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PubMed2003

The surprisingly facile thermal dehalogenation of chlorinated aromatics by a hydroaromatic donor solvent. Tautomerization of chlorinated phenols and anilines.

Up to 600 K, chlorinated benzenes and naphthalenes are inert in a hydrogen atom donating solvent such as 9,10-dihydroanthracene. However, when a hydroxyl or amine group is attached to the 2 or 4 position relative to chlorine, a surprisingly facile and selective hydrodehalogenation occurs at temperatures between 530 and 630 K. These features are the result of the onset of tautomeric equilibria for the chlorophenols or -anilines, creating the corresponding enones or imines, respectively, as reactive intermediates. The mechanism of dehalogenation involves the rate-determining transfer of a hydrogen atom from the solvent to the reactive intermediate according to a reverse radical disproportionation (RRD), followed by elimination of chlorine. The reactivity of mono- and dichlorophenols, chloroanilines, 4-chloro-1-naphthol, and 4-chloro-1-naphthylamine dissolved in 9,10-dihydroanthracene has been investigated. By means of density functional theory (DFT) calculations, the energies for the tautomers and their hydrogen affinities have been established. The experimental selectivities could be adequately reproduced by the computed data.

Journal Article↗
PubMed2004

Aryl cations from aromatic halides. Photogeneration and reactivity of 4-hydroxy(methoxy)phenyl cation.

The photochemistry of 4-chlorophenol (1) and 4-chloroanisole (2) has been examined in a range of solvents and found to lead mainly to reductive dehalogenation, through a homolytic path in cyclohexane and a heterolytic path in alcohols. Heterolysis of 1 and 2 in methanol and 2,2,2-trifluoroethanol offers a convenient access to triplet 4-hydroxy- and 4-methoxyphenyl cations. These add to pi nucleophiles, viz., 2,3-dimethyl-2-butene, cyclohexene, and benzene, giving the arylated products in medium to good yields. Wagner-Meerwein hydride and alkyl migration are evidence for the cationic mechanism of the addition to alkenes. Arylation (with no rearrangement) was obtained to some extent also in nonprotic polar solvents such as MeCN and ethyl acetate, reasonably via an exciplex and with efficiency proportional to the nucleophilicity of the trap (2,3-dimethyl-2-butene > cyclohexene >> benzene).

Journal Article↗
PubMed2005

Highly efficient nitration of phenolic compounds in solid phase or solution using Bi(NO3)3.5H2O as nitrating reagent.

[reaction: see text] Bi(NO(3))(3).5H(2)O was used as an efficient nitrating reagent in the nitration of phenolic compounds to give nitrated phenols in good to high yields. The nitration reaction proceeded smoothly by grinding 1 equiv of phenol, 2-methylphenol, 4-methylphenol, or 4-chlorophenol and Bi(NO(3))(3).5H(2)O, and the nitration of other phenolic compounds could be performed in acetone at ambient temperature (22-30 degrees C).

Journal Article↗
PubMed2005

Synthesis of new visible light active photocatalysts of Ba(In(1/3)Pb(1/3)M'(1/3))O3 (M' = Nb, Ta): a band gap engineering strategy based on electronegativity of a metal component.

