Four new rod-coil diblock molecules, which had well-defined para-phenylene oligomers (PPP, from biphenyl to quinquephenyl) as rigid segments and poly(ethylene oxide) (PEO, M-w ca. 750) as flexible segments, were synth...Four new rod-coil diblock molecules, which had well-defined para-phenylene oligomers (PPP, from biphenyl to quinquephenyl) as rigid segments and poly(ethylene oxide) (PEO, M-w ca. 750) as flexible segments, were synthesized. The chemical structure and the number of repeating unit in PEO coil and PPP rod were characterized by H-1-NMR and MALDI-TOF mass spectrometry. The diblock oligomers showed good solubility in common organic solvents and aggregated in water as characterized by a blue shift in UV-vis absorption spectra, a red shift in emission spectra, quenching of the fluorescence and formation of the microfibrilla and fractal-like structures. The formation of different supramolecular structures meant that this effort might lead to commercial important highly organized functional materials.展开更多
The self-assembly of five narrowly distributed novel rod-coil diblock copolymers, poly(styrene-block-(2, 5-bis[4-methoxy-phenyl]oxycarbonyl) styrene) (PS-b-PMPCS), in p-xylene, a selective solvent at room temperature,...The self-assembly of five narrowly distributed novel rod-coil diblock copolymers, poly(styrene-block-(2, 5-bis[4-methoxy-phenyl]oxycarbonyl) styrene) (PS-b-PMPCS), in p-xylene, a selective solvent at room temperature, was studied. Therod-coil copolymers, which have the same PS length but different PMPCS length, were synthesized by 2,2,6,6-tetramethyl-I-piperidinyloxy (TEMPO) mediated living free radical polymerization. The influence of the rod length on the self-assemblymorphology was studied by transmission electron microscopy (TEM). At a concentration of 2.0 mg/mL, those copolymerswith relatively shorter PMPCS length (copolymers 1 and 2) form individual spherical micelles; those with relatively longerPMPCS length (copolymer 3 and 4) form 'pearl chains' coexisting with individual spherical micelles; the ones with longestPMPCS length form 'pearl chains' coexisting with occasionally formed nanofibers. The diameter of all the morphologieswas controlled by the rod length. This gives us a way to govern the self-assembly morphology by altering the length of oneblock in the block copolymer.展开更多
The rich phase behavior of block copolymers(BCPs)has drawn great attention in recent years.However,the double diamond(DD)phase is rarely obtained because of the competition between the minimization of interfacial ener...The rich phase behavior of block copolymers(BCPs)has drawn great attention in recent years.However,the double diamond(DD)phase is rarely obtained because of the competition between the minimization of interfacial energy and packing frustration.Here,a rod-coil BCP containing mesogen-jacketed liquid crystalline polymer is designed to acquire ordered bicontinuous network nanostructures.The reduction of internal energy originating from the orientational interaction among the rod blocks can compensate for the free energy penalty of packing frustration to stabilize the DD structure.The resulting BCP can also experience lamellae-to-DD and double gyroid-to-lamellae transitions by changing the annealing temperature.These results make the rod-coil BCP an excellent candidate for the self-assembly of ordered network structures,demonstrating great potential in nanopatterning and metamaterials.展开更多
The self-assembly of the linear rod-coil multiblock copolymers is studied by applying self-consistent-field lattice techniques in a three-dimensional （3D） space. Compared to the copolymer with one rod, the copolymer...The self-assembly of the linear rod-coil multiblock copolymers is studied by applying self-consistent-field lattice techniques in a three-dimensional （3D） space. Compared to the copolymer with one rod, the copolymer with more rods （mrod≥ 2） exhibits rich order-order phase transitions with increasing temperature, where the ordered morphology changes from strips to perforated lamellae and finally to lamellae. In addition, taking the copolymer with mrod = 2 as a representative, we fiarther study the effects of the volume fractions of the rods, the spacer coils and the end coils on the phase behaviors respectively, by which the detailed self-assembled mechanism of the linear rod-coil multiblock copolymers is revealed. Our results are expected to provide guidance for the design of the rod-coil materials.展开更多
Poly(phenylquinoline)-block-poly(ethylene glycol)(PPQ-b-PEG) rod-coil block co- polymers possess the self-assembly behavior in selective solvents. The copolymers in the mixed solvents of V(trifluoroacetic acid, TFA)︰...Poly(phenylquinoline)-block-poly(ethylene glycol)(PPQ-b-PEG) rod-coil block co- polymers possess the self-assembly behavior in selective solvents. The copolymers in the mixed solvents of V(trifluoroacetic acid, TFA)︰V(dichloromethane, DCM)=1︰1 can self-assemble into polymer hollow microspheres with diameters of a few micrometers. The polymer hollow micro- spheres are monodisperse, and the diameters of them increase with an increased polymerization degree of the PPQ rigid-rod block. The solution concentration has no effect on the microsphere diameter, but spherical surface shows burrs when the solution concentration is too low. It has been found that the obtained dilute solution has the strongest absorption peak at 376 nm and strongest emissionpeak at 604 nm by the spectroscopy analysis.展开更多
