Dioxygen activations constitute one of core issues in copper-dependent metalloenzymes. Upon O_(2) activation, copper-dependent metalloenzymes such as particulate methane monooxygenases(pM MOs), lytic polysaccharide mo...Dioxygen activations constitute one of core issues in copper-dependent metalloenzymes. Upon O_(2) activation, copper-dependent metalloenzymes such as particulate methane monooxygenases(pM MOs), lytic polysaccharide monooxygenases(LPMOs) and binuclear copper enzymes PHM and DβM, are able to perform various challenging C–H bond activations. Meanwhile, various copper-oxygen core containing complexes have been synthetized to mimic the active species of metalloenzymes. Dioxygen activation by mononuclear copper active site may generate various copper-oxygen intermediates, including Cu(Ⅱ)-superoxo, Cu(Ⅱ)-hydroperoxo, Cu(Ⅱ)-oxyl as well as the Cu(Ⅲ)-hydroxide species. Intriguingly, all these species have been invoked as the potential active intermediates for C–H/O–H activations in either biological or synthetic systems. Due to the poor understanding on reactivities of copper-oxygen complex, the nature of active species in both biological and synthetic systems are highly controversial. In this account, we will compare the reactivities of various mononuclear copper-oxygen species between biological systems and the synthetic systems. The present study is expected to provide the consistent understanding on reactivities of various copper-oxygen active species in both biological and synthetic systems.展开更多
Carbonyl peroxy radicals (RC(O)O2) are the ubiquitous radical intermediates in the atmospheric oxidation of volatile organic compounds. In this work, theoretical studies are carried out to explore the role of the unim...Carbonyl peroxy radicals (RC(O)O2) are the ubiquitous radical intermediates in the atmospheric oxidation of volatile organic compounds. In this work, theoretical studies are carried out to explore the role of the unimolecular H-migration in the carbonyl peroxy radicals by using quantum chemistry and kinetics calculations. The results showed that H-migration could be significant in the atmosphere at least in CH3CH2CH2C(O)O2 and (CH3)2CHCH2C(O)O2 with rates of ∽0.012 and -0.58^-1 at 298 K. Subsequent reactions of CH3CHCH2C(O)OOH would lead to the products with multi-functional groups, which might affect the aerosol formation process;while (CH3)2CCH2C(O)OOH would transform to formaldehyde and acetone in a few steps. These processes would be important for the atmospheric modelling of volatile organic compounds under low-NOx conditions.展开更多
In order to f urther improve the photosensitizing activity of hypocrellin B(HB), the complex o f 5,8 di Br HB with Al 3+ was designed and synthesized in high yield. Th e complex of aluminium ion with 5,8 di Br HB is a...In order to f urther improve the photosensitizing activity of hypocrellin B(HB), the complex o f 5,8 di Br HB with Al 3+ was designed and synthesized in high yield. Th e complex of aluminium ion with 5,8 di Br HB is a new water soluble perylene quinonoid derivative with enhanced absorption over HB in the phototherapeutic wi ndow (600-900 nm). Electron paramagnetic resonance (EPR) measurement and 9,10 diphenyl anthracene bleaching methods were used to investigate the photosensiti zing activity of [Al 2(5,8 di Br HB)Cl 4] n in the prese nce of oxygen. Singlet oxygen, superoxide anion radical, hydroxyl radical can be generated by [Al 2(5,8 di Br HB)Cl 4] n photosensit ization. The results showed that the production of hydroxyl radical ( · OH) by [Al 2(5,8 di Br HB)Cl 4] n photosensitization comes from the Fenton Haber Weiss reaction and the decom position of DMPO 1O 2 adduct. Formation of H 2O 2 as one of main intermedi ates in the photogeneration of hydroxyl radical was detected by using the cataly zed oxidation of the DPD reagent by the POD enzyme method. Moreover, the experim ents of EPR spin trap and catalase enzyme excluded the effect of organoperoxide on DPD oxidization. These results further support the proposed mechanism of · OH formation.展开更多
There has been carried out the process of noncatalytic oxidation of natural methane in the presence of hydrogen peroxide at the temperatures 840-880 ℃ what permitted to obtain hydrogen with high yield of hydrogen (...There has been carried out the process of noncatalytic oxidation of natural methane in the presence of hydrogen peroxide at the temperatures 840-880 ℃ what permitted to obtain hydrogen with high yield of hydrogen (74%) with inconsiderable quantity of CO (0.4%) in converted gas. As observed in the experiment, a variation of H2O2 concentration in the aqueous solution and other basic parameters of the process may induce the synthesis of gas with given H2:CO ratio for its further application in methanol or ammonia synthesis. In the latter process low CO concentration is required. Compared with the common high-temperature conversion of natural gas and further carbon oxide conversion on a catalyst, the current process promotes process simplification: the reaction is implemented at relatively low temperature (860-900 ℃ instead of 1400-1600 ℃for existing non-catalytic processes of methane conversion) and an additional unit for catalytic conversion of carbon oxide is excluded (in NH3 production). The mechanism of chemical conjugation in the CH4-H2O2-H2O system was elucidated and the inducing effect of H2O2 decomposition on the desired (secondary) reaction was quantitavely estimated. An adequate kinetic model was formulated on the basis of the proposed free-radical scheme.展开更多
