Synthesis of porous divinylbiphenyl copolymers and their sorptive properties towards phenol and its derivatives

Seven porous divinylbiphenyl polymers having the same nominal crosslinking degree (51.8 wt.%) have been synthesized using suspension polymerization method in the presence of the following inert diluents or their mixtures: toluene, heptane, dodecane, isooctane. The use of various inert diluents was aimed at changing the extent of polymeric network-diluent interactions. The obtained polymers have specific surface area in the range 50-300 m²/g depending on the type and amount of inert diluents used during polymerization. Their sorptive properties have been studied using dilute (0.5 mmol/l) aqueous solutions of phenol and its derivatives (2-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol, 2,6-dimethylphenol, 4-hydroxyphenol). It has been found that sorption, at low equilibrium concentration, follows the order: 2,4,5-trichlorophenol > 2,4-dichlorophenol > 2-chlorophenol > 2,6-dimethylphenol > phenol > 4-hydroxyphenol. Full characteristic of the porous structure of polymers has been obtained by nitrogen adsorption at 77K.     

Acute Toxicity of Cresols to Pseudomonas — An Initial Oxygen Uptake Method

Acute toxicity of cresols to both Pseudomonas I and II was estimated by an initial oxygen uptake method. Inhibition studies of toluene and cresols on the oxidation of either benzoate by Pseudomnas I or phenol by Pseudomonas II were analyzed and expressed as oxygen uptake rates. Double reciprocal plots for the inhibiton by cresols of oxygen uptake in Pseudomonas, two physical constants, Vmaxi and Ki, were obtained. The Vmaxi of o?, m? and p-cresol were 80%, 81% and 57% of Vmax in Pseudomnas I, and 10%, 25% and 36% in Pseudomonas II, respectively. Thus, the toxicity to Pseudomonas I decreases in the order p- > o- ≥ m-cresol, whereas to Pseudomonas II, the order is changed to o- > m- > p-cresol. This difference in the toxicity order is probably due to the allosteric effect of p-cresol towards Pseudomonas II. Inasmuch as most compounds inhibit noncompetively, the relative toxicity of different compounds can be estimated by a new toxicity parameter RI (relative inhibition) which is defined as 100/Ki. By comparing the RI value of each compound, the toxicity to Pseudomonas I decreases in the order m-chlorophenol > p-cresol > p-chlorophenol > o-cresol ≥ m-cresol > o-chlorophenol > toluene > phenol.     

Carbon monolith: Preparation,characterization and application as microextraction fiber

A carbon monolith was synthesized via a polymerization–carbonization method, styrene and divinylbenzene being adopted as precursors and dodecanol as a porogen during polymerization. The resultant monolith had bimodal porous substructure, narrowly distributed nano skeleton pores and uniform textural pores or throughpores. The carbon monolith was directly used as an extracting fiber, taking place of the coated silica fibers in commercially available solid-phase microextraction device, for the extraction of phenols followed by gas chromatography–mass spectrometry. Under the studied conditions, the calibration curves were linear from 0.5 to 50 ng mL⁻¹ for phenol, o-nitrophenol, 2,4-dichlorophenol and p-chlorophenol. The limits of detection were between 0.04 and 0.43 ng mL⁻¹. The recoveries of the phenols spiked in real water samples at 10 ng mL⁻¹ were between 85% and 98% with the relative standard deviations below 10%. Compared with the commercial coated ones (e.g. PDMS, CW/DVB and DVB/CAR/PDMS), the carbon monolith-based fiber had advantages of faster extraction equilibrium and higher extraction capacity due to the superior pore connectivity and pore openness resulting from its bimodal porous substructure.     

Solid-phase microextraction of phenol compounds using a fused-silica fiber coated with beta-cyclodextrin-bonded silica particles.

