Phosphite (Phi)-based fungicides are used to control the oomycete Phytophthora infestans which causes late blight disease, the most devastating disease in potatoes. In order to examine the effects of Phi-based fungici...Phosphite (Phi)-based fungicides are used to control the oomycete Phytophthora infestans which causes late blight disease, the most devastating disease in potatoes. In order to examine the effects of Phi-based fungicides on potato tubers through foliar or post-harvest application, a metabolite profiling approach based on gas chromatography coupled to mass spectrometry (GC-MS) has been established. A total of 132 metabolites were detected using the GC-MS approach. Among these, 34 metabolites were identified after normalization and annotated with a compound name with standard mass spectral library. Metabolomic analysis of Phi-treated plants showed significant differences in the levels of many metabolites especially amino acids. Multivariate statistical approaches, such as principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA), were employed to explore the relationships between metabolites to detect group differences. A good discrimination between the control and the Phi-treated plants was observed, which demonstrated that significant changes in the metabolite profile have been caused by the two different Phi applications (foliar or post-harvest). This finding suggests that the alteration of specific metabolite levels by accumulation of Phi can lead to resistance against the pathogen.展开更多
A new compound. methyl 4. 6-O-benzylidene-a-D-glucopyranoside 2. 3-cyclicphosphite ethyl ester was synthesized via the reaction of methyl 4. 6-O-benzylidene-a-D-glucopyranoside and ethyl dichlorophosphite. Its structu...A new compound. methyl 4. 6-O-benzylidene-a-D-glucopyranoside 2. 3-cyclicphosphite ethyl ester was synthesized via the reaction of methyl 4. 6-O-benzylidene-a-D-glucopyranoside and ethyl dichlorophosphite. Its structure was confirmed by NMR and MSspectral methods.展开更多
In this paper the reaction of substituted β-nitrostyrene with O,O-dialkyl phosphite under cocatalysis of trimethylsilyl chloride （TMS-C1） and triethylamine （or other acidbinding agent） has been first studied and ...In this paper the reaction of substituted β-nitrostyrene with O,O-dialkyl phosphite under cocatalysis of trimethylsilyl chloride （TMS-C1） and triethylamine （or other acidbinding agent） has been first studied and the new cyclization reaction leading to the formation of product Ⅱ, as a new class of derivatives of 1-hydroxyindoles, difficultly accessible or inaccessible with usual methods has been observed. In the related reaction it is surprising that when the Arbuzov rearrangement occurs under mild conditions, the addition, reduction and cyclization as a one-pot reaction take place simultaneously with the formation of products Ⅰ, Ⅱ, Ⅲ. By controlling the reaction conditions the products were formed almost in specificity, and thus the most interesting cyclic products Ⅱ<sub>a-h</sub> containing phosphorus-carbon bond were obtained. Their structures were confirmed by elemental analysis, IR, <sup>1</sup>H or <sup>31</sup>p NMR and MS spectra. The crystal structure of representative compound Ⅱ<sub>h</sub> was determined by X-ray展开更多
The asymmetric Pudovik reaction of chiral fluoroalkyl α,β-unsaturated ketimines derivated from(R)-tert-butanesulfinamide and diphenyl phosphite was achieved in the presence of Rb2CO3 at room temperature.A series of ...The asymmetric Pudovik reaction of chiral fluoroalkyl α,β-unsaturated ketimines derivated from(R)-tert-butanesulfinamide and diphenyl phosphite was achieved in the presence of Rb2CO3 at room temperature.A series of fluoroalkylated α-amino phosphonates were prepared in good yields with high diastereoselectivities.展开更多
Triethyl Phosphite is the intermediate of producing nervous toxin of organic phosphate,which is involved in the chemicals of schedule 3. in Convention On The Prohibition Of The Development,Production,Stockpiling And U...Triethyl Phosphite is the intermediate of producing nervous toxin of organic phosphate,which is involved in the chemicals of schedule 3. in Convention On The Prohibition Of The Development,Production,Stockpiling And Use Of Chemical Weapons And On Their Destruction.A method for the determination of triethyl phosphate was established by GC-MS/SIM.Average recovery was 96.3%-111.5% with linear range between concentration and peak area varying from 0.546-10.928 mg/L and the detection limits were 0.011 ng.展开更多
A chemically closed-loop-recyclable biodegradable polymer,poly(p-dioxanone)(PPDO),is one of the ideal candidates for single-use plastic products due to its suitability for different application scenarios.Fascinatingly...A chemically closed-loop-recyclable biodegradable polymer,poly(p-dioxanone)(PPDO),is one of the ideal candidates for single-use plastic products due to its suitability for different application scenarios.Fascinatingly,when PPDO wastes can be collected,its monomer p-dioxanone(PDO) will be obtained through chemical recycling of these wastes;when cannot be collected,the wastes are able to be biodegraded into harmless substances.However,unsatisfied thermal stability and low crystallization rate of PPDO restrict its wider applications.Herein,based on end-group regulation,we simultaneously realized the significant enhancement of thermal stability and crystallization of PPDO through the simple melt processing with tributyl phosphite(TBP) or triphenyl phosphite(TPP).The model reactions were conducted to investigate the reaction mechanism and theoretical products during the preparation of PPDO/phosphite compounds.Two kinds of phosphites were proved to act as the end-capped reagent and chain extender in the melt processing,while TBP presented better reactivity.As a result,the activation energy of thermal decomposition was largely elevated,and the unprecedented T_(5%)(the temperature at a weight loss of 5%) and Tmax(the temperature at a maximum rate of weight loss) of PPDO were obtained,i.e.,T_(5%)of ~330 ℃ and Tmaxof ~385 ℃ in N_(2) atmosphere,T_(5%)of ~240 ℃ and Tmaxof ~317 ℃ in air atmosphere,respectively.Furthermore,the increased crystallization rate,crystallinity,crystalline orderliness,and realizable monomer recovery(yield >90%,purity >99.9%) of PPDO/phosphite compounds were confirmed.展开更多
