This study demonstrates the fabrication of mesoporous tungsten trioxide(WO_(3))-decorated flexible polyimide(PI)electrodes for the highly sensitive detection of catechol(CC)and hydroquinone(HQ),two environmental pollu...This study demonstrates the fabrication of mesoporous tungsten trioxide(WO_(3))-decorated flexible polyimide(PI)electrodes for the highly sensitive detection of catechol(CC)and hydroquinone(HQ),two environmental pollutants.Organic-inorganic composite dots are formed on flexible PI electrodes using evaporation-induced self-assembly(EISA)and electrospray methods.The EISA process is induced by a temperature gradient during electrospray,and the heated substrate partially decomposes the organic parts etched by O_(2) plasma,creating mesoporous structures.Differential pulse voltammetry and cyclic voltammetry demonstrate a linear correlation between analyte concentration and the electrochemical response.Computational studies support the spontaneous adsorption of CC and HQ molecules on model WO_(3) surfaces.The proposed sensor shows high sensitivity,a wide linear range,and a low detection limit for both individual and simultaneous determination of CC and HQ.Real sample analysis on river water confirms practical applicability.The WO_(3)-decorated PI electrode presents an efficient and reliable approach for detecting these pollutants,contributing to environmental safety measures.展开更多
It is of great significance to design epoxy coatings with superior antibacterial properties and high adhesive properties, as well as excellent processing, superior durability, and high transparency. However, it is sti...It is of great significance to design epoxy coatings with superior antibacterial properties and high adhesive properties, as well as excellent processing, superior durability, and high transparency. However, it is still a challenge because of the common complex design and synthesis. Herein, the bio-based monomer protocatechuic acid(PCA) was used as raw material, the catechol structure with high bonding and antibacterial properties was introduced into the flexible alkane segment of ethylene glycol diglycidyl ether(EGDE) through an efficient, and green method, and it was cured with isophorone diamine(IPDA) to prepare corresponding thermosets. The cured resins exhibited excellent allaround qualities, particularly in bonding and antibacterial. When 30% PCA was added to pure epoxy resin, the adhesion between substrate and coating increased from 4.40 MPa to 13.60 MPa and the antibacterial rate of coating against E. coli and S. aureus could approach 100%. All of this is due to the fact that the catechol structure present in PCA has the ability to interact with various substrates and alter the permeability of bacterial cell membranes. The architecture of this method offers a fresh approach to dealing with the issues of challenging raw material selection and complex synthesis techniques.展开更多
Synthetic polymer membranes are widely used in many applications,including,among others,water purification,protein separation,and medicine.However,the use of existing polymer membranes faces major challenges,such as t...Synthetic polymer membranes are widely used in many applications,including,among others,water purification,protein separation,and medicine.However,the use of existing polymer membranes faces major challenges,such as the trade-off between permeability and selectivity,membrane fouling,and poor mechanical strength.To address these problems the authors have focused their research on surface/interfacial tailoring and the structure-property relationship of polymer membranes used in liquid separation systems.Progress has been made as follows:(1)a methodology for membrane surface functionalization and nanofiltration(NF)membrane preparation based on mussel-inspired catecholic chemistry was proposed and established;(2)a class of mechanically robust and environmentally-responsive composite membranes with hydrogel pore-filled in rigid macroporous supports was designed and developed;(3)a methodology for surface tailoring and antifouling modification of polymer membranes based on amphiphilic copolymers was created and the scientific implications for amphiphilic polymer membranes elaborated;(4)an adsorption membrane with both filtration and adsorption functions was designed and developed to achieve rapid removal of trace micropollutants,including heavy metal ions,organic dyes,plasticizer,antibiotics,and others.This mini-review briefly summarizes this work.展开更多
Density functional theory (DFT) at B3LYP/6-31G(d,p) level was employed to calculate intramolecular hydrogen bond enthalpies (HIHB), O-H charge differences, O-H bond lengths and bond orders for various substituted cate...Density functional theory (DFT) at B3LYP/6-31G(d,p) level was employed to calculate intramolecular hydrogen bond enthalpies (HIHB), O-H charge differences, O-H bond lengths and bond orders for various substituted catechols and their radicals generated after H-abstraction. It was found that although the charge difference between hydrogen-bonded H and O played a role in determining HIHB, HIHB was mainly governed by the hydrogen bond length. As the oxygen-centered radical has great tendency to form a chemical bond with the H atom, hydrogen bond lengths in catecholic radicals are systematically shorter than those in catechols. Hence, the HIHB for the former are higher than those for the latter.展开更多
