While the accelerated polymerization of N-carboxyanhydrides (NCAs) has been utilized to synthesize versatile polypeptide materials in an efficient manner with minimized side reactions, the preparation of polypeptide-b...While the accelerated polymerization of N-carboxyanhydrides (NCAs) has been utilized to synthesize versatile polypeptide materials in an efficient manner with minimized side reactions, the preparation of polypeptide-based inorganic/organic hybrid materials with the acceleration strategy remained largely unexplored. Herein, we report the accelerated ring-opening polymerization (ROP) of NCAs mediated by amine-modified inorganic nano-initiators, such as mesoporous silica nanoparticles (MSN-NH2), which is driven by the cooperative effect of the neighboring α-helical polypeptide chains in a dichloromethane (DCM)/water biphasic system. Well-defined nano-hybrids were prepared within 15 min from non-purified NCA monomers, through in situ purification and subsequent ultrafast polymerization process. NCAs can be rapidly initiated by amino groups of MSN uniformly dispersed at the interface of DCM and water, and subsequently formed the well-defined polypeptides within 15 min. The prepared inorganic/organic nano-hybrid with MSN as the core and polypeptide as the shell adopted spherical morphology and uniform size distribution due to the excellent controllability of ROP. Besides, this system is also suitable for a variety of NCAs and inorganic nano-initiators. This research allows efficient and rapid preparation of inorganic/organic nano-hybrids, and further promotes the extensive application of this material in the biomedical fields.展开更多
The combined influence of chemical composition,molecular weight(MW)and molecular weight distribution(D)on the functions and performances of polymeric materials necessitates simultaneous satisfaction of multidimensiona...The combined influence of chemical composition,molecular weight(MW)and molecular weight distribution(D)on the functions and performances of polymeric materials necessitates simultaneous satisfaction of multidimensional requirements during polymer synthesis.However,the complexity of polymerization reactions often dissuades chemists when precisely accessing diversified polymer targets.Herein,we developed a machine learning(ML)-assisted systematical polymerization planning(SPP)platform for addressing this challenge.With ML model providing integrated navigation of the reaction space,this approach can conduct multivariate analysis to uncover complex interactions between the polymerization result and conditions,prescribing optimal reaction conditions to achieve discretionary polymer targets concerning three dimensions including chemical composition,MWandD values.Given the increasing importance of polymerization in advanced material engineering,this ML-assisted SPP platform provides a universal strategy to access tailored polymers with on-demand prediction of polymerization parameters.展开更多
基金supported by the National Natural Science Foundation of China(22101194 and 52273144)Science and Technology Department of Jiangsu Province(BK20210733).
文摘While the accelerated polymerization of N-carboxyanhydrides (NCAs) has been utilized to synthesize versatile polypeptide materials in an efficient manner with minimized side reactions, the preparation of polypeptide-based inorganic/organic hybrid materials with the acceleration strategy remained largely unexplored. Herein, we report the accelerated ring-opening polymerization (ROP) of NCAs mediated by amine-modified inorganic nano-initiators, such as mesoporous silica nanoparticles (MSN-NH2), which is driven by the cooperative effect of the neighboring α-helical polypeptide chains in a dichloromethane (DCM)/water biphasic system. Well-defined nano-hybrids were prepared within 15 min from non-purified NCA monomers, through in situ purification and subsequent ultrafast polymerization process. NCAs can be rapidly initiated by amino groups of MSN uniformly dispersed at the interface of DCM and water, and subsequently formed the well-defined polypeptides within 15 min. The prepared inorganic/organic nano-hybrid with MSN as the core and polypeptide as the shell adopted spherical morphology and uniform size distribution due to the excellent controllability of ROP. Besides, this system is also suitable for a variety of NCAs and inorganic nano-initiators. This research allows efficient and rapid preparation of inorganic/organic nano-hybrids, and further promotes the extensive application of this material in the biomedical fields.
基金This work was supported by the National Natural Science Foundation of China(21971044,21704016)Fudan University and State Key Laboratory of Molecular Engineering of Polymers。
文摘The combined influence of chemical composition,molecular weight(MW)and molecular weight distribution(D)on the functions and performances of polymeric materials necessitates simultaneous satisfaction of multidimensional requirements during polymer synthesis.However,the complexity of polymerization reactions often dissuades chemists when precisely accessing diversified polymer targets.Herein,we developed a machine learning(ML)-assisted systematical polymerization planning(SPP)platform for addressing this challenge.With ML model providing integrated navigation of the reaction space,this approach can conduct multivariate analysis to uncover complex interactions between the polymerization result and conditions,prescribing optimal reaction conditions to achieve discretionary polymer targets concerning three dimensions including chemical composition,MWandD values.Given the increasing importance of polymerization in advanced material engineering,this ML-assisted SPP platform provides a universal strategy to access tailored polymers with on-demand prediction of polymerization parameters.
