The temperature monitoring of treated cancer cells is critical in photothermal therapy.Current methods of detecting intracellular temperatures have low accuracy and poor spatial resolution,which limits their applicati...The temperature monitoring of treated cancer cells is critical in photothermal therapy.Current methods of detecting intracellular temperatures have low accuracy and poor spatial resolution,which limits their application to photothermal therapy.Herein,a strategy for targeted recognition and selective capture of MCF-7 breast cancer cells based on fluorescent polymer poly(N-isopropylacrylamide-benzoxadiazole-2-vinyl-4,4-dimethyl azlactone,PNMV)and modified gold nanobipyramids(Au NBPs-PNMV)was developed for temperature sensing during photothermal therapy.A mucin-1 protein aptamer(Apt)was applied to selectively target mucin-1 protein overexpressed on the surfaces of the MCF-7 cells,which can reduce interference by affinity interaction between the Apt and proteins.During photothermal therapy,the significant Au NBPs photothermal effect increases the fluorescence intensity of PNMV with temperature.Irradiation of MCF-7 cells cultured with Au NBPs-PNMV@Apt by an 808 nm laser increases the temperature of the system,while the cells can be inactivated because of the remarkable Au NBPs-PNMV@Apt photothermal effect.The results indicate that variation in the fluorescence of Au NBPs-PNMV@Apt can be applied as thermometers to monitor the intracellular effect of photothermal therapy.展开更多
In recent years,cellulose-based fluorescent polymers have received considerable attention.However,conventional modification methods face challenges such as insolubility in most solvents,fluorescence instability,and en...In recent years,cellulose-based fluorescent polymers have received considerable attention.However,conventional modification methods face challenges such as insolubility in most solvents,fluorescence instability,and environmental risks.In this study,a novel biosynthesis strategy was developed to fabricate fluorescent cellulose by adding fluorescent glucose derivatives to a bacterial fermentation broth.The metabolic activity of bacteria is utilized to achieve in situ polymerization of glucose and its derivatives during the synthesis of bacterial cellulose.Owing to the structural similarity between triphenylamine-modified glucose(TPA-Glc N)and glucose monomers,the TPA-Glc N were efficiently assimilated by the bacterial cells and incorporated into the cellulose matrix,resulting in a uniform distribution of fluorescence.The fluorescence color and intensity of the obtained cellulose could be adjusted by varying the amount of the fluorescent glucose derivatives.Compared to the fluorescent cellulose synthesized through physical dyeing,the fluorescence of the products obtained by in situ polymerization showed higher intensity and stability.Furthermore,fluorescent bacterial cellulose can be hydrolyzed into nanocellulose-based ink,which demonstrates exceptional anti-counterfeiting capabilities under UV light.This biosynthesis method not only overcomes the limitations of traditional modification techniques but also highlights the potential of microbial systems as platforms for synthesizing functional polymers.展开更多
The multifaceted regulation of the chiroptical properties and self-assembly behaviors of chiral fluorescent polymers is of great significance yet remains challenging to achieve.Herein,a series of novel salen-based chi...The multifaceted regulation of the chiroptical properties and self-assembly behaviors of chiral fluorescent polymers is of great significance yet remains challenging to achieve.Herein,a series of novel salen-based chiral fluorescent polymers with aggregation-induced emission and varied substitution manners were facilely and efficiently synthesized.Multiple factors were systematically investigated on the chiroptical properties and self-assembly performance of these polymers,which include molecular structures,solvent environments,metal coordination,and liquid crystal(LC)assemblies.Sutle change in the solvent composition can lead to diverse assembly morphologies of all these chiral polymers,from single-handed helical fibers,helical toroids or loops,to spherical structures,consequently leading to an aggregation-reduced circular dichroism(CD)phenomenon.The polymers bearing salen units show highly selective and reversible coordination with Zn^(2+)and can also induce multiple responses in the absorption,luminescence,CD,and circularly polarized luminescence(CPL)of these chiral fluorescent polymers via a coordination-and dissociation-initiated self-assembly tuning.Furthermore,a small amount of the chiral fluorescent polymer in can induce achiral nematic 4-cyano-4′-n-pentylbiphenyl(5CB)to form ordered chiral nematic LC phase with significant improvement in their CD and CPL signal.The absolute absorption and luminescent dissymmetry factors of the resulting supramolecular assemblies can reach the order of 10^(−1).展开更多
Based on the combination of B21C7/dialkylammonium salt host-vip interactions and tetraphenylethylene （TPE）-based aggregation-induced emission （AIE） effect, a fluorescent supramolecular crosslinked polymer gel wa...Based on the combination of B21C7/dialkylammonium salt host-vip interactions and tetraphenylethylene （TPE）-based aggregation-induced emission （AIE） effect, a fluorescent supramolecular crosslinked polymer gel was successfully prepared. Compared with the solution of TPE-containing small molecules, this gel exhibited remarkable fluorescence enhancement due to the AIE effect of TPE units. The ＂gelation induced fluorescence emission＂ phenomenon can be explained by the hindered intramolecular rotation of phenyl rings of TPE. Because of the reversibility and stimuli-responsiveness of the B21C7/dialkylammonium salt host-vip interactions, the transition between the fluorescent supramolecular crosslinked polymer gel and the disassembled sol with very weak fluorescence can be realized by adding pH and thermal stimuli. This novel material contributes to the development of supramolecular chemistry, polymer science and fluorescent materials and offers a new method to construct functional supramolecular materials.展开更多
