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Objective: This study evaluated the influence of Nd:YAG laser on the evaporation degree (ED) of the solvent components in total-etch and self-etch adhesives., Materials and Methods: The ED of Gluma Comfort Bond (Heraeus-Kulzer) one-step self-etch adhesive, and Adper Single Bond 2 (3M ESPE), and XP Bond (Dentsply) total-etch adhesives was determined by weight alterations using two techniques: Control--spontaneous evaporation of the solvent for 5 min; Experimental--Nd:YAG laser irradiation for 1 min, followed by spontaneous evaporation for 4 min. The weight loss due to evaporation of the volatile components was measured at baseline and after 10 s, 20 s, 30 s, 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s, 110 s, 2 min, 3 min, 4 min, and 5 min., Results: Evaporation of solvent components significantly increased with Nd:YAG laser irradiation for all adhesives investigated. Gluma Comfort Bond showed significantly higher evaporation of solvent components than Adper Single Bond 2 and XP Bond. All the adhesives lost weight quickly during the first min of Nd:YAG laser irradiation., Conclusion: The application of Nd:YAG laser on adhesives before light curing had a significant effect on the evaporation of the solvent components, and the ED of Gluma Comfort Bond one-step self-etch adhesive was significantly higher than with Adper Single Bond 2 and XP Bond total-etch adhesives., Clinical Relevance: The use of the Nd:YAG laser on the uncured adhesive technique can promote a greater ED of solvents, optimizing the longevity of the adhesive restorations.

4-Aminoimidazole-5-carbonitrile (AICN) was suggested as a prebiotically plausible precursor of purine nucleobases and nucleotides. Although it can be formed in a sequence of photoreactions, AICN is immune to further irradiation with UV-light. We present state-of-the-art multi-reference quantum-chemical calculations of potential energy surface cuts and conical intersection optimizations to explain the molecular mechanisms underlying the photostability of this compound. We have identified the N-H bond stretching and ring-puckering mechanisms that should be responsible for the photochemistry of AICN in the gas phase. We have further considered the photochemistry of AICN-water clusters, while including up to six explicit water molecules. The calculations reveal charge transfer to solvent followed by formation of an H3O(+) cation, both of which occur on the (1)πσ* hypersurface. Interestingly, a second proton transfer to an adjacent water molecule leads to a (1)πσ*/S0 conical intersection. We suggest that this electron-driven proton relay might be characteristic of low-lying (1)πσ* states in chromophore-water clusters. Owing to its nature, this mechanism might also be responsible for the photostability of analogous organic molecules in bulk water.

We investigate the acid-base proton exchange reaction in a microsolvated bifunctional chromophore by means of quantum chemical calculations. The UV/vis spectroscopy shows that equilibrium of the keto- and enol-forms in the electronic ground state is shifted to the keto conformation in the excited state. A previously unknown mechanism involving a hydroxide ion transport along a short water wire is characterized energetically, which turns out to be competitive with the commonly assumed proton transport. Both mechanisms are shown to have a concerted character, as opposed to a step-wise mechanism. The alternative mechanism of a hydrogen atom transport is critically examined, and evidence for strong solvent dependence is presented. Specifically, we observe electrostatic destabilization of the corresponding πσ* state by the aqueous solvent. As a consequence, no conical intersections are found along the reaction pathway.

Ruthenium-exchanged FAU-Y zeolite (RuY) was used as a recyclable catalyst for regioselective ring-opening of epoxides with indoles under irradiation of sonic waves. It was found that a solvent free process, under the above mentioned conditions provides good yields of the desired 3-alkylated indole derivatives., (Copyright © 2011 Elsevier B.V. All rights reserved.)

