Ultrasound promoted aminolysis of epoxides in aqueous media: a rapid procedure with no pH adjustment for additive-free synthesis of beta-aminoalcohols

An efficient and environmentally friendly procedure promoted by ultrasound irradiation is developed for stereoselective ring opening of various epoxides with aromatic and aliphatic amines under aqueous conditions in the presence of no catalyst or additive. Chemoselectivity of the protocol is shown by competition of piperidine and aniline to react with different epoxides resulting in exclusive formation of the respective products of piperidine.     

β-carboline as a probe for the sonolysis of alcohols and chloromethanes

Sonolysis at 20 and 500 kHz of alcohols, chloromethanes and dilute mixtures of the latter in the former was studied by ultraviolet spectrophotometry in the presence of β-carboline. Acidic degradation products were detected at low frequency sonication, especially for solutions of carbon tetrachloride in alcohols.     

Ultrasonics in isocyanide-based multicomponent reactions: A new,efficient and fast method for the synthesis of fully substituted 1,3,4-oxadiazole derivatives under ultrasound irradiation

A fast and convenient approach to the synthesis of fully substituted 1,3,4-oxadiazoles via three-component reaction of aromatic carboxylic acids, acenaphthoquinone, and (N-isocyanimino)triphenylphosphorane under ultrasound irradiation is described. Furthermore, a series of compounds were synthesized and characterized by melting point, IR, NMR and MS. Utilization of easy reaction conditions, very high to excellent yields, and short reaction times makes this manipulation potentially very useful.     

Ultrasound promoted regioselective synthesis of beta-iodoethers from olefin-I2-alcohol

Regioselective synthesis of β-iodoethers in high yields by sonicating alkene and alcohol in the presence of iodine in a bath at 35 kHz is reported.     

Study of the interfacial structure and chemistry of CVD κ-Al2O3/TiC multilayer coatings

This article describes the interfacial regions in CVD grown TiC/κ-Al₂O₃ multilayers. A number of microanalytical techniques were used including HREM, EDX and EELS. Occasionally, the first 50 nm of the alumina layers deposited on the intermediate TiC layers grew as a cubic alumina, heavily faulted, containing small amounts of sulphur (S), maybe as a stabiliser. The presence of slightly rounded TiC (111) facets may act as preferred nucleation sites for the cubic Al₂O₃ phase, with a ‘cube on cube’ orientation relationship. In this way the nucleation of κ-Al₂O₃ is less favourable. After some tens of nanometres the cubic phase cannot be stabilised any longer and the layer continues to grow as κ-Al₂O₃. A number of observations point towards the reaction zone (RZ) being η- and/or γ-Al₂O₃. The diffraction work and the FFT analysis of the HREM images show that the RZ is an fcc phase with a=7.9 Å, which matches with η- and γ-Al₂O₃. The EELS Al fine structure indicate more tetrahedral Al ions than in κ-Al₂O₃, as in η- and γ-Al₂O₃. The RZ contains small amounts of S, as has been reported for γ-Al₂O₃. Due to the structural similarities between η- and γ-Al₂O₃ it was not possible to determine which of these cubic phases is present in the RZ.     

Nucleophile‐electrophile interactions in the reaction of oxiranes with carboxylic acids in the presence of tertiary amines

The nucleophile‐electrophile interactions in the reaction system “N,N‐dimethylaniline – acetic acid – epichlorohydrin” have been investigated using kinetic methods and computer modeling. The observed orders of reactions have been determined for the overall reaction as well as for individual stages. The kinetic equations have been proposed; the activation parameters of the reactions have been evaluated. The behavior of the initial (amine) and intermediate (carboxylate) nucleophiles has been detailed in reaction pathway. Amine reacts with oxirane activated by acidic reagent while carboxylate‐anion—with both activated and nonactivated epichlorohydrin. The mechanism of oxirane ring opening by acid reagent in the presence of tertiary amine has been proposed, which comprise parallel‐consecutive compensation stages of reaction product formation. It has been demonstrated that the observed reaction order with respect to acid reactant depends upon the nature of electrophilic reagent (activated/nonactivated oxirane) and the ratio of the rates of compensation stages.     

