Ultrasound and microwave assisted synthesis of dihydroxyacetophenone derivatives with or without 1,2-diazine skeleton

A thorough study concerning O-alkylation and α-bromination of dihydroxyacetophenone (DA) and N-alkylation of 1,2-diazine, under ultrasound (US) and microwave (MW) irradiation as well as under conventional thermal heating (TH) is presented. Under US and MW irradiation the yields are higher, the amount of used solvent decreases substantially, the reaction time decreases considerable (from hours or days to minutes) and the consumed energy decreases, consequently the O-alkylation, α-bromination and N-alkylation methods could be considered environmentally friendly. A selective and efficient way to either bis-O-alkylation or mono-O-alkylation of DA has been found, the relative position of the two hydroxyl groups on the phenyl moiety being compulsory. A selective and efficient way for α-bromination in heterogeneous catalysis of DA derivatives under US irradiation is presented. The N-alkylation reaction of DA under US and MW irradiation proved to be the most convenient setup procedure for these types of reactions. Overall, the use of US proved to be more efficient than MW or TH.     

Room temperature soft chemical route for nanofibrous wurtzite ZnO thin film synthesis

Room temperature soft chemical deposition route has been utilized to grow thin films of ZnO on glass substrate. Annealing at 673 K removed zinc hydroxide phase and nanofibrous ZnO films with wurtzite crystal structure were obtained. Decrease in the room temperature electrical resistivity from 10⁷ to 10⁴ Ω cm was observed after annealing. The nanofibrous ZnO thin films were sensitive to the explosive liquefied petroleum gas (LPG) and the maximum response of 17% at 698 K under the exposure of 6500 ppm of LPG was obtained.     

An emerging reactor technology for chemical synthesis: Surface acoustic wave-assisted closed-vessel Suzuki coupling reactions

In this paper we demonstrate the use of an energy-efficient surface acoustic wave (SAW) device for driving closed-vessel SAW-assisted (CVSAW), ligand-free Suzuki couplings in aqueous media. The reactions were carried out on a mmolar scale with low to ultra-low catalyst loadings. The reactions were driven by heating resulting from the penetration of acoustic energy derived from RF Raleigh waves generated by a piezoelectric chip via a renewable fluid coupling layer. The yields were uniformly high and the reactions could be executed without added ligand and in water. In terms of energy density this new technology was determined to be roughly as efficient as microwaves and superior to ultrasound.     

Evaluation of an alternative modification route for layered silicates and synthesis of poly(styrene) layered silicate nanocomposites by in-situ suspension polymerisation

The organically modified montmorillonites (o-MMT) used in this study were prepared in a semi-solid state in molten long chain alkyl (hydrogenated tallow (HT) or stearyl) dimethyl/aryl ammonium chloride intercalant (quat), within a Brabender Plasticorder W50E chamber. The effect of quat level and structure was investigated using WAXS, FTIR (DRIFTS) and solvent swelling/dispersion viscosity studies. It was found that mono-stearyl (or HT) quats were the most suitable intercalants for the in-situ polymerised PS matrix nanocomposites produced. The distearyl (or HT) quats generally led to reduced interfacial effects in the composites and reduced toluene dispersion viscosity due to the close proximity of long alkyl tails within the molecules facilitating their self-assembly into ordered arrays, which were difficult for toluene to penetrate (toluene was used as a probe to gauge compatibility with styrene). Substitution of a benzyl group (for a methyl) led to increased compatibility with styrene/toluene, though the detrimental effect of two long alkyl groups was not overcome. PS matrix nanocomposites have been formed via in-situ free radical suspension polymerisation of styrene/organo-montmorillonite (o-MMT) dispersions. These composites displayed evidence of large interfacial area relative to the volume fraction of montorillonite added; this was manifested as a reduction in melt flow rate, broadening of the molar mass distribution (increase in M _w) and an increase in thermal stability, relative to the unfilled matrix. However, wide angle X-ray scattering (WAXS) patterns of the composites revealed a strong (001) reflection (d = 3.3–3.4 nm) together with clear (002) and (003) reflections. Therefore a mixed intercalated/flocculated morphology, with no significant exfoliation into single platelets, was indicated.     

