This paper describes the synthesis and free radical ring-opening polymerization of 2-methyl-and 2-methyl-9-n-butyl (-7-methylene-1, 4, 6-trioxaspiro (4, 4) nonane). The structures of the two polymers were verified by ...This paper describes the synthesis and free radical ring-opening polymerization of 2-methyl-and 2-methyl-9-n-butyl (-7-methylene-1, 4, 6-trioxaspiro (4, 4) nonane). The structures of the two polymers were verified by IR, 'H and ^(13)C NMR spectra. The substituent on 9-position of 7-methylene-trioxaspiro (4, 4) nonane affects the structure of polymer and polymerization activity. The polymerization mechanism is discussed.展开更多
A new bicyclic alkaloid, 3-phenyl-3-hydroxy-9-methyl-9-azabicyclo [4.2.1] nonane, has been synthesized from tropinone and its structure was determined by single crystal X-ray diffraction.
In our synthetic studies toward huperzine A, a diastereoselective α＇-alkylation of the α-amido-γ-methyl hexenone 4 was real- ized through a dianion intermediate which significantly enhanced the reactivity. Under t...In our synthetic studies toward huperzine A, a diastereoselective α＇-alkylation of the α-amido-γ-methyl hexenone 4 was real- ized through a dianion intermediate which significantly enhanced the reactivity. Under the attempted Heck reaction conditions, an unexpected and unprecedented palladium-catalyzed intramolecular T-arylation of 3 was observed, which generated 18 with bicyclo[3.3, l]nonane framework in satisfactory yield.展开更多
The effect of metallic ions on the nitrolysis of DAPT [3,7-diacetyl-1,3,5,7-tetraazabicyclo（3.3.1）nonane] and HA （hexamine） was investigated by experimental and theoretical approaches. The combinatorial reagent, M...The effect of metallic ions on the nitrolysis of DAPT [3,7-diacetyl-1,3,5,7-tetraazabicyclo（3.3.1）nonane] and HA （hexamine） was investigated by experimental and theoretical approaches. The combinatorial reagent, M（NO3）n/Ac20/NH4NO3 （M=Mg2＋, Cu2＋, Pb2＋, Bi3＋, Fe3＋ and Zr4＋）, was found to be efficient in the experiment of the nitrolysis of DAPT. A key intermediate during the nitrolysis of DAPT was detected by 1H NMR. The formation mechanism of the intermediate was proposed and analyzed. Some discrepant results for the nitrolysis of DAPT and HA catalyzed by different metallic nitrates were explained based on hard-soft and acid-base principle and stabilized energy of ion-complex. From the latter point of view, some cations with high polarizable ligands, e.g., O802CF3-, （CF3SO2）2N-, and （C4F9SO2）2N-, can increase the yields. Two newly designed catalysts, Cu[（CF3SO2）2N]2 and Cu[（C4F9SO2）2N]2, were tested to be highly efficient.展开更多
The purpose of this study was to use. a three-component photoinitiation system comprising 1wt% CQ （camphorquinone）, 2wt% DMAEMA （2-（dimethylamino） ethyl meth acrylate） and 2wt% ph^2I^＋PF6^- （diphenyliodonium h...The purpose of this study was to use. a three-component photoinitiation system comprising 1wt% CQ （camphorquinone）, 2wt% DMAEMA （2-（dimethylamino） ethyl meth acrylate） and 2wt% ph^2I^＋PF6^- （diphenyliodonium hexafluorophosphate） to initiate the copolymerization of the matrix resins which combine bisphenol-S-bis （3-methacrylate-2-hydroxy propyl） ether （BisS-GMA） with the expanding monomer unsaturated spiro orthoesters 2-methylene-l,4,6-tdspiro[4,4] nonane （MTOSN）, for minimizing the volumetric shrinkage that generally occurs during polymerization. It was hypothesized that MTOSN would expand volumetrically during polymerization under the three-component photoinitiator system and further reductions in volumetric shrinkage would be obtained. The performance study which consists of degree of conversion and condition of the ring-opening reactions of MTOSN, volumetric shrinkage and mechanical properties including tensile bond strength, compressive strength and Vicker＇s hardness were carried out respectively by Fourier transfer infrared, the dilatometer and the universal testing machine. The results supported that the dental composites based on the expanding monomer and three-component photoinitiator system engendered a greater decrease of volumetric shrinkage and better mechanieal properties.展开更多
