Benzene-free synthesis of catechol: interfacing microbial and chemical catalysis

The toxicity of aromatics frequently limits the yields of their microbial synthesis. For example, the 5% yield of catechol synthesized from glucose by Escherichia coli WN1/pWL1.290A under fermentor-controlled conditions reflects catechol's microbial toxicity. Use of in situ resin-based extraction to reduce catechol's concentration in culture medium and thereby its microbial toxicity during its synthesis from glucose by E. coli WN1/pWL1.290A led to a 7% yield of catechol. Interfacing microbial with chemical synthesis was then explored where glucose was microbially converted into a nontoxic intermediate followed by chemical conversion of this intermediate into catechol. Intermediates examined include 3-dehydroquinate, 3-dehydroshikimate, and protocatechuate. 3-Dehydroquinate and 3-dehydroshikimate synthesized, respectively, by E. coli QP1.1/pJY1.216A and E. coli KL3/pJY1.216A from glucose were extracted and then reacted in water heated at 290 degrees C to afford catechol in overall yields from glucose of 10% and 26%, respectively. The problematic extraction of these catechol precursors from culture medium was subsequently circumvented by high-yielding chemical dehydration of 3-dehydroquinate and 3-dehydroshikimate in culture medium followed by extraction of the resulting protocatechuate. After reaction of protocatechuate in water heated at 290 degrees C, the overall yields of catechol synthesized from glucose via chemical dehydration of 3-dehydroquinate and chemical dehydration of 3-dehydroshikimate were, respectively, 25% and 30%. Direct synthesis of protocatechuate from glucose using E. coli KL3/pWL2.46B followed by its extraction and chemical decarboxylation in water gave a 24% overall yield of catechol from glucose. In situ resin-based extraction of protocatechaute synthesized by E. coli KL3/pWL2.46B followed by chemical decarboxylation of this catechol percursor was then examined. This employment of both strategies for dealing with the microbial toxicity of aromatic products led to the highest overall yield with catechol synthesized in 43% overall yield from glucose.     

Verteilung des Kieselsäure-Brenzcatechin-Komplexes zwischen wäßrigen Lösungen und organischen Lösungsmitteln

The extraction of silicic acid as catechol complex by different organic solvents in presence of various organic bases has been studied. The influence of pH as well as of catechol und diphenylguanidine concentrations was tested. Ca. 100% extraction of silicic acid can be achieved at pH 9.2–9.3 by nitrobenzene, if the concentration of catechol in the aqueous phase is 0.5 M and that of diphenylguanidine in the organic phase > 0.25 M.     

从邻苯二酚合成3,4-亚甲二氧基苯甲醇

胡椒醇;从邻苯二酚合成3;4-亚甲二氧基苯甲醇     

Study on catalytic synthesis of 1,3-benzodioxoles by HY zeolite

The acetalization and ketalization of various aldehydes and ketones with catechol by using HY zeolite as catalyst were studied. Effect of the reaction time, mole ratio of reactants, and amount of catalyst on the yield of benzodioxoles were investigated. Results show that HY is an efficient catalyst for the acetalization and ketalization with high conversion and selectivity in mild conditions. The best reaction conditions: molar ratio of catechol to aldehydes or ketones is 1:1.4, catalyst amount is 3.5 g/l mol catechol, reaction time is 5 h. Under these conditions, the conversion and selectivity were over 50% and 97%, respectively. Translated from Huaxue Tongbao 2006, 69(6) (in Chinese)     

A catechol electrode based on spinach leaves

Minced spinach leaf (Spinacea oleracea) has a high activity of catechol oxidase (dimerizing) (EC 1.1.3.14), which is utilized for the determination of catechol by coupling the spinach tissue with a Clark oxygen electrode. The calibration graph for catechol is linear over the range 2×10^?5–8×10^?4 M (RSD 3%). The sensor retains its enzyme activity for at least 18 days. 4-Methylcatechol and glycolate interfere; glucose and ascorbate do not.     

HAIMCM-41介孔分子筛催化1，3-苯并二嗯茂烷合成的研究

研究了HAlMCM-41分子筛催化邻苯二酚与环己酮、丁酮、丙酮、丙醛、丁醛、异丁醛、戊醛、正己醛、正辛醛、苯甲醛、二苯甲酮等十余种醛(酮)的缩合反应.考察了反应时间、酚与醛(酮)的配比、HA1MCM-41分子筛用量、硅铝比、催化剂重用次数等因素对邻苯二酚与醛(酮)反应的影响.结果表明,当邻苯二酚与醛(酮)物质的量比为1:1.4,催化剂用量为3.5g/mol邻苯二酚,反应4h,分子筛n(SiO_2)/n(Al_2O_3)为15时,选择性一般在99.4%以上,转化率也一般在85.6%以上,因此,HAlMCM-41分子筛对邻苯二酚与醛(酮)的反应有较好的催化性能.     

