digermacyclobutadiene

The first reactions of the "digermyne" Ar'GeGeAr' (1, Ar' = C6H3-2,6-Dipp2, Dipp = C6H3-2,6-iPr2) with alkynes are reported. 1 reacts with 1 equiv of H5C6CCC6H5 to afford the 1,2-digermacyclobutadiene 2 in high yield, while it reacts with 2 equiv of the less hindered alkyne Me3SiCCH to yield an unexpected bicyclic compound 3. Molecular structures of 2 and 3 were determined by X-ray crystallography. A possible mechanism for the formation of 3 is discussed. The high reactivity of 1, even at room temperature, emphasizes the fundamental differences between the GeGe and CC multiple bonds.     

催化动力学光度法测定痕量锰（Ⅱ）

研究了在Ｎａ２ＨＰＯ４－ＮａＯＨ介质中，Ｍｎ（Ⅱ）催化高碘酸钾氧化镁试剂１［４－（对硝基苯偶氮）间苯二酚］的反应及其动力学条件，建立了一种高灵敏、高选择性测定痕量Ｍｎ（Ⅱ）的新方法。可测０．０１－２．５μｇ／２５ｍＬ范围的锰（Ⅱ），方法的检测限为６．４３×１０＾－１１ｇｍ／ｍＬ。     

便携式温度计校验仪的研制

介绍便携式温度计校验仪的工作原理及研制过程。对该仪器的恒温槽体机械结构、制冷器和散热器的设计、恒温槽体温度测量及控制等进行了详细叙述。该仪器提供的温度场稳定、均匀，在-20～100℃范围内可任意设定温度。解决了温度计现场快速校准的问题。     

碳纳米管添加剂对质子交换膜燃料电池低铂载量膜电极性能的影响研究

以碳纳米管（CNT）作为低铂载量膜电极（CCM）催化层（0.1 mg_Pt·cm^-2）添加剂，研究了CNT的添加方式对催化层微观结构以及膜电极性能的影响.结果表明，与常规低铂载量催化层相比，在其表面喷涂一层CNT或将CNT均匀分散到Pt/C催化层中均有利于提升低铂载量膜电极的输出性能，在70℃和100%相对湿度条件下最高输出功率比常规低铂载量膜电极的0.522 W·cm^-2分别提升了22.4%和60.0%，并且均匀分散添加方式优于分层添加方式.其原因在于分层添加CNT后改善了低铂催化层和气体扩散层之间的接触界面，降低了催化层与扩散层间的接触电阻，而均匀分散添加方式除了可降低界面接触电阻外，还显著改善了低铂催化层中的气体传输，大幅提升了Pt催化剂的利用效率，使得膜电极电化学反应电阻明显降低.进一步对均匀分散添加方式中CNT的载量进行优化，表明CNT添加量为37.5 μg·cm^-2时电池输出性能最佳，70℃和100%相对湿度条件下的最大输出功率达到0.91 W·cm^-2.本研究工作表明，将CNT均匀分散添加到催化层中是一种有效提升低铂载量膜电极性能的方法.     

黄色含硫硅酸盐类无毒新颜料的制备

研究新型无毒无机颜料,逐步取代如铅铬黄、镉黄等无机颜料,日益引人注意。我们以价廉易得的自云石凹凸棒、蒙脱石、凹凸棒石粘土矿为原料,制得黄色硅酸盐类无毒新型颜料。研究了该类颜料的骨架结构与成分,及其发色机理。工艺过程如下:     

Epoxide assisted sol-gel synthesis of rutile NixTi1-3xSb2xO2 solid solution nanoparticles

Rutile Ni _x Ti_1-3x Sb_2x O₂ solid solution nanoparticles were synthesized by a sol-gel route using propylene oxide as a gelation agent. Titanium oxide nanopowder and 12% TiCl₃ solution were used as the source for titanium to investigate the influence of the titanium precursors on the formation of the target materials. It was found that the nanoparticles prepared using 12% TiCl₃ solution showed a much lower phase formation temperature (700°C) as compared to those prepared from TiO₂ nanoparticles (1000°C). This lower phase formation temperature allowed a substantial reduction of the aggregation of the particles during calcination leading to the formation of nearly mono-dispersed nanoparticles of about 20 nm. The results of this work show that the epoxide assisted sol-gel method is capable to produce titanium-based ternary oxide solid solution nanoparticles, owing to the formation of a highly homogeneous precursor gel intermediate.