Sonochemical rate enhanced by a new nanomagnetic embedded core/shell nanoparticles and catalytic performance in the multicomponent synthesis of pyridoimidazoisoquinolines

A sonochemical approach for the one-pot three-component synthesis of pyridoimidazoisoquinolines via by using phthalaldehyde, trimethylsilylcyanide and aminopyridines the presence of a catalytic amount of a new nanomagnetic catalyst Fe₃O₄@SiO₂-CO-C₆H₄-NH₂ is described. The characterization of the nanocatalyst and the product was done by various methods, such as FT-IR, SEM, EDX, TGA/DTA, NMR, MS and CHN analyses. This is the first design, preparation, characterization and application of the present core/shell nanomaterial and also the first ultrasound irradiated synthesis of the biologically and pharmaceutically important fused polycyclic compounds in ethanol as a green solvent. This novel protocol offers several advantages such as high yields, short reaction times, environmentally-friendly reaction media, easily isolation of the products, simple preparation and recoverability of the nanocatalyst by an external magnet and reusing several times without significant decrease in catalytic activity.     

An insight into the reaction kinetics of CH3 + O2(a1Δg) and its enhancement effect on methane ignition

The reaction between CH₃ and O₂(a¹?_g) is crucial to understand the effects of electronically excited oxygen in plasma-assisted combustion of methane and other hydrocarbons. In the present work, multireference quantum chemical methods were used to investigate the potential energy surface of CH₃ + O₂(a¹?_g). The RRKM/master equation simulation was employed to compute the rate coefficients of various pathways to this reaction over the temperature range of 300–2000 K and a pressure range of 0.1–100 atm. Special attention has been paid to the nonadiabatic transition between the excited state and ground state, which directly leads to a quenching channel from CH₃ + O₂(a¹?_g) to CH₃ + O₂(X³∑_g^?). This quenching reaction has been overlooked by previous theoretical and kinetic modeling studies. We also conducted kinetic modeling to examine the effect of this reaction on the ignition enhancement of methane oxidation. Although the channel of CH₃ + O₂(a¹?_g) quenching to CH₃ + O₂(X³∑_g^?) has nonnegligible rate constants comparing with other reaction channels, modeling result with the inclusion of 5% O₂(a¹?_g) in molecular oxygen shows that the titled reactions shorten the ignition delay time of methane by more than twenty times at 900 K, 1 atm. The ignition enhancement is mainly from the chain branching channels to CH₂O + OH and CH₃O + O which has been greatly promoted by excess energy from O₂(a¹?_g). The present study uncovers the kinetic mechanism of this nonadiabatic reaction and provides reasonable rate coefficients for further kinetic modeling of plasma-assisted combustion of methane and other hydrocarbons.     

Sonochemical temperature controlled synthesis of pellet-, laminate- and rice grain-like morphologies of a Cu(II) porous metal–organic framework nano-structures

Nano-structures of the Cu(II) metal–organic framework, {Cu(BDT)(DMF)·CH₃OH·0.25DMF}_n (1), which BDT²⁻ is 1,4-benzeneditetrazolate, have been synthesized by the reaction of H₂BDT with Cu(NO₃)₂·6H₂O via ultrasonic irradiation in three different temperatures, which causes different morphologies. The products were characterized by IR spectroscopy, elemental analysis, scanning electron microscopy and X-ray powder diffraction. This study demonstrates that sonochemistry is a suitable method for preparation of metal–organic framework nano-structures and temperature is an effective parameter on morphologies of Cu(II) metal–organic framework nano-structures.     

Spin-lattice relaxation by tunnelling motions of methyl groups in some organic compounds

The proton spin-lattice relaxation times, T₁, of methyl groups in (CH₃CO)₂O, CH₃COCl, CH₃ COBr and (CH₃)₂S₂ have been measured below melting points at 52 MHz. The observed T₁ minima display the presence of tunnelling rotation. From the fit of the experimental results the ground, the first excited state tunnelling frequencies and the energy difference between the ground and the first excited states of the compounds have been estimated.     