This work reports the transesterification of soybean oil with ethanol using two commercial immobilized lipases under the influence of ultrasound irradiation. The experiments were performed in an ultrasonic water bath, following a sequence of experimental designs to assess the effects of temperature, enzyme and water concentrations, oil to ethanol molar ratio and output irradiation power on the reaction yield. Results show that ultrasound-assisted lipase-catalyzed transesterification of soybean oil with ethanol might be a potential alternative route to conventional alkali-catalyzed method, as high reaction yields (~90 wt.%) were obtained at mild irradiation power supply (~100 W), and temperature (60 °C) in a relatively short reaction time, 4h, using Lipozyme RM IM as catalyst. The repeated use of the catalyst under the optimum experimental condition resulted in a decay in both enzyme activity and product conversion after two cycles. The use of Novozym 435 led to lower conversions (about 57%) but the enzyme activity was stable after eight cycles of use, showing, however, a reduction in product conversion after the forth cycle., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Nano-structures of AgBr have been prepared by reaction between AgNO(3) and KBr under ultrasound irradiation. Particle sizes and morphology of nanoparticle are depending on temperature, power of sonicating, reaction time and concentration. The effects of these parameters in growth and morphology of the nano-structures have been studied. Results suggest that an increasing of temperature, sonication power and concentration led to a decreasing of particle size. The samples were characterized with powder X-ray diffraction (XRD) and scanning electron microscopy (SEM)., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Introduction: In the nuclear industry 1,4-dioxane is used as a solvent in liquid scintillation technique for measuring low-energy beta-emitters such as ³H or C¹⁴ in aqueous media. Improper disposal of 1,4-dioxane can contaminate the ground and surface waters. Conventional wastewater treatment processes like chemical treatment, air stripping, carbon adsorption, and biological treatment are ineffective for the degradation of 1,4-dioxane., Methods: In the present study, the kinetics of degradation of 1,4-dioxane using advanced oxidation processes viz., H₂O₂ alone, Fe(II) + H₂O₂, UV (15 W) + H₂O₂, UV (15 W) + Fe(II) + H₂O₂, US (130 KHz) + Fe(II) + H₂O₂, and sunlight + Fe(II) + H₂O₂ at pH 3.0 was investigated. The optimization of Fe (II) for the processes using Fe (II) + H₂O₂ was carried out., Conclusions: The kinetics of degradation using sunlight + Fe (II) + H₂O₂ was found to be fastest when compared to the other processes. The degradation was found to follow first-order kinetics. Formation of acidic intermediates was suspected from the observed pH changes during the degradation processes.

The transformation of the synthesized allicin, using conventional method, the influence of ultrasound and microwaves, in different organic solvents (acetonitrile, acetone, methanol, and chloroform), at various temperatures (room temperature, 45 °C, and 55 °C) was investigated. Allicin degradation kinetic was monitored by HPLC. Allicin transformation under the effect of microwaves is faster than transformations performed under the influence of ultrasound or by conventional method. Increase of the temperature accelerates allicin transformation. Pharmacologically active compounds of (E)-ajoene, (Z)-ajoene, 3-vinyl-4H-1,2-dithiin, 2-vinyl-4H-1,3-dithiin, and diallyl disulfide were isolated from the mixture of transformation products of allicin under the influence of microwaves in methanol at 55 °C, which is according to kinetic parameters (highest values of the order of reaction and the lowest activation energy) the optimal method.

The action of high intensity cavitation on several liquid halocarbons (C(2)Cl(4) CCl(4), CHCl(3), C(2)H(2)Br(4)) and other organic solvents (acetone, benzene and their mixtures) was investigated by recording multibubble sonoluminescence UV-Vis spectra over the temperature range between 246 and 298 K. The temperature induced variation of some thermophysical properties of the solvents Favours the interpretations of their role in determining the salient characteristics of the recorded spectra. We observed that high volatility does not necessarily quench sonoluminescence emission and that argon flow plays a key role in the appearance of radical emission lines. While for each investigated substance the intensity of C*(2) emission lines was clearly correlated to temperature, a comparative test between different halocarbons did not show a clear correlation with vapour pressure. Following recently reported results which evidenced the formation of dynamically differentiated populations of emitting bubbles in sulphuric acid, we performed MBSL experiments in liquid mixtures of halocarbons and sulphuric acid to investigate the correlation between the production of emitting species and the halocarbon volatility., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Given earlier observations that microwave frequencies can have a substantial effect on the photoactivity of a well-known photocatalyst (TiO(2)), in the synthesis of 3,6-diphenyl-4-n-butylpyridazine through a Diels-Alder process, and in the one-pot solvent-free synthesis of a room-temperature ionic liquid, we proceeded to examine the frequency effects of the 5.8 and 2.45 GHz microwave (MW) radiation in the synthesis of gold nanoparticles in non-polar media, such as oleylamine, which have a low dielectric constant (ε'), and we further examine differences in shape and size under otherwise identical temperature conditions when the synthesis of the gold nanoparticles was carried out in an ethylene glycol polar medium in the presence of polyvinylpyrrolidone. Whereas a change in microwave frequency from 2.45 to 5.8 GHz at equal microwave power levels led to the synthesis of gold nanoparticles in the non-polar media, a change in the microwave frequency had no effect on the size and shape of the gold nanoparticles synthesized in polar media for identical microwave power levels.