Silicon oxide(SiO_(x))has received remarkable attention as a next-generation battery material;however,the sudden decrease in the cycling retention constitutes a significant challenge in facilitating its application.Tr...Silicon oxide(SiO_(x))has received remarkable attention as a next-generation battery material;however,the sudden decrease in the cycling retention constitutes a significant challenge in facilitating its application.Tris(2,2,2-trifluoroethyl)phosphite(TTFP),which can control parasitic reactions such as the pulverization of SiO_(x)anode materials and electrolyte decomposition,has been proposed to improve the lifespan of the cell.The electrochemical reduction of TTFP results in solid-electrolyte interphase(SEI)layers that are mainly composed of LiF,which occur at a higher potential than the working potential of the SiO_(x)anode and carbonate-based solvents.The electrolyte with TTFP exhibited a substantial improvement in cycling retention after 100 cycles,whereas the standard electrolyte showed acutely decreased retention.The thickness of the SiO_(x)anode with TTFP also changed only slightly without any considerable delamination spots,whereas the SiO_(x)anode without TTFP was prominently deformed by an enormous volume expansion with several internal cracks.The cycled SiO_(x)anode with TTFP exhibited less increase in resistance after cycling than that in the absence of TTFP,in addition to fewer decomposition adducts in corresponding X-ray photoelectron spectroscopy(XPS)analyses between the cycled SiO_(x)anodes.These results demonstrate that TTFP formed SEI layers at the SiO_(x)interface,which substantially reduced the pulverization of the SiO_(x)anode materials;in addition,electrolyte decomposition at the interface decreased,which led to improved cycling retention.展开更多
Phosphorus(P)deficiency is one of the main constraints on crop production in Arenosols(acid sandy soil).The high cost of P fertilizers may represent an insurmountable obstacle in many poor countries,leaving the exploi...Phosphorus(P)deficiency is one of the main constraints on crop production in Arenosols(acid sandy soil).The high cost of P fertilizers may represent an insurmountable obstacle in many poor countries,leaving the exploitation of their own calcareous and phosphate rocks as the only low-cost and long-term alternative.Biochar is suggested to have positive effects on soil properties;however,there is no published research on the synergistic effects of biochar and rocky materials in modifying soil properties.The aim of this study was to investigate the chemical and biochemical responses of an acid Arenosol treated with phosphate rock(PR),calcareous rock(CR),and biochar(BC),and the implications for corn yield.A soil from Marracuene District,Mozambique was used,where corn was grown for 90 d with the soil treated with:no addition(control),water-soluble zinc phosphite fertilizer(WSP),PR,WSP+CR,WSP+BC,WSP+CR+BC,PR+BC,and PR+CR+BC.Biochar was produced by pyrolysis of babycorn peels for 4 h at 450?C and applied at 11 g kg-1.The soil pHH2 Oincreased from about 4.54 in the control to 7.38 in the PR+CR+BC treatment.Easily oxidizable organic carbon,cation exchange capacity,and available P were higher in the treatments containing BC than in the control.The treatments containing CR and/or BC led to the highest activities of alkaline phosphomonoesterase,phosphodiesterase,andα-glucosidase,which increased P availability and gave the greatest biomass and yields.We suggest that biochar provides additional soluble P and supplies adsorption sites for phosphate,preventing its evolution to unavailable forms.Thus,PR applied together with BC contributed to an 840%yield increase compared to the control.The treatments containing WSP and BC facilitated phosphite oxidation to phosphate and increased crop yield.展开更多
A new strategy for the synthesis of unsymmetrical phosphotri-esters was reported: an alcohol was converted to unsymmetrical dialkyl phosphites firstly, which then reacted with the second alcohol or phenol to afford re...A new strategy for the synthesis of unsymmetrical phosphotri-esters was reported: an alcohol was converted to unsymmetrical dialkyl phosphites firstly, which then reacted with the second alcohol or phenol to afford required unsymmitrical triesters in the presence of iodine in high yields under exceptionally mild conditions.展开更多
文摘Phosphite (Phi)-based fungicides are used to control the oomycete Phytophthora infestans which causes late blight disease, the most devastating disease in potatoes. In order to examine the effects of Phi-based fungicides on potato tubers through foliar or post-harvest application, a metabolite profiling approach based on gas chromatography coupled to mass spectrometry (GC-MS) has been established. A total of 132 metabolites were detected using the GC-MS approach. Among these, 34 metabolites were identified after normalization and annotated with a compound name with standard mass spectral library. Metabolomic analysis of Phi-treated plants showed significant differences in the levels of many metabolites especially amino acids. Multivariate statistical approaches, such as principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA), were employed to explore the relationships between metabolites to detect group differences. A good discrimination between the control and the Phi-treated plants was observed, which demonstrated that significant changes in the metabolite profile have been caused by the two different Phi applications (foliar or post-harvest). This finding suggests that the alteration of specific metabolite levels by accumulation of Phi can lead to resistance against the pathogen.