A novel solid-phase microextraction (SPME) fiber was prepared by coating an HPLC beta-cyclodextrin bonded silica stationary phase (CDS) on the surface of a fused-silica fiber. The fiber was evaluated for the determination of five phenol compounds (phenol, 2,4-dimethylphenol, 4-nitrophenol, 3-chlorophenol, 4-methylphenol). Compared with commercially available polymer coatings, the CDS coating showed high sensitivity and fast velocity of mass transfer for phenol compounds because of its porous structure and a unique molecular structure of beta-cyclodextrin. In addition, the CDS coating was proved to be very stable at a relatively high temperature (up to 300 degrees C). The method was suitable for the determination of phenol compounds in aqueous samples. The determination of 4-nitrophenol in soil by microwave-assisted extraction (MAE) coupled to solid-phase microextraction was also investigated.     

Cationic polymerization behavior of hydroxystyrenes

Solution polymerizations of o-, m- and p-hydroxystyrene with boron trifluoride etherate were investigated. The results of infrared and ultraviolet spectroscopic investigations of the polymers thus obtained indicate that p-hydroxystyrene polymer consisted mainly of the structure formed through the normal vinyl polymerization mechanism, whereas o- and m-hydroxystyrene polymers contained considerable portions of the structures due to the reaction of the vinyl group with the phenol nucleus. The rate of polymerization and the intrinsic viscosity of the polymer decreased in the order p-hydroxystyrene ? o-hydroxystyrene > m-hydroxystyrene. It was of interest that on the cationic polymerization only p-hydroxystyrene gave polymer of high molecular weight. Plausible polymerization mechanisms were considered. Solid-state polymerization of p-hydroxystyrene at solid carbon dioxide temperature with the use of boron trifluoride etherate was also investigated. Appreciable polymerization occurred only at fairly high catalyst concentrations.     

Potentiometric determination of the protonation constants of some phenols in 1.0 mol/L NaCl at 25°C

The potentiometric determination of the protonation constants of phenol, 2-chlorophenol, 2-nitrophenol, 2,4-dichlorophenol and 2-methylphenol in 1.0 mol/L NaCl at 25°C is presented. An automated system has been used in the experiments. The determination of the constants has been carried out using both graphical and numerical methods.     

EPR investigations of gamma-irradiated novolacs

EPR investigations of γ-irradiated phenol, p-chlorophenol, o-chlorophenol, 3,5-dichlorophenol and p-cresol novolac are presented. The elimination of a chlorine atom from the phenolic ring must be assumed in the case of chlorinated novolacs. The corresponding aryl radical could only be detected in the case of 3,5-dichlorophenol novolac in a large amount. Furthermore phenoxy and cyclohexadienyl radicals were found in the spectra. The radiation chemical as well as the resist sensitivity are enhanced by chlorination but there is no definite correlation between them.     

Chelating behavior of new chelating resins derived from n-(o-hydroxybenzyl)iminodiacetic acid

The chelating behavior of a new resin prepared by polycondensation of N-(o-hydroxybenzyl) iminodiacetic acid (o-HDA) with phenol and formaldehyde, is compared with that of the monomer, with p-HDA resin and p-HDA monomer, and with Chelex-100. The order of chelate stability for the o-HDA resin is Cu(II) > Ni(II) > Zn(II) > Co(II). An unusually high stability of the o-HDA and o-HDA resin iron(III) chelates in acidic solution is attributed to the participation of the o-hydroxyl group in the coordination process.     

On the structure of negative ions formed by dissociative electron attachment by monochlorophenol molecules

The energetics of negative ion formation by resonant dissociative electron attachment by o-, m-, and p-chlorophenol molecules was studied. The structures of some fragment ions and their neutral partners were established. Hidden rearrangement processes leading to the formation of oxy anions by the detachment of chlorine atoms from molecular ions were found. The O—H bond dissociation energies for o-, m-, and p-chlorophenol molecules were 3.74±0.11, 3.72±0.17, and 3.94±0.11 eV, respectively.     

