Use of an injection port for thermochemolysis–gas chromatography/mass spectrometry: Rapid profiling of biomaterials

A simple and direct approach was developed for thermochemolytic analysis of a wide range of biomolecules present in plant materials using an injection port of a gas chromatograph/mass spectrometer (GC/MS) and a novel solids injector consisting of a coiled stainless steel wire placed inside a modified needle syringe. Optimum thermochemolysis (or Thermally Assisted Hydrolysis/Methylation) was achieved by using a suitable methanolic solution of trimethylsulfonium hydroxide (TMSH) or tetramethylammonium hydroxide (TMAH) with an injection port temperature of 350 °C. Intact, methylated flavonoids, saccharides, phenolic and fatty acids, lignin dimers and diterpene resin acids were identified. Samples include tea leaves, hemicelluloses, lignin isolates and herbal medicines. Unexpected chromatographic results using TMAH reagent revealed the presence of intact methylated trisaccharides (658 Da) and structurally informative dimer lignin markers.     

Surfactant effect on the conductivity behavior of CsH2PO4: Characterization by electrochemical impedance spectroscopy

Cesium dihydrogen phosphate (CDP) nanoparticles were synthesized using the surfactants cetyltrimethyl ammonium bromide (CTAB), polyoxyethylene-polyoxypropylene (F-68) and (F-68:CTAB) with molar ratio 0.06. The samples conductivity such as CDP_CTAB, CDP_F-68 and CDP_{(F-68:CTAB)0.06} was studied by impedance spectroscopy in the frequency range 0.01 Hz to 1 MHz. The Nyquist plots were drawn at different temperatures of 210, 230 and 260 °C, which are defined below transition, phase transition and above transition, respectively. The measured conductivities obey the Arrhenius relation. The influence of surfactants on conductivity are more significant at higher temperature due to grain boundary. The conductivity of CDP_CTAB increased slightly with increasing temperature to 260 °C, whereas the conductivity of other samples decreased with increasing temperature over 230 °C. The results indicated that the conductivities increase in the order of CDP_CTAB>CDP_{(F-68:CTAB)0.06}>CDP_F-68. These are in accordance to the ion exchange capacities of the samples that the surfactant shows a direct influence on the samples proton mobility. It is found that the conductivity of CsH₂PO₄ is influenced by surfactant type.     

Olefin epoxidation with H2O2 in the presence of Mn(II) dicarboxylate coordination polymer catalysts

Abstract  

The Mn(II) dicarboxylate coordination polymers [Mn(μ-terephthalate)(H₂O)₂] _n , [Mn(μ-oxalate)(H₂O)₂] _n , and [Mn(μ-d-(−)-tartrate)] _n were prepared in water and characterized by FT-IR spectroscopy and CHN analysis. Particles of the terephthalate catalyst were also synthesized, by reaction of terephthalic acid and MnCl₂·4H₂O by a sonochemical method. The catalytic potential of these coordination polymers as slow-release sources of catalytically active Mn species was tested in the oxidation of cyclooctene to its epoxide in acetonitrile, using hydrogen peroxide as oxygen source. For the terephthalate species the catalytic activity was found to increase with increasing dielectric constant and dipole moment of the solvent (being highest in acetonitrile), with reaction temperature to a maximum at 60 °C, and with an imidazole co-catalyst (highest activity found for a imidazole-to-catalyst molar ratio of 20:1). Good activity with more than 64% conversion in 24 h was obtained for epoxidation of cyclooctene and cyclohexene, whereas low yields only were obtained from aryl-substituted olefins. Some exo versus endo regioselectivity was found for norbornene.     

Semi-empirical and ab initio quantum chemical characterisation of pyridine derivatives as HCl inhibitors of aluminium surface

Quantum chemical methods are becoming ever more prevalent for assessing surface interactions of different molecules using cluster models and semi-empirical, ab initio Hartree–Fock and density functional theory (DFT) studies considering the standard potential energy surfaces. Examination of the efficacy of some pyridine derivatives to counter aluminium corrosion in hydrochloric acid using ab initio and semi-empirical quantum chemical deductions and its comparison with the available experimental data forms the basis of this research. It is believed that the inhibition efficiency has lucid correlation with the total energy of inhibitor molecules and highest occupied molecular orbital energy levels calculated by DFT study methods and thus the adsorption energy for the pyridine on Al₁, Al₅, Al₁₄, Al₁₈ and Al₂₆ clusters are determined to assess the convergence of the results with respect to size of the cluster. Subsequently, Al₂₆ is used for the inhibitor/aluminium cluster interface investigations. Results highlight the reaction between pyridine molecules and appropriately active sites such as corners and steps or kinks and screw dislocations towards which pyridine molecules are attracted as is evident from a three times rise in adsorption energy from (−35) to (−107) kJ mol⁻¹. Therefore, inhibition mechanism is primarily associated with local properties. Interactions take place between the surface defect and the nitrogen group of the pyridine molecule however, the possibility of ion pair formation between protonated pyridine and chloride ion and its influence on the general adsorption of pyridine on aluminium is also examined. The interaction energies of pyridine and aluminium cluster with the natural bond orbital are also reported.     

A New Approach for Optimization of Distributed Quantum Circuits

International Journal of Theoretical Physics - In the present work, a novel approach was proposed to optimize the teleportation cost in Distributed Quantum Circuits (DQCs) by applying a new...     

Dehydration of acetonitrile using cross-linked sodium alginate membrane containing nano-sized NaA zeolite

Pervaporation (PV) separation of water–acetonitrile mixture using sodium alginate (NaAlg) based mixed matrix membranes (MMM) comprising different amounts of nano NaA zeolite (10, 20 and 30 wt%) is investigated in various concentrations of water and temperatures. The prepared membranes are modified by sulfosuccinic acid (SSA) as a crosslinking agent. NaAlg-NaA/SSA membranes are synthesized by a solution casting technique. The process and membrane performance including separation factor, flux and activation energy of permeation are determined. Results reveal that adding of nano zeolite may lead to an increase in the flux and the separation factor of sodium alginate membrane up to 123 and 169%. In addition, using MMM in dehydration of a feed containing 30 wt% of water shows much better performance than alginate membrane. Furthermore, the activation energy of water permeation through MMM is predicted lower than sodium alginate membrane which reflects the facilitated permeation of water through MMM.     

Fast and Efficient Nitration of Salicylic Acid and Some Other Aromatic Compounds over H_3PO_4/TiO_2-ZrO_2 Using Nitric Acid

TiO₂‐ZrO₂ (1/1)‐surf with Ti and Zr molar ratio of 1/1 was prepared with surfactant through a sol‐gel method. The optimum experimental condition was investigated for nitration of salicylic acid. Then, a number of nitration reactions were carried out with a variety of aromatic compounds in the optimum condition. The 25 wt% H₃PO₄/TiO₂‐ZrO₂ (1/1)‐surf catalyst showed good selectivity and yield in a short time for the nitration of salicylic acid and some other aromatic compounds.     

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.