Facile preparation of graphene nitride by irradiating MHz ultrasound.

The present study aimed at developing a simple sonochemical method to prepare graphene nitride from the mixture of graphite and aqueous ammonia solution. Ultrasound of 1.6 MHz was irradiated to the sample in a fabricated sonoreactor at predetermined ultrasonic power and duration. The one-pot method succeeded in the preparation of graphene nitride. The generation was proven by XPS analysis in finding N1S peak in the spectrum. Detail analysis of N1s peak suggested that the major nitrogen species was pyrrolic type. Furthermore, the presence of CO bond proved the oxidation by OH radical. The reaction product had the value of N/C as high as 0.08, which is comparable to reported values for ultrasonic preparation of graphene nitride. The fact indicates that the significance of chemical effects of MHz range ultrasound, and the finding of the simple preparation method will accelerate practical application of graphene nitride.

Evaluation of Mass-transfer Performance of Emulsion-flow Column with Height of Transfer Unit (HTU) and Number of Theoretical Plates, and Comparison of HTU with Column-type Extractors.

The performance of iodine extraction in the emulsion-flow column was evaluated using an indicator of difficulty in separation, height of transfer unit, HTU and of the number of theoretical plates, Nth. Resulting HTU values ranged from 0.15 to 0.78 m and Nth changed from 0.58 to 1.3. HTU values were formulated in accordance with operating liquid velocities. Despite a 30% margin of error, HTU values were found to be useful in predicting column performance. Observed HTU values were compared with those of conventional extraction columns with or without mechanical agitation. The emulsion-flow column meets the top-level performance of extractors without mechanical agitation, such as packed and spray columns, and performs in the middle range of agitated extractors, although these sacrifice the structure simplicity to assure stable counter-current operation. The advantage of the emulsion-flow column is better HTU values with stable counter-current operation in a simple column structure.

Improved ultrasonic degradation of hydrophilic and hydrophobic aldehydes in water by combined use of atomization and UV irradiation onto the mist surface.

Ultrasonic irradiation of 430 kHz, which induces both the chemical effect of pyrolysis and the physical effect of atomization, was carried out to achieve highly effective decomposition of organic substances in water with UV254 irradiation and H2O2 addition. To investigate the influence of physicochemical properties of the substrate on the degradation rate, three different aldehydes, namely, formaldehyde, acetaldehyde, and benzaldehyde, were selected as model substrates. Upon ultrasonic irradiation alone, the removal ratio of the hydrophobic substrate benzaldehyde reached 100% after 120 min, whereas the removal ratios of the hydrophilic substrates formaldehyde and acetaldehyde were only 21.1% and 53.0%, respectively. By combining ultrasonic atomization and UV254 irradiation, formaldehyde and acetaldehyde underwent effective gas-phase decomposition on the surfaces of the mist particles. Photolysis by UV254 irradiation mainly affected for the decomposition of aldehydes on the mist surface rather than the reaction of hydroxyl radicals derived from H2O2 made by water sonolysis. However, the addition of H2O2 effectively improved the decomposition and mineralization rates for both hydrophilic and hydrophobic aldehydes owing to the generation of hydroxyl radicals on the surfaces of the mist particles, which greatly contributed to the gas-phase decomposition. Consequently, the effective decomposition of organic pollutants was achieved regardless of their physicochemical properties in aqueous media.

Effect of ultrasonic frequency on size distributions of nanosized mist generated by ultrasonic atomization.

Ultrasonic atomization is used to produce fine liquid mists with diameter ranges below 100nm. We investigated the effect of the frequency on the size distribution of ultrasonic mist. A bimodal distribution was obtained for the mist generated by ultrasonic atomization with a wide-range particle spectrometer. The peak diameter decreased with increasing frequency, and the number concentration of the mist increased in the smaller range. We determined the relation between the size distribution of the mist and the ultrasonic frequency, and we proposed a generation mechanism for the ultrasonic nanosized mist based on the amount of water vapor around the liquid column. Increasing the power intensity and density by changing the surface diameter of the ultrasonic oscillator affected the number concentration and size distribution of the nanosized mist. Using this technique, the diameter of the mist can be controlled by changing the frequency of the ultrasonic transducer.

Size-selective separation of submicron particles in suspensions with ultrasonic atomization.

Aqueous suspensions containing silica or polystyrene latex were ultrasonically atomized for separating particles of a specific size. With the help of a fog involving fine liquid droplets with a narrow size distribution, submicron particles in a limited size-range were successfully separated from suspensions. Performance of the separation was characterized by analyzing the size and the concentration of collected particles with a high resolution method. Irradiation of 2.4MHz ultrasound to sample suspensions allowed the separation of particles of specific size from 90 to 320nm without regarding the type of material. Addition of a small amount of nonionic surfactant, PONPE20 to SiO2 suspensions enhanced the collection of finer particles, and achieved a remarkable increase in the number of collected particles. Degassing of the sample suspension resulted in eliminating the separation performance. Dissolved air in suspensions plays an important role in this separation.

Growth and size control in anti-solvent crystallization of glycine with high frequency ultrasound.

Antisolvent crystallization of glycine was performed under ultrasonic irradiation of 1.6 MHz. The irradiation enhanced both the growth of α-glycine crystal and the uniformity in the crystal size. The degree of both enhancement effects increased with increasing ultrasonic power. While under the irradiation of 20 kHz ultrasound, no growth enhancement was observed, but the crystal size reduced as was reported in the literature. To elucidate the mechanism of growth enhancement, another experiment was designed and conducted to avoid the effect of nucleation from the sonocrystallization. The result suggests that the ultrasound enhances the incorporation of microcrystals to larger crystals. Probably, the collision between solid particles is intensified by the disturbance characterized by the high frequency ultrasound. The crystal growth was modeled with an apparent reaction of microcrystal and larger crystal. The result of the growth experiment was successfully predicted with a rate equation for pseudo first order reaction with a single parameter of rate constant. The rate constant linearly increased with the ultrasonic power. The analysis enables quantitative evaluation of the ultrasonic effect on the crystal growth.

