Construction of multiporphyrin arrays using ruthenium and rhodium coordination to phosphines

The synthesis of linear multiporphyrin arrays with mono- and bisphosphine-substituted porphyrins as ligand donors and ruthenium(II) or rhodium(III) porphyrins as ligand acceptors is described. With appropriate amounts of the building blocks mixed, linear dimeric and trimeric arrays have been synthesized and analyzed by (1)H NMR and (31)P NMR spectroscopy. The Ru/Rh acceptor porphyrins can be located either at the periphery or in the center of the array. Likewise, the monophosphine porphyrins can be positioned at the periphery, thus allowing a high degree of freedom in the overall composition of the arrays. This way, both donor and acceptor porphyrins can act as chain extenders or terminators. One of the trimeric complexes with two nickel and one ruthenium porphyrin has also been analyzed by X-ray crystallography. Attempts have also been made to synthesize higher order arrays by mixing appropriate amounts of the porphyrins; however, from the NMR data it cannot be concluded if monodisperse five, seven, or nine porphyrin arrays are present or if the solutions are composed of a statistical mixture of smaller and larger arrays.     

短尾蝮新突触前毒素和细胞毒素的纯化及部分序列

用反相高效液相色谱技术对中国产短尾蝮蛇(Agkistrodon blomhoffii brevicaudus)毒中的毒性蛋白重新进行了纯化,结果从中获得了3个由约122个氨基酸残基构成的毒蛋白(AgTx-1,AgTx-2和AgTx-3)。三者对小鼠的LD_(50)分别为0.075,0.51和6.6mg/kg。在小鸡颈二腹肌标本上的毒理分析表明,AgTx-1和AgTx-2均在阻遏接头传递之后,亦不影响肌肉对乙酰胆碱的敏感性。在AgTx-3的作用下,标本的间接收缩则由于舒张不全而逐渐变小,最后停止在挛缩状态。部分氨基酸序列测定结果又表明,AgTx-1和AgTx-2的N-端32肽序列完全相同。考虑到AgTx-1的LD_(50)在粗毒中的含量及其序列等均与前文报道的β-AgTx极为相似,故我们认定它们为同一毒素,并定名为β_1-AgTx。而AgTx-2则应是新的突触前毒素,相应地定名为β_2-AgTx,至于AgTx-3便是新发现的细胞毒素。     

Role of Cell Surface Lipopolysaccharides in Escherichia coli K12 adhesion and transport

The influence of bacterial surface lipopolysaccharides (LPS) on cell transport and adhesion has been examined by use of three mutants of Escherichia coli K12 with well-characterized LPS of different lengths and molecular composition. Two experimental techniques, a packed-bed column and a radial stagnation point flow system, were employed to investigate bacterial adhesion kinetics onto quartz surfaces over a wide range of solution ionic strengths. Although the two systems capture distinct deposition (adhesion) mechanisms because of their different hydrodynamics, similar deposition kinetics trends were observed for each bacterial strain. Bacterial deposition rates were directly related to the electrostatic double layer interaction between the bacteria and quartz surfaces, in qualitative agreement with classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. However, DLVO theory does not fully explain the deposition behavior for the bacterial strain with the lengthy, uncharged O-antigen portion of the LPS. Neither the length nor the charge characteristics of the LPS molecule directly correlated to deposition kinetics, suggesting a complex combination of cell surface charge heterogeneity and LPS composition controls the bacterial adhesive characteristics. It is further suggested that bacterial deposition behavior is determined by the combined influence of DLVO interactions, LPS-associated chemical interactions, and the hydrodynamics of the deposition system.     

Quality evaluation of Flos lonicerae through a simultaneous determination of seven saponins by HPLC with ELSD

A new HPLC coupled with evaporative light scattering detection (ELSD) method has been developed for the simultaneous quantitative determination of seven major saponins, namely macranthoidin B (1), macranthoidin A (2), dipsacoside B (3), hederagenin-28-O-beta-D-glucopyranosyl(6-->1)-O-beta-D-glucopyranosyl ester (4), macranthoside B (5), macranthoside A (6), and hederagenin-3-O-alpha-L-arabinopyranosyl(2-->1)-O-alpha-L-rhamnopyranoside (7) in Flos Lonicerae, a commonly used traditional Chinese medicine (TCM) herb. Simultaneous separation of these seven saponins was achieved on a C18 analytical column. The mobile phase consisted of (A) acetonitrile-acetic acid (95:0.5) and (B) 0.5% aqueous acetic acid using a gradient elution of 29%A at 0-10 min, 29-46%A at 10-25 min and 46%A at 25-30 min. The drift tube temperature of ELSD was set at 106 degrees C, and with the nitrogen flow-rate of 2.6 l/min. All calibration curves showed good linear regression (r2>0.9922) within test ranges. This method showed good reproducibility for the quantification of these seven saponins in Flos Lonicerae with intra- and inter-day variations of less than 3.0% and 6.0%, respectively. The validated method was successfully applied to quantify seven saponins in five sources of Flos Lonicerae, which provides a new basis of overall assessment on quality of Flos Lonicerae.