Improved sonolytic hydrolysis of peptides in aqueous solution with addition of 1,4-benzenedithiol

Described here is the sonolytic hydrolysis of peptides achieved by treatment of aqueous solution to which the radical scavenger 1,4-benzenedithiol (1,4-BDT), which has hydrogen donating ability, has been added. Mass spectrometric analysis of the products of sonolytic hydrolysis gave information about amino acid sequence of the peptides without any byproducts. The additive 1,4-BDT improves the sonolytic hydrolysis of peptides in terms of the rate of hydrolysis reaction and the amount of additive required when compared to catechol, a previously reported additive. The sonolytic hydrolysis of peptides differs from both acid hydrolysis and hydrogen atom-induced dissociation named matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD), in characteristics. We propose a mechanistic reaction for the sonolytic hydrolysis of peptides, based on the mechanisms of both acid hydrolysis and MALDI-ISD processes. The sonolytic hydrolysis of peptides upon addition of hydrogen donating radical scavengers can be rationalized via the attachment of a hydrogen atom to the carbonyl oxygen with subsequent hydrolysis.     

Sonolytic degradation of hazardous organic compounds in aqueous solution

Benzene, chlorobenzene, 1,2-, 1,3-, 1,4-dichlorobenzene, biphenyl, and polychlorinated biphenyls such as 2-, 4-chlorobiphenyl and 2,2′-dichlorobiphenyl in aqueous solutions have been subjected to sonolysis with 200 kHz ultrasound at an intensity of 6 W cm⁻² under an argon atmosphere. 80–90% of initial amount of these compounds were degraded by 30–60 min of sonication when the initial concentrations were 10–100 μmol l⁻¹. The degradation rate of these compounds increased with increase in their vapor pressures. In all cases of sonolysis of chlorinated organic compounds, an appreciable amount of liberated chloride ion was observed.     

Sonolytic degradation of acetic acid in aqueous solutions

In this work, ultrasonic degradation of acetic acid, which is one of the most resistant carboxylic acids to oxidize, was investigated. The effects of parameters such as ultrasonic power, initial concentration, addition of NaCl or several oxides were studied on the degradation of acetic acid. Acetic acid was sonicated indirectly using an ultrasonic bath with 40 kHz. It was observed that degradation degree increased with decreasing power and initial concentration and with increasing NaCl concentration. Initial degradation degree was enhanced with addition of zeolite and SiO(2).     

Characterization of the end products of the hydrolysis of iron in aqueous solution

A characterization of the iron phases precipitated from aerated solutions of iron(II) sulfate heptahydrate was made using Mössbauer spectroscopy. The experimental conditions for the preparation of the samples were varied. The results are used to the further understanding of rust formation during atmospheric corrosion.     

Surface characterisation of ethylene-propylene-diene rubber upon exposure to aqueous acidic solution

Two types of pure ethylene propylene diene rubbers were exposed to two different acids for varying period of time. Surface characterisation was carried out using X-ray photoelectron spectroscopy (XPS). Two EPDM rubbers selected for this study were comparable in co-monomer compositions but significantly different with respect to molar mass and the presence of long chain branching. Both rubbers contained 5-ethylidene-2-norbornene (ENB) as diene. Solution cast films of pure EPDM samples were exposed in two different acidic solutions, viz. chromosulphuric (Cr (VI)/H₂SO₄) and sulphuric acid (H₂SO₄) (20%, v/v) at ambient temperature from 1 to 12 weeks. XPS analysis indicated that several oxygenated species were formed on the surface of both rubbers after exposure. It was postulated from the XPS analyses that both aqueous acidic solutions attacked the olefinic double bonds (CC) of ENB. Furthermore, 20% Cr (VI)/H₂SO₄ also attacked the allylic carbon-hydrogen (CH) bonds of ENB resulting in more oxygenated species on the surface compared to 20% H₂SO₄ under identical conditions. Cr (VI) in the 20% Cr (VI)/H₂SO₄ was found to play an important role in alteration of surface chemistry. Studies using a model system consisting of EPDM mixed with Cr (VI) and Cr (III) salts revealed that the change of oxidation state from Cr (VI) to Cr (III) as a consequence of direct involvement of Cr (VI) in the chemical alteration of EPDM surfaces. Interestingly, the presence of long chain branching and molar mass did not significantly influence the chemical processes owing to the acid treatment.     

