In the past decades,porphyrins,phthalocyanines and related materials have attracted significant attention due to their diverse and brilliant structures[1,2],as well as their unique electronic structures and photophysi...In the past decades,porphyrins,phthalocyanines and related materials have attracted significant attention due to their diverse and brilliant structures[1,2],as well as their unique electronic structures and photophysical properties which could be applicable in a wide range of areas[3–5].展开更多
Heteroatom doping has the potential to alter the electronic structure and optical properties of nanographenes,thereby expanding the scope of their utility in various applications.In this work we demonstrate a strategy...Heteroatom doping has the potential to alter the electronic structure and optical properties of nanographenes,thereby expanding the scope of their utility in various applications.In this work we demonstrate a strategy to introduce an oxygen atom directly and precisely into backbone of the already formed metal-nanographene complexes.Treating metal-nanographene complexes HBCP-M(M=Cu,Ag,Au)with Davis’oxaziridine produces oxygen-doped complexes HBCP-OM(M=Cu,Ag,Au)with adj-CONN coordination in one step.Compared with original metal complexes,the electronic structure,photophysical properties and molecular conformations of HBCP-OM show sharp changes,as indicated by steady and fs-transient absorption(TA)spectroscopies,DFT calculations and crystal structure analysis.Moreover,the reduction of coordination cavity of HBCP-OM due to oxygen insertion affects the metal-ligand interaction.This leads that HBCP-OCu,possessing a relatively small Cu(III)cation,exhibits an extended near-infrared(NIR)absorption beyond 1300 nm that is not observed inHBCP-OAg and HBCP-OAu.展开更多
Cation recognition by cationic receptors is typically challenging due to coulombic repulsion.In this study,we designed a hexacationic receptor,namely,3NDI^(6+).This tricycle naturally adopts a sandwichlike conformatio...Cation recognition by cationic receptors is typically challenging due to coulombic repulsion.In this study,we designed a hexacationic receptor,namely,3NDI^(6+).This tricycle naturally adopts a sandwichlike conformation as its hexafluorophosphate salt([3NDI^(6+)@2PF6^(−)]·4PF6^(−))but then recognizes two chloride anions upon treatment with a chloride anion source.The recognition of the first chloride anion(as an allosteric modulator)facilitates conformational regulation fromthe sandwich-like conformation with a collapsed cavity to a preorganized capsule-like conformation.After conformational switching,the second chloride anion is further recognized to form the inclusion complex[3NDI^(6+)⊃2Cl^(−)]^(4+).The chloridecontaining hexacationic capsule([3NDI^(6+)⊃2Cl^(−)]^(^(4+)))was found to recognize various cations(e.g.,K+from KCl),as supported by the crystal structure of the potassium complex,which revealed a single anionic[KCl_(2)]–entity within the capsule.Prior to conversion to the chloride anion-bound capsule-like form,no evidence of cation recognition is seen by[3NDI^(6+)@2PF_(6)^(−)]·4PF6^(−).The ability to accommodate a cation within the cationic framework of 3NDI^(^(6+))(as[3NDI^(^(6+))⊃2Cl^(−)]·4Cl^(−))is ascribed to specific anion(as Cl^(−))recognition and formation of a capsule-like species,rather than simple charge balance effects.This study presents a new strategy for cation recognition by a cationic capsule that underscores the promise of allosteric control over small-molecule receptor systems.展开更多
An increased demand for iron is a hallmark of cancer cells and is thought necessary to promote high cell proliferation,tumor progression and metastasis.This makes iron metabolism an attractive therapeutic target.Unfor...An increased demand for iron is a hallmark of cancer cells and is thought necessary to promote high cell proliferation,tumor progression and metastasis.This makes iron metabolism an attractive therapeutic target.Unfortunately,current iron-based therapeutic strategies often lack effectiveness and can elicit off-target toxicities.We report here a dual-therapeutic prodrug,DOXjade,that allows for iron chelation chemo-photothermal cancer therapy.This prodrug takes advantage of the clinically approved iron chelator deferasirox(ExJade®)and the topoisomerase 2 inhibitor,doxorubicin(DOX).Loading DOXjade onto ultrathin 2D Ti_(3)C_(2) MXene nanosheets produces a construct,Ti_(3)C_(2)-PVP@DOXjade,that allows the iron chelation and chemotherapeutic functions of DOXjade to be photo-activated at the tumor sites,while potentiating a robust photothermal effect with photothermal conversion efficiencies of up to 40%.Antitumor mechanistic investigations reveal that upon activation,Ti_(3)C_(2)-PVP@DOXjade serves to promote apoptotic cell death and downregulate the iron depletion-induced iron transferrin receptor(TfR).A tumor pH-responsive iron chelation/photothermal/chemotherapy antitumor effect was achieved both in vitro and in vivo.The results of this study highlight what may constitute a promising iron chelation-based phototherapeutic approach to cancer therapy.展开更多
