Traditional fluorescent probes typically display blueshifted emission in rigidifying media;however,a newly developed class of rigidochromic fluorophores derived from phenanthridine demonstrates remarkable redshifted e...Traditional fluorescent probes typically display blueshifted emission in rigidifying media;however,a newly developed class of rigidochromic fluorophores derived from phenanthridine demonstrates remarkable redshifted emission under similar conditions.Pyridine,with similar N-heterostructure to those of phenanthridine group,is considered a promising candidate for achieving comparable rigidity-induced redshift behavior.In this work,we synthesized eight organic fluorophores featuring diverse functional units and substitutes by systematically combining pyridine with carbazole,triazatruxene(TAT),and tetraphenylethylene(TPE),respectively.These molecules exhibit significant emission redshifts(up to 225 nm,a record high value ever reported)or notable emission intensity changes as the rigidity of the polymer matrix increases,along with unique acid responsiveness.The differences in polar-πinteractions between fluorophores and polymers diversify the emission behavior,advancing the development of secure printing and intelligent optical materials.By embedding these fluorophores into polymer films with helical phase structures,redshifted emission with tunable chirality was achieved.Notably,leveraging the acid-responsive properties of these fluorophores,a time-dependent light-controlled dynamic encryption system was constructed,successfully enabling multi-level information encryption.This research greatly expands the scope of rigidochromic fluorophores,and their applications in anti-counterfeiting and information storage.展开更多
Palladium-catalyzed highly meta-selective C—H iodination of phenylacetic acid,benzylphosphonate and benzylsulfonate scaffolds with molecular I2 is developed using a pyridine-type template.The practical ester linkages...Palladium-catalyzed highly meta-selective C—H iodination of phenylacetic acid,benzylphosphonate and benzylsulfonate scaffolds with molecular I2 is developed using a pyridine-type template.The practical ester linkages enable the directing template easily installed and readily removed.The substrate scope is broad,and alkyl,methoxyl,trifluomethyl,and halo substituents are compatible with this reaction.Further transformations of ibuprofen iodide intermediates by Pd-catalyzed C—C and C-heteroatom bond formation illustrate the broad utility of this method.展开更多
Organic fluorescent materials with multistimuli-responsive behaviors have attracted much attention because of their promising applications in diverse fields.Most chromophores exhibit bright emission in either dilute s...Organic fluorescent materials with multistimuli-responsive behaviors have attracted much attention because of their promising applications in diverse fields.Most chromophores exhibit bright emission in either dilute solutions or aggregation states,which inevitably suffer from the aggregation-caused quenching(ACQ)problem or encounter serious energy loss at low concentration.To overcome these limitations,dual-state emissive(DSE)materials with bright emission in both solution and solid states have been developed.However,most DSE materials only involve one or two stimulus-responsive behaviors.Herein,through combining characteristics of imidazopyridine N1 as well as manipulation of electronic structure and intermolecular interaction,DSE molecule TPA-IPBA with four multistimuli-responsive behaviors has been rationally and accurately prepared,which could be easily converted to ACQ(TPA-IPB)and AIE(aggregation-induced emission)(TPA-IPBCN)molecules.Under external stimuli,four types of multistimuli-responsive behaviors have been successfully achieved,including solvatochromism(redshift of 124 nm),mechanofluorochromism(redshift of 6 or 30 nm),reversible tricolor acidichromism(redshift of 148 nm)and solidphase polymorphism with solvent-dependent solid emission(from B-state to G-state,redshift of 52 nm).We explained four types of multistimuli-responsive behaviors in detail through nuclear magnetic resonance spectroscopies,theoretical calculations,single crystal analysis,and PXRD characterization.In addition,on the basis of our biological research on imidazo[1,2-α]-pyridines,we found that TPA-IPBA serves as a fluorescent probe to dynamically detect biological lipid droplets with high co-localization ability(PC=0.95).These results provide new insight into developing DSE materials via a delicate manipulation of molecular structure with acceptor-dependent tunable multistimuli-responsive properties and bioimaging applications.展开更多
基金supported by National Natural Science Foundation of China(22275193,22275189,and 52473201)the Natural Science Foundation of Fujian Province(2024J09055)+3 种基金Fujian Provincial Department of Science and Technology(202310030)Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Science,CXZX-2022-GH09(E255KF0101)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZR115)Foundation for the Excellent Postdoctoral of Fujian Province,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences(E055AJ01,E355AJ01).
