Phenanthrene degradation in subcritical water

Subcritical water (<374 °C and <221 bar) has unique characteristics such as dramatically decreased dielectric constant, surface tension, and viscosity with increasing temperature, allowing for dissolution and reaction of organics in high-temperature water to occur. Additionally, the dissociation constant of water at temperatures of 200-300 °C is three orders of magnitude greater than that of ambient water, which may also contribute to the reactivity of subcritical water with certain organic compounds. In this study, the degradation and oxidation of phenanthrene in subcritical water were investigated. Both deionized water and water with 3% hydrogen peroxide were used in the degradation and oxidation studies. The effect of temperature on degradation efficiency has been determined with a temperature range of 100-350 °C. When the temperature was increased from 150 to 350 °C, the amount of phenanthrene degraded varied from 6 to 243 μg in each milliliter of deionized water. However, these quantities were increased to 195 μg at 150 °C and 3680 μg at 350 °C in each milliliter of water with 3% hydrogen peroxide. Several degradation products including phenol, benzoic acid, and ketones were identified by using gas chromatography/mass spectrometry (GC/MS).     

Electrochemistry in solids prepared by sol-gel processes

Sol-gel chemistry provides a route to preparing inorganic polymers with ionically conducting properties by room temperature synthetic routes. The products, which are rigid solids, are well-suited as media for conventional electrochemical techniques such as cyclic voltammetry. This property, when combined with their ability to host a wide variety of species, has allowed development of a variety of devices of interest in electrochemistry and analytical chemistry. Examples include cathodes for fuels cells, electrochromic devices, biosensors, and amperometric sensors for analytes in the gas phase. In this review, the emphasis will be on reported applications to analytical chemistry; however, studies on the general properties of these materials and on their use in electrochemical science also will be summarized because they may provide the basis for further development of sensors.     

Organic reactions in subcritical and supercritical water

This review describes applications to several important organic reactions in subcritical and supercritical water.

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Hairy particles prepared by living radical graft-polymerization

Novel particles having designed hairs were prepared by living radical graft-polymerization on core particles. The living radical species used in this study was a kind of photo-iniferter, N, N-diethyl-thiocarbamate. Main component of hair was poly(N-isopropylacrylamide) (PNIPAM) which was a representative thermo-sensitive polymer. The polymerization was carried out by UV irradiation at room temperature that was lower than the transition temperature of PNIPAM. Incorporation of a small amount of acrylic acid into the hair caused significant change in the properties of hairy particles. The mode of comonomer charge also enabled to design the hair structure on the particles.     

Demetalisation of soils by continuous acidified subcritical water extraction

Acidified subcritical water is proposed for the continuous extraction of metals (namely, lead, copper, cadmium, arsenic, selenium and mercury) from soils prior to: (a) continuous derivatisation (by hydride formation for As and Se, and cold vapour formation for Hg) and determination by atomic fluorescence; and (b) determination by Graphite Furnace-Atomic Absorption Spectrometry for Pb, Cu and Cd. Soil samples (5 g) were subjected to 90-min dynamic extraction with water modified with 4% (v/v) HNO(3) at 200 degrees C and 30 bar. A univariate optimisation of the variables related to derivatisation (for As, Se and Hg) and detection (for all of them), and a multifactorial optimisation of the variables affecting the continuous extraction step were performed. A kinetics study of the extraction process was performed in order to control the lowering of metals in the soil. The method was compared with the EPA-3051 reference method. The good reproducibility of the method, together with its safety and low cost, make it a good alternative for the demetalisation of contaminated soil.     

Determining gold in water by anion-exchange batch extraction

This paper describes a batch procedure for determining gold in natural waters. It is completely adaptable to field operations. The water samples are filtered and acidified before they are equilibrated with an anion-exchange resin by shaking. The gold is then eluted with acetone-nitric acid solution, and the eluate evaporated to dryness. The residue is taken up in hydrobromic acid-bromine solution and the gold is extracted with methyl isobutyl ketone. The extract is electrothermally atomized in an atomic-absorption spectrophotometer. The limit of determination is 1 ng/1.     

