Moderate antioxidative efficiencies of flavonoids during peroxidation of methyl linoleate in homogeneous and micellar solutions

The relative reactivities as well as the stoichiometric coefficients for a number of flavonoids, catechols, and—for comparison—standard phenolic antioxidants were determined by analyzing the kinetics of oxygen consumption in organic and micellar systems, with peroxidation initiated by lipid- and water-soluble azo initiators. The results demonstrated that the flavonoids did not behave as classic phenolic antioxidants such as α-tocopherol, but showed only moderate chain-breaking activities. The results were in line with other structure-activity relationship studies on the importance of the B-ring catechol structure, the 2,3-double bond, and the 3,5-hydroxy groups. The data are discussed in view of possible explanations of the deviations flavonoids reveal in their behavior compared with regular phenolic antioxidants.     

Physiological deterioration of cassava roots

Rapid post-harvest physiological deterioration of cassava roots (Manihot esculenta Crantz) appears to be due essentially to wound responses, comparable to those observed in other plant storage organs. The wound responses observed include: increased activity of phenylalanine ammonia lyase, an enzyme associated with phenol biosynthesis; increased activity of peroxidase and polyphenol oxidase; formation of phenols/polyphenols including leucoanthocyanidins, catechins, sco-poletin and condensed tannins, and often the formation of a wound periderm. In cassava, the responses did not remain localised at wound surfaces in roots when held at low storage humidity but spread through the roots causing a discolouration of the vascular tissue and storage parenchyma. Roots stored at high humidity showed a more typical wound response with localised production of phenols and periderm formation.     

Effects of multiple weak interactions on the binding of phenolic compounds by polymeric adsorbents

To investigate the effects of multiple weak interactions on the binding of phenolic compounds by polymeric adsorbents, macroporous polystyrene (PS) resin and PS‐based adsorbents with different hydrogen‐bond acceptor atoms (PS CH₂( OCH₂CH₂)_n OCH₃, n = 0, 1, 2, and 3, denoted as PS‐EG₀, PS‐EG₁, PS‐EG₂, and PS‐EG₃) were prepared. The phenol adsorption strength order on these adsorbents was PS/PS‐EG₀ < PS‐EG₁ < PS‐EG₂ < PS‐EG₃, indicating that the adsorption on PS and PS‐EG₀ was driven by hydrophobic and π–π interactions, and the adsorption on PS‐EG₁, PS‐EG₂, and PS‐EG₃ was driven by a hydrogen bond in addition to hydrophobic and π–π interactions. PS‐EG₂ may adsorb a second phenol molecule on each binding site and PS‐EG₃ may adsorb second and third ones. The adsorption strength of resorcinol increased in the order of PS, PS‐EG₁, and PS‐EG₂, indicating that the adsorption was driven by 0, 1, and 2 hydrogen bonds in addition to hydrophobic and π–π interactions. Similarly, the adsorption of phloroglucinol on PS, PS‐EG₁, PS‐EG₂, and PS‐EG₃ was driven by 0, 1, 2, and 3 hydrogen bonds in addition to hydrophobic and π–π interactions because the adsorption strength increased in this order. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4652–4658, 2006     

Vanadium species in new catalysts for the selective oxidation of methane to formaldehyde: Activation of the catalytic sites

New vanadium oxide supported on mesoporous silica catalysts for the oxidation of methane to formaldehyde were investigated by infrared and Raman spectroscopies to identify and characterize the molecular structure of the most active and selective catalytic sites. In situ and operando experiments have been conducted in order to understand the redox and hydroxylation/dehydroxylation processes of the vanadium species. (SiO)₂VO(OH) species were identified in these catalysts in reaction conditions and shown to undergo a deprotonation at 580 °C under vacuum, leading to a site giving a photoluminescence band at 550 nm attributed to reverse radiative decay from the excited triplet state:

(V⁴⁺–O⁻)^*  (V⁵⁺O²⁻). An activation mechanism of vanadium monomeric species with electrophilic oxygen species is proposed.     

Electrochemical pre-treatment of effluents containing chlorinated compounds using an adsorbent

Electrochemical pre-treatment of industrial wastewater to remove refractory and/or toxic organic components, making them more amenable to biological treatment, is likely to be more cost-effective than using a physical or chemical process for complete organic removal. This paper demonstrates the use of a carbon-based adsorbent material that preferentially removes chlorinated organic compounds. Electrochemical regeneration of the adsorbent is shown to be a quick, easy and cheap process, because the adsorbent is both highly electrically conducting and non-porous. High regeneration rates over a number of cycles were obtained by passing a charge of 25 C g⁻¹ through a bed of adsorbent particles, at a current density of 20 mA cm⁻² for 10 min. The energy required to remove a kg of COD from an industrial wastewater was calculated to be 27 kWh.     

