Pulse radiolysis studies of 2‐ and 3‐hydroxybenzyl alcohols: inhibition of dehydration of ·OH‐(hydroxybenzyl alcohols) adducts by H2PO4− ions

Reactions of ·OH/O ^.? radicals and H‐atoms as well as specific oxidants such as Cl₂^.? and N₃· radicals have been studied with 2‐ and 3‐hydroxybenzyl alcohols (2‐ and 3‐HBA) at various pH using pulse radiolysis technique. At pH 6.8, ·OH radicals were found to react quite fast with both the HBAs (k = 7.8 × 10⁹ dm³ mol^?1 s^?1 with 2‐HBA and 2 × 10⁹ dm³ mol^?1 s^?1 with 3‐HBA) mainly by adduct formation and to a minor extent by H‐abstraction from ? CH₂OH groups. ·OH‐(HBA) adduct were found to undergo decay to give phenoxyl type radicals in a pH dependent way and it was also very much dependent on buffer‐ion concentrations. It was seen that ·OH‐(2‐HBA) and ·OH‐(3‐HBA) adducts react with HPO₄^2? ions (k = 2.1 × 10⁷ and 2.8 × 10⁷ dm³ mol^?1 s^?1 at pH 6.8, respectively) giving the phenoxyl type radicals of HBAs. At the same time, this reaction is very much hindered in the presence of H₂PO ions indicating the role of phosphate ion concentration in determining the reaction pathway of ·OH adduct decay to final stable product. In the acidic region adducts were found to react with H⁺ ions. At pH 1, reaction of ·OH radicals with HBAs gave exclusively phenoxyl type radicals. Proportion of the reducing radicals formed by H‐abstraction pathway in ·OH/O ^.? reactions with HBAs was determined following electron transfer to methyl viologen. H‐atom abstraction is the major pathway in O ^.? reaction with HBAs compared to ·OH radical reaction. H‐atom reaction with 2‐ and 3‐HBA gave transient species which were found to transfer electron to methyl viologen quantitatively. Copyright © 2010 John Wiley & Sons, Ltd.     

Cationic gemini surfactants as pseudostationary phases in micellar electrokinetic chromatography. Part I: Effect of head group

Two cationic gemini surfactants with pyrrolidinium or alkyl ammonium head groups with but-2-yne spacers, but with the same length hydrocarbon chain have been characterized with respect to their aggregation behaviors and separation power as pseudostationary phases (PSPs) for micellar electrokinetic chromatography (MEKC). They were compared with a commonly used PSP, sodium dodecylsulfate (SDS). The results suggest that the head groups of the surfactants have some effect on physicochemical properties such as critical micelle concentration (CMC), C₂₀, γ_CMC, partial specific volume, methylene selectivity and mobilities of the surfactants. CMC values of G1, G2 and SDS in pure water were found to be 0.82, 0.71, and 8.08 mM, respectively; they were reduced to 0.21, 0.11, and 3.0 mM when measured in 10 mM phosphate buffer at pH 7.0. G1 (α_CH2=2.74${\alpha }_{\text{C}{\text{H}}_2}=2.74$) and G2 (α_CH2=2.48${\alpha }_{\text{C}{\text{H}}_2}=2.48$) provided the most and the least hydrophobic environment, respectively. According to their partial specific volumes, geminis were found to have more flexible structures as compared with sodium dodecylsulfate. The effects of the head group structure were also characterized with the linear solvation energy relationship (LSER) model, which was able to evaluate the role of solute size, polarity/polarizability, and hydrogen bonding on retention and selectivity. The cohesiveness, hydrogen bond acidic and basic character of the surfactant systems were found to have the most significant influence on selectivity and MEKC retention of the gemini surfactants. It should be noted that with their large positive coefficient a values, G1 and G2 were found to be stronger HB acceptors than anionic and most of the cationic surfactants studied in the literature.     

A Novel Circuit Architecture for High Performance of High-order Subharmonic Mixers

A novel circuit architecture for high performance of high-order subharmonic (SH) mixers is proposed in this paper. According to the specified harmonic mixing order, one or more mixer diodes sub-arrays and corresponding power divider as well as phase shift network for RF and LO signals are arranged in the circuit. This proposed SH mixer circuit has improved conversion loss, wide dynamic range and high port isolation for high-order SH mixers. By phase cancellation of idle frequencies, the proposed SH mixer circuit can eliminate complicated design procedure of idle frequency circuits; by phase cancellation of leakage LO power to RF and IF port, and leakage RF power to LO port, the mixer circuit can get high port isolation in LO-IF/RF and RF-LO. The increased antiparallel diode pairs in each sub-array will also lead to well performance by lowering effective series resistance. The proposed SH mixer circuit can be easily realized with power divider and phase shift network for RF and LO signals. Supported in part by National Natural Science Foundation of China (NSFC) under Grants 60621002 and in part by NSFC under Grants 60471017.     

