Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and of...Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.展开更多
Extracellular matrix(ECM)undergoes dynamic inflation that dynamically changes ligand nanospacing but has not been explored.Here we utilize ECM-mimicking photocontrolled supramolecular ligand-tunable Azo^(+)self-assemb...Extracellular matrix(ECM)undergoes dynamic inflation that dynamically changes ligand nanospacing but has not been explored.Here we utilize ECM-mimicking photocontrolled supramolecular ligand-tunable Azo^(+)self-assembly composed of azobenzene derivatives(Azo^(+))stacked via cation-πinteractions and stabilized with RGD ligand-bearing poly(acrylic acid).Near-infrared-upconverted-ultraviolet light induces cis-Azo^(+)-mediated inflation that suppresses cation-πinteractions,thereby inflating liganded self-assembly.This inflation increases nanospacing of“closely nanospaced”ligands from 1.8 nm to 2.6 nm and the surface area of liganded selfassembly that facilitate stem cell adhesion,mechanosensing,and differentiation both in vitro and in vivo,including the release of loaded molecules by destabilizing water bridges and hydrogen bonds between the Azo^(+)molecules and loaded molecules.Conversely,visible light induces trans-Azo^(+)formation that facilitates cation-πinteractions,thereby deflating self-assembly with“closely nanospaced”ligands that inhibits stem cell adhesion,mechanosensing,and differentiation.In stark contrast,when ligand nanospacing increases from 8.7 nm to 12.2 nm via the inflation of self-assembly,the surface area of“distantly nanospaced”ligands increases,thereby suppressing stem cell adhesion,mechanosensing,and differentiation.Long-term in vivo stability of self-assembly via real-time tracking and upconversion are verified.This tuning of ligand nanospacing can unravel dynamic ligand-cell interactions for stem cell-regulated tissue regeneration.展开更多
The transport of anions across cell membranes is diffi cult because of the negatively charged outer surfaces of cell membranes.To overcome this limitation,herein,we report a system for transporting aromatic anions acr...The transport of anions across cell membranes is diffi cult because of the negatively charged outer surfaces of cell membranes.To overcome this limitation,herein,we report a system for transporting aromatic anions across cellular membranes via self-assembly using a synthetic imidazolium-fused aromatic amphiphile.The amphiphile with cationic and aromatic groups in close proximity to each other could interact with anionic pyranine via electrostatic and aromatic interactions to form supramolecular vesicles.Supramolecular vesicles based on the synthetic imidazoliumfused aromatic amphiphile and pyranine complex transport anionic aromatic pyranine across the membranes of live MCf-7 cells without cytotoxicity.展开更多
In light of the burgeoning successes of cancer immunotherapy,glioblastoma(GBM)remains refractory due to an immunosuppressive microenvironment originating from its molecular heterogeneity.Thus,identifying promising the...In light of the burgeoning successes of cancer immunotherapy,glioblastoma(GBM)remains refractory due to an immunosuppressive microenvironment originating from its molecular heterogeneity.Thus,identifying promising therapeutic targets for treating GBM and discovering methodologies to effectively regulate them is still a tremendous challenge.Here we describe photodynamic protein tyrosine phosphatase 1B(PTP1B)proteolysis mediated by a proteolysis-targeting chimera(PROTAC)nanoassembly.The PTP1B-targeting PROTAC is conjugated with a photosensitizer via a cathepsin B(Cat B)-cleavable peptide,which spontaneously forms nanoassemblies due to intermolecularπ-πstack-ing interactions.In GBM models,PROTAC nanoassemblies significantly accumulate in the tumor region across the disrupted blood-brain barrier(BBB),triggering a burst release of the photosensitizer and active PROTAC by Cat B-mediated enzymatic cleavage.Upon laser irradiation,photodynamic therapy(PDT)synergizes with PROTAC-mediated PTP1B proteolysis to induce potent immunogenic cell death(ICD)in tumor cells.Subsequently,persistent PTP1B degradation by nanoassemblies in Cat B-overexpressed intratumoral T cells downregulates exhaustion markers,reinvigorating their function-ality.These sequential processes of photodynamic PTP1B proteolysis ultimately augment T cellmediated antitumor immunity as well as protective immunity,completely eradicating the primary GBM and preventing its recurrence.Overall,our findings underscore the therapeutic potential of combining PDT with PROTAC activity for GBM immunotherapy.展开更多
Exhausted T(Tex)cells are a distinct subset of T cells that arise in response to prolonged antigen exposure during chronic infections or cancer.Although Tex cells exhibit reduced functionality,they still retain some p...Exhausted T(Tex)cells are a distinct subset of T cells that arise in response to prolonged antigen exposure during chronic infections or cancer.Although Tex cells exhibit reduced functionality,they still retain some protective abilities.Exhausted CD8+T cells are a heterogeneous group consisting of four subsets:progenitor,intermediate,effector,and terminally exhausted.Each subset is characterized by distinct transcriptional,epigenetic,and functional traits[1].Recent studies have indicated that the progenitor and intermediate Tex subsets are mainly responsible for the proliferative surge observed during anti-PD-1 immunotherapy,which results in the production of a large pool of functional effector cells,thereby sustaining the antitumor immune response[2].However,blocking the PD-1 pathway alone typically fails to achieve lasting disease control in most patients.Simultaneous blockade of PD-1 and other immune checkpoint receptors can enhance CD8+T-cell-mediated immunity,leading to more effective treatment outcomes.展开更多
基金supported by Basic Science Research Program(Priority Research Institute)through the NRF of Korea funded by the Ministry of Education(2021R1A6A1A10039823)by the Korea Basic Science Institute(National Research Facilities and Equipment Center)grant funded by the Ministry of Education(2020R1A6C101B194)。
文摘Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.RS-2023-00208427,2021R1I1A1A01046207,2021R1A2C2005418,2022R1A2C2005943,and 2022M3H4A1A03076638)supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(No.RS-2023-00271399 and RS-2023-00275654)+1 种基金supported by a Korea University Grant and KIST intramural programHAADF-STEM was conducted with the support of the Seoul center in Korea Basic Science Institute(KBSI).