Polycyclic aromatic hydrocarbons （PAHs） in soil retain for a quite long period due to their hydrophobicity and aggregation properties. Biofilm-forming marine bacterial consortium （named as NCPR）, composed of Steno...Polycyclic aromatic hydrocarbons （PAHs） in soil retain for a quite long period due to their hydrophobicity and aggregation properties. Biofilm-forming marine bacterial consortium （named as NCPR）, composed of Stenotrophomonas acidaminiphila NCW702, Alcaligenes faecalis NCW402, Pseudomonas mendocina NR802, Pseudornonas aeruginosa N6P6, and Pseudomonas pseudoalcaligenes NP103, was used for the bioremediation of PAHs in a soil microcosm. Phenanthrene and pyrene were used as reference PAHs. Parameters that can affect PAH degradation, such as chemotaxis, solubility of PAHs in extracellular polymeric substances （EPS）, and catechol 2,3-dioxygenase （C230） activity, were evaluated. P. aeruginosa N6P6 and P. pseudoalcaligenes NP103 showed chemotactic movement towards both the reference PAHs. The solubility of both the PAHs was increased with an increase in EPS concentration （extracted from all the 5 selected isolates）. Significantly （P 〈 0.001） high phenanthrene （70.29%） and pyrene （55.54%） degradation was observed in the bioaugmented soil microcosm. The C230 enzyme activity was significantly （P 〈 0.05） higher in the bioaugmented soil mi- crocosm with phenanthrene added at 173.26 ± 2.06 nmol rain-1 mg-1 protein than with pyrene added at 61.80 ± 2.20 nmol min-1 mg-1 protein. The C230 activity and gas chromatography-mass spectrometer analyses indicated catechol pathway of phenanthrene metabolism. However, the metabolites obtained from the soil microcosm added with pyrene revealed both the catechol and phthalate pathways for pyrene degradation.展开更多
Bacterium strain EVA17 was isolated from an oil-contaminated soil, and identified as Sphingomonas sp. based on analysis of 16S rDNA sequence,cellular fatty acid composition and physiological-chemical tests. The salicy...Bacterium strain EVA17 was isolated from an oil-contaminated soil, and identified as Sphingomonas sp. based on analysis of 16S rDNA sequence,cellular fatty acid composition and physiological-chemical tests. The salicylate hydroxylase and catechol 2,3-dioxygenase(C23O) were detected in cell-free lysates, suggesting a pathway for phenanthrene catabolism via salicylate and catechol. Alignment showed that both of the C23O and GST genes of the strain EVA17 had high similarity with homologues of strains from genus Sphingomonas. The phylogenetic analysis based on 16S rDNA and C23O gene sequence indicated that EVA17 should be classified into genus Sphingomonas, although the two phylogenetic trees were slightly different from each other. The results of co-amplification and sequence determination indicated that GST gene should be located upstream of the C23O gene.展开更多
Biomass wastes(almond shell and olive tree pruning) were used in this work as raw materials for the extraction of high purity lignin by different delignification methods. A pretreatment stage was carried out to remove...Biomass wastes(almond shell and olive tree pruning) were used in this work as raw materials for the extraction of high purity lignin by different delignification methods. A pretreatment stage was carried out to remove the major hemicelluloses content in the solid feedstocks. Afterward, two sulfur-free pulping processes(soda and organosolv) were applied to extract the largest fraction of lignin. The extracted lignin contained in the liquors was isolated using selective precipitation methods to design a tailor-made technique for obtaining high-purity lignin(in all cases more 90% of purity was reached). Soda process allowed the extraction of more lignin(around 40%–47%) than organosolv process(lower than 20%) regardless of the lignocellulosic source employed.Once the different lignin samples were isolated and characterized, they were depolymerized for the obtaining of small phenolic compounds. Three main streams were produced after the reaction: phenolic enriched oil, residual lignin and coke. After the purification of these fractions, their quantifications and characterization were conducted.The most abundant product of the reaction was residual lignin generated by the undesirable repolymerization of the initial lignin with yields around 30%–45%. The yield of the stream enriched in phenolic oil was higher than 20%. Coke, the lowest added-value product, presented a yield lower than 12% in all the cases. Lignin from organosolv presented higher phenolic oil yields, mainly due to their lower molecular size. This parameter was, thus, considered a key factor to obtain higher yields.展开更多
In this study, extractive distillation has been applied to separate catechol （CAT） from carbofuran phenol （CFP） with high purity and yield. The relative volatility of CFP to CAT was measured, and the choice of sep...In this study, extractive distillation has been applied to separate catechol （CAT） from carbofuran phenol （CFP） with high purity and yield. The relative volatility of CFP to CAT was measured, and the choice of separating agents was investigated. The experimental results indicated that CFP/CAT is an azeotropic system with an azeotropic point at 93.40℃/0.400 kPa and an azeotropic mixture containing 49.96% of CFP and 50.04% of CAT. Data from the determination of the relative volatility have shown that separating agents such as diglycol and 4-butylcatechol （4-TBC） are able to increase the relative volatility up to 1.90. In one shot process batch extractive distillation of CFP mixture with 3% （by mass） diglycol as separating agent, the purity and yield of the obtained CFP was 99.0% and 95.0%, respectively, while the distillation without separating agent provided a purity and yield of only 98.0% and 90.0%, respectively, There was no residual separating agent found in the product.展开更多