We have synthesized new, efficient, visible light active photocatalysts through the incorporation of highly electronegative non-transition metal Pb or Sn ions into the perovskite lattice of Ba(In(1/3)Pb(1/3)M'(1/3))O3 (M = Sn, Pb; M' = Nb, Ta). X-ray diffraction, X-ray absorption spectroscopic, and energy dispersive spectroscopic microprobe analyses reveal that tetravalent Pb or Sn ions exist in the B-site of the perovskite lattice, along with In and Nb/Ta ions. According to diffuse UV-vis spectroscopic analysis, the Pb-containing quaternary metal oxides Ba(In(1/3)Pb(1/3)M'(1/3))O3 possess a much narrower band gap (E(g) approximately 1.48-1.50 eV) when compared to the ternary oxides Ba(In(1/2)M'(1/2))O3 (E(g) approximately 2.97-3.30 eV) and the Sn-containing Ba(In(1/3)Sn(1/3)M'(1/3))O3 derivatives (E(g) approximately 2.85-3.00 eV). Such a variation of band gap energy upon the substitution is attributable to the broadening of the conduction band caused by the dissimilar electronegativities of the B-site cations. In contrast to the ternary or the Sn-substituted quaternary compounds showing photocatalytic activity under UV-vis irradiation, the Ba(In(1/3)Pb(1/3)M'(1/3))O3 compounds induce an efficient photodegradation of 4-chlorophenol under visible light irradiation (lambda > 420 nm). The present results highlight that the substitution of electronegative non-transition metal cations can provide a very powerful way of developing efficient visible light harvesting photocatalysts through tuning of the band structure of a semiconductive metal oxide.

Adsorption↗
PubMed2005

Visible light active platinum-ion-doped TiO2 photocatalyst.

Platinum-ion-doped TiO2 (Pt(ion)-TiO2) was synthesized by a sol-gel method, and its visible light photocatalytic activities were successfully demonstrated for the oxidative and reductive degradation of chlorinated organic compounds. Pt(ion)-TiO2 exhibited a yellow-brown color, and its band gap was lower than that of undoped TiO2 by about 0.2 eV. The flat band potential of Pt(ion)-TiO2 was positively shifted by 50 mV compared with that of undoped TiO2. X-ray absorption spectroscopy and X-ray photoelectron spectroscopy analyses showed that the Pt ions substituted in the TiO2 lattice were present mainly in the Pt(IV) state with some Pt(II) on the sample surface. Pt(ion)-TiO2 exhibited higher photocatalytic activities than undoped TiO2 under UV irradiation as well. The visible light activity of Pt(ion)-TiO2 was strongly affected by the calcination temperature and the concentration of Pt ion dopant, which were optimal at 673 K and 0.5 atom %, respectively. Under visible irradiation, Pt(ion)-TiO2 degraded dichloroacetate and 4-chlorophenol through an oxidative path and trichloroacetate via a reductive path. The activity of Pt(ion)-TiO2 was not reduced when used repeatedly under visible light. However, visible-light-illuminated Pt(ion)-TiO2 could not degrade substrates such as tetramethylammonium and trichloroethylene, which are degraded with UV-illuminated TiO2. The characteristics and reactivities of Pt(ion)-TiO2 as a new visible light photocatalyst were investigated in various ways and discussed in detail.

Journal Article↗
PubMed2006

Kinetics of liquid phase semiconductor photoassisted reactions: supporting observations for a pseudo-steady-state model.

The kinetics of liquid phase semiconductor photocatalytic and photoassisted reactions are an area of some debate, reignited recently by an article by Ollis(1) in which he proposed a simple pseudo-steady-state model to interpret the Langmuir-Hinshelwood type kinetics, commonly observed in such systems. In the current article, support for this model, over other models, is provided by a reinterpretation of the results of a study, reported initially in 1999,(2) of the photoassisted mineralization of 4-chlorophenol, 4-CP, by titania films and dispersions as a function of incident light intensity, I. On the basis of this model, these results indicate that 4-CP is adsorbed more strongly on P25 TiO2 when it is in a dispersed, rather than a film form, due to a higher rate constant for adsorption, k(1). In addition, the kinetics of 4-CP removal appear to depend on I(beta), where beta = 1 or 0.6 for when the TiO2 is in a film or a dispersed form, respectively. These findings are discussed both in terms of the pseudo-steady-state model and other popular kinetic models.

Journal Article↗
PubMed2005

Photocatalytic storing of O2 as H2O2 mediated by high surface area CuO. Evidence for a reductive-oxidative interfacial mechanism.