Temperature Aspect of CH<Subscript>3</Subscript>OH effect on the rate of cyclohexene hydrocarbomethoxylation catalyzed by the Pd(OAc)<Subscript>2</Subscript>–PPh<Subscript>3</Subscript>–<Emphasis Type="Italic">p</Emphasis>-toluenesulfonic acid system

In the temperature range of 353–368 K, quantitative characteristics of the effect of the CH₃OH concentration on cyclohexene hydrocarbomethoxylation catalyzed by the Pd(OAc)₂–PPh₃–p-toluenesulfonic acid system are determined. It is shown that, in the temperature range covered, the dependence of the reaction rate on the CH₃OH concentration passes through a maximum. The results are interpreted in terms of a catalytic cycle involving hydride–, alkyl–and acyl–palladium complexes of cationic type as intermediates, supplemented by ligand exchange reactions that transfer part of the catalyst into an inactive form. The effective constants for the earlier obtained kinetic equation are estimated. Based on the temperature dependences of the effective constants and the activated complex theory, the effective activation energies, as well as the enthalpy, entropy, and Gibbs energy changes for the ligand exchange reactions between the Pd(CH₃OH)₂(PPh₃)₂ and Pd(CO)₂(PPh₃)₂ complexes are estimated. It is established that, at 373 K, this reaction is close to the state of equilibrium.     

Synthesis and regularities of combustion of acetoxymethylnitroamines. Impact sensitivity of secondary alkylnitroamines

The use of the nitrolysis of cyclic amines and of the direct synthesis from primary nitroamines made it possible to obtain acetates of methylolnitroamines of general formula AcO(CH₂NNO₂) _n R(n = 1–6). A number of high explosives, nitroamines, were synthesized: DNA ((CH₃NNO₂)₂CH₂), DMNA ((CH₃)₂NNO₂), DNA-2 ((CH₃NNO₂CH₂)₂), TRIS ((CH₃NNO₂CH₂)₂NNO₂), and TETRA ((CH₃NNO₂CH₂NNO₂)₂CH₂). The regularities of the combustion of the synthesized compounds were studied, and their characteristics were compared. Stress curve measurements were used to estimate the impact sensitivity of alkylnitroamines. A number of basic macroscopic characteristics of the nitroamines studied and nitroamine-ammonium perchlorate mixtures, including the heat of explosion. For comparison, the characteristics of regular high explosive are given.     

When hydrogen is slower than methane to ignite

Hydrogen (H₂) is known to be the fastest fuel to ignite among all practical combustion fuels. In this study, for the first time, longer ignition delay times (IDTs) for the H₂ and H₂ blended CH₄ mixtures were measured compared to those for pure CH₄. This work investigates the ignition characteristics of H₂, CH₄, and 50% CH₄/50% H₂ mixtures using a rapid compression machine at pressures ranging from 20 to 50 bar and at equivalence ratios (φ) from 0.5 to 2.0 in air in the temperature range 858–1080 K. The experimental IDTs are simulated using a newly updated kinetic mechanism, NUIGMech1.3, and good agreement is observed. At lower temperatures the IDTs of H₂, CH₄, and the 50% CH₄/50% H₂ mixtures are similar to one another, and the IDTs of the 50% CH₄/50% H₂ mixtures are longer than those for pure CH₄ at temperatures below 930 K. At temperatures below 890–925 K, depending on the operating pressure and equivalence ratio, the hydrogen mixtures are the slowest to ignite, with IDTs being 2.5 times longer than those recorded for CH₄ at a pressure of 40 bar at 890 K for φ = 1.0, and at 875 K for φ = 2.0. At low temperatures alkyl (Ṙ = ĊH₃ and Ḣ) radicals add to O₂ producing RȮ₂ radicals, which then react with HȮ₂ radicals forming ROOH (H₂O₂ and CH₃OOH) and O₂. For H₂, the self-recombination of HȮ₂ radicals leads to chain propagation which inhibits reactivity, whereas for CH₄, the reaction between RȮ₂ (CH₃OȮ) and HȮ₂ leads to chain branching, increasing reactivity. Furthermore, CH₃OOH decomposes more easily to produce CH₃Ȯ and ȮH radicals than does H₂O₂ to produce two ȮH radicals. Thus, mixtures containing higher H₂ concentrations are slower to ignite compared to those with higher CH₄ concentrations at low temperatures.     

Ultrasound promoted the synthesis of N-propargylic β-enaminones

The synthesis of 14 novel N-propargylic β-enaminones from the reaction of β-alkoxy vinyltrihalomethyl[carboxyethyl] ketones [R³C(O)CHC(R¹)OMe, where R³ = CF₃, CCl₃, CO₂Et and R¹ = Me, Et, Pr, Bu, i-Pent, CH₂CH₂CO₂Me] with propargyl amines [R²NHCH₂CCH, where R² = Pr, PhCH₂] is reported. Yields, solvents and reaction times needed for reaction completion, by microwave irradiation (MW), conventional thermal heating (TH) and under ultrasound irradiation (US) are compared. The best results were obtained under US irradiation in good to excellent yields (70-93%).     