Analytical study of an asymmetric 1D statistical model for chemical reactions

An analytical study is presented for the asymmetric FGZ reaction model, involving two different species A and B (only B can spontaneously desorb) in contact with a bath containing A and B with the same concentration. The expected values of the density and the pair correlation functions are calculated and their time behaviour is analysed in detail. This also allows to define an average time-dependent fragmentation index describing quantitatively the evolution of the topology (connectivity) of the clusters. In addition, when the system is doomed to end its evolution in the A-poisoned state, the distribution law P(T) of the times T_k at which this occurs is investigated numerically. It turns out that, in the case where a single isolated B is present in the initial state, this law is well enough represented by a stretched exponential in the log variable: P(T) = C^ste exp[− α(1n T)^ß].     

Microwave synthesis of YAG:Eu by sol-gel methodology

Yttrium-aluminum oxides are interesting compounds and they have been extensively used as host for lasers and phosphors, due to their stable physical and chemical properties. The fabrication of yttrium-aluminum garnet (YAG) has been investigated thoroughly. Single-crystal YAG is expensive and to produce it a new way has been investigated. This process consists of modifying the methodology of reagents mixture and the process of heating them. The microwave irradiation is used to heat-treat the oxide mixture. The traditional synthesis of YAG powders occurs through the reaction of aluminum and yttrium powders at high temperatures. With this work we investigated the preparation of YAG by non-hydrolytic sol-gel route as an alternative methodology to obtain yttrium-aluminum matrix from inorganic precursors (yttrium and aluminum chloride). The preparation of the gel was carried out in an oven-dried glassware. The AlCl₃, YCl₃ and ethanol were reacted in reflux under argon atmosphere. Europium III chloride was added as a structural probe. The powder was dried and heat-treated in modified microwaves. The samples were pre-treated at 50 and 800^oC during 1 h and then heated in microwaves for 30 s, 2 and 4 min. The formation process and structure of the powders were studied by means of X-ray diffraction (XRD), photoluminescence (PL) and transmission electronic microscopy (TEM). XRD presents only picks corresponding to the YAG phase and confirmed by TEM. PL date showed that the YAG phase was formed in 2 min with the samples pre-treated at 50 °C. For the samples pre-treated at 800 °C, the YAG phase appears in 30 s. The excitation spectra present a maximum of 394 nm corresponding to the ⁵L₆ level and emission spectra of Eu III ion present bands characteristic transitions arising from the ⁵D₀→⁷F_J (J=1, 2, 3, 4) monifolds excited at their maximum. The magnetic dipole ⁵D₀→⁷F₁ transition presents more intensity than the electric dipole ⁵D₀→⁷F₂ transition. This methodology showed efficiency in obtaining YAG phase.     

A facile and environmentally friendly chemical route for the synthesis of metastable VO2 nanobelts

Metastable VO₂ nanobelts, designated as VO₂ (B), were successfully fabricated by a facile hydrothermal route in the presence of V₂O₅ and glucose. The samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), transmission electron microscopy (TEM), selected area electronic diffraction (SAED), high-resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) techniques. The main synthesis parameters such as temperature, reaction time and molar ratio of the starting materials have been also discussed. The results showed that pure B phase VO₂ nanobelts with high crystallinity can be prepared easily at 180 °C in 24 h at the molar ratio of V₂O₅:glucose=1:1. Typically, the belt-like products were 0.6-1.2 μm long, 80-150 nm wide and 20-30 nm thick. It is noted that the whole process is free of any harmful reducing reagents and surfactants, and valuable gluconic acid can be formed as the main by-product. From an economic and environmental point of view, the present approach is particularly fit for the synthesis of VO₂ (B) nanobelts on a large scale.     

Spray drying: An alternative synthesis method for polycationic oxide compounds

Synthesis of polycationic compounds by the spray-drying technique is an interesting alternative in the domain of aqueous precursor synthesis methods. Spray drying yields high quality samples with good reproducibility. The possibility of scaling up for production of large quantities with fast processing time is well established by the commercial availability of powders of various compositions. In this paper, we have discussed the advantages and limitations of this method and demonstrated its interest by synthesizing a few polycationic compounds selected for their attractive properties of thermoelectricity [Bi_1.68Ca₂Co_1.69O₈, La_0.95A_0.05CoO₃ (A=Ca, Sr, Ba)] or magnetoresistance [La_0.70A_0.30MnO₃ (A=Sr, Ba)]. We have confirmed the quality of these samples by reporting their structure, magnetic and transport properties.     