CuO powders with a high specific surface area are shown to be able to produce H(2)O(2) in aqueous solution under simulated light irradiation. The highest rate of peroxide production was observed under mild experimental conditions using O(2) and a large surface area photocatalyst CuO irradiated with a solar simulator having light intensities between 60 and 90 mW/cm(2). The CuO employed had a specific surface area (SSA) of 64.8-70.1 m(2)/g and was prepared in a tubular furnace by controlled thermal decomposition of precipitated copper oxalate. The CuO particles produced were 1 mum cubes with primary particles around 15 nm. No peroxide was produced under the same conditions with commercial CuO, with SSA 200 times lower. The CuO synthesized during this work was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), specific surface area [Brunauer-Emmett-Teller (BET)], porosity, and X-ray photoelectron spectroscopy (XPS). From XPS, it was observed that only Cu(II) was present in the unused and used CuO. This indicates that the redox transient species involving other Cu oxidation states disappear very fast during the reaction, regenerating Cu(II) during H(2)O(2) production. Diverse experiments provided some evidence for the possible interfacial reaction mechanism leading to H(2)O(2), following the initial step of O(2)(-)(.) formation on the CuO surface under irradiation with photons, with energies exceeding the band gap of CuO. A photocatalyzed degradation of a concentrated 4-chlorophenol (4-CP) solution was observed under solar-simulated light in the presence of CuO.

Adsorption↗
PubMed2005

Visible light photocatalysis with platinized rutile TiO2 for aqueous organic oxidation.

Platinized rutile TiO2 samples containing varying concentrations of Pt were synthesized using Kemira (KE, BET surface area 50 m2/g, from Finland), and Toto HT0270 (HT, BET surface area 2.9 m2/g, from Japan) as the starting materials by solution mixing followed by sintering the precursors. Photocatalytic activities were established for phenol oxidation under visible light (wavelength >400 nm). Our results show optimal performance for 8 wt % platinized KE (8 wt % Pt/KE) and (1/2) wt % platinized HT rutile samples. The specific roles of O2 and visible light were examined using the 8 wt % Pt/KE sample in either N2 gas ambient or no illumination. Separately, 8 wt % platinized SiO2 was tested to compare its performance with that of platinized rutile TiO2. Several other chemicals containing different functional groups (formic acid, salicylic acid, 4-chlorophenol, 2,4,6-trichlorophenol, diethyl phosphoramidate) were selected for photooxidation tests with (1/2) wt % platinized HT rutile. X-ray diffraction reveals Pt metal clusters segregating on the surface of rutile TiO2 particles with increasing Pt weight percent. The Pt cluster surface area broadly increases, while the effective optical band gap steadily decreases with platinization of the rutile samples. These results suggest that Pt clusters on the surface of rutile TiO2 particles serve to mediate electron transfer from rutile to O2, thus facilitating photooxidation of organic chemicals.

Journal Article↗
PubMed2006

Some aspects of physico-chemical properties of TiO2 nanocolloids with respect to their age, size, and structure.

Aqueous colloidal solutions of quantum sized particles of titanium dioxide (Q-TiO2) undergo an aging process since the moment of their preparation. In course of time, the mean size of nanoparticles is gradually increasing and some of their physicochemical properties are changing as well. In the present study, the decrease of the blue spectral shift of the semiconductor absorption threshold was measured to determine the corresponding changes of band gap energy of the Q-TiO2 particles. In parallel, the decrease of the specific surface area of these particles was followed through their complexation with 2-coumaric acid. The formation kinetics and thermodynamic equilibrium of these surface charge-transfer complexes were investigated in detail by means of UV/vis absorption spectroscopy. Besides, the size and shape of the Q-TiO2 particles aged 2, 4, and 10 years were compared employing direct observation by means of high resolution transmission electron microscopy. On the basis of real particle images, a model of nanocrystalline anatase was developed. The specific surface areas estimated through complexation with 2-coumaric acid were confronted with the numbers of appropriate titanium atoms located on the particle surface that were calculated from a model of anatase nanocrystals of different sizes. The photocatalytic activity, which represents the most important quality of anatase from practical point of view, was repeatedly determined through photocatalytic degradation of 4-chlorophenol in a colloidal solution of Q-TiO2 particles during its aging at 4 degrees C for three years. The corresponding reaction rate was increasing rapidly in the first weeks; it almost tripled in 68 days, and afterward it approached a limiting value. On the whole, the initial value increased four times in three years. Voltammetry at hanging mercury drop as the last method for aging description did not show any significant change of voltammetric behavior in a short two months period. However, while compared to preceding results of a similar TiO2 system, new redox processes of Q-TiO2 colloids were observed in the negative potential range. Besides the reduction of surface protons reported previously, two new pairs of peaks appeared.

