Sonochemical reactions occurring in organic solvents: reaction kinetics and reaction site of radical trapping with 1,1-diphenyl-2-picrylhydrazyl

The reaction of 1,1-diphenyl-2-picrylhydrazyl (DPPH) with a radical intermediate was investigated in the sonolysis of several organic solvents. The rate of the DPPH consumption in the sonolysis of methanol obeyed first-order kinetics at low concentrations of DPPH, while the rate became zero-order as the concentration of DPPH further increased. The radical trapping reactions of DPPH were found to be considerably slow compared with the formation of hydrogen molecules in the sonolysis of alcohols and hydrocarbons. These results indicate that H atoms formed in the solvent sonolysis quickly react to form stable molecules such as hydrogen in the cavitation bubble and/or at the interface region. The rates of the DPPH consumption were strongly dependent on the vapor pressure and relative evaporation rate of the solvents. It was proposed that the optimum vapor pressure exists for an effective formation of radical species.     

Sonochemistry of aqueous solutions of amino acids and peptides. A spin trapping study

The sonolysis of argon-saturated neutral aqueous solutions of several amino acids and peptides was investigated by ESR and spin trapping. The water-soluble non-volatile spin trap, 3,5-dibromonitrosobenzene sulfonate, was found to be particularly useful for ESR and spin trapping investigations of sonochemical reactions. By comparison with analogous experiments in which hydroxyl radicals were generated by u.v.-photolysis of solutions containing hydrogen peroxide, the amino acid and peptide radicals produced by sonolysis could be identified. These observations can be explained by the reactions of hydrogen atoms and hydroxyl radicals which are the primary products of the sonolysis of water.     

Effect of ultrasound frequency on pulsed sonolytic degradation of octylbenzene sulfonic acid

It has been shown that pulsed ultrasound can influence the amount of surfactant that can adsorb to and decompose at the surface of cavitation bubbles. However, the effect of ultrasound frequency on this process has not been considered. The current study investigates the effect of ultrasound frequency on the pulsed sonolytic degradation of octyl benzenesulfonate (OBS). Furthermore, the effect of pulsing and ultrasound frequency on the rate of *OH radical formation was determined. OBS degradation rates were compared to the rates of *OH radical formation. In this way, conclusions were made regarding the relative importance of accumulation of OBS at cavitation bubble surfaces versus sonochemical activity to the sonochemical decomposition of OBS under different conditions of sonolysis. Comparisons of the data in this way indicate that sonolytic degradation of OBS depends on both the sonochemical activity (i.e., *OH yield) and the accumulation of OBS on cavitation bubble surfaces. However, under a certain set of pulsing and ultrasound frequency exposure conditions, enhanced accumulation of OBS at the gas/solution interface of cavitation bubbles is the sole mechanism of enhanced degradation due to pulsing. On the basis of this finding, conclusions on how pulsing at various ultrasound frequencies affects cavitation bubbles were made.     

Characterization of alkali induced formation of lanthionine, trisulfides, and tetrasulfides from peptide disulfides using negative ion mass spectrometry

Peptide disulfides are unstable under alkaline conditions, resulting in the formation of products containing lanthionine and polysulfide linkages. Electrospray ionization mass spectrometry has been used to characterize major species obtained when cyclic and acyclic peptide disulfides are exposed to alkaline media. Studies on a model cyclic peptide disulfide () and an acyclic peptide, oxidized glutathione, bis (^γGlu - Cys - Gly - COOH), are described. Disulfide cleavage reactions are initiated by the abstraction of C^αH or C^βH protons of Cys residues, with subsequent elimination of H₂S or H₂S₂. The buildup of reactive thiol species which act on intermediates containing dehydroalanine residues, rationalizes the formation of lanthionine and polysulfide products. In the case of the cyclic peptide disulfide, the formation of cyclic products is facilitated by the intramolecular nature of the Michael addition reaction of thiols to the dehydroalanine residue. Mass spectral evidence for the intermediate species is presented by using alkylation of thiol groups as a trapping method. Mass spectral fragmentation in the negative ion mode of the peptides derived from trisulfides and tetrasulfides results in elimination of S₂.     