Molecular mechanism of gelation upon the addition of water to a solution of poly(acrylonitrile) in dimethylsulfoxide

The solidification of a solution of poly(acrylonitrile) (PAN) in dimethylsulfoxide (DMSO) upon introduction of water into the solution is studied by Raman spectroscopy. In the absence of water, DMSO molecules are found to produce dipole-dipole bonds with PAN molecules. Upon the introduction of water, DMSO molecules produce hydrogen bonds with it and bands at 1005 and 1015 cm⁻¹ appear in the Raman spectrum, which are assigned to the valence vibrations of S=O bonds involved in the hydrogen bonds. Simultaneously, water molecules produce hydrogen bonds with PAN molecules: R-C≡N...H-O-H...N≡C-R, where R is the carbon skeleton of a PAN molecule. Accordingly, a band at 2250 cm⁻¹ arises in the Raman spectrum, which is assigned to the valence vibrations of C≡N bonds producing hydrogen bonds with a water molecule. When the water content is low and the DMSO concentration is high, the length of the hydrogen bonds varies in wide limits and the band at 2250 cm⁻¹ is wide. As the water content rises, DMSO molecules come out of PAN, the variation of the hydrogen bond length in it decreases (the band at 2250 cm⁻¹ narrows), and a high-viscosity system (gel) arises that consists of PAN molecules bonded to water molecules via “equally strong” hydrogen bonds.     

Sonolysis of chlorinated compounds in aqueous solution

To examine the reaction rates of sonochemical degradation of aqueous phase carbon tetrachloride, trichloroethylene and 1,2,3-trichloropropane at various temperatures, power intensities, and saturating gases, the batch tests were carried out. The degradations of chlorinated hydrocarbons were analyzed as pseudo first order reactions and their reaction rate constants were in the range of 10(-1)-10(-3)/min. The reaction was fast at the low temperature with higher power intensity. Also, the reaction went fast with the saturating gas with high specific heat ratio, high solubility and low thermal conductivity. The main mechanism of destruction of chemicals was believed the thermal combustion in the bubble.     

Optical manipulation of proteins in aqueous solution

Optical trapping of lysozyme, cytochrome c, or myoglobin based on photon pressure generated by focusing 1064 nm laser beam in an aqueous solution was explored. For all the proteins, microparticle formation was observed at the focal point under an optical microscope. Furthermore, the microparticles were identified to the molecular assemblies of the corresponding protein by means of confocal Raman microspectroscopy. For lysozyme, molecular clusters in solution were optically trapped to form the microparticle and it took more than 1 h to produce the microparticle. By contrast, molecular assembling proceeded within 1 min for cytochrome c and myoglobin. Since heme in cytochrome c or myoglobin would have a high polarizability, that would contribute to rapid assembling of the protein. Thus we demonstrated that a focused laser beam was a powerful tool to manipulate protein molecules in solution.     

Effect of ultrasound on ester hydrolysis in aqueous ethanol.

Kinetics of the acid-catalyzed hydrolysis of ethyl acetate in ethanol-water binary solutions were investigated without sonication and under ultrasound at 22 kHz. Rate enhancements by 1.03-2.4 times were found with a minimum at 18 wt.% and a maximum at 45 wt.% of ethanol. The results suggest that ultrasonic acceleration of the reaction may be interrelated to the perturbation of the molecular structure of the binary solvent.     

Sonolytic degradation of endocrine disrupting chemical 4-cumylphenol in water

The sonolytic degradation of endocrine disrupting compound 4-cumylphenol (4-CyP) in aqueous solution was investigated. The influence of operating parameters for sonication process such as 4-CyP initial concentration, frequency, power, pH, temperature and saturating gas was examined. The extent of degradation was inversely proportional to the initial substrate concentration. The rate of 4-CyP degradation was frequency dependent. The degradation rate increased proportionally with increasing ultrasonic power from 20 to 100 W and temperature in the range of 20-50°C. The most favorable degradation pH was acidic media. Destruction in the presence of saturating gas follows the order: argon>air>nitrogen. The 4-CyP degradation was inhibited in the presence of nitrogen gas owing to the free radical scavenging effect in vapor phase within the bubbles of cavitation. The ultrasonic degradation of 4-CyP was clearly promoted in the presence of bromide anions and the promoting effect on degradation increased with increasing bromide concentration. At low 4-CyP concentration (0.05 mg L(-1)), bicarbonate ion drastically enhanced the rate of 4-CyP degradation. Experiments conducted using pure and natural water demonstrated that the sonolytic treatment was more efficient in the natural water compared to pure water.     

Phase behavior of DODAB aqueous solution

Phase behavior of DODAB aqueous solution, prepared without sonication, was studied by adiabatic scanning calorimetry. Measurements revealed four phase transitions with the temperatures 35.2, 39.6, 44.6, and 52.4°C at heating and one transition at the temperature 40.4°C at cooling. The first three transitions at heating occur in unilamellar vesicles. The first and third transitions correspond to the subgel-gel and gelliquid phase transitions, corresponding enthalpy jumps are equal to 33 and 49 kJ/mol. The second transition appears after some aging and is similar to gel-ripple phase transition in a DPPC solution, with the enthalpy jump under the transition exceeding 7.4 kJ/mol. The transition occurs in unilamellar vesicles. The transition at the temperature 52.4°C occurs in another subsystem of the solution, which we believe to be multilamellar vesicles. The enthalpy jump at this transition is equal to 97 kJ/mol, and data analysis suggests that this is a subgel-liquid transition. The phase transition at cooling is the liquid-gel transition in unilamellar vesicles. During the measurements, a slow evolution of the solution occurs, consisting in a change of concentrations of unilamellar and multilamellar vesicles. This transformation mainly occurs at low temperatures.     

