Analysis of endosulfan isomers and endosulfan sulfate in air and tomato leaves by gas chromatography with electron-capture detection and confirmation by gas chromatography-mass spectrometry

Rapid analytical methods for the determination of endosulfan isomers and endosulfan-sulfate in air and plant samples were developed. The insecticides were trapped from air using a column containing Florisil and extracted with a low volume of ethyl acetate, assisted by sonication. Pesticide residues were determined by gas chromatography with electron-capture detection using a nonpolar capillary column. Residue identities were confirmed by gas chromatography coupled with mass spectrometry. Recoveries of these compounds from air samples were always higher than 78% with an RSD lower than 11% and the detection limits obtained were at least 0.3 ng/l air. Leaf samples were homogenised with ethyl acetate and extracts cleaned-up on an aluminium oxide column. Pesticides were eluted with a hexane-ethyl acetate (80:20, v/v) mixture. Recoveries obtained from plant samples were higher than 78% with an RSD lower than 14% and detection limits in leaves were 0.02 microg/g for each pesticide. These methods were applied to study the volatilisation of endosulfan from tomato leaves under laboratory conditions. A volatilisation rate near 1% of the initial amount of endosulfan per hour was obtained during the first 24 h at room temperature.     

Reaction of Lithium Cellulosate with Episulfides

The reactions of propylene, ethylene, and styrene sulfide with cotton fabrics in the form of their lithium cellulosate derivative, obtained by metallation with lithium methoxide, were studied. Both graft and homo-polymerization took place and in the reaction with propylene and ethylene sulfide, cotton fabrics with high polysulfide content were obtained. With propylene sulfide 50% of the monomer polymerized was grafted. The effects of monomer concentration, cellulosate degree of substitution, reaction time, and solvent on the polymerization were investigated. In contrast with propylene and ethylene sulfide, only small conversions were obtained in the reaction with styrene sulfide. The results were attributed to steric effects.     

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.     

Molecular dynamics simulations of p-tert-butylcalix[4]arene with small guest molecules

Classical molecular dynamics simulations were used to study p-tert-butylcalix[4]arene inclusion compounds with xenon, nitrogen, hydrogen, methane, and sulfur dioxide guest molecules. The calixarene units were taken to be rigid and the intermolecular molecular interactions were modeled as a sum of the van der Waals interactions with parameters from the AMBER force field and electrostatic interactions. Simulations of the high-density alpha phase and low-density beta0 phase of p-tert-butylcalix[4]arene were used to test the force field. The predicted densities of the two phases were found to agree with experimental measurements at 173 K to within 5 %. Simulations were performed with guests placed inside the calixarene cages of the beta0 phase. Guest-host ratios of 1:1 to 1:4 were considered. Changes in the unit-cell volume and density of the phases with the addition of guest molecules and the inclusion energies for the guests were determined. Finally, the dynamics of the guest motion inside the cages were characterized by determining the root-mean-square displacements and velocity autocorrelation functions of the xenon and nitrogen guests.     

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.     

3种方法测定植物源性农产品中霉灵残留量

建立了测定大豆、糙米、黄瓜、甜菜等6种植物源性农产品中(噁)霉灵残留的气相色谱-火焰光度法(GC-FPD)、气相色谱-氮磷检测法(GC-NPD)和液相色谱-串联质谱法(LC-MS/MS).GC-FPD法采用丙酮-正己烷提取样品,O,O-二甲基硫代磷酰氯衍生,GC-FPD分析,外标法定量;GC-NPD法采用丙酮-正己烷提取样品,十八烷基键合硅胶(C18)净化,GC-NPD分析,外标法定量;LC-MS/MS法,样品采用乙腈提取,石墨化碳黑(GCB)净化,LC-MS/MS分析,基质匹配外标法定量.结果表明,(噁)霉灵的响应值与其浓度间呈良好的线性关系,3种方法的相关系数均大于0.998.在3个加标浓度下,GC-FPD法中(噁)霉灵的日间平均回收率为82%~96%,日间相对标准偏差(RSD)为3.4%~12.1%,方法的定量下限为0.25 mg/kg (甜菜为0.05 mg/kg);GC-NPD法的日间平均回收率为81%~103%,日间RSD为4.1%~14.3%,定量下限为0.25 mg/kg (甜菜为0.05 mg/kg);LC-MS/MS法的日间平均回收率为74%~110%,日间RSD为2.5%~10.7%,定量下限为0.05 mg/kg.3种方法均具有良好的准确性和稳定性,可满足(噁)霉灵残留分析的要求.     