Efficacy of natural oils and conventional chemicals in the physical extraction of 4-hydroxybenzoic acid from aqueous solution

4-hydroxybenzoic acid (4-HBA) is a phenolcarboxylic acid and a valuable chemical with various pharmacological properties and a wide range of industrial applications. The present work is envisioned to retrieve 4-HBA from aqueous solution through physical extraction using natural oils (mustard oil, sunflower oil and soyabean oil) and chemicals (MIBK and 1-octanol) as solvent. The experimental evaluation of extraction equilibrium using aforesaid solvents is reported in the form of distribution coefficient (K_D), extraction efficiency (E_P %), partition coefficient (P) and dimerization constant (D). The results were analysed using several physicochemical aspects of the solvents utilized, such as the solvent polarity parameter, dielectric constant, and dipole moment. Further, the comparison of these extraction results was made with the results of our previous study which was with the solvents sesame oil, canola oil, benzene, toluene and p-ether. The results may be arranged in the increasing order with respect to average K_D and average E_P % for natural oils as canola oil (0.23, 18.85%) < mustard oil (0.25, 20.45%) < sunflower oil (0.27, 21.00%) < soyabean oil (0.34, 25.06%) < sesame oil (0.49, 33.24%) and for chemicals as benzene (0.08, 7.5%) < toluene (0.09, 8.25%) < p-ether (0.09, 8.32%) < MIBK (2.55, 71.41%) < 1-octanol (5.01, 83.01%).     

Nature of the transient species formed in the pulse radiolysis of 4‐hydroxybenzyl alcohol in aqueous solutions: observation of equilibrium in the reaction of OH‐adducts with HPO ions

Reactions of ^. OH/O ^.? radicals, H‐atoms as well as specific oxidants such as N and Cl radicals with 4‐hydroxybenzyl alcohol (4‐HBA) in aqueous solutions have been investigated at various pH values using the pulse radiolysis technique. At pH 6.8, ^. OH radicals were found to react with 4‐HBA (k = 6 × 10⁹ dm³ mol^?1 s^?1) mainly by contributing to the phenyl moiety and to a minor extent by H‐abstraction from the ? CH₂OH group. ^. OH radical adduct species of 4‐HBA, i.e., ^. OH‐(4‐HBA) formed in the addition reaction were found to undergo dehydration to give phenoxyl radicals of 4‐HBA. Decay rate of the adduct species was found to vary with pH. At pH 6.8, decay was very much dependent on phosphate buffer ion concentrations. Formation rate of phenoxyl radicals was found to increase with phosphate buffer ion concentration and reached a plateau value of 1.6 × 10⁵ s^?1 at a concentration of 0.04 mol dm^?3 of each buffering ion. It was also seen that ^. OH‐(4‐HBA) adduct species react with HPO ions with a rate constant of 3.7 × 10⁷ dm³ mol^?1 s^?1 and there was no such reaction with H₂PO ions. However, the rate of reaction of ^. OH‐(4‐HBA) adduct species with HPO ions decreased on adding KH₂PO₄ to the solution containing a fixed concentration of Na₂HPO₄ which indicated an equilibrium in the H⁺ removal from ^. OH‐(4‐HBA) adduct species in the presence of phosphate ions. In the acidic region, the ^. OH‐(4‐HBA) adduct species were found to react with H⁺ ions with a rate constant of 2.5 × 10⁷ dm³ mol^?1 s^?1. At pH 1, in the reaction of ^. OH radicals with 4‐HBA (k = 8.8 × 10⁹ dm³ mol^?1 s^?1), the spectrum of the transient species formed was similar to that of phenoxyl radicals formed in the reaction of Cl radicals with 4‐HBA at pH 1 (k = 2.3 × 10⁸ dm³ mol^?1 s^?1) showing that ^. OH radicals quantitatively bring about one electron oxidation of 4‐HBA. Reaction of ^. OH/O ^.? radicals with 4‐HBA by H‐abstraction mechanism at neutral and alkaline pH values gave reducing radicals and the proportion of the same was determined by following the extent of electron transfer to methyl viologen. H‐atom abstraction is the major pathway in the reaction of O ^.? radicals with 4‐HBA compared to the reaction of ^. OH radicals with 4‐HBA. At pH 1, transient species formed in the reactions of H‐atoms with 4‐HBA (k = 2.1 × 10⁹ dm³ mol^?1 s^?1) were found to transfer electrons to methyl viologen quantitatively. Copyright © 2009 John Wiley & Sons, Ltd.     

Selective multistage extraction process of biomolecules from vine shoots by a combination of biological,chemical, and physical treatments

A multistep extraction process was proposed to recover polyphenols, reducing sugars, and soluble lignin from vine shoots. A physical pretreatment by high voltage electrical discharges (HVED) was followed by an enzymatic hydrolysis and a final delignification step by alkaline hydrolysis. HVED before enzymatic hydrolysis enhanced the extraction of polyphenols (+72%), reducing sugars (+43%), and soluble lignin (+104%) as compared to control experiments (enzymatic hydrolysis). HVED also reinforced the subsequent delignification process by reducing 10% lignin content in exhausted residues. Identification and quantification of ferulic acid, resveratrol, p-coumaric acid, and hydroxybenzoic acid were carried out using high-performance liquid chromatography.