The determination method of catechol by fluorescence quenching was developed.The assay was based on the combination of the unique property of gold nanoparticles with tyrosinase enzymatic reaction.In the presence of ty...The determination method of catechol by fluorescence quenching was developed.The assay was based on the combination of the unique property of gold nanoparticles with tyrosinase enzymatic reaction.In the presence of tyrosinase,the fluorescence of gold nanoparticles was quenched by catechol which can be employed to detect catechol.Under the optimal conditions,a linear range 5.0×10^(-7)-1.0×10^(-3) mol L^(-1) and a detection limit 1.0×10^(-7) mol L^(-1) of catechol were obtained.o-Quinone intermediate produced...展开更多
Bacterial-feeding nematodes can promote the bacterial activity through feeding.Bacterial abundance and their activity affect the degradation of polycyclic aromatic hydrocarbons(PAH) such as phenanthrene.The effects of...Bacterial-feeding nematodes can promote the bacterial activity through feeding.Bacterial abundance and their activity affect the degradation of polycyclic aromatic hydrocarbons(PAH) such as phenanthrene.The effects of bacterial-feeding nematodes,bacteria,and their interactions on the degradation of phenanthrene with or without glucose were studied through a microcosm experiment.The results showed that up to 57.0%of phenanthrene in mineral medium contaminated with phenanthrene was degraded in the control with bacteria alone and bacteria with the presence of nematodes and/or glucose increased the degradation of phenanthrene by 25.6%to 36.6%.Although both nematode and bacteria abundance decreased gradually,catechol 2,3-dioxygenase(C230) activity increased during the incubation period.Compared with bacteria alone,the presence of nematodes significantly increased C230 activity as well as the abundance of bacteria;this effect was more pronounced when glucose was present.The results imply that nematodes might promote the removal of phenanthrene from medium by stimulating bacteria and C230 activities.展开更多
The liquid phase alkylation of catechol with tert-butyl alcohol to produce4-tert-butyl catechol (4-TBC) was carried out over MCM-41, HZSM-5, H-exchanged montmorillonite andnovel acidic porous montmorillonite heterostr...The liquid phase alkylation of catechol with tert-butyl alcohol to produce4-tert-butyl catechol (4-TBC) was carried out over MCM-41, HZSM-5, H-exchanged montmorillonite andnovel acidic porous montmorillonite heterostructures (PMHs). Upon all catalysts tested, 4-TBC is themain product and 3-tert-butyl catechol (3-TBC) and 3,5-di-tert-butyl catechol are the sideproducts. The synthetic PMHs showed higher conversion of catechol and better selectivity to 4-TBCcompared to other solid acid catalysts tested. Over the PMHs derived from H-exchangedmontmorillonite through template extraction processes, the suitable reaction temperature is ca 410K, the ratio of catechol to tert-butyl alcohol is 1:2. Increasing the amount of catalyst (lowerweight hourly space velocity) can improve the conversion of catechol and influence the selectivityslightly. The reasonable reaction time is ca 8 h. The type and strength of acidity ofH-montmorillonite and PMH were determined by pyridine adsorption FT-IR and ammoniatemperature-programmed desorption techniques. The medium and strong acid sites are conducive toproducing 4-TBC and the weak acid sites to facilitating the 3-TBC formation. The differences betweenthe PMHs from calcination and those from extraction are attributed to proton migration and aciditychange in the gallery surface.展开更多
Ti-containing phosphate（ Ti-P-O ） catalysts with different molar ratios of P to Ti （0--2. 0 ） were synthesized and characterized by XRD, N2-adsorption/desorption, IR and temperature-programmed desorption （TPD） m...Ti-containing phosphate（ Ti-P-O ） catalysts with different molar ratios of P to Ti （0--2. 0 ） were synthesized and characterized by XRD, N2-adsorption/desorption, IR and temperature-programmed desorption （TPD） methods. The catalytic properties of Ti-P-O samples in the vapor-phase O-methylation of catechol with methanol were also studied. The catechol conversion increases with the increase of the molar ratio of P to Ti in a range of 0-0. 33, while a further increase in the P content leads to a decrease of the catalytic activity. Meanwhile, the selectivities of the catalysts to the main product（guaiacol） increase gradually with the increase of the molar ratio of P to Ti. The presence of relatively strong Lewis acidic and/or basic sites in the P-free catalyst should be responsible for the formation of C-alkylation products. The weak acid-base characteristics of the catalysts are favourable for the mono-O-methylation of catechol. In comparison with the Lewis acidic sites, the Bronsted acidic sites on the catalysts are more active for the title reaction.展开更多
A mixed self-assembled monolayers （SAMs） of thioctic acid （T-COOH） and thioctic acid amide （T-NH2） were used to immobilize tyrosinase for fabricating biosensor. The results showed that the mixed SAMs prepared fr...A mixed self-assembled monolayers （SAMs） of thioctic acid （T-COOH） and thioctic acid amide （T-NH2） were used to immobilize tyrosinase for fabricating biosensor. The results showed that the mixed SAMs prepared from solution at the ratio of 1：4 provided an excellent microenvironment for enzymatic reaction between tyrosinase and substrate. The biosensor exhibited a fast response and high sensitivity for sensing substrate.展开更多