Properties of novel gel particles with projections and preparations of composite particles with gold nanoparticles

Mono-dispersed gel particles with projections were prepared by dispersion polymerization with ethyleneglycol dimethacrylate and a polyethyleneglycol (PEG) block macro azo initiator in H₂O/ethanol solutions. The effects of molecular weight of PEG blocks and polymerization conditions on the morphology and some properties were examined for the gel particles. The diameters and the extent of coagulation were different with the polymerization conditions. Relatively large specific areas and large swelling ratio with H₂O were obtained, and these values were related with the polymerization conditions. By mixing the gel particles with gold nanoparticles in solutions, composite particles were formed, which were composed of gold nanoparticles adsorbed on the gel particles. Interaction between gold nanoparticles and reactive azo groups remained in the gel particles concerned for the formation of the composite particles.     

Preparation and characterization of dendrimer-templated Ag-Cu bimetallic nanoclusters

Ag-Cu bimetallic nanoclusters with different shapes were prepared by a co-complexation method in the presence of PAMAM dendrimers. Small and evenly sized spherical Ag-Cu bimetallic nanoparticles were obtained with N2H4.H2O as the reducing agent, and long rod-shaped bimetallic nanoclusters were prepared with NaBH4 as the reducing agent. The mechanisms of formation of Ag-Cu bimetallic nanolusters with different shapes were discussed. The different shapes of the cluster were likely caused by the differences in the reduction rate of metal ions with NaBH4 and N2H4.H2O. Structure characterization by TEM, UV-vis spectra, EDX, and TGA showed that, in the presence of PAMAM dendrimers, Ag-Cu alloy bimetallic nanorods were obtained with NaBH4 reduction, and Ag-Cu bimetallic nanoparticles were prepared with N2H4.H2O as the reducing agent.     

Simultaneous determination of residual antiparasitic lactones in bovine muscle and liver by liquid chromatography with fluorescence detection

Abamectin, doramectin, eprinomectin, ivermectin, milbemectin, and moxidectin in bovine muscle and liver were extracted with acetonitrile. The extracts were partitioned with n-hexane and then evaporated to dryness. The residue was cleaned up on Bond Elute NH2 cartridge, and the drugs were eluted from the cartridge with methanol-ethyl acetate (3 + 7). The eluate was evaporated to dryness, and residues were derivatized with N,N-dimethylformamide-acetic anhyride-1-methylimidazole. The derivatives were determined by liquid chromatography with fluorescence detection. Recoveries of the 6 drugs were 79.6-63.8% in muscle and 71.6-60.6% in liver at 0.01 ppm levels. The quantitation limits were 5 ppb for each drug.     

Comparative Proteomic Analysis of Human Benign Prostatic Hyperplastic Tissue Before and After Irradiation with Radioactive Nuclide

The expressed proteins were extracted from human benign prostatic hyperplastic tissues obtained with transurethral resection of the prostate before and after their irradiation with radioactive nuclide. The proteins were separated by two-dimensional gel electrophoresis and analyzed by mass spectrometry. Four proteins were differentially expressed and were identified with a database search. Three were associated with the regulation of cell motion and one was lactate dehydrogenase B, which plays an important r...     

