Norbornene derivatives exo,endo-2-[2-(3,5-di-tert-butyl-4-hydroxyphenoxy)-acetoxy]methyl-5-norbornene(M1) and 3,3,5,5-tetramethyl-4-piperidinyl 5-norbornene-exo,endo-2-carboxylate(M2)were synthesized and polymerized b...Norbornene derivatives exo,endo-2-[2-(3,5-di-tert-butyl-4-hydroxyphenoxy)-acetoxy]methyl-5-norbornene(M1) and 3,3,5,5-tetramethyl-4-piperidinyl 5-norbornene-exo,endo-2-carboxylate(M2)were synthesized and polymerized by RuCl_2(=CHPh)(PCy_3)_2 to prepare a novel kind of bi-functional polymer bearing sterically hindered phenol(SHP)and hindered amine(HLAS)groups via ring-opening metathesis polymerization(ROMP).The resulting copolymers were characterized by gel permeation chromatography(GPC),~1H-NMR and differen...展开更多
Chinese college students reading in a foreign language seem to read with less understanding and at a considerably slower speed. The factors that hinder Chinese college students' English reading were analyzed at th...Chinese college students reading in a foreign language seem to read with less understanding and at a considerably slower speed. The factors that hinder Chinese college students' English reading were analyzed at the lexical level, the syntactic level,and the discourse level. And then, several reading strategies were recommended to overcome such reading difficulties.展开更多
Copolymerization of propylene and hindered piperidine monomers was carried out over a high activity supported Ziegler-Natta catalyst, using Al(C2H5)(3) as cocatalyst. Factors which affect the copolymerization were stu...Copolymerization of propylene and hindered piperidine monomers was carried out over a high activity supported Ziegler-Natta catalyst, using Al(C2H5)(3) as cocatalyst. Factors which affect the copolymerization were studied, The copolymers exhibited high light stability without adding extra light stabilizers. A self-stabilized polypropylene was prepared.展开更多
Sphingosine-1-phosphate(S1P)is an important lipid mediator that regulates a diverse range of intracellular cell signaling pathways that are relevant to tissue engineering and regenerative medicine.However,the precise ...Sphingosine-1-phosphate(S1P)is an important lipid mediator that regulates a diverse range of intracellular cell signaling pathways that are relevant to tissue engineering and regenerative medicine.However,the precise function of S1P in dental pulp stem cells(DPSCs)and its osteogenic differentiation remains unclear.We here investigated the function of S1P/S1P receptor(S1PR)-mediated cellular signaling in the osteogenic differentiation of DPSCs and clarified the fundamental signaling pathway.Our results showed that S1P-treated DPSCs exhibited a low rate of differentiation toward the osteogenic phenotype in association with a marked reduction in osteogenesis-related gene expression and AKT activation.Of note,both S1PR1/S1PR3 and S1PR2 agonists significantly downregulated the expression of osteogenic genes and suppressed AKT activation,resulting in an attenuated osteogenic capacity of DPSCs.Most importantly,an AKT activator completely abrogated the S1P-mediated downregulation of osteoblastic markers and partially prevented S1P-mediated attenuation effects during osteogenesis.Intriguingly,the pro-inflammatory TNF-αcytokine promoted the infiltration of macrophages toward DPSCs and induced S1P production in both DPSCs and macrophages.Our findings indicate that the elevation of S1P under inflammatory conditions suppresses the osteogenic capacity of the DPSCs responsible for regenerative endodontics.展开更多
The representative azo and anthraquinone dyes containing an insulated hindered piperidinegroup were synthesized.The effect of these pendent groups on lightfastness properties of the dyeswas studied,both in ethyl aceta...The representative azo and anthraquinone dyes containing an insulated hindered piperidinegroup were synthesized.The effect of these pendent groups on lightfastness properties of the dyeswas studied,both in ethyl acetate solution and on cellulose acetate and polyester films.The differ-ent trend of fading rates of azo dyes and anthraquinone dyes in solution and on substrates suggestsdifferent fading mechanisms operating in each case.展开更多
