Increased sensitivity of autoantibody determination by coupled-particle light-scattering assay by poly(ethylene glycols)-modified beads

New kinds of coatings by using polyethylene glycols were studied and were applied to a qualitative homogeneous immunoassay that exploits the agglutination reaction for the detection of autoimmune antibodies in a complex matrix. We used a piece of new technology, the Copalis^™, which uses a special optical-sizing flow particle analysis and a semiconductor laser as a light source.

Polystyrene microbeads coated with the antigen were used as markers and were put in contact with the serum sample. Different polyethylene glycols were synthesised and tested, optimising the experimental parameters. Human serum specimens were evaluated and we obtained a higher sensitivity with good discrimination between negative and positive samples. All the experimental steps are easy, rapid and enable us to process many samples in a short period of time.     

Two pairs of chlorine-containing phenylpropanoid enantiomers from Acorus tatarinowii

Two pairs of chlorine-containing phenylpropanoid enantiomers (1a/1b and 2a/2b) were isolated from the rhizomes of Acorus tatarinowii. Interestingly, these optical isomers (1a/1b and 2a/2b) were co-existed in the same plant, which were characterized as the first halogen-containing natural products from the genus Acorus. Their structures and absolute configurations were elucidated by a combination of spectroscopic analysis and a single-crystal X-ray diffraction, assisted by a modified Mosher's method. The phenylpropanoid isomers (1a/1b and 2a/2b) were evaluated for their antioxidant activities using DPPH assay and cytotoxic activities against five human cancer cell lines.     

膜催化研究II. 多孔无要膜的制备与表征及其反应器对甲醇脱氢反应的促进作用

采用溶胶-凝胶法制备了多孔氧化铝膜, 并通过DSC、TGA、SEM、N~2吸附和气体透过率测定等手段, 对膜的性能进行了表征。结果表明, 用这种方法制备的多孔氧化铝膜是一种均匀无裂痕和具有较窄孔径分布(约4nm)的膜材料。将此多孔氧化铝膜制成膜反应器后, 用于甲醇催化脱氢制甲醛的反应, 发现甲醇转化率比常规反应器有较大幅度的提高。同时首次尝试采用溶胶-凝胶法将催化活性组分直接负载到多孔氧化铝膜上, 从而得到了一种具有催化活性的多孔膜, 并考察了它的反应活性。文中对由这两种多孔膜及钯/陶瓷复合膜制成的反应器的特点进行了比较。     

新型含1,2,4-三唑基的1,5-苯并硫氮杂的合成和表征

以α-溴代苯乙酮为原料,在三乙胺作用下制备α-(1,2,4-三唑-1-基)-芳基乙酮(1a～1c),再与芳香醛发生羟醛缩合反应制备相应的含三唑基的查尔酮2a～2l,将中间体2a～2l同邻氨基硫酚合成新型的2,4-二芳基-3-(1,2,4-三唑-1-基)-2,3-二氢-1,5-苯并硫氮杂(3a～3l).所得化合物的结构经元素分析,IR,MS和1HNMR确认,同时用X射线衍射法测定了化合物2a和3a的晶体结构.     

Changes in the mechanical properties of tooth-colored direct restorative materials in relation to time

The objective of this study was to determine the flexural strength, flexural modulus, Vickers hardness of a packable composite (Surefil), and an ormocer (Definite) in comparison with a microhybrid composite (Z-100), a microfil composite (Silux Plus) and a polyacid-modified composite resin (Dyract). Flexural strength and flexural modulus were determined using a three-point bending device. Microhardness was measured with a Vickers indentor. The specimens of each material were prepared according to manufacturer's instructions. The specimens were stored in artificial saliva at pH 6, all at 37°C. The groups were tested at the beginning of the test, at 3 months and at 6 months. Flexural strength values of Surefil and Definite showed a progressive increase. The highest MPa values were determined for Surefil (134.4 MPa) and the lowest MPa values were obtained for Dyract (59.6 MPa). The highest flexural modulus values were revealed for Surefil (10.000 GPa). Z-100, Silux Plus and Definite showed a tendency to decline in relation to time for their flexural modulus. GPa values of Silux Plus were stable at 3 and 6 months. Vickers hardness numbers showed that Surefil was the hardest and Dyract was the weakest material. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis,characterization, and antimicrobial activity of some novel poly(ether ketone)s