Control over structural-dimensional characteristics of tungsten disulfide particles in aerosol-assisted chemical vapor deposition

Solutions of ammonium thiotungstate in dimethylformamide were used to synthesize spherical tungsten disulfide particles with average radius of 500–100 nm by the method of aerosol-assisted chemical vapor deposition. Nanoparticles with composition close to stoichiometric tungsten disulfide are formed at pyrolysis temperatures not lower than 800°C. It was found that the average particle radius linearly decreases as the reagent concentration in solution becomes lower, and the nebulizer power has no effect within the range under study on the size characteristics and structure of the particles obtained. It was demonstrated that the particles have a layered structure that is formed in all probability by S–W–S packets, which must provide high antifriction properties of the material in its use as a high-temperature solid lubricant. The results obtained indicate that the size of tungsten disulfide particles can be controlled in a wide range in the course of the aerosol-assisted chemical vapor deposition. This may be of interest for developing a technology for creating high-temperature wear-resistant antifriction coatings.     

A synergetic effect in nitrous acid formation by sonolysis of nitric acid in the presence of nitrous oxide

A synergetic effect is found in the sonochemical formation of HNO₂ in HNO₃ solution in the presence of an N₂O–Ar gaseous mixture. The maximum rate of HNO₂ formation is observed at an N₂O : Ar ratio of 15 : 85 (v/v). During the sonolysis of 4 M HNO₃ solutions, the rate of HNO₂ formation increases multifold due to the synergetic effect. The rate of sonochemical hydrazine decomposition in nitrate solutions also increases considerably in the presence of N₂O.     

Multibubble sonolysis and sonoluminescence in molten elementary sulfur and sulfur—styrene mixture

The effect of saturation with argon, as well as styrene and iodine additives on the temperature dependence of multibubble sonoluminescence intensity in molten sulfur at 120–230 °C was studied. The shape of the temperature dependence with a maximum at 170–200 °C is determined by the viscosity variations related to the changes in the molecular structure of molten elemental sulfur. At high temperatures, cyclooctasulfane (S₈) molecules break to radical products, which then undergo polymerization that can be slowed down by the additives. Sulfurization of styrene during sonolysis of a sulfur—styrene mixture resulting in products of the thiophene series was detected. Unlike thermal sulfurization that affords 2,5-diphenylthiophene as a major product, sonochemical sulfurization results mainly in 2,4-diphenylthiophene. The mechanism of 2,4-diphenylthiophene formation initiated by the reaction of styrene molecules with S⁺ ions produced upon fragmentation of S₈ within cavitation bubbles is proposed. The glow of electronically excited S⁺* ions is responsible for the band with a maximum at 560 nm in the sonoluminescence spectrum of molten sulfur, which is suppressed by the styrene additive.     

Investigation of radical intermediates in polymer sonochemistry

There is current interest in using high-intensity ultrasound to perform a range of chemical transformations, including polymerisation reactions. In this work, the technique of radical trapping, primarily using DPPH, has been used to measure radical production rates in a range of monomer and related systems when exposed to high intensity ultrasound. It has been shown that realistic rates of production can be obtained around room temperature equivalent to thermal decomposition rates > 100°C, making sonication a viable method for initiating polymerisation. Rates of initiation in a twophase organic in water system have also been measured. Some of the initiating species have been identified recording the ESR spectra of adducts with spin traps, although further analysis is needed before the complete range of radicals produced can be identified.     

