Conversion and Hydrothermal Decomposition of Major Components of Mint Essential Oil by Small-Scale Subcritical Water Treatment.

Thermal stabilities of four major components (l-menthol, l-menthone, piperitone, and l-menthyl acetate) of Japanese mint essential oil were evaluated via subcritical water treatment. To improve experimental throughput for measuring compound stabilities, a small-scale subcritical water treatment method using ampoule bottles was developed and employed. A mixture of the four major components was treated in subcritical water at 180-240 °C for 5-60 min, and then analyzed by gas chromatography. The results indicated that the order of thermal resistance, from strongest to weakest, was: l-menthyl acetate, l-menthol, piperitone, and l-menthone. In individual treatments of mint flavor components, subsequent conversions of l-menthyl acetate to l-menthol, l-menthol to l-menthone, l-menthone to piperitone, and piperitone to thymol were observed in individual treatments at 240 °C for 60 min. As the mass balance between piperitone and thymol was low, the hydrothermal decomposition of the components was considered to have occurred intensely during, or after the conversion. These results explained the degradation of mint essential oil components under subcritical water conditions and provided the basis for optimizing the extraction conditions of mint essential oils using subcritical water.

Evaluation of solvent property of air-water interface based on the fluorescence spectra of 1,2'-dinaphthylamine in the aqueous solution of ultrafine bubbles.

Solvent property of air-water interface was evaluated based on the fluorescence spectra of 1,2'-dinaphthylamine in water containing ultrafine bubbles (average diameter: 103 nm, standard deviation: 38 nm). Among naphthylamine derivatives whose fluorescence spectra were responsive to microscopic hydrophobicity, 1,2'-dinaphthylamine (DN) was selected because its wavelength of the maximum emission (λmax) was significantly dependent on the concentration and microenvironment of the ultrafine bubble. The λmax value of DN in water was 486 nm, while it shifted to shorter wavelength (408 nm) in the presence of 1.09 × 109 mL-1 of ultrafine bubbles. The shift of λmax value indicates that DN adsorbs on the surfaces of ultrafine bubbles and exists in hydrophobic region rather than in bulk water. By comparing with the λmax values in different solvents, the surface of ultrafine bubble was found to have similar solvent property to ethyl ether or ethyl acetate that are widely used as extracting solvents for hydrophobic organic compounds.

Removal and detoxification of iprodione in water using didodecyldimethylammonium bromide-montmorillonite organoclay and manganese dioxide.

Combination of organoclay sorption with manganese(IV) oxide (MnO2) catalyzed catechol oxidation was studied for the removal of a dicarboximide fungicide, iprodione, from water. Iprodion in water was sorbed on didodecyldimethylammonium bromide (DDAB)-modified montmorillonite (MT) organoclay and converted into the degraded product, 3,5-dichloroaniline (DCA). The degree of sorption increased by the modification with DDAB, because of the formation of a hydrophobic region for the incorporation of iprodione and negligibly interfered by coexisting MnO2. The half-life for the degradation of irodione in water at 25 °C was 7 days, whreas it reduced to 15 min in the organoclay. The activation energy, 65.4 ± 4.8 kJ mol-1, for the first-order reaction in the aqueous solution (pH 7.0) decreased to 43.9 ± 1.8 kJ mol-1 in the organoclay, indicating the catalytic activity of the organoclay that accelerates the hydrolysis reaction of iprodione. In the coexistence of appropriate amounts of MnO2 and catechol, the degraded product, DCA, reacted with oxidized products of catechol to form a water-insoluble precipitate and was successfully eliminated from water. The results obtained in the present study strongly suggest the applicability of the combined method of organoclay sorption method and MnO2-catalyzed oxidation for the diffusion control of toxic agrochemicals.

Surfactant-free air bubble flotation-coagulation for the rapid purification of chloroquine.