1-Hexanesulphonic acid sodium salt was found to be an efficient catalyst for the green synthesis of alpha-aminophosphonates by the coupling of aldehydes/ketone, an amine and triethyl phosphite under ultrasound irradiation at ambient temperature for appropriate time to furnish the desired product in good to excellent yield under solvent-free condition. This catalyst provides clean conversion; greater selectivity and easy workup make this protocol practical and economically attractive., ((c) 2010 Elsevier B.V. All rights reserved.)

Mild and efficient Fischer esterification reactions of lactic acid with a variety of straight chain aliphatic alcohols, cyclohexanol and benzyl alcohol were successfully performed using two novel Brønsted acidic ionic liquids that bear an aromatic sulfonic acid group on the imidazolium or pyridinium cation under ultrasound irradiation. These reactions carried out smoothly with good to excellent conversion rate (78-96%) and satisfactory yields (73-92%) in shorter reaction time (4-6h) at room temperature when the amount of ionic liquids was 20 mol%. These ionic liquids could be recovered readily and recycled five times without any significant loss in their catalytic activity., ((c) 2010 Elsevier B.V. All rights reserved.)

Montmorillonite K-10 and KSF were found to be highly efficient, environmentally friendly and recyclable heterogeneous catalysts for the selective synthesis of a variety of 2-aryl-5,6-dihydro-4H-1,3-oxazines from arylnitriles and 3-amino-1-propanol under ultrasound irradiation. This new methodology provides excellent yields in short reaction times (10-25 min). The reaction work-up is very simple and the catalysts can be easily separated from the reaction mixture and reused several times in subsequent reactions. This catalytic system also exhibits excellent chemoselectivity in the synthesis of mono-oxazines from dinitriles., ((c) 2010 Elsevier B.V. All rights reserved.)

This paper presents a novel solvent free method of synthesis of trans-chalcones. The method was based on ultrasound irradiation of the reagents (aryl methyl ketones and aryl aldehydes) in presence of commercial acid-montmorillonites as catalysts. The trans-chalcones were synthesized in high yields (85-95%) and excellent selectivity in a short reaction time.

Highly crystalline metal oxide nanoparticles of TiO(2), WO(3), and V(2)O(5) were synthesized in just a few minutes by reacting transition metal chloride with benzyl alcohol using ultrasonic irradiation under argon atmosphere in a non-aqueous solvent. The sonochemical process was conducted at a relatively low temperature, 363 K. A unique crystallization process of these nanoparticles has been observed and characterized by powder X-ray diffraction (PXRD), high resolution scanning electron microscopy (HRSEM), and BET. The particles' size and shape measured from HRSEM reveal "quasi" zero-dimensional, spherical TiO(2) particles in the range of 3-7 nm. The V(2)O(5) particles have a "quasi" one-dimensional ellipsoidal morphology, with lengths in the range of 150-200 nm and widths varying between 40 and 60 nm. The WO(3) particles were obtained as "quasi" two-dimensional platelets with square shapes having facets ranging from 30 to 50 nm. The thickness of these platelets was between 2 and 7 nm. The mechanism of the reactions leading to these three metal oxide nanoparticles in a non-aqueous system is substantiated by Nuclear Magnetic Resonance (NMR), and Electron Spin Resonance (ESR).

Photochemically induced dynamic nuclear polarization (photo-CIDNP) of nuclei other than (1)H offers a tremendous potential for sensitivity enhancement in liquid state NMR under mild, physiologically relevant conditions. Photo-CIDNP enhancements of (15)N magnetization are much larger than those typically observed for (1)H. However, the low gyromagnetic ratio of (15)N prevents a full fruition of the potential signal-to-noise gains attainable via (15)N photo-CIDNP. Here, we propose two novel pulse sequences, EPIC- and CHANCE-HSQC, tailored to overcome the above limitation. EPIC-HSQC exploits the strong (1)H polarization and its subsequent transfer to non-equilibrium N(z) magnetization prior to (15)N photo-CIDNP laser irradiation. CHANCE-HSQC synergistically combines (1)H and (15)N photo-CIDNP. The above pulse sequences, tested on tryptophan (Trp) and the Trp-containing protein apoHmpH, were found to display up to 2-fold higher sensitivity than the reference NPE-SE-HSQC pulse train (based on simple (15)N photo-CIDNP followed by N-H polarization transfer), and up to a ca. 3-fold increase in sensitivity over the corresponding dark pulse schemes (lacking laser irradiation). The observed effects are consistent with the predictions from a theoretical model of photo-CIDNP and prove the potential of (15)N and (1)H photo-CIDNP in liquid state heteronuclear correlation NMR.