Volatile metal β-diketonates — new precursors for the sonochemical synthesis of nanosized materials — sonolysis of thorium(IV) β-diketonates

Ultrasonic irradiation (22 kHz, Ar atmosphere) of Th(IV) β-diketonates Th(HFAA)₄ and Th(DBM)₄, where HFAA and DBM are hexafluoroacetylacetone and dibenzoylmethane respectively, causes them to decompose in hexadecane solutions, forming solid thorium compounds. The first-order rate constants for Th(IV) β-diketonate degradation were found to be (9.3±0.8)×10⁻³ for Th(HFAA)₄ and (3.8±0.4)×10⁻³ min⁻¹ for Th(DBM)₄, (T=92°C, I=3 W cm⁻²). The rate of the sonochemical reaction increased with the rising β-diketonate volatility and decreased with the rising hydrocarbon solvent vapor pressure. Solid sonication products consisted of a mixture of thorium carbide ThC₂ and Th(IV) β-diketonate partial degradation products. The average ThC₂ particle size was estimated to be about 2 nm. ThC₂ formation was attributed to the high-temperature reaction occurring within the cavitating bubble. The thorium β-diketonate partial degradation products formed in the liquid reaction zones surrounding the cavitating bubbles.     

Fabrication and growth rate estimation of PrBa2Cu3O7−δ single crystal by the modified top seeded crystal pulling method

Recently, we succeeded in fabricating single crystals of PrBa₂Cu₃O_7−δ by a modified top seeded crystal pulling method called the SRL-CP (Solute Rich Liquid-Crystal Pulling) method. Y₂O₃ and MgO polycrystalline crucibles and a MgO single crystal crucible were used to grow the single crystals. The crystal growth temperature was set in the range of 968°C to 972°C. The grown crystals were identified as PrBa₂Cu₃O_7−δ by X-ray diffraction. In the case of using Y₂O₃ crucibles the composition of the grown crystals was Y_xPr_1−xBa₂Cu₃O_7−δ (0.48 < x < 0.57) and in the case of using MgO crucibles a relatively small amount of Mg contamination to the grown crystals occurred at a typical concentration of approximately 1 at.% of the sum of cations. According to the crystal growth model of the SRL-CP method [1–5], a maximum growth rate of 1.7 × 10⁻⁵ cm/s was calculated with the aid of the phase diagram studies we reported earlier [6]. This value is reasonably in agreement with the experimental results.     

The structure of dielectric β-SiC thin films of hollow glass waveguide for CO2 laser power delivery

A novel type of hollow glass waveguide with β-SiC dielectric films was manufactured by a modified chemical vapor deposition method. FTIR absorption spectra and SEM results show that the change of film structure is responsible for the phenomena of the blue shift and the narrow width of the fundamental absorption band of β-SiC, and that the microfissures at the films provide the heterocrystallization centers for promoting the formation of β-SiC crystal. The influences of the concentration of hydrogen gas passed through the system and the reaction temperature are discussed with regard to the film structure.     

Ultrasound promoted efficient method for the cleavage of 3-aryl-2,3-epoxyl-1-phenyl-1-propanone with indole

An efficient synthesis of 3-aryl-3-hydroxy-2-(1H-indol-3-yl)-1-phenyl-1-propanone via the cleavage of epoxides with indole promoted by ultrasound irradiation was carried out in good yields by using montmorillonite K10-ZnCl₂ within 2–5 h at room temperature. This method provides several advantages such as operational simplicity, high yield and mild conditions.     

Field-induced pinning effect of Nd(Ba1−xNdx)2Cu3O7−δ single crystals grown by the traveling-solvent floating-zone method

We have studied the superconducting properties of Nd(Ba_1−xNd_x)₂Cu₃O_7−δ (Nd123, x ≈ 0.1) single crystals grown by the traveling-solvent floating-zone method under 0.1% O₂ in Ar atmosphere. The enhancement of the magnetization with increasing field is observed in the hysteresis (M-H) loop in fields both parallel and perpendicular to the c-axis of the Nd123 single crystals as well as in the bulk crystals prepared by the oxygen-controlled-melt-growth (OCMG) method. The composition variation of Ba/Nd is observed in the matrix of Nd123 crystals by an analytical TEM equipped with a cold field-emission gun. It turns out that the enhancement is due to the field-induced pinning effect ascribed to the weak superconducting Nd---Ba substitution regions in the Nd123 matrix.     

Asymptotics of eigenvalues of the Schrödinger operator with a strong δ-interaction on a loop

In this paper we investigate the operator H_β=−Δ−βδ(·−Γ) in , where β>0 and Γ is a closed C⁴ Jordan curve in . We obtain the asymptotic form of each eigenvalue of H_β as β tends to infinity. We also get the asymptotic form of the number of negative eigenvalues of H_β in the strong coupling asymptotic regime.     

