A PPh_(3)-catalyzed ring-opening addition reaction of cyclopropenones with alkyl bromides has been successfully established.This reaction offers a concise and practical approach for the assembly ofα,β-disubstituted ...A PPh_(3)-catalyzed ring-opening addition reaction of cyclopropenones with alkyl bromides has been successfully established.This reaction offers a concise and practical approach for the assembly ofα,β-disubstituted acrylates with exclusive E-stereoselectivity at room temperature.Mechanistic investigations indicated that both the hydrogen atom on vinyl group and one oxygen atom on ester group ofα,β-disubstituted acrylates derive from H2O in dimethyl sulfoxide(DMSO).Furthermore,a gram-scale experiment and late-stage modification of the products were accomplished,thereby expanding the application potential of this methodology in organic synthesis.展开更多
Two new C2-symmetrical bidentate phosphoramidite ligands were synthesized and employed in the Rh-catalyzed asymmetric hydrogenation of β-（acylamino）acrylates, up to 89% ee with full conversions was obtained.
Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this stu...Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this study,a novel p H/glutathione dual-responsive pesticide delivery system was constructed through the synthesis of disulfide-bridged hollow mesoporous organosilica nanospheres(HMONs)via the St??ber method,followed by poly(acrylic acid)(PAA)coating through distillation-precipitation polymerization to form HMONs@PAA nanocomposites.The resulting abamectin-loaded system(Abamectin-HMONs@PAA)demonstrated a 12.73% pesticide loading capacity and significantly improved photostability,retaining twice as much active ingredient as free abamectin after 250 h of UV irradiation(36 W).Release studies revealed p H-and glutathione-dependent characteristics,with cumulative releases in acidic conditions exceeding those in neutral and alkaline environments by 18.66% and 40.98%,respectively,and a 14.2% increase in glutathione-containing solution(0.2 mmol·L^(-1) in 70% ethanol)after 97 h.Bioassays showed superior performance against Plutella xylostella,with a 13.33% reduction in survival rate compared to conventional suspension at equivalent dosage(40 mg·L^(-1)),while maintaining efficacy after extensive rainfall simulation(20 events over 10 days).This study provides a promising approach for developing environmentally responsive nanopesticides with enhanced durability and controlled-release properties,offering significant potential for sustainable crop protection.展开更多
In ultraviolet cured-in-place-pipe(UV-CIPP)pipeline rehabilitation,resin performance critically determines repair effectiveness.Current UV-curable resins exhibit high volatile organic compound(VOC)emissions and inadeq...In ultraviolet cured-in-place-pipe(UV-CIPP)pipeline rehabilitation,resin performance critically determines repair effectiveness.Current UV-curable resins exhibit high volatile organic compound(VOC)emissions and inadequate post-cure toughness,which compromise fatigue resistance during service.To address these issues,we synthesized hydroxyl-terminated polyurethane acrylate prepolymers using diphenylmethane diisocyanate(MDI),polypropylene glycol(PPG),and hydroxyethyl methacrylate(HEMA).Fourier transform infrared spectroscopy(FTIR)confirmed successful prepolymer synthesis.We developed UV-curable resins by incorporating various crosslinking monomers and optimized the formulations through mechanical property analysis.Testing revealed that the polyurethane-acrylic UV-cured resin system combines polyurethane's mechanical excellence with acrylics'high UV-curing activity.The PPG200/MDI/HEMA formulation achieved superior performance,with a tensile strength of 55.31 MPa,an impact toughness of 22.7 kJ/m^(2),and a heat deflection temperature(HDT)of 132℃.The optimized system eliminates volatile components while maintaining high reactivity,addressing critical limitations in trenchless pipeline rehabilitation.The improved mechanical properties meet the operational demands of underground pipes,suggesting practical applicability in trenchless pipeline repair.展开更多
Waterborne acrylic coatings are widely utilized due to their cost-effectiveness,high transparency,strong resistance to weather and chemicals,impressive mechanical properties,and excellent adhesion to various substrate...Waterborne acrylic coatings are widely utilized due to their cost-effectiveness,high transparency,strong resistance to weather and chemicals,impressive mechanical properties,and excellent adhesion to various substrates.In these coatings,a reactive emulsifier containing phosphate groups can be integrated into the molecular chain during polymerization,which enhances the coating's compactness and corrosion resistance.This work focuses on the synthesis of styrene-butyl acrylate(St-BA)latex and methyl methacrylate-butyl acrylate(MMA-BA)latex using the reactive phosphate emulsifier ANPEO_(10)-P_(1) through seed emulsion polymerization,achieving a conversion rate of approximately 99%and a solid content close to 50%.The resulting coatings from St-BA and MMA-BA latexes demonstrated long-term corrosion protection for carbon steel and aluminum alloy due to in-situ phosphatization,effectively preventing flash rust.Notably,the MMA-BA coating exhibited remarkable durability,enduring immersion for up to 1224 h(51 d)on Q 235 carbon steel before reaching the failure threshold(|Z|0.01 Hz£106Ω·cm^(2))on Q 235 carbon steel.On 5052 aluminum alloy,the St-BA coating maintained|Z|0.01 Hz>10^(8)Ω·cm^(2) for 480 h(20 d).Furthermore,the corrosion resistance of St-BA and MMA BA coatings on Q 235 steel sheet and 5052 aluminum alloy surpassed that of commercially available MMA-BA and St BA coatings after immersion in a 3.5 wt%NaCl aqueous solution.This work also delves into the anticorrosion mechanism of MMA-BA and St-BA coatings.展开更多
文摘A PPh_(3)-catalyzed ring-opening addition reaction of cyclopropenones with alkyl bromides has been successfully established.This reaction offers a concise and practical approach for the assembly ofα,β-disubstituted acrylates with exclusive E-stereoselectivity at room temperature.Mechanistic investigations indicated that both the hydrogen atom on vinyl group and one oxygen atom on ester group ofα,β-disubstituted acrylates derive from H2O in dimethyl sulfoxide(DMSO).Furthermore,a gram-scale experiment and late-stage modification of the products were accomplished,thereby expanding the application potential of this methodology in organic synthesis.
