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161.
Chen H Chen H Cooks RG Bagheri H 《Journal of the American Society for Mass Spectrometry》2004,15(11):1675-1688
Nitro-reduction by the vinyl halide radical cation CH2 = CH-X+* (X = Cl or Br) converts nitroaromatics into arylnitrenium ions, significant intermediates in carcinogenesis, and the present study reports on the scope and regioselectivity of this versatile reaction. The reaction is general for different kinds of substituted nitroaromatics; para/meta substitutents have little effect on the reaction while ortho substitutents result in low yields of arylnitrenium ions. The phenylnitrenium ion PhNH+ can be generated by chemical ionization (CI) of nitrobenzene using 1,2-dichloroethane as the reagent gas or by atmospheric pressure chemical ionization (APCI) of 1,2-dichloroethane solution doped with nitrobenzene. The chemical reactivities of the arylnitrenium ions include one-step ion/molecule reactions with nucleophiles ethyl vinyl ether and 1,3-dioxolanes, respectively, involving the direct formation of new CN bonds and synthesis of indole and benzomorpholine derivatives. The indole formation reaction parallels known condensed phase chemistry, while the concise morpholine-forming reaction remains to be sought in solution. The combination of collision-induced dissociation (CID) with novel ion/molecule reactions should provide a selective method for the detection of explosives such as TNT, RDX and HMX in mixtures using mass spectrometry. In addition to the reduction of the nitro group, reduction of methyl phenyl sulfone PhS(O)2Me to the thioanisole radical cation PhSMe+* occurs using the same chemical ionization reagent 1,2-dichloroethane. This probably involves an analogous reduction reaction by the reagent ion CH2 = CH-Cl+*. 相似文献
162.
Deformation mechanism of epoxy/clay nanocomposite 总被引:2,自引:0,他引:2
Polymer-layered silicate nanocomposites have been noticed recently due to their outstanding properties. The mechanical properties and deformation mechanism of epoxy/montmorillonite nanocomposites under compressive and flexural loadings were investigated. A reduction in compressive and flexural yield stress and also glass transition temperature with increasing the amount of organoclay was observed. This change in mechanical behavior of epoxy can be explained with observation of plastic deformation mechanism. The study of deformation mechanism revealed that presence of organoclay accelerates shear yielding in epoxy. Microscopic evaluation illustrated that nanoparticles in this system act as initiation sites for shear bands, and thus, enable the epoxy to undergo massive shear yielding. 相似文献
163.
A modified in-tube solid phase microextraction (SPME) technique in conjunction with a high performance liquid chromatography (HPLC) was developed for the trace determination of polycyclic aromatic hydrocarbons (PAHs) in water samples. The extraction device contained a regular HPLC syringe, replacing the metallic needle by two concentric fused silica capillary tubes. The capillary tubes were coated with polydimethylsiloxane (PDMS) as the sorbent and were attached to the syringe by a homemade interface made from polyether ether ketone (PEEK). The sorption of analytes was achieved by frequent withdrawing and ejecting the water sample from/into a vial via the capillary tubes. For the desorption step, an aliquot of organic solvent was withdrawn and subsequently injected directly into the HPLC system. Limits of detection for the elected PAHs were between 0.001 and 0.006 g L–1 with a RSD of 2.6–6.3%. 相似文献
164.
Mechanisms of antioxidant action: The catalytic rôle of iodine in the stabilisation of polypropylene
It is shown that I2 is an effective melt stabiliser for polypropylene at 190°C in a closed mixer but that it is much less effective in an open mixer. The formation of HI and unsaturation in the polymer show that a catalytic antioxidant mechanism (CB-A/CB-D) is involved in the antioxidant activity of I2 in a closed mixer similar to that occurring in the stabilisation of polyolefins with galvinoxyl and nitroxyl radicals.The processed polymer shows slightly greater uv stability than the control with no additive but is essentially similar to the control in thermal oxidative stability. The volatility of HI in an air oven probably accounts for the fact that it has no CB-D activity under these conditions. 相似文献
165.
Bin Zhao Ningwei Li Tianfa Xie Yousef Bagheri Chungwen Liang Puspam Keshri Yubing Sun Mingxu You 《Chemical science》2020,11(32):8558
Cells are physically contacting with each other. Direct and precise quantification of forces at cell–cell junctions is still challenging. Herein, we have developed a DNA-based ratiometric fluorescent probe, termed DNAMeter, to quantify intercellular tensile forces. These lipid-modified DNAMeters can spontaneously anchor onto live cell membranes. The DNAMeter consists of two self-assembled DNA hairpins of different force tolerance. Once the intercellular tension exceeds the force tolerance to unfold a DNA hairpin, a specific fluorescence signal will be activated, which enables the real-time imaging and quantification of tensile forces. Using E-cadherin-modified DNAMeter as an example, we have demonstrated an approach to quantify, at the molecular level, the magnitude and distribution of E-cadherin tension among epithelial cells. Compatible with readily accessible fluorescence microscopes, these easy-to-use DNA tension probes can be broadly used to quantify mechanotransduction in collective cell behaviors.A DNA-based fluorescent probe to quantify the magnitude and distribution of tensile forces at cell–cell junctions. 相似文献
166.
