In this study,a series of porous intelligent hydrogels were synthesized by radiation exhibiting the lower critical solution temperature（LCST） and fast response involving a combination of A’-isopropyl acrylamideas m...In this study,a series of porous intelligent hydrogels were synthesized by radiation exhibiting the lower critical solution temperature（LCST） and fast response involving a combination of A’-isopropyl acrylamideas monomer, polyethylene glycol（PEG） as pore-forming agent and N,N-methylene-bis-acrylamide as crosslinking agent.The hydrogels were analyzed by Fourier transform infrared spectroscopy,and the influence of radiation doses on their swelling and thermal behaviors were studied.Their surface morphologies were examined by scanning electron microscopy.The results showed that PEG molecules only acted as pore-forming agent in the cross-linked polymerization.Their swelling ratios reduced with increasing radiation doses.The LCST was around 37℃,and varied little with the radiation doses.The frozen water content of PNIPAM/PEG6000 hydrogel reduced with increasing the radiation dose,and was greater than that of PN1PAM hydrogel at 15 kGy.Hydrogel macropores were prepared by PEG agent,and the hydrogels without PEG had a dense surface.The porous hydrogels are expected to be applied in the field of artificial intelligence material.展开更多
Negatively thermo-responsive 2D membranes,which mimic the stomatal opening/closing of plants,have drawn substantial interest for tunable molecular separation processes.However,these membranes are still restricted sign...Negatively thermo-responsive 2D membranes,which mimic the stomatal opening/closing of plants,have drawn substantial interest for tunable molecular separation processes.However,these membranes are still restricted significantly on account of low water permeability and poor dynamic tunability of 2D nanochannels under temperature stimulation.Here,we present a biomimetic negatively thermo-responsive MXene membrane by covalently grafting poly(N-isopropylacrylamide)(PNIPAm)onto MXene nanosheets.The uniformly grafted PNIPAm polymer chains can enlarge the interlayer spacings for increasing water permeability while also allowing more tunability of 2D nanochannels for enhancing the capability of gradually separating multiple molecules of different sizes.As expected,the constructed membrane exhibits ultrahigh water permeance of 95.6 L m^(-2) h^(-1) bar^(-1) at 25℃,which is eight-fold higher than the state-of-the-art negatively thermoresponsive 2D membranes.Moreover,the highly temperature-tunable 2D nanochannels enable the constructed membrane to perform excellent graded molecular sieving for dye-and antibiotic-based ternary mixtures.This strategy provides new perspectives in engineering smart 2D membrane and expands the scope of temperature-responsive membranes,showing promising applications in micro/nanofluidics and molecular separation.展开更多
The practical application of energetic materials, particularly 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(CL-20), is frequently impeded by phase transition challenges. In this study, we propose a novel...The practical application of energetic materials, particularly 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(CL-20), is frequently impeded by phase transition challenges. In this study, we propose a novel strategy to enhance the stability of CL-20 by employing a thermo-sensitive polymer,poly(N-isopropylacrylamide)(PNIPAM), to modulate its phase transitions. Our approach involves the use of an in-situ polymerized polydopamine(PDA) shell as a platform for surface grafting through atom transfer radical polymerization, yielding a core-shell structured CL-20@PDA-PNIPAM. Through comprehensive characterization, the successful grafting of PNIPAM is confirmed, significantly enhanced the phase stability of CL-20. Notably, our core-shell structure exhibits a 13℃ increase in phase transition temperature compared to raw CL-20, thereby delaying the ε→a phase transition by over 80 min under combined thermal and solvent conditions. The enhanced stability is attributed to the hydrophobic nature of PNIPAM above its low critical solution temperature in water, which effectively shields the CL-20 crystal. These findings provide new insights into enhancing the stability and safety of energetic materials in complex environments, highlighting the potential of our molecular switch mechanism.展开更多
By employing molecular theory, we systematically investigate the shift of solubility of poly（N-isopropylacrylamide）（PNIPAM） brushes in sodium halide solutions. After considering PNIPAM–water hydrogen bonds, water...By employing molecular theory, we systematically investigate the shift of solubility of poly（N-isopropylacrylamide）（PNIPAM） brushes in sodium halide solutions. After considering PNIPAM–water hydrogen bonds, water–anion hydrogen bonds, and PNIPAM–anion bonds and their explicit coupling to the PNIPAM conformations, we find that increasing temperature lowers the solubility of PNIPAM, and results in a collapse of the layer at high enough temperatures. The combination of the three types of bonds would yield a decrease in the solubility of PNIPAM following the Hofmeister series： Na Cl＆gt;Na Br＆gt;Na I. PNIPAM–water hydrogen bonds are affected by water–anion hydrogen bonds and PNIPAM–anion bonds. The coupling of polymer conformations and the competition among the three types of bonds are essential for describing correctly a decrease in the solubility of PNIPAM brushes, which is determined by the free energy associated with the formation of the three types of bonds. Our results agree well with the experimental observations, and would be very important for understanding the shift of the lower critical solution temperature of PNIPAM brushes following the Hofmeister series.展开更多
