New syntheses and chemistry of hexafluorotropone

Two new routes to hexafluorotropone have been developed, one from hexachlorotropone and a superior synthesis from hexafluorobenzene. Hexafluorotropone was found to be a very weak base, with a conjugate acid pK(a) of -6.2 +/- 0.5. The tropone adds in [6 + 4] fashion to cyclopentadiene and photocyclizes to hexafluorobicyclo[3.2.0]hepta-3,6-dien-2-one. Lithium hydroxide in benzene transforms the tropone into pentafluorotropolone, which functions as a bidentate ligand.     

Morphology and degradation of biodegradable poly(L-lactide-co-β-malic acid)

Poly(L -lactide-co-β-malic acid) was obtained after the hydrogenolysis of the copolymer of L -lactide (L-LA) and β-benzyl malate (MA). ¹H-NMR demonstrated that the composition of the copolymer was identical to the feeding dose. Thermal property study revealed the morphology of the copolymer could be changed from semi-crystalline to amorphous with increasing hydrophilic β-malic acid content. The copolymers with 8 and 13 mol% β-malic acid content possessed enough mechanical property for fabricating cell scaffold. Degradation result demonstrated that most of the hydrophilic β-malic acid units broke down from the copolymer within 1 week and the ester bond between L -lactide and β-malic acid hydrolyzed prior to the inner ester bond of poly(L -lactide) (PLLA). Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis of a tweezer-like bis(arylthiaalkoxy)calix[4]arene as a cation sensor for ion-selective electrodes: an investigation of the influence of neighboring halogen atoms on cation selectivity

Two novel tweezer-like 25,27-dihydroxy-26,28-bis(phenylthiaethoxy)calix[4]arenes 6 and 7 were synthesized by the reaction of 25,27-dihydroxy-26,28-bis(bromoethoxy)calix[4]arenes 3 and 4 for the evaluation of their ion-selectivity in ion-selective electrodes (ISEs). X-ray structural analysis indicated that calix[4]arene 7 is in an interesting infinite linear aggregate via self-inclusion. For investigation of the influences of substitutes on the behavior of the ISEs, the halogen substituted aryl analogues of 25,27-dihydroxy-26,28-bis(arylthiaethoxy)calix[4]arenes 8-12 were also synthesized and their ISE performances were evaluated under the same conditions. ISEs based on 6-12 as neutral ionophores were prepared, and their selectivity coefficients for Ag+ (log KAg,M(pot)) were investigated against other alkali metal, alkaline-earth metal, lead, ammonium ions and some transition metal ions using the fixed interference method (FIM). These ISEs showed excellent Ag+ selectivity over most of the interfering cations examined, except for Hg2+ having relative smaller interference (log KAg,Hg(pot) < or = 2.1). The 19F NMR spectra of 9 and 9.AgClO4 were recorded for investigation the fluorine environments in the complex. The 19F NMR spectra strongly suggested that the fluorine atoms on ionophore 9 participated in ligation with silver cation.     

Correlation of infinite dilution activity coefficients of solvents in polymer solutions using connectivity indices

In this work, correlations for the estimation of the infinite dilution activity coefficients of non-polar solvents in polystyrene (PS), poly(vinyl acetate) (PVAc), poly(n-butyl methacrylate) (PBMA), poly(dimethyl siloxane), poly(methyl methacrylate) (PMMA), poly(ethylene oxide) (PEO), poly(vinyl chloride) (PVC), polyisobutylene and polyethylene (PE), and that of polar solvents in PS, PVAc, PBMA, PMMA, PEO, PVC and PE are proposed. A total of 205 polymer/non-polar solvent systems with 1708 data points, and 118 polymer/polar solvent systems with 695 data points were used to develop the correlations. The overall average errors were 9.6% and 11.3%, respectively, significantly lower than other predictive models. Since the new correlations require only the connectivity indices of the solvents in the calculations, and the connectivity indices can be calculated easily once the molecular structure of the substance in question is known, they are easy to apply, and are useful for process design and development.     

Synthesis and in vitro biological evaluation of novel 2-aminoimidazolone derivatives as anti-tumor agents

Novel 2-aminoimidazolone derivatives were synthesized.Most compounds displayed strong anticancer activities against human carcinoma cells in vitro.Compounds 8a,8b and 8j exhibited optimal activity superior to 5-FU in most cancer cells tested.Especially,the lC₅₀s of 8b（12.6-21.5μmol/L） against five tumor cells were 1 -4 fold less than those of 5-FU（18.4-56.1μmol/L） in vitro.Furthermore,comp以ound 8b could induce SMMC-7721 cell apoptosis in a dose-dependent manner.Therefore,our novel findings may provide a new framework for the design of new 2-aminoimidazolone derivatives for the treatment of cancer.     

A SERS-based immunoassay for porcine circovirus type 2 using multi-branched gold nanoparticles

We report on a facile immunoassay for porcine circovirus type 2 (PCV2) based on surface enhanced Raman scattering (SERS) using multi-branched gold nanoparticles (mb-AuNPs) as substrates. The mb-AuNPs in the immunosensor act as Raman reporters and were prepared via Tris base-induced reduction and subsequent reaction with p-mercaptobenzoic acid (pMBA). They possess good stability and high SERS activity. Subsequently, the modified mb-AuNPs were covalently conjugated to the monoclonal antibody (McAb) against the PCV2 cap protein to form SERS immuno nanoprobes. These were captured in a microtiterplate via a immunoreaction in the presence of target antigens. The effects of antibody concentration, reaction time and temperature on the sensitivity of the immunoassay were investigated. Under optimized assay conditions, the Raman signal intensity at 1,076 cm^?1 increases logarithmically with the concentrations of PCV2 in the concentration ranging from 8?×?10² to 8?×?10⁶ copies per mL. The limit of detection is 8?×?10² copies per mL. Compared to conventional detecting methods such as those based on PCR, the method presented here is rapid, facile and very sensitive.