Electropolymerization of chlorinated phenols on a Pt electrode in alkaline solution. Part II: An electrochemical quartz crystal microbalance study

Electropolymerization of phenol and mono-, di-, tri-, pentachlorophenols was studied using EQCM on a Pt electrode at 0.78 V (SHE) in 1 M NaOH solution containing 0.1 M of the corresponding phenol. The highest electropolymerization rate was found for ortho-substituted chlorophenols indicating a weak fouling of the electrode. Low electropolymerization rates for para-substituted chlorophenols suggest a low permeability of the polymer film, resulting in rapid electrode fouling. The EQCM data suggest that electropolymerization of chlorophenols occurs without Cl-elimination for the monomers with unsubstituted ortho and para positions. Dechlorination is most pronounced for electropolymerization of para-substituted isomers. The mechanism of electropolymerization of chlorophenols is discussed.     

Phenolic compounds from vacuum pyrolysis of wood wastes

Various softwood and hardwood bark residues, primary sludges and softwood sawdust residues were processed by vacuum pyrolysis in a laboratory scale batch reactor. The pyrolysis oil, water, charcoal, and gas were recovered and analyzed. The pyrolysis oils were analyzed in details for their content in phenolic compounds after derivatization to their acetyl derivatives. The influence of temperature, heating rate, feedstock bed thickness, particle size and feedstock water pretreatment on the yield of phenols was investigated. The highest yield of phenols was obtained when hardwood bark was soaked in water for 48 hours and pyrolyzed at a temperature of 450°C and a heating rate of 10°C/min. Pyrolysis performance was evaluated in terms of total phenolic yield and composition.     

New acid catalyst comprising heteropoly acid on a mesoporous molecular sieve MCM-41

New solid acid catalysts, consisting of heteropoly acid (HPA) H₃PW₁₂O₄₀ (PW) supported on a mesoporous pure-silica molecular sieve MCM-41, have been prepared and characterized by nitrogen physisorption, X-ray diffraction, FT-IR, and³¹P magic angle spinning NMR. The PW/MCM-41 compositions with PW loadings from 10 to 50 wt% have 30 Å uniformly-sized mesopores. HPA retains the Keggin structure on the MCM-41 surface and forms finely dispersed HPA species. No HPA crystal phase is developed even at HPA loadings as high as 50 wt%. PW/MCM-41 exhibits higher catalytic activity than H₂SO₄ or bulk PW in liquid-phase alkylation of 4-t-butylphenol (TBP) by isobutene and styrene. In the alkylation of TBP by styrene, PW/MCM-41 shows a size selectivity compared to bulk PW and PW/SiO₂, providing higher yields of a 2-(1-phenylethyl)-4-t-butylphenol, at the expense of the more bulky 2,6-bis-(1-phenylethyl)-4-t-butylphenol. The PW/MCM-41 compositions, having strong acid sites and a regular mesoporous system, are promising catalysts for the acid-type conversion and formation of organic compounds of large molecular size.     

GAC-BAF联合工艺处理高浓度含酚废水

采用活性炭（GAC）吸附-曝气生物滤池（BAF）降解联合工艺处理高浓度含酚废水,对GAC吸附、再生,BAF降解,GAC—BAF联合工艺运行工况进行了研究。结果表明：该联合工艺能有效降解含酚废水;GAC吸附容量与进水流量无关,吸附效果在原水进水pH=3．0、温度20±2℃下达到最佳;反冲进水碱性条件下对GAC解吸再生有利,反冲流量对再生有一定影响;BAF对含酚废水的容忍浓度为1100mg／L,GAC再生废水进入BAF之前需稀释至微生物适宜的pH值和苯酚浓度;GAC—BAF联合工艺中GAC柱进水流量的选择应确保BAF床有足够时间对已吸附饱和的另一平行GAC柱完成再生。该联合工艺将GAC吸附和BAF生物降解结合成连续运行的方式,使得苯酚废水处理过程不受GAC再生的影响,解决了传统GAC吸附和生物降解不适宜处理高浓度含酚废水的缺点。     

化学模式识别——岭回归分光光度测定混合酚

将苯酚、间甲酚、对氯酚、邻氯酚和间氯酚等5种挥发酚与MBTH反应显色后,用分光光度法测定,能获极难分辨的混合物的吸收光谱.本文采用聚类分析对波长-吸光度数据进行特征删选后,再以因子分析-岭回归法解析光谱,成功的确定了混合体系中的物种数、种类和含量.将该法用于印染废水中5种酚的同时定性与定量测定,结果令人满意.