Three titanium-containing aluminum phosphate catalysts with a general formula Al 0.77 Ti 0.23 PO 4 were prepared by the sol-gel method at room temperature(APTS), and a nonuniform precipitation procedure at ro...Three titanium-containing aluminum phosphate catalysts with a general formula Al 0.77 Ti 0.23 PO 4 were prepared by the sol-gel method at room temperature(APTS), and a nonuniform precipitation procedure at room temperature(APTR) and under reflux(APTF), respectively. The structural features and the surface properties of the three catalysts were determined by means of the physical adsorption of nitrogen at liquid N 2 temperature, XRD, UV-Vis, NH 3-TPD and IR of adsorbed pyridine. The vapor phase O-alkylation of catechol with ethanol over the prepared catalysts was studied. It was found that the activity and the selectivity of these catalysts are greatly dependent on the preparation method, and catalyst APTF shows the highest activity and selectivity. The characterization evidence indicates that the weak Brnsted acid sites were more effective for the reaction.展开更多
Catechol pollutants(CATPs)serving as chelating agents could coordinate with many metal ions to form various CATPs-metal complexes.Little information is available on the effects of complexation of metal ions on CATPs d...Catechol pollutants(CATPs)serving as chelating agents could coordinate with many metal ions to form various CATPs-metal complexes.Little information is available on the effects of complexation of metal ions on CATPs degradation.This work presents a systematical study of·OH-mediated degradation of catechol and catechol-metal complexes over the whole pH range in advanced oxidation processes(AOPs).Results show that the pH-dependent complexation of metal ions(Zn^(2+),Cu^(2+),Ti^(4+)and Fe^(3+))promotes the deprotonation of catechol under neutral and even acidic conditions.The radical adduct formation(RAF)reactions are both thermodynamically and kinetically favorable for all dissociation and complexa-tion species,and-OH/-O-group-containing C positions are more vulnerable to·OH attack.The kinetic results show that the complexation of the four metal ions offers a wide pH range of effectiveness for catechol degradation.At pH 7,the apparent rate constant(k_(app))values for different systems follow the order of catechol+Ti^(4+)≈catechol+Zn^(2+)>catechol+Cu^(2+)>catechol+Fe^(3+)>catechol.The mechanistic and kinetic results would greatly improve our understanding of the degradation of CATPs-metal and other organics-metal complexes in AOPs.The toxicity assessment indicates that the·OH-based AOPs have the ability for decreasing the toxicity and increasing the biodegradability during the processes of catechol degradation.展开更多
Adsorption of catechol from aqueous solution with the hypercrosslinked polymeric adsorbent NDA-100 and its derivatives AH-1, AH-2 and AH-3 aminated by dimethylamine, the commercial resin Amberlite XAD-4 and weakly bas...Adsorption of catechol from aqueous solution with the hypercrosslinked polymeric adsorbent NDA-100 and its derivatives AH-1, AH-2 and AH-3 aminated by dimethylamine, the commercial resin Amberlite XAD-4 and weakly basic anion exchanger resin D301 was compared. It was found that the aminated hypercrosslinked resins had the highest adsorption capacities among the tested polymers. The empirical Freundlich equation was successfully employed to describe the adsorption process. Specific surface area and micropore structure of the adsorbent, in company with tertiary amino groups on matrix affected the adsorption performance towards catechol. In addition, thermodynamic study was carried out to interpret the adsorption mechanism. Kinetic study testified that the tertiary amino groups on the polymer matrix could decrease the adsorption rate and increase the adsorption apparent activation energy.展开更多
The selective H2O2 oxidation reaction of phenol to catechol on Ln-ZrO2 catalyst has improved the selectivity to 85%, to compare with the conventional titania catalyst. With addition of rare earth such as lanthanum, ne...The selective H2O2 oxidation reaction of phenol to catechol on Ln-ZrO2 catalyst has improved the selectivity to 85%, to compare with the conventional titania catalyst. With addition of rare earth such as lanthanum, neodymium, to zirconia as catalyst, the selectivity is increased by 72% and 60% respectively in comparison with the bare titania catalyst.展开更多
Electrochemical oxidation of 4-methyl catechol（1a） is investigated in the presence of 1,3-indandione（3）as nucleophile in phosphate buffer solution（0.2 mol/L,pH 6） mixed with ethanol as organic green solvent（50...Electrochemical oxidation of 4-methyl catechol（1a） is investigated in the presence of 1,3-indandione（3）as nucleophile in phosphate buffer solution（0.2 mol/L,pH 6） mixed with ethanol as organic green solvent（50/50） using cyclic voltammetry and controlled-potential coulometry.The results indicated thatquinones derived from electro-oxidation of 1a,participated in a 1,4-Michael addition reaction with1,3-indandione（3） under ECCE mechanism.In this direction,a new bis-quinone was synthesized in high yield and good purity using a facile and convenient electrochemical pathway by carbon anode electrodes in an undivided cell.展开更多