Aromatic amphiphilic molecules（1） consisting of three biphenyl groups linked together with ether bonds as a rigid rod segment and poly（ethylene oxide） with the number of repeating units of 17 as a coil segment wer...Aromatic amphiphilic molecules（1） consisting of three biphenyl groups linked together with ether bonds as a rigid rod segment and poly（ethylene oxide） with the number of repeating units of 17 as a coil segment were synthesized, and their self-assembly behavior in the bulk state and aqueous solution was investigated. In bulk, molecules 1 self-assembled into 1-D lamellar structure in the solid state or smectic A phase in the liquid crystalline phase via the cooperative effects of ？-？ stacking, micro-phase separation and hydrogen bond interactions. In dilute aqueous solutions, molecules 1 were observed to selfassemble into cylindrical micelles owned uniform diameter and length of hundreds of nanometers.展开更多
The aggregation behavior of cyclic rod-coil （RC） diblock copolymers in dilute solutions is investigated through dissipative particle dynamics simulation. By varying the rod length and coil length, cyclic RC copolyme...The aggregation behavior of cyclic rod-coil （RC） diblock copolymers in dilute solutions is investigated through dissipative particle dynamics simulation. By varying the rod length and coil length, cyclic RC copolymers in selective solvents exhibit various morphologies, including spherical miceUe, vesicle, bilayer disc, and ribbon bundle structure. Compared with the equivalent linear RC copolymer, only spherical micelle and barrel bundle phase are observed. Rod length is the major factor that controls the liquid-crystalline behavior of RC copolymer systems, while the coil length has a secondary effect on the aggregate morphology. The size of rod bundle varies with the coil length, especially for the end-to- end ribbon bundle and side-by-side barrel bundle, which are assembled by cyclic and linear RC copolymer solutions. This finding indicates that the ribbon bundle or nanofiber-like structure in cyclic RC copolymers can be obtained by controlling the rod length and coil length, and thus the optical and electrical properties of RC copolymer would be further controlled and optimized. Results illustrate that cyclization of a linear RC copolymer induces remarkable differences in the rod arrangement and aggregation behavior, thereby indicating the competition between interfacial energy, rod orientational entropy, coil stretching entropy, and packing constraints.展开更多
Good film formation is one of basic requirements for organic optoelectronic materials to achieve the capability for fabrication of large area devices. Small molecular optoelectronic compounds have a definite chemical ...Good film formation is one of basic requirements for organic optoelectronic materials to achieve the capability for fabrication of large area devices. Small molecular optoelectronic compounds have a definite chemical structure and clear device performance, and thus are welcomed in the field. However, they are generally suffering from poor film formation, especially in a large area. For addressing it, this contribution proposes and demonstrates a strategy, that is, changing them into poly（rod-coil） polymers. With one optoelectronic compound [BDT（DTBT）2] and three poly（rod-coil） polymers （P1, P2, and P3） having different non-conjugated coil segments as examples, the work clearly shows that the change to poly（rod-coil） polymers keeps many basic optoelectronic properties of the refer- ence compound, including light absorption in solution, bandgap and frontier orbital energy levels, but suppresses strong intermolecular interactions and crystalline structure in film state. Further comparisons on film formation quality on glass and ITO glass illustrate that all the three polymers have a better film formation property than the reference compound.展开更多
基金This work has been supported by the National Natural Science Foundation of China (Grants 29874003 and 29992590-4), the Research Fund for Doctoral Program of Higher Education (Grant 99000136) and the Teaching and Research Award Fund for Outstanding Young
文摘Four new rod-coil diblock molecules, which had well-defined para-phenylene oligomers (PPP, from biphenyl to quinquephenyl) as rigid segments and poly(ethylene oxide) (PEO, M-w ca. 750) as flexible segments, were synthesized. The chemical structure and the number of repeating unit in PEO coil and PPP rod were characterized by H-1-NMR and MALDI-TOF mass spectrometry. The diblock oligomers showed good solubility in common organic solvents and aggregated in water as characterized by a blue shift in UV-vis absorption spectra, a red shift in emission spectra, quenching of the fluorescence and formation of the microfibrilla and fractal-like structures. The formation of different supramolecular structures meant that this effort might lead to commercial important highly organized functional materials.