Phthalocyanines as an alternative to soluble polymer-supported platforms in organic synthesis

Some small molecules, such as phthalocyanines, capable of exhibiting greatly enhanced capacities and acting as internal tags, are shown to be effective as replacements for polydisperse polyethylene glycols, in soluble polymer-supported type synthesis of some piperidine and piperazine derivatives.     

Room temperature synthesis and characterization of ultralong Cd(OH)2 nanowires: a simple and template-free chemical route

Ultralong Cd(OH)₂ nanowires were fabricated in high yield by a convenient chemical method using alkali medium at room temperature without using any templates. The preparation conditions induce a unilateral growth of nanowires, despite the absence of any template. The length of the nanowires reached several hundreds of micrometers, giving an aspect ratio of a few thousands. The X-ray diffraction shows that the Cd(OH)₂ nanostructures crystallized in the wurtzite structure without any special orientation. The photoluminescence spectrum of Cd(OH)₂ nanostructures appears as two emission bands: one related to green emission at 475–510 nm, and the other related to deep level emission at 510–540 nm. Also the formation mechanisms of the nanowires are presented. The growth mechanism involves the irreversible and specifically oriented self-assembly of primary nanocrystals and results in the formation of the nanowires.     

Multicomponent synthesis of benzoxazinones via tandem Ugi/Mitsunobu reactions: an unexpected cine-substitution

A short (2 steps) synthesis of diverse benzoxazinones by coupling the Ugi multicomponent reaction with an intramolecular Mitsunobu substitution is reported. The cyclization step proceeds via an unexpected cine substitution.     

A new route for the synthesis of nitrides: The solvothermal preparation of GaN

Abstract

A new solvothermal route for the synthesis of nitrides is proposed using liquid NH3 as solvent in supercritical conditions, Such a preparation method was applied to the synthesis of GaN using gallium metal as starting material.

GaN is a wide band-gap semi-conductor (3.4eV). It is a very attractive nitride due to its various applications in micro- and opto-electronics [1,2]. Consequently, many research groups are interested in synthesising GaN. Two methods have been principally developed:

(i) synthesis of thin films by epitaxy [3,4]

(ii) synthesis of bulk GaN by high pressure method [5,6].

The new proposed process leads to fine microcrystallites of GaN with the wurtzite-type structure. The chemical purity can be optimised versus the synthesis mechanism. The size and shape of the crystallites would be influenced by the nature of the nitriding additive and the thermodynamical conditions (pressure and temperature) used for the synthesis.     

Microwave-assisted synthesis of carbon-supported carbides catalysts for hydrous hydrazine decomposition

Microwave-assisted synthesis of carbon-supported Mo₂C and WC nanomaterials was studied. Two different routes were utilized to prepare MoO₃ (WO₃) - C precursors that were then subjected to microwave irradiation in an inert atmosphere. The effect of synthesis conditions, such as irradiation time and gas environment, was investigated. The structure and formation mechanism of the carbide phases were explored. As-synthesized nanomaterials exhibited catalytic activity for hydrous hydrazine (N₂H₄·H₂O) decomposition at 30–70 ^°C. It was shown that the catalyst activity significantly increases if microwave irradiation is applied during the decomposition process. Such conditions permit complete conversion of hydrazine to ammonia and nitrogen within minutes. This effect can be attributed to the unique nanostructure of the catalysts that includes microwave absorbing carbon and active carbide constituents.     

The application of reed-vibration mechanical spectroscopy for liquids to detect chemical reactions of an acrylic structural adhesive

There remain a number of unsolved problems about chemical reactions, and it is significant to explore new detection methods because they always offer some unique information about reactions from new points of view. For the first time, the solidification course of a modified two-component acrylic structural adhesive is measured by using reed-vibration mechanical spectroscopy for liquids （RMS-L） in this work, and results show that there are four sequential processes of mechanical spectra with time. The in-depth analyses indicate that RMS-L can detect in real-time the generation and disappearance of active free radicals, as well as the chemical cross-link processes in the adhesive. This kind of real-time detection will undoubtedly facilitate the study of the chemical reaction dynamics controlled by free radicals.     

Strange beta: an assistance system for indoor rock climbing route setting

This paper applies the mathematics of chaos to the task of designing indoor rock-climbing routes. Chaotic variation has been used to great advantage on music and dance, but the challenges here are quite different, beginning with the representation. We present a formalized system for transcribing rock climbing problems and then describe a variation generator that is designed to support human route-setters in designing new and interesting climbing problems. This variation generator, termed strange beta, uses chaos to introduce novelty. We validated this approach with a large blinded study in a commercial climbing gym, in cooperation with experienced climbers and expert route setters. The results show that strange beta can help a human setter produce routes that are at least as good as, and in some cases better than, those produced in the traditional manner.     