基金The authors would like to thank the National Natural Science Foundation of China （No. 20472083） for financial support of this work.
文摘Two new C2-symmetrical bidentate phosphoramidite ligands were synthesized and employed in the Rh-catalyzed asymmetric hydrogenation of β-（acylamino）acrylates, up to 89% ee with full conversions was obtained.
基金financially supported by the Jiangsu Forestry Science and Technology Innovation and Promotion Project(No.LYKJ-Nanjing[2022]02)the Jiangsu Agricultural Science and Technology Innovation Fund(No.CX(23)3090)。
文摘Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this study,a novel p H/glutathione dual-responsive pesticide delivery system was constructed through the synthesis of disulfide-bridged hollow mesoporous organosilica nanospheres(HMONs)via the St??ber method,followed by poly(acrylic acid)(PAA)coating through distillation-precipitation polymerization to form HMONs@PAA nanocomposites.The resulting abamectin-loaded system(Abamectin-HMONs@PAA)demonstrated a 12.73% pesticide loading capacity and significantly improved photostability,retaining twice as much active ingredient as free abamectin after 250 h of UV irradiation(36 W).Release studies revealed p H-and glutathione-dependent characteristics,with cumulative releases in acidic conditions exceeding those in neutral and alkaline environments by 18.66% and 40.98%,respectively,and a 14.2% increase in glutathione-containing solution(0.2 mmol·L^(-1) in 70% ethanol)after 97 h.Bioassays showed superior performance against Plutella xylostella,with a 13.33% reduction in survival rate compared to conventional suspension at equivalent dosage(40 mg·L^(-1)),while maintaining efficacy after extensive rainfall simulation(20 events over 10 days).This study provides a promising approach for developing environmentally responsive nanopesticides with enhanced durability and controlled-release properties,offering significant potential for sustainable crop protection.
基金Funded by the National Natural Science Foundation of China(No.52473077)China Three Gorges Corporation(No.202403190)。
文摘In ultraviolet cured-in-place-pipe(UV-CIPP)pipeline rehabilitation,resin performance critically determines repair effectiveness.Current UV-curable resins exhibit high volatile organic compound(VOC)emissions and inadequate post-cure toughness,which compromise fatigue resistance during service.To address these issues,we synthesized hydroxyl-terminated polyurethane acrylate prepolymers using diphenylmethane diisocyanate(MDI),polypropylene glycol(PPG),and hydroxyethyl methacrylate(HEMA).Fourier transform infrared spectroscopy(FTIR)confirmed successful prepolymer synthesis.We developed UV-curable resins by incorporating various crosslinking monomers and optimized the formulations through mechanical property analysis.Testing revealed that the polyurethane-acrylic UV-cured resin system combines polyurethane's mechanical excellence with acrylics'high UV-curing activity.The PPG200/MDI/HEMA formulation achieved superior performance,with a tensile strength of 55.31 MPa,an impact toughness of 22.7 kJ/m^(2),and a heat deflection temperature(HDT)of 132℃.The optimized system eliminates volatile components while maintaining high reactivity,addressing critical limitations in trenchless pipeline rehabilitation.The improved mechanical properties meet the operational demands of underground pipes,suggesting practical applicability in trenchless pipeline repair.
基金Project(52373065)supported by the National Natural Science Foundation of ChinaProject(2220004002898)supported by the Zhuhai Industry University Research Cooperation and Basic and Applied Research Projects,China。
文摘Waterborne acrylic coatings are widely utilized due to their cost-effectiveness,high transparency,strong resistance to weather and chemicals,impressive mechanical properties,and excellent adhesion to various substrates.In these coatings,a reactive emulsifier containing phosphate groups can be integrated into the molecular chain during polymerization,which enhances the coating's compactness and corrosion resistance.This work focuses on the synthesis of styrene-butyl acrylate(St-BA)latex and methyl methacrylate-butyl acrylate(MMA-BA)latex using the reactive phosphate emulsifier ANPEO_(10)-P_(1) through seed emulsion polymerization,achieving a conversion rate of approximately 99%and a solid content close to 50%.The resulting coatings from St-BA and MMA-BA latexes demonstrated long-term corrosion protection for carbon steel and aluminum alloy due to in-situ phosphatization,effectively preventing flash rust.Notably,the MMA-BA coating exhibited remarkable durability,enduring immersion for up to 1224 h(51 d)on Q 235 carbon steel before reaching the failure threshold(|Z|0.01 Hz£106Ω·cm^(2))on Q 235 carbon steel.On 5052 aluminum alloy,the St-BA coating maintained|Z|0.01 Hz>10^(8)Ω·cm^(2) for 480 h(20 d).Furthermore,the corrosion resistance of St-BA and MMA BA coatings on Q 235 steel sheet and 5052 aluminum alloy surpassed that of commercially available MMA-BA and St BA coatings after immersion in a 3.5 wt%NaCl aqueous solution.This work also delves into the anticorrosion mechanism of MMA-BA and St-BA coatings.