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF),funded by the Ministry of Education(RS-202300243390 and 2020R1A5A1018052)supported by the Basic Science Research Program through the National Research Foundation of Korea,funded by the Ministry of Education(2022R1A3B1078163)supported by the Technology Innovation Program(Publicprivate joint investment semiconductor R&D program[K-CHIPS])to foster high-quality human resources(RS-2023-00235484)funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea)(1415187770)。
文摘This study demonstrates the fabrication of mesoporous tungsten trioxide(WO_(3))-decorated flexible polyimide(PI)electrodes for the highly sensitive detection of catechol(CC)and hydroquinone(HQ),two environmental pollutants.Organic-inorganic composite dots are formed on flexible PI electrodes using evaporation-induced self-assembly(EISA)and electrospray methods.The EISA process is induced by a temperature gradient during electrospray,and the heated substrate partially decomposes the organic parts etched by O_(2) plasma,creating mesoporous structures.Differential pulse voltammetry and cyclic voltammetry demonstrate a linear correlation between analyte concentration and the electrochemical response.Computational studies support the spontaneous adsorption of CC and HQ molecules on model WO_(3) surfaces.The proposed sensor shows high sensitivity,a wide linear range,and a low detection limit for both individual and simultaneous determination of CC and HQ.Real sample analysis on river water confirms practical applicability.The WO_(3)-decorated PI electrode presents an efficient and reliable approach for detecting these pollutants,contributing to environmental safety measures.
基金financially supported by the National Natural Science Foundation of China (Nos.U1909220 and 52003283)Science and Technology Innovation 2025 Major Project of Ningbo (Nos.2021Z092, 2022Z111 and 2022Z160)+1 种基金Defense Industrial Technology Development Program (No.JCKY2021513B001)the Research Project of Technology Application for Public Welfare of Ningbo City (No.202002N3122)。
文摘It is of great significance to design epoxy coatings with superior antibacterial properties and high adhesive properties, as well as excellent processing, superior durability, and high transparency. However, it is still a challenge because of the common complex design and synthesis. Herein, the bio-based monomer protocatechuic acid(PCA) was used as raw material, the catechol structure with high bonding and antibacterial properties was introduced into the flexible alkane segment of ethylene glycol diglycidyl ether(EGDE) through an efficient, and green method, and it was cured with isophorone diamine(IPDA) to prepare corresponding thermosets. The cured resins exhibited excellent allaround qualities, particularly in bonding and antibacterial. When 30% PCA was added to pure epoxy resin, the adhesion between substrate and coating increased from 4.40 MPa to 13.60 MPa and the antibacterial rate of coating against E. coli and S. aureus could approach 100%. All of this is due to the fact that the catechol structure present in PCA has the ability to interact with various substrates and alter the permeability of bacterial cell membranes. The architecture of this method offers a fresh approach to dealing with the issues of challenging raw material selection and complex synthesis techniques.
基金Project supported by the National Natural Science Foundation of China(Nos.51828301,51773175,and 51973185)the Fundamental Research Funds for the Central Universities,China。
文摘Synthetic polymer membranes are widely used in many applications,including,among others,water purification,protein separation,and medicine.However,the use of existing polymer membranes faces major challenges,such as the trade-off between permeability and selectivity,membrane fouling,and poor mechanical strength.To address these problems the authors have focused their research on surface/interfacial tailoring and the structure-property relationship of polymer membranes used in liquid separation systems.Progress has been made as follows:(1)a methodology for membrane surface functionalization and nanofiltration(NF)membrane preparation based on mussel-inspired catecholic chemistry was proposed and established;(2)a class of mechanically robust and environmentally-responsive composite membranes with hydrogel pore-filled in rigid macroporous supports was designed and developed;(3)a methodology for surface tailoring and antifouling modification of polymer membranes based on amphiphilic copolymers was created and the scientific implications for amphiphilic polymer membranes elaborated;(4)an adsorption membrane with both filtration and adsorption functions was designed and developed to achieve rapid removal of trace micropollutants,including heavy metal ions,organic dyes,plasticizer,antibiotics,and others.This mini-review briefly summarizes this work.
基金supported by the National Natural Science Foundation of China (Grant No. 30100035).
文摘Density functional theory (DFT) at B3LYP/6-31G(d,p) level was employed to calculate intramolecular hydrogen bond enthalpies (HIHB), O-H charge differences, O-H bond lengths and bond orders for various substituted catechols and their radicals generated after H-abstraction. It was found that although the charge difference between hydrogen-bonded H and O played a role in determining HIHB, HIHB was mainly governed by the hydrogen bond length. As the oxygen-centered radical has great tendency to form a chemical bond with the H atom, hydrogen bond lengths in catecholic radicals are systematically shorter than those in catechols. Hence, the HIHB for the former are higher than those for the latter.