Vibrational relaxation time measurements in CH4 and CH4-rare gas mixtures

With a spectrophone vibrational relaxation times in CH₄ and in mixtures of CH₄ with rare gases were measured. Both the amplitude and the phase method were used. The two infrared active modes of CH₄ (ν₄ and ν₃) were investigated separately. The relaxation times, at one atmosphere, after exciting the lowest mode ν₄, were found to be: τ(CH₄-CH₄) = 1.65 μs; τ(CH₄-He) = 1.97 μs; τ(CH₄-Ne) = 8.6 μs; τ(CH₄-Ar) = 12 μs and τ(CH₄-Kr) ≈ 60 μs. From these values one may in that vibrational-rotational (V-R) energy transfer is the dominant relaxation mechanics. By exciting the higher mode the first step in the deactivation of ν₃ was found to be a V-V transfer to the lowest modes ν₄, ν₂.     

Pressure-Broadened Linewidth Measurements in the ν2Band of the CH3Radical

Pressure broadening coefficients for an infrared transition of the methyl radical have been measured for the first time. CH₃radicals, generated by pyrolyzing di-tert-butyl peroxide in a flow of either N₂or Ar, were probed using a tunable diode laser and a multipass absorption cell. The Lorentz half-width of theQ(6,6) line of the ν₂band of CH₃at 607.024 cm⁻¹was measured as a function of pressure at 295 K. The broadening coefficients (HWHM) areb(Ar) = 0.0310 ± 0.0012 cm⁻¹atm⁻¹andb(N₂) = 0.0390 ± 0.0020 cm⁻¹atm⁻¹. These coefficients are lower than those for CH₄–Ar, N₂broadening. This may be due to a lower polarizability or smaller effective hard collision diameter for CH₃relative to CH₄.     

Predictive model of decontamination efficiency of gaseous pollutant by non-equilibrium plasma

During non-equilibrium plasma (NEP) reactions, chemical bonds of pollutant compound are broken by energy generated in the reactor so that the pollutants are decontaminated. In this study, the energy conversion factor (E_f) is defined as the ratio of the dissociation energy of chemical bonds destroyed in NEP reaction system to the energy inputted in plasma reactor. The energy conversion factor of chemical bonds (E_f,i), S–H, C–Cl, C–S, C–H, C–C etc., were determined by decontamination experiments of H₂S and 2-CEES in plasma reactor. Based on the E_f,is, the predictive model of NEP decontamination efficiency of gaseous pollutant was developed and applied to predict decontamination efficiency of CH₃CH₂SH, in which all E_f,is of chemical bonds are known as described above. It was shown by the decontamination experiment of CH₃CH₂SH that the predictive value was well agreed to experimental data. Therefore, the model can be used to predict decontamination efficiency of those pollutants in which all E_f,is of chemical bonds have been determined. An improved model is also produced by the analysis of predictive error.     

Structure dependent luminescence characterization of green–yellow emitting Sr2SiO4:Eu2+ phosphors for near UV LEDs

This paper reports on the luminescence properties of mixtures of α- and β-(Sr_0.97Eu_0.03)₂SiO₄ phosphors. These phosphors were prepared by 3 different synthesis techniques: a modified sol–gel/Pechini method, a co-precipitation method and a combustion method. The structural and optical properties of these phosphors were compared to those of solid state synthesized powders. The emission spectra consist of a weak broad blue band centered near 460 nm and a strong broad green–yellow band centered between 543 and 573 nm depending on the crystal structure. The green–yellow emission peak blue-shifts as the amount of β phase increases and the photoluminescence emission intensity and quantum efficiency of the mixed phase powders is greater than those of predominant α-phase powders when excited between 370 and 410 nm. Thus, (Sr_1?xEu_x)₂SiO₄ with larger proportion of the β phase are more promising candidates than single α-phase powders for use as a green–yellow emitting phosphor for near UV LED applications. Finally the phosphors prepared by the sol–gel/Pechini method, which have larger amount of β phase, have a higher emission intensity and quantum efficiency than those prepared by co-precipitation or combustion synthesis.     