文摘A new compound. methyl 4. 6-O-benzylidene-a-D-glucopyranoside 2. 3-cyclicphosphite ethyl ester was synthesized via the reaction of methyl 4. 6-O-benzylidene-a-D-glucopyranoside and ethyl dichlorophosphite. Its structure was confirmed by NMR and MSspectral methods.
基金Project supported by the National Natural Science Foundation of China. This paper was reported at CHAC, Kobe, Japan, 1987.
文摘In this paper the reaction of substituted β-nitrostyrene with O,O-dialkyl phosphite under cocatalysis of trimethylsilyl chloride （TMS-C1） and triethylamine （or other acidbinding agent） has been first studied and the new cyclization reaction leading to the formation of product Ⅱ, as a new class of derivatives of 1-hydroxyindoles, difficultly accessible or inaccessible with usual methods has been observed. In the related reaction it is surprising that when the Arbuzov rearrangement occurs under mild conditions, the addition, reduction and cyclization as a one-pot reaction take place simultaneously with the formation of products Ⅰ, Ⅱ, Ⅲ. By controlling the reaction conditions the products were formed almost in specificity, and thus the most interesting cyclic products Ⅱ<sub>a-h</sub> containing phosphorus-carbon bond were obtained. Their structures were confirmed by elemental analysis, IR, <sup>1</sup>H or <sup>31</sup>p NMR and MS spectra. The crystal structure of representative compound Ⅱ<sub>h</sub> was determined by X-ray
基金Financial support from the National Natural Science Foundation of China(No.21172243)is gratefully acknowledged.
文摘The asymmetric Pudovik reaction of chiral fluoroalkyl α,β-unsaturated ketimines derivated from(R)-tert-butanesulfinamide and diphenyl phosphite was achieved in the presence of Rb2CO3 at room temperature.A series of fluoroalkylated α-amino phosphonates were prepared in good yields with high diastereoselectivities.
文摘Triethyl Phosphite is the intermediate of producing nervous toxin of organic phosphate,which is involved in the chemicals of schedule 3. in Convention On The Prohibition Of The Development,Production,Stockpiling And Use Of Chemical Weapons And On Their Destruction.A method for the determination of triethyl phosphate was established by GC-MS/SIM.Average recovery was 96.3%-111.5% with linear range between concentration and peak area varying from 0.546-10.928 mg/L and the detection limits were 0.011 ng.
基金supported by the National Key R&D Program of China (2021YFB3801904)the National Natural Science Foundation of China (U19A2095)+2 种基金the Institutional Research Fund from Sichuan University (2020SCUNL205)the Fundamental Research Funds for the Central Universitiesthe 111 Project (B20001)。
文摘A chemically closed-loop-recyclable biodegradable polymer,poly(p-dioxanone)(PPDO),is one of the ideal candidates for single-use plastic products due to its suitability for different application scenarios.Fascinatingly,when PPDO wastes can be collected,its monomer p-dioxanone(PDO) will be obtained through chemical recycling of these wastes;when cannot be collected,the wastes are able to be biodegraded into harmless substances.However,unsatisfied thermal stability and low crystallization rate of PPDO restrict its wider applications.Herein,based on end-group regulation,we simultaneously realized the significant enhancement of thermal stability and crystallization of PPDO through the simple melt processing with tributyl phosphite(TBP) or triphenyl phosphite(TPP).The model reactions were conducted to investigate the reaction mechanism and theoretical products during the preparation of PPDO/phosphite compounds.Two kinds of phosphites were proved to act as the end-capped reagent and chain extender in the melt processing,while TBP presented better reactivity.As a result,the activation energy of thermal decomposition was largely elevated,and the unprecedented T_(5%)(the temperature at a weight loss of 5%) and Tmax(the temperature at a maximum rate of weight loss) of PPDO were obtained,i.e.,T_(5%)of ~330 ℃ and Tmaxof ~385 ℃ in N_(2) atmosphere,T_(5%)of ~240 ℃ and Tmaxof ~317 ℃ in air atmosphere,respectively.Furthermore,the increased crystallization rate,crystallinity,crystalline orderliness,and realizable monomer recovery(yield >90%,purity >99.9%) of PPDO/phosphite compounds were confirmed.
