Poly(lactic acid)(PLA) as a bio-based polymer with biodegradability and biocompatibility has attracted much attention. To manipulate its properties for different applications, regulation of crystal structure and cryst...Poly(lactic acid)(PLA) as a bio-based polymer with biodegradability and biocompatibility has attracted much attention. To manipulate its properties for different applications, regulation of crystal structure and crystalline morphology becomes an attractive research topic. In this work, the structure evolution of layered samples containing an amorphous poly(D-lactide)(PDLA) layer and a crystalline poly(L-lactide)(PLLA)layer with highly oriented edge-on α lamellar crystals after annealing at 150 ℃ or/and after melt-recrystallization has been studied by AFM, FTIR,and TEM combined with electron diffraction. The results demonstrate that melt recrystallization of the as-prepared sample leads to the formation of abundant randomly oriented PLA stereo-complex(PLA SC) crystals. Annealing at 150 ℃ results in the formation of a small amount of oriented PLA SC crystals at the interface. These PLA SC crystals show great impact on the recrystallization behavior of sample after melting at 190 ℃ and then crystallizing at 90 ℃. First, they impede the mutual diffusion of the overlying PDLA and underlying PLLA, and thus reduce their stereocomplexation ability as manifested by the decreased amount of PLA SC crystals. Second, they act as substrate to initiate the epitaxial crystallization of the overlying PDLA and underlying PLLA, which ensures the production of a highly oriented structure of PDLA and PLLA after melt recrystallization again.展开更多
A catalytic asymmetric tandem reaction including a chiral aldehyde catalyzed conjugated addition and an intramolecular lactamization is reported in this work.Under the optimal reaction conditions,various fully substit...A catalytic asymmetric tandem reaction including a chiral aldehyde catalyzed conjugated addition and an intramolecular lactamization is reported in this work.Under the optimal reaction conditions,various fully substituted pyroglutamic acids bearing three vicinal chiral centers were generated in good-to-excellent yields and stereoselectivities.A reasonable reaction mechanism is proposed to illustrate the observed stereoselective control results.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 52027804 and 22022501)Postgraduate Independent Innovation Project (No. B2022KY004,Qingdao University of Science and Technology)。
文摘Poly(lactic acid)(PLA) as a bio-based polymer with biodegradability and biocompatibility has attracted much attention. To manipulate its properties for different applications, regulation of crystal structure and crystalline morphology becomes an attractive research topic. In this work, the structure evolution of layered samples containing an amorphous poly(D-lactide)(PDLA) layer and a crystalline poly(L-lactide)(PLLA)layer with highly oriented edge-on α lamellar crystals after annealing at 150 ℃ or/and after melt-recrystallization has been studied by AFM, FTIR,and TEM combined with electron diffraction. The results demonstrate that melt recrystallization of the as-prepared sample leads to the formation of abundant randomly oriented PLA stereo-complex(PLA SC) crystals. Annealing at 150 ℃ results in the formation of a small amount of oriented PLA SC crystals at the interface. These PLA SC crystals show great impact on the recrystallization behavior of sample after melting at 190 ℃ and then crystallizing at 90 ℃. First, they impede the mutual diffusion of the overlying PDLA and underlying PLLA, and thus reduce their stereocomplexation ability as manifested by the decreased amount of PLA SC crystals. Second, they act as substrate to initiate the epitaxial crystallization of the overlying PDLA and underlying PLLA, which ensures the production of a highly oriented structure of PDLA and PLLA after melt recrystallization again.
基金We are grateful for financial support from NSFC(22071199,21871223)the Chongqing Science Technology Commission(cstccxljrc201701,cstc2018jcyjAX0548).
文摘A catalytic asymmetric tandem reaction including a chiral aldehyde catalyzed conjugated addition and an intramolecular lactamization is reported in this work.Under the optimal reaction conditions,various fully substituted pyroglutamic acids bearing three vicinal chiral centers were generated in good-to-excellent yields and stereoselectivities.A reasonable reaction mechanism is proposed to illustrate the observed stereoselective control results.
