Lignin from Annual Plants as Raw Material Source for Flavors and Basic Chemicals

The enzymatic conversion of lignins, possibly in combination with electrochemical oxidation, makes aromatics such as syringol, guaiacol, vanillin and catechol available in the qualities required by the fragrance industry. The lignins were obtained by soda digestion from wheat straw and Miscanthus, characterized and then converted with laccases. The overall yield amounted up to 9 wt % with a product spectrum confined to four substances. Catechol was the major product, with a fraction of ≈75 %. It can easily be isolated by extraction with acetone.     

Enzymic browning of sulphocatechol

When sulphur dioxide inhibits the enzymic browning of catechol catalysed by mushroom tyrosinase, the main reaction product is 4-sulphocatechol. When assessed for its browning potential, this product appears to be unreactive and does not inhibit the enzyme.     

Environmentally friendly, heterogeneous acid and base catalysis for the methylation of catechol: Chances for the control of chemo-selectivity

The properties of catalysts with (i) Brønsted-type acidity (H-mordenite and Al/P mixed oxide), (ii) Lewis-type acidity (Al trifluoride) or (iii) basic characteristics (Mg/Fe mixed oxide) were investigated in the gas-phase methylation of catechol. When methanol was used as the methylating agent, H-mordenite and AlF₃ gave high selectivities to guaiacol (the product of O-methylation) under mild reaction conditions, that is at very low catechol conversions. An increase in temperature led to the transformation of guaiacol to phenol and cresols, and to considerable catalyst deactivation. The basic catalyst Mg/Fe/O also favored an extensive degradation of guaiacol to phenol. On the mildly acidic catalyst Al/P mixed oxide a stable catalytic performance and a high selectivity to guaiacol at 40% catechol conversion were obtained. When methylformate, a more reactive methylating agent, was used with AlF₃ and Mg/Fe mixed oxide as catalysts, higher catechol conversions and slower deactivation rates could be achieved under mild reaction conditions, with a low extent of guaiacol degradation. However, methylformate rapidly decomposed when temperatures above 350 °C were used. Finally, tests were made by reacting catechol and diethoxymethane with acid catalysts, with the aim of synthesizing methylenedioxybenzene. The latter product was obtained with high selectivity, but with very low yield, due to both catalyst deactivation and decomposition of diethoxymethane.     

Analysis of microbial adaptation at enzyme level for enhancing biodegradation rate of BTX

Catechol was found to be a common intermediate in the degradation of benzene and toluene byAlcaligenes xyhsoxidans Y234, and the ring cleavage of the catechol mediated by catechol 1,2-dioxygenase was a rate-determining step. Since benzene induced higher level of catechol 1,2-dioxygenase than toluene, the cells pre-adapted to benzene showed higher degradation rate of benzene and toluene. The degradation rate ofm-xylene was also increased significantly when benzene-adapted cells were inoculated.m-Xylene was metabolized via 3-methyl catechol which was effectively cleaved by catechol 1,2-dioxygenase.     

Recovery of germanium from real fly ash leachates by ion-exchange extraction

Germanium recovery from real fly ash (FA) leachates was studied using ion-exchange procedures. The procedure was based on germanium complexation with catechol (CAT) in an aqueous solution followed by the retention of the Ge-CAT complex onto a conventional strongly basic anionic resin (IRA-900). A centred composite rotatable design (CCRD) with two factors was employed for experimental design and analysis of the results. The factors examined during sorption tests were CAT amount and resin dosage. Optimum values of these parameters were: a CAT/Ge molar ratio of 9 and resin/Ge dosage of 3, obtaining 96.1% germanium retention. The obtained response surface and mathematical model are significant with high correlation coefficients (R² = 0.8794).The maximum amount of retained germanium was calculated to be 215.5 mg/g resin. The elution of the germanium complex was achieved with acid solutions in an ethanol matrix.     

