To understand and control the interfacial properties of polydiacetylenes(PDAs)vesicles withπ-conjugated backbone is very important for their colorimetric sensing of chemical and biological targets.In this work,we ado...To understand and control the interfacial properties of polydiacetylenes(PDAs)vesicles withπ-conjugated backbone is very important for their colorimetric sensing of chemical and biological targets.In this work,we adopted 10,12-pentacosadiynoic acid(PCDA)as the model molecule to prepare PDAs vesicles in aqueous solution with different forms(from monomer to blue-to-purple-to-red phase)by controlling the UV irradiation dose.The variations of the interfacial conformation of PDAs vesicles during chromatic transitions were inspected by the adsorption behaviors of probe molecules(4-(4-diethylaminostyry)-1-methylpyridinium iodide,D289)on vesicle surface with surface-specific second harmonic generation(SHG)and zeta potential measurements.Resonant SHG signal from D289 adsorbed on vesicle surface attenuated sharply,and the adsorption free energy as well as the corresponding two-photon fluorescence signal decreased slightly in chromatic transitions.While,the change in the surface density of the adsorbed D289 molecules for PDAs vesicles with different forms was relatively small as estimated from zeta potential measurements.The attenuation of the SHG intensity was thus attributed to the overall order-disorder transition and the changed orientation of D289 molecules caused by the gradual distortion of carboxyl head group driven by backbone perturbation.展开更多
We report a facile approach to water-dispersible polydiacetylene/rare earth ions nanocomposites with reversible thermochromism. The nanocomposites were prepared by doping rare earth ions Dy^3＋ or Sin^3＋ into layer-s...We report a facile approach to water-dispersible polydiacetylene/rare earth ions nanocomposites with reversible thermochromism. The nanocomposites were prepared by doping rare earth ions Dy^3＋ or Sin^3＋ into layer-structured 10,12-pentacosadiynoic acid （PCDA） nanopar- ticles to obtain PCDA/rare earth ions nanocomposites （PCDA-RE） and subsequently annealing PCDA-RE at the temperature slightly higher than the melting point of pure PCDA crystals, followed by topochemically polymerizing the annealed PCDA-RE. The polymerized PCDA-RE, i.e. poly（10,12-pentacosadiynoic acid）/rare earth ions nanocomposites （PDARE： PDA-Dy or PDA-Sm）, are largely reversible （PDA-Sm） or even completely reversible （PDA-Dy） in the thermochromism, while, without the doping, pure PDA is completely irreversible. It is confirmed that, PDA-RE are also layer-structured with a d-spacing of 5.4 nm, higher than the d-spacing of pure PDA （4.7 nm）. In PDA-RE, the rare earth ions form a layer in-between and interact strongly with the PDA bilayers, being responsible for the high degree or even the complete reversibility. This is the first example to make PDA completely reversible through the doping of rare earth ions; the annealing process is essential for the complete reversibility since it removes any defects in the structure.展开更多
A new type of diacetylene monomer which includes a biphenylcarboxylic acid group as its head group is synthesized.Polymerization was performed after monomer form spherical vesicle by self-assembly in the water.The pol...A new type of diacetylene monomer which includes a biphenylcarboxylic acid group as its head group is synthesized.Polymerization was performed after monomer form spherical vesicle by self-assembly in the water.The polydiacetylene displayed completely thermochromic color change in the range of 20-95℃ owing to the presence of strong π-π interaction caused by biphenyl group and hydrogen bonding between head group.展开更多
The thermochromic mechanism and the structure-property regulation principle of reversible thermochromic polydiacetylene(PDA)materials have always been a challenging issue.In this work,a series of diacetylene monomers(...The thermochromic mechanism and the structure-property regulation principle of reversible thermochromic polydiacetylene(PDA)materials have always been a challenging issue.In this work,a series of diacetylene monomers(m-PCDA)containing phenyl and amide or carboxyl groups were synthesized from 10,12-pentacosadiynoic acid(PCDA)through the esterification or amidation reactions.The effects of the number and the distribution of the functional groups in m-PCDA molecules on their solid-state polymerization capability,and the thermochromic mechanism of their corresponding polymers(m-PDA)were investigated and discussed in detail.The results show that the m-PCDA monomers containing both benzene ring and groups that can form hydrogen bonding interactions have strong intermolecular interaction,and are easy to carry out the solid phase polymerization under 254-nm UV irradiation to obtain the corresponding new thermochromic m-PDA materials.The thermochromic behavior of m-PDA depends on its melting process.The initial color-change temperature(blue to red)is determined by the onset melting tem perature,and the temperature range in which reversible color recovery can be achieved by repeat heating-cooling treatment is determined by its melting range.According to the proposed thermochromic mechanism of PDA,various new PDA materials with precise thermochromic temperatu res and reversible thermochromic temperature ra nges can be designed and synthesized through the appropriate introduction of benzene ring and groups that can form hydrogen bonding interactions into the molecular structure of linear diacetylene monomer.This work provides a perspective to the precise molecular structure design and the property regulation of the reversible thermochromic PDA materials.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.21403292,No.21403293,No.21473249,and No.21673285),and the funding from the Shenzhen city(No.JCYJ20170307150520453).