Supramolecular hydrogels based on short peptides linked with conformational switch

Short peptides appropriately linked with an azobenzene conformational switch were found to be motif and pH dependant supramolecular hydrogelators. The hydrogelation properties of the short peptides linked with the conformational switch were studied in detail with respect to dependence on amino acid residue, pH and salt effect. The presence of amino acids with aromatic side chains such as Phe and Tyr was found to be favorable for the short peptides to gel water at an appropriate pH range. Cationic amino acid residues such as Arg and Lys in the short peptides were found to be unfavorable for hydrogelation. pH and salt effect were also found to be important factors for the hydrogelation properties of the short peptides. A series of short peptides with bioactive sequences were linked with the conformational switch and their hydrogelation properties were investigated. Photoresponsive supramolecular hydrogels were realized based on the E-/Z- transition of the conformational switch upon light irradiation. Proper combination of amino acid residues in the short peptides resulted in smart supramolecular hydrogels with responses to multiple stimuli.     

Silicon-Containing Condensation Polymers Derived from Long-Chain Fatty Acids

Silicon-containing condensation polymers were prepared starting from difunctional silicon-containing carboxylic acids or diols derived from long-chain fatty acids. Polyesters were synthesized by reaction of diacids containing siloxane linkages with diols, and diols containing siloxane linkages with various diacids. 1,3-Bis (10-carboxydecyl)tetramethyldisiloxane was condensed with various diamines to yield polyamides. 1,3-Bis(11-hydroxyundecyl)tetramethyldisiloxane and 1,3-bis [9(10)-hydroxyoctadecyl]tetramethyldisiloxane were condensed with diisocyanates to yield polyurethanes. Polycarbonates were synthesized by reacting the diols containing siloxane linkages with ethyl chloroformate. Some polybenzimidazols were synthesized by heating the diesters of the silicon-containing carboxylic acids with 3,3′ -diaminobenzidine. Some of the polyurethanes and polybenzimidazoles were thermally stable up to 300°C as indicated by TGA.     

Superhydrophobic films of electrospun fibers with multiple-scale surface morphology

Superhydrophobic nanofiber films were created from electrospun nanofibers with undulated surfaces at multiple scales in micrometers and nanometers. The electrospun nanofibers were produced out of aqueous solutions which contained water-soluble polymers and different colloids: monodisperse silica or polystyrene microspheres for larger particles and monodisperse silica nanoparticles for smaller particles. Various types of fibrous films were produced depending on the properties of the dispersing medium, the effects of additives, and the compositions of the bidisperse colloids. When polystyrene microspheres were used as sacrificial templates, macropores were left behind in the nanofibers during the removal of polystyrene microspheres by calcination. The nonwoven films of electrospun nanofibers, which were decorated with silica microspheres or macropores, could be continuously produced with considerable ease under a relatively wide range of operating conditions. The surface properties of the films were characterized by contact angle measurement and an X-ray photoelectron spectrometer. Through the surface modification of the electrospun nanofibers with fluorinated silane coupling agents, superhydrophobic surfaces with low sliding angles were successfully prepared.     

Spectroscopic,structure, and DFT studies of cationic palladium(II) complexes with imidazole derivative ligands

Two palladium(II) complexes with imidazole derivative ligands have been synthesized. The molecular structures of the complexes were determined by X-ray crystallography and their spectroscopic properties were studied. Based on the crystal structures, computational investigations were carried out to determine the electronic structures of the complexes. The electronic spectra were calculated with use of time-dependent DFT method, and the transitions were correlated with the molecular orbitals of the complexes. The emission of the complex with 1-methylimidazole was examined.     

Boron analysis in biological material: microwave digestion procedure and determination by different methods

Investigations were made on the determination of boron in biological material. A procedure using the microwave digestion technique was optimised. The analyses were performed by photometry with azomethine-H, fluorimetry with carminic acid, inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. The matrix interferences, the interferences caused by iron and the detection limits were investigated for these methods. Determinations were performed for plant material, wheat, milk, meat and blood plasma. Recoveries and precision of all methods were studied. To test accuracy and precision, four NBS reference materials were analysed and the results compared with the values in literature. Good recoveries were found with all methods, except the fluorimetric technique. The boron content found in the NBS standard reference materials agreed well with data reported before. Best precision was obtained for the two ICP methods. The azomethine-H method gave good results when material of high boron content was analysed. With the carminic acid method no reliable results were achieved.     