In this work, we investigate the effects of thiocyanate anions on the switching and the structure of poly(Nisopropylacrylamide)(PNIPAM) brushes using a molecular theory. Our model takes into consideration the PNIPAM–...In this work, we investigate the effects of thiocyanate anions on the switching and the structure of poly(Nisopropylacrylamide)(PNIPAM) brushes using a molecular theory. Our model takes into consideration the PNIPAM–anion bonds, the electrostatic effects and their explicit coupling to the PNIPAM conformations. It is found that at low thiocyanate anion concentration, as the anion concentration of thiocyanate increases, thiocyanate anions are more associated with PNIPAM chains through the PNIPAM–anion bonds, which contributes to stronger electrostatic repulsion and leads to an increase of lower critical solution temperature(LCST). By analyzing the average volume fractions of PNIPAM brushes,it is found that the PNIPAM brush presents a plateau structure. Our results show that the thiocyanate anions promote phase segregation due to the PNIPAM–anion bonds and the electrostatic effect. According to our model, the reduction of LCST can be explained as follows: at high thiocyanate anion concentration, with the increase of thiocyanate concentration, more ion bindings occurring between thiocyanate anions and PNIPAM chains will result in the increase of the hydrophobicity of PNIPAM chains;when the increase of electrostatic repulsion is insufficient to overcome the hydrophobic interaction of PNIPAM chains, it will lead to the reduction of brush height and LCST at high thiocyanate anion concentration. Our theoretical results are consistent with the experimental observations, and provide a fundamental understanding of the effects of thiocyanate on the LCST of PNIPAM brushes.展开更多
基金Supported by the Key Science and Technology Project of Henan Province(No.102101210100)the Natural Science Foundation ofHenan Province(No. 2011 B430023)
文摘In this study,a series of porous intelligent hydrogels were synthesized by radiation exhibiting the lower critical solution temperature（LCST） and fast response involving a combination of A’-isopropyl acrylamideas monomer, polyethylene glycol（PEG） as pore-forming agent and N,N-methylene-bis-acrylamide as crosslinking agent.The hydrogels were analyzed by Fourier transform infrared spectroscopy,and the influence of radiation doses on their swelling and thermal behaviors were studied.Their surface morphologies were examined by scanning electron microscopy.The results showed that PEG molecules only acted as pore-forming agent in the cross-linked polymerization.Their swelling ratios reduced with increasing radiation doses.The LCST was around 37℃,and varied little with the radiation doses.The frozen water content of PNIPAM/PEG6000 hydrogel reduced with increasing the radiation dose,and was greater than that of PN1PAM hydrogel at 15 kGy.Hydrogel macropores were prepared by PEG agent,and the hydrogels without PEG had a dense surface.The porous hydrogels are expected to be applied in the field of artificial intelligence material.
基金supported by the National Nature Science Foundation of China(No.22278179,U23A20688)the National Key Research and Development Program of China(2021YFB3802600)+3 种基金the Fundamental Research Funds for the Central Universities(JUSRP622035)National First-Class Discipline Program of Light Industry Technology and Engineering(LIFE2018-19)MOE&SAFEA for the 111 Project(B13025)Natural Science Foundation of Xinjiang Uygur Autonomous Region(2022D01D030).
文摘Negatively thermo-responsive 2D membranes,which mimic the stomatal opening/closing of plants,have drawn substantial interest for tunable molecular separation processes.However,these membranes are still restricted significantly on account of low water permeability and poor dynamic tunability of 2D nanochannels under temperature stimulation.Here,we present a biomimetic negatively thermo-responsive MXene membrane by covalently grafting poly(N-isopropylacrylamide)(PNIPAm)onto MXene nanosheets.The uniformly grafted PNIPAm polymer chains can enlarge the interlayer spacings for increasing water permeability while also allowing more tunability of 2D nanochannels for enhancing the capability of gradually separating multiple molecules of different sizes.As expected,the constructed membrane exhibits ultrahigh water permeance of 95.6 L m^(-2) h^(-1) bar^(-1) at 25℃,which is eight-fold higher than the state-of-the-art negatively thermoresponsive 2D membranes.Moreover,the highly temperature-tunable 2D nanochannels enable the constructed membrane to perform excellent graded molecular sieving for dye-and antibiotic-based ternary mixtures.This strategy provides new perspectives in engineering smart 2D membrane and expands the scope of temperature-responsive membranes,showing promising applications in micro/nanofluidics and molecular separation.