Retention mechanisms in subcritical water reversed-phase chromatography

Differences in the properties of subcritical water and conventional water/acetonitrile and water/methanol mobile phases for reversed phase separations are explored. Using van’t Hoff plots enthalpies and entropies of transfer are compared among the mobile phases while linear solvation energy relationships are used to quantify contributions to retention based on a solute's polarizability, dipolarity, hydrogen bond donating ability, hydrogen bond accepting ability, and molecular size. Results suggest the presence of acetonitrile or methanol in the mobile phase may decrease dispersive interactions of the solute with the stationary phase compared to subcritical water, thereby lowering enthalpic contributions to retention. Enthalpic contributions are found to drive the retention of a methylene group in all systems studied.     

Morphology control of magnetic latex particles prepared from oil in water ferrofluid emulsion

The use of magnetic latex particles as solid support in biomedical applications is favourable when homogeneous and well-defined core–shell polymer particles are used. Accordingly, this paper concerns with the synthesis of magnetic poly(styrene–divinylbenzene) latex particles using emulsion polymerization of styrene (St) and divinylbenzene (DVB) monomers in the presence of preformed oil in water organic ferrofluid emulsion droplets as seed. The key parameters which affect on formation and morphology of the prepared magnetic latexes were investigated, including type of magnetic emulsion, St/DVB monomers ratio, DVB amount, type of initiator and surfactant nature. In this study, two different magnetic emulsions were used, low and high octane content magnetic emulsions. The magnetic emulsions were stabilized using different types of surfactants including AP, Triton X 405 and SDS. In addition, four different initiators, including AIBN, V50, ACPA and KPS were examined. The morphology of the prepared magnetic latexes was investigated using transmission electron microscopy. In addition, particle size and size distribution, magnetic content and magnetic properties of the prepared magnetic latexes were also examined, using various techniques, e.g. dynamic light scattering, thermal gravimetric analysis and vibrating sample magnetometer, respectively. The results showed that the morphology type (Janus like, moon like and/or core–shell) of the prepared magnetic latex particles could be controlled depending mainly on the used formulation. In fact, the use of styrene monomer leads to anisotropic morphology. Whereas, the progressive use of DVB in presence of KPS intiator leads to a well-defined magnetic core and polymer shell structure.

Spectroelectrochemical processes in polyaniline films prepared by different methods

Basic in situ spectroelectrochemical methods of the studying of the polyaniline electrosynthesis processes and doping-dedoping of the polyaniline films prepared by different procedures are overviewed. The advantages of the combining of different spectroelectrochemical methods in a single experiment are discussed and the extra information on the processes of electrosynthesis and electrochemical doping-dedoping of polyaniline prepared by the combinations of methods is analyzed. Components of the polyaniline electronic absorption spectra are analyzed and spectroelectrochemical properties of polyaniline films prepared by vacuum evaporation are studied by a complex of methods; the results of the studies are presented.     

pH- and thermosensitive polyaniline colloidal particles prepared by enzymatic polymerization

Polyaniline colloids were prepared by enzymatic polymerization using chitosan and poly(N-isopropylacrylamide) as steric stabilizers. The resulting nanoparticles undergo flocculation by changing the pH or temperature of the aqueous dispersions. The environmentally responsive behavior of these colloids contrasts with that of polyaniline colloids synthesized using poly(vinyl alcohol) as the steric stabilizer. The colloid size was a function of the steric stabilizers and ranged from approximately 50 nm for polyaniline particles prepared in the presence of chitosan and partially hydrolyzed poly(vinyl alcohol) up to 350 nm for the particles synthesized using poly(N-isopropylacrylamide). UV-visible and Fourier transform infrared spectroscopic studies indicate that polyaniline colloids are spectroscopically similar to those obtained by traditional dispersion polymerization of aniline by chemical oxidation. These polyaniline colloids have potential applications in thermochromic windows and smart fluids.     

