Acidic ionic liquids catalyst in homo and graft polymerization of ε-caprolactone

Biodegradable polycaprolactone was prepared by ring-opening polymerization in presence of ionic liquids as efficient, inexpensive, nontoxic, and easily handled acid catalysts. The resulting polymer exhibited good yield and inherent viscosity between 0.10 and 0.18 dL/g. The chemical structure of obtained polymer was verified by the ¹H-NMR and Fourier transform infrared spectroscopy (FT-IR) spectra. In continuation, the obtained polymer was applied to improve quality level and mechanical properties and also to reduce the hydrophilic properties of the starch, so the ring-opening polymerization of ε-caprolactone was investigated in the presence of starch hydroxyl groups as initiator and ionic liquid as catalyst. The obtained starch-grafted-polycaprolactone was verified by ¹H-NMR, FT-IR spectra, and field emission scanning electron microscopy analysis.     

Laser induced-thermal lens spectrometry in combination with dispersive liquid-liquid microextraction for trace analysis

An ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME) was developed as a new approach for the extraction of organophosphorus pesticides (OPs) in water samples prior to high-performance liquid chromatography with diode array detection (HPLC-DAD). The use of a surfactant as an emulsifier in the UASEME method could enhance the dispersion of water-immiscible extraction solvent into aqueous phase and is favorable for the mass-transfer of the analytes from aqueous phase to the organic phase. Several variables that affect the extraction efficiency, including the kind and volume of the extraction solvent, the type and concentration of the surfactant, salt addition, ultrasound emulsification time and temperature, were investigated and optimized. Under the optimum experimental conditions, the calibration curve was linear in the concentration range from 1 to 200 ng mL(-1) for the seven OPs (isocarbophos, phosmet, parathion, parathion-methyl, fenitrothion, fonofos and phoxim), with the correlation coefficients (r) varying from 0.9973 to 0.9998. High enrichment factors were achieved ranging from 210 to 242. The established UASEME-HPLC-DAD method has been successfully applied for the determination of the OPs in real water samples. The limits of detection were in the range between 0.1 and 0.3 ng mL(-1). The recoveries of the target analytes over the three spiked concentration levels of the compounds (10, 50, and 100 ng mL(-1), respectively) in rain, reservoir and well water samples were between 83% and 106% with the relative standard deviations varying from 3.3% to 5.6%.     

DC-Pulsed Plasma for Dry Reforming of Methane to Synthesis Gas

The carbon dioxide reforming of methane to synthesis gas under DC-pulsed plasma was investigated. The effects of specific input energy and feed ratio on the product distribution and also feed conversion was studied. At the input energy of about 11 eV/molecule per methane and/or carbon dioxide the feed conversion of 38% for CH₄ and 28% for CO₂ and product selectivity of 74% has been attained for H₂ and CO at feed flow rate of 90 ml/min. The energy consumption in this work displays potential to further study and optimization of the process. The importance of the electron impact reactions in the process was discussed. The results show that by prudent tuning of system variables, the process be able to run in the way of synthesis gas, instead of hydrocarbon production.     

An ionic 2D inorganic-organic hybrid of tris[((1H-tetrazol-5-yl)methyl)morpholine] dodecatungstophosphate(Ⅴ) pentahydrate:Synthesis X-ray crystal structure and spectroscopic characterizations

<正>A unique ionic hybrid material[C_6H_(12)N_5O]_3[(PO_4)W__(12)O_(36)]·5H_2O has been synthesized from the reaction of((1H-tetrazole-5- yl)methyl)morpholine andα-H_3[(PO_4)W_(12)O_(36)]·21H_2O.It has successfully been characterized by elemental analysis,IR and ~1H NMR spectroscopies,TGA and single-crystal X-ray diffraction method.The title compound is constructed from the three [C_6H_(12)N_5O]~+ cations andα-Keggin[(PO_4)W_(12)O_(36)]~(3-) polyoxoanion.The most remarkable structural feature of this hybrid can be described as two-dimensional inorganic infinite plane-like(2D/∞)[(PO_4)W_(12)O_(36)]~(3-)) which forming via van der Waals interactions along the x axis.     

PVA-Based Sol–Gel Synthesis and Characterization of CdO–ZnO Nanocomposite

CdO–ZnO nanocomposite was fabricated by a sol–gel pyrrolysis method based on the poly vinyl alcohol (PVA) polymeric network. The prepared nanocomposite was carefully characterized using scanning electron microscopy, X-Ray dispersive energy analysis, ICP-atomic emission spectroscopy, X-Ray diffraction, transmission electron microscopy and UV–visible spectroscopy. The structure, composition, and morphology of this composite depend on a number of aspects: the amounts of cadmium salt, zinc salt, and PVA in the initial solution, the solvent composition, and the pyrrolysis temperature. The obtained results showed that the nanocomposite had excellent linear nanoclusters created from nanograins. Each nanograin was made of a CdO core, completely covered by ZnO layers. Total diameter of each nanograin was 70–90 nm.     

Competitive Self and Induced Aggregation of Calix[4]arene Ethers and Their Interaction with Pinacyanol Chloride and Methylene Blue in Nonaqueous Media

Long chain calix[4]arene ethers have been examined for aggregation in nonaqueous solvents by using UV-vis molecular absorbance spectroscopy. It has been observed that tetraalkylated (alkyl = hexadecyl and octadecyl, respectively) calix[4]arene ethers tend to aggregate in chloroform and tetrahydrofuran, possibly via π–π stacking interactions of the phenyl moieties, and the aggregation process appears to be facilitated by the alkyl chains. The analogous dialkylated compounds do not show any self-aggregation, plausibly due to strong hydrogen bonding between the –OH and the –O– of calix aryl ether which seems to disrupt the aggregation process. Addition of the anionic surfactant sodium dodecylsulfate (SDS) appears to hinder the aggregation process in nonpolar chloroform but the same surfactant facilitates aggregation in the polar tetrahydrofuran. The cationic surfactant (cetyltrimethyl ammonium bromide) and the nonionic surfactant (Brij-35) have no effect on this aggregation process. Unexpectedly, SDS induces aggregation of dialkylated calix[4]arene ethers in chloroform. It has been observed that the aggregated form of the tetraalkylated calix[4]arene ethers tend to increase the dimerization efficiency of cationic dyes (pinacyanol chloride and methylene blue) in chloroform.     

Density functional theory study of the regio‐ and stereoselectivity of 1,3-dipolar cycloaddition reactions between 2-ethylthio-4-phenyl-1-azetin and some substituted nitrile oxides

The mechanism (regio- and stereoselectivity) of 1,3-dipolar cycloaddition (1,3-DC) of 2-ethylthio-4-phenyl-1-azetin 1 with benzonitrile oxide 2a, 2-aminobenzonitrile oxide 2b and 2-azidobenzonitrile oxide 2c has been investigated by density functional theory-based reactivity indices and activation energy calculations at B3LYP/6-31G(d,p) level of theory in the gas and solvent phase. Thermodynamic and kinetic parameters of the possible ortho/meta regioisomeric and endo/exo stereoisomeric pathways have been determined. In order to rationalize complete endo selective fashion provided by these 1,3-DC cycloadditions, a natural steric analysis between NLMOs i,j for TS1ox and TS1on and also a second-order interaction energy, E ², analysis between the donor–acceptor orbitals in these TSs were carried out. In all cases, the ortho pathways are more favorable compared to the meta alternatives and it is found that the endo pathway is preferred. Our results show that these cycloadditions follow an asynchronous one-step mechanism with a nonpolar character. Theoretical data are in good agreement with the experimental results.