Researchers have put significant efforts on developing versatile fluorescent polymeric systems due to their promising biological/biomedical labelling, tracking, monitoring, imaging, and diagnostic applications. Howeve...Researchers have put significant efforts on developing versatile fluorescent polymeric systems due to their promising biological/biomedical labelling, tracking, monitoring, imaging, and diagnostic applications. However, complicated organic/polymeric synthesis or post-modification of these functionalized platforms is still a big obstacle for their further application and thereby provides clear motivation for exploring alternative strategies for the design and fabrication of easily available fluorescent systems. The marriage of supramolecular polymers and fluorescent imaging can provide a facile and dynamic manner instead of tedious and time-consuming synthesis due to the dynamic and reversible nature of noncovalent interactions. Herein, based on water-soluble pillararene/paraquat molecular recognition, we successfully prepare two amphiphilic polypseudorotaxanes which can self-assemble into supramolecular polymersomes in water. These polymersomes can be reversibly destroyed and reformed by tuning the solution p H. Attributed to the aggregation-induced emission of tetraphenylethylene groups,intense fluorescence can be introduced into the obtained supramolecular polymersomes. Furthermore, p H-triggered release of an encapsulated water-insoluble drug(doxorubicin) from the self-assembled fluorescent supramolecular polymersomes is also investigated.展开更多
Folic acid functionalized PFBT-COOH and PFBT-NH2 polymer dots were prepared using a nano precipitation method, and their applications for tumor imaging in vitro and in vivo were demonstrated for the first time. The sy...Folic acid functionalized PFBT-COOH and PFBT-NH2 polymer dots were prepared using a nano precipitation method, and their applications for tumor imaging in vitro and in vivo were demonstrated for the first time. The syn- thesized FA-PFBT-COOH polymer dots were 50--60 nm in diameter with a zeta potential of greater than -30 mV in water, while the synthesized FA-PFBT-NH2 polymer dots were 90-- 105 nm in diameter with a zeta potential of greater than -20 mV in water. Furthermore, the FA-PFBT-COOH polymer dots produced stronger fluorescence in- tensity in water solution as well as in the cells than the FA-PFBT-NH2 polymer dots, and were able to image H1299 tumors in living mice after intravenous injection. This study showed the great potentials of FA-PFBT-COOH poly- mer dots as fluorescent nanoprobes for biomedical imaging.展开更多
In this work,on-chip three-dimensional(3D)photonic integrated optical sources based on active fluorescent polymer waveguide microdisks are proposed for light display application.Fluorescent green and red oligomers wit...In this work,on-chip three-dimensional(3D)photonic integrated optical sources based on active fluorescent polymer waveguide microdisks are proposed for light display application.Fluorescent green and red oligomers with high-efficiency photoluminescence are doped into epoxy crosslinking SU-8 polymer as the waveguide gain medium.The microdisk-based on-chip optically pumping light sources are designed and fabricated using the organic functionalized materials by direct UV written process.The promising stacking dual-microdisk structures with double gain layers could provide white signal light source generated perpendicular to the chip,and green signal light source stimulated in the chip.The approach could realize the monolithically on-chip assembled vertical and horizontal bright emitters.The optical pumping threshold power is obtained as 50 mW with continuous-wave(CW)pumping.The average gain coefficient of a white light source is measured by vertical fiber coupling as 112 dB/W,and that of green light source by horizontal fiber coupling as 137 dB/W,respectively.The rising and falling response time of the on-chip optical sources are 60 and 80μs under modulating pulsed pumping.This technique is very promising for achieving 3D integrated light display application,including photonic circuits and optical information encryption.展开更多
Nonconjugated polymer dots(PDs)without largely conjugated structures entitle their advantages such as environment friendliness,nontoxicity,and intrinsic fluorescence.However,color-tunable PDs remain a challenge.Herein...Nonconjugated polymer dots(PDs)without largely conjugated structures entitle their advantages such as environment friendliness,nontoxicity,and intrinsic fluorescence.However,color-tunable PDs remain a challenge.Herein,polyvinyl pyrrolidone(PVP)and ascorbic acid(AA)are used to synthesize nonconjugated PDs,namely,PA PDs with intensive blue emission.The introduction of a third component,m-phenylenediamine(MPD),redshifted the emission to green.The asprepared color-tunable blue to green emissive PDs exhibit excellent properties,whether in solution or in solid state,originated from the mechanism of clusteringtriggered emission(CTE)induced by the overlap of electron-rich atoms,the strong inter/intrachain interaction.The quantum yields of blue and green PDs reached up to 15.07%and 28.22%,respectively.Furthermore,PA PDs were successfully applied to the highly efficient photocatalytic degradation for dyes:methylene blue(MB)and methyl orange(MO)were degraded by 89.9%and 93.8%within 20 min under visible light,respectively.展开更多
A simple and effective polymer fluorescent thermosensitive system was successfully developed based on the synergistic effect of excimer/monomer interconversion of pyrene derivatives and electrostatic interaction betwe...A simple and effective polymer fluorescent thermosensitive system was successfully developed based on the synergistic effect of excimer/monomer interconversion of pyrene derivatives and electrostatic interaction between polyelectrolyte and charged fluorophore. As for the system, the excimer-monomer conversion, thermosensitive behavior and thermo-responsive reversibility were investigated experimentally. Temperature variation and temperature-distribution induced fluorescence changes can be observed directly by naked eyes. Thus, this polymer system holds promise for serving as a fluorescent thermometer.展开更多