Platinum nanoparticle catalysed coupling of phenol derivatives with 4-aminoantipyrine in aqueous medium

The oxidative coupling of phenols with 4-aminoantipyrine (AmNH₂) has been studied by UV–visible spectroscopy using platinum nanoparticles as catalyst. The rate of antipyrilquinoneimine dye formation depends on the nature of substrates, temperature, pH, and the use of microheterogeneous media such as sodium dodecylsulphate (SDS), cetyl trimethylammonium bromide (CTAB) and Triton X-100 (TX-100). The reactivity trend observed for differently substituted phenols follows the order: 3,5-dimethylphenol > phenol > o-chlorophenol > o-nitrophenol. The rate of dye formation is greater at acid pH than at basic pH and the optimum pH is 5.4. A reaction pathway is proposed, involving the activation of o-chlorophenol with AmNH₂ by metal nanoparticles and concomitant reactions of free radicals. Transmission electron microscopy results show that the particle size is 20 nm for the platinum nanoparticles involved in catalysis. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Determination of phenols by flow injection and liquid chromatography with on-line quinine-sensitized photo-oxidation and quenched luminol chemiluminescence detection

An on-line quinine-sensitized photo-oxidation with quenched chemiluminescence (CL) detection method is developed for phenols using flow injection (FI) and liquid chromatography (LC). This detection method is based on the decrease of light emission from the luminol CL reaction due to the photo-oxidation of phenols that scavenge the photogenerated reactive oxygen species (e.g. singlet oxygen () and superoxide (O₂⁻)). On-line photo-oxidation is achieved using a coil photo-reactor made from fluoroethylene-propylene copolymer tubing ( mm i.d.) coiled around a mercury UV lamp. A buffer of pH 7 and a concentration of 350 μM for quinine sulfate are determined optimum for the sensitized photo-oxidation. Using a carrier system flow rate of 60 μl/min, calibration curves taken by FI for 10 phenolic compounds in aqueous solutions showed this decreasing sensitivity order: 4-chlorophenol, phenol, 4-nitrophenol, 3-hydroxy-l-kynurenine, 2-nitrophenol, salicylate, 3-nitrophenol, catechol, 2,4-dinitrophenol, and 2,4-dichlorophenol. This detection method using two tandem coil photo-reactors is also applied for the LC separation of phenol, 4-nitrophenol and 4-chlorophenol on an octadecyl (C18) silica LC column using acetonitrile-H₂O (40:60, v/v) as a mobile phase. The quenched CL detection limits (about 1 μM or 20 pmol) for phenol and 4-chlorophenol are comparable to those for UV detection at 254 nm. Some selectivity in the quenched CL detection is evident by no interference in the FI phenol response even when benzaldehyde and phenethanol concentrations are 8 and 15 times that of phenol.     

Nitrosation kinetics of phenolic components of foods and beverages

The kinetics of the reactions between sodium nitrite and phenol or m-, o-, or p-cresol in potassium hydrogen phthalate buffers of pH 2.5–5.7 were determined by integration of the monitored absorbance of the C-nitroso reaction products. At pH > 3, the dominant reaction was C-nitrosation through a mechanism that appears to consist of a diffusion-controlled attack on the nitrosatable substrate by NO⁺/NO₂H₂⁺ ions followed by a slow proton transfer step; the latter step is supported by the observation of basic catalysis by the buffer which does not form alternative nitrosating agents as nitrosyl compounds. The catalytic coefficients of both anionic forms of the buffer have been determined. The observed order of substrate reactivities (o-cresol ≈ m-cresol > phenol ≫ p-cresol) is explained by the hyperconjugative effect of the methyl group in o- and m-cresol, and by its blocking the para position in p-cresol. Analysis of a plot of ΔH^# against ΔS^# shows that the reaction with p-cresol differs from those with o- and m-cresol as regards the formation and decomposition of the transition state. The genotoxicity of nitrosatable phenols is compared with their reactivity with NO⁺/NO₂H₂⁺. © 1997 John Wiley & Sons, Inc.     