Al-P-Ti-Si-O体系催化剂上乙醇和邻苯二酚的O-乙基化反应

采用常规沉淀法制备了Al-P-Ti-Si-O体系催化剂,并研究了邻苯二酚与乙醇在该催化剂上的气相O-乙基化反应,考察了催化剂组成对催化剂结构、酸性和反应性能的影响.结果表明,催化活性随表面酸量的增大而增大,选择性则随酸强度的降低而增高.对催化剂活性中心的研究表明,B酸中心是反应的可能活性中心.在适当条件下,Al₁-P_1.30Ti_0.30-Si_0.17催化剂上邻苯二酚转化率和目标产物收率分别可达到96%和90%,并在100h稳定性实验中没有活性衰减.     

Electrochemical sensing of catechol using a glassy carbon electrode modified with a composite made from silver nanoparticles, polydopamine, and graphene

We report on the modification of a glassy carbon electrode with a composite consisting of silver nanoparticles (AgNPs), polydopamine, and graphene to give an electrochemical sensor for catechol. The composite was characterized by transmission electron microscopy, and the electrochemical behavior of catechol at the modified electrode was studied by cyclic voltammetry. The electrochemical response is greatly enhanced and thought to result from a combination of beneficial effects including the good conductivity and large surface area of the AgNPs, the high conductivity of graphene, the synergistic effects of the composite, and the increased quantity of catechol that is adsorbed on the surface of the electrode. Differential pulse voltammetric responses are proportional to the concentration of catechol between 0.5 and 240?μM levels of catechol, and the detection limit is 0.1?μM (S/N?=?3). The performance of the sensor was evaluated with catechol-spiked water samples, and recoveries range from 96.5 % to 103.1 %. The results indicated that the composite presented here is a promising substrate for use in electrochemical sensing.

HMCM-22分子筛催化1,3-苯并二噁茂烷类化合物合成的研究

研究了HMCM-22分子筛催化邻苯二酚与环己酮、丁酮、丙酮、丙醛、丁醛、异丁醛、戊醛、异戊醛、正己醛、正辛醛、苯甲醛、二苯甲酮等十余种醛(酮)的缩合反应.考察了反应时间、酚与醛(酮)的配比、HMCM-22分子筛用量等因素对酚与醛(酮)反应的影响.结果表明,当酚与醛(酮)摩尔比为1∶1.4,催化剂用量为3.5 g/1mol醛(酮),反应5 h,选择性一般在97%以上,转化率也一般在70%以上,表明HMCM-22分子筛对邻苯二酚与醛(酮)的反应有较好的催化性能.     

Encapsulation of L-dopa and catechol in bovine serum albumin nanocarrier using desolvation method and their in vitro release studies

In the current study, the interaction between L-dopa and bovine serum albumin (BSA) as well as catechol and BSA is investigated separately. In order to achieve the optimum values for encapsulated efficiency (EE), the content of crosslinker/BSA, organic/aqueous phase, drug/BSA, stirring rate, and pH were closely studied taking the advantage of Taguchi method. Particle characterization was carried out using transmission electron microscopy and dynamic light scattering techniques. The most appropriate catechol and L-dopa nanoparticles in the size range of 100 nm and 65 nm, respectively, and at optimized conditions of drug/BSA = 0.1, pH = 7.4, crosslinker/BSA = 0.084, organic/aqueous phase = 4 and stirring rate 400 rpm were obtained. The most favorable EE (encapsulation efficiency) and LC (loading capacity) for L-dopa and catechol was estimated to be 88.1% and 83.6%, respectively, and the calculated LC% was achieved 93.4% and 89.7% for L-dopa and catechol, respectively. The chromatographic analyses results were also found to be in a good agreement with the obtained data for the calculated EE% and LC% values. in vitro release of loaded drugs from nanoparticles in phosphate-buffered saline (pH = 7.4, incubated at 37 ± 0.5°C under stirring rate of 100 rpm) showed the release of 78% catechol and 89% L-dopa during 480 min and 510 min, respectively.