From pirazoloquinolines to annulated azulene dyes: UV–VIS spectroscopy and quantum chemical study

Paper reports UV–Vis absorption and photoluminescence spectra of 6-R derivatives (R=CH₃, O–CH₃, C(C₆H₅)₃, C₆H₅–N–C₁₀H₇) of 4-(2-chlorophenyl)-1,3-diphenyl-1H-pyrazolo[3,4-b]quinoline, belonging to pyrazoloquinoline (PQ) family, likewise its regioisomeric products 10-R derivatives of 6-phenyl-6H-5,6,7-triazadibenzo[f,h]naphtho[3,2,1-cd]azulene representing cyclized seven-membered annulated azulene (AA) dyes. Cyclization of PQs into AAs is accompanied by a significant red shift of the first optical absorption band. This finding agrees with the results of quantum-chemical calculations performed by means of the semiempirical method PM3. As the solvent polarity rises all the dyes exhibit a blue shift of the first absorption band and a red shift of the fluorescence band. Such opposite trends in solvatochromic behavior have been reproduced within the semiempirical calculations in combination with the Lippert–Mataga dielectric polarization model. Depending on solvent polarity AA dyes emit light in the green, green–yellow or orange range of the visible spectrum what may be of interest for potential luminescent or electroluminescent applications.     

Can (H2O) n (n = 1–2) as effective catalysts in the CH2OO + H2S reaction under tropospheric conditions?

The addition reaction of CH₂OO?+?H₂S → HSCH₂OOH without and with catalyst X (X?=?H₂O and (H₂O)₂) has been investigated by CCSD(T)-F12a/VTZ-F12//B3LYP/aug-cc-pVTZ method and canonical variational transition state theory with small curvature tunneling correction. When H₂O was introduced in the CH₂OO?+?H₂S reaction, it not only acts as a catalyst for producing HSCH₂OOH, but also plays as a reactant to forming HOCH₂OOH. The formation channel of HSCH₂OOH is more important than the formation channel of HOCH₂OOH with its calculated rate constant larger by 11.0–43.2 times within the temperature 280–320?K. Then, (H₂O)₂ catalysed CH₂OO?+?H₂S → HSCH₂OOH reaction has been taken into account with its rate lower 1.9–4.2 times than the reaction of CH₂OO?+?H₂S → HSCH₂OOH with water. Also, CH₂OO?+?H₂S with H₂O cannot compete with the CH₂OO?+?H₂S reaction without water. This is different from CH₂OO?+?(H₂O)₂ reaction, which is about 4 orders of magnitude larger than the rate constant for CH₂OO?+?H₂O reaction. Such discrepancy is possible because C(CH₂OO)···O(H₂O) interaction has been enhanced more obviously by H₂O as compared to that of C(CH₂OO)···O(H₂S) interaction.     

PMR spin lattice relaxation by reorientational motions of NH3 and CH3 groups in some organic compounds

The spin-lattice relaxation times, T₁, of protons in o, m, p-phenylene-diamine dihydrochlorides C₆H₄(NH₂)₂·2HCl, phenylhydrazinium chloride C₆H₅NHNH₃Cl, hexaethylbenzene C₆(CH₂CH₃)₆, tetrabutylammonium bromide [CH₃(CH₂)₃]₄NBr, iodide [CH₃(CH₂)₃]₄NI, tetraheptylammonium bromide [CH₃(CH₂)₆]₄NBr and iodide [CH₃(CH₂)₆]₄NI powders have been measured between 400 and 100 K at 60MHz. The experimental results have been explained by considering the reorientational motions of ?NH₃⁺ and ?CH₃ groups about C₃ axes and their role of behaving as sinks to rapid spin diffusion of the ring protons of the phenylene and the methylene protons. The observed T₁, minima in all these substances turn out to be the measures of the ratios between the total number of protons and the number of reorienting ?NH₃⁺ or ?CH₃ protons. Therefore it has been concluded that the T₁, minima of ?NH₃⁺ and ?CH₃ groups, when obtainable can indicate their number present in a solid sample.     

One-pot green fabrication and antibacterial activity of thermally stable corn-like CNC/Ag nanocomposites

Corn-like cellulose nanocrystals/silver (CNC/Ag) nanocomposites were prepared by formic acid/hydrochloric acid hydrolysis of commercial microcrystalline cellulose (MCC), and redox reaction with silver ammonia aqueous solution (Ag(NH₃)₂(OH)) in one-pot green synthesis, in which the preparation and modification of CNCs were performed simultaneously and the resultant modified CNCs could be as reducing, stabilizing and supporting agents for silver nanoparticles. The influences of the Ag⁺ ion concentrations on the morphology, microstructure, and properties of the CNC/Ag nanocomposites were investigated. It is found that corn-like CNC/Ag nanocomposites containing Ag nanoparticles with diameter of about 20–40 nm were obtained. Compared to the MCCs, high crystallinity of 88.5 % and the maximum degradation temperature (T _max) of 364.5 °C can be achieved. Moreover, the CNC/Ag nanocomposites showed strong antibacterial activity against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. Furthermore, such nanocomposites can act as bifunctional nanofillers to improve thermal stability, mechanical property, and antibacterial activity of commercial poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and poly(lactic acid).     