Hindered phenol compound 3,9-bis{1,1-dimethyl-2[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}- 2,4,8,10-tetraoxaspiro[5,5]-undecane (AO-80) is a polymorphous material with different physical structures...Hindered phenol compound 3,9-bis{1,1-dimethyl-2[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}- 2,4,8,10-tetraoxaspiro[5,5]-undecane (AO-80) is a polymorphous material with different physical structures. The initial AO- 80 is highly crystalline, whereas AO-80 obtained by cooling from its molten state is an amorphous material. Annealing treatment below the melting point of AO-80 results in structural development. The mixture of chlorinated polyethylene (CPE) and vitrified AO-80 particles exhibits a dramatic change in the dynamic mechanical properties during heat treatment at 130'C. This change can be attributed to the decomposition of the vitrified AO-80 particles and the hybridization of two constituents. The vitrified AO-80 particles can crystallize again in a CPE matrix by annealing at 100'C, but this crystal is different from that of the initial AO-80 in its microstructure. In addition, the incorporation of CPE chains caused a dramatic increase in the modulus. As a result, the AO-80 crystal particles that contain some CPE chains act as multifunctional cross- links and the CPE/AO-80 hybrid was found to be a new type of elastomer.展开更多
A series of di-n-hexyl alkyl phosphonates with bulky substituent on phosphorus was synthesized by PTC P-alkylation using crown ether.Upon saponification of the resulting di-n-hexyl alkylphosphonates in the presence of...A series of di-n-hexyl alkyl phosphonates with bulky substituent on phosphorus was synthesized by PTC P-alkylation using crown ether.Upon saponification of the resulting di-n-hexyl alkylphosphonates in the presence of crown ether or quaternary ammonium halide, corresponding mono-hexyl esters of alkyl phosphonic acids were prepared.Ultrasonic wave, as we found, can catalyze the reaction between dialkyl phosphite & metallic sodium and hydrolysis of dihexyl alkyl phosphonates.A series of di-t-alkyl phosphinic acids were synthesized by the reaction of Grignard reagent with PCl_3 followed by oxidation with 30% H_2O_2.It was found that the reaction between dibutyl phosphite and Grignard reagent of t-alkyl chloride is a new synthetic method for the preparation of mono-esters of highly hindered alkyl phosphonic acids.展开更多
In this study,a series of hindered urea bond(HUB)containing polyurethane-urea methacrylate prepolymers and a none HUB containing polyurethane methacrylate prepolymer were prepared using isobornyl methacrylate as the r...In this study,a series of hindered urea bond(HUB)containing polyurethane-urea methacrylate prepolymers and a none HUB containing polyurethane methacrylate prepolymer were prepared using isobornyl methacrylate as the reactive diluent via one-pot procedure.The prepolymers were characterized fully by various techniques.Then,their thermosets were fabricated via UV curing in presence of a photo initiator,and their mechanical property and thermal behavior were investigated and compared.Different from the none HUB containing thermoset,the HUB containing thermosets(defined as PUT)could be recycled and reprocessed by hot press under relatively mild conditions with high recovery ratio of mechanical property.Furthermore,zinc oxide(ZnO)nanoparticles were modified with 3-(trimethoxysilyl)propyl methacrylate and the modified ZnO(defined as ZnO-TPM)was dispersed and polymerized into PUT matrix to prepare their nanocomposites.The influence of ZnO-TPM on the mechanical performance of the composites was evaluated,which indicated that the Young’s modulus and tensile strength increased gradually to the maximum values at ZnO-TPM content of 1 wt%and then decreased.The composites also displayed good reprocessability with improved recovery ratio compared to the pure PUT sample.In addition,the composite materials exhibited strong UV absorption capacity,implying their potential application in the circumstance where UV-shielding was required.展开更多