Journal Article↗
PubMed2006

Nucleation and growth characteristics of a binary low-mass organogel.

The system of bis(2-ethylhexyl) sodium sulfosuccinate and 4-chlorophenol, when dissolved in a nonpolar organic solvent, forms an organogel. The fibers of this organogel are formed through a nucleation-growth phenomenon. By reducing evaporation of the pregel solution, the fibers can be directed to grow with extremely long persistence lengths. Alignment of multiple fibers is achieved by inducting growth at the air-solution interface. The interplay of two zones, one above the critical nucleation concentration and the other below, allows orientation to be accomplished as fiber growth proceeds. The observations have implications for the use of the organogel as a template for materials synthesis.

Journal Article↗
PubMed2002

Increased activity of in situ catalysts for alkyne metathesis.

[reaction: see text] Reaction of an enyne (1,1-diphenyl-pent-1-ene-3-yne) with a preheated mixture of Mo(CO)6/4-chlorophenol/3-hexyne at 130 degrees C furnished 1,1,6,6-tetraphenylhex-1,5-diene-3-yne in an 80% yield. If the starting material was heated with a mixture of Mo(CO)6 and 4-chlorophenol under identical conditions, no reaction was observed.

Journal Article↗
PubMed2003

An oxygen-bonded c8-deoxyguanosine nucleoside adduct of pentachlorophenol by peroxidase activation: evidence for ambident c8 reactivity by phenoxyl radicals.

The ability of the carcinogenic environmental toxin pentachlorophenol (PCP, 1) to react with DNA bases has been assessed using MS and NMR. Treatment of PCP (100 microM) with horseradish peroxidase (HRP/H(2)O(2)) or myeloperoxidase (MPx/H(2)O(2), from human leukocytes) in the presence of excess deoxyguanosine (dG, 2 mM) led to the isolation and identification of the oxygen-bonded C8-dG nucleoside adduct 4. The reaction was absolutely specific for dG; no detectable adduct(s) was observed from HRP/H(2)O(2) and PCP in the presence of deoxyadenosine, deoxycytidine, or thymidine. Formation of 4 was also specific for peroxidase activation that is known to oxidize PCP into the phenoxyl radical. Treatment of PCP/dG with rat liver microsomes (RLM) failed to generate 4; instead, an adduct derived from the benzoquinone electrophile tetrachloro-1,4-benzoquinone (chloranil) was observed in the extracted ion chromatogram from the RLM/NADPH-treated PCP/dG sample. The adduct 4 is the first structurally characterized O-bonded phenolic DNA nucleoside adduct and highlights the ambident electrophilicity of phenoxyl radicals (O- vs C-) in reaction at C8 of dG, as we have previously demonstrated that the para-chlorophenolic toxin, ochratoxin A (2), reacts at C8 of dG to give the C-bonded adduct 3 via the intermediacy of the OTA phenoxyl radical. Given that PCP is known to induce DNA adduct formation in vivo and human exposure has been linked to incidences of leukemia, the adduct 4 could play a key role in PCP-mediated carcinogenesis.