Accessing local dynamics within a single macromolecule is the key to understand the physical origin of the viscoelasticity and especially the glass transition. In order to extract specific information on the dynamics ...Accessing local dynamics within a single macromolecule is the key to understand the physical origin of the viscoelasticity and especially the glass transition. In order to extract specific information on the dynamics of the branch point of a star polymer around its glass transition temperature, four-arm star poly （n-butyl methacrylate） with a fluorescent core was synthesized using perylene diimide as initiator and polymerization conducted via atom transfer radical polymerization. The process is found to be effective in positioning the fluorophore at the branch point with the fluorophore intact, which allows the successful application of single molecule fluorescence defocus imaging in examining the local site- sensitive dynamics. The power spectra of rotation trajectories, the population of rotating fluorophores as well as the distribution of angular displacement were used to revel the difference in local dynamics between branch point and the arm＇s end. It is discovered that the local dynamics at the core of the star polymer is much less activated than that at the arm＇s end. The results demonstrate the strong effect dues to the topological constrain at the branch point and the more free space at the arm＇s end.展开更多
Polyacrylamide microspheres have been suc- cessfully used to reduce water production in reservoirs, but it is impossible to distinguish polyacrylamide microspheres from polyacrylamide that is used to enhance oil recov...Polyacrylamide microspheres have been suc- cessfully used to reduce water production in reservoirs, but it is impossible to distinguish polyacrylamide microspheres from polyacrylamide that is used to enhance oil recovery and is already present in production fluids. In order to detect polyacrylamide microspheres in the reservoir pro- duced fluid, fluorescent polyacrylamide microspheres P（AM-BA-AMCO）, which fluoresce under ultraviolet irradiation, were synthesized via an inverse suspension polymerization. In order to keep the particle size distribu- tion in a narrow range, the synthesis conditions of the polymerization were studied, including the stirring speed and the concentrations of initiator, NaaCO3, and dispersant. The bonding characteristics of microspheres were deter- mined by Fourier transform infrared spectroscopy. The surface morphology of these microspheres was observed under ultraviolet irradiation with an inverse fluorescence microscope. A laboratory evaluation test showed that the fluorescent polymer microspheres had good water swelling capability, thus they had the ability to plug and migrate in a sand pack. The plugging rate was 99.8 % and the residual resistance coefficient was 800 after microsphere treatment in the sand pack. Furthermore, the fluorescent microspheres and their fragments were accurately detected under ultra- violet irradiation in the produced fluid, even though theyhad experienced extrusion and deformation in the sand pack.展开更多
Two new coordination polymers containing rigid bis（triazole）, namely, [Ni（btb）_（0.5）（nph）（H_2O）]_n（1） and [Zn（btb）（SO_4）]_n（2）（btb = 4,4a-bis（1,2,4-triazolyl-1-yl）-biphenyl, H_2nph = 3-nitrophthal...Two new coordination polymers containing rigid bis（triazole）, namely, [Ni（btb）_（0.5）（nph）（H_2O）]_n（1） and [Zn（btb）（SO_4）]_n（2）（btb = 4,4a-bis（1,2,4-triazolyl-1-yl）-biphenyl, H_2nph = 3-nitrophthalic acid） have been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a 3D trinodal（3,4,4）-connected sqc69 topology. Complex 2 presents a 2D uninodal 4-connected sql network, which is further packed into a 3D supramolecular framework by C-H···O hydrogen bonds. Thermal stabilities and fluorescence properties of two complexes have been discussed in detail.展开更多
The two-photon fluorescence properties and ultrafast responses of a hyperbranched polyyne （hb-DPP-J2） with triphenylamine as the central core, Diketo-Pyrrolo-Pyrrole as the connecting unit and electron acceptor are ...The two-photon fluorescence properties and ultrafast responses of a hyperbranched polyyne （hb-DPP-J2） with triphenylamine as the central core, Diketo-Pyrrolo-Pyrrole as the connecting unit and electron acceptor are studied. The polymer has a D-π-A-π-D conjugated structure along the extended polyyne w-bridge systems, and the effective condugated unit repeats itself in the whole hyperbranehed polymer chain. The polymer exhibits a large two-photon absorption cross section and high fluorescence quantum yields. The ultrafast dynamic results give a deep understanding of the excited energy transfer processes under excitation, and reveal a long relaxation lifetime of the intramolecular charge transfer （ICT） state.展开更多
Using a rigid azo ligand 4-[（8-hydroxy-5-quinolinyl）azo]-benzoic acid（H2 L）,a new supramolecular compound [Zn（L）（H2O）2]n（1） has been solvothermally synthesized and structurally characterized by X-ray single-...Using a rigid azo ligand 4-[（8-hydroxy-5-quinolinyl）azo]-benzoic acid（H2 L）,a new supramolecular compound [Zn（L）（H2O）2]n（1） has been solvothermally synthesized and structurally characterized by X-ray single-crystal diffraction,infrared spectrum,elemental analysis,power X-ray diffraction and thermal analysis.Compound 1 crystallizes in monoclinic,space group C2/c with a = 30.372（8）,b = 11.415（3）,c = 9.248（3） A,β = 106.94（3）o,V = 3067.20（15）A3,C（16）H（13）N3O5Zn,Mr = 392.66,Z = 8,Dc = 1.701 Mg/m^3; F（000） = 1600,μ = 1.636 mm^-1,reflections collected：7290,reflections unique：2735,R（int）= 0.0282,R = 0.0351,wR（all data） = 0.0919,GOOF on F^2 = 1.036.Compound 1 exhibits a one-dimensional（1 D） zig-zag chain structure connected into a three-dimensional（3D） supramolecular network through hydrogen bonding interactions.Fluorescent property and electrochemical property were detected on compound 1.展开更多