Exploration of exotic phenomena in magnetic topological systems is at the frontier of condensed matter physics,holding a significant promise for applications in topological spintronics.However,complex magnetic structu...Exploration of exotic phenomena in magnetic topological systems is at the frontier of condensed matter physics,holding a significant promise for applications in topological spintronics.However,complex magnetic structures carrying nontrivial topological properties hinder its progresses.Here,we investigate the pressure effect on the novel topological kagome magnets GdV_(6)Sn_(6) and TbV_(6)Sn_(6) to dig out the interplay between magnetic Gd/Tb layers and nonmagnetic V-based kagome sublattice.The pressure-tuned magnetic transition temperature Tm in both the compounds exhibit a turning point at the critical pressure P_(c),accompanied with a sign reversal in anomalous Hall effect(AHE).The separation of intrinsic and extrinsic contributions using the Tian-Ye-Jin scaling model suggests that the intrinsic mechanism originating from the electronic Berry curvature holds the priority in the competition with extrinsic mechanism in AHE.The above-mentioned findings can be attributed to the combined effect of pressure-tuned band topology and magnetic interaction in segregated layers.Our results provide a practical route to design and manipulate the intrinsic AHE in magnetic topological materials.展开更多
In this contribution,we reported the preparation of vitrimers by using commodity thermoplastics via post crosslinking with hindered urea bonds(HUBs).First,three hindered urea diisocyanates(HUDIs)were synthesized via t...In this contribution,we reported the preparation of vitrimers by using commodity thermoplastics via post crosslinking with hindered urea bonds(HUBs).First,three hindered urea diisocyanates(HUDIs)were synthesized via the reactions of N,N'-di-tert-butylethylenediamine,N,N'-diethylethylenediamine,and piperazine with isophorone diisocyanate(IPDI).Thereafter,these HUDIs were used as the crosslinking agents to crosslink poly(hydroxyether of bisphenol A)(PH),a commodity thermoplastics.Fourier transform infrared(FTIR)spectroscopy and dynamic mechanical thermal analyses(DMTA)indicated that the PH thermosets were successfully obtained.It was found that the thermosets displayed the behavior of vitrimers.The PH thermosets can be reprocessed at elevated temperature without using catalyst and the mechanical strengths of vitrimers were recovered as high as 95%.The reprocessing properties are attributable to dynamic exchange reaction of hindered urea bonds,contingent on types of hindered urea bonds.展开更多
基金Sasakawa Scientific Research Grant from the Japan Science Society.
文摘Norbornene derivatives exo,endo-2-[2-(3,5-di-tert-butyl-4-hydroxyphenoxy)-acetoxy]methyl-5-norbornene(M1) and 3,3,5,5-tetramethyl-4-piperidinyl 5-norbornene-exo,endo-2-carboxylate(M2)were synthesized and polymerized by RuCl_2(=CHPh)(PCy_3)_2 to prepare a novel kind of bi-functional polymer bearing sterically hindered phenol(SHP)and hindered amine(HLAS)groups via ring-opening metathesis polymerization(ROMP).The resulting copolymers were characterized by gel permeation chromatography(GPC),~1H-NMR and differen...
文摘Chinese college students reading in a foreign language seem to read with less understanding and at a considerably slower speed. The factors that hinder Chinese college students' English reading were analyzed at the lexical level, the syntactic level,and the discourse level. And then, several reading strategies were recommended to overcome such reading difficulties.
文摘Copolymerization of propylene and hindered piperidine monomers was carried out over a high activity supported Ziegler-Natta catalyst, using Al(C2H5)(3) as cocatalyst. Factors which affect the copolymerization were studied, The copolymers exhibited high light stability without adding extra light stabilizers. A self-stabilized polypropylene was prepared.
基金supported by a National Research Foundation of Korea(NRF)MRC grant(2018R1A5A2020732)by a grant of the Basic Science and Engineering Research Program(2018R1A2B2001867)funded by the Korean government to E.J.C.by the Bio&Medical Technology Development Program(NRF2017M3A9E4047243)funded by the Ministry of Science,ICT and Future Planning,the Republic of Korea to H.R.K.