Animals↗
PubMed1999

Fate of the herbicides mecoprop, dichlorprop, and 2,4-D in aerobic and anaerobic sewage sludge as determined by laboratory batch studies and enantiomer-specific analysis.

Aerobic degradation experiments with the racemic mixtures of mecoprop and dichlorprop revealed that activated sludge collected from the aeration tank of a municipal waste water treatment plant degraded both enantiomers of mecoprop and dichlorprop within 7 days, albeit in an enantioselective manner; the (S) enantiomers were preferentially degraded. Mecoprop, dichlorprop, and 2,4-D were completely metabolized under aerobic conditions, as shown by the 86-98% elimination of dissolved organic carbon. Under anaerobic conditions, the concentration of 2,4-D decreased exponentially with a first-order reaction rate constant of 0.24 per day and without a lag-phase. After an incubation time of 17 days, 2,4-D was completely removed. 2,4-Dichlorophenol was the main metabolite of anaerobic 2,4-D degradation; only traces of 4-chlorophenol were detected. In contrast, the chiral phenoxypropionic acid herbicides mecoprop and dichlorprop persisted under anaerobic conditions during 49 days of incubation.

2,4-Dichlorophenoxyacetic Acid↗
PubMed2004

Phenol and lactone receptors in the distal sensilla of the Haller's organ in Ixodes ricinus ticks and their possible role in host perception.

Extract of steer wool odor was found to excite olfactory receptor(s) in a wall-pore olfactory sensillum on the distal knoll of the Haller's organ. Three active volatile compounds were revealed in this odor by gas chromatography. Electrophysiological experiments revealed two types of receptors (sensory neurons) within the sensilla examined. One type of receptor responded only to phenolic derivatives, such as o-chlorophenol, o-bromophenol, o-methylphenol, 2,6-dichlorophenol, 2,6-dibromophenol, 2,4,6-trichlorophenol, but not to o-nithrophenol, p-methylphenol, 2,5-dichlorophenol, 3,5-dichlorophenol, 2,6-dinithrophenol, 2,6-dimethylphenol, and pentachlorophenol. The other type of receptor responded only to gamma-valerolactone. It is assumed that these cells play an important role in perception of a host from long distances (10-15 m), which is typical of Ixodes ricinus ticks.

Animals↗
PubMed2001

In vivo gene delivery into ocular tissues by eye drops of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) polymeric micelles.

The primary objective of this study was to investigate the feasibility of using PEO-PPO-PEO non-ionic copolymeric micelles as a carrier for eye-drop gene delivery of plasmid DNA with lacZ gene in vivo. Using pyrene fluorescence probe methods, zeta potential, and dynamic light scattering test (DLS), the ability of micelle formation of these block copolymers with plasmid was studied. Gene expressions were visualized by both the quality of enzymatic color reaction using X-gal staining and by the quantification of the substrate chlorophenol red galactopyranoside (CPRG) in enucleated eyes on day 2 after gene transfer. In addition, microscopy to identify the types of cell showing uptake and expression of the transferred gene was used. We found that the block polymeric micelles were formed above 0.1% (w/v) of block copolymer with a size of 160 nm and a zeta potential of -4.4 mV. After 2 days of topically delivery three times a day, the most intense gene expression was observed on days 2 and 3. Reporter expression was detected around the iris, sclera, conjunctiva, and lateral rectus muscle of rabbit eyes and also in the intraocular tissues of nude mice upon in vivo topical application for 48 h with a DNA/polymeric micelle formulation. Furthermore, after two enhancement treatments, the transport mechanisms of the block copolymeric micelles were found through endocytosis in tissues by enhancement through the tight junction pathway. Thus, efficient and stable transfer of the functional gene could be achieved with PEO-PPO-PEO polymeric micelles through topical delivery in mice and rabbits. These in vivo experiments indicate the possible potential use of block copolymers for DNA transfer.