Based on the building block of 2-phenyl-4,6-di（pyridin-2-yl）pyrimidine （L = C20H14N4）, a Cu（I） polymer [（CuC20H14N4）（CuCl2）]∞ and a salt with H2SO4 [（C20H16N4）（HSO4）2] have been synthesized by hydrother...Based on the building block of 2-phenyl-4,6-di（pyridin-2-yl）pyrimidine （L = C20H14N4）, a Cu（I） polymer [（CuC20H14N4）（CuCl2）]∞ and a salt with H2SO4 [（C20H16N4）（HSO4）2] have been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction. In the Cu（Ⅰ） polymer, although the central metal ions of Cu（Ⅰ） directly coordinate with the building block L, they still do not assembly expected grid-type complexes and there exists a one-dimensional chain constructed through coordinate bonds. In the salt, hydrogen bonds along with two kinds of π…π supramoleuclar interactions fabricate two-dimensional （2D） networks which further generate a 3D supramolecular architecture via interlayer π…π interactions. Fluorescent spectra show that the L emits blue fluorescence and its Cu（Ⅰ） polymer and salt decrease the fluorescent intensity.展开更多
Over the last decades,various tissue-clearing techniques have broken the ground for the optical imaging of whole organs and whole-organisms,providing complete representative data sets of three-dimensional biological s...Over the last decades,various tissue-clearing techniques have broken the ground for the optical imaging of whole organs and whole-organisms,providing complete representative data sets of three-dimensional biological structures.Along with advancements in this field,the development of fluorescent markers for staining vessels and capillaries has offered insights into the complexity of vascular networks and their impact on disease progression.Here we describe the use of a modified water-soluble chitosan linked to cyanine dyes in combination with ethyl cinnamate-based optical tissue clearing for the 3D visualization of tissue vasculature in depth.The water-soluble fluorescent Chitosans have proven to be an optimal candidate for labeling both vessels and capillaries ex vivo thanks to their increased water solubility,high photostability,and optical properties in the near-infrared window.In addition,the nontoxicity of these markers broadens their applicability to in vitro and in vivo biological applications.Despite the availability of other fluorescent molecules for vascular staining,the present study,for the first time,demonstrates the potential of fluorescent chitosans to depict vessels at the capillary level and opens avenues for advancing the diagnostic field by reducing the complexity and costs of the currently available procedures.展开更多
Compared with conventional π-conjugated polymers,poly（arylene ether）s（PAEs） may take advantages of excellent thermal properties,well-defined effective conjugated length and no catalyst contamination.Recently,thei...Compared with conventional π-conjugated polymers,poly（arylene ether）s（PAEs） may take advantages of excellent thermal properties,well-defined effective conjugated length and no catalyst contamination.Recently,their applications have been extended from engineering plastics to optoelectronic materials.In this review,various kinds of functional PAEs used as fluorescent polymers,host polymers and phosphorescent polymers in organic light-emitting diodes（OLEDs） are outlined,and their molecular design,synthesis and device performance are overviewed.展开更多
A novel peroxyoxalate chemiluminescence system has been designed for the determination of Triton X-100 （TX-100）, in which a hydrophobic fluorescent conjugated polymer, poly[2,5-bisnonyloxy-1,4-phenyleneethynylene-9,...A novel peroxyoxalate chemiluminescence system has been designed for the determination of Triton X-100 （TX-100）, in which a hydrophobic fluorescent conjugated polymer, poly[2,5-bisnonyloxy-1,4-phenyleneethynylene-9,10-anthrylene] （PPEA） was employed as a fluorophor. A strong enhanced intensity of chemiluminescence （CL） was observed in the presence of TX-100, due to the improved emission efficiency of PPEA in the presence of TX-100. Under optimum conditions, the detection range of Triton X-100 is between 1.0 ×10 ^-7 and 1.0 ×10 ^-4 mol·L ^-1, with a detection limit at 6.0×10 ^-8 moloL 1. The relative standard deviation is 2.4% （n=6） for 1.0×10 ^-6 mol·L ^-1Triton X-100. This method provides satisfying results in the detection of TX-100 in nature water and biological samples with high sensitivity and wide linear range.展开更多
The preparation and performance characterization of〈50 nm spirobenzopyran-based photochromic nanocomposites with photoswitchable fluorescence are presented.The nanocomposites were fabricated by means of a modifed min...The preparation and performance characterization of〈50 nm spirobenzopyran-based photochromic nanocomposites with photoswitchable fluorescence are presented.The nanocomposites were fabricated by means of a modifed miniemulsion polymerization process,in which the hydrophobic spirobenzopyran was covalently attached to the polymer chains and the matched fluorescent dyes were noncovalently embedded in the nanoscale cross-linked polymeric matrix,respectively.The obtained nanocomposites with a high relative fluorescence quantum yield（Q）exhibited superior fluorescent photoswitchable performance due to the effective photo-induced intermolecular energy transfer.The stability of photomerocyanine was also improved.展开更多
基金the National Natural Science Foundation of China(Nos.22074148,21874138,21635008,21727809)。
文摘The temperature monitoring of treated cancer cells is critical in photothermal therapy.Current methods of detecting intracellular temperatures have low accuracy and poor spatial resolution,which limits their application to photothermal therapy.Herein,a strategy for targeted recognition and selective capture of MCF-7 breast cancer cells based on fluorescent polymer poly(N-isopropylacrylamide-benzoxadiazole-2-vinyl-4,4-dimethyl azlactone,PNMV)and modified gold nanobipyramids(Au NBPs-PNMV)was developed for temperature sensing during photothermal therapy.A mucin-1 protein aptamer(Apt)was applied to selectively target mucin-1 protein overexpressed on the surfaces of the MCF-7 cells,which can reduce interference by affinity interaction between the Apt and proteins.During photothermal therapy,the significant Au NBPs photothermal effect increases the fluorescence intensity of PNMV with temperature.Irradiation of MCF-7 cells cultured with Au NBPs-PNMV@Apt by an 808 nm laser increases the temperature of the system,while the cells can be inactivated because of the remarkable Au NBPs-PNMV@Apt photothermal effect.The results indicate that variation in the fluorescence of Au NBPs-PNMV@Apt can be applied as thermometers to monitor the intracellular effect of photothermal therapy.
