Degradation of phenolic compounds with hydrogen peroxide catalyzed by enzyme from Serratia marcescens AB 90027

In this paper, the degradation of phenolic compounds using hydrogen peroxide as oxidizer and the enzyme extract from Serratia marcescens AB 90027 as catalyst was reported. With such an enzyme/H2O2 combination treatment, a high chemical oxygen demand (COD) removal efficiency was achieved, e.g., degradation of hydroquinone exceeded 96%. From UV-visible and IR spectra, the degradation mechanisms were judged as a process of phenyl ring cleavage. HPLC analysis shows that in the degradation p-benzoquinone, maleic acid and oxalic acid were formed as intermediates and that they were ultimately converted to CO2 and H2O. With the enzyme/H2O2 treatment, vanillin, hydroquinone, catechol, o-aminophenol, p-aminophenol, phloroglucinol and p-hydroxybenzaldehyde were readily degraded, whereas the degradation of phenol, salicylic acid, resorcinol, p-cholorophenol and p-nitrophenol were limited. Their degradability was closely related to the properties and positions of their side chain groups. Electron-donating groups, such as -OH, -NH2 and -OCH3 enhanced the degradation, whereas electron-withdrawing groups, such as -NO2, -Cl and -COOH, had a negative effect on the degradation of these compounds in the presence of enzyme/H2O2. Compounds with -OH at ortho and para positions were more readily degraded than those with -OH at meta positions.     

Immobilization of β-cyclodextrin on gold surfaces by chemical derivatization of an 11-amino-1-undecanthiol self-assembled monolayer

A new methodology for the covalent functionalization of a SAM of 11-amino-1-undecanethiol, previously adsorbed on polycrystalline Au, was successfully applied in order to immobilize a β-CD layer on surface. A two steps synthetic strategy is proposed based on the activation of the SAM with di-(N-succinimidyl) carbonate for the further inclusion of the β-CD. The modification of the SAM was followed by PM-FTIRRAS, AFM imaging, CV, and EIS which confirmed the introduction of β-CD layer. The AFM images allowed the identification of homogeneously distributed β-CD aggregates over the Au grain microstructure. The electrode was characterized in the presence of electroactive species in solution, with the ability to form inclusion complexes with the β-CD cavity. Contrary to the reported for other thiolated CD derivative films, the results of this study showed the formation of well-packed and compact structures which strongly reduce non-specific adsorption phenomena. The redox response of the probes at the β-CD electrode was shown to appear at higher potentials with respect to the response at bare Au. Good correlation was found between the increase of the hydroquinone oxidation peak and, both, the scan rate used in CV experiments (typical behavior of surface-confined species) and the hydroquinone concentration. In the case of dopamine, the processes seem to shifted out of the potential window of SAM stability. The results suggest that this problem could be overcome by improving the design of the device.     

Alkylation of hydroquinone with methyl-tert-butyl-ether and tert-butanol

The alkylation of hydroquinone yields industrially important compounds, amongst which tert-butylhydroquinone is a very important precursor for its use in pharmaceuticals and in developing photographic plates. Twenty per cent (w/w) dodecatungstophosphoric acid supported on K10 montmorillonite clay (DTP/K10) was found to be a very efficient and novel catalyst in comparison with several others for alkylation of hydroquinone with different alkylating agents such as methyl-tert-butyl-ether (MTBE) and tert-butanol at 150°C in an autoclave. A summary of characterisation of DTP/K10 is provided and related to the activity. Various reaction parameters were also investigated and a kinetic model was built. The rate of alkylation with MTBE was much faster than that with tert-butanol. The reaction follows a typical second order kinetics at a fixed catalyst loading with weak adsorption of both the species. The energy of activation was found to be 19.34 kcal/mol.     

Mechanisms of Hydroquinone-Induced Growth Reduction in Leafy Spurge

Field observations indicate leafy spurge (Euphorbia esula) is inhibited by the presence of Antennaria microphylla. Hydroquinone (HQ), one of several compounds isolated from A. microphylla has been shown to inhibit leafy spurge seed germination, root elongation, and callus culture growth. The present study was designed to analyze the effects of HQ on water relations and photosynthesis of leafy spurge. Plants grown in 0.25 mM HQ had consistently higher leaf diffusive resistance and lower transpiration rates than control plants (P < 0.05). Chlorophyll fluorescence was significantly lower than controls (P < 0.05) towards the end of the treatment period. At the end of the treatment, tissue from 0.25 mM HQ plants had higher levels of ¹³C, indicating there had been a sustained interference with stomatal function. These data suggest that a disruption of the plant water balance is one mechanism of leafy spurge inhibition by A. microphylla.     

Electrochemical detection of hydroquinone by graphene and Pt-graphene hybrid material synthesized through a microwave-assisted chemical reduction process

We have synthesized graphene and Pt-graphene hybrid material by a microwave-assisted chemical reduction process and evaluated their application as electrode materials towards the electrochemical detection of hydroquinone. Graphene modified glass carbon electrode (GCE) showed a good performance for detecting hydroquinone due to the unique properties of graphene which increased the active surface area of the electrode and accelerated the electron transfer. The linear detection range of hydroquinone concentration was 20–115 μM with a sensitivity of 1.38 μA μM⁻¹ cm⁻²; the detection limit was estimated to be 12 μM (S/N = 3). The electrocatalytic activity of the Pt-graphene modified GCE was further improved due to the enhanced electron transfer and the linear detection range was 20–145 μM with the sensitivity of 3.56 μA μM⁻¹ cm⁻², detection limit 6 μM (S/N = 3).     