基金supported in part by the Department of Biotechnology, Ministry of Science and Technology, Government of India (No. BT/PR14998/GBD/ 27/279/2010)
文摘Polycyclic aromatic hydrocarbons （PAHs） in soil retain for a quite long period due to their hydrophobicity and aggregation properties. Biofilm-forming marine bacterial consortium （named as NCPR）, composed of Stenotrophomonas acidaminiphila NCW702, Alcaligenes faecalis NCW402, Pseudomonas mendocina NR802, Pseudornonas aeruginosa N6P6, and Pseudomonas pseudoalcaligenes NP103, was used for the bioremediation of PAHs in a soil microcosm. Phenanthrene and pyrene were used as reference PAHs. Parameters that can affect PAH degradation, such as chemotaxis, solubility of PAHs in extracellular polymeric substances （EPS）, and catechol 2,3-dioxygenase （C230） activity, were evaluated. P. aeruginosa N6P6 and P. pseudoalcaligenes NP103 showed chemotactic movement towards both the reference PAHs. The solubility of both the PAHs was increased with an increase in EPS concentration （extracted from all the 5 selected isolates）. Significantly （P 〈 0.001） high phenanthrene （70.29%） and pyrene （55.54%） degradation was observed in the bioaugmented soil microcosm. The C230 enzyme activity was significantly （P 〈 0.05） higher in the bioaugmented soil mi- crocosm with phenanthrene added at 173.26 ± 2.06 nmol rain-1 mg-1 protein than with pyrene added at 61.80 ± 2.20 nmol min-1 mg-1 protein. The C230 activity and gas chromatography-mass spectrometer analyses indicated catechol pathway of phenanthrene metabolism. However, the metabolites obtained from the soil microcosm added with pyrene revealed both the catechol and phthalate pathways for pyrene degradation.
文摘Bacterium strain EVA17 was isolated from an oil-contaminated soil, and identified as Sphingomonas sp. based on analysis of 16S rDNA sequence,cellular fatty acid composition and physiological-chemical tests. The salicylate hydroxylase and catechol 2,3-dioxygenase(C23O) were detected in cell-free lysates, suggesting a pathway for phenanthrene catabolism via salicylate and catechol. Alignment showed that both of the C23O and GST genes of the strain EVA17 had high similarity with homologues of strains from genus Sphingomonas. The phylogenetic analysis based on 16S rDNA and C23O gene sequence indicated that EVA17 should be classified into genus Sphingomonas, although the two phylogenetic trees were slightly different from each other. The results of co-amplification and sequence determination indicated that GST gene should be located upstream of the C23O gene.
基金the Spanish Ministry of Economy and Competitiveness(CTQ2013-41246-R)the Department of Education of the Basque Government(project IT1008-16)the University of the Basque Country(postdoctoral fellowship no.ESPDOC15/044)for financially supporting this work
文摘Biomass wastes(almond shell and olive tree pruning) were used in this work as raw materials for the extraction of high purity lignin by different delignification methods. A pretreatment stage was carried out to remove the major hemicelluloses content in the solid feedstocks. Afterward, two sulfur-free pulping processes(soda and organosolv) were applied to extract the largest fraction of lignin. The extracted lignin contained in the liquors was isolated using selective precipitation methods to design a tailor-made technique for obtaining high-purity lignin(in all cases more 90% of purity was reached). Soda process allowed the extraction of more lignin(around 40%–47%) than organosolv process(lower than 20%) regardless of the lignocellulosic source employed.Once the different lignin samples were isolated and characterized, they were depolymerized for the obtaining of small phenolic compounds. Three main streams were produced after the reaction: phenolic enriched oil, residual lignin and coke. After the purification of these fractions, their quantifications and characterization were conducted.The most abundant product of the reaction was residual lignin generated by the undesirable repolymerization of the initial lignin with yields around 30%–45%. The yield of the stream enriched in phenolic oil was higher than 20%. Coke, the lowest added-value product, presented a yield lower than 12% in all the cases. Lignin from organosolv presented higher phenolic oil yields, mainly due to their lower molecular size. This parameter was, thus, considered a key factor to obtain higher yields.
基金Supported by the National High Technology Research and Development Program of China(2006AA03Z460)
文摘In this study, extractive distillation has been applied to separate catechol （CAT） from carbofuran phenol （CFP） with high purity and yield. The relative volatility of CFP to CAT was measured, and the choice of separating agents was investigated. The experimental results indicated that CFP/CAT is an azeotropic system with an azeotropic point at 93.40℃/0.400 kPa and an azeotropic mixture containing 49.96% of CFP and 50.04% of CAT. Data from the determination of the relative volatility have shown that separating agents such as diglycol and 4-butylcatechol （4-TBC） are able to increase the relative volatility up to 1.90. In one shot process batch extractive distillation of CFP mixture with 3% （by mass） diglycol as separating agent, the purity and yield of the obtained CFP was 99.0% and 95.0%, respectively, while the distillation without separating agent provided a purity and yield of only 98.0% and 90.0%, respectively, There was no residual separating agent found in the product.