基金supported by the National Natural Science Foundation of China(No.22376111)Shandong Provincial Natural Science Foundation(No.ZR2024YQ026)+2 种基金for Excellent Young Scholars,Taishan Scholar Foundation of Shandong Province(No.tsqn202408237)Youth Innovation Team Project for Talent Introduction and Cultivation in Universities of Shandong Province(No.096-1622002)the Research Foundation for Distinguished Scholars of Qingdao Agricultural University(No.663-1117015)。
文摘In recent years,cellulose-based fluorescent polymers have received considerable attention.However,conventional modification methods face challenges such as insolubility in most solvents,fluorescence instability,and environmental risks.In this study,a novel biosynthesis strategy was developed to fabricate fluorescent cellulose by adding fluorescent glucose derivatives to a bacterial fermentation broth.The metabolic activity of bacteria is utilized to achieve in situ polymerization of glucose and its derivatives during the synthesis of bacterial cellulose.Owing to the structural similarity between triphenylamine-modified glucose(TPA-Glc N)and glucose monomers,the TPA-Glc N were efficiently assimilated by the bacterial cells and incorporated into the cellulose matrix,resulting in a uniform distribution of fluorescence.The fluorescence color and intensity of the obtained cellulose could be adjusted by varying the amount of the fluorescent glucose derivatives.Compared to the fluorescent cellulose synthesized through physical dyeing,the fluorescence of the products obtained by in situ polymerization showed higher intensity and stability.Furthermore,fluorescent bacterial cellulose can be hydrolyzed into nanocellulose-based ink,which demonstrates exceptional anti-counterfeiting capabilities under UV light.This biosynthesis method not only overcomes the limitations of traditional modification techniques but also highlights the potential of microbial systems as platforms for synthesizing functional polymers.
基金National Natural Science Foundation of China,Grant/Award Number:22271197Ministry of Science and Technology of China,Grant/Award Number:2021YFA1501600+6 种基金Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2023A1515011578Natural Science Foundation of Guangdong Province,Grant/Award Number:2021A1515010192Guangdong Provincial Key Laboratory of Luminescence fromMolecular Aggregates,Grant/Award Number:2019B030301003Shenzhen Science and Technology Program,Grant/Award Numbers:RCYX20221008092924059,JCYJ20220531102601003,JCYJ20210324094607021Shenzhen Key Laboratory of Functional Aggregate Materials,Grant/Award Number:ZDSYS20211021111400001Open Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates,Grant/Award Number:2023B12120600032035 Research Excellence Program of Shenzhen University,Grant/Award Number:2023C001。
文摘The multifaceted regulation of the chiroptical properties and self-assembly behaviors of chiral fluorescent polymers is of great significance yet remains challenging to achieve.Herein,a series of novel salen-based chiral fluorescent polymers with aggregation-induced emission and varied substitution manners were facilely and efficiently synthesized.Multiple factors were systematically investigated on the chiroptical properties and self-assembly performance of these polymers,which include molecular structures,solvent environments,metal coordination,and liquid crystal(LC)assemblies.Sutle change in the solvent composition can lead to diverse assembly morphologies of all these chiral polymers,from single-handed helical fibers,helical toroids or loops,to spherical structures,consequently leading to an aggregation-reduced circular dichroism(CD)phenomenon.The polymers bearing salen units show highly selective and reversible coordination with Zn^(2+)and can also induce multiple responses in the absorption,luminescence,CD,and circularly polarized luminescence(CPL)of these chiral fluorescent polymers via a coordination-and dissociation-initiated self-assembly tuning.Furthermore,a small amount of the chiral fluorescent polymer in can induce achiral nematic 4-cyano-4′-n-pentylbiphenyl(5CB)to form ordered chiral nematic LC phase with significant improvement in their CD and CPL signal.The absolute absorption and luminescent dissymmetry factors of the resulting supramolecular assemblies can reach the order of 10^(−1).