Effects of microalloying with Cd and Ag on the precipitation process of Al–4Cu–0.3Mg (wt%) alloy at 200°C

The present work investigates the effects of individual and combined additions of Cd and Ag on precipitation processes in an Al–4Cu–0.3Mg (wt%) alloy. Analytical scanning transmission electron microscopy revealed that microalloying with Cd stimulates nucleation of θ′ phase on {001} planes and that Cd-rich particles form on the rim and broad facets of the θ′ platelets. We interpret these observations to suggest that Cd nucleates heterogeneously at the θ′– interface and that θ′ can also nucleate heterogeneously at the Cd– interface. In the quinary alloy, it was observed that Ag and Cd additions seem to work independently resulting in a fine and uniform dispersion of both Ω and θ′. Furthermore, the hardening effect of the {111} Ω phase appears to be more potent than other precipitates formed in this system since the hardness of the quinary alloy was intermediate between the Al–Cu–Mg–Ag and the Al–Cu–Cd alloys.     

Ultrasound and heat enhanced persulfate oxidation activated with Fe0 aggregate for the decolorization of C.I. Direct Red 23

Effluents from the paper printing and textile industries are often heavily contaminated with azo dyes. Azo dyes are difficult to oxidize biologically. This work investigated the decolorization of an azo dye, C.I. Direct Red 23 (DR23), by persulfate (PS) activated with Fe⁰ aggregates (PS/Fe⁰). Ultrasound (US) and heat were used as enhancement tools in the PS oxidation system. Neither US-activated PS nor thermally activated PS was effective in oxidizing DR23. However, the decolorization was significantly enhanced by PS/Fe⁰ combined with US (PS/Fe⁰/US) or heat (PS/Fe⁰/55 °C). Approximately 95% decolorization of 1 × 10⁻⁴ M DR23 was achieved within 15 min in the PS/Fe⁰/US system at an initial pH of 6.0, PS of 5 × 10⁻³ M, Fe⁰ of 0.5 g/L and US irradiation of 106 W/cm² (60 kHz). Complete decolorization was achieved within 10 min in the Fe⁰/PS/55 °C system. The rate of decolorization doubled when US was introduced in the PS/Fe⁰ system during the treatment of different initial dye concentrations. The dependence of dye and true color (ADMI) depletion on PS concentration has been discussed. DR23 was completely degraded based on the disappearance of aromatic groups of UV–vis spectra and the variation of TOC mineralization. The observed pseudo-first-order decolorization rate was substantially enhanced by increasing temperature. The Arrhenius activation energy for the PS activated with Fe⁰ was estimated as 8.98 kcal/mol, implying that higher temperature is beneficial for the DR23 decolorization. The addition of US into the PS/Fe⁰ system did not incur a substantial increase in electricity, whereas the mineralization of DR23 occurred quickly. Thus, both PS/Fe⁰/US and heated PS/Fe⁰ systems are practically feasible for the effective degradation of the direct azo dye in textile wastewater.     

Synthesis of novel bis(β‐cyclodextrin)s linked with aromatic diamine and their molecular recognition with model substrates

Novel β‐cyclodextrin (β‐CD) dimers with aromatic diamine linkers, 1,3‐(aminomethyl)‐benzylamine‐bridged bis(6‐amino‐6‐deoxy‐β‐CD) (2) , 4,4′‐diaminodiphenylmethano‐bridged bis(6‐amino‐6‐deoxy‐β‐CD) (3) , and 4,4′‐ ethylenedianiline‐bridged bis(6‐amino‐6‐deoxy‐β‐CD) (4) , were synthesized. The inclusion complexation behaviors of these compounds, together with 4,4′‐aminophenyl ethyl‐bridged bis(6‐amino‐6‐deoxy‐β‐CD) (5) , with substrates such as acridine red (AR), neutral red (NR), ammonium 8‐anilino‐1‐naphthalenesulfonate (ANS), sodium 2‐(p‐toluidinyl) naphthalenesulfonate (TNS), rhodamine B (RhB), and brilliant green (BG), were investigated by ultraviolet, fluorescence, circular dichroism, and 2D NMR spectroscopy. The results indicated that the two linked CD units cooperatively bound to a guest, and the molecular binding affinity toward substrates, especially curved guest ANS and linear guests such as NR and AR, was increased. The linker length between two CD units played a crucial role in the molecular recognition of the hosts with guest dyes. The binding constants of the hosts for AR, TNS, ANS, and RhB decreased with increasing linker length in hosts 2‐4 . Moreover, structurally similar hosts 3 and 5 exhibited very different binding behavior for the guests. Host 5 showed much higher Ks values toward positively charged guests and lower Ks toward negatively charged guests than host 3 . The 2D NMR spectra of hosts 3 and 5 with RhB were acquired to understand the binding difference between 3 and 5 . The molecular binding ability and selectivity of model substrates by these hosts were sufficiently investigated to reveal not only the cooperative contributions of the linker group and CD cavities upon inclusion complexation with dye guest molecules, but also the controlling factors for the molecular selective binding. Copyright © 2008 John Wiley & Sons, Ltd.     