The harmof Aspergillus flavus(A.flavus)and aflatoxin is a severe food safety problemworldwide,which causes huge economic losses every year.Therefore,it is urgent to control the growth of A.flavus and the biosynthesis ...The harmof Aspergillus flavus(A.flavus)and aflatoxin is a severe food safety problemworldwide,which causes huge economic losses every year.Therefore,it is urgent to control the growth of A.flavus and the biosynthesis of aflatoxin.Plant-derived natural compounds are superior to synthetic fungicide in inhibiting the growth of A.flavus benefiting from their high safety to the environment,humans and stock,and low cost.This study aimed to evaluate the antifungal effects and potential antifungal mechanisms of three plant-derived compounds(octanal,nonanal and decanal)against A.flavus.We determined the minimum inhibitory concentrations(MICs)and action mechanism of the three volatile aldehydes on A.flavus and also performed calcofluor white(CW)staining for visualizing the distribution of septa.Cell respiration metabolism and the pathogenicity on maize kernels were also carried out to evaluate the efficacy of the three volatile aldehydes on the growth of A.flavus.The results showed that the three volatile aldehydes could inhibit the germination of spores and mycelial growth of A.flavus,the MICs on spores and mycelia were:octanal(1.0 and 0.5μL/mL),nonanal(0.5 and 2.0μL/mL),and decanal(1 and 5μL/mL).The three volatile aldehydes could strongly damage the integrity of both the cell wall and the cell membrane of A.flavus.Meanwhile,they could decrease the content of total lipid and inhibit respiration metabolism of A.flavus cell.Results of in vitro antifungal test showed that all the three volatile aldehydes could effectively prevent the growth of A.flavus on maize kernels.The study revealed that octanal,nonanal and decanal could effectively inhibit the growth of A.flavus both in culture medium and on maize kernels to different extent.The results confirmed that the plant-derived compounds could be developed into promising antifungal agents applied in the preservation of grains.This study provides a theoretical basis for the research and application of potential antifungal agents.展开更多
The volatile compounds from horse and pony hairs and skin were analyzed to determine bioactive molecules that are kairomones used for host location by blood-feeding diptera. In this study, horse and pony hair samples ...The volatile compounds from horse and pony hairs and skin were analyzed to determine bioactive molecules that are kairomones used for host location by blood-feeding diptera. In this study, horse and pony hair samples were extracted with organic solvents (pentane or hexane) and analyzed by gas chromatography-mass spectrometry analysis (GC-MS) with closed electron ionization (CEI). Using the GC-MS analysis, we observed a compound peak, which could not be identified by comparison to mass spectra in the mass spectral library. This unknown compound was often the largest peak in the chromatogram and had a retention index and mass spectral fragmentation similar to nonanal. However, there were several differences in the fragmentation pattern. When compared to a nonanal reference standard, it was evident that this was a different compound. Hydrodistillation of pony hair was another extraction method to obtain the unknown component in higher concentrations. Analysis of this extract with GC-flame ionization detector (FID) with GC-MS confirmed the same unknown peak. Further experiments and analysis with the various mass spectroscopy tools gave the possible molecular ion with mass-to-charge ratio (<em>m/z</em>) 142, corresponding to the unknown component.展开更多
A new method of enantioselective synthesis of （S,S）-2,8-diazobicyclo [4.3.0] nonane was found by using （R）-2-amino-2- phenyl-ethanol as chiral induction reagent. The entire synthetic process included 8 steps which...A new method of enantioselective synthesis of （S,S）-2,8-diazobicyclo [4.3.0] nonane was found by using （R）-2-amino-2- phenyl-ethanol as chiral induction reagent. The entire synthetic process included 8 steps which were easy to operate with high yield. The purification method was only simple recrystallization or even used directly in the next step without further purifica- tion. The total yield was 29%.展开更多
The unusual tricyclo[6.4.0.0^4,9]dodecane framework was constructed in eight linear steps in 13%overall yield.An innovative strategy accessing the framework from bicyclo[3.3.1]nonanes was employed.The key steps involv...The unusual tricyclo[6.4.0.0^4,9]dodecane framework was constructed in eight linear steps in 13%overall yield.An innovative strategy accessing the framework from bicyclo[3.3.1]nonanes was employed.The key steps involve a Robinson annulation,a base induced decarboxylation and epimerization in a single step,and an intramolecular alkylation.展开更多
基金Supported by National Natural Science Foundation of China
文摘This paper describes the synthesis and free radical ring-opening polymerization of 2-methyl-and 2-methyl-9-n-butyl (-7-methylene-1, 4, 6-trioxaspiro (4, 4) nonane). The structures of the two polymers were verified by IR, 'H and ^(13)C NMR spectra. The substituent on 9-position of 7-methylene-trioxaspiro (4, 4) nonane affects the structure of polymer and polymerization activity. The polymerization mechanism is discussed.
