Development and certification of a coal fly ash certified reference material for selected polycyclic aromatic hydrocarbons

The development and certification of a coal fly ash certified reference material (CRM) for polycyclic aromatic hydrocarbons (PAH) is described; this is the first natural matrix CRM for organic environmental analysis in China. The homogeneity and stability of this material have been tested by HPLC. The concentrations of several PAH were determined by use of two independent, different methods--solvent extraction-HPLC analysis with UV detection coupled with fluorescence detection (FLD) and solvent extraction, isolation with a silica column, and GC analysis with flame ionization detection (FID). Five certified values were determined: phenanthrene 7.1 +/- 2.6 microg g(-1), anthracene 2.0 +/- 0.8 microg g(-1), fluoranthene 7.4 +/- 1.9 microg g(-1), pyrene 7 +/- 2 microg g(-1), and benzo[a]pyrene 1.3 +/- 0.3 microg g(-1). Reference values for several other PAH are also suggested.     

pKa calculations in solution and proteins with QM/MM free energy perturbation simulations: a quantitative test of QM/MM protocols

The accuracy of biological simulations depends, in large part, on the treatment of electrostatics. Due to the availability of accurate experimental values, calculation of pKa provides stringent evaluation of computational methods. The generalized solvent boundary potential (GSBP) and Ewald summation electrostatic treatments were recently implemented for combined quantum mechanical and molecular mechanics (QM/MM) simulations by our group. These approaches were tested by calculating pKa shifts due to differences in electronic structure and electrostatic environment; the shifts were determined for a series of small molecules in solution, using various electrostatic treatments, and two residues (His 31, Lys 102) in the M102K T4-lysozyme mutant with large pKa shifts, using the GSBP approach. The calculations utilized a free energy perturbation scheme with the QM/MM potential function involving the self-consistent charge density functional tight binding (SCC-DFTB) and CHARMM as the QM and MM methods, respectively. The study of small molecules demonstrated that inconsistent electrostatic models produced results that were difficult to correct in a robust manner; by contrast, extended electrostatics, GSBP, and Ewald simulations produced consistent results once a bulk solvation contribution was carefully chosen. In addition to the electrostatic treatment, the pKa shifts were also sensitive to the level of the QM method and the scheme of treating QM/MM Coulombic interactions; however, simple perturbative corrections based on SCC-DFTB/CHARMM trajectories and higher level single point energy calculations were found to give satisfactory results. Combining all factors gave a root-mean-square difference of 0.7 pKa units for the relative pKa values of the small molecules compared to experiment. For the residues in the lysozyme, an accurate pKa shift was obtained for His 31 with multiple nanosecond simulations. For Lys 102, however, the pKa shift was estimated to be too large, even after more than 10 nanosecond simulations for each lambda window; the difficulty was due to the significant, but slow, reorganization of the protein and water structure when Lys 102 was protonated. The simulations support that Lys 102 is deprotonated in the X-ray structure and the protein is highly destabilized when this residue is protonated.     

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.     

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。     

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.     

锂离子蓄电池正极材料LiFePO4研究进展

锂离子电池正极材料正在向着高比能量、长寿命、低成本、环境友好的方向发展,而具有橄榄石结构的LiFePO_4正极材料以其结构稳定、成本低、无污染等优点成为21世纪最理想的绿色电源,但自身也存在缺点。综述了锂离子电池正极材料LiFePO_4的研究进展。系统地阐述了LiFePO_4的晶体结构特征及性能、多种合成方法以及掺杂多种导电材料和控制晶体生长制备纳米粉体对材料性能的影响。对该材料的应用前景进行了展望,并提出了下一步可能的研究趋势。