文摘To understand and control the interfacial properties of polydiacetylenes(PDAs)vesicles withπ-conjugated backbone is very important for their colorimetric sensing of chemical and biological targets.In this work,we adopted 10,12-pentacosadiynoic acid(PCDA)as the model molecule to prepare PDAs vesicles in aqueous solution with different forms(from monomer to blue-to-purple-to-red phase)by controlling the UV irradiation dose.The variations of the interfacial conformation of PDAs vesicles during chromatic transitions were inspected by the adsorption behaviors of probe molecules(4-(4-diethylaminostyry)-1-methylpyridinium iodide,D289)on vesicle surface with surface-specific second harmonic generation(SHG)and zeta potential measurements.Resonant SHG signal from D289 adsorbed on vesicle surface attenuated sharply,and the adsorption free energy as well as the corresponding two-photon fluorescence signal decreased slightly in chromatic transitions.While,the change in the surface density of the adsorbed D289 molecules for PDAs vesicles with different forms was relatively small as estimated from zeta potential measurements.The attenuation of the SHG intensity was thus attributed to the overall order-disorder transition and the changed orientation of D289 molecules caused by the gradual distortion of carboxyl head group driven by backbone perturbation.
基金V.ACKNOWLEDGEMENTSThisworkwassupportedbytheNationalNatu-ralScienceFoundationofChina（No.21334001andNo.91127030）.V. ACKNOWLEDGEMENTS This work was supported by the National Natu- ral Science Foundation of China （No.21334001 and No.91127030）.
文摘We report a facile approach to water-dispersible polydiacetylene/rare earth ions nanocomposites with reversible thermochromism. The nanocomposites were prepared by doping rare earth ions Dy^3＋ or Sin^3＋ into layer-structured 10,12-pentacosadiynoic acid （PCDA） nanopar- ticles to obtain PCDA/rare earth ions nanocomposites （PCDA-RE） and subsequently annealing PCDA-RE at the temperature slightly higher than the melting point of pure PCDA crystals, followed by topochemically polymerizing the annealed PCDA-RE. The polymerized PCDA-RE, i.e. poly（10,12-pentacosadiynoic acid）/rare earth ions nanocomposites （PDARE： PDA-Dy or PDA-Sm）, are largely reversible （PDA-Sm） or even completely reversible （PDA-Dy） in the thermochromism, while, without the doping, pure PDA is completely irreversible. It is confirmed that, PDA-RE are also layer-structured with a d-spacing of 5.4 nm, higher than the d-spacing of pure PDA （4.7 nm）. In PDA-RE, the rare earth ions form a layer in-between and interact strongly with the PDA bilayers, being responsible for the high degree or even the complete reversibility. This is the first example to make PDA completely reversible through the doping of rare earth ions; the annealing process is essential for the complete reversibility since it removes any defects in the structure.
基金supported by National High Technology Research and Development Program of China(863 program)(No. 2009AA035002)the Fundamental Research Funds for the Central Universities(No.22A201514002)
文摘A new type of diacetylene monomer which includes a biphenylcarboxylic acid group as its head group is synthesized.Polymerization was performed after monomer form spherical vesicle by self-assembly in the water.The polydiacetylene displayed completely thermochromic color change in the range of 20-95℃ owing to the presence of strong π-π interaction caused by biphenyl group and hydrogen bonding between head group.
基金financially supported by the National Natural Science Foundation of China(No.51973205)the Fundamental Research Funds for the Central Universities(Nos.WK9110000066,WK3450000005 and WK3450000006)。
文摘The thermochromic mechanism and the structure-property regulation principle of reversible thermochromic polydiacetylene(PDA)materials have always been a challenging issue.In this work,a series of diacetylene monomers(m-PCDA)containing phenyl and amide or carboxyl groups were synthesized from 10,12-pentacosadiynoic acid(PCDA)through the esterification or amidation reactions.The effects of the number and the distribution of the functional groups in m-PCDA molecules on their solid-state polymerization capability,and the thermochromic mechanism of their corresponding polymers(m-PDA)were investigated and discussed in detail.The results show that the m-PCDA monomers containing both benzene ring and groups that can form hydrogen bonding interactions have strong intermolecular interaction,and are easy to carry out the solid phase polymerization under 254-nm UV irradiation to obtain the corresponding new thermochromic m-PDA materials.The thermochromic behavior of m-PDA depends on its melting process.The initial color-change temperature(blue to red)is determined by the onset melting tem perature,and the temperature range in which reversible color recovery can be achieved by repeat heating-cooling treatment is determined by its melting range.According to the proposed thermochromic mechanism of PDA,various new PDA materials with precise thermochromic temperatu res and reversible thermochromic temperature ra nges can be designed and synthesized through the appropriate introduction of benzene ring and groups that can form hydrogen bonding interactions into the molecular structure of linear diacetylene monomer.This work provides a perspective to the precise molecular structure design and the property regulation of the reversible thermochromic PDA materials.
