Porphyrins and their derivatives,such as peroxidases,hemoglobin,cytochromes,and chlorophylls,play essential roles in biological processes,particularly within photosystem Ⅰ and Ⅱ.Inspired by nature,we present a simpl...Porphyrins and their derivatives,such as peroxidases,hemoglobin,cytochromes,and chlorophylls,play essential roles in biological processes,particularly within photosystem Ⅰ and Ⅱ.Inspired by nature,we present a simple and effective strategy for constructing a porphyrin-based supramolecular system to enhance the photosensitizing efficiency of porphyrins through a coordination-driven self-assembly process.In this work,a monofunctionalized tetraphenylethene(TPE)-based cage(1)with a pyridine group and a hydrophobic cavity was designed and synthesized.This covalent molecular cage can interact with zinc tetraphenyl porphyrin(2)through axial coordination of pyridine with the zinc ion,forming a coordinated complex(3).In solution,the ditopic complex 3,with both host and vip moieties,spontaneously assembles into a cyclic[c2]daisy chain(3_(2)).The self-assembly of 3_(2) combines the advantages of TPE and porphyrin units,leading to improved charge separation,efficient intersystem crossing,and stable triplet states.These features highly enhance the generation of reactive oxygen species(ROS).As a result,3_(2),as a photocatalyst,exhibits rapid catalytic oxidation of nicotinamide adenine dinucleotide(NADH),with a high turnover frequency of 13.4 min^(−1).By combining the cytotoxic effects of ROS and the disruption of the intracellular redox balance involving NADH,3_(2) functions as a supramolecular photosensitizer that demonstrates effective photodynamic therapy with good biocompatibility and biosafety in a hypoxic environment.展开更多
Detection of nucleoside derivatives has paramount importance because they are the essential biomolec-ular units for all life.Herein,we report a host-vip approach by using a fluorescent tetraphenylethene-based octaca...Detection of nucleoside derivatives has paramount importance because they are the essential biomolec-ular units for all life.Herein,we report a host-vip approach by using a fluorescent tetraphenylethene-based octacationic cage as host and 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt(HPTS)as vip and fluorescent indicator to form non-fluorescent 1:1:1 host-(endo-exo)vip complex in water.This new host-(endo-exo)vip complex can be successfully used for detecting nucleosides(e.g.,ATP and GTP),DNA(e.g.,sm-DNA),and antibiotics(e.g.,Penicillin G)with off-on fluorescence response via a competitive host-vip exchange with HPTS as exo-vip in water.Furthermore,this on-off-on fluorescent host-vip com-plex is also used for cell imaging based on ATP concentration in HeLa cells.Therefore,this study not only provides insight into the construction of a supramolecular probe with on-off-on fluorescence via host-vip complexation and exchange in solution,but also realizes a universal method for detecting and monitoring biomolecules.展开更多
The hydrogen-bonded(H-bonded)base pairs,double H-bonded A•T and triple H-bonded G•C in DNA,are important units for storing,encoding,and expressing genetic information.Owing to the interference from water,however,the f...The hydrogen-bonded(H-bonded)base pairs,double H-bonded A•T and triple H-bonded G•C in DNA,are important units for storing,encoding,and expressing genetic information.Owing to the interference from water,however,the formation of H-bonded base pairs from short deoxynucleotide fragments such as mono-or di-deoxynucleotide are not easily achieved in aqueous solutions.展开更多
Chirality transfer,induction,and circularly polarized luminescence(CPL)using supramolecular hosts,such as macrocycles and cages,have been explored for wide-ranging applicationsin chiral recognition,sensing,catalysis,a...Chirality transfer,induction,and circularly polarized luminescence(CPL)using supramolecular hosts,such as macrocycles and cages,have been explored for wide-ranging applicationsin chiral recognition,sensing,catalysis,and chiroptical functional materials.Herein,we report the adaptive chirality of an achiral tetraphenylethene(TPE)-basedoctacationic cage(1)inducedby bindingwith enantiopure deoxynucleotides(A,T,C,and G)throughhost-vip(H-G)complexationinwater.The hydrophobic cavity of the cage efficiently stabilizes the hydrogen-bonded dimerization of deoxynucleotides(A_(2),T_(2),C_(2),and G_(2))to form H-G complexes in 1∶2 ratios.Given the photophysical properties and dynamic rotational conformation of the TPE units of the cage,cage⊃deoxynucleotide complexes exhibited excellent chiroptical propertiesbased on chirality transfer andinduction from the chiral vip to the achiral host.For this supramolecular system,the cage showed a unique adaptive chirality of the double clockwise-typed(PP)rotational conformation of the two TPE units,which was induced by chiral vips(e.g.,A_(2),T_(2),C_(2),and G_(2))through H-G complexation in water.Furthermore,the adaptive chirality of the cage⊃deoxynucleotide complexes successfully induced CPL signals in homogeneous aqueous solutions.This study provides insights for the construction of adaptive chirality from an achiral TPE-based octacationic cage with dynamic conformational nature,and might facilitate further design of chiral functional materials for several applications,such as chiral recognition,sensing,displays,catalysis,and other chiral fluorescent supramolecular systems based on aqueous H-G complexation.展开更多
基金supported by the National Natural Science Foundation of China(grant nos.22371229 and 22301241)the National Key R&D Program of China,Synthetic Biology Research(grant no.2023YFA0913600).