12 hybrid photocatalysts consisting of titania (TiO(2)) and an adsorbent such as mordenite were investigated for the photocatalytic decomposition of toluene, a major indoor contaminant in indoor air. The highest decomposition rate was obtained with the use of mordenite and silicon dioxide (SiO(2)) as additives to TiO(2). The photocatalytic activities of hybrid photocatalysts in decomposing toluene are 1.33 times as high as pure P25 at the net weight loading of 0.49 mg/cm(2) under the test condition. Scanning electron microscopy (SEM) images confirmed that the hybrid photocatalyst films were very porously distributed; TiO(2) was adsorbed on the surface of mordenite and SiO(2), increasing the reaction area of TiO(2). The unimolecular Langmuir-Hishelwood model and mass-transfer-based (MTB) method were used to evaluate the reaction coefficients and adsorption equilibrium coefficients of hybrid photocatalysts. It is evidenced that the reaction areas of two hybrid photocatalysts were 1.52 and 1.64 times larger than that of P25, respectively, which is the major reason to make the high removal efficiency of toluene.

A factor currently limiting the clinical utility of x-ray CT polymer gel dosimetry is the overall low dose sensitivity (and hence low dose resolution) of the system. Hence, active research remains in the investigation of polymer gel formulations with increased CT dose response. An ideal polymer gel dosimeter will exhibit a sensitive CT response which is linear over a suitable dose range, making clinical implementation reasonably straightforward. This study reports on the variations in rate and form of the CT dose response of irradiated polymer gels manufactured with glycerol, which is a co-solvent that permits dissolution of additional bisacrylamide above its water solubility limit (3% by weight). This study focuses on situations where the concentration of bisacrylamide is kept at or below its water solubility limit so that the influence of the co-solvent on the dose response can be explored separately from the effects of increased cross-linker concentration. CT imaging and Raman spectroscopy are used to construct dose-response curves for irradiated gels varying in (i) initial total monomer (%T) and (ii) initial co-solvent concentration. Results indicate that: (i) for a fixed glycerol concentration, gel response increases linearly with %T. Furthermore, the functional form of the dose response remains constant, in agreement with a previous model of polymer formation. (ii) Polymer gels with constant %T and increasing co-solvent concentrations also show enhanced CT response. In addition, the functional form of the response is altered in these gels as co-solvent concentration is increased. Raman data indicate that the fraction of bis-acrylamide incorporated into polymerization, as opposed to cyclization, increases as co-solvent concentration increases. The changes in functional form indicate varying polymer yields (per unit dose), akin to relative fractional monomer/cross-linker (i.e. %C) changes in earlier studies. These results are put into context of the model of polymer formation. The implications of these results on the clinical utility of polymer gels with co-solvent are highlighted.

The switching of a molecular length of azobenzene between its trans and cis forms by photoirradiation originates various photoresponsive systems in the molecular level and/or nanolevel. Recently, we and another group separately reported that some azobenzene-modified mesoporous silicas remarkably promote the release of molecules from the inside of the mesopore to the outside, when the lights, both UV and visible lights, were irradiated simultaneously. In these cases, the release rates of molecules were enhanced by the impeller-like effect of molecular motion of azobenzene moiety attributed to the continuous photoisomerization between the trans and cis isomers. This paper presents that azobenzene-substituent-tethered amorphous silica gel could promote the development of solvents in chromatography systems by photoirradiation. In column chromatography system where azobenzene-tethered silica gel was packed, the irradiation of both UV and visible lights increased the effluent rate of the developing solvents. The single irradiation of UV light scarcely enhanced the rate, while the visible light irradiation longer than 400 nm in wavelength also accelerated the development of the solvent moderately. The same kinds of phenomena were observed when this photopromoted chromatography system was applied to thin layer chromatography (TLC). Hydrocarbon developing solvents in the regions, where UV and visible lights were irradiated, moved up the TLC plate higher than those without photoirradiation. When the pyrene solution in the developing solvent was utilized in the chromatography systems, the similar photoacceleration of pyrene development was observed at the same level as the developing solvents.