Particle-particle chemistry between micrometer-sized PbSO4 and CaCO3 particles in turbulent flow initiated by liquid water

A mixture of natural and anthropogenic particles is ubiquitous in the troposphere and exerts an important influence on air quality. This work reports the study of mixing and heterogeneous chemistry of particles of natural-like mineral dust (CaCO(3)) and anthropogenic-like microparticle (PbSO(4)) in turbulent air flow under varying relative humidity. Sparse monolayers of laboratory-generated particles were collected on substrates using impaction. The grain size distribution and chemistry of micrometer-sized particles were determined as CaCO(3)-PbSO(4) internal and external mixtures by Raman imaging, scanning electron microscopy, and time-of-flight static secondary ionization mass spectrometry. The condensation of a thin water layer on mixed aggregates initiates the formation of complex internal mixtures of Pb(3)(CO(3))(2)(OH)(2), PbCO(3), CaSO(4)·2H(2)O, CaCO(3), and PbSO(4) fine particles. These heterogeneous chemistry processes which may occur in ambient air can increase dramatically the amounts of hazardous breathable particles.     

Spectrophotometric determination of fluoxetine by batch and flow injection methods

A rapid, simple, and accurate spectrophotometric method is presented for the determination of fluoxetine by batch and flow injection analysis methods. The method is based on fluoxetine competitive complexation reaction with phenolphthalein-beta-cyclodextrin (PHP-beta-CD) inclusion complex. The increase in the absorbance of the solution at 554 nm by the addition of fluoxetine was measured. The formation constant for fluoxetin-beta-CD was calculated by non-linear least squares fitting. Fluoxetine can be determined in the range 7.0 x 10(-6)-2.4 x 10(-4) mol l(-1) and 5.0 x 10(-5)-1.0 x 10(-2) mol l(-1) by batch and flow methods, respectively. The limit of detection and limit of quantification were respectively 4.13 x 10(-6) mol l(-1) and 1.38 x 10(-5) mol l(-1) for batch and 2.46 x 10(-5) mol l(-1) and 8.22 x 10(-5) mol l(-1) for flow method. The sampling rate in flow injection analysis method was 80+/-5 samples h(-1). The method was applied to the determination of fluoxetine in pharmaceutical formulations and after addition to human urine samples.     

Thermal stability of fatty acids in subcritical water

In this work, hydrolytic reaction conditions of various temperatures (300–370 °C) and times (0–30 min) at a constant pressure of 20 MPa were applied to the thermal decomposition of three kinds of fatty acids (FAs), stearic acid, oleic acid, and linoleic acid, in subcritical water. The degradation characteristics were investigated from the derived data, and the thermal stability of FAs in subcritical water was estimated. The primary reactions we observed were isomerization and pyrolysis of FAs. The main pathway of degradation was deduced by analyzing the contents of pyrolyzed products. We found that more saturated FAs have greater thermal stability in subcritical water. All FAs remained stable at 300 °C or below. Based on these results, we recommend that hydrolysis of vegetable oils and fats using subcritical water should be carried out below 300 °C (at 20 MPa) and for less than 30 min to obtain high-yield FA production.     

C掺杂ZrO_2四方纯相粉体的甲醇溶剂热制备及热稳定性研究

在ZrO(NO_3)_2·2H_2O-CO(NH_2)_2-CH_3OH溶剂热过程中,水的缺乏使得甲醇通过其甲氧基与Zr~(4+)发生亲核取代或以分子配位,直接参与锆盐的水解-缩聚反应,形成具有[ZrO_z(OH)_p(OCH_3)_q·rCH_3OH]_n结构的无机聚合物;同时,甲醇对聚合物低的溶解能力强烈抑制了Ostwald熟化过程,阻碍了溶剂热产物的晶化与热力学支持的结构重排。尿素通过其水解作用与锆盐竞争体系中的水及锆物种骨架上的羟基,这不仅导致无机聚合物中Zr-O-Zr键合相对Zr-OH键合的比例增加,使得溶剂热产物发生结构重排的几率进一步下降;而且也一定程度上增加了溶剂热产物中甲氧基的含量。含有大量甲氧基团的溶剂热产物经400℃焙烧后,形成C掺杂ZrO_2。C掺杂与溶剂效应共同稳定了ZrO_2的四方相。在500-600℃中等温度、空气气氛焙烧过程中,C掺杂ZrO_2四方相结构显示了良好的热稳定性;提高焙烧温度至700℃,游离于颗粒表面的C被完全氧化去除,固溶于晶格中的C也部分脱溶,导致了部分四方相失稳转变成单斜相。     

