An efficient synthesis of α-aryl β-(N-tosyl)amino phosphonate derivatives from α-diazophosphonate

The α-diazophosphonate was added to aryl (N-tosyl)imine to give β-aryl β-(N-tosyl)amino α-diazophosphonates, which were further subjected to TsOH-catalyzed diazo decomposition to yield α-aryl β-(N-tosyl)enaminophosphonates through 1,2 aryl migration. The α-aryl β-(N-tosyl)enamino phosphonates were hydrogenated to give α-aryl β-(N-tosyl)amino phosphonates.     

Supramolecular assemblies of a naturally derived sophorolipid

Acidic sophorolipid (SL) molecules derived from yeasts represent a novel type of asymmetrical bolaamphiphiles due to their unique structural features that include an asymmetrical polar head size (disaccharide vs COOH), a kinked hydrophobic core (cis-9-octadecenoic chain), and a non-amide polar-nonpolar linkage. Light microscopy, small- and wide-angle X-ray scattering, FT-IR spectroscopy, and dynamic laser light scattering were used to investigate the supramolecular structures of the self-assembled aggregates of SL molecules at different pH values. In acidic conditions (pH < 5.5), giant twisted and helical ribbons of 5-11 microm width and several hundreds of micrometers length were observed for the first time. Increase in solution pH values slowed ribbon formation, decreased ribbon yield, and increased the helicity and entanglements of the giant ribbons. An interdigitated lamellar packing model of acidic SL-COOH molecules with a long period of 2.78 nm, stabilized by both the strong hydrophobic association between the cis-9-octadecenoic chains and strong disaccharide-disaccharide hydrogen bonding, is proposed. The neutralization of SL-COOH in water to SL-COONa produced clear solutions with the formation of short-range ordered aggregates. At concentrations below 1.0 mg/mL, the size of self-assembled aggregates increased as the concentration increased. At concentrations above 1.0 mg/mL, narrowly distributed micellar aggregates with a constant hydrodynamic radius (R(h)) of about 100 nm are formed. The large micelles show strong angular dependence with the fast mode appearing at scattering angle theta >/= 60 degrees.     

Crystal engineering of a versatile building block toward the design of novel inorganic-organic coordination architectures

Six novel inorganic-organic coordination supramolecular networks based on a versatile linking unit 4-pyridylthioacetate (pyta) and inorganic Co(II), Cu(II), Ag(I), Zn(II), Mn(II) and Pb(II) salts have been prepared in water medium and structurally characterized by single-crystal X-ray diffraction analysis. Reaction of CoCl(2).6H(2)O with Hpyta afforded a neutral mononuclear complex [Co(pyta)(2)(H(2)O)(4)](1), which exhibits a two-dimensional (2-D) layered architecture through intermolecular O-HO interactions. Reaction of CuCl(2.2H(2)O with Hpyta yielded a neutral one-dimensional (1-D) coordination polymer [[Cu(pyta)(2)(H(2)O].0.5H(2)O](n)(2) consisting of rectangle molecular square units, which show a three-dimensional (3-D) supramolecular network through S...S and O-H...O weak interactions. However, when AgNO(3), Zn(OAc)(2).2H(2)O or MnCl(2).4H(2)O salts were used in the above self-assembled processes, the neutral 2-D coordination polymers [Ag(pyta)](n)(3), [[Zn(pyta)(2)].4H(2)O](n)(4) or [[Mn(pyta)(2)(H(2)O)]](n)(5) with different topologies were obtained, respectively. While substituting the transition metal ions used in 1-5 with Pb(OAc)(2).3H(2)O, a one-dimensional coordination polymer [Pb(pyta)(2)](n)(6), which shows a novel 2-fold interpenetrating 2-D supramolecular architecture through weak SS interactions, was isolated. It is interesting to note that the building block pyta anion exhibits different configurations and coordination modes in the solid structures of complexes 1-6. These results indicate that the versatile nature of this flexible ligand, together with the coordination preferences of the metal centers, play a critical role in construction of these novel coordination polymers or supramolecules. The spectral and thermal properties of these new materials have also been investigated.     

A new isocoumarin from bark of Pellodendron chinense

A new isocoumarin, 3-acetyl-3,4-dihydro-5,6-dimethoxy-1H-2-benzopyran-1-one, was isolated from the cortex of Phellodendron chinense schneid. The structure was determined on the basis of spectroscopic evidences.     