Organic phase PPO biosensor based on hydrophilic films of electropolymerized polypyrrole

We described herein, the construction of an organic phase enzyme electrode (OPEE) via polyphenol oxidase (PPO) entrapment within a hydrophilic polypyrrole film electrogenerated from on a new bispyrrolic derivative (1) containing a long hydrophilic spacer. The so-called “adsorption step procedure” was adopted for the preparation of the organic phase PPO biosensor. The amperometric detection of catechol was carried out in anhydrous chloroform at −0.2 V versus Ag/AgCl. The electroanalytical parameters of the biosensor strongly depend on its configuration and on the hydration state of the enzyme matrix. The best sensitivity obtained for catechol in chloroform was 15.6 mA M⁻¹ cm⁻².     

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.     

Antioxidant activity of compounds isolated from the pyroligneous acid, Rhizophora apiculata

The polyphenols (CPAE II) was isolated from the dichloromethane extract of the pyroligneous acid, Rhizophora apiculata by simultaneous acid base and solvent extraction method. Its qualitative and quantitative composition was studied by gas chromatography mass spectroscopy (GC/MS) and out of 57 peaks, 52 compounds were identified, representing 95.47% of the total polyphenols. The CPAE II was then fractionated to four fractions (F1–F4) by means of thin layer chromatography and silica gel column chromatography with dichloromethane, dichloromethane/chloroform/ethyl acetate mixture (8:1:1; 4:3:3, v/v/v), and ethyl acetate, respectively. The antioxidant properties of the CPAE II and the fractions were evaluated. Among the four fractions, fraction 1 (F1) was the most potent in DPPH radical scavenging activity and molybdenum (VI) reducing power. It was subjected to further purification by means of silica gel column chromatography with hexane, hexane/diethyl ether mixture (9:1, 6:1, 3:1, v/v), and diethyl ether, respectively. 2,6-Dimethoxyphenol (syringol) and dihydroxybenzenes (catechol and 3-methoxycatechol) were isolated and identified by GC/MS, ¹H NMR, ¹³C NMR spectral analyses, and confirmed by GC co-injection with authentic standards. Syringol, catechol and 3-methoxycatechol constitute 39.08, 4.21 and 1.10% of F1, respectively. Their antioxidant activities were evaluated by DPPH radical scavenging activity, ABTS radical cation scavenging activity, phosphomolybdenum and ferric reducing antioxidant power (FRAP). The trend in antioxidant capacity was similar in all the four assays, with dihydroxybenzenes > 2,6-dimethoxyphenols, although discrepancies in the ranking within the dihydroxybenzenes were present. These three compounds which showed significant antioxidant activities were isolated for the first time from the pyroligneous acid, R. apiculata.     

Photocatalytic oxidation and ozonation of catechol over carbon-black-modified nano-TiO2 thin films supported on Al sheet

The photocatalytic activity of the carbon-black-modified nano-TiO2) (CB-TiO2) thin films was 1.5 times higher than that of TiO2 thin films in degrading Reactive Brilliant Red X-3B. Photocatalytic oxidation and ozonation of catechol over CB-TiO2 thin films supported on Al sheet was investigated. The experiments showed that ozone concentrations had an important effect on TOC removal. The combined photocatalysis with UV irradiation and ozonation (TiO2/UV/O3) process considerably increased TOC removal rate compared to combined photocatalysis with UV irradiation and oxygen oxidation (TiO2/UV/O2) process, ozonation alone (O3) process, combined ozonation and UV irradiation (UV/O3) process. The complete mineralization of catechol followed pseudo-zero-order kinetics dependent upon ozone (oxygen) concentration and indicated catechol concentration did not affect the kinetics during UV/O3 and TiO2/UV/O3 (O2) processes. The kinetic study showed that the rate constants in the complete mineralization of catechol with TiO2/UV/O3 are 1.32-1.80 times higher than that of UV/O3 with the same concentration of ozone. The rate constants are 2.56-5.36 times higher than the maximal rate constants of TiO2/UV/O2 and 4.68-9.8 times higher than the maximal rate constants of TiO2/UV.