Cure rate of DGEBA/MDA/GN/HQ system by differential scanning calorimetry analysis

To compare investigations of the cure kinetics of DGEBA/MDA/GN/HQ system by different methods, the fractional life method, Kissinger equation, Barrett method and integral method were used. From the fractional life method, reaction orders were between 0.77 and 0.93 but had no correlation with cure temperature, and from the Kissinger equation, the activation energy was 11.08 kcal mol⁻¹ and pre-exponential factor was 2.78×10³ s⁻¹. For the second-order reaction by the Barrett method and integral method, the activation energy was 20 kcal mol⁻¹ and the pre-exponential factor was 8.5×10⁸ s⁻¹. By comparison of the Barrett model with experimental data, it was found that the Barrett model was useful for predicting the cure time at a given temperature.     

对苯二甲醚合成新工艺

介绍了一条对苯二甲醚的合成新方法,该方法利用化学平衡移动的原理,在反应的同时将产物移出反应体系,使得反应更为充分,不但提高了反应收率,而且大幅度降低了辅助原材料硫酸二甲酯的用量,同时因产物是与水蒸汽一同馏出,所得产品纯度极高,不需精制及可得到高纯度产品。     

Selective O-Alkylation Reaction of Hydroquinone with Methanol over Cs Ion-Exchanged Zeolites

O-alkylation reaction of hydroquinone with excess methanol was performed by using alkali metal ion-exchanged zeolite catalysts in a slurry type reactor to substitute the solid zeolite catalysts for the homogeneous liquid phase catalysts. This was also done to produce selectively mono-alkylated 4-methoxyphenol, a valuable intermediate for the perfume, flavor, food and photo industries. The effects of the basicity of various zeolites and reaction conditions such as temperature, reaction time and the amount of catalyst on the catalytic activity and selectivity were tested to maximize the yield of 4-methoxyphenol. Thus far, 84% selectivity at 95% conversion of hydroquinone was obtained at the optimum reaction conditions (240 ‡C, reaction with 0.6 g catalyst for 16 h), which was thought to result from the strong basic property and shape selectivity of the Cs ion-exchanged NaX zeolite.     

High sensitive simultaneous determination of catechol and hydroquinone at mesoporous carbon CMK-3 electrode in comparison with multi-walled carbon nanotubes and Vulcan XC-72 carbon electrodes

The simultaneous voltammetric determination of catechol (CC) and hydroquinone (HQ) has been achieved at a mesoporous carbon CMK-3 modified electrode in phosphate buffer solution (pH 7.0). At the electrode both CC and HQ can cause a pair of quasi-reversible and well-defined redox peaks and their peak potential difference increases. In comparison with multi-walled carbon nanotubes (MWCNTs) and Vulcan XC-72 carbon modified electrodes the CMK-3 modified electrode shows larger peak currents and higher adsorbed amounts for the two dihydroxybenzene isomers. This is related to the higher specific surface area of CMK-3. Under the optimized conditions, the linear concentration ranges for CC and HQ are 5 × 10⁻⁷ to 3.5 × 10⁻⁵ M and 1 × 10⁻⁶ to 3 × 10⁻⁵ M, respectively. In the presence of 5 μM isomer, the linear concentration range of CC (or HQ) is 5 × 10⁻⁷ to 2.5 × 10⁻⁵ M (or 5 × 10⁻⁷ to 2.0 × 10⁻⁵ M). The sensitivity for CC or HQ is 41 A M⁻¹ cm⁻² or 52 A M⁻¹ cm⁻², which is close to that without isomer. The detection limits (S/N = 3) for CC and HQ are 1 × 10⁻⁷ M after preconcentration on open circuit for 240 s.     

Highly sensitive and simultaneous determination of hydroquinone and catechol at poly(thionine) modified glassy carbon electrode

A simple and highly sensitive electrochemical method for the simultaneous and quantitative detection of hydroquinone (HQ) and catechol (CT) was developed, based on a poly(thionine)-modified glassy carbon electrode (GCE). The modified electrode showed excellent electrocatalytic activity and reversibility towards the oxidation of both HQ and CT in 0.1 M phosphate buffer solution (PBS, pH 7.0). The peak-to-peak separations (ΔE_p) between oxidation and reduction waves in CV were decreased significantly from 262 and 204 mV at the bare GCE, to 63 and 56 mV, respectively for HQ and CT at the poly(thionine) modified GCE. Furthermore, the redox responses from the mixture of HQ and CT were easily resolved in both CV and DPV due to a difference in the catalytic activity of the modified GCE to each component. The peak potential separation of ca. 0.1 V was large enough for the simultaneous determination of HQ and CT electrochemically. The oxidation peak currents of HQ and CT were linear over the range from 1 to 120 μM in the presence of 100 and 200 μM of HQ and CT, respectively. The modified electrode showed very high sensitivity of 1.8 and 1.2 μA μM⁻¹ cm⁻² for HQ and CT, respectively. The detection limits (S/N = 3) for HQ and CT were 30 and 25 nM, respectively. The developed sensor was successfully examined for real sample analysis with tap water and revealed stable and reliable recovery data.