Low molecular weight poly(ether ketone)s were synthesized from phenol, 1,4‐phenylenedioxy diacetylchloride, chloroacetylchloride, and dichloroalkanes [1,2‐dichloroethane and dichloromethane] by a Friedel–Crafts reaction with anhydrous aluminum chloride as a catalyst and carbon disulfide as a solvent. The conditions for the preparation of the poly(ether ketone)s and the chlorine contents obtained with the Carius method were examined, and a reaction scheme for each resin was established. The molecular weights and polydispersities of the resins were obtained by gel permeation chromatography. The polyketones were characterized by IR spectroscopy. The characteristic frequencies due to different functional groups were assigned. The thermal properties of the resins were studied with thermogravimetry and differential scanning calorimetry. The characteristic temperatures of thermal degradation for the poly(ether ketone)s were evaluated with thermogravimetric analysis. The kinetic parameters for the decomposition reactions of the resins were obtained with Broido and Doyle's method, and the heats of fusion were obtained from differential scanning calorimetry thermograms. The polyketones were thermally stable up to 200 °C. All the polyketones were tested for their microbial properties against bacteria, fungi, and yeast. The effect of poly(ether ketone)s on the growth of these microorganisms was investigated, and the polyketones were found to inhibit the growth of the microorganisms to a considerable extent. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2335–2344, 2003     

气相色谱法测定茶叶中的噻嗪酮、甲胺磷、乙酰甲胺磷及三唑磷残留

建立了同时测定茶叶中噻嗪酮、甲胺磷、乙酰甲胺磷和三唑磷4种农药残留量的测定方法。在45 ℃加温条件下,用乙酸乙酯-正己烷混合溶剂提取及活性炭色谱柱净化,用不同配比的乙酸乙酯-正己烷混合液梯度洗脱待测组分,以DB-210毛细管色谱柱分离、氮磷检测器测定。结果表明,上述4种农药在10 min内能很好地分离;样品加标回收率(n=3)为73.4%~96.9%。方法的变异系数为2.49%~3.35%,茶叶（干重）中4种农药的定量检测下限为7.0~12.0 μg/kg。     

中药材黄芪中有机氮农药残留量的液相色谱检测方法

研究了中药材黄芪中有机氮农药（包括涕灭威、呋喃丹、西维因、甲霜灵）残留量的液相色谱测定方法。采用混合溶剂提取,经Florisil及中性氧化铝柱层析净化后,再经Florisil小柱进一步净化及相转移,进入HyperOSD2C18柱分析,流动相为V（乙腈）∶V（水）=38∶62的混合液。检测波长为220nm,用外标法进行定量,当添加水平为0.07×10     

Synthesis and photochemistry of side-chain liquid crystal polymers based on cinnamate esters

The syntheses of three methacrylate monomers with cinnamate ester side-chains and of a further monomer with a corresponding cinnamide side-chain are described. Two of the monomers, with isomeric structures, were thermotropic liquid crystals. Although the clearing points were very similar the crystal melting points differed by 8°C. One compound also exhibited a monotropic smectic phase, behavior not shown by its isomer. The other two monomers were not liquid crystalline. The monomers were polymerized by free radical polymerization, both as homopolymers and as copolymers with methyl methacrylate. In the case of one of the mesogenic ester monomers, copolymers with a cyanophenyl benzoate monomer were also prepared. Three of the four monomers formed thermotropic liquid crystalline homopolymers and the copolymers with the benzoate monomer were also liquid crystalline. The monomers were considered as photoactive components of polymeric liquid crystals. As a preliminary investigation of their photochemistry, copolymers with methyl methacrylate were prepared and irradiated in solution with a broad-band source. Under these conditions two of the materials show a facile photo-Fries rearrangement of the aryl cinnamate ester group. © 1992 John Wiley & Sons, Inc.     