Effect of aerosol chemical vapor deposition on characteristics of MoS<Subscript>2</Subscript> particles

Influence exerted by the main technological parameters in the process in which nano- and microparticles of molybdenum disulfide are formed by the aerosol chemical vapor deposition method from a gas phase containing aerosol particles of (NH₄)₂MoS₄?C₃H₇NO solutions on the dimension characteristics, structure, and composition of the products being formed was studied. It was shown that the shape, size, and structure of the particles being formed are determined by the processes occurring in the first, streamwise, reactor zone. The temperature of this zone is the most important technological parameter. The concentration of ammonium thiomolybdate in solution makes it possible to gradually vary the size of disulfide particles in a wide range (from tens of nanometers to micrometers). In the conditions under study, the technological conditions have no effect on the chemical composition of the products being synthesized, which is always described by the formula MoS₂. The results obtained can be used in development of industrial apparatus and technology for synthesis of molybdenum disulfide nano- and microparticles to be used as the antifriction component of lubricating materials.     

S-alkylation and S-amination of methyl thioethers--derivatives of closo-[B(12)H(12)](2-). synthesis of a boronated phosphonate, gem-bisphosphonates, and dodecaborane-ortho-carborane oligomers

A variety of S-alkylated products was prepared by alkylation of methyl thioethers [MeSB(12)H(11)](2-) (5), [1-(MeS)-2(7,12)-(Me(2)S)B(12)H(10)](-) (6-8), and [1,2(7,12)-(MeS)(2)B(12)H(10)](2-) (9-11) with alkyl halides and tosylates in acetonitrile. Since these methyl thioethers can be prepared easily in B-10-enriched form on a large scale and due to their chemical versatility, they are potentially very attractive boron entities for the design and synthesis of therapeutics for boron neutron capture therapy of cancer. It was found that alkylation of 6-8 can be complicated by an equilibrium which establishes between, on the one hand, one of the former species and, on the other hand, 1,2(7,12)-(Me(2)S)(2)B(12)H(10) (2-4) and [1,2(7,12)-(MeS)(2)B(12)H(10)](2-) (9-11). A boronated phosphonate 1-(MeS(CH(2))(4)P(O)(OEt)(2))-7-(Me(2)S)B(12)H(10) (14g) and a gem-bisphosphonate 1-(MeS(CH(2))(3)CH[P(O)(OEt)(2)](2))-7-(Me(2)S)B(12)H(10) (14h) were prepared from thioether 7 and the corresponding iodide and tosylate, respectively, and subsequently converted to their sodium salts. The propargyl sulfonium salts obtained by alkylation of thioethers 7, 8, 10, and 11 with propargyl bromide have been further converted to two- and three-cage oligomers containing both ortho-carborane and dodecaborane moieties. Methyl thioethers derived from closo-[B(12)H(12)](2-) are excellent participants in Michael addition reactions in the presence of a strong acid. The sulfonium salts with tertiary alkyl and vinyl substituents have been prepared by this method. Methyl thioethers 5-11 react with hydroxylamine-O-sulfonate yielding the corresponding aminosulfonium salts, albeit in lower yields as compared to those in the alkylation reactions. Several derivatives of methyl thioethers 5-11 have been characterized by single-crystal X-ray diffraction.     

芳香族硝基化合物与苯硫酚钠盐的亲核取代反应: 自由基IPSO取代机理

作者通过苯硫酚钠盐与对硝基苯甲酸甲酯(1), 对硝基苯甲酸苯酯(2), 间硝基苯甲酸甲酯(3), 3,5-二硝基苯甲酸甲酯(4)和对二硝基苯(5)反应研究, 用自旋捕获技术检测到苯硫基自由基; 同时, 从产物混合物中分离到二苯基二硫化物PhSSPh。提出苯硫基自由基与芳香族硝基化合物1,2,3,4和5反应的自由基IPSO亲核取代机理。     

Photoinduced electron transfer chemistry of phthalimdes: an efficient tool for CC-bond formation

A collection of intra- and intermolecular photoinduced electron transfer (PET) reactions is presented which all are based on the phthalimide chromophore as the oxidizing species. Electron-donating groups versatile for PET processes are ethers, thioethers, amines, alkenes, arenes, and carboxylates as well as α-trialkylsilyl activated heteroatom-substituents. These reactions can be efficiently applied for the synthesis of five- and six-membered ring heterocycles, medium-sized and macrocyclic products such as macrolides, cyclopeptides, crown ethers or thioethers as well as (from intermolecular processes) Grignard-alike products.     

