It is still challenging for conductive polymer composite-based electromagnetic interference(EMI)shielding materials to achieve long-term stability while maintaining high EMI shielding effectiveness(EMI SE),especially ...It is still challenging for conductive polymer composite-based electromagnetic interference(EMI)shielding materials to achieve long-term stability while maintaining high EMI shielding effectiveness(EMI SE),especially undergoing external mechanical stimuli,such as scratches or large deformations.Herein,an electrostatic assembly strategy is adopted to design a healable and segregated carbon nanotube(CNT)/graphene oxide(GO)/polyurethane(PU)composite with excellent and reliable EMI SE,even bearing complex mechanical condition.The negatively charged CNT/GO hybrid is facilely adsorbed on the surface of positively charged PU microsphere to motivate formation of segregated conductive networks in CNT/GO/PU composite,establishing a high EMI SE of 52.7 dB at only 10 wt%CNT/GO loading.The Diels–Alder bonds in PU microsphere endow the CNT/GO/PU composite suffering three cutting/healing cycles with EMI SE retention up to 90%.Additionally,the electrostatic attraction between CNT/GO hybrid and PU microsphere helps to strong interfacial bonding in the composite,resulting in high tensile strength of 43.1 MPa and elongation at break of 626%.The healing efficiency of elongation at break achieves 95%when the composite endured three cutting/healing cycles.This work demonstrates a novel strategy for developing segregated EMI shielding composite with healable features and excellent mechanical performance and shows great potential in the durable and high precision electrical instruments.展开更多
Due to the high electrophilic nature of azo-dienophiles, azo-Diels–Alder proceeds rapidly even without the need of a catalyst and is therefore regarded as the “click reaction”. This spontaneity causes strong backgr...Due to the high electrophilic nature of azo-dienophiles, azo-Diels–Alder proceeds rapidly even without the need of a catalyst and is therefore regarded as the “click reaction”. This spontaneity causes strong background reaction and poses a daunting challenge to chemists for developing the catalytic asymmetric version. Reported herein is the first catalytic asymmetric dearomative azo-Diels–Alder reaction between2-vinylindoles and triazoledione. This protocol makes use of the high energy barrier of dearomatization to avert the strong background reaction of azo-Diels–Alder reaction, allowing the implementation of the projected reaction at ambient temperature. Density functional theory calculations have been performed to gain insights into the reaction mechanism and the origins of the enantioselectivity. By using this method,a variety of tetracyclic indole derivatives have been readily prepared in good to excellent yields and with excellent diastereo-and enantio–selectivities(33 examples, up to 97% yield and >99% ee, >20:1 dr).展开更多
Zigzag hydrocarbon belts have been fascinating chemists and materials scientists for decades because of their aesthetically appealing molecular structures,outstanding physical properties and intriguing chemical reacti...Zigzag hydrocarbon belts have been fascinating chemists and materials scientists for decades because of their aesthetically appealing molecular structures,outstanding physical properties and intriguing chemical reactivities predicted by theoretical calculations,and potential applications as unique macrocyclic hosts in supramolecular chemistry.They may also serve as templates or seeds to grow structurally well-defined uniform zigzag carbon nanotubes.While there have been continuous computational studies on the structures and properties of belt[n]arenes or[n]cyclacenes since they were proposed as hypothetical molecules in 1954,the synthesis of(partially)conjugated zigzag hydrocarbon belts remains a great challenge,with no progress being reported in the past 20 years.Very recently,we have been witnessing the renaissance of synthetic interest in zigzag hydrocarbon belts,and the formation of the first fully conjugated one is on the horizon.This minireview focuses on the understanding of belt[n]arenes based on theoretical calculations and the synthesis and structure of zigzag hydrocarbon belts.Perspectives on the strategies to isolate and characterize the fully conjugated belt[n]arenes and on the applications of zigzag hydrocarbon belts are also discussed.展开更多