We report here a water-soluble metal cation sensor system based on the as-prepared or reduced form of an expanded porphyrin,texaphyrin.Upon metal complexation,a change in the redox state of the ligand occurs that is a...We report here a water-soluble metal cation sensor system based on the as-prepared or reduced form of an expanded porphyrin,texaphyrin.Upon metal complexation,a change in the redox state of the ligand occurs that is accompanied by a color change from red to green.Although long employed for synthesis in organic media,we have now found that this complexation-driven redox behavior may be used to achieve the naked eye detectable colorimetric sensing of several number of less-common metal ions in aqueous media.Exposure to In(Ⅲ),Hg(Ⅱ),Cd(Ⅱ),Mn(Ⅱ),Bi(Ⅲ),Co(Ⅱ),and Pb(Ⅱ)cations leads to a colorimetric response within 10 min.This process is selective for Hg(Ⅱ)under conditions of competitive analysis.Furthermore,among the subset of responseproducing cations,In(Ⅲ)proved unique in giving rise to a ratiometric change in the ligand-based fluorescence features,including an overall increase in intensity.The cation selectivity observed in aqueous media stands in contrast to what is seen in organic solvents,where a wide range of texaphyrin metal complexes may be prepared.The formation of metal cation complexes under the present aqueous conditions was confirmed by reversed phase highperformance liquid chromatography,ultra-violet-visible absorption and fluorescence spectroscopies,and highresolution mass spectrometry.展开更多
Through-space conjugation(TSC)is a noncovalently electronic interaction that is emerging as a potential complement to through-bond conjugation(TBC)-based strategies for constructing luminescent materials.However,the d...Through-space conjugation(TSC)is a noncovalently electronic interaction that is emerging as a potential complement to through-bond conjugation(TBC)-based strategies for constructing luminescent materials.However,the design of efficient luminogens based on TSC is currently challenging due to a lack of established structure-property understanding.This is particularly true in the case of luminogens displaying aggregation-induced emission(AIE)effects.In this work,three terphenyl derivatives were prepared,and their photophysical properties were systemically studied.It was found that relative to the corresponding m-and p-linked analogues,the electronic interaction of TBC is weakened while the strength of TSC is commensurately enhanced in the constitutional isomer containing an o-linked fjordtype subunit.Within this set of luminogens,the presence of a fjord-type arrangement promotes a transformation from aggregation-caused quenching to AIE.Further investigations involving congeneric quaterphenyl and pentphenyl isomers support the universality of the fjord-type unit as a framework for synthesizing AIE-active luminogens(AIEgens)with inherent TSC.This work not only provides a novel set of AIEgens but also establishes the utility of TSC in controlling the photophysical properties of nonconventional and twisted luminogens.展开更多
stable neutral Fe(IV)complex(Fe-HDCL),readily accessible on the g scale,was found to possess high water solubility and good stability(<5%degradation over 4 h upon photoirradiation).Fe-HDCL is green and absorbs ligh...stable neutral Fe(IV)complex(Fe-HDCL),readily accessible on the g scale,was found to possess high water solubility and good stability(<5%degradation over 4 h upon photoirradiation).Fe-HDCL is green and absorbs light effectively in the visible region(500–800 nm)with aλmax at 650 nm(ɛ=7830 M^(−1)cm^(−1)).Fe-HDCL also exhibits photothermal(PT)behavior comparable to single-wall carbon nanotubes in the solid state.In aqueous solution,high PT conversion(η=72.6%)is achieved,and a strong hyperthermia-based inhibition of cell growth is observed upon subjecting Fe-HDCL to near-infrared 730 nm laser photoirradiation.Initial biological studies in vitro and in vivo confirmed that Fe-HDCL is biocompatible,clears readily,and allows the visual detection of blood vessels.Upon subjecting mice to intravenous injection at low doses(e.g.,50μmol·kg^(−1)),Fe-HDCL also permits the photoacoustic(PA)imaging of kidneys and the evaluation of renal fibrosis in mouse models.In addition,Fe-HDCL allows PA-based imaging of brain tissues,presumably reflecting its ability to pass through the blood-brain barrier.We thus propose that Fe-HDCL has a role to play as PT agent and as a photodiagnostic.展开更多
文摘In the past decades,porphyrins,phthalocyanines and related materials have attracted significant attention due to their diverse and brilliant structures[1,2],as well as their unique electronic structures and photophysical properties which could be applicable in a wide range of areas[3–5].