Effect of ultrasound on the reaction of trans-β-methylstyrene with lead tetraacetate

The detail of the reaction of trans-β-methylstyrene with lead tetraacetate in acetic acid was studied. The effect of ultrasonic irradiation using a horn-type reactor was examined and discussed from the viewpoint of the switching of the mechanism from mainly ionic to mainly radical.     

A computational insight into the interaction of methylated lysines with aromatic amino acid cages

Posttranslational lysine methylations in histone proteins are recognized by specific reader proteins. The interaction proceeds through the binding of methylated lysine to the aromatic cages created by the combinations of tryptophan and/or tyrosine and/or phenylalanine, and it is specific to the degree of methylation of lysine residue. The chemical recognition is based on cation‐π interaction between positively charged lysine and the π system of the aromatic groups. In this study, the energetics of the binding of model methylated Lys to the model aromatic amino acids as well as aromatic cages are investigated with density functional theory calculations. Molecular orbitals corresponding to the bound complexes and separate lysine and aromatic amino acid components are analyzed. Finally, using single‐point energy calculations, the feasibility of comparing binding energies/affinities of methylated lysines with different methylation degrees is shown, using available crystal structures of the bound model complexes.     

Assembly of Nanoconjugates as New Kind Inhibitor of the Aggregation of Amyloid Peptides Associated with Alzheimer's Disease

The inhibition of amyloid‐β (Aβ) aggregation has been regarded as the primary therapeutic strategy for Alzheimer's diseases (AD). Currently, many kinds of amyloid inhibitors have been explored, but these inhibitors have their own drawbacks. This study proposes and demonstrates a new kind of inhibitor in this work by making use of protease endowed with high selectivity to prevent Aβ aggregation. To do this, a nanoconjugate that is composed of chymotrypsin, Aβ aptamer, and gold nanoparticle is designed and fabricated. The nanoconjugate can actively capture Aβ through interaction between the aptamer and Aβ, and destroy the target peptides through proteolysis mediated by the adjacent protease molecules. Compared with the conventional inhibitors that only passively bind with Aβ, this new kind of inhibitor may provide a novel insight to control Aβ aggregation. The multivalent binding and efficient enzymatic reaction toward Aβ may also enable a more complete clearance of Aβ, which might achieve a better treatment effect for AD in the future.     

Influence of structural defects on the insertion behavior of γ-MnO2: comparison of H and Li

In an attempt to correlate the crystallographic disorder of γ-MnO₂ compounds to their cationic uptake, the influence of their structural defects on their lithium and proton insertion behavior has been studied and compared. The rate of structural defects in the starting γ-MnO₂ compounds strongly modifies both the voltage vs. cation composition profiles (in terms of shape, average voltage of each electrochemical process, polarization and cycled capacity) and the cycling behavior during the first cycles. This work illustrates that the relationships between structure and cation insertion behavior are different for Li and for proton. The study allows to select for better performing samples in terms of maximum cycled capacity: Li insertion is favored by a very small amount of initial disorder (i.e. a low rate of structural defects in starting compound), while proton insertion requires maximum initial disorder (i.e. an intermediate rate of structural defects). Extrapolation of the results demonstrates the interest of Ramsdellite γ-MnO₂ compounds for cathode applications of rechargeable Li batteries.     

DFT study the interaction of β‐cyclodextrin with benzyl azide and phenyl acetylene in synthesis of 1,2,3‐triazoles

The phenyl acetylene and benzyl azide cycloaddition reaction in water in the presence of β‐cyclodextrin (β‐CD) as a phase transfer catalyst (PTC) can get a better yield in a shorter time. The interaction between β‐CD and phenyl acetylene or benzyl azide plays an important role in this reaction. This paper studies the complexes of β‐CD with phenyl acetylene and benzyl azide using density functional theory (DFT) method. In order to find out the orientations of guests in the cavity of β‐CD, binding energy and deformation energy are investigated, and the calculated results are confirmed by ¹H nuclear magnetic resonance (¹HNMR). The data from single point energy indicate that the inclusion complexes can improve the solubilities of phenyl acetylene and benzyl azide in water. The ¹³C and ¹⁵N spectra show that the most obvious variation concentrates on C₆ and C₈ of phenyl acetylene and N₁₅ of benzyl azide in complexes. Mulliken charge and frontier orbital are employed for revealing the charge distribution. The effect of β‐CD is discussed in terms of the calculated parameters. Copyright © 2014 John Wiley & Sons, Ltd.