Objective To devellop directly molecular evolution Of nitrite oxido-reductase using DNA-shuffling technique because nitrobacteria grow extremelly slow and are unable to nitrify effectively inorganic nitrogen in wastew...Objective To devellop directly molecular evolution Of nitrite oxido-reductase using DNA-shuffling technique because nitrobacteria grow extremelly slow and are unable to nitrify effectively inorganic nitrogen in wastewater treatmem. Methods The norB gene coding the ntitrite oxido-reductase in nitrobacteria was cloned and sequenced. Then, directed molecular evolution of nitrite oxido-reductase was developed by DNA-shuffling of 15 norB genes from different nitrobacteria. Results After DNA-shuffling with sexual PeR and staggered extension process PCR, the sequence was differem from its parental DNA fragmems and the homology ranged from 98% to 99%. The maximum nitrification rate of the modified bacterium of X16 by DNA-shuffling was up to 42.9 mg/L.d, which was almost 10 times higher than that of its parental bacteria. Furthermore, the modified bacterium had the same characteristics of its parental bacteria of E. coli and could grow rapidly in normal cultures. Conclusion DNA-shuffling was successfully used to engineer E. coli, which had norB gene and could degrade inorganic nitrogen effectively.展开更多
It has been generally unclear over the mechanism of inhibitory influence of silicate on structural rearrangement or solely physical adsorption onto manganese dioxide （MnO2） about the decomposition of hydrogen peroxi...It has been generally unclear over the mechanism of inhibitory influence of silicate on structural rearrangement or solely physical adsorption onto manganese dioxide （MnO2） about the decomposition of hydrogen peroxide （H2O2）. Consequently, several experiments were carried out by using MnO2 as a catalyst for the decomposition of H2O2 in a concentration series under certain concentrations of silicates. The silicates were analyzed by using a molybdenum blue colorimetric method. The results showed that the determination of silicates was inhibited by H2O2, whose inhibitory effect was greatly increased by increasing its concentration, but not limited by pH. SEM-EDX （scanning electron microscopy-energy dispersive x-ray spectrometry） results showed that the adsorption of silicates onto the surface of MnO2 was not purely via a structural rearrangement, with increasing Mn atoms protruding on the outer surface by covering oxygen and silicon atoms. XRD （X-ray diffraction） and FTIR （Fourier transform infrared） spectra results further revealed no significant total crystal structural changes in MnO2 after the adsorption of silicates, but only a small shift of 0.21° at 2e from 56.36° to 56.15° , and a FTIR vibration showed at around 1 050 cm-1. The results, therefore, showed that silicate adsorption onto MnO2 took place via both surface adsorption and structural rearrangement by interfacial reaction.展开更多
The AIEt3-promoted tandem reductive rearrangement reactions of epoxides was studied at B3LYP/6- 31C（d,p） level. For the model compound α-hydroxy epoxides, two possible reaction pathways Ⅰ and Ⅱ were calculated. T...The AIEt3-promoted tandem reductive rearrangement reactions of epoxides was studied at B3LYP/6- 31C（d,p） level. For the model compound α-hydroxy epoxides, two possible reaction pathways Ⅰ and Ⅱ were calculated. The main difference is the order of ethylene release and six- to five-member ring rearrangement. The ring contraction rearrangement in pathway Ⅰ is the first step and this step is the rate controlling step with a free energy barrier of 116.62 kJ/mol. For pathway Ⅱ, the ethylene release occurs first, and is followed by a six-member ring opening reaction which is the rate controlling step, and the barrier is 251.38 kJ/mol. The reason for such high barrier is that the ethylene release results in the following reaction being more difficult. The results show that pathway Ⅰ （C-C rearrangement and then ethylene release） is more favorable, which is consistent with experimental results.展开更多
An efficient method for the preparation of 2-deoxy-glycopyranosides was developed by using 2,3-anhydrothioglycosides as the glycosylating agents.The reaction proceeded by the Cu(OTf)_2-mediated rearrangement of 2,3-an...An efficient method for the preparation of 2-deoxy-glycopyranosides was developed by using 2,3-anhydrothioglycosides as the glycosylating agents.The reaction proceeded by the Cu(OTf)_2-mediated rearrangement of 2,3-anhydrothiosugars.And high anomeric stereoselectivity was achieved.The disclosed methodology may find applications in the preparation of many biologically important 2-deoxy-glycosides.展开更多
Biphenyl moiety represents a unique structural motif of many natural and unnatural products with biological interests, and dehydrogenative couplings of two aryl C–H bonds under oxidative conditions is unambiguously t...Biphenyl moiety represents a unique structural motif of many natural and unnatural products with biological interests, and dehydrogenative couplings of two aryl C–H bonds under oxidative conditions is unambiguously the most efficient and direct preparation of these compounds. However, higher oxidation potential of benzene derivatives makes such oxidative couplings much more difficult than other arenes. Only very limited advances have been achieved on direct formation of the crucial C–C bond between two phenyl derivatives by dehydrogenative phenyl coupling in the last two decades. This article briefly summarized and commented a number of representative recent achievements in this attractive field, including homo-, cross-and intramolecular rearrangement and couplings, as well as their applications in organic synthesis.展开更多
基金supported by the Young National Natural Science Foundation of China(No.21302096)the Young Natural Science Foundation of Jiangsu Province(Nos.BK20171449,BK20130962)+1 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYLX16_0844)the Project Fund from the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
基金This study was supported by the National High Technology Research and Development Program of China (863 Program) (No. 2001AA214191).