Synthesis of LiNi1/3Co1/3Mn1/3O2 cathode material by a modified sol–gel method for lithium-ion battery

LiNi_1/3Co_1/3Mn_1/3O₂ was prepared by a modified sol–gel method, selecting ethylene diamine tetraacetic acid and citric acid as the co-chelating agent. The mole ratios of ethylene diamine tetraacetic acid (EDTA) to metal ion (Mⁿ⁺) were 0:1, 1:1 and 2:1. The obtained samples were characterized by XRD, BET and SEM. The XRD showed that LiNi_1/3Co_1/3Mn_1/3O₂ had good crystallinity and well-ordered layered structure. After calcined at 850 °C, the LiNi_1/3Co_1/3Mn_1/3O₂ particles exhibited a three-dimensional space network structure, which was greatly correlated with the ratio of EDTA to metal ion. The LiNi_1/3Co_1/3Mn_1/3O₂ obtained from a mole ratio of 1:1 (EDTA:Mⁿ⁺) had the best electrochemical performance. The reversible capacities were reached 168 and 100 mAh/g at 1C and 10C discharge rate, respectively. The result of the cycling performance showed a high capacity maintenance ratio of 89.3 % at 1C and 25 °C after 50 cycles. The further electrochemical performance was evaluated by electrochemical impedance spectroscopy and cyclic voltammetry.     

Preparation and photocatalytic antibacterial property of nitrogen doped TiO2 nanoparticles

Nitrogen doped TiO₂ (N-TiO₂) nanoparticles with about 30 nm in size were produced by a sol–gel method and characterized respectively by UV–vis, X-ray diffraction (XRD), Transmission electron microscopy, X-ray photoelectron spectroscopy (XPS). Their photocatalytic antibacterial properties were evaluated by the antibacterial ratio against Escherichia coli in dark and under simulated sunlight respectively. The XRD pattern showed that the doped nano-TiO₂ was mainly composed of anatase phase. The XPS spectra of the N-TiO₂ sample indicated that TiO₂ was doped by nitrogen atom. The nitrogen doping created a new N 2p state slightly above the valence band top consists of O 2p state, and this pushes up the valence band top and decreased the band gap. Which leaded to the absorption edge was red-shifted to the visible light region of UV–vis spectra of nitrogen doped nano-TiO₂ comparing with pure nano-TiO₂. The antibacterial percentage of N-TiO₂ against E. coli reached to 90 % under simulated sunlight for 2 h, which was much better than that in dark, also than that of pure nano-TiO₂. The photo-catalytic antibacterial activity was activated under visible light. The structure and integrity of cell wall and cell membrane were destructed, and even caused the bacteria death.     

焙烧处理下二氧化钛/钛酸盐纳米材料晶型和形貌的变化规律研究

通过调控酸碱浓度, 在水热条件下得到了金红石、锐钛矿、板钛矿、钛酸钠等一系列TiO₂/钛酸盐产物. 对上述TiO₂、酸洗处理后的钛酸盐等一系列不同晶型、不同形貌的样品进行焙烧处理, 系统性地研究焙烧温度的逐渐升高对产物晶型转变和形貌演化的规律性影响. 给出了水热酸碱浓度以及焙烧温度两个因素与TiO₂/钛酸盐纳米材料晶型和形貌变化行为关系的二维示意图. 依据奥斯特瓦尔德阶梯规则、经典热力学理论以及定向附着生长机理, 对TiO₂/钛酸产物的晶型晶体生长、晶型转变和形貌演化机理进行了探讨.     

Analysis of Biological Samples Using Paper Spray Mass Spectrometry: An Investigation of Impacts by the Substrates, Solvents and Elution Methods

Paper spray has been developed as a fast sampling ionization method for direct analysis of raw biological and chemical samples using mass spectrometry (MS). Quantitation of therapeutic drugs in blood samples at high accuracy has also been achieved using paper spray MS without traditional sample preparation or chromatographic separation. The paper spray ionization is a process integrated with a fast extraction of the analyte from the raw sample by a solvent, the transport of the extracted analytes on the paper, and a spray ionization at the tip of the paper substrate with a high voltage applied. In this study, the influence on the analytical performance by the solvent–substrate systems and the selection of the elution methods was investigated. The protein hemoglobin could be observed from fresh blood samples on silanized paper or from dried blood spots on silica-coated paper. The on-paper separation of the chemicals during the paper spray was characterized through the analysis of a mixture of the methyl violet 2B and methylene blue. The mode of applying the spray solvent was found to have a significant impact on the separation. The results in this study led to a better understanding of the analyte elution, on-paper separation, as well as the ionization processes of the paper spray. This study also helps in establishing a guideline for optimizing the analytical performance of paper spray for direct analysis of target analytes using mass spectrometry.