文摘Sphingosine-1-phosphate(S1P)is an important lipid mediator that regulates a diverse range of intracellular cell signaling pathways that are relevant to tissue engineering and regenerative medicine.However,the precise function of S1P in dental pulp stem cells(DPSCs)and its osteogenic differentiation remains unclear.We here investigated the function of S1P/S1P receptor(S1PR)-mediated cellular signaling in the osteogenic differentiation of DPSCs and clarified the fundamental signaling pathway.Our results showed that S1P-treated DPSCs exhibited a low rate of differentiation toward the osteogenic phenotype in association with a marked reduction in osteogenesis-related gene expression and AKT activation.Of note,both S1PR1/S1PR3 and S1PR2 agonists significantly downregulated the expression of osteogenic genes and suppressed AKT activation,resulting in an attenuated osteogenic capacity of DPSCs.Most importantly,an AKT activator completely abrogated the S1P-mediated downregulation of osteoblastic markers and partially prevented S1P-mediated attenuation effects during osteogenesis.Intriguingly,the pro-inflammatory TNF-αcytokine promoted the infiltration of macrophages toward DPSCs and induced S1P production in both DPSCs and macrophages.Our findings indicate that the elevation of S1P under inflammatory conditions suppresses the osteogenic capacity of the DPSCs responsible for regenerative endodontics.
文摘The representative azo and anthraquinone dyes containing an insulated hindered piperidinegroup were synthesized.The effect of these pendent groups on lightfastness properties of the dyeswas studied,both in ethyl acetate solution and on cellulose acetate and polyester films.The differ-ent trend of fading rates of azo dyes and anthraquinone dyes in solution and on substrates suggestsdifferent fading mechanisms operating in each case.
基金This work was financially supported by the "The National High Technology Research and Development Program " of theMinistry of Science and Technology of China (the registered number is 2002AA333020).
文摘Hindered phenol compound 3,9-bis{1,1-dimethyl-2[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}- 2,4,8,10-tetraoxaspiro[5,5]-undecane (AO-80) is a polymorphous material with different physical structures. The initial AO- 80 is highly crystalline, whereas AO-80 obtained by cooling from its molten state is an amorphous material. Annealing treatment below the melting point of AO-80 results in structural development. The mixture of chlorinated polyethylene (CPE) and vitrified AO-80 particles exhibits a dramatic change in the dynamic mechanical properties during heat treatment at 130'C. This change can be attributed to the decomposition of the vitrified AO-80 particles and the hybridization of two constituents. The vitrified AO-80 particles can crystallize again in a CPE matrix by annealing at 100'C, but this crystal is different from that of the initial AO-80 in its microstructure. In addition, the incorporation of CPE chains caused a dramatic increase in the modulus. As a result, the AO-80 crystal particles that contain some CPE chains act as multifunctional cross- links and the CPE/AO-80 hybrid was found to be a new type of elastomer.
基金Project Supported by National Science Foundation of China.
文摘A series of di-n-hexyl alkyl phosphonates with bulky substituent on phosphorus was synthesized by PTC P-alkylation using crown ether.Upon saponification of the resulting di-n-hexyl alkylphosphonates in the presence of crown ether or quaternary ammonium halide, corresponding mono-hexyl esters of alkyl phosphonic acids were prepared.Ultrasonic wave, as we found, can catalyze the reaction between dialkyl phosphite & metallic sodium and hydrolysis of dihexyl alkyl phosphonates.A series of di-t-alkyl phosphinic acids were synthesized by the reaction of Grignard reagent with PCl_3 followed by oxidation with 30% H_2O_2.It was found that the reaction between dibutyl phosphite and Grignard reagent of t-alkyl chloride is a new synthetic method for the preparation of mono-esters of highly hindered alkyl phosphonic acids.