文摘A new bicyclic alkaloid, 3-phenyl-3-hydroxy-9-methyl-9-azabicyclo [4.2.1] nonane, has been synthesized from tropinone and its structure was determined by single crystal X-ray diffraction.
基金supported by the National Natural Science Foundation of China (20902101 & 21172246)National Basic Research Program of China (973 Program) (2010CB833206)
文摘In our synthetic studies toward huperzine A, a diastereoselective α＇-alkylation of the α-amido-γ-methyl hexenone 4 was real- ized through a dianion intermediate which significantly enhanced the reactivity. Under the attempted Heck reaction conditions, an unexpected and unprecedented palladium-catalyzed intramolecular T-arylation of 3 was observed, which generated 18 with bicyclo[3.3, l]nonane framework in satisfactory yield.
文摘The effect of metallic ions on the nitrolysis of DAPT [3,7-diacetyl-1,3,5,7-tetraazabicyclo（3.3.1）nonane] and HA （hexamine） was investigated by experimental and theoretical approaches. The combinatorial reagent, M（NO3）n/Ac20/NH4NO3 （M=Mg2＋, Cu2＋, Pb2＋, Bi3＋, Fe3＋ and Zr4＋）, was found to be efficient in the experiment of the nitrolysis of DAPT. A key intermediate during the nitrolysis of DAPT was detected by 1H NMR. The formation mechanism of the intermediate was proposed and analyzed. Some discrepant results for the nitrolysis of DAPT and HA catalyzed by different metallic nitrates were explained based on hard-soft and acid-base principle and stabilized energy of ion-complex. From the latter point of view, some cations with high polarizable ligands, e.g., O802CF3-, （CF3SO2）2N-, and （C4F9SO2）2N-, can increase the yields. Two newly designed catalysts, Cu[（CF3SO2）2N]2 and Cu[（C4F9SO2）2N]2, were tested to be highly efficient.
基金Funded by the National Natural Science Foundation of China(No.50673065)
文摘The purpose of this study was to use. a three-component photoinitiation system comprising 1wt% CQ （camphorquinone）, 2wt% DMAEMA （2-（dimethylamino） ethyl meth acrylate） and 2wt% ph^2I^＋PF6^- （diphenyliodonium hexafluorophosphate） to initiate the copolymerization of the matrix resins which combine bisphenol-S-bis （3-methacrylate-2-hydroxy propyl） ether （BisS-GMA） with the expanding monomer unsaturated spiro orthoesters 2-methylene-l,4,6-tdspiro[4,4] nonane （MTOSN）, for minimizing the volumetric shrinkage that generally occurs during polymerization. It was hypothesized that MTOSN would expand volumetrically during polymerization under the three-component photoinitiator system and further reductions in volumetric shrinkage would be obtained. The performance study which consists of degree of conversion and condition of the ring-opening reactions of MTOSN, volumetric shrinkage and mechanical properties including tensile bond strength, compressive strength and Vicker＇s hardness were carried out respectively by Fourier transfer infrared, the dilatometer and the universal testing machine. The results supported that the dental composites based on the expanding monomer and three-component photoinitiator system engendered a greater decrease of volumetric shrinkage and better mechanieal properties.