基金This work was financially supported by the National Research Foundation of Korea financially(NRF)(No.NRF-2022R1F1A1069039)the Core Research Institute(CRI)Program,the Basic Science Research Program through the National Research Foundation of Korea(NRF),Ministry of Education(No.NRF-2017R1A6A1A06015181)the Technology Innovation Program(No.20011905)funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea).
文摘Silicon oxide(SiO_(x))has received remarkable attention as a next-generation battery material;however,the sudden decrease in the cycling retention constitutes a significant challenge in facilitating its application.Tris(2,2,2-trifluoroethyl)phosphite(TTFP),which can control parasitic reactions such as the pulverization of SiO_(x)anode materials and electrolyte decomposition,has been proposed to improve the lifespan of the cell.The electrochemical reduction of TTFP results in solid-electrolyte interphase(SEI)layers that are mainly composed of LiF,which occur at a higher potential than the working potential of the SiO_(x)anode and carbonate-based solvents.The electrolyte with TTFP exhibited a substantial improvement in cycling retention after 100 cycles,whereas the standard electrolyte showed acutely decreased retention.The thickness of the SiO_(x)anode with TTFP also changed only slightly without any considerable delamination spots,whereas the SiO_(x)anode without TTFP was prominently deformed by an enormous volume expansion with several internal cracks.The cycled SiO_(x)anode with TTFP exhibited less increase in resistance after cycling than that in the absence of TTFP,in addition to fewer decomposition adducts in corresponding X-ray photoelectron spectroscopy(XPS)analyses between the cycled SiO_(x)anodes.These results demonstrate that TTFP formed SEI layers at the SiO_(x)interface,which substantially reduced the pulverization of the SiO_(x)anode materials;in addition,electrolyte decomposition at the interface decreased,which led to improved cycling retention.
基金the Applied Research and Multi-sectorial Program(FIAM)(project contract No.5.2.1)granted by the Italian Cooperation and Development Agency(ICDA)to the Universidade Eduardo Mondlane
文摘Phosphorus(P)deficiency is one of the main constraints on crop production in Arenosols(acid sandy soil).The high cost of P fertilizers may represent an insurmountable obstacle in many poor countries,leaving the exploitation of their own calcareous and phosphate rocks as the only low-cost and long-term alternative.Biochar is suggested to have positive effects on soil properties;however,there is no published research on the synergistic effects of biochar and rocky materials in modifying soil properties.The aim of this study was to investigate the chemical and biochemical responses of an acid Arenosol treated with phosphate rock(PR),calcareous rock(CR),and biochar(BC),and the implications for corn yield.A soil from Marracuene District,Mozambique was used,where corn was grown for 90 d with the soil treated with:no addition(control),water-soluble zinc phosphite fertilizer(WSP),PR,WSP+CR,WSP+BC,WSP+CR+BC,PR+BC,and PR+CR+BC.Biochar was produced by pyrolysis of babycorn peels for 4 h at 450?C and applied at 11 g kg-1.The soil pHH2 Oincreased from about 4.54 in the control to 7.38 in the PR+CR+BC treatment.Easily oxidizable organic carbon,cation exchange capacity,and available P were higher in the treatments containing BC than in the control.The treatments containing CR and/or BC led to the highest activities of alkaline phosphomonoesterase,phosphodiesterase,andα-glucosidase,which increased P availability and gave the greatest biomass and yields.We suggest that biochar provides additional soluble P and supplies adsorption sites for phosphate,preventing its evolution to unavailable forms.Thus,PR applied together with BC contributed to an 840%yield increase compared to the control.The treatments containing WSP and BC facilitated phosphite oxidation to phosphate and increased crop yield.
基金Project supported by the National Natural Science Foundation of China (No. 29772047).
文摘A new strategy for the synthesis of unsymmetrical phosphotri-esters was reported: an alcohol was converted to unsymmetrical dialkyl phosphites firstly, which then reacted with the second alcohol or phenol to afford required unsymmitrical triesters in the presence of iodine in high yields under exceptionally mild conditions.