A simple and rapid separation method based on surfactant-free air bubble flotation and coagulation was designed for the purification of chloroquine (CQ) from its crude product. An open glass column having a sintered glass filter (for column chromatography) was used as a flotation vessel. The flotation was conducted by pouring the crude CQ into the aqueous solution containing 0.1% (v/v) of 2-propanol followed by feeding air through the glass filter to generate air bubbles. At pH 12, CQ was enriched into the foam temporary generating on the surface of water to form the coagulates within 90 s after the start of the air bubble flotation. On the other hand, reactants; 4,7-dichloroquinoline and 4-amino-1-diethylaminopentane, as well as generated impurities remained in the bulk aqueous solution. The result of dynamic surface tension measurement indicated that CQ molecules selectively adsorbed on the air-water interface and the coagulates more strongly adsorbed the interface. Adsorption and coagulation of CQ molecules on the air-water interface were also reproduced in the calculation results of a molecular dynamic simulation. The coagulates were collected from the surface of water by suction and then poured into another flotation vessel for conducting repeated separation. The time required for the respective separation process including air bubble flotation and collection by suction was within 5 min. After three-times separation, highly purified (> 99.0%) CQ was obtained with a yield of 72 ± 8%. The amounts of reactants and other impurities reduced into undetectable levels.

Effect of air bubbles on the membrane filtration of rhodamine B.

Effect of air bubbles on the membrane filtration of a basic dye, rhodamine B (RB), using a hydrophilic PTFE membrane filter (pore size: 0.20 µm) was studied. The air bubbles were generated by vigorously mixing the aqueous solution containing 0.05% (v/v) of 1-butanol with a shaft generator of a homogenizer. RB being far smaller than the pore size of the membrane filter could not be rejected without air bubbles, but it was rejected by the membrane filter in the presence of air bubbles. The rejection ratio increased with increasing the rotation speed of the shaft generator because of the increase in the amount of air bubbles and therefore the increase in the surface area of air bubbles for the adsorption of RB. On the other hand, another basic dye, methylene blue (MB), was negligibly rejected in the same condition. Dynamic surface tension measurement of aqueous solutions containing different amounts of dye indicated that RB strongly adsorbed to the air-water interface, while MB hardly adsorbed. The results obtained in the present study strongly suggest the potential usefulness of air bubbles for the selective microfiltration of dissolved organic molecules or ions.

Concentration of chlorophenols in water to dialkyated catinonic surfactant-silica gel admicelles.

Chlorophenols including monochlorophenol, dichlorophenol, trichlorophenol, tetrachlorophenol, and pentachlorophenol in water were extracted into dialkylated cationic surfactant-silica gel admicelles. The dialkylated cationic surfactants such as didecyldimethylammonium bromide (DC10) and didodedyldimethylammonium bromide (DC12) sorbed on silica gel surfaces to form admicelles at pH 9. Approximately 200mg of DC10 was quantitatively sorbed on 1g of silica gel. The sorption further increased by further addition of DC10. This is in contrast to the fact that the maximum sorption of mono-alkylated cetyltrimethyammonium chloride (CTAC) was only ca. 100mg. Based on the fluorescent spectra of a molecular probe, N-phenyl-1-naphthylamine, DC10- and DC12-silica gel admicelles were more hydrophobic than CTAC-silica gel admicelles. The extents of the extraction of chlorophenols into DC10-silica gel admicelles were greater than those into CTAC-silica gel admicelles. However, the extractions to DC12-silica gel admicelles were insufficient due to leakage of DC12 vesicles. Consequently, DC10-silica gel admicelles were the most adequate for concentrating chlorophenols in water. An admicelle column was prepared by passing aqueous buffer solution of DC10 through a Bond Elut Jr. silica gel solid-phase extraction cartridge. It was successfully applied to the 500-fold concentration of chlorophenols including hydrophilic mono-substituted chlorophenol in water samples prior to their HPLC analysis.

Polymer-mediated extraction of the fluorescent compounds derived by Hantzsch reaction with dimedone for the sensitive determination of aliphatic aldehydes in air.

An extraction method based on the thermo-responsive precipitation of a water-soluble polymer, poly(N-isopropylacrylamide) [PNIPAAm], was applied to the concentration of dimedone (5,5-dimethylcycrohexane-1,3-dion) derivatives for the highly sensitive determination of aldehydes in air. Aliphatic aldehydes including formaldehyde, acetaldehyde, propanal, 1-butanal, 1-heptanal, and 1-hexanal in air were well solubilized into the aqueous solution of dimedone and ammonium acetate by mixing the solution and air sample in a polyvinyl fluoride bag. Fluorescent derivatives of aldehydes that had formed by the Hantzsch reaction with dimedone were concentrated by polymer-mediated extraction. The recoveries of the fluorescent compounds increased with increasing the carbon number of aldehyde and were more than 80% for the derivatives from aldehydes having more than three carbon atoms under the optimal conditions. Microgram per m3 (sub-ppb) levels of the aliphatic aldehydes, propanal, 1-butanal, 1-heptanal, and 1-hexanal, in ambient air were successfully determined by HPLC separation with fluorometric detection. The sampling volume and time required were only 1l and 20 s, respectively.