基金supported by National Natural Science Foundation of China(Grant Nos.U2130207,21875232,12372342)Foundation of President of China Academy of Engineering Physics(Grant Nos.YZJJZQ2023008,YZJJZQ2022006)the Foundation of China Academy of Engineering Physics(Grant Nos.CX20210015,CX20210027)。
文摘The practical application of energetic materials, particularly 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(CL-20), is frequently impeded by phase transition challenges. In this study, we propose a novel strategy to enhance the stability of CL-20 by employing a thermo-sensitive polymer,poly(N-isopropylacrylamide)(PNIPAM), to modulate its phase transitions. Our approach involves the use of an in-situ polymerized polydopamine(PDA) shell as a platform for surface grafting through atom transfer radical polymerization, yielding a core-shell structured CL-20@PDA-PNIPAM. Through comprehensive characterization, the successful grafting of PNIPAM is confirmed, significantly enhanced the phase stability of CL-20. Notably, our core-shell structure exhibits a 13℃ increase in phase transition temperature compared to raw CL-20, thereby delaying the ε→a phase transition by over 80 min under combined thermal and solvent conditions. The enhanced stability is attributed to the hydrophobic nature of PNIPAM above its low critical solution temperature in water, which effectively shields the CL-20 crystal. These findings provide new insights into enhancing the stability and safety of energetic materials in complex environments, highlighting the potential of our molecular switch mechanism.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.21264016,11464047,and 21364016)the Joint Funds of Xinjiang Natural Science Foundation,China(Grant No.2015211C298)
文摘By employing molecular theory, we systematically investigate the shift of solubility of poly（N-isopropylacrylamide）（PNIPAM） brushes in sodium halide solutions. After considering PNIPAM–water hydrogen bonds, water–anion hydrogen bonds, and PNIPAM–anion bonds and their explicit coupling to the PNIPAM conformations, we find that increasing temperature lowers the solubility of PNIPAM, and results in a collapse of the layer at high enough temperatures. The combination of the three types of bonds would yield a decrease in the solubility of PNIPAM following the Hofmeister series： Na Cl＆gt;Na Br＆gt;Na I. PNIPAM–water hydrogen bonds are affected by water–anion hydrogen bonds and PNIPAM–anion bonds. The coupling of polymer conformations and the competition among the three types of bonds are essential for describing correctly a decrease in the solubility of PNIPAM brushes, which is determined by the free energy associated with the formation of the three types of bonds. Our results agree well with the experimental observations, and would be very important for understanding the shift of the lower critical solution temperature of PNIPAM brushes following the Hofmeister series.
基金Project supported by the Joint Funds of Xinjiang Natural Science Foundation(Grant No.2019D01C333)the National Natural Science Foundation of China(Grant Nos.11847610 and 21764015)the National Basic Research Program of China(Grant No.2015CB857100)
文摘In this work, we investigate the effects of thiocyanate anions on the switching and the structure of poly(Nisopropylacrylamide)(PNIPAM) brushes using a molecular theory. Our model takes into consideration the PNIPAM–anion bonds, the electrostatic effects and their explicit coupling to the PNIPAM conformations. It is found that at low thiocyanate anion concentration, as the anion concentration of thiocyanate increases, thiocyanate anions are more associated with PNIPAM chains through the PNIPAM–anion bonds, which contributes to stronger electrostatic repulsion and leads to an increase of lower critical solution temperature(LCST). By analyzing the average volume fractions of PNIPAM brushes,it is found that the PNIPAM brush presents a plateau structure. Our results show that the thiocyanate anions promote phase segregation due to the PNIPAM–anion bonds and the electrostatic effect. According to our model, the reduction of LCST can be explained as follows: at high thiocyanate anion concentration, with the increase of thiocyanate concentration, more ion bindings occurring between thiocyanate anions and PNIPAM chains will result in the increase of the hydrophobicity of PNIPAM chains;when the increase of electrostatic repulsion is insufficient to overcome the hydrophobic interaction of PNIPAM chains, it will lead to the reduction of brush height and LCST at high thiocyanate anion concentration. Our theoretical results are consistent with the experimental observations, and provide a fundamental understanding of the effects of thiocyanate on the LCST of PNIPAM brushes.