Solid + liquid phase diagrams,NMR and colorimetric measurements of mixtures

Solid+liquid equilibrium, NMR and colorimetric measurements have been made for the mixtures of o-phenylenediamine+phenol, p-phenylenediamine+hydroquinone, m-phenylenediamine+phenol, m-phenylenediamine+hydroquinone, p-phenylenediamine+phenol, and p-phenylenediamine+hydroquinone. The types and melting temperatures of the complexes formed in these mixtures were ascertained from phase diagrams. The nature of the complexes was ascertained from colorimetric and NMR data.     

Photodissociation and collision-induced dissociation of molecular ions from methylphenol and chloromethylphenol

The photodissociation of molecular ions from a series of methylphenols and chloromethylphenols was studied using Fourier transform ion cyclotron resonance mass spectrometry (FTMS). The photodissociation spectra contain both UV and visible absorption maxima. The positions of these bands correlate well with solution electronic absorption spectra and photoelectron spectra, respectively, suggesting that photodissociating populations of the molecular ions have not rearranged. The molecular ion of benzyl alcohol can be readily distinguished from the isomeric 2- and 4-methylphenol ions on the basis of the position and intensity of the photodissociation bands, and the identity of the photoproduct. The p-chlorophenol isomers, 4-chloro-2-methylphenol and 4-chloro-3-methylphenol, cannot be distinguished by their photodissociation spectra. Minor differences exist between these spectra and that of the o-chlorophenol isomer 2-chloro-5-methylphenol, suggesting that the relative positions of the chloro and hydroxy groups may have a greater effect on photodissociation than the position of the methyl group. For comparison, low-energy collision-induced dissociation using FTMS was also performed on the same ions.     

Structure-dependent reversible mechanochromism of D-π-A triphenylamine derivatives

Three simple non-planar D-π-A TPA-based isomers (TPA-o, TPA-m, and TPA-p) were designed and synthesized via Suzuki reaction with higher yields. It was found that all of the three compounds had intramolecular charge transfer (ICT) properties resulting from electron donation from triphenylamine to the formyl moiety. Interestingly, TPA-based derivatives solids exhibited not only reversible mechanochromic behaviors, but structure-dependent emission properties. The solid emission studies illustrated that their fluorescence color could change reversibly between bright blue (455?nm), blue (445?nm), cyan (479?nm), and bright blue-green (497?nm), bright blue (460?nm), yellowish-green (511?nm) through grinding and dichloromethane (DCM) fuming treatment, giving the large spectral red-shifts of 42, 15, and 32?nm, respectively. The MFC activities of the three compounds are increased with the sequence of TPA-o (42?nm)?>?TPA-p (32?nm)?>?TPA-m (15?nm). The single crystal structure, powder X-ray diffraction (PXRD) and DSC studies indicated that the reversible phase change from crystalline to amorphous was responsible for MFC properties. This work demonstrated the feasibility of tuning the solid-state optical properties of fluorescent organic compounds by combining the simple alteration of chemical structure and the physical change of aggregate morphology under external stimuli. And these results will be of great help in understanding structure-property relationships of MFC mechanisms and designing new more MFC materials.     

Degradation of substituted phenols with different oxygen sources catalyzed by Co(II) and Cu(II) phthalocyanine complexes

Research on substituted phenol degradations has received substantial attention. In this work, effective Co(II) and Cu(II) phthalocyanine complexes as catalysts were studied to degrade toxic phenols to harmless products. The effect of various process parameters, such as initial concentration of phenol, catalyst, oxygen sources, and temperature on the degradation reaction was investigated to achieve maximum degradation efficiency. The catalytic activities of Co(II) and Cu(II) phthalocyanines were evaluated for oxidation of phenolic compounds such as p-nitrophenol, o-chlorophenol, 2,3-dichlorophenol, and m-methoxyphenol. Co(II) phthalocyanine displayed good catalytic performance in degradation of 2,3-dichlorophenol to 2,3-dichlorobenzaldehyde and 2,3-dichloro-1,4-benzoquinone with the highest TON and TOF values within 3?h at 50?°C. The fate of catalyst during the degradation process was followed by UV–Vis spectroscopy.     