CdTe量子点DNA荧光纳米探针的合成及表征

采用水相合成法合成了巯基乙酸(TGA)修饰的水溶性CdTe量子点,通过反相微乳液法制备了二氧化硅及壳聚糖修饰的核壳型复合荧光纳米粒子,将其与DNA吸附连接,得到CdTe量子点DNA荧光纳米探针。用扫描电镜、透射电镜、荧光光谱、红外光谱、紫外光谱、ζ电位等测试方法对产物的理化性质进行了分析表征。结果表明制备了表面富含氨基的复合荧光纳米粒子,其对DNA具有良好的吸附作用。     

GC-MS方法诊断新生儿苯丙酮尿症

用甲醇提取血样中的苯丙氨酸(Phe)、酪氨酸(Tyr),提取液离心去蛋白质,用正丁醇将其中的苯丙氨酸和酪氨酸丁酯比,再用三氟醋酸酐酰化后进行GC-MS分析,测定Phe,Tyr特征离子峰面积,用外标法计算出Phe和Tyr的摩尔浓度,根据Phe和Tyr摩尔浓度比值来诊断新生儿苯丙酮尿症(PKU)。     

Synthesis,characterization, thermal properties,and antimicrobial activity of 4‐chloro‐3‐methyl phenyl methacrylate/8‐quinolinyl methacrylate copolymers

4‐Chloro‐3‐methyl phenyl methacrylate (CMPM) and 8‐quinolinyl methacrylate (8‐QMA) were synthesized through the reaction of 4‐chloro‐3‐methyl phenol and 8‐hydroxy quinoline, respectively, with methacryloyl chloride. The homopolymers and copolymers were prepared by free‐radical polymerization with azobisisobutyronitrile as the initiator at 70 °C. Copolymers of CMPM and 8‐QMA of different compositions were prepared. The monomers were characterized with IR spectroscopy and ¹H NMR techniques. The copolymers were characterized with IR spectroscopy. UV spectroscopy was used to obtain the compositions of the copolymers. The monomer reactivity ratios were calculated with the Fineman–Ross method. The molecular weights and polydispersity values of the copolymers were determined with gel permeation chromatography. The thermal stability of the polymers was evaluated with thermogravimetric analysis under a nitrogen atmosphere. The homopolymers and copolymers were tested for their antimicrobial activity againstbacteria, fungi, and yeast. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 157–167, 2005     

Equilibrium analysis of reactions of metal-pyridylazoresorcinolato chelates with quaternary ammonium ion, nonionic surfactant and polyethylene glycol in aqueous solution by capillary zone electrophoresis.

The resolutions of metal-4-(2-pyridylazo)resorcinol chelates by capillary zone electrophoresis (CZE) were investigated in the presence of some interacting reagents; also, equilibrium reactions between the chelates and the interacting reagents were analyzed in an aqueous solution. Among nine metal chelates formed in aqueous solution, the chelates of VV, FeII, CoIII, NiII, and CuII were resolved and detected by CZE, while other chelates were decomposed during electrophoretic migration. The electrophoretic mobility of the chelates of FeII, NiII, and CuII increased with increasing pH of the migrating solution; also, the acid-dissociation constants of these three chelates were determined by analyzing the mobility change. The ion-association constants of the five anionic chelates and pyridylazoresorcinolate ion with quaternary ammonium ions were also determined by analyzing the mobility change. The binding behavior of the ligand and its chelates with nonionic surfactant micelle, as well as with polyethylene glycol, were investigated, and their binding constants were determined through the mobility change. When Brij 35 was used as a nonionic surfactant interacting with the anionic chelates, the FeII chelate decomposed at Brij 35 concentrations over 6.67 mM. The equilibrium constants and the reactivity were compared with each other.