Animals↗
PubMed2000

Derivative spectrophotometry in the analysis of mixtures of phenols and herbicides.

Derivative spectrophotometry (zero-crossing technique) was applied to the determination of selected phenols and herbicides in two-component mixtures. Methyl- and chlorophenols (3-methylphenol, 2,3- and 3,4-dimethylphenol, 2,5-, 2,6- and 3,4-dichlorophenol and 2,4,5-trichlorophenol) and triazine, uracil and urea herbicides (simazine, propazine, hexazinone, bromacil and metoxuron) were examined. The RSD values ranged between 0.05 and 4% and the recoveries obtained were between 97 and 110%. The developed derivative spectrophotometric method was also applied as a complementary technique for the separation of overlapping peaks of sample compounds obtained by HPLC with diode-array detection. Metoxuron and 3-methylphenol, metoxuron and 2,5-dichlorophenol and simazine and 2,6-dichlorophenol were determined simultaneously by this method at the level of 1 x 10(-3) g l-1.

Environmental Pollutants↗
PubMed2001

Trace level determination of phenols as pentafluorobenzyl derivatives by gas chromatography-negative-ion chemical ionization mass spectrometry.

A method for the trace level determination of 11 phenols as pentafluorobenzyl (PFB) derivatives by gas chromatography-mass spectrometry (GC-MS) with negative-ion chemical ionization (NICI) is described. First, the conditions for the PFB derivatisation of phenols were optimized and were found to be reaction temperature 80 degrees C and reaction time 5 h. Second, the detection limits using selected ion monitoring (SIM) were compared between trimethylsilylated (TMS) derivatives in the electron ionization (EI) mode and PFB derivatives in the NICI mode. The responses for the PFB derivatives in the NICI mode were 3.3-61 times higher than those of the TMS derivatives in the EI mode. The instrumental detection limits using NICI-SIM ranged from 2.6 to 290 fg. This method was applied to the analysis of phenols in river water using solid-phase extraction. The recoveries of the phenols from a river water sample spiked with standards at 100 ng l-1 with 2-chlorophenol, 4-chloro-3-methylphenol and pentachlorophenol and at 1000 ng l-1 with phenol, 2,4-dimethylphenol, 2,4-dichlorophenol, 2-nitrophenol, 2,4,6-trichlorophenol and 4-nitrophenol were 81.2-106.3% (RSD 5.1-8.0%), except for 2-methyl-4,6-dinitrophenol and 2,4-dinitrophenol, for which the recoveries were 5.8 and 4.2%, respectively, because water contained in the acetone eluate interfered with the derivatisation of these compounds with two electrophilic nitro groups.

Gas Chromatography-Mass Spectrometry↗
PubMed2002

Photocatalytic degradation of 4-chlorophenoxyacetic acid in the presence of an iron complex and hydrogen peroxide.

The photoinitiated transformation of 4-chlorophenoxyacetic acid (CPA) in aqueous solutions is described in detail. The photocatalytic system consists of CPA, hydrogen peroxide (no oxygen) and the complex iron(m) acetylacetonate Fe(acac)3. Special attention was paid to the choice of irradiation wavelength in order to separate the contribution of the iron-photocatalyzed reaction from that of direct photoreactions This was achieved by selecting a wavelength of 365 nm, which is absorbed exclusively by the iron complex. We specified the conditions for effective photocatalytic degradation of CPA with high quantum yields which depend on the concentration of Fe(acac)3. The reaction is primarily initiated by absorption of 365 nm radiation by Fe(acac)3 followed by the photoreduction of Fe(III)(acac)3 to Fe(II)(acac)2 and subsequently by the Fenton reaction with hydrogen peroxide producing highly reactive hydroxyl radicals OH*. The main degradation intermediates are phenol and 4-chlorophenol, which are further mineralized during continuous irradiation.

Journal Article↗