From elementary reactions to evaluated chemical mechanisms for combustion models

Methods of determining rate data for elementary reactions for combustion applications, using experimental and theoretical methods, are briefly reviewed. The approaches are illustrated by reference to recent research in three areas: (i) reactions of OH with C₂H₄ and C₂H₂, where theory, tuned by reference to experiment, has provided a substantial contribution to the determination of rate data for these complex reactions, over a wide range of temperatures; (ii) reactions between alkyl radicals and O₂, where theory and experiment have been closely allied in discerning the details of mechanisms for small alkyl radicals; much remains to be done with larger radicals; (iii) reactions of methylene and the interactions between chemical reaction and the conversion of the singlet state into the triplet, where theory has played little part thus far. Comments are also made on the process of evaluating rate data for elementary reactions for incorporation in chemical mechanisms for use in combustion models.     

Controlled synthesis, characterization and optical properties of CdS nanocrystalline thin films via chemical bath deposition (CBD) route

In this study, the CdS nanocrystalline thin films obtained from an ammonia-free chemical bath deposition process. The crystallites with a size range of 10–20 nm in diameter with zinc blend (cubic) and wurtzite (hexagonal) crystal structure and strong photoluminescence were prepared from the mixture solutions of: cadmium chloride dihydrate as a cadmium source, thiourea as a sulfur source and sodium citrate dihydrate as a complexing agent for cadmium ions. The well-cleaned glass used as a substrate for thin films deposition. The obtained samples were characterized by the techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), atomic force microscopy (AFM) and fluorescence spectroscopy. Also, the effect of two parameters such as pH and temperature of reaction on the synthesis of CdS nanocrystals was studied. Finally, it was found the CdS nanocrystals showed sharp excitation features and strong “band-edge” emission.     

Transport mean free path for magneto-transverse light diffusion: an alternative approach

This paper presents a derivation of the transport mean free path for magneto-transverse light diffusion, ℓ*_⊥, in an arbitrary random mixture of Faraday-active and non-Faraday-active Mie scatterers. This derivation is based on the standard radiative transfer equation. The expression of the transport mean free path obtained previously from the Bethe-Salpeter equation, for the case where only Faraday-active scatterers are present, is recovered. This simpler formulation can include the case of homogeneous mixtures of Faraday-active and non-Faraday-active scatterers.     

Optimal reactions for the synthesis of superheavy nucleus 270Hs

The superheavy nucleus 270 Hs iS expected to be a "double-magic" deformed nucleus.We have calculated its cross sections of evaporation residue for the reactions 248Cm(26Mg,4n)270Hs,244pu(30Si,4n)270Hs,238U(36S,4n)270Hs and 226Ra(48Ca,4n)270Hs using a two-parameter Smoluchowski equation.It is found from our results that 226Ra(48Ca,4n)270Hs and 238U(36S,4n)270Hs are two optimal reactions for the synthesis of the superheavy nucleus 270Hs due to their large negative Q-values.     

Ultrasound in synthesis: natural products and supersonic reactions?

Sonochemical syntheses of a number of useful reagents such as samarium diiodide, sodium phenylselenide, tertiary alkoxides and the reducing agent [(PPh₃P)CuH]₆ are discussed. The rates of these sonochemical reactions can be increased by the addition of electron-transfer agents, such as benzophenone ketyls. These results would not be expected on the basis of mechanical effects alone and lend support to proposals that ultrasound acts preferentially on single electron-transfer processes. Ultrasound also allows the rapid and efficient generation of tetracarbonyliron, which can be trapped by simple organic compounds, such as conjugated dienes, vinyl epoxides and allylic alcohols. In the latter cases, this allows the facile preparation of π-allyltricarbonyliron lactone and lactam complexes that can be converted to give a range of biologically active β-, γ- and δ-lactones, including a number of alkaloids and antibiotics. In addition, the δ-lactone products have been incorporated into several complex multi-step syntheses of macrocyclic natural products. The synthesis of key fragments of the potent antiparasitic agent avermectin B1a demonstrates that the sonochemical reaction conditions are fully compatible with the synthesis of highly functionalized molecules.