Reaction intermediates of methanol synthesis and the water–gas-shift reaction on the ZnO(0001) surface

The polar Zn-ZnO(0001) surface is involved in the catalysis of methanol synthesis and the water–gas-shift reaction. We use density functional theory calculations to explore the favorable binding geometries and energies of adsorption of several molecular species relevant to these reactions, namely carbon monoxide (CO), carbon dioxide (CO₂), water (H₂O) and methanol (CH₃OH). We also consider several proposed reaction intermediates, including hydroxymethyl (CH₂OH), methoxyl (CH₃), formaldehyde (CH₂O), methyl (CH₃), methylene (CH₂), formic acid (HCOOH), formate (HCOO), formyl (HCO), hydroxyl (OH), oxygen (O) and hydrogen (H). For each, we identify the preferred binding geometry at a coverage of 1/4 monolayers (ML), and report calculated vibrational frequencies that could aid in the identification of these species in experiment. We further explore the effects on the binding energy when the adsorbate coverage is lowered to 1/9 and 1/16 ML.     

Investigation of the kinetics of OH∗ and CH∗ chemiluminescence in hydrocarbon oxidation behind reflected shock waves

The temporal variation of chemiluminescence emission from OH^?(A² Σ ⁺) and CH^?(A² Δ) in reacting Ar-diluted H₂/O₂/CH₄, C₂H₂/O₂ and C₂H₂/N₂O mixtures was studied in a shock tube for a wide temperature range at atmospheric pressures and various equivalence ratios. Time-resolved emission measurements were used to evaluate the relative importance of different reaction pathways. The main formation channel for OH^? in hydrocarbon combustion was studied with CH₄ as benchmark fuel. Three reaction pathways leading to CH^? were studied with C₂H₂ as fuel. Based on well-validated ground-state chemistry models from literature, sub-mechanisms for OH^? and CH^? were developed. For the main OH^?-forming reaction CH+O₂=OH^?+CO, a rate coefficient of k ₂=(8.0±2.6)×10¹⁰ cm³?mol^?1?s^?1 was determined. For CH^? formation, best agreement was achieved when incorporating reactions C₂+OH=CH^?+CO (k ₅=2.0×10¹⁴ cm³?mol^?1?s^?1) and C₂H+O=CH^?+CO (k ₆=3.6×10¹²exp(?10.9 kJ?mol^?1/RT) cm³?mol^?1?s^?1) and neglecting the C₂H+O₂=CH^?+CO₂ reaction.     

Methanol synthesis from methane and oxygen with [Ga Cr]/Cu–Zn–Al catalyst in a dielectric barrier discharge

Direct methanol synthesis by methane (CH₄) oxidation has been thoroughly investigated in the presence of copper–zinc–alumina (CZA) catalyst doped with Ga and Cr. Low thermal plasma condition has been selected as the reaction media to allow high excitation level of stable gases, i.e., methane (CH₄) and oxygen (O₂). It shows that CZA catalyst produced a good reaction performance in the plasma process by increasing methanol production more than twice higher than noncatalytic plasma process. A catalytic modification of CZA catalyst by Ga and Cr addition was conducted to boost the yield of methanol production. The presence of Ga and Cr led to the increment of methanol yield ca. 20–25 % compared to pure or original CZA catalyst.     

Novel Method for the Oxidation of Aliphatic Hydrocarbons to Alcohols

A novel method for the conversion of hydrocarbons to alcohols using a reaction of gas-phase oxidation by oxygen in the presence of boron trichloride has been developed and described in detail. The reaction represents radical long-chain alkoxylation of boron trichloride. It proceeds at moderate temperatures of 150–180°C and atmospheric pressures of less than one atmosphere, resulting in methane conversion to (CH₃O)_3–nBCl_n (n = 0–2) and ethane conversion to (CH₃CH₂O)_3–nBCl_n (n = 0–2). The hydrolysis of the reaction products generates CH₃OH and C₂H₅OH, respectively. The yield of methanol reaches up to 55% at the conversion of methane of ~15% at the early stages of the reaction. The yield of ethanol is at least 65% of the reacted ethane nearly to the end of the reaction.