基金The financial support of the National Natural Science Foundation of China (Grants. 29992590-4 and 20134010)
文摘The self-assembly of five narrowly distributed novel rod-coil diblock copolymers, poly(styrene-block-(2, 5-bis[4-methoxy-phenyl]oxycarbonyl) styrene) (PS-b-PMPCS), in p-xylene, a selective solvent at room temperature, was studied. Therod-coil copolymers, which have the same PS length but different PMPCS length, were synthesized by 2,2,6,6-tetramethyl-I-piperidinyloxy (TEMPO) mediated living free radical polymerization. The influence of the rod length on the self-assemblymorphology was studied by transmission electron microscopy (TEM). At a concentration of 2.0 mg/mL, those copolymerswith relatively shorter PMPCS length (copolymers 1 and 2) form individual spherical micelles; those with relatively longerPMPCS length (copolymer 3 and 4) form 'pearl chains' coexisting with individual spherical micelles; the ones with longestPMPCS length form 'pearl chains' coexisting with occasionally formed nanofibers. The diameter of all the morphologieswas controlled by the rod length. This gives us a way to govern the self-assembly morphology by altering the length of oneblock in the block copolymer.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.51921002,22203015 and 51725301)Natural Science Foundation of Fujian Province(No.2021J01591)the National Key R&D Program of China(No.2018YFB0703702).The suggestions and help offered by Prof.Rong-Ming Ho of National Tsing Hua University are greatly appreciated.The authors acknowledge the scientists at the synchrotron X-ray beamline 1W2A at Beijing Synchrotron Radiation Facility(BSRF)and the synchrotron X-ray beamline BL16B1 at Shanghai Synchrotron Radiation Facility(SSRF)for their assistance on the SAXS experiments.
文摘The rich phase behavior of block copolymers(BCPs)has drawn great attention in recent years.However,the double diamond(DD)phase is rarely obtained because of the competition between the minimization of interfacial energy and packing frustration.Here,a rod-coil BCP containing mesogen-jacketed liquid crystalline polymer is designed to acquire ordered bicontinuous network nanostructures.The reduction of internal energy originating from the orientational interaction among the rod blocks can compensate for the free energy penalty of packing frustration to stabilize the DD structure.The resulting BCP can also experience lamellae-to-DD and double gyroid-to-lamellae transitions by changing the annealing temperature.These results make the rod-coil BCP an excellent candidate for the self-assembly of ordered network structures,demonstrating great potential in nanopatterning and metamaterials.
基金supported by the National Natural Science Foundation of China (Nos. 20804047, 20774096 and 20734003)Programs and the Fund for Creative Research Groups (No. 50921062)subsidized by the Special Funds for National Basic Research Program of China (Nos. 2009CB930100, 2010CB631100)
文摘The self-assembly of the linear rod-coil multiblock copolymers is studied by applying self-consistent-field lattice techniques in a three-dimensional （3D） space. Compared to the copolymer with one rod, the copolymer with more rods （mrod≥ 2） exhibits rich order-order phase transitions with increasing temperature, where the ordered morphology changes from strips to perforated lamellae and finally to lamellae. In addition, taking the copolymer with mrod = 2 as a representative, we fiarther study the effects of the volume fractions of the rods, the spacer coils and the end coils on the phase behaviors respectively, by which the detailed self-assembled mechanism of the linear rod-coil multiblock copolymers is revealed. Our results are expected to provide guidance for the design of the rod-coil materials.