Evaluation of interactions between metal ions and nonionic surfactants in high-concentration HCl using low-pressure high-performance liquid chromatography with low-flow-resistance polystyrene-based monolithic column.

A method for evaluating the interactions between metal ions and nonionic surfactants in aqueous solutions containing high-concentration HCl, using gas pressure-driven low-pressure high-performance liquid chromatography (LP-HPLC) as a highly acid-resistant HPLC system, was developed. To construct the LP-HPLC for this purpose, poly(styrene-co-divinylbenzene)-based low-flow-resistance monolithic columns tolerant to highly acidic conditions were prepared using low-conversion thermal polymerization. Thermal polymerization at 65 °C for 1.5 h (monomer conversions, 33% for styrene and 59% for divinylbenzene) allowed preparation of a column with both high separation efficiency (around 60,000 plates m(-1) for alkylbenzenes) and a quite low back pressure of 0.14 MPa at a linear flow rate of 1 mm s(-1) (2.8 × 10(-13) m(2) in permeability). The base column prepared under the above conditions was coated with a nonionic surfactant, polyoxyethylene nonylphenyl ether (PONPE, average oxyethylene unit numbers (n) = 3, 7.5, 15, and 20), and used for evaluation of the interactions between PONPEs and metal ions in 6 M HCl. The interactions between PONPEs and Au(III), Ga(III), Fe(III), Zn(II), and Cu(II) were successfully evaluated using both breakthrough and chromatographic methods. Furthermore, a study of the effect of the polyoxyethylene (POE) chain length revealed that the use of PONPE with the longer POE moiety enhanced the magnitude of the interaction together with the increase in the amount of oxyethylene (OE) units coated on the monolith. Moreover, the interactions of metal ions with a single OE unit were almost constant in the range of n = 7.5-20, whereas the suppression of the interaction between Au(III) with the shortest PONPE chain (n = 3) was also observed.

Quantitative approach to ultrasonic emulsion separation.

Ultrasound of 2 MHz was irradiated to the emulsion prepared from canola oil and water and flocculation of the oil droplets occurred immediately. By putting the emulsion sample in a thin glass cell and setting it in bath type irradiation equipment, the progress of the separation was quantitatively monitored with the optical absorbance. The use of the cell enables visual observation of the behavior of oil droplets. Pictures show the formation of flocks of the dispersed phase and the appearance of checkered pattern consisting of flocks at a regular interval. The observation indicates that the action of radiation forces on oil droplets, which causes the flocculation. The flocks started to rise after stopping irradiation with holding their shape. The rising rate of the flocks was significantly greater than that of oil droplets in the original emulsion. Ultrasonic irradiation caused a rapid decrease in the absorbance, which expresses a progress of the separation. Effects of two major operation parameters, power and time on the separation degree were examined. The degree improved with increasing power input and irradiation time. The dataset was arranged in a plot of normalized separation degree against the input energy. The plot suggests that effective separation was attained with a lower power input and a longer irradiation time. The plot provides a guide for setting condition for the separation.

Enrichment of surfactant from its aqueous solution using ultrasonic atomization.

Dilute aqueous solutions of dodecyl-benzenesulfonic acid sodium salt (DBS-Na) and polyoxyethylenenonylphenyl ethers (PONPEs) were ultrasonically atomized. The surfactants were concentrated in collected mist droplets. The enrichment ratio increased with decreasing surfactant concentration. Depending on the surfactant's molecular weight and affinity to water, different enrichment ratio was observed in the range of low feed concentrations. For anionic surfactant, DBS-Na, the enrichment ratio was significantly improved by KCl addition and a peak appeared on the plot of the ratio against KCl concentration. Addition of NaCl or CaCl2 . 2H2O to the surfactant solution also enhanced the enrichment ratio; however, the effect was relatively small. Such behaviors of the ratio were interpreted as enhanced interfacial adsorption of the surfactant and a lack of supply of surfactant monomers from liquid bulk because of slow breaking of surfactant micelles. Time required for collecting an amount of mist was also observed. Among the three salt systems, the time for KCl system was twice as long as others. This fact suggested that the formation of smaller droplets in KCl system.

Preparation and supramolecular properties of unadulterated glycosyl liposomes from a bis(alpha-D-mannopyranosyl)-[60]fullerene conjugate.

The bis(alpha-D-mannopyranosyl)-[60]fullerene conjugate 3 was prepared by thermal coupling of C60 and either 2-azidoethyl 2,3,4,6-tetra-O-acetyl- or 2,3;4,6-di-O-isopropylidene-alpha-D-mannopyranoside (Scheme). Compound 3 was found to readily self-assemble. Dynamic-light-scattering (DLS) and atomic-force microscopy (AFM) experiments supported that the amphiphilic compound gives rise to nano-sized supramolecular structures during sugar deprotection (Ac-group removal) performed in MeOH/CH2Cl2 solution. Encapsulation studies with an aqueous suspension of 3 showed that the self-assembling structure envelopes Ba2+ and the fluorescent dye Acridine Red during its formation, which indicates that it resembles a bilayer vesicle or an unadulterated liposome with an inner hollow space. In addition to this notable property, the unique molecular geometry of the spatially arranged mannosyl surface residues of 3 gives rise to strong binding of the carbohydrate-recognizing lectin Con A. Hence, the polar amphiphilic end of 3 mimics the structure of 3,6-branched tri-alpha-D-mannoside (6; Fig. 3), a natural ligand of the Con A protein.