B. Bagheri M. Karttunen B. Baumeier 《The European physical journal. Special topics》2016,225(8-9):1743-1756
Electronic excitations in dilute solutions of poly para phenylene ethynylene (poly-PPE) are studied using a QM/MM approach combining many-body Green's functions theory within the GW approximation and the Bethe-Salpeter equation with polarizable force field models. Oligomers up to a length of 7.5?nm (10 repeat units) functionalized with nonyl side chains are solvated in toluene and water, respectively. After equilibration using atomistic molecular dynamics (MD), the system is partitioned into a quantum region (backbone) embedded into a classical (side chains and solvent) environment. Optical absorption properties are calculated solving the coupled QM/MM system self-consistently and special attention is paid to the effects of solvents. The model allows to differentiate the influence of oligomer conformation induced by the solvation from electronic effects related to local electric fields and polarization. It is found that the electronic environment contributions are negligible compared to the conformational dynamics of the conjugated PPE. An analysis of the electron-hole wave function reveals a sensitivity of energy and localization characteristics of the excited states to bends in the global conformation of the oligomer rather than to the relative of phenyl rings along the backbone. 相似文献
167.
1,3-Benzoxazoles via oxidative cyclization of corresponding o-hydroxyarylidene anilines was synthesized in the presence of KMnO4/HOAc system. This system also was applied for the one-pot synthesis of 1,3-benzoxazoles from o-amino phenols and aldehydes. The both protocols were processed at room temperature under solvent-free conditions with good to excellent yields. 相似文献
168.
Microwave‐assisted extraction and high‐throughput monolithic‐polymer‐based micro‐solid‐phase extraction of organophosphorus,triazole, and organochlorine residues in apple 下载免费PDF全文
Habib Bagheri Ali Es'haghi Ali Es‐haghi Fatemeh Basiripour 《Journal of separation science》2016,39(3):576-583
A high‐throughput micro‐solid‐phase extraction device based on a 96‐well plate was constructed and applied to the determination of pesticide residues in various apple samples. Butyl methacrylate and ethylene glycol dimethacrylate were copolymerized as a monolithic polymer and placed in the cylindrically shaped stainless‐steel meshes of 96‐micro‐solid‐phase extraction device and used as an extracting unit. Before the micro‐solid‐phase extraction, microwave‐assisted extraction was employed to facilitate the transfer of the pesticide residues from the apple matrix to liquid media. Then, 1 mL of the aquatic samples was transferred into the 96‐well plate and the 96‐micro‐solid‐phase extraction device was applied for the extraction of the selected pesticides. Influential parameters, such as sorbent‐to‐sorbent reproducibility, microwave‐assisted extraction time, ionic strength and micro‐solid‐phase extraction time, were optimized. The limits of quantitation were below 120 μg/kg, which are lower than the maximum residue limits. The developed method was successfully implemented for the extraction and determination of the selected pesticides from 20 different apple samples gathered from local markets. Phosalone was identified and quantified at the concentration level of 147 (±16.4) μg/kg in one of the samples. 相似文献
169.
Maryam Masjedi-Arani Davood Ghanbari Masoud Salavati-Niasari Samira Bagheri 《Journal of Cluster Science》2016,27(1):39-53
In this work spherical SiO2 nanoparticles were synthesized by sonochemical method using a new Schiff-base as a capping agent. The silica nanoparticles were obtained by hydrolysis of tetraethyl orthosilicate in aqueous alcohol solution. The effect of different parameters such as molar concentration of Schiff-base ligands and ultrasonic irradiation on the morphology and size of the products was examined. The results demonstrated that applying the appropriate amount of Schiff-base could be effective in control of particle size. The influence of SiO2 nanostructures on the flame retardancy of the poly styrene, poly vinyl alcohol, cellulose acetate and ethyl cellulose was studied. In-situ and ex situ nanocomposites were investigated and results confirm that flame retardancy of in situ nanocomposites were better than ex situ samples. HO···Si–O–Si···OH barrier prevents reaching of flame, heat and oxygen to the polymeric nanocomposites. 相似文献
170.
H. Bagheri M. Nekoomanesh S. Hakim Y. Jahani H. S. Tan Z. Q. Fan 《Polymer Science Series A》2016,58(2):283-291
The interfacial adhesion and molecular structure of an in-reactor polypropylene/ethylene propylene rubber alloy were studied with respect to the rheological behavior and final properties of the alloy. The polymer alloys have similar structural parameters but different impact properties. The samples were characterized by gel permeation chromatography, thermal analysis, rheological analysis and mechanical testing. Fractionation of samples showed that the quantities of components are the same. Gel permeation chromatography results showed that molecular weight distribution of all components were similar. Thermal analysis results showed that the crystal size of two samples was the same but the crystal contents were different. In studying the impact strength, it was revealed that a large difference exists between the two samples. The small amplitude oscillation rheometry indicates that the rheological parameters have a glaring difference in both samples that can be an evidence of interfacial adhesion in the in-reactor alloys having so many similar structural parameters. 相似文献