基金supported by the National Natural Science Foundation of China(No.20875059)
文摘The determination method of catechol by fluorescence quenching was developed.The assay was based on the combination of the unique property of gold nanoparticles with tyrosinase enzymatic reaction.In the presence of tyrosinase,the fluorescence of gold nanoparticles was quenched by catechol which can be employed to detect catechol.Under the optimal conditions,a linear range 5.0×10^(-7)-1.0×10^(-3) mol L^(-1) and a detection limit 1.0×10^(-7) mol L^(-1) of catechol were obtained.o-Quinone intermediate produced...
基金supported by the Shandong Academy of Agricultural Sciences Youth Fund,China(No.2014QNM49)the National Key Technology R&D Program during the 12th Five-Year Plan Period (No.2012BAD15B02)+1 种基金the Program of Taishan Scholars for Overseas Experts,Chinathe Key Project of Science and Technology Innovation of Shandong Academy of Agricultural Sciences,China(No.2014CXZ01)
文摘Bacterial-feeding nematodes can promote the bacterial activity through feeding.Bacterial abundance and their activity affect the degradation of polycyclic aromatic hydrocarbons(PAH) such as phenanthrene.The effects of bacterial-feeding nematodes,bacteria,and their interactions on the degradation of phenanthrene with or without glucose were studied through a microcosm experiment.The results showed that up to 57.0%of phenanthrene in mineral medium contaminated with phenanthrene was degraded in the control with bacteria alone and bacteria with the presence of nematodes and/or glucose increased the degradation of phenanthrene by 25.6%to 36.6%.Although both nematode and bacteria abundance decreased gradually,catechol 2,3-dioxygenase(C230) activity increased during the incubation period.Compared with bacteria alone,the presence of nematodes significantly increased C230 activity as well as the abundance of bacteria;this effect was more pronounced when glucose was present.The results imply that nematodes might promote the removal of phenanthrene from medium by stimulating bacteria and C230 activities.
基金Supported by the National Natural Science Foundation of China (No. 20376075) the Natural Science Foundation of Zhejiang Province (No. 201057).
文摘The liquid phase alkylation of catechol with tert-butyl alcohol to produce4-tert-butyl catechol (4-TBC) was carried out over MCM-41, HZSM-5, H-exchanged montmorillonite andnovel acidic porous montmorillonite heterostructures (PMHs). Upon all catalysts tested, 4-TBC is themain product and 3-tert-butyl catechol (3-TBC) and 3,5-di-tert-butyl catechol are the sideproducts. The synthetic PMHs showed higher conversion of catechol and better selectivity to 4-TBCcompared to other solid acid catalysts tested. Over the PMHs derived from H-exchangedmontmorillonite through template extraction processes, the suitable reaction temperature is ca 410K, the ratio of catechol to tert-butyl alcohol is 1:2. Increasing the amount of catalyst (lowerweight hourly space velocity) can improve the conversion of catechol and influence the selectivityslightly. The reasonable reaction time is ca 8 h. The type and strength of acidity ofH-montmorillonite and PMH were determined by pyridine adsorption FT-IR and ammoniatemperature-programmed desorption techniques. The medium and strong acid sites are conducive toproducing 4-TBC and the weak acid sites to facilitating the 3-TBC formation. The differences betweenthe PMHs from calcination and those from extraction are attributed to proton migration and aciditychange in the gallery surface.
基金Supported by the Development Project of Science and Technology of Jilin Province(Nos. 20050309-1 and 20040563), the Spe-cialized Research Fund for the Doctoral Program of Higher Education(No.20040183003), CNPC(No.JTGS 20040010), and the Na-tional Natural Science Foundation of China(No.20403006)
文摘Ti-containing phosphate（ Ti-P-O ） catalysts with different molar ratios of P to Ti （0--2. 0 ） were synthesized and characterized by XRD, N2-adsorption/desorption, IR and temperature-programmed desorption （TPD） methods. The catalytic properties of Ti-P-O samples in the vapor-phase O-methylation of catechol with methanol were also studied. The catechol conversion increases with the increase of the molar ratio of P to Ti in a range of 0-0. 33, while a further increase in the P content leads to a decrease of the catalytic activity. Meanwhile, the selectivities of the catalysts to the main product（guaiacol） increase gradually with the increase of the molar ratio of P to Ti. The presence of relatively strong Lewis acidic and/or basic sites in the P-free catalyst should be responsible for the formation of C-alkylation products. The weak acid-base characteristics of the catalysts are favourable for the mono-O-methylation of catechol. In comparison with the Lewis acidic sites, the Bronsted acidic sites on the catalysts are more active for the title reaction.