文摘Objective To devellop directly molecular evolution Of nitrite oxido-reductase using DNA-shuffling technique because nitrobacteria grow extremelly slow and are unable to nitrify effectively inorganic nitrogen in wastewater treatmem. Methods The norB gene coding the ntitrite oxido-reductase in nitrobacteria was cloned and sequenced. Then, directed molecular evolution of nitrite oxido-reductase was developed by DNA-shuffling of 15 norB genes from different nitrobacteria. Results After DNA-shuffling with sexual PeR and staggered extension process PCR, the sequence was differem from its parental DNA fragmems and the homology ranged from 98% to 99%. The maximum nitrification rate of the modified bacterium of X16 by DNA-shuffling was up to 42.9 mg/L.d, which was almost 10 times higher than that of its parental bacteria. Furthermore, the modified bacterium had the same characteristics of its parental bacteria of E. coli and could grow rapidly in normal cultures. Conclusion DNA-shuffling was successfully used to engineer E. coli, which had norB gene and could degrade inorganic nitrogen effectively.
基金Supported by the Provincial Basic Research Program of Hebei Education Department(ZD2015110)the National Special Project on Key Technologies and Demonstration of Wetland Ecological Restoration in the Haihe River Basin(2014ZX07203008)
文摘It has been generally unclear over the mechanism of inhibitory influence of silicate on structural rearrangement or solely physical adsorption onto manganese dioxide （MnO2） about the decomposition of hydrogen peroxide （H2O2）. Consequently, several experiments were carried out by using MnO2 as a catalyst for the decomposition of H2O2 in a concentration series under certain concentrations of silicates. The silicates were analyzed by using a molybdenum blue colorimetric method. The results showed that the determination of silicates was inhibited by H2O2, whose inhibitory effect was greatly increased by increasing its concentration, but not limited by pH. SEM-EDX （scanning electron microscopy-energy dispersive x-ray spectrometry） results showed that the adsorption of silicates onto the surface of MnO2 was not purely via a structural rearrangement, with increasing Mn atoms protruding on the outer surface by covering oxygen and silicon atoms. XRD （X-ray diffraction） and FTIR （Fourier transform infrared） spectra results further revealed no significant total crystal structural changes in MnO2 after the adsorption of silicates, but only a small shift of 0.21° at 2e from 56.36° to 56.15° , and a FTIR vibration showed at around 1 050 cm-1. The results, therefore, showed that silicate adsorption onto MnO2 took place via both surface adsorption and structural rearrangement by interfacial reaction.
基金ACKNOWLEDGMENTS This work was supported by the Chinese Academy of Sciences, the Specialized Research Fund for the Doctoral Program of Higher Education, the National Basic Research Program of China （No.2007CB815204）, and the China Postdoctoral Science Foundation （No.20070420726 and No.20070410793）.
文摘The AIEt3-promoted tandem reductive rearrangement reactions of epoxides was studied at B3LYP/6- 31C（d,p） level. For the model compound α-hydroxy epoxides, two possible reaction pathways Ⅰ and Ⅱ were calculated. The main difference is the order of ethylene release and six- to five-member ring rearrangement. The ring contraction rearrangement in pathway Ⅰ is the first step and this step is the rate controlling step with a free energy barrier of 116.62 kJ/mol. For pathway Ⅱ, the ethylene release occurs first, and is followed by a six-member ring opening reaction which is the rate controlling step, and the barrier is 251.38 kJ/mol. The reason for such high barrier is that the ethylene release results in the following reaction being more difficult. The results show that pathway Ⅰ （C-C rearrangement and then ethylene release） is more favorable, which is consistent with experimental results.
基金National Natural Science Foundation of China (Grant No.20732001)Ministry of Science and Technology of China(Grant No.2009ZX09501-011).
文摘An efficient method for the preparation of 2-deoxy-glycopyranosides was developed by using 2,3-anhydrothioglycosides as the glycosylating agents.The reaction proceeded by the Cu(OTf)_2-mediated rearrangement of 2,3-anhydrothiosugars.And high anomeric stereoselectivity was achieved.The disclosed methodology may find applications in the preparation of many biologically important 2-deoxy-glycosides.
基金supported by the National Natural Science Foundation of China(21472087)
文摘Biphenyl moiety represents a unique structural motif of many natural and unnatural products with biological interests, and dehydrogenative couplings of two aryl C–H bonds under oxidative conditions is unambiguously the most efficient and direct preparation of these compounds. However, higher oxidation potential of benzene derivatives makes such oxidative couplings much more difficult than other arenes. Only very limited advances have been achieved on direct formation of the crucial C–C bond between two phenyl derivatives by dehydrogenative phenyl coupling in the last two decades. This article briefly summarized and commented a number of representative recent achievements in this attractive field, including homo-, cross-and intramolecular rearrangement and couplings, as well as their applications in organic synthesis.