Hydrogen bonding in aqueous solution of NaClO4

The ternary system NaClO₄–H₂O–D₂O has been studied, using the Raman spectroscopy. Analysis of the uncoupled OD band of HDO clearly shows that the contour of the band consists of two components only. A new approach has been developed for the quantitative evaluation of the mole fraction of bonded OD groups as a function of perchlorate concentration. It is practically impossible to measure the absolute intensity of Raman scattering. Nevertheless, it is feasible to obtain the specific coefficients of scattering per bonded OD group from the ratio of integrated intensities of the components. For this purpose, the concept of negative ‘phantom’ concentration was introduced, at which all the OD groups must be bonded. As a result, the concentration dependence of the mole fraction of bonded OD groups has been derived. It was found that the infinite network of hydrogen bonds in bulk water ceases to exist at a mole fraction of NaClO₄ above ～0.03–0.035. At higher concentration of perchlorate only residual finite clusters of water molecules can take place. However, the infinite percolation in the system remains. The important fact resulting from the data treatment is that the average number of hydrogen bonds per water molecule in pure water is 2.6?±?0.2.     

Sonochemical degradation of cyclic nitroxides in aqueous solution

The sonochemical degradation of eight five- and six-membered nitroxides has been studied by EPR spectroscopy after exposure to ultrasound at a frequency of 354 kHz in argon-saturated aqueous solution. Concentration vs. time profiles do not follow a simple rate law. Octanol/water partition functions have been determined for all eight nitroxides, and an excellent linear correlation has been found between initial decomposition rates and hydrophobicity (log K(octanol/water)). Variation of initial rate with concentration was investigated for one compound (TEMPONE) and is largely consistent with an equilibrium distribution of substrate between bulk solution and the gas/liquid interface.     

Selective growth of ZnO nanorods in aqueous solution

ZnO nanorod arrays find applications in solar energy conversion, light emission and other promising areas. One approach to generate ZnO nanorods is the cost efficient aqueous chemical growth (ACG). Usually the ACG process is based on a nucleation step followed by growth of ZnO nanorods in aqueous solution at temperatures below 95 C.We report on the fabrication of homogeneous, large scale arrays of nanorods on various substrate materials (Si, glass, polymer) by ACG. PL-measurements show surprisingly good optical quality although the rods were grown at low temperature.Even though we have developed patterning of these arrays with photolithographic techniques, a bottom up approach for lateral patterning is important concerning further applications especially for mass-production. The substrates with patterned metal layers were employed to realize selective growth of nanorods. The experiments were carried out on Ti-, Ag- and Pt-patterned substrates. Selective growth on metal structured glass substrates was developed and is described.     

Photobleaching mechanisms of Radachlorin photosensitizer in aqueous solution

The time dependence of the fluorescence intensity of aqueous solutions of Radachlorin photosensitizer at different concentrations and the influence of the dissolved oxygen concentration on the fluorescence dynamics are analyzed. The experimental results are interpreted based on the numerical solution of the system of kinetic equations describing the photochemical processes that lead to the formation and degradation of singlet oxygen in solution. The influence of possible mechanisms of photosensitizer photobleaching is analyzed. It is shown that the main photobleaching mechanism under our experimental conditions is the chemical reaction between the photosensitizer in the triplet state and dissolved oxygen molecules. Two rate constants of electron-transfer chemical reactions, which are important for understanding the nature of the occurring photoprocesses, are determined.     

Luminol-碳酸钠水溶液的声致发光

作者用Luminol-碳酸钠水溶液的声致发光拍摄了预置剪纸图案的照片,同时获得了这种溶液的声致发射光谱和光致荧光光谱。分析表明,由Luminol增强的碳酸钠水溶液的声致发光主要发生在可见光区域;就声致发光和光致荧光的发射波长而言,这种溶液的声激发和光激发具有一定程度的等效性。     

Dielectric study of aqueous solution of acetonitrile

Time domain reflectometry method has been used in the frequency range of 10 MHz to 10 GHz to determine dielectric properties of aqueous solutions of acetonitrile in temperature range of 0°C to 40°C. The calibration method based on the least squares fit method has been used. The excess permittivity, activation energy, Kirkwood correlation factor and activation energy of acetonitrile-water system have also been determined. The dielectric data show that acetonitrile molecules interact such that the dipoles have a tendency to remain antiparallel.     

Single Pulse-Laser Induced Breakdown Spectroscopy in aqueous solution

In this paper the flexibility of Laser Induced Breakdown Spectroscopy (LIBS) has been proved for the analysis of water solutions. The plasma is generated directly in the bulk of a water solution by a Q-switched Nd:YAG laser (1064). The emission signal of four different solutions has been studied: AlCl₃, NaCl, CaCO₃ and LiF. The basic mechanisms influencing the emission signal and the experimental tricks for the optimization of the detection mode have been pointed out. PACS 52.70.Kz; 52.80.Wq; 39.30.+p