Ultraviolet-visible and infrared transient-absorption spectroscopy are used to investigate the transfer of energy from nitrite to water during the photo-dissociation of NO2-(aq). Nitrite is dissociated by photo-excitation at 200 nm. About 40% of the photo-fragments recombine and relax on a 3 ps timescale, while diffusive recombination accounts for another 10% of the fragments during the subsequent 50 ps. The infrared transient-absorption spectra of the photo-dissociation of nitrite solvated in H2O and D2O show no evidence of excited vibrations after 0.5 ps. Instead they reveal a sub-0.5 ps change in the infrared absorption similar to what is observed when the temperature of water is increased. Since this spectral change is associated with the weakening of the hydrogen-bond network, we infer that excess energy from the dissociation of nitrite is dissipated to the local hydrogen-bonded water network in less than 0.5 ps. The rapid change in the infrared absorption is followed by a slower (50 ps) component associated with the energy dissipation to the solvent as the photo-fragments diffusively recombine and relax.

Steady-state and nanosecond laser flash photolysis measurements of 4-methoxybenzyl alcohol (1a), 4-methoxy-alpha-methylbenzyl alcohol (1b), 4,4'-dimethoxydiphenylmethanol (1c) and 4-methoxy-alpha,alpha'-dimethylbenzyl alcohol (1d) were carried out in air-equilibrated CH(2)Cl(2) and CH(3)CN solutions, in the presence of 9,10-dicyanoanthracene (DCA) and N-methylquinolinium tetrafluoroborate (NMQ(+)BF(4)(-)) as sensitizers. In particular, steady-state irradiation with DCA produced carbonyl compounds and, with NMQ(+)BF(4)(-), carbonyl compounds, ethers (substrates 1a-c ) and styrene (substrate 1d ) while time-resolved investigations gave evidence of charged species produced upon irradiation. The effect of solvent polarity on the reactivity was investigated; in the case of DCA, the reactivity increased with the solvent polarity, while the opposite was obtained when NMQ(+)BF(4)(-) was used. Quantum mechanical calculations at semiempirical (INDO/1-CI) and DFT (B3LYP/6-311G(d)) levels were used to support transient assignments and to obtain the charge and spin density distributions, respectively. The different photooxidation mechanisms operative with the neutral and charged sensitizer were rationalized in terms of the reactivity of free and complexed radical cations, respectively.

Time-resolved conversion of a series of beta-hydroxy arylethyl radicals with electron-donating and -withdrawing aromatic substituents to their corresponding styrene radical cation via heterolytic loss of the beta-hydroxy leaving group was examined with nanosecond laser flash photolysis. In all cases, the reaction was catalyzed by added perchloric acid. Radicals 2a-d reacted via a pre-equilibrium protonation mechanism in acidic 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), and measuring rate constants for radical cation formation as a function of acid content allowed for the determination of absolute rate constants ranging from 3.6 x 10(6) to 3.8 x 10(7) s(-1) for the loss of water from the protonated beta-hydroxy arylethyl radicals 2a-d, as well as the acidity constants, pKa approximately 1.5 (in HFIP), for the protonated radicals. The 4-methoxy-substituted beta-hydroxy arylethyl radical 2e reacted by rate determining protonation in HFIP with a second-order rate constant of k(H+) = 7.8 x 10(8) M(-1) s(-1). However, in acetonitrile, 2,2,2-trifluoroethanol, and mixtures of these two solvents, 2e reacted by pre-equilibrium protonation, allowing for solvent effects on the rate constant for loss of water from the protonated radical 2e to be determined. With use of these data, substituent electronic effects on the kinetics of the beta-heterolysis reaction are discussed. Differences in the effect of solvent on the rate constant for loss of water from the protonated beta-hydroxy arylethyl radicals and other beta-substituted arylethyl radicals are also discussed.

Coordination and solvation structures of the Cu(+)(NH(3))(n) ions with n = 3-8 are studied by infrared photodissociation spectroscopy in the NH-stretch region with the aid of density functional theory calculations. Hydrogen bonding between NH(3) molecules is absent for n = 3, indicating that all NH(3) molecules are bonded directly to Cu(+) in a tri-coordinated form. The first sign of hydrogen bonding is detected at n = 4 through frequency reduction and intensity enhancement of the infrared transitions, implying that at least one NH(3) molecule is placed in the second solvation shell. The spectra of n = 4 and 5 suggest the coexistence of multiple isomers, which have different coordination numbers (2, 3, and 4) or different types of hydrogen-bonding configurations. With increasing n, however, the di-coordinated isomer is of growing importance until becoming predominant at n = 8. These results signify a strong tendency of Cu(+) to adopt the twofold linear coordination, as in the case of Cu(+)(H(2)O)(n).