Palladium‐coated stainless‐steel wire as a solid‐phase microextraction fiber

A novel palladium solid‐phase microextraction coating was fabricated on a stainless‐steel wire by a simple in situ oxidation–reduction process. The palladium coating exhibited a rough microscaled surface and its thickness was about 2 μm. Preparation conditions (reaction time and concentration of palladium chloride and hydrochloric acid) were optimized in detail to achieve sufficient extraction efficiency. Extraction properties of the fiber were investigated by direct immersion solid‐phase microextraction of several polycyclic aromatic hydrocarbons and phthalate esters in aqueous samples. The extracted analytes were transferred into a gas chromatography system by thermal desorption. The effect of extraction and desorption conditions on extraction efficiency were investigated. Under the optimum conditions, good linearity was obtained and correlation coefficients between 0.9908 and 0.9990 were obtained. Limits of detection were 0.05–0.10 μg/L for polycyclic aromatic hydrocarbons and 0.3 μg/L for phthalate esters. Their recoveries for real aqueous samples were in the range from 97.1 to 121% and from 89.1 to 108%, respectively. The intra‐ and interday tests were also investigated with three different addition levels, and satisfactory results were also obtained.     

Syntheses of Hitherto Unknown Thiazole,Ylidene and Pyridinethione Derivatives Having a Piperidin‐1‐yl Moiety and Their Use as Antimicrobial Agents

The novel hydrazone derivatives 2a‐c were prepared by treatment of aldehydes 1a,b with some hydrazines. Thiocarbamoyl functional group in compound 2a was subjected to cyclization reactions with some α‐halocarbonyl reagents and furnished the novel thiazoles 4‐6 , 8 and 9 . Enaminonitrile 10 and pyridinone 13 derivatives were synthesized by interaction of active methylene compound 2b with N,N‐dimethylformamide‐dimethylacetal and ketene dithioacetal 11 , respectively. Aliphatic, aromatic and heteroaromatic active methylene compounds were condensed with aldehydes 1a,b to afford the new ylidenes 15a‐d , 19a,b , 20 and 21 . Substituted pyridinethiones 22 and 23 were prepared in high yields by cyclocondensation of 15c with malononitrile and ethyl cyanoacetate, respectively. Indeno[1,2‐b]pyridines 26a,b were obtained by the reaction of ylidenes 19a,b with cyanothioacetamide in ethanol and in the presence of sodium ethoxide under reflux. The structures of the synthesized compounds were established from their analytical and spectral data. The prepared compounds were also screened for their antimicrobial activity.     

Optically Active Helical Lanthanide Complexes: Storable Chiral Lewis Acidic Catalysts for Enantioselective Diels–Alder Reaction of Siloxydienes

Lanthanide triflates and a series of hexadentate chiral ligand complexes were synthesized. X‐ray‐quality crystals were obtained from mixtures of the lanthanide complexes, which were helical in shape. The complexes showed Lewis acidity and catalyzed the enantioselective Diels–Alder reaction of electron‐rich siloxydienes. The complexes were stable enough to be stored at ambient temperature on a laboratory bench and retained their Lewis acidity even after a month.     

高效液相色谱法测定谷子幼苗中的GA_1和GA_3

建立了同时测定谷子幼苗中赤霉素Ａ１（ＧＡ１）和赤霉素Ａ３（ＧＡ３）的高效液相色谱（ＨＰＬＣ）方法。采用ＯＤＳ Ｃ１８色谱柱,以磷酸盐缓冲液和甲醇为流动相,ＧＡ１和ＧＡ３在１０ｍｉｎ内获得良好分离。利用该方法对谷子的两个正常栽培品种及其矮秆突变体的幼苗进行了测定。测定结果表明,谷子幼苗中同时含有ＧＡ１和ＧＡ３两种活性赤霉素,它们各自的质量比是影响谷子株高的重要因素。     

Characterization and Wettability of ZnO Film Prepared by Chemical Etching Method

ZnO thin films were prepared by a chemical etching method and their wettability was investigated. The structure and surface composition structure were characterized by means of scanning electron microscopy, X-ray photoelectronic spectrometry(XPS), X-ray diffraction(XRD) and Raman spectrometry. These analyses reveal that the etched films were large-scale micro-nanohierarchical structures composed of a Zn core and a ZnO coating. Superhydrophobic surfaces with water contact angles of over 150o were obtained by n-octadecanethiol(ODT) modification. The XPS and Raman results indicate that ODT molecules were bound to the ZnO surface with the S head group by forming Zn-S bond.     