文摘Based on the combination of B21C7/dialkylammonium salt host-vip interactions and tetraphenylethylene （TPE）-based aggregation-induced emission （AIE） effect, a fluorescent supramolecular crosslinked polymer gel was successfully prepared. Compared with the solution of TPE-containing small molecules, this gel exhibited remarkable fluorescence enhancement due to the AIE effect of TPE units. The ＂gelation induced fluorescence emission＂ phenomenon can be explained by the hindered intramolecular rotation of phenyl rings of TPE. Because of the reversibility and stimuli-responsiveness of the B21C7/dialkylammonium salt host-vip interactions, the transition between the fluorescent supramolecular crosslinked polymer gel and the disassembled sol with very weak fluorescence can be realized by adding pH and thermal stimuli. This novel material contributes to the development of supramolecular chemistry, polymer science and fluorescent materials and offers a new method to construct functional supramolecular materials.
基金financially supported by the National Natural Science Foundation of China (No. 21861130352)Newton Advanced Fellowships of The Royal Society (No. NAF\R10066)
文摘Researchers have put significant efforts on developing versatile fluorescent polymeric systems due to their promising biological/biomedical labelling, tracking, monitoring, imaging, and diagnostic applications. However, complicated organic/polymeric synthesis or post-modification of these functionalized platforms is still a big obstacle for their further application and thereby provides clear motivation for exploring alternative strategies for the design and fabrication of easily available fluorescent systems. The marriage of supramolecular polymers and fluorescent imaging can provide a facile and dynamic manner instead of tedious and time-consuming synthesis due to the dynamic and reversible nature of noncovalent interactions. Herein, based on water-soluble pillararene/paraquat molecular recognition, we successfully prepare two amphiphilic polypseudorotaxanes which can self-assemble into supramolecular polymersomes in water. These polymersomes can be reversibly destroyed and reformed by tuning the solution p H. Attributed to the aggregation-induced emission of tetraphenylethylene groups,intense fluorescence can be introduced into the obtained supramolecular polymersomes. Furthermore, p H-triggered release of an encapsulated water-insoluble drug(doxorubicin) from the self-assembled fluorescent supramolecular polymersomes is also investigated.
文摘Folic acid functionalized PFBT-COOH and PFBT-NH2 polymer dots were prepared using a nano precipitation method, and their applications for tumor imaging in vitro and in vivo were demonstrated for the first time. The syn- thesized FA-PFBT-COOH polymer dots were 50--60 nm in diameter with a zeta potential of greater than -30 mV in water, while the synthesized FA-PFBT-NH2 polymer dots were 90-- 105 nm in diameter with a zeta potential of greater than -20 mV in water. Furthermore, the FA-PFBT-COOH polymer dots produced stronger fluorescence in- tensity in water solution as well as in the cells than the FA-PFBT-NH2 polymer dots, and were able to image H1299 tumors in living mice after intravenous injection. This study showed the great potentials of FA-PFBT-COOH poly- mer dots as fluorescent nanoprobes for biomedical imaging.
基金National Key Research and Development(R&D)Program of China(2019YFB2203001)National Natural Science Foundation of China(NSFC,No.62171195).
文摘In this work,on-chip three-dimensional(3D)photonic integrated optical sources based on active fluorescent polymer waveguide microdisks are proposed for light display application.Fluorescent green and red oligomers with high-efficiency photoluminescence are doped into epoxy crosslinking SU-8 polymer as the waveguide gain medium.The microdisk-based on-chip optically pumping light sources are designed and fabricated using the organic functionalized materials by direct UV written process.The promising stacking dual-microdisk structures with double gain layers could provide white signal light source generated perpendicular to the chip,and green signal light source stimulated in the chip.The approach could realize the monolithically on-chip assembled vertical and horizontal bright emitters.The optical pumping threshold power is obtained as 50 mW with continuous-wave(CW)pumping.The average gain coefficient of a white light source is measured by vertical fiber coupling as 112 dB/W,and that of green light source by horizontal fiber coupling as 137 dB/W,respectively.The rising and falling response time of the on-chip optical sources are 60 and 80μs under modulating pulsed pumping.This technique is very promising for achieving 3D integrated light display application,including photonic circuits and optical information encryption.
基金Fundamental Scientific Research Business Expenses of Central Universities,Grant/Award Number:2342021DUT21ZD211。
文摘Nonconjugated polymer dots(PDs)without largely conjugated structures entitle their advantages such as environment friendliness,nontoxicity,and intrinsic fluorescence.However,color-tunable PDs remain a challenge.Herein,polyvinyl pyrrolidone(PVP)and ascorbic acid(AA)are used to synthesize nonconjugated PDs,namely,PA PDs with intensive blue emission.The introduction of a third component,m-phenylenediamine(MPD),redshifted the emission to green.The asprepared color-tunable blue to green emissive PDs exhibit excellent properties,whether in solution or in solid state,originated from the mechanism of clusteringtriggered emission(CTE)induced by the overlap of electron-rich atoms,the strong inter/intrachain interaction.The quantum yields of blue and green PDs reached up to 15.07%and 28.22%,respectively.Furthermore,PA PDs were successfully applied to the highly efficient photocatalytic degradation for dyes:methylene blue(MB)and methyl orange(MO)were degraded by 89.9%and 93.8%within 20 min under visible light,respectively.
