Design and characterization of [(Et)3 N-H]FeCl4 as a nanomagnetic ionic liquid catalyst for the synthesis of xanthene derivatives under solvent-free conditions

The triethylamine-based nanomagnetic ionic liquid, [(Et)₃ N-H]FeCl₄, was synthesized, and its structural and chemical characteristics were detected. The thermogravimetric analysis indicated its high thermal stability with a decomposition temperature higher than 300 °C. Additionally, [(Et)₃ N-H]FeCl₄ was used to efficiently catalyze the synthesis of xanthene derivatives under solvent-free conditions at 120 °C. [(Et)₃ N-H]FeCl₄ was recycled and reused at least five times.

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Application of Monte Carlo simulation method to polymerization kinetics over Ziegler–Natta catalysts

In the current work, the Monte Carlo simulation method was applied to ethylene polymerization over Ziegler–Natta catalysts. As expected, polymerization over each center of a Ziegler–Natta catalyst leads to a polymer having a Schultz–Flory molecular weight distribution. Notwithstanding, the total molecular weight distribution obtained by all catalyst centers together is at least twice as broad as that of each center. As another interesting finding, the introduction of hydrogen to the reaction deactivates the catalyst active centers and thereby reduces the catalyst activity. Nevertheless, it does not mainly affect the polymerization kinetics. In addition, the polymer molecular weight falls as hydrogen is added to the reaction since it acts as a strong transfer agent. The same effect is seen when cocatalyst concentration increases. Hydrogen also widens the polymer molecular weight distribution. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 45–56, 2009     

Effect of upstream velocity profile and integral flow straighteners on turbine flowmeters

One of the most important factors determining the shape of the calibration curve for a given turbine meter is the change in the upstream velocity distribution with flowrate. A theoretical model is evolved which can be used to predict the effects of velocity profile, viscosity and swirl on the calibration curve. It has also been used to explain the calibration curve of a commercial meter having a geometry very different from that for which the theory was developed. The effect of different types of integral flow straighteners on turbine meters is also investigated and found to depend on both the number of vanes and their length. A correlation is suggested for radial-vaned flow-straighteners     

A silica fiber coated with a ZnO-graphene oxide nanocomposite with high specific surface for use in solid phase microextraction of the antiepileptic drugs diazepam and oxazepam

A novel ZnO-graphene oxide nanocomposite was prepared and is shown to be a viable coating on fused silica fibers for use in solid phase microextraction (SPME) of diazepam and oxazepam from urine, this followed by thermal desorption and gas chromatographic quantitation using a flame ionization detector. A central composite design was used to optimize extraction time, salt percentage, sample pH and desorption time. Limits of detection are 0.5 μg·L^?1 for diazepam and 1.0 μg·L^?1 for oxazepam. Repeatability and reproducibility for one fiber (n?=?4), expressed as the relative standard deviation at a concentration of 50 μg·L^?1, are 8.3 and 11.3% for diazepam, and 6.7 and 10.1% for oxazepam. The fiber-to-fiber reproducibility is <17.6%. The calibration plots are linear in the 5.0–1000 μg·L^?1 diazepam concentration range, and from 1.0–1000 μg·L^?1 in case of oxazepam. The fiber for SPME has high chemical and thermal stability (even at 280 °C) after 50 extractions, and does not suffer from a reduction in the sorption capacity.

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Graphical abstract A hydrothermal method was introduced for preparation of ZnO- GO nano composite on a fused silica fiber as solid phase microextraction with high mechanical, chemical stability and long service life

     

Synthesis of pH‐responsive magnetic yolk–shell nanoparticles: A comparison between conventional etching and new deswelling approaches

Iron oxide (Fe₃O₄) magnetic nanoparticles as movable cores were used to synthesize yolk–shell nanoparticles with pH‐responsive shell composed of ethylene glycol dimethacrylate (EGDMA)‐crosslinked poly(acrylic acid) (PAA) via two different routes. In the first more common route, Fe₃O₄ nanoparticles were coated with silica layer via the Stöber process to yield Fe₃O₄@SiO₂ core–shell nanoparticles, subsequently used as seeds in the distillation precipitation copolymerization of AA and EGDMA to yield Fe₃O₄@SiO₂@P(AA‐EGDMA). The silica layer was selectively removed through alkali etching to yield Fe₃O₄@air@P(AA‐EGDMA). In the second route, Fe₃O₄ nanoparticles without any stabilization were used as seeds in the distillation precipitation copolymerization of AA and EGDMA to yield Fe₃O₄@P(AA‐EGDMA) core–shell nanoparticles. The nanoparticles were subsequently dispersed in acidic medium of pH = 2. Yolk–shell Fe₃O₄@air@P(AA‐EGDMA) nanoparticles were formed through deswelling of crosslinked PAA because of protonation of carboxyl groups at low pH values. Various techniques were utilized to investigate the characteristics of the synthesized core–shell nanoparticles. Formation of yolk–shell nanostructure was observed for both synthesis routes, namely etching of silica layer and deswelling approaches, from vibrating sample magnetometry and transmission electron microscopy results. Both types of nanoparticles showed pH‐responsive behaviour, i.e. decrease in absorption with increase in pH, as examined using UV–visible spectroscopy.     