Removal and degradation of ß-lactam antibiotics in water using didodecyldimethylammonium bromide-modified montmorillonite organoclay.

ß-Lactam antibiotics including penicillin G, nafcillin, cefazolin, cefotaxime, and oxacilline in water were rapidly removed and degraded by using didodecyldimethylammonium bromide (DDAB)-montmorillonite (MT) organoclay. Removal of antibiotics increased with increasing the amount of organoclay added and the amount of DDAB sorbed on MT. Extents of organoclay sorption of antibiotics were represented by the binding constants to DDAB molecules and correlated to the aqueous-octanol distribution coefficients. The degradation rate of ß-lactam antibiotics was found to significantly increase by the organoclay sorption. Even under the mild conditions (25°C and pH 7), penicillin G (m/z=335) nearly completely (>98%) degraded into penicilloic acid (m/z=353) missing ß-lactam ring within 2h. The first-order reaction rate of the primary degradation increased with increasing in temperature. The activation energy estimated from the Arrhenius plot was 49kJmol(-1) and lower than the value (83.5kJmol(-1)) in water, strongly suggesting catalytic activity of DDAB-MT organoclay. The applicability to wastewater treatment was demonstrated by using secondary effluents of municipal sewage treatment plants and synthesized hospital wastewaters.

Concentration of polyaromatic hydrocarbons in water to sodium dodecyl sulfate-gamma-alumina admicelle.

Polyaromatic hydrocarbons (PAHs) in water were concentrated into sodium dodecyl sulfate (SDS)-gamma-alumina and di-2-ethylhexyl sodium sulfosuccinate (Aerosol-OT, AOT)-gamma-alumina admicelles. The comparison of the binding constants (Kad[={adsorbed concentration of the solute (mol/g surfactant)}/{the concentration in the bulk aqueous phase (mol/ml)}] indicated almost the same extraction abilities of the both admicelles. However, better and more reproducible recovery was obtained in the concentration of PAHs into the SDS-gamma-alumina admicelle. PAHs in tobacco smoke that were trapped in water were successfully concentrated into SDS-gamma-alumina admicelle for the HPLC analysis.

Solid phase extraction of some precious metals from hydrochloric acid to polystyrene-divinylbenzene porous resin impregnated with polyoxyethylene-type nonionic surfactant.

The solid phase extraction of gold(III), platinum(II), and palladium(II) to surfactant-impregnated polystyrene-divinylbenzene porous resin (XAD-4) was studied. The extracting media could be prepared just by mixing the resin in aqueous surfactant solutions. XAD-4 impregnated with a nonionic surfactant, polyethylene glycol monooleyl ether, was useful for extracting gold(III) from hydrochloric acid. The extractions of platinum(II) and palladium(II) were improved in the use of XAD-4 impregnated with a nitrogen-containing nonionic surfactant, polyethylene glycol stearyl amine. On the other hand, base metals such as copper(II), cobalt(II), nickel(II) and zinc(II), were hardly extracted.

Concentration of chlorophenols in water with sodium dodecylsulfate-gamma-alumina admicelles for high-performance liquid chromatographic analysis.

Chlorophenols in water were sorbed onto sodium dodecylsulfate (SDS)-alumina (gamma-form) admicelles. The extent of sorption increased with increasing amount of SDS and decreasing solution pH. Conditions for good recovery were obtained when 100 mg SDS and 1.5 g alumina was used at pH 2. However, the yield decreased with a further increase in the SDS concentration due to the formation of normal SDS micelles. The extent of sorption also increased with increasing hydrophobicity of the chlorophenol, indicating that hydrophobic interactions predominate for the collection of analytes. When a cartridge column filled with admicelles was used, >90% of tetrachlorophenol and pentachlorophenol in 200 ml of water samples were rapidly recovered. The sorbed analytes were eluted with 1 ml acetonitrile. The accuracy and precision of the present method were demonstrated for the HPLC analysis with ultraviolet (290 nm) detection of microg l(-1) levels of tetrachlorophenol and pentachlorophenol in river water samples.