基金financially supported by the Science and Technology Planning Project of Guangdong Province(No.2014A010105009)the National Key Basic Research Program of China(No.2013CB834702)+1 种基金the National Natural Science Foundation of China(Nos.21574044 and 21474031)the Fundamental Research Funds for the Central Universities(No.2015ZY013)
文摘A simple and effective polymer fluorescent thermosensitive system was successfully developed based on the synergistic effect of excimer/monomer interconversion of pyrene derivatives and electrostatic interaction between polyelectrolyte and charged fluorophore. As for the system, the excimer-monomer conversion, thermosensitive behavior and thermo-responsive reversibility were investigated experimentally. Temperature variation and temperature-distribution induced fluorescence changes can be observed directly by naked eyes. Thus, this polymer system holds promise for serving as a fluorescent thermometer.
基金supported by National Basic Research Program of China(No. 2014CB643601)
文摘Accessing local dynamics within a single macromolecule is the key to understand the physical origin of the viscoelasticity and especially the glass transition. In order to extract specific information on the dynamics of the branch point of a star polymer around its glass transition temperature, four-arm star poly （n-butyl methacrylate） with a fluorescent core was synthesized using perylene diimide as initiator and polymerization conducted via atom transfer radical polymerization. The process is found to be effective in positioning the fluorophore at the branch point with the fluorophore intact, which allows the successful application of single molecule fluorescence defocus imaging in examining the local site- sensitive dynamics. The power spectra of rotation trajectories, the population of rotating fluorophores as well as the distribution of angular displacement were used to revel the difference in local dynamics between branch point and the arm＇s end. It is discovered that the local dynamics at the core of the star polymer is much less activated than that at the arm＇s end. The results demonstrate the strong effect dues to the topological constrain at the branch point and the more free space at the arm＇s end.
基金supported by the National Natural Science Foundation of China (No.21273286)Doctoral Program Foundation of the Education Ministry (No.20130133110005)
文摘Polyacrylamide microspheres have been suc- cessfully used to reduce water production in reservoirs, but it is impossible to distinguish polyacrylamide microspheres from polyacrylamide that is used to enhance oil recovery and is already present in production fluids. In order to detect polyacrylamide microspheres in the reservoir pro- duced fluid, fluorescent polyacrylamide microspheres P（AM-BA-AMCO）, which fluoresce under ultraviolet irradiation, were synthesized via an inverse suspension polymerization. In order to keep the particle size distribu- tion in a narrow range, the synthesis conditions of the polymerization were studied, including the stirring speed and the concentrations of initiator, NaaCO3, and dispersant. The bonding characteristics of microspheres were deter- mined by Fourier transform infrared spectroscopy. The surface morphology of these microspheres was observed under ultraviolet irradiation with an inverse fluorescence microscope. A laboratory evaluation test showed that the fluorescent polymer microspheres had good water swelling capability, thus they had the ability to plug and migrate in a sand pack. The plugging rate was 99.8 % and the residual resistance coefficient was 800 after microsphere treatment in the sand pack. Furthermore, the fluorescent microspheres and their fragments were accurately detected under ultra- violet irradiation in the produced fluid, even though theyhad experienced extrusion and deformation in the sand pack.
基金supported by the National Natural Science Foundation of China(No.51474086)Natural Science Foundation-Steel and Iron Foundation of Hebei Province(B2015209299)the Graduate Student Innovation Fund of North China University of Science and Technology(2015S13)
文摘Two new coordination polymers containing rigid bis（triazole）, namely, [Ni（btb）_（0.5）（nph）（H_2O）]_n（1） and [Zn（btb）（SO_4）]_n（2）（btb = 4,4a-bis（1,2,4-triazolyl-1-yl）-biphenyl, H_2nph = 3-nitrophthalic acid） have been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a 3D trinodal（3,4,4）-connected sqc69 topology. Complex 2 presents a 2D uninodal 4-connected sql network, which is further packed into a 3D supramolecular framework by C-H···O hydrogen bonds. Thermal stabilities and fluorescence properties of two complexes have been discussed in detail.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11404048,61205154 and 11375034the Fundamental Research Funds for the Central Universities under Grant Nos 3132015233,3132013104,3132014337,3132015144 and3132015152+1 种基金the State Key Laboratory of Fine Chemicals(KF1409)the Program for Liaoning Excellent Talents in University under Grant No LJQ2014051
文摘The two-photon fluorescence properties and ultrafast responses of a hyperbranched polyyne （hb-DPP-J2） with triphenylamine as the central core, Diketo-Pyrrolo-Pyrrole as the connecting unit and electron acceptor are studied. The polymer has a D-π-A-π-D conjugated structure along the extended polyyne w-bridge systems, and the effective condugated unit repeats itself in the whole hyperbranehed polymer chain. The polymer exhibits a large two-photon absorption cross section and high fluorescence quantum yields. The ultrafast dynamic results give a deep understanding of the excited energy transfer processes under excitation, and reveal a long relaxation lifetime of the intramolecular charge transfer （ICT） state.
基金Supported by the National Science Foundation of China(No.20831002 and 21531003)Project of Science and Technology Development of Jilin City(No.20166024)
文摘Using a rigid azo ligand 4-[（8-hydroxy-5-quinolinyl）azo]-benzoic acid（H2 L）,a new supramolecular compound [Zn（L）（H2O）2]n（1） has been solvothermally synthesized and structurally characterized by X-ray single-crystal diffraction,infrared spectrum,elemental analysis,power X-ray diffraction and thermal analysis.Compound 1 crystallizes in monoclinic,space group C2/c with a = 30.372（8）,b = 11.415（3）,c = 9.248（3） A,β = 106.94（3）o,V = 3067.20（15）A3,C（16）H（13）N3O5Zn,Mr = 392.66,Z = 8,Dc = 1.701 Mg/m^3; F（000） = 1600,μ = 1.636 mm^-1,reflections collected：7290,reflections unique：2735,R（int）= 0.0282,R = 0.0351,wR（all data） = 0.0919,GOOF on F^2 = 1.036.Compound 1 exhibits a one-dimensional（1 D） zig-zag chain structure connected into a three-dimensional（3D） supramolecular network through hydrogen bonding interactions.Fluorescent property and electrochemical property were detected on compound 1.