Humins are common undesirable sideproducts during many acid-catalyzed reactions in renewable biomass platform conversion. However, few studies have been reported to the efficient utilization of humins.For the first ti...Humins are common undesirable sideproducts during many acid-catalyzed reactions in renewable biomass platform conversion. However, few studies have been reported to the efficient utilization of humins.For the first time, the selective catalytic conversion of biomass-derived humins into cyclic hydrocarbons with high conversion rate and selectivity is presented using a home-made Ru/W-P-Si-O bifunctional catalyst. The multistage polymerization structure of humins was studied through controlled experiments.Results show that the CAC bond network can be efficiently depolymerized at a mild reaction temperature of 340–380 °C, catalyzed by the cooperative catalysis of nano-Ru particles and porous strong Lewis solid acid. Particularly, 95.4% conversion of humins was achieved under the optimal condition with up to 88.3%yield of cyclic hydrocarbons. The detailed composition after liquefaction was also analyzed. This study paves the way for the efficient production of cyclic and aromatic hydrocarbons from furan-derived humin polymer through Lewis acid-catalyzed Diels–Alder reactions between furan rings.展开更多
A direct asymmetric tandem reaction of a-nitro ketones with b g-unsaturated a-ketoesters was found to be catalyzed by a bifunctional rosin-derived thiourea and gave 5-nitro-2-actoxyl-2-pentenates in excellent ee value...A direct asymmetric tandem reaction of a-nitro ketones with b g-unsaturated a-ketoesters was found to be catalyzed by a bifunctional rosin-derived thiourea and gave 5-nitro-2-actoxyl-2-pentenates in excellent ee values and yields,a much better result than previously reported.Furthermore,through theoretical analysis,literature research and experimental verifications,a new mechanism involving an inverse-electron-demand Diels–Alder（IEDDAR） and a retro-Henry reaction was proposed.展开更多
基金The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China(Grant Nos.51973142,51721091,21878194)the National Key Research and Development Program of China(2018YFB0704200)the funds of the State Key Laboratory of Solidification Processing(Northwestern Polytechnical University)(SKLSP201918).
文摘It is still challenging for conductive polymer composite-based electromagnetic interference(EMI)shielding materials to achieve long-term stability while maintaining high EMI shielding effectiveness(EMI SE),especially undergoing external mechanical stimuli,such as scratches or large deformations.Herein,an electrostatic assembly strategy is adopted to design a healable and segregated carbon nanotube(CNT)/graphene oxide(GO)/polyurethane(PU)composite with excellent and reliable EMI SE,even bearing complex mechanical condition.The negatively charged CNT/GO hybrid is facilely adsorbed on the surface of positively charged PU microsphere to motivate formation of segregated conductive networks in CNT/GO/PU composite,establishing a high EMI SE of 52.7 dB at only 10 wt%CNT/GO loading.The Diels–Alder bonds in PU microsphere endow the CNT/GO/PU composite suffering three cutting/healing cycles with EMI SE retention up to 90%.Additionally,the electrostatic attraction between CNT/GO hybrid and PU microsphere helps to strong interfacial bonding in the composite,resulting in high tensile strength of 43.1 MPa and elongation at break of 626%.The healing efficiency of elongation at break achieves 95%when the composite endured three cutting/healing cycles.This work demonstrates a novel strategy for developing segregated EMI shielding composite with healable features and excellent mechanical performance and shows great potential in the durable and high precision electrical instruments.