Protein separation with surfactant-coated polystyrene involving Cibacron Blue 3GA-conjugated triton X-100.

Through mixing of porous polystyrene particles (Amberlite XAD-4), non-ionic surfactants, and surfactant-conjugated substrates (affinity ligand) in an aqueous solution led to the formation of a novel medium (affinity admicelle) for protein separation. The ligand (CB-Triton) was synthesized by mixing a triazine dye (Cibacron Blue 3GA (CB)) and a polyoxyethylene-type non-ionic surfactant (Triton X-100) in weakly alkaline solutions. Triton X-100 and CB-Triton were competitively sorbed onto XAD-4. Albumin (bovine serum), alcohol dehydrogenase (yeast), and lysozyme (chicken egg) having specific interaction to CB were collected onto the affinity admicelle. On the other hand, the collection of ovalubmin (chicken egg white), having no binding ability to CB, was negligibly small. Lysozyme in 100 microl of chicken egg white, diluted with 900 microl of 10 mM Tris-HCl (pH 7.4), was successfully collected on 18 mg of CB-Triton admicelles and, then, it was eluted with 1 ml of aqueous solution of 100 mM phosphate (pH 7.4). The recovery based on the activity for the lysis of micrococcus and the concentration factor were 60% and 40 (n = 3), respectively.

Protein separation with surfactant-coated octadecylsilyl silica involving Cibacron blue 3GA-conjugated nonionic surfactant.

A novel medium for protein separation, namely affinity admicelle, was prepared by mixing of octadecylsilyl (ODS) silica gels, a polyoxyethylene-type nonionic surfactant (Triton X-100), and a surfactant-conjugated substrate (affinity ligand) in an aqueous solution. The ligand was synthesized by mixing a triazine dye (Cibacron Blue 3GA, CB) and a polyethylene glycol monooleyl ether (C18EO7, C18EO10, or C18EO20) having different length of polyoxyethylene moiety in weakly alkaline solutions. The amount of Triton X-100 sorbed on 1 g of ODS silica was 0.2 mmol. Affinity ligands having highly hydrophobic oleyl group were predominantly sorbed on ODS silica. The losses of Triton X-100 and affinity ligand were within 0.3% and negligible by washing the admicelles were with a 25-fold volume of 1 mM Tris-HCl solution (pH 7.4). The coating ODS silica with Triton X-100 was effective to prevent the irreversible sorption of albumin (bovine, serum). An NADH-dependent enzyme, alcohol dehydrogenase (ADH, yeast), was successfully collected on the admicelles involving CB-conjugated ligands (CB-C18EO20). The maximum collection of ADH to 90 mg/ml of affinity admicelles was 68+/-4%. However, CB-C18EO7 and CB-C18EO10 having shorter polyoxyethylene unit were not available, suggesting the requirement of the spacer moiety in the affinity ligand. The recovery and purification factor based on the ratio of activity (unit)/protein (mg) from Whatman DE52-treated yeast extract was 27% and 12, respectively.

Aerosol-OT-gamma-alumina admicelles for the concentration of hydrophobic organic compounds in water.

A novel admicelle composing of a dialkylated anionic surfactant, di-2-ethylhexyl sodium sulfosuccinate (Aerosol-OT, AOT) and gamma-alumina was prepared by mixing them in acidic aqueous solution. The amount of the maximum sorption of AOT on 1 g of alumina at pH 2 was ca. 130 mg. By comparing the fluorescence spectra of N-phenyl-1-naphthylamine in different solvents, the solvent property of AOT-gamma-alumina admicelles was corresponding to that of toluene or diethyl ether. Thus, the AOT-gamma-alumina admicelles had greater hydrophobicity than SDS-gamma-alumina admicelles having similar hydrophobicity to 1-octanol or ethyl acetate. Hydrophobic organic compounds, chlorophenols having more than three chloro substituents, octylphenol, nonylphenol, dibutyl phthalate was almost quantitatively (98% or more) collected onto AOT admicelles composing of 1.5 g gamma-alumina and 150 mg AOT. The greater collection yields rather than those in SDS-admicellar system were ascribable to greater hydrophobicity and stability of AOT admicelles. After the 500-fold concentration, traces (nM) of organic contaminants in water samples were successfully detected with an HPLC having a photometric detector.