Sonochemistry and sonoluminescence of room-temperature ionic liquids

The sonication of ionic organic liquids leads to decomposition of the liquids. Multibubble sonoluminescence spectra and headgas analysis reveal a variety of decomposition products from the sonolysis of N,N'-dialkylimidazolium ionic liquids. The decomposition is a result of acoustic cavitation, which generates localized hot spots from the implosive collapse of bubbles in the ionic liquids. Despite the negligible vapor pressure of the ionic liquids, reaction still occurs in a heated shell of the bubbles or from microdroplets thrown into the collapsing bubbles.     

Preparation of nanoparticles by reducing intermediate radicals formed in sonolytical pyrolysis of surfactants

Metal nanoparticles with a narrow size distribution could be prepared by sonolysis of aqueous solutions of metal cations in the presence of surfactants such as sodium dodecyl sulfate, polyethylene glycol monostearate, etc. The role of the surfactans is not only to stabilize formed particles, but also to produce reductive radicals in pyrolysis or hydrogen abstraction of OH radicals from surfactants. Particles with a smaller size could be obtained in a faster reduction rate with dilute metal cations concentration. Pt(IV) is consecutively reduced in two steps to Pt(0)via Pt(II). By comparing the sonolytical reduction withγ-ray radiolysis, two kinds of organic reducing radicals are proposed to contribute to the reduction. One (R_ab) is an intermediate radical which is produced by hydrogen abstraction of OH radical from surfactant and effective only on the reduction of Pt(II) to Pt(0). The other (R_py) is also an intermediate radical which is produced by thermal decomposition of surfactant at the interface between the cavity and bulk solution and effective on the reduction of Pt(IV) to Pt(II).     

Disulfide‐centered poly(methyl acrylates): Four different stimuli to cleave a polymer

A series of poly(methyl acrylates) incorporating a disulfide center was subjected to four different stimuli to cleave the S S bond, as the weakest member of the chain. Four polymers with molecular weights in the range of 25–93 kDa were synthesized via Cu‐based atom transfer radical polymerization starting from a difunctionalized disulfide‐containing initiator. In tetrahydrofuran, the labile disulfide center was cleaved directly by mechanical force generated by ultrasound irradiation, whereas in chloroform, competing cleavage was also triggered by radical species that were generated by non‐mechanical sonolysis. A reductive cleavage was observed upon treatment with reducing agent, and a clean reversal of the cleavage via oxidation could be obtained if the terminal bromide was first removed via hydrogenolysis. This modified polymer allowed studies on a fourth strategy for the cleavage of the disulfide, namely, dynamic covalent exchange reactions with a fluorine labeled small molecule. While partially based on established protocols, this comparative study underscores the versatility of the disulfide bond for applications in stimuli‐responsive and adaptive materials. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1404–1411     

Synergistic effect of sonolysis and photocatalysis in the degradation kinetics of effluent solution

In this study, degradation of the effluent solution using sonolysis, sonocatalysis, photocatalysis and sonophotocatalysis was investigated. For this purpose, an artificial effluent solution (AES) containing Acid Black 1 and Acid Blue 62 dyestuffs was prepared. The initial AES concentration, catalyst amount, light intensity and the power of ultrasound energy were chosen as the reaction parameters.The degradation rate of AES followed the pseudo-first order kinetics inconcentration of artificial effluent solution. The results showed that the sonophotocatalysis (US + UV + TiO₂) was more effective in the degradation than sonolysis (US), sonocatalysis (US + TiO2) and photocatalysis (UV + TiO₂) performed individually. The highest and lowest degradation rates were obtained in sonophotocatalytic process and sonolytic process (US), respectively. It was found also that the synergistic effect between sonolysis and photocatalysis processes is the main reason why the maximum degradation is achievable in the sonophotocatalytic process.     