Background: Millions of people have at least one tattoo. Complex and light absorbing molecules are implanted in the skin. When tattooed skin receives UV radiation or natural sunlight, photochemical cleavage of the pigments may occur. As a first step, we dissolved pigments in a suitable solvent and analyzed them after light irradiation., Methods: The widespread Pigment Red 22 was dissolved in different solvents. The solutions were irradiated with either UVB radiation (up to 8 h) or with natural sunlight (110 days). After irradiation, the solutions were analyzed by means of liquid chromatography and mass spectrometry., Results: A clear cleavage of the pigment was detected in all solvents and the primary decomposition products were identified. In tetrahydrofuran and dioxane, the pigment concentration decreased significantly during UVB irradiation, whereas the pigment was completely destroyed during sunlight exposure. In chloroform and dichloromethane, the pigment concentration decreased slightly during UVB irradiation, whereas the pigment was almost completely destroyed during sunlight exposure., Conclusion: Since chloroform and dichloromethane do not affect the cleavage process, these solvents are optimal for such in vitro experiments. We have shown the cleavage of the tattoo pigment Red 22 when exposed to UVB radiation or natural sunlight. The decomposition products are hazardous showing a potential risk of being toxic or even carcinogenic. At present, a risk assessment is not feasible since the concentration of pigments and their decomposition products in skin are unknown.

Effects of high-intensity ultrasonication on functional and structural properties of aqueous bovine serum albumin (BSA) solutions were investigated. The functional properties of BSA were altered by ultrasonication. Surface activity of BSA increased. Minimal changes were observed in the global structure of BSA but surface charge increased particularly at basic pH values (e.g. pH>9). While dynamic light scattering measurements indicated that the particle size increased up to 3.4 times after 90 min of sonication, no significant increase in the oligomeric state of BSA using blue native PAGE was observed. The amount of free sulfhydryl groups in BSA after 90 min of sonication decreased. The increased particle size and decreased number of free sylfhydryl groups may be attributed to formation of protein aggregates. Surface hydrophobicity increased and circular dichroism spectroscopy and FTIR analysis indicated changes in the secondary structure of BSA. We hypothesize that mechanical, thermal and chemical effects of ultrasonication resulted in structural changes in BSA that altered the functional properties of the macromolecule which may be attributed to the formation of an ultrasonically induced state that differs from a thermally, mechanically or solvent induced state.

In the industrial cleaning processes either organic solvents or water solutions are used as the cleaning media. The primary causative factor of ultrasonic cleaning is cavitation. Below are presented results of investigations into the influence of temperature, gas content and the solution level in an ultrasonic cleaner on cavitation intensity in the tap water. Previous investigations have revealed a great deal of information on the influence of the above factors on the cavitation intensity and these are confirmed. It has now been found that the tap water reaches the highest cavitation intensity at temperatures below 20 degrees C but during heating at higher temperatures (20-40 degrees C) a second peak of cavitation intensity may appear-depending on the height of water in the bath and air content.

Chlorinated hydrocarbons are widely used in chemical industries as solvents and intermediates for pesticides and dyes manufacture. Their presence was documented in rivers, groundwaters and seawaters. In this work, the oxidation of 1,2-dichlorobenzene in aqueous solutions by means of Fe(III) homogeneous photocatalysis under UV lamp and sunlight irradiations is studied. The results show that the best working conditions are found for pH=3.0 and initial [Fe(III)] concentration equal to 1.0x10(-4) molL(-1) although the investigated system can be utilized even at pH close to 4.0 but with slower abatement kinetics. Some dicholoroderivatives, such as 2,3-dichlorophenol, 3,4-dichlorophenol and 2-chlorophenol, are identified as oxidation intermediates. The values of the kinetic constant for the photochemical reoxidation of Fe(II) to Fe(III) are evaluated by a mathematical model in the range 1.58-3.78 Lmol(-1)s(-1) and 0.69-0.78 Lmol(-1)s(-1) for the systems irradiated by UV lamp and sunlight, respectively.