Effect of surface modification with various thiol compounds on colloidal stability of gold nanoparticles

Gold nanoparticles (AuNPs) are attractive materials due to their special optical and electronic properties. However, they tend to aggregate particularly in the presence of thiol‐containing compounds. In this study, to investigate the effect of surface conjugation with thiol‐containing compounds on colloidal stability, thiol compounds with various structures as modifying agents were used. To this end, AuNPs were synthesized and stabilized by trisodium citrate in aqueous solution, and then modified with thiol‐containing compounds, namely cysteamine hydrochloride (MEA, containing primary amine groups), 2‐mercaptoethanol (BME, containing hydroxyl groups), 1‐dodecanthiol (LCA, containing long‐chain alkyl groups) and thioglycolic acid (TGA, containing carboxylic acid groups). We studied the effect of thiol ligands on solution stability of colloidal AuNPs and on the formation of aggregates originating from the modification process using UV–visible spectroscopy, dynamic light scattering, field emission scanning electron microscopy and transmission electron microscopy. Results showed that surface modification with MEA, BME and LCA led to the formation of aggregates. However, conjugation with TGA showed a concentration‐dependent behaviour: surface modification with low concentration resulted in the formation of aggregates whereas that with high concentration of TGA did not disturb the colloidal stability of AuNPs. Finally, the effect of surface modification on temperature increase of solutions originating from infrared light irradiation was studied, where the temperature increase depends on the surface‐modifying compound.     

Hydrothermal synthesis and characterization of a layered cobalt phenylphosphonate, Co(PhPO3)(H2O)

We report the hydrothermal synthesis and characterization of a layered cobalt phenylphosphonate. Unlike most metal phosphonates reported to date, the structure was solved by single crystal X-ray diffraction (SC-XRD). Co(ii) centres are hexa-coordinated by oxygen and the octahedra corner-share into a layer. The layers are capped by phenylphosphonate groups, where the phenyl groups define a hydrophobic bilayer region. The material was also characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and SQUID (superconducting quantum interference device) magnetometry. The material undergoes an antiferromagnetic transition at a relatively low Néel temperature of 4.0 K, while the Curie-Weiss temperature of -76.5 K reflects the low-dimensionality of the magnetic structure. The effective magnetic moment of 5.01 micro(B) per Co(2+) verifies a high-spin configuration and an octahedral coordination of the metal centres. This layered material was correctly predicted in the literature from powder data, adds to the structural diversity of the cobalt phosphonates, and may be useful as an intercalation or exfoliation compound.     

Matrix‐grafted multiwalled carbon nanotubes/poly(methyl methacrylate) nanocomposites synthesized by in situ RAFT polymerization: A kinetic study

A new approach was developed to functionalize multiwalled carbon nanotubes (MWCNTs) with a polymerizable methyl methacrylate (MMA) groups, and the structure of functionalized MWCNTs were characterized by FTIR, Raman, XPS, and TEM. Using the strategy of “grafting through,” poly(methyl methacrylate) (PMMA) chains were grafted onto the surface of MWCNTs during the in situ synthesis of MWCNT/PMMA nanocomposites over reversible addition‐fragmentation chain transfer (RAFT) polymerization. Kinetics of RAFT‐mediated polymerization of MMA in the presence of MMA‐grafted MWCNTs was studied by using gas chromatography and gel permeation chromatography. To further study, attached polymers were detached and their molecular characteristics were compared to freely formed chains. Results of kinetic studies showed that the utilized commercial chain transfer agent strictly reduced the rate of polymerization as well as relatively controlled molecular weights and narrow molecular weight distributions of free chains. MWCNTs showed a radical activity, retarding the polymerization and reducing the rate of reaction. The effect of MWCNTs concentrations on molecular weights and polydispersity indexes (PDI) was different at the surface and in the bulk. The molecular weights of free chains increased, and the PDI was decreased with increasing MWCNTs. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 555–569, 2012     

A Comparative Study of Pyrolysis Liquids by Slow Pyrolysis of Industrial Hemp Leaves,Hurds and Roots

This study assessed the pyrolysis liquids obtained by slow pyrolysis of industrial hemp leaves, hurds, and roots. The liquids recovered between a pyrolysis temperature of 275–350 °C, at two condensation temperatures 130 °C and 70 °C, were analyzed. Aqueous and bio-oil pyrolysis liquids were produced and analyzed by proton nuclear magnetic resonance (NMR), gas chromatography–mass spectrometry (GC-MS), and atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (APPI FT-ICR MS). NMR revealed quantitative concentrations of the most abundant compounds in the aqueous fractions and compound groups in the oily fractions. In the aqueous fractions, the concentration range of acetic acid was 50–241 gL⁻¹, methanol 2–30 gL⁻¹, propanoic acid 5–20 gL⁻¹, and 1-hydroxybutan-2-one 2 gL⁻¹. GC-MS was used to compare the compositions of the volatile compounds and APPI FT-ICR MS was utilized to determine the most abundant higher molecular weight compounds. The different obtained pyrolysis liquids (aqueous and oily) had various volatile and nonvolatile compounds such as acetic acid, 2,6-dimethoxyphenol, 2-methoxyphenol, and cannabidiol. This study provides a detailed understanding of the chemical composition of pyrolysis liquids from different parts of the industrial hemp plant and assesses their possible economic potential.