文摘Porphyrins and their derivatives,such as peroxidases,hemoglobin,cytochromes,and chlorophylls,play essential roles in biological processes,particularly within photosystem Ⅰ and Ⅱ.Inspired by nature,we present a simple and effective strategy for constructing a porphyrin-based supramolecular system to enhance the photosensitizing efficiency of porphyrins through a coordination-driven self-assembly process.In this work,a monofunctionalized tetraphenylethene(TPE)-based cage(1)with a pyridine group and a hydrophobic cavity was designed and synthesized.This covalent molecular cage can interact with zinc tetraphenyl porphyrin(2)through axial coordination of pyridine with the zinc ion,forming a coordinated complex(3).In solution,the ditopic complex 3,with both host and vip moieties,spontaneously assembles into a cyclic[c2]daisy chain(3_(2)).The self-assembly of 3_(2) combines the advantages of TPE and porphyrin units,leading to improved charge separation,efficient intersystem crossing,and stable triplet states.These features highly enhance the generation of reactive oxygen species(ROS).As a result,3_(2),as a photocatalyst,exhibits rapid catalytic oxidation of nicotinamide adenine dinucleotide(NADH),with a high turnover frequency of 13.4 min^(−1).By combining the cytotoxic effects of ROS and the disruption of the intracellular redox balance involving NADH,3_(2) functions as a supramolecular photosensitizer that demonstrates effective photodynamic therapy with good biocompatibility and biosafety in a hypoxic environment.
基金supported by the National Natural Science Foun-dation of China(Nos.22122108,21971208 and 21771145)the Natu-ral Science Basic Research Plan for Distinguished Young Scholars in Shaanxi Province of China(No.2021JC-37)the Fok Ying Tong Education Foundation(No.171010).
文摘Detection of nucleoside derivatives has paramount importance because they are the essential biomolec-ular units for all life.Herein,we report a host-vip approach by using a fluorescent tetraphenylethene-based octacationic cage as host and 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt(HPTS)as vip and fluorescent indicator to form non-fluorescent 1:1:1 host-(endo-exo)vip complex in water.This new host-(endo-exo)vip complex can be successfully used for detecting nucleosides(e.g.,ATP and GTP),DNA(e.g.,sm-DNA),and antibiotics(e.g.,Penicillin G)with off-on fluorescence response via a competitive host-vip exchange with HPTS as exo-vip in water.Furthermore,this on-off-on fluorescent host-vip com-plex is also used for cell imaging based on ATP concentration in HeLa cells.Therefore,this study not only provides insight into the construction of a supramolecular probe with on-off-on fluorescence via host-vip complexation and exchange in solution,but also realizes a universal method for detecting and monitoring biomolecules.
基金supported by the National Natural Science Foundation of China(nos.22122108,21971208,and 21771145)the Natural Science Basic Research Plan for Distinguished Young Scholars in Shaanxi Province of China(no.2021JC-37)+1 种基金the Fok Ying Tong Education Foundation(no.171010)the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(no.2019B030301003)from South China University of Technology.
文摘The hydrogen-bonded(H-bonded)base pairs,double H-bonded A•T and triple H-bonded G•C in DNA,are important units for storing,encoding,and expressing genetic information.Owing to the interference from water,however,the formation of H-bonded base pairs from short deoxynucleotide fragments such as mono-or di-deoxynucleotide are not easily achieved in aqueous solutions.
基金supported by the National Natural Science Foundation of China(nos.21971208 and 21771145)the Fok Ying Tong Education Foundation(no.171010)+1 种基金the State Key Laboratory of Luminescent Materials and Devices(no.2019-skllmd-20)Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(no.2019B030301003)from South China University of Technology。
文摘Chirality transfer,induction,and circularly polarized luminescence(CPL)using supramolecular hosts,such as macrocycles and cages,have been explored for wide-ranging applicationsin chiral recognition,sensing,catalysis,and chiroptical functional materials.Herein,we report the adaptive chirality of an achiral tetraphenylethene(TPE)-basedoctacationic cage(1)inducedby bindingwith enantiopure deoxynucleotides(A,T,C,and G)throughhost-vip(H-G)complexationinwater.The hydrophobic cavity of the cage efficiently stabilizes the hydrogen-bonded dimerization of deoxynucleotides(A_(2),T_(2),C_(2),and G_(2))to form H-G complexes in 1∶2 ratios.Given the photophysical properties and dynamic rotational conformation of the TPE units of the cage,cage⊃deoxynucleotide complexes exhibited excellent chiroptical propertiesbased on chirality transfer andinduction from the chiral vip to the achiral host.For this supramolecular system,the cage showed a unique adaptive chirality of the double clockwise-typed(PP)rotational conformation of the two TPE units,which was induced by chiral vips(e.g.,A_(2),T_(2),C_(2),and G_(2))through H-G complexation in water.Furthermore,the adaptive chirality of the cage⊃deoxynucleotide complexes successfully induced CPL signals in homogeneous aqueous solutions.This study provides insights for the construction of adaptive chirality from an achiral TPE-based octacationic cage with dynamic conformational nature,and might facilitate further design of chiral functional materials for several applications,such as chiral recognition,sensing,displays,catalysis,and other chiral fluorescent supramolecular systems based on aqueous H-G complexation.