Solid-phase synthesis of diketopiperazines (DKPs) was preformed using various combinations of resins (polystyrene, TentaGel, ArgoGel, and PEGA) and solvents (toluene, tert-butyl alcohol, water, and toluene/2-butanol (1:4, v/v). The DKPs were synthesized from solid-phase bound dipeptides via intramolecular aminolysis. Both thermal and microwave-assisted solid-phase synthesis of DKPs gave high yields of products independently of resin and organic solvent used; however, only the PEGA resin resulted in high yields of DKPs in water independent of heating method. The short reaction times, high yields, and the possibility to run reactions in water when an appropriate resin is used makes the microwave-assisted solid-phase synthesis the method of choice. The method should be suitable for solid-phase synthesis of diketopiperazine-based libraries.

Agglomerated nanorods of hydroxyapatite have been synthesized using monetite as a precursor in a NaOH solution. Monetite consisting of nanosheets has been successfully synthesized by a one-step microwave-assisted method using CaCl(2).2.5H(2)O, NaH(2)PO(4), and sodium dodecyl sulfate (SDS) in water/ethylene glycol (EG) mixed solvents. The effects of the molar ratio of water to EG and the reaction time on the products were investigated. The products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infrared spectrometry (FTIR).

A pilot-scale plug-flow reactor was built to investigate its performance in treating airborne propylene glycol monomethyl ether acetate (PGMEA) via ozonation, ultraviolet (UV) photolysis and UV/O3 technologies. Governing factors, such as the initial molar ratio of ozone (O3) to PG-MEA, UV volumetric electric power input, and moisture content in the influent airstream, were investigated. A 1-L batch reactor was used to investigate some photodegradation characteristics of PGMEA in advance. Experiments were conducted at a fixed influent PGMEA concentration of approximately 50 ppm and an ambient temperature of 26 degrees C. A gas space time of 85 sec in the plug-flow reactor was kept for either ozonation or photolysis reaction, whereas a gas space time of 170 sec was used for the UV/O3 degradation. Results show that an initial molar ratio of O3 to PGMEA of >2.91 and an UV volumetric electric input power of 0.294 W/L(-1) sufficed to obtain PGMEA decompositions of >90% by UV/O3. Kinetic analyses indicate that all types of PGMEA decomposition are pseudo-first order with respect to its concentration. Moisture content (relative humidity = 15-99%) and UV volumetric electric input power (0.147 and 0.294 W/L(-1)) were major factors that strongly affect the PGMEA degradation rate.

It was shown that preliminary exposure of a solvent (water) to low-intensity laser radiation reduces the tryptophan fluorescence intensity, and this fluorescence quenching effect is retained throughout the temperature range explored (from 8 up to 50 degrees C). The effects found are interpreted as resulting from changes in solvent properties induced by the action of electromagnetic radiation on interaction of water molecules with solute.

The enantioselective hydrogenation of 1-phenyl-1,2-propanedione was carried out over Pt/Al2O3, Pt/SiO2, Pt/SF (silica fiber), Pt/C catalysts modified with cinchonidine under ultrasonic irradiation. The initial rate, regioselectivity and enantioselectivity were investigated for different catalyst pretreatments, solvents and ultrasonic powers. The ultrasound effects were very catalyst dependent. The sonication significantly enhanced enantioselectivity and activity of the Pt/SF (silica fiber) catalyst. For the other Pt supported catalysts the reaction rate, enantioselectivity and regioselectivity increased moderately. The choice of solvent influenced the impact of ultrasound effect, namely in mesitylene, which has the lowest vapor pressure, the highest ultrasound enhancement was observed. The effect of sonication on catalysts surface was studied by transmission electron microscopy and scanning electron microscopy (SEM). No significant change in the metal particle size distribution due to sonication was observed. However, in the case of the Pt/SF catalyst, acoustic irradiation induced morphological changes on the catalyst particle surface (SEM), which might be the cause for enhancement of the initial reaction rate and enantioselectivity.