Fibre optic fluorometric enzyme sensors for hydrogen peroxide and lactate,based on horseradish peroxidase and lactate oxidase

An optical biosensor for the determination of hydrogen peroxide based on immobilized horseradish peroxidase is described. The fluorescence of the dimeric product of the enzyme catalysed oxidation of homovanillic acid is utilized to determine the concentration of H₂O₂. The membrane-bound enzyme is attached to a bifurcated fibre bundle permitting excitation and detection of the fluorescence by a fluorometer. The response of the sensor is linear from 1 to 130 M hydrogen peroxide; the coefficient of variation is 3%. The sensor is stable for more than 10 weeks. The operating pH for maximal sensor response is 8.15. This allows the sensor to be used in combination with oxidase reactions producing hydrogen peroxide, as is demonstrated with a co-immobilized lactate oxidase-horseradish peroxidase optode for the determination of L-lactate. The fluorescence intensity of this sensor depends linearly on the concentration of lactate between 3 and 200 M and a throughput of 10 samples per hour is possible. The precision is in the same range as that of the monoenzyme optode. The lifetime of the bienzyme sensor for lactate is considerably shorter than that of the peroxidase sensor; it is limited by the stability of the immobilized lactate oxidase enzyme. The sensor has been applied to the determination of lactate in control serum.     

Remarkable nanosize effect of zirconia in Au/ZrO2 catalyst for CO oxidation

Nanosize effect of ZrO2 in Au/ZrO2 catalyst was studied by deposition-precipitation of Au nanoparticles in similar sizes (4-5 nm) on ZrO2 nanoparticles of varying sizes. The catalysts were characterized with XRD, TEM, XPS, and nitrogen adsorption to understand the effect of ZrO2 particle size on the catalytic nanostructures. Nanocomposite Au/ZrO2 catalysts consisting of comparably sized Au-metal (4-5 nm) and ZrO2 (5-15 nm) nanoparticles are found advantageous over those containing similarly sized Au-metal but larger ZrO2 (40-200 nm) particles for CO oxidation. This finding may have important implications on the designed preparation of advanced nanostructured catalysts and other chemical materials.     

Debye type dielectric relaxation and the glass transition of alcohols

Many hydrogen-bonded liquids, especially glass-forming cases, display a dielectric relaxation behavior that differs qualitatively from that of other simple liquids. The majority of models aimed at explaining this unusual dielectric behavior associate the prominent Debye process with structural relaxation, viscous flow, and the glass transition. We perform dielectric and calorimetric studies of glass-forming mixtures of 2-ethylhexylamine and 2-ethyl-1-hexanol across the entire composition range. The kinetic glass transition temperature derived from the large dielectric Debye peak decreases, whereas that of the much smaller and asymmetrically broadened peak increases upon addition of amine. Only the latter feature coincides with the calorimetric glass transition results, implying that molecular structure and dielectric polarization fluctuate on time scales that can differ by orders of magnitude in many hydrogen-bonding liquids.     

Immunoassay of P-glycoprotein on single cell by capillary electrophoresis with laser induced fluorescence detection

The cellular mechanism based on P-glycoprotein (PGP) for its drug pump function has become very important in multidrug resistance (MDR) research. A method has been established to characterize PGP on single K562 cell by coupling capillary electrophoresis with laser induced fluorescence detection. A permeable intact cell after the immunoassay binding with fluorescence labeling antibody was injected into the capillary and directly separated without lysis. It was found that once 5-10 optional cells were detected in batch, the PGP amount on this cell line could be outlined and calculated clearly. The PGP amount on K562 MDR cell line is 3.88 times higher than that on K562 sensitive cell line. These two cell lines with immunoassay binding were also analyzed by injection of multi-cells in order to improve the throughput. A resistance factor so called multidrug resistance multiple (MRM) was introduced to evaluate the MDR difference between cell lines. The MRM values of the cell line K562 measured by single cell analysis are well correlated with those by flow cytometry, which also prove the validity of our method in single cell analysis for the possibility of cancer diagnosis, pharmacokinetics and drug screening in future.     

倾斜交叉差分式激光热透镜光谱法特性研究

本文描述了一个倾斜交叉、差分式激光热透镜光谱法。采用本方法可消除较高的溶剂空白的影响。文章讨论了调制频率和泵浦光功率对热透镜信号的影响,给出了检测Cu~(2+)的工作曲线,讨论了影响方法灵敏度的诸因素,提出了可能的改进方案。     

2,2′-对苯二甲硫基二乙酸配合物的合成及表征

本文报道了配体 2 ,2′-对苯二甲硫基二乙酸和过渡金属铜 ( )、钴 ( )、镍 ( )配合物的合成。经元素分析、X射线衍射分析、红外光谱、差热 -热重分析等推算了它们的组成并指认了谱带的归属。对铜 ( )配合物进行了电子顺磁共振谱研究。