基金Supported by the Doctor Foundation of Shandong Province(No.BS2010CL021)Natural Science Foundation of Jiangsu Provincial Department of Education(No.14KJA150003)Jiangsu Key Laboratory for Chemistry of Low-dimensional Materials(JSKC12106)
文摘Based on the building block of 2-phenyl-4,6-di（pyridin-2-yl）pyrimidine （L = C20H14N4）, a Cu（I） polymer [（CuC20H14N4）（CuCl2）]∞ and a salt with H2SO4 [（C20H16N4）（HSO4）2] have been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction. In the Cu（Ⅰ） polymer, although the central metal ions of Cu（Ⅰ） directly coordinate with the building block L, they still do not assembly expected grid-type complexes and there exists a one-dimensional chain constructed through coordinate bonds. In the salt, hydrogen bonds along with two kinds of π…π supramoleuclar interactions fabricate two-dimensional （2D） networks which further generate a 3D supramolecular architecture via interlayer π…π interactions. Fluorescent spectra show that the L emits blue fluorescence and its Cu（Ⅰ） polymer and salt decrease the fluorescent intensity.
基金supported by the Ministry of Science,Research and the Arts Baden-Württemberg and the German Research Foundation through Grants INST 35/1314-1 FUGG and INST 35/1503-1 FUGG and the support of the LIMa Live Cell Imaging at Microscopy Core Facility Platform Mannheimsupporting Stellaris 8 imaging sessions onsite.This study has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant agreement no.813839(RenalToolBox).E.Vsupported through a grant from Regione Emilia-Romagna within the call“Bando Alte Competenze per la Ricerca ed il Trasferimento Tecnologico POR FSE 2014/2020”(to S.B.and L.R.).
文摘Over the last decades,various tissue-clearing techniques have broken the ground for the optical imaging of whole organs and whole-organisms,providing complete representative data sets of three-dimensional biological structures.Along with advancements in this field,the development of fluorescent markers for staining vessels and capillaries has offered insights into the complexity of vascular networks and their impact on disease progression.Here we describe the use of a modified water-soluble chitosan linked to cyanine dyes in combination with ethyl cinnamate-based optical tissue clearing for the 3D visualization of tissue vasculature in depth.The water-soluble fluorescent Chitosans have proven to be an optimal candidate for labeling both vessels and capillaries ex vivo thanks to their increased water solubility,high photostability,and optical properties in the near-infrared window.In addition,the nontoxicity of these markers broadens their applicability to in vitro and in vivo biological applications.Despite the availability of other fluorescent molecules for vascular staining,the present study,for the first time,demonstrates the potential of fluorescent chitosans to depict vessels at the capillary level and opens avenues for advancing the diagnostic field by reducing the complexity and costs of the currently available procedures.
基金the National Natural Science Foundation of China(Nos.51573182,51203149,21204084,91333205)the 973 Project(No.2015CB655000)for financial support of this research
文摘Compared with conventional π-conjugated polymers,poly（arylene ether）s（PAEs） may take advantages of excellent thermal properties,well-defined effective conjugated length and no catalyst contamination.Recently,their applications have been extended from engineering plastics to optoelectronic materials.In this review,various kinds of functional PAEs used as fluorescent polymers,host polymers and phosphorescent polymers in organic light-emitting diodes（OLEDs） are outlined,and their molecular design,synthesis and device performance are overviewed.
基金Project supported by the National Natural Science Foundation of China （No. 20875003）.
文摘A novel peroxyoxalate chemiluminescence system has been designed for the determination of Triton X-100 （TX-100）, in which a hydrophobic fluorescent conjugated polymer, poly[2,5-bisnonyloxy-1,4-phenyleneethynylene-9,10-anthrylene] （PPEA） was employed as a fluorophor. A strong enhanced intensity of chemiluminescence （CL） was observed in the presence of TX-100, due to the improved emission efficiency of PPEA in the presence of TX-100. Under optimum conditions, the detection range of Triton X-100 is between 1.0 ×10 ^-7 and 1.0 ×10 ^-4 mol·L ^-1, with a detection limit at 6.0×10 ^-8 moloL 1. The relative standard deviation is 2.4% （n=6） for 1.0×10 ^-6 mol·L ^-1Triton X-100. This method provides satisfying results in the detection of TX-100 in nature water and biological samples with high sensitivity and wide linear range.
文摘The preparation and performance characterization of〈50 nm spirobenzopyran-based photochromic nanocomposites with photoswitchable fluorescence are presented.The nanocomposites were fabricated by means of a modifed miniemulsion polymerization process,in which the hydrophobic spirobenzopyran was covalently attached to the polymer chains and the matched fluorescent dyes were noncovalently embedded in the nanoscale cross-linked polymeric matrix,respectively.The obtained nanocomposites with a high relative fluorescence quantum yield（Q）exhibited superior fluorescent photoswitchable performance due to the effective photo-induced intermolecular energy transfer.The stability of photomerocyanine was also improved.