Sonoluminescence of aqueous solutions of sulfuric acid and sulfur dioxide

Sonoluminescence (SL) of aqueous solutions of sulfuric acid and sulfur dioxide enhances with an increase in their concentration and reaches a maximum at 16 and 0.05 mol L^–1, respectively. The further increase in the concentration of these substances decreases the SL intensity. The SL spectra of the solutions have a broad maximum at 450 nm. Excited SO₂ molecules formed in sulfuric acid due to sonolysis are luminescence emitters. The proposed mechanism of bright SL in these systems is based on the energy transfer from the electron-excited sonolysis products to the SO₂ molecules in cavitation bubbles.     

N-Heterocyclic Carbene Mediated Sulfur Extrusion of Disulfides

The sulfur extrusion from organic disulfides is a highly useful reaction recognised for the first time over 40 years ago. Unfortunately, it is mainly performed by aminophosphines, such as hexamethylphosphorus triamine, which is known to be very carcinogenic. This limits the application of the extrusion reaction especially for the synthesis of pharmaceutical products. We have developed a new method, using N-heterocyclic carbenes (NHCs), generated from the corresponding stable imidazolium salts in combination with a base to transform a broad scope of benzylic disulfides to thioethers. In addition disulfide containing esters as well as cystine undergo this reaction.     

Photochemistry of Aryl Vinyl Sulfides and Aryl Vinyl Ethers: Evidence for the Formation of Thiocarbonyl and Carbonyl Ylides

Aryl vinyl thioethers 5a and 9a and aryl vinyl ethers 5b and 9b form ylide intermediates following laser irradiation at 308 nm. In benzene, the ylides possess long-lived absorption bands in the 600-800 nm region with a second weaker band at approximately 460 nm. In methanol, a known quencher of zwitterionic species, the lifetimes are reduced significantly. The decay kinetics measured within the long wavelength absorption envelope vary with wavelength, indicating the presence of more than one ylide species. Formation of the ylides occurs via a naphthalene-like triplet state in the case of aryl vinyl ethers, while for the thioethers the multiplicity of the ylide precursor could be either singlet or triplet. Product formation in benzene for 5a and 5b involves ring closure of the ylide to produce dihydrothiophene and dihydrofuran products, respectively. For short periods of irradiation (either lamps or laser) a mixture of cis- and trans-fused products is observed, while for prolonged irradiation only the cis-fused compound is detected, suggesting a photoenolization mechanism for conversion of trans to cis. In addition to products derived from ring closure, 9a provides intramolecular addition product 12. Conversely, the ylide derived from 9b gives rise to the [3 + 2] cycloaddition product 13.     

α-Conotoxin ImI incorporating stable cystathionine bridges maintains full potency and identical three-dimensional structure

The two disulfide bonds of α-conotoxin ImI, a peptide antagonist of the α7 nicotinic acetylcholine receptor (nAChR), were systematically replaced with isosteric redox-stable cystathionine thioethers. Regioselective thioether formation was accomplished on solid support through substitution of a γ-chlorohomoalanine by an intramolecular cysteine thiol to produce hybrid thioether/disulfide analogues (2 and 3) as well as a dual cystathionine analogue (4) that were found to be structurally homologous to α-conotoxin ImI by (1)H NMR. The antagonistic activity at the α7 nAChR of cystathionine analogue 3 (pIC(50) = 6.41 ± 0.09) was identical to that of α-conotoxin ImI (1, pIC(50) = 6.41 ± 0.09), whereas those of 2 (pIC(50) = 5.96 ± 0.09) and 4 (pIC(50) = 5.89 ± 0.09) showed a modest decrease. The effect of oxidation of the thioethers to sulfoxides was also investigated, with significant changes in the biological activities observed ranging from a >30-fold reduction (2S═O) to a 3-fold increase (3S═O(B)) in potencies.