基金the generous financial support from Natural Science Foundation of Henan Province (No.222300420084)application research plan of Key Scientific Research Projects in Colleges and Universities of Henan Province (No.22A150056)+1 种基金the Youth Innovation Team Program in Colleges and Universities of Shandong Province (No.2022KJ228)National Natural Science Foundation of China (No.22208302)。
文摘Due to the high electrophilic nature of azo-dienophiles, azo-Diels–Alder proceeds rapidly even without the need of a catalyst and is therefore regarded as the “click reaction”. This spontaneity causes strong background reaction and poses a daunting challenge to chemists for developing the catalytic asymmetric version. Reported herein is the first catalytic asymmetric dearomative azo-Diels–Alder reaction between2-vinylindoles and triazoledione. This protocol makes use of the high energy barrier of dearomatization to avert the strong background reaction of azo-Diels–Alder reaction, allowing the implementation of the projected reaction at ambient temperature. Density functional theory calculations have been performed to gain insights into the reaction mechanism and the origins of the enantioselectivity. By using this method,a variety of tetracyclic indole derivatives have been readily prepared in good to excellent yields and with excellent diastereo-and enantio–selectivities(33 examples, up to 97% yield and >99% ee, >20:1 dr).
基金the National Science Foundation of China(grant nos.21732004,21821001,and 91427301)Tsinghua University Initiative Scientific Research Program for financial support.
文摘Zigzag hydrocarbon belts have been fascinating chemists and materials scientists for decades because of their aesthetically appealing molecular structures,outstanding physical properties and intriguing chemical reactivities predicted by theoretical calculations,and potential applications as unique macrocyclic hosts in supramolecular chemistry.They may also serve as templates or seeds to grow structurally well-defined uniform zigzag carbon nanotubes.While there have been continuous computational studies on the structures and properties of belt[n]arenes or[n]cyclacenes since they were proposed as hypothetical molecules in 1954,the synthesis of(partially)conjugated zigzag hydrocarbon belts remains a great challenge,with no progress being reported in the past 20 years.Very recently,we have been witnessing the renaissance of synthetic interest in zigzag hydrocarbon belts,and the formation of the first fully conjugated one is on the horizon.This minireview focuses on the understanding of belt[n]arenes based on theoretical calculations and the synthesis and structure of zigzag hydrocarbon belts.Perspectives on the strategies to isolate and characterize the fully conjugated belt[n]arenes and on the applications of zigzag hydrocarbon belts are also discussed.
基金supported financially by the National Natural Science Foundation of China (No. 21972056)Natural Science Foundation of Inner Mongolia, China (Nos. 2018LH02009 and 2019BS02012)+1 种基金Science Foundation of High Education Institutes of Inner Mongolia, China (No. NJZY20071)Science Foundation Inner Mongolia University of Technology (No. ZZ201804)。
文摘Humins are common undesirable sideproducts during many acid-catalyzed reactions in renewable biomass platform conversion. However, few studies have been reported to the efficient utilization of humins.For the first time, the selective catalytic conversion of biomass-derived humins into cyclic hydrocarbons with high conversion rate and selectivity is presented using a home-made Ru/W-P-Si-O bifunctional catalyst. The multistage polymerization structure of humins was studied through controlled experiments.Results show that the CAC bond network can be efficiently depolymerized at a mild reaction temperature of 340–380 °C, catalyzed by the cooperative catalysis of nano-Ru particles and porous strong Lewis solid acid. Particularly, 95.4% conversion of humins was achieved under the optimal condition with up to 88.3%yield of cyclic hydrocarbons. The detailed composition after liquefaction was also analyzed. This study paves the way for the efficient production of cyclic and aromatic hydrocarbons from furan-derived humin polymer through Lewis acid-catalyzed Diels–Alder reactions between furan rings.
基金the National Natural Science Foundation of China (Nos. 21071068 and 21372107)the Fundamental Research Funds for the Central Universities (No. lzujbky-2012-k08)
文摘A direct asymmetric tandem reaction of a-nitro ketones with b g-unsaturated a-ketoesters was found to be catalyzed by a bifunctional rosin-derived thiourea and gave 5-nitro-2-actoxyl-2-pentenates in excellent ee values and yields,a much better result than previously reported.Furthermore,through theoretical analysis,literature research and experimental verifications,a new mechanism involving an inverse-electron-demand Diels–Alder（IEDDAR） and a retro-Henry reaction was proposed.