文摘In this study,a series of hindered urea bond(HUB)containing polyurethane-urea methacrylate prepolymers and a none HUB containing polyurethane methacrylate prepolymer were prepared using isobornyl methacrylate as the reactive diluent via one-pot procedure.The prepolymers were characterized fully by various techniques.Then,their thermosets were fabricated via UV curing in presence of a photo initiator,and their mechanical property and thermal behavior were investigated and compared.Different from the none HUB containing thermoset,the HUB containing thermosets(defined as PUT)could be recycled and reprocessed by hot press under relatively mild conditions with high recovery ratio of mechanical property.Furthermore,zinc oxide(ZnO)nanoparticles were modified with 3-(trimethoxysilyl)propyl methacrylate and the modified ZnO(defined as ZnO-TPM)was dispersed and polymerized into PUT matrix to prepare their nanocomposites.The influence of ZnO-TPM on the mechanical performance of the composites was evaluated,which indicated that the Young’s modulus and tensile strength increased gradually to the maximum values at ZnO-TPM content of 1 wt%and then decreased.The composites also displayed good reprocessability with improved recovery ratio compared to the pure PUT sample.In addition,the composite materials exhibited strong UV absorption capacity,implying their potential application in the circumstance where UV-shielding was required.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFA1402203)the Shanghai Municipal Science and Technology Major Project(Grant No.2019SHZDZX01)+5 种基金supported by the National Key R&D Program of China(Grants No.2023YFA1406100)the Double First-Class Initiative Fund of ShanghaiTech Universitysupported by the National Natural Science Foundation of China(Grant No.52272265)supported by the National Science Basic Research Plan in the Shaanxi Province of China(Grant No.2024JC-YBQN-0390)supported by the open project from State Key Laboratory of Surface Physics and Department of Physics,Fudan University(Grant No.KF2022-13)supported by the National Natural Science Foundation of China(Grant No.52302010)。
文摘Exploration of exotic phenomena in magnetic topological systems is at the frontier of condensed matter physics,holding a significant promise for applications in topological spintronics.However,complex magnetic structures carrying nontrivial topological properties hinder its progresses.Here,we investigate the pressure effect on the novel topological kagome magnets GdV_(6)Sn_(6) and TbV_(6)Sn_(6) to dig out the interplay between magnetic Gd/Tb layers and nonmagnetic V-based kagome sublattice.The pressure-tuned magnetic transition temperature Tm in both the compounds exhibit a turning point at the critical pressure P_(c),accompanied with a sign reversal in anomalous Hall effect(AHE).The separation of intrinsic and extrinsic contributions using the Tian-Ye-Jin scaling model suggests that the intrinsic mechanism originating from the electronic Berry curvature holds the priority in the competition with extrinsic mechanism in AHE.The above-mentioned findings can be attributed to the combined effect of pressure-tuned band topology and magnetic interaction in segregated layers.Our results provide a practical route to design and manipulate the intrinsic AHE in magnetic topological materials.
基金the National Natural Science Foundation of China(Nos.51973113,51133003,and 21774078).
文摘In this contribution,we reported the preparation of vitrimers by using commodity thermoplastics via post crosslinking with hindered urea bonds(HUBs).First,three hindered urea diisocyanates(HUDIs)were synthesized via the reactions of N,N'-di-tert-butylethylenediamine,N,N'-diethylethylenediamine,and piperazine with isophorone diisocyanate(IPDI).Thereafter,these HUDIs were used as the crosslinking agents to crosslink poly(hydroxyether of bisphenol A)(PH),a commodity thermoplastics.Fourier transform infrared(FTIR)spectroscopy and dynamic mechanical thermal analyses(DMTA)indicated that the PH thermosets were successfully obtained.It was found that the thermosets displayed the behavior of vitrimers.The PH thermosets can be reprocessed at elevated temperature without using catalyst and the mechanical strengths of vitrimers were recovered as high as 95%.The reprocessing properties are attributable to dynamic exchange reaction of hindered urea bonds,contingent on types of hindered urea bonds.