Distribution of olfactory marker protein on a tissue section of vomeronasal organ measured by AFM

Distribution of olfactory marker protein (OMP) on a tissue section of vomeronasal organ (VNO) was successfully measured by atomic force microscopy (AFM). Anti-OMP antibodies were covalently crosslinked with the tip of the AFM and were used as a probe to observe the distribution of OMP on a tissue section. First, force measurements were performed using a glass surface on which OMP was covalently immobilized to verify the success of tip modification. Clear differences of interaction forces were observed between a specific pair and the control experiments, indicating that the tip preparation succeeded. Next, distributions of OMP on the tissue section were observed by AFM and were compared with immunohistochemical observations. For large scale observation, a microbead was used as a probe in the AFM measurements. The results of the AFM measurements were well overlapped with that of immunohistochemistry, confirming the reliability of our method. A mapping of the AFM measurement with high resolution was also successfully obtained, which showed an advantage of the application of the AFM measurement in analysis of proteins on the tissue section.     

碳微线圈的合成、表征及形态研究

以镍为催化剂,在助剂噻吩的作用下,采用乙炔高温热解法合成了规则、均匀、具有双螺旋结构的碳微线圈.用同一次实验所得的产物,从水平与垂直两个方向研究了碳微线圈形态的变化与分布规律,并进一步通过改变反应器的结构做了比较实验,结合SEM,TEM,SAED和XRD等表征手段对这一规律进行分析研究.结果表明,反应气流的流向以及催化剂在反应过程中发生的物理和化学变化是导致碳微线圈形态变化的两个重要原因.另外,对碳微线圈的结构、生长机理以及噻吩的作用进行了初步研究.     

Synthesis and degradabilities of polyesters from 1,4:3,6-dianhydrohexitols and aliphatic dicarboxylic acids

Six different polyesters ( 6a–6c and 7a–7c ) were prepared by the bulk polycondensations of the respective combinations of 1,4:3,6-dianhydro-D-glucitol ( 3 ) and 1,4:3,6-dianhydro-D-mannitol ( 4 ) with succinyl dichloride ( 5a ), glutaryl dichloride ( 5b ), and adipoyl dichloride ( 5c ) at 140–180°C. Polyesters having number average molecular weights up to 2.6 ×10⁴ were obtained in high yields. Only polyester 7a based on 4 and 5a was partially crystalline, whereas all the other polyesters were amorphous. Thin films of these polyesters except that of 7a were spontancously hydrolyzed in a neutral phosphate buffer solution at 50°C, whereas they were reluctant to be hydrolyzed at 27°C. The polyesters were more or less degraded at 27°C by treatment with an activated sludge or by prolonged burial in soil. © 1995 John Wiley & Sons, Inc.     

Crystalline lanthanum hydroxycarbonates with controlled phases and varied morphologies prepared on non-crystalline substrates

Lanthanum hydroxycarbonate crystals with controlled phases and varied morphologies were prepared on the surface of a non-crystalline substrate, glass. The phases and morphologies of the crystals were controlled conveniently by varying the reaction temperature and the quantity of starting materials. Orthorhombic crystals were obtained at 160 °C, distributed individually on the substrate and had a flaky rhombic shape. Hexagonal crystals were obtained at 180 °C. The crystals had a rhomboidal shape, were uniform and continuous enough to form a solid film on the substrate. The substrates were corroded under the hydrothermal conditions and offered a coarse surface for the crystal growth. The hexagonal lanthanum hydroxycarbonate was discovered to show significant second harmonic generation, which would be of interest for developing novel optical materials.     

Effect of Alkyl Chain Length of N-Alkyl-N′-(2-benzylphenyl)ureas on Gelation

Urea derivatives that were substituted with a 2-benzylphenyl group and an alkyl group functioned as low molecular weight gelators for various organic solvents and ionic liquids. Urea derivatives with long alkyl chains were effective for the gelation of polar solvents. However, they were not suitable for the gelation of non-polar solvents, whereas urea derivatives with short alkyl chains were effective. Ionic liquids were similar to polar solvents in that urea derivatives with long alkyl chains were the most effective gelators. The physical properties of the formed supramolecular gels were analyzed by dynamic viscoelasticity measurements using a rheometer.