Diagnostic significance of carbamazepine and trigger zones in trigeminal neuralgia.

OBJECTIVE: To investigate the relationship between the efficacy of carbamazepine (CBZ) and the presence of the trigger zone for diagnosis of trigeminal neuralgia (TN). Study design CBZ was administered to 61 patients with suspected TN. All patients underwent intracranial examination by magnetic resonance imaging or computed tomography. The final diagnosis was established by oral and maxillofacial surgeon and neurosurgeon. RESULTS: Of the 61 patients, 50 were finally diagnosed as having TN and 6 as having atypical facial pain. CBZ was effective for pain relief in 45 of the 50 TN patients (90%), and in 5 of the 11 patients (45%) with other diseases (P <.005). However, CBZ also relieved pain in some patients other than TN. Thirty of the 31 patients (97%) with a distinct trigger zone and 20 of the 30 (67%) without a trigger zone were diagnosed as having TN (P<0.005). CONCLUSION: The efficacy of CBZ is an auxiliary indicator of TN and the presence of a distinct trigger zone is a strong indicator of TN.

Effective collection of hydrophobic organic pollutants in water with aluminum hydroxide and hydrophobically modified polyacrylic acid.

Polyacrylic acid was hydrophobically modified with dodecylamine and used as a coagulant for coprecipitation of hydrophobic organic pollutants from water. The polymer coagulant induced effective aggregation of aluminum hydroxide having hydrophobic regions which are essential for the incorporation of hydrophobic organic pollutants. Recoveries of the organic pollutants increased with increasing the dodecylamine content, which indicated that the dodecylamine moiety played an important role in the formation of hydrophobic area on the precipitate. Different hydrophobic organic pollutants that had hardly been removed by the conventional coprecipitation were successfully collected by the proposed method.

Surfactant-coated aluminum hydroxide for the rapid removal and biodegradation of hydrophobic organic pollutants in water.

The removal of hydrophobic organic pollutants in water to surfactant-coated aluminum hydroxide [surfactant-Al(OH)(3)] was investigated. Anionic surfactants such as sodium dodecyl sulfate (SDS), sodium bis(2-ethylhexyl)sulfosuccinate (AOT), and sodium oleate were sorbed on positively charged aluminum hydroxide at pH 7 and formed hydrophobic aggregates that can incorporate hydrophobic organic pollutants in water. Because of the hydrophobic interaction and decrease in the positive charge, surfactant-Al(OH)(3) was coagulated into precipitates that can readily be separated from water. Hydrophobic organic pollutants such as alkylphenols, polycyclic aromatic hydrocarbons, estrogens, chlorinated antifungals, and pesticides were well collected to the precipitates and thus efficiently removed from water. The collection of hydrophobic organic pollutants was correlated to their aqueous-octanol distribution coefficient. The decomposition of hydrophobic organic pollutants was examined using a bacterial agent (Bacillus subtilis). Hydrophobic organic compounds collected to AOT-Al(OH)(3) or sodium oleate-Al(OH)(3) were insufficiently decomposed. On the other hand, nonylphenol, octylphenol, and pendimethalin collected to SDS-Al(OH)(3) were decomposed within 1 week. The decomposition was accelerated by the collection to SDS-Al(OH)(3).

Removal of phenols in water using chitosan-conjugated thermo-responsive polymers.

A chitosan-conjugated thermo-responsive polymer containing 15% chitosan, PNIPAAm-15CS, was used for the removal of different phenols in water. The polymer was synthesized by a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide-mediated condensation of poly(N-isopropylacrylamide-co-acrylic acid) and chitosan in the aqueous solution (pH 6). At 30 °C, phenol, 4-methylphenol, 4-methoxyphenol, and 4-chlorophenol were converted to dark brown oxidized compounds by the tyrosinase-induced enzymatic reaction and subsequently bound to the amino moiety of PNIPAAm-15CS. In the presence of 1.0 g L(-1) PNIPAAm-15 CS and 50 k UL(-1) tyrosinase, phenols (20 mg L(-1)) decreased to undetectable levels (<0.01 mg L(-1)) within 2h. By the vigorous mixing of the solution at 40 °C, the polymer deposited and became a small coagulate that can be easily taken up from water. Accompanying the polymer deposition, the oxidized compounds were completely (>98%) removed. The proposed method was successfully applied to the removal of phenols from wastewaters.