文摘Traditional fluorescent probes typically display blueshifted emission in rigidifying media;however,a newly developed class of rigidochromic fluorophores derived from phenanthridine demonstrates remarkable redshifted emission under similar conditions.Pyridine,with similar N-heterostructure to those of phenanthridine group,is considered a promising candidate for achieving comparable rigidity-induced redshift behavior.In this work,we synthesized eight organic fluorophores featuring diverse functional units and substitutes by systematically combining pyridine with carbazole,triazatruxene(TAT),and tetraphenylethylene(TPE),respectively.These molecules exhibit significant emission redshifts(up to 225 nm,a record high value ever reported)or notable emission intensity changes as the rigidity of the polymer matrix increases,along with unique acid responsiveness.The differences in polar-πinteractions between fluorophores and polymers diversify the emission behavior,advancing the development of secure printing and intelligent optical materials.By embedding these fluorophores into polymer films with helical phase structures,redshifted emission with tunable chirality was achieved.Notably,leveraging the acid-responsive properties of these fluorophores,a time-dependent light-controlled dynamic encryption system was constructed,successfully enabling multi-level information encryption.This research greatly expands the scope of rigidochromic fluorophores,and their applications in anti-counterfeiting and information storage.
基金Shanghai Institute of Materia Medica,Chinese Academy of Sciences,National Natural Science Foundation of China(No.21772211)Youth Innovation Promotion Association CAS(Nos.2014229 and 2018293)+4 种基金Institutes for Drug Discovery and Development,Chinese Academy of Sciences(No.CASIMM0120163006)Science and Technology Commission of Shanghai Municipality(No.17JC1405000)Program of Shanghai Academic Research Leader(No.19XD1424600)National Science&Technology Major Project“Key New Drug Creation and Manufacturing Program”,China(No.2018ZX09711002-006)the State Key Laboratory of Natural and Biomimetic Drugs for financial support。
文摘Palladium-catalyzed highly meta-selective C—H iodination of phenylacetic acid,benzylphosphonate and benzylsulfonate scaffolds with molecular I2 is developed using a pyridine-type template.The practical ester linkages enable the directing template easily installed and readily removed.The substrate scope is broad,and alkyl,methoxyl,trifluomethyl,and halo substituents are compatible with this reaction.Further transformations of ibuprofen iodide intermediates by Pd-catalyzed C—C and C-heteroatom bond formation illustrate the broad utility of this method.
基金supported by the National Natural Science Foundation of China(21803059,22401267)the Training Program for Young Backbone Teachers in Higher Education Institutions of Henan Province(2024GGJS011)the Natural Science Foundation of Henan Province(252300421282)。
文摘Organic fluorescent materials with multistimuli-responsive behaviors have attracted much attention because of their promising applications in diverse fields.Most chromophores exhibit bright emission in either dilute solutions or aggregation states,which inevitably suffer from the aggregation-caused quenching(ACQ)problem or encounter serious energy loss at low concentration.To overcome these limitations,dual-state emissive(DSE)materials with bright emission in both solution and solid states have been developed.However,most DSE materials only involve one or two stimulus-responsive behaviors.Herein,through combining characteristics of imidazopyridine N1 as well as manipulation of electronic structure and intermolecular interaction,DSE molecule TPA-IPBA with four multistimuli-responsive behaviors has been rationally and accurately prepared,which could be easily converted to ACQ(TPA-IPB)and AIE(aggregation-induced emission)(TPA-IPBCN)molecules.Under external stimuli,four types of multistimuli-responsive behaviors have been successfully achieved,including solvatochromism(redshift of 124 nm),mechanofluorochromism(redshift of 6 or 30 nm),reversible tricolor acidichromism(redshift of 148 nm)and solidphase polymorphism with solvent-dependent solid emission(from B-state to G-state,redshift of 52 nm).We explained four types of multistimuli-responsive behaviors in detail through nuclear magnetic resonance spectroscopies,theoretical calculations,single crystal analysis,and PXRD characterization.In addition,on the basis of our biological research on imidazo[1,2-α]-pyridines,we found that TPA-IPBA serves as a fluorescent probe to dynamically detect biological lipid droplets with high co-localization ability(PC=0.95).These results provide new insight into developing DSE materials via a delicate manipulation of molecular structure with acceptor-dependent tunable multistimuli-responsive properties and bioimaging applications.