Excess volumes of mixing of 1,2-dichloroethane and aromatic hydrocarbons

Excess volumes of mixing, V^E, for binary mixtures of 1,2-dichloroethane with benzene, toluene, o^?, m^?, and p-xylenes have been determined at 308.15 K over the complete composition range. V^E is positive for all these mixtures and varies in the order m-xylene >o-xylene >p-xylene > benzene > toluene. The experimental data have been analyzed in terms of the Prigogine's average potential cell model coupled with Balescu's theory. The calculated V^E values do not agree with the corresponding experimental values.     

Partial molar volumes of organic solutes in water. VIII. Nitrobenzene and nitrophenols at T=298 K to T=573 K and pressures up to 30 MPa

Density data for dilute aqueous solutions of nitrobenzene and three isomeric nitrophenols (2-, 3-, or 4-nitro-1-hydroxybenzene) are presented together with partial molar volumes at infinite dilution calculated from the experimental data. The measurements were performed at T=298.15 K up to either T=573.15 K (nitrobenzene, m-nitrophenol) or T=548.15 K (p-nitrophenol) or T=523.15 K (o-nitrophenol) and at either atmospheric pressure, or at pressures close to the saturated vapor pressure of water, and also at p=30 MPa. The data were obtained using a high-temperature high-pressure flow vibrating-tube densimeter for measurements at elevated pressures and a commercial vibrating-tube cell DMA 602HT for measurements at atmospheric pressure.     

A comparison of the relative energies of isomeric intermediates formed in electrophilic,radical, and nucleophilic aromatic substitution reactions

The relative energetics of isomeric σ-complex intermediates formed in electrophilic, free radical, and nucleophilic attack of Cl, H, and Me on PhCl and PhMe are compared for all positions: o, m, p, and ipso. The results are presented as ΔH, computed by the MINDO/3 method, for the appropriate isodesmic reaction with benzene. For the chlorobenzene intermediates, there is a marked increase in the relative preference for the ipso-position as the reactions change from electrophilic to free radical to nucleophilic. For toluene intermediates, the order of stability-p > o > m > ipso-is seen in all reactions except for one case, free radical methylation. In general, the free radical intermediates show the smallest range of energy differences. Comparison of predictions from these calculations with experimental results (largely partial rate factors and product ratios) shows some qualitative agreement.     

Liquid crystalline and photoactive poly[4,4′-stilbeneoxy]alkylbiphenylphosphates

A series of liquid crystalline and photoactive polymers were synthesized from biphenylphosphorodichloridate with various 4,4′-bis(m-hydroxyalkyloxy)stilbenes (m = 2, 4, 6, 8, 10) in chloroform by solution polycondensation method using an acid scavenger. The resultant polymers were characterized by inherent viscosity, FT-IR, ¹H, ¹³C and ³¹P NMR spectroscopies. The liquid crystalline (LC) properties were studied using HOPM and DSC and it was inferred that out of the five polymers synthesized, higher methylene chain containing polymers (m = 6, 8, 10) exhibited LC properties. Thermogravimetric analysis revealed that all the polymers were stable in between 290 and 367 °C and underwent degradation thereafter. The thermal stability and char yield of the polymers decreased with increase in flexible methylene chain. The photochemical properties of these polymers were investigated by UV and fluorescence spectroscopy. Crosslinking proceeds via 2π-2π cycloaddition reaction of the -CHCH- of the stilbene moieties. The rate of crosslinking increases with increase in methylene chain length in the polymer backbone. The fluorescence spectra showed that the longer methylene spacer containing polymers exhibited larger red-shifts than the shorter spacer containing polymers.