基金Beijing Normal University(BNU)was supported by National Natural Science Foundation of China(grant no.22275020 to X.-S.K.)BNU startup funding(grant no.312232114 to X.-S.K.)+4 种基金Yonsei University was supported by the National Research Foundation of Korea(NRF)funded by the Korea Government(MSIT)(No.RS-2025-00523354 to J.K.)Kyungpook National University was supported by the NRF funded by the Korea Government(MSIT)(No.RS-2024-00343229 and RS-2024-00404760 to J.O.)Austin was supported by the Robert A.Welch Foundation(F-0018 to J.L.S.)by the National Science Foundation(CHE-2304731 to J.L.S.)Prof.Changgui Zhao at BNU for helpful suggestions.
文摘Heteroatom doping has the potential to alter the electronic structure and optical properties of nanographenes,thereby expanding the scope of their utility in various applications.In this work we demonstrate a strategy to introduce an oxygen atom directly and precisely into backbone of the already formed metal-nanographene complexes.Treating metal-nanographene complexes HBCP-M(M=Cu,Ag,Au)with Davis’oxaziridine produces oxygen-doped complexes HBCP-OM(M=Cu,Ag,Au)with adj-CONN coordination in one step.Compared with original metal complexes,the electronic structure,photophysical properties and molecular conformations of HBCP-OM show sharp changes,as indicated by steady and fs-transient absorption(TA)spectroscopies,DFT calculations and crystal structure analysis.Moreover,the reduction of coordination cavity of HBCP-OM due to oxygen insertion affects the metal-ligand interaction.This leads that HBCP-OCu,possessing a relatively small Cu(III)cation,exhibits an extended near-infrared(NIR)absorption beyond 1300 nm that is not observed inHBCP-OAg and HBCP-OAu.
基金the National Key Research and Development Program of China(grant no.2021YFA0910100)the National Natural Science Foundation of China(grant nos.22035006,22320102001,and 22350007)+3 种基金the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(grant no.SN-ZJU-SIAS-006)the“pioneer”and“Leading Goose”R&D Program of Zhejiang(grant no.2025C04010)the Leading Innovation Team grant from the Department of Science and Technology of Zhejiang Province(grant no.2022R01005)for financial support.F.Hthanks the Chemistry Instrumentation Center of Zhejiang University for technical support.We are grateful for the access to the research facilities in Chemistry Department of the University of Hong Kong(HKU).Thework in Austinwas supported by the Robert A.Welch Foundation(F-0018 to J.L.S.).We thank HKU for their continued support of this research.
