A facile method is reported to controllably fabricate one dimensional （1D） polymer nan,astructures via metallogel template polymerization. The metallogel was prepared through coordination interactions between silver...A facile method is reported to controllably fabricate one dimensional （1D） polymer nan,astructures via metallogel template polymerization. The metallogel was prepared through coordination interactions between silver ions and a ligand （L） bearing three pyridyl groups in tetrahydrofuran （THF）. The diameters of the metallogel nanofibers could be tuned by the gel concentration （GC）. Due to its high thermal stability and facility of removal, the metallogel was used as the template for radical polymerization of diacryolyl-2,6-diaminopyridine （DADAP） to form poly-diacryolyl-2,6-diaminopyridine （PDADAP） nanostructures. The gradually eroding of the templates by PDADAP provided us an effective way to fabricate various nanostructures of the polymer. We have demonstrated that different 1D nanostructures, including n^noribbons, nanotubes and nanowires, could be selectively fabricated by adjusting polymerization time, monomer concentration and GC. The rheological properties of the gel samples were tested by a rheometer. As prolonging the reaction time, more and more polymers were formed and the strength of the resulting polymer gels became higher and higher. The simple preparation process, easy controlled microstructures and adequate gel strength would make it a facile synthetic method for different 1D polymer nanosturctures.展开更多
The hierarchical self-assembly(HSA) strategy widely utilized in biological systems has been applied in artificial systems to orchestrate small building blocks into complex functional architectures. The non-interfering...The hierarchical self-assembly(HSA) strategy widely utilized in biological systems has been applied in artificial systems to orchestrate small building blocks into complex functional architectures. The non-interfering interactions glue various building blocks together and produce new species with attractive properties. Herein, we functionalized NHC-based assemblies with orthogonal host–guest interaction to fabricate metal-carbene based supramolecular polymer gel. A series of unique crown etherappended cylinder-like trinuclear AuIhexacarbene assemblies [Au_(3)(L)_(2)](PF_(6))_(3)(L=D1–D4, A1–A4) were synthesized from the corresponding trisimidazolium salts H_(3)-L(PF_(6))_(3)(L=D1–D4, A1–A4) in which the N-wingtip of the imidazole moieties were substituted with three identical crown ether groups of different sizes(B15C5, B18C6, B21C7, DB24C8). The gold carbene assembly is able to complex six ammonium salts without disrupting the underlying metal-carbene cylinders. In addition, the supramolecular polymer metallogel featuring a multiple-responsiveness can be formed by using [Au_(3)(A_(4))_(2)](PF_(6))_(3) appended with DB24C8 as the core and bisammonium salt as the cross-linker. The case of introducing orthogonal interaction to NHC moiety by N-wingtip substitution demonstrates the feasibility and the power of such strategy to expand the NHC-based supramolecular system and endow them with novel properties.展开更多
Hydrazine hydrate(DH)is an important fine chemical intermediate and as fuel for rockets,however,it also has serious toxic for humans and environment.Developing novel materials and methods for sensitive detection of DH...Hydrazine hydrate(DH)is an important fine chemical intermediate and as fuel for rockets,however,it also has serious toxic for humans and environment.Developing novel materials and methods for sensitive detection of DH in water and air is an important task.In order to effectively detect DH,a novel conductive supramolecular polymer metallogel(PQ-Ag)has been constructed by the coordination of bis-5-hydroxyquinoline functionalized pillar[5]arene(PQ5)with Ag+.The metallogel PQ-Ag could realize the multi-channel sensitive detection of DH through naked-eye,fluorescence,and electrochemical methods.The lowest limit of detection(LOD)is 0.1 mg/m^(3)in air and 2.68×10^(−8)mol/L in water,which is lower than the standard of the US Environmental Protection Agency(EPA)for DH of maximum allowable concentration in drinking water.More importantly,an electronic device for DH detection based on the metallogel PQ-Ag was designed and prepared,which can realize conveniently and efficiently multi-channel detection and alert of DH through sound and light alarms not only in water but also in air.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.20874055 and 21174079)Hi-tech Research and Development Program(863 plan) of China(No.2009AA062903)
文摘A facile method is reported to controllably fabricate one dimensional （1D） polymer nan,astructures via metallogel template polymerization. The metallogel was prepared through coordination interactions between silver ions and a ligand （L） bearing three pyridyl groups in tetrahydrofuran （THF）. The diameters of the metallogel nanofibers could be tuned by the gel concentration （GC）. Due to its high thermal stability and facility of removal, the metallogel was used as the template for radical polymerization of diacryolyl-2,6-diaminopyridine （DADAP） to form poly-diacryolyl-2,6-diaminopyridine （PDADAP） nanostructures. The gradually eroding of the templates by PDADAP provided us an effective way to fabricate various nanostructures of the polymer. We have demonstrated that different 1D nanostructures, including n^noribbons, nanotubes and nanowires, could be selectively fabricated by adjusting polymerization time, monomer concentration and GC. The rheological properties of the gel samples were tested by a rheometer. As prolonging the reaction time, more and more polymers were formed and the strength of the resulting polymer gels became higher and higher. The simple preparation process, easy controlled microstructures and adequate gel strength would make it a facile synthetic method for different 1D polymer nanosturctures.