基金This study was funded by the Doctor Research Fund of Henan University of Technology(grant number 2019BS019)the Natural Science Research Projects of Education Department of Henan Province(21A550005).
文摘The harmof Aspergillus flavus(A.flavus)and aflatoxin is a severe food safety problemworldwide,which causes huge economic losses every year.Therefore,it is urgent to control the growth of A.flavus and the biosynthesis of aflatoxin.Plant-derived natural compounds are superior to synthetic fungicide in inhibiting the growth of A.flavus benefiting from their high safety to the environment,humans and stock,and low cost.This study aimed to evaluate the antifungal effects and potential antifungal mechanisms of three plant-derived compounds(octanal,nonanal and decanal)against A.flavus.We determined the minimum inhibitory concentrations(MICs)and action mechanism of the three volatile aldehydes on A.flavus and also performed calcofluor white(CW)staining for visualizing the distribution of septa.Cell respiration metabolism and the pathogenicity on maize kernels were also carried out to evaluate the efficacy of the three volatile aldehydes on the growth of A.flavus.The results showed that the three volatile aldehydes could inhibit the germination of spores and mycelial growth of A.flavus,the MICs on spores and mycelia were:octanal(1.0 and 0.5μL/mL),nonanal(0.5 and 2.0μL/mL),and decanal(1 and 5μL/mL).The three volatile aldehydes could strongly damage the integrity of both the cell wall and the cell membrane of A.flavus.Meanwhile,they could decrease the content of total lipid and inhibit respiration metabolism of A.flavus cell.Results of in vitro antifungal test showed that all the three volatile aldehydes could effectively prevent the growth of A.flavus on maize kernels.The study revealed that octanal,nonanal and decanal could effectively inhibit the growth of A.flavus both in culture medium and on maize kernels to different extent.The results confirmed that the plant-derived compounds could be developed into promising antifungal agents applied in the preservation of grains.This study provides a theoretical basis for the research and application of potential antifungal agents.
文摘The volatile compounds from horse and pony hairs and skin were analyzed to determine bioactive molecules that are kairomones used for host location by blood-feeding diptera. In this study, horse and pony hair samples were extracted with organic solvents (pentane or hexane) and analyzed by gas chromatography-mass spectrometry analysis (GC-MS) with closed electron ionization (CEI). Using the GC-MS analysis, we observed a compound peak, which could not be identified by comparison to mass spectra in the mass spectral library. This unknown compound was often the largest peak in the chromatogram and had a retention index and mass spectral fragmentation similar to nonanal. However, there were several differences in the fragmentation pattern. When compared to a nonanal reference standard, it was evident that this was a different compound. Hydrodistillation of pony hair was another extraction method to obtain the unknown component in higher concentrations. Analysis of this extract with GC-flame ionization detector (FID) with GC-MS confirmed the same unknown peak. Further experiments and analysis with the various mass spectroscopy tools gave the possible molecular ion with mass-to-charge ratio (<em>m/z</em>) 142, corresponding to the unknown component.
文摘A new method of enantioselective synthesis of （S,S）-2,8-diazobicyclo [4.3.0] nonane was found by using （R）-2-amino-2- phenyl-ethanol as chiral induction reagent. The entire synthetic process included 8 steps which were easy to operate with high yield. The purification method was only simple recrystallization or even used directly in the next step without further purifica- tion. The total yield was 29%.
基金Financial support from TianJin Municipal Science and Technology Commission(No.11ZCKFSY06200) is greatly acknowledged
文摘The unusual tricyclo[6.4.0.0^4,9]dodecane framework was constructed in eight linear steps in 13%overall yield.An innovative strategy accessing the framework from bicyclo[3.3.1]nonanes was employed.The key steps involve a Robinson annulation,a base induced decarboxylation and epimerization in a single step,and an intramolecular alkylation.