The rates and products of the sonochemical reactions of benzene, 1,4-cyclohexadiene, 1,3-cyclohexadiene, cyclohexene, and cyclohexane in selected organic solvents have been investigated. The sonochemical reactions of these educts in the investigated organic solvents follow first-order kinetics. Generally, they are sonicated more rapidly in polar than in non-polar solvent; higher volatility of the solute results in faster sonolysis in the organic solvents. However, the sonication of cyclohexane in n-decane and the sonication of benzene in n-propanol are exceptional cases. Since cyclohexane exhibits a much higher lipophilicity and benzene a much higher hydrophilicity than other educts, it might be more difficult to transfer either educt from the bulk liquid into the cavitation bubbles. In tetrachloroethylene, the reactivity of the tested educts with in situ generated chlorine as well as chlorine-containing radical intermediates can accelerate the rate of sonochemical reactions under the employed conditions. In n-propanol and n-decane, the pyrolysis during the collapse of the cavitation bubbles is the only reaction pathway of sonolysis. In tetrachloroethylene, the pyrolysis during the collapse of the cavitation bubbles and the free radical reaction in the bulk liquid may occur simultaneously. Except for the products generated from sonolysis, products formed from chlorine transformations (substitution or addition reactions) are detected. Benzene is hardly decomposed in tetrachloroethylene. However, when FeCl3 is added into the reaction system, benzene is sonoconverted rapidly, and the product chlorobenzene was detected. In organic solvents, the sonoreaction rates and the sonoproducts are dependent on the physicochemical properties of the solvents used, as well as the volatility, the polarity and the reactivity of educts.

In an optical tweezers experiment intense laser light is tightly focused to intensities of MW/cm(2) in order to apply forces to submicron particles or to measure mechanical properties of macromolecules. It is important to quantify potentially harmful or misleading heating effects due to the high light intensities in biophysical experiments. We present a model that incorporates the geometry of the experiment in a physically correct manner, including heat generation by light absorption in the neighborhood of the focus, balanced by outward heat flow, and heat sinking by the glass surfaces of the sample chamber. This is in contrast to the earlier simple models assuming heat generation in the trapped particle only. We find that in the most common experimental circumstances, using micron-sized polystyrene or silica beads, absorption of the laser light in the solvent around the trapped particle, not in the particle itself, is the most important contribution to heating. To validate our model we measured the spectrum of the Brownian motion of trapped beads in water and in glycerol as a function of the trapping laser intensity. Heating both increases the thermal motion of the bead and decreases the viscosity of the medium. We measured that the temperature in the focus increased by 34.2 +/- 0.1 K/W with 1064-nm laser light for 2200-nm-diameter polystyrene beads in glycerol, 43.8 +/- 2.2 K/W for 840-nm polystyrene beads in glycerol, 41.1 +/- 0.7 K/W for 502-nm polystyrene beads in glycerol, and 7.7 +/- 1.2 K/W for 500-nm silica beads and 8.1 +/- 2.1 K/W for 444-nm silica beads in water. Furthermore, we observed that in glycerol the heating effect increased when the bead was trapped further away from the cover glass/glycerol interface as predicted by the model. We show that even though the heating effect in water is rather small it can have non-negligible effects on trap calibration in typical biophysical experimental circumstances and should be taken into consideration when laser powers of more than 100 mW are used.

The products of the radiolysis of deaerated aqueous solutions of ethylene at atmospheric pressure are butane, hexane, octane, decane, acetaldehyde, butyraldehyde, ethanol, butanol, and hydrogen perioxide. Product yields, especially those of the aldehydes and hydrogen peroxide, increase with increasing ethylene concentration and decrease with increasing pH and radiation dose. Addition of efficient electron scavengers increases the yields of oxidized products and decreases the yields of reduced products. The results are compatible with a mechanism in which OH radicals add to rather than abstract from ethylene. Computer-aided analysis of the kinetics of competing reactions indicates that the low yields of aldehydes are related to the ability of these compounds to act as internal scavengers of solvated electrons.

The reactions of thymine in aqueous solution with radiation-induced radicals OH, H, and e-aq were studied under various conditions. Competition studies using scavengers of OH radicals (methanol, ethanol, iodide) or of e-aq and/or H atoms (N2O, H+, O2) led to the conclusion that OH and H radicals destroy the chromophoric group of thymine, but e-aq does not. A trace of O2 proved to be necessary to obtain maximal destruction. Removal of the last traces of O2 resulted in a decrease of the destruction yield, possibly through restitution reactions. It was found that (1) alcohol radicals destroy thymine, even in the presence of O2; (2) the rate constant, k(OH + thymine) = 4.3 X 10(9) M(-1) sec(-1) (from competition with iodide); and (3) k(H + thymine) = 8 X 10(8) M(-1) sec(-1) (from competition with O2 in acid solution).