基金supported by the National Natural Science Fund for Distinguished Young Scholars of China (22025107)the National Youth Top-notch Talent Support Program of China+1 种基金the Key Science and Technology Innovation Team of Shaanxi Province (2019TD-007,2019JLZ-02)the FM&EM International Joint Laboratory of Northwest University。
文摘The hierarchical self-assembly(HSA) strategy widely utilized in biological systems has been applied in artificial systems to orchestrate small building blocks into complex functional architectures. The non-interfering interactions glue various building blocks together and produce new species with attractive properties. Herein, we functionalized NHC-based assemblies with orthogonal host–guest interaction to fabricate metal-carbene based supramolecular polymer gel. A series of unique crown etherappended cylinder-like trinuclear AuIhexacarbene assemblies [Au_(3)(L)_(2)](PF_(6))_(3)(L=D1–D4, A1–A4) were synthesized from the corresponding trisimidazolium salts H_(3)-L(PF_(6))_(3)(L=D1–D4, A1–A4) in which the N-wingtip of the imidazole moieties were substituted with three identical crown ether groups of different sizes(B15C5, B18C6, B21C7, DB24C8). The gold carbene assembly is able to complex six ammonium salts without disrupting the underlying metal-carbene cylinders. In addition, the supramolecular polymer metallogel featuring a multiple-responsiveness can be formed by using [Au_(3)(A_(4))_(2)](PF_(6))_(3) appended with DB24C8 as the core and bisammonium salt as the cross-linker. The case of introducing orthogonal interaction to NHC moiety by N-wingtip substitution demonstrates the feasibility and the power of such strategy to expand the NHC-based supramolecular system and endow them with novel properties.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.22065031,22061039)the Top Leading Talents Project of Gansu Province,the Key R&D program of Gansu Province(No.21YF5GA066)+1 种基金Gansu Province College Industry Support Plan Project(No.2022CYZC-18)Natural Science Foundation of Gansu Province(Nos.2020-0405-JCC-630,20JR10RA088).
文摘Hydrazine hydrate(DH)is an important fine chemical intermediate and as fuel for rockets,however,it also has serious toxic for humans and environment.Developing novel materials and methods for sensitive detection of DH in water and air is an important task.In order to effectively detect DH,a novel conductive supramolecular polymer metallogel(PQ-Ag)has been constructed by the coordination of bis-5-hydroxyquinoline functionalized pillar[5]arene(PQ5)with Ag+.The metallogel PQ-Ag could realize the multi-channel sensitive detection of DH through naked-eye,fluorescence,and electrochemical methods.The lowest limit of detection(LOD)is 0.1 mg/m^(3)in air and 2.68×10^(−8)mol/L in water,which is lower than the standard of the US Environmental Protection Agency(EPA)for DH of maximum allowable concentration in drinking water.More importantly,an electronic device for DH detection based on the metallogel PQ-Ag was designed and prepared,which can realize conveniently and efficiently multi-channel detection and alert of DH through sound and light alarms not only in water but also in air.