文摘Cation recognition by cationic receptors is typically challenging due to coulombic repulsion.In this study,we designed a hexacationic receptor,namely,3NDI^(6+).This tricycle naturally adopts a sandwichlike conformation as its hexafluorophosphate salt([3NDI^(6+)@2PF6^(−)]·4PF6^(−))but then recognizes two chloride anions upon treatment with a chloride anion source.The recognition of the first chloride anion(as an allosteric modulator)facilitates conformational regulation fromthe sandwich-like conformation with a collapsed cavity to a preorganized capsule-like conformation.After conformational switching,the second chloride anion is further recognized to form the inclusion complex[3NDI^(6+)⊃2Cl^(−)]^(4+).The chloridecontaining hexacationic capsule([3NDI^(6+)⊃2Cl^(−)]^(^(4+)))was found to recognize various cations(e.g.,K+from KCl),as supported by the crystal structure of the potassium complex,which revealed a single anionic[KCl_(2)]–entity within the capsule.Prior to conversion to the chloride anion-bound capsule-like form,no evidence of cation recognition is seen by[3NDI^(6+)@2PF_(6)^(−)]·4PF6^(−).The ability to accommodate a cation within the cationic framework of 3NDI^(^(6+))(as[3NDI^(^(6+))⊃2Cl^(−)]·4Cl^(−))is ascribed to specific anion(as Cl^(−))recognition and formation of a capsule-like species,rather than simple charge balance effects.This study presents a new strategy for cation recognition by a cationic capsule that underscores the promise of allosteric control over small-molecule receptor systems.
基金supported by the National Natural Science Foundation of China(Grant No.11904239,Y.W.W)the Creative Research Initiative of National Research Foundation of Korea(NRF)(CRI project No.2018R1A3B1052702,J.S.K.)+1 种基金Initial support for the work in Austin came from the National Institutes of Health(CA 68682 to J.L.S.)with subsequent funding from the Robert A.Welch Foundation(F-0018 to J.L.S.)supported by Brain Pool Program through the funded by the Ministry of Science and ICT(Grant No.2020H1D3A1A02080172,M.L.).
文摘An increased demand for iron is a hallmark of cancer cells and is thought necessary to promote high cell proliferation,tumor progression and metastasis.This makes iron metabolism an attractive therapeutic target.Unfortunately,current iron-based therapeutic strategies often lack effectiveness and can elicit off-target toxicities.We report here a dual-therapeutic prodrug,DOXjade,that allows for iron chelation chemo-photothermal cancer therapy.This prodrug takes advantage of the clinically approved iron chelator deferasirox(ExJade®)and the topoisomerase 2 inhibitor,doxorubicin(DOX).Loading DOXjade onto ultrathin 2D Ti_(3)C_(2) MXene nanosheets produces a construct,Ti_(3)C_(2)-PVP@DOXjade,that allows the iron chelation and chemotherapeutic functions of DOXjade to be photo-activated at the tumor sites,while potentiating a robust photothermal effect with photothermal conversion efficiencies of up to 40%.Antitumor mechanistic investigations reveal that upon activation,Ti_(3)C_(2)-PVP@DOXjade serves to promote apoptotic cell death and downregulate the iron depletion-induced iron transferrin receptor(TfR).A tumor pH-responsive iron chelation/photothermal/chemotherapy antitumor effect was achieved both in vitro and in vivo.The results of this study highlight what may constitute a promising iron chelation-based phototherapeutic approach to cancer therapy.
基金supported by the National Institutes of Health(Grants CA68682 to J.L.S.)the Robert A.Welch Foundation(F0018).
文摘We report here a water-soluble metal cation sensor system based on the as-prepared or reduced form of an expanded porphyrin,texaphyrin.Upon metal complexation,a change in the redox state of the ligand occurs that is accompanied by a color change from red to green.Although long employed for synthesis in organic media,we have now found that this complexation-driven redox behavior may be used to achieve the naked eye detectable colorimetric sensing of several number of less-common metal ions in aqueous media.Exposure to In(Ⅲ),Hg(Ⅱ),Cd(Ⅱ),Mn(Ⅱ),Bi(Ⅲ),Co(Ⅱ),and Pb(Ⅱ)cations leads to a colorimetric response within 10 min.This process is selective for Hg(Ⅱ)under conditions of competitive analysis.Furthermore,among the subset of responseproducing cations,In(Ⅲ)proved unique in giving rise to a ratiometric change in the ligand-based fluorescence features,including an overall increase in intensity.The cation selectivity observed in aqueous media stands in contrast to what is seen in organic solvents,where a wide range of texaphyrin metal complexes may be prepared.The formation of metal cation complexes under the present aqueous conditions was confirmed by reversed phase highperformance liquid chromatography,ultra-violet-visible absorption and fluorescence spectroscopies,and highresolution mass spectrometry.