基金financially supported by the Scientific Research Foundation of State Education Ministry of China (Jiaowaisiliu[2008]890)Research Foundation of Education Department of Hebei Province of China(No. 2007132)
文摘A mixed self-assembled monolayers （SAMs） of thioctic acid （T-COOH） and thioctic acid amide （T-NH2） were used to immobilize tyrosinase for fabricating biosensor. The results showed that the mixed SAMs prepared from solution at the ratio of 1：4 provided an excellent microenvironment for enzymatic reaction between tyrosinase and substrate. The biosensor exhibited a fast response and high sensitivity for sensing substrate.
基金Supported by the Foundation of Science of Jilin Province Science and Technique Com mittee( No.990 5 4 6 )
文摘Three titanium-containing aluminum phosphate catalysts with a general formula Al 0.77 Ti 0.23 PO 4 were prepared by the sol-gel method at room temperature(APTS), and a nonuniform precipitation procedure at room temperature(APTR) and under reflux(APTF), respectively. The structural features and the surface properties of the three catalysts were determined by means of the physical adsorption of nitrogen at liquid N 2 temperature, XRD, UV-Vis, NH 3-TPD and IR of adsorbed pyridine. The vapor phase O-alkylation of catechol with ethanol over the prepared catalysts was studied. It was found that the activity and the selectivity of these catalysts are greatly dependent on the preparation method, and catalyst APTF shows the highest activity and selectivity. The characterization evidence indicates that the weak Brnsted acid sites were more effective for the reaction.
基金This work was supported by the National Natural Science Foundation of China(Nos.21777087,21876099 and 21477065)the Fundamental Research Fund of Shandong University(No.2018JC015).
文摘Catechol pollutants(CATPs)serving as chelating agents could coordinate with many metal ions to form various CATPs-metal complexes.Little information is available on the effects of complexation of metal ions on CATPs degradation.This work presents a systematical study of·OH-mediated degradation of catechol and catechol-metal complexes over the whole pH range in advanced oxidation processes(AOPs).Results show that the pH-dependent complexation of metal ions(Zn^(2+),Cu^(2+),Ti^(4+)and Fe^(3+))promotes the deprotonation of catechol under neutral and even acidic conditions.The radical adduct formation(RAF)reactions are both thermodynamically and kinetically favorable for all dissociation and complexa-tion species,and-OH/-O-group-containing C positions are more vulnerable to·OH attack.The kinetic results show that the complexation of the four metal ions offers a wide pH range of effectiveness for catechol degradation.At pH 7,the apparent rate constant(k_(app))values for different systems follow the order of catechol+Ti^(4+)≈catechol+Zn^(2+)>catechol+Cu^(2+)>catechol+Fe^(3+)>catechol.The mechanistic and kinetic results would greatly improve our understanding of the degradation of CATPs-metal and other organics-metal complexes in AOPs.The toxicity assessment indicates that the·OH-based AOPs have the ability for decreasing the toxicity and increasing the biodegradability during the processes of catechol degradation.
文摘Adsorption of catechol from aqueous solution with the hypercrosslinked polymeric adsorbent NDA-100 and its derivatives AH-1, AH-2 and AH-3 aminated by dimethylamine, the commercial resin Amberlite XAD-4 and weakly basic anion exchanger resin D301 was compared. It was found that the aminated hypercrosslinked resins had the highest adsorption capacities among the tested polymers. The empirical Freundlich equation was successfully employed to describe the adsorption process. Specific surface area and micropore structure of the adsorbent, in company with tertiary amino groups on matrix affected the adsorption performance towards catechol. In addition, thermodynamic study was carried out to interpret the adsorption mechanism. Kinetic study testified that the tertiary amino groups on the polymer matrix could decrease the adsorption rate and increase the adsorption apparent activation energy.
文摘The selective H2O2 oxidation reaction of phenol to catechol on Ln-ZrO2 catalyst has improved the selectivity to 85%, to compare with the conventional titania catalyst. With addition of rare earth such as lanthanum, neodymium, to zirconia as catalyst, the selectivity is increased by 72% and 60% respectively in comparison with the bare titania catalyst.
基金Semnan University Research Council,Semnan,Iran for financial supports to this work
文摘Electrochemical oxidation of 4-methyl catechol（1a） is investigated in the presence of 1,3-indandione（3）as nucleophile in phosphate buffer solution（0.2 mol/L,pH 6） mixed with ethanol as organic green solvent（50/50） using cyclic voltammetry and controlled-potential coulometry.The results indicated thatquinones derived from electro-oxidation of 1a,participated in a 1,4-Michael addition reaction with1,3-indandione（3） under ECCE mechanism.In this direction,a new bis-quinone was synthesized in high yield and good purity using a facile and convenient electrochemical pathway by carbon anode electrodes in an undivided cell.