基金the National Key Basic Research“973”Program of China(Grant No.5130702002).
文摘Poly(phenylquinoline)-block-poly(ethylene glycol)(PPQ-b-PEG) rod-coil block co- polymers possess the self-assembly behavior in selective solvents. The copolymers in the mixed solvents of V(trifluoroacetic acid, TFA)︰V(dichloromethane, DCM)=1︰1 can self-assemble into polymer hollow microspheres with diameters of a few micrometers. The polymer hollow micro- spheres are monodisperse, and the diameters of them increase with an increased polymerization degree of the PPQ rigid-rod block. The solution concentration has no effect on the microsphere diameter, but spherical surface shows burrs when the solution concentration is too low. It has been found that the obtained dilute solution has the strongest absorption peak at 376 nm and strongest emissionpeak at 604 nm by the spectroscopy analysis.
基金financially supported by the National Natural Science Foundation of China(Nos.21304009,31471639,21562043,21206083 and 21164013)the Program for Liaoning Excellent Talents in University(Nos.LJQ2014125 and LR2014033)the Liaoning Provincial Science&Technology Department(No.2015103020)
文摘Aromatic amphiphilic molecules（1） consisting of three biphenyl groups linked together with ether bonds as a rigid rod segment and poly（ethylene oxide） with the number of repeating units of 17 as a coil segment were synthesized, and their self-assembly behavior in the bulk state and aqueous solution was investigated. In bulk, molecules 1 self-assembled into 1-D lamellar structure in the solid state or smectic A phase in the liquid crystalline phase via the cooperative effects of ？-？ stacking, micro-phase separation and hydrogen bond interactions. In dilute aqueous solutions, molecules 1 were observed to selfassemble into cylindrical micelles owned uniform diameter and length of hundreds of nanometers.
基金financially supported by the National Natural Science Foundation of China(No.21474076)the Natural Science Foundation of Zhejiang(Nos.Z13F20019 and LY15B040005)the Science and Technology of Wenzhou(No.G20140054)
文摘The aggregation behavior of cyclic rod-coil （RC） diblock copolymers in dilute solutions is investigated through dissipative particle dynamics simulation. By varying the rod length and coil length, cyclic RC copolymers in selective solvents exhibit various morphologies, including spherical miceUe, vesicle, bilayer disc, and ribbon bundle structure. Compared with the equivalent linear RC copolymer, only spherical micelle and barrel bundle phase are observed. Rod length is the major factor that controls the liquid-crystalline behavior of RC copolymer systems, while the coil length has a secondary effect on the aggregate morphology. The size of rod bundle varies with the coil length, especially for the end-to- end ribbon bundle and side-by-side barrel bundle, which are assembled by cyclic and linear RC copolymer solutions. This finding indicates that the ribbon bundle or nanofiber-like structure in cyclic RC copolymers can be obtained by controlling the rod length and coil length, and thus the optical and electrical properties of RC copolymer would be further controlled and optimized. Results illustrate that cyclization of a linear RC copolymer induces remarkable differences in the rod arrangement and aggregation behavior, thereby indicating the competition between interfacial energy, rod orientational entropy, coil stretching entropy, and packing constraints.
文摘Good film formation is one of basic requirements for organic optoelectronic materials to achieve the capability for fabrication of large area devices. Small molecular optoelectronic compounds have a definite chemical structure and clear device performance, and thus are welcomed in the field. However, they are generally suffering from poor film formation, especially in a large area. For addressing it, this contribution proposes and demonstrates a strategy, that is, changing them into poly（rod-coil） polymers. With one optoelectronic compound [BDT（DTBT）2] and three poly（rod-coil） polymers （P1, P2, and P3） having different non-conjugated coil segments as examples, the work clearly shows that the change to poly（rod-coil） polymers keeps many basic optoelectronic properties of the refer- ence compound, including light absorption in solution, bandgap and frontier orbital energy levels, but suppresses strong intermolecular interactions and crystalline structure in film state. Further comparisons on film formation quality on glass and ITO glass illustrate that all the three polymers have a better film formation property than the reference compound.