文摘Dioxygen activations constitute one of core issues in copper-dependent metalloenzymes. Upon O_(2) activation, copper-dependent metalloenzymes such as particulate methane monooxygenases(pM MOs), lytic polysaccharide monooxygenases(LPMOs) and binuclear copper enzymes PHM and DβM, are able to perform various challenging C–H bond activations. Meanwhile, various copper-oxygen core containing complexes have been synthetized to mimic the active species of metalloenzymes. Dioxygen activation by mononuclear copper active site may generate various copper-oxygen intermediates, including Cu(Ⅱ)-superoxo, Cu(Ⅱ)-hydroperoxo, Cu(Ⅱ)-oxyl as well as the Cu(Ⅲ)-hydroxide species. Intriguingly, all these species have been invoked as the potential active intermediates for C–H/O–H activations in either biological or synthetic systems. Due to the poor understanding on reactivities of copper-oxygen complex, the nature of active species in both biological and synthetic systems are highly controversial. In this account, we will compare the reactivities of various mononuclear copper-oxygen species between biological systems and the synthetic systems. The present study is expected to provide the consistent understanding on reactivities of various copper-oxygen active species in both biological and synthetic systems.
基金supported by the National Key Research Development Program (No.2017YFC0212800)the National Natural Science Foundation of China (No.21477038 and No.21677051)the Natural Science Foundation of Guangdong Province (No.2016A030311005)
文摘Carbonyl peroxy radicals (RC(O)O2) are the ubiquitous radical intermediates in the atmospheric oxidation of volatile organic compounds. In this work, theoretical studies are carried out to explore the role of the unimolecular H-migration in the carbonyl peroxy radicals by using quantum chemistry and kinetics calculations. The results showed that H-migration could be significant in the atmosphere at least in CH3CH2CH2C(O)O2 and (CH3)2CHCH2C(O)O2 with rates of ∽0.012 and -0.58^-1 at 298 K. Subsequent reactions of CH3CHCH2C(O)OOH would lead to the products with multi-functional groups, which might affect the aerosol formation process;while (CH3)2CCH2C(O)OOH would transform to formaldehyde and acetone in a few steps. These processes would be important for the atmospheric modelling of volatile organic compounds under low-NOx conditions.
文摘In order to f urther improve the photosensitizing activity of hypocrellin B(HB), the complex o f 5,8 di Br HB with Al 3+ was designed and synthesized in high yield. Th e complex of aluminium ion with 5,8 di Br HB is a new water soluble perylene quinonoid derivative with enhanced absorption over HB in the phototherapeutic wi ndow (600-900 nm). Electron paramagnetic resonance (EPR) measurement and 9,10 diphenyl anthracene bleaching methods were used to investigate the photosensiti zing activity of [Al 2(5,8 di Br HB)Cl 4] n in the prese nce of oxygen. Singlet oxygen, superoxide anion radical, hydroxyl radical can be generated by [Al 2(5,8 di Br HB)Cl 4] n photosensit ization. The results showed that the production of hydroxyl radical ( · OH) by [Al 2(5,8 di Br HB)Cl 4] n photosensitization comes from the Fenton Haber Weiss reaction and the decom position of DMPO 1O 2 adduct. Formation of H 2O 2 as one of main intermedi ates in the photogeneration of hydroxyl radical was detected by using the cataly zed oxidation of the DPD reagent by the POD enzyme method. Moreover, the experim ents of EPR spin trap and catalase enzyme excluded the effect of organoperoxide on DPD oxidization. These results further support the proposed mechanism of · OH formation.
文摘There has been carried out the process of noncatalytic oxidation of natural methane in the presence of hydrogen peroxide at the temperatures 840-880 ℃ what permitted to obtain hydrogen with high yield of hydrogen (74%) with inconsiderable quantity of CO (0.4%) in converted gas. As observed in the experiment, a variation of H2O2 concentration in the aqueous solution and other basic parameters of the process may induce the synthesis of gas with given H2:CO ratio for its further application in methanol or ammonia synthesis. In the latter process low CO concentration is required. Compared with the common high-temperature conversion of natural gas and further carbon oxide conversion on a catalyst, the current process promotes process simplification: the reaction is implemented at relatively low temperature (860-900 ℃ instead of 1400-1600 ℃for existing non-catalytic processes of methane conversion) and an additional unit for catalytic conversion of carbon oxide is excluded (in NH3 production). The mechanism of chemical conjugation in the CH4-H2O2-H2O system was elucidated and the inducing effect of H2O2 decomposition on the desired (secondary) reaction was quantitavely estimated. An adequate kinetic model was formulated on the basis of the proposed free-radical scheme.