Degradation of benzoic acid and its derivatives in subcritical water

In this research, the stability of benzoic acid and three of its derivatives (anthranilic acid, salicylic acid, and syringic acid) under subcritical water conditions was investigated. The stability studies were carried out at temperatures ranging from 50 to 350 °C with heating times of 10–630 min. The degradation of the benzoic acid derivatives increased with rising temperature and the acids became less stable with longer heating time. The three benzoic acid derivatives showed very mild degradation at 150 °C. Severe degradation of benzoic acid derivatives was observed at 200 °C while their complete degradation occurred at 250 °C. However, benzoic acid remained stable at temperatures up to 300 °C. The degradation products of benzoic acid and the three derivatives were identified and quantified by HPLC and confirmed by GC/MS. Anthranilic acid, salicylic acid, syringic acid, and benzoic acid in high-temperature water underwent decarboxylation to form aniline, phenol, syringol, and benzene, respectively.     

Hydroxyl radical reactivity with nitrobenzene in subcritical and supercritical water

The bimolecular rate constants of the addition reaction between hydroxyl radical (*OH) and nitrobenzene (C(6)H(5)NO(2)) were measured in subcritical and supercritical water (SCW) at temperatures between ambient and 390 degrees C. The measured bimolecular rate constants showed distinctly non-Arrhenius behavior (i.e., essentially no increase with temperature) from ambient to 350 degrees C, but increased in the slightly subcritical and supercritical region between 350 and 390 degrees C. These data were modeled reasonably well over the entire temperature range with a three-step reaction mechanism, originally proposed by Ashton et al.(1) This model includes the formation of a pi-complex intermediate as the precursor of the nitrohydroxycyclohexadienyl radical.     

Nanometer-sized gelatin particles prepared by means of gamma-ray irradiation

Nanometer-sized gelatin particles have been prepared by means of gamma-ray irradiation and characterized by static and dynamic light scattering combined with circular dichroism (CD) measurements. The molecular weight of the nanoparticles was much larger than that of the original gelatin molecules, whereas the hydrodynamic radius was much smaller. Radius of gyration evaluated from the angular dependence of the static light scattering intensity decreased with increasing irradiation dose. CD spectra of the gelatin nanoparticles were independent of temperature, and it is suggested that the nanoparticles consist of highly and randomly packed gelatin and their conformation is stable against the temperature change.     

Temperature-sensitive hairy particles prepared by living radical graft polymerization

Four types of temperature-sensitive hairy particles were prepared by living radical graft polymerization using a photoiniferter. The hairs were poly(N-isopropylacrylamide) (N), poly(N-isopropylacrylamide)ran-poly(acrylic acid) (NA), and diblock copolymers composed of N and NA. The block copolymer was attached to the particle in different modes, that is, one has a N-block inner and a NA-block outer but the other has the inverse arrangement. The acrylic acid content in NA was adjusted to be only 1%, but NA had a higher transition temperature by 5 degrees C than N in a neutral aqueous solution. The sequence of blocks attached onto the particle was the key factor to control the temperature responsiveness of the particle. The hairy particles exhibited a two-step transition with increasing temperature under certain conditions. The hairy particle also responded to the pH and ionic strength. Some unique behaviors of the hairy particles were studied in detail in terms of electrophoretic mobility and adsorption of dye molecules as well as swelling/deswelling.     

Separation and characterization of particles in natural water and soil using flow field-flow fractionation

Flow field-flow fractionation (FlFFF) is used to characterize particles in natural water (ground and surface water) and soil. The opposed flow sample concentration (OFSC) mode of FlFFF (OFSC-FlFFF) is employed, where the colloidal sample is continuously fed into the channel so that the particles are focused into a narrow band near the inlet of the FlFFF channel before the separation is initiated. There is no need for stopping the flow for the sample relaxation, which is usually required in conventional FlFFF operations. First, the OFSC-FlFFF is tested with mixtures of polystyrene latex spheres. Then the OFSC-FlFFF procedure is optimized for the analysis of particles in natural water and soil by varying various experimental parameters including the flow rates. Ground water of up to 100 mL has been successfully loaded, concentrated, and characterized by OFSC-FlFFF. Results show that the OFSC-FlFFF provides a simplified alternative to existing off-line concentration procedures, and it shows high potential for application to analysis of dilute colloidal particles in environmental water. The composition of the samples was analyzed using atomic absorption spectrometry.