基金F.H.thanks National Key Research and Development Program of China (grant no.2021YFA0910100)National Natural Science Foundation of China (grant no.22035006)+5 种基金Zhejiang Provincial Natural Science Foundation of China (grant no.LD21B020001)the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study (grant no.SN-ZJU-SIAS-006)the Leading Innovation Team grant from Department of Science and Technology of Zhejiang Province (grant no.2022R01005)for financial supportH.Z.thanks the National Science Foundation of China (grant no.22205197)for supportY.-Q.H.acknowledges support from the Chinese Postdoctoral Science Foundation (grant no.2022M712735)J.L.S.thanks the Robert A.Welch Foundation for chair support (grant no.F-0018).
文摘Through-space conjugation(TSC)is a noncovalently electronic interaction that is emerging as a potential complement to through-bond conjugation(TBC)-based strategies for constructing luminescent materials.However,the design of efficient luminogens based on TSC is currently challenging due to a lack of established structure-property understanding.This is particularly true in the case of luminogens displaying aggregation-induced emission(AIE)effects.In this work,three terphenyl derivatives were prepared,and their photophysical properties were systemically studied.It was found that relative to the corresponding m-and p-linked analogues,the electronic interaction of TBC is weakened while the strength of TSC is commensurately enhanced in the constitutional isomer containing an o-linked fjordtype subunit.Within this set of luminogens,the presence of a fjord-type arrangement promotes a transformation from aggregation-caused quenching to AIE.Further investigations involving congeneric quaterphenyl and pentphenyl isomers support the universality of the fjord-type unit as a framework for synthesizing AIE-active luminogens(AIEgens)with inherent TSC.This work not only provides a novel set of AIEgens but also establishes the utility of TSC in controlling the photophysical properties of nonconventional and twisted luminogens.
基金supported by the National Natural Science Foundation of China(grant no.21877080 to H.Y.)the Shanghai Engineering Research Centre of Green Energy Chemical Engineering(grant no.18DZ2254200 to H.Y.)+2 种基金the Open Project of State Key Laboratory of Chemistry and Molecular Engineering of Medicinal Resources(grant no.CMEMR 2023-B04 to Z.X.W.)supported by the Robert A.Welch Foundation(grant no.F-0018 to J.L.S.)Finally,we sincerely thank Suzhou Tomo Wave Laboratories for their technical support.
文摘stable neutral Fe(IV)complex(Fe-HDCL),readily accessible on the g scale,was found to possess high water solubility and good stability(<5%degradation over 4 h upon photoirradiation).Fe-HDCL is green and absorbs light effectively in the visible region(500–800 nm)with aλmax at 650 nm(ɛ=7830 M^(−1)cm^(−1)).Fe-HDCL also exhibits photothermal(PT)behavior comparable to single-wall carbon nanotubes in the solid state.In aqueous solution,high PT conversion(η=72.6%)is achieved,and a strong hyperthermia-based inhibition of cell growth is observed upon subjecting Fe-HDCL to near-infrared 730 nm laser photoirradiation.Initial biological studies in vitro and in vivo confirmed that Fe-HDCL is biocompatible,clears readily,and allows the visual detection of blood vessels.Upon subjecting mice to intravenous injection at low doses(e.g.,50μmol·kg^(−1)),Fe-HDCL also permits the photoacoustic(PA)imaging of kidneys and the evaluation of renal fibrosis in mouse models.In addition,Fe-HDCL allows PA-based imaging of brain tissues,presumably reflecting its ability to pass through the blood-brain barrier.We thus propose that Fe-HDCL has a role to play as PT agent and as a photodiagnostic.