文摘Extracellular matrix(ECM)undergoes dynamic inflation that dynamically changes ligand nanospacing but has not been explored.Here we utilize ECM-mimicking photocontrolled supramolecular ligand-tunable Azo^(+)self-assembly composed of azobenzene derivatives(Azo^(+))stacked via cation-πinteractions and stabilized with RGD ligand-bearing poly(acrylic acid).Near-infrared-upconverted-ultraviolet light induces cis-Azo^(+)-mediated inflation that suppresses cation-πinteractions,thereby inflating liganded self-assembly.This inflation increases nanospacing of“closely nanospaced”ligands from 1.8 nm to 2.6 nm and the surface area of liganded selfassembly that facilitate stem cell adhesion,mechanosensing,and differentiation both in vitro and in vivo,including the release of loaded molecules by destabilizing water bridges and hydrogen bonds between the Azo^(+)molecules and loaded molecules.Conversely,visible light induces trans-Azo^(+)formation that facilitates cation-πinteractions,thereby deflating self-assembly with“closely nanospaced”ligands that inhibits stem cell adhesion,mechanosensing,and differentiation.In stark contrast,when ligand nanospacing increases from 8.7 nm to 12.2 nm via the inflation of self-assembly,the surface area of“distantly nanospaced”ligands increases,thereby suppressing stem cell adhesion,mechanosensing,and differentiation.Long-term in vivo stability of self-assembly via real-time tracking and upconversion are verified.This tuning of ligand nanospacing can unravel dynamic ligand-cell interactions for stem cell-regulated tissue regeneration.
基金the National Research Foundation of Korea(NRF)grants funded by the Korean government(MSIT)(RS-2024-00352931,NRF-2022R1A4A1031687, RS-2024-00408951)the KIST Institutional Program(2 V10330-24-P042)a Korea University grant.
文摘The transport of anions across cell membranes is diffi cult because of the negatively charged outer surfaces of cell membranes.To overcome this limitation,herein,we report a system for transporting aromatic anions across cellular membranes via self-assembly using a synthetic imidazolium-fused aromatic amphiphile.The amphiphile with cationic and aromatic groups in close proximity to each other could interact with anionic pyranine via electrostatic and aromatic interactions to form supramolecular vesicles.Supramolecular vesicles based on the synthetic imidazoliumfused aromatic amphiphile and pyranine complex transport anionic aromatic pyranine across the membranes of live MCf-7 cells without cytotoxicity.
基金supported by grants from the National Research Foundation(NRF)of Korea,funded by the Ministry of Science(RS-2025-02219039,RS-2021-NR061836,RS-202400343156,NRF-2022R1A2C2006861,RS-2024-00463774,RS2022-NR068161 and RS-2024-00405287)the Intramural Research Program of KIST.
文摘In light of the burgeoning successes of cancer immunotherapy,glioblastoma(GBM)remains refractory due to an immunosuppressive microenvironment originating from its molecular heterogeneity.Thus,identifying promising therapeutic targets for treating GBM and discovering methodologies to effectively regulate them is still a tremendous challenge.Here we describe photodynamic protein tyrosine phosphatase 1B(PTP1B)proteolysis mediated by a proteolysis-targeting chimera(PROTAC)nanoassembly.The PTP1B-targeting PROTAC is conjugated with a photosensitizer via a cathepsin B(Cat B)-cleavable peptide,which spontaneously forms nanoassemblies due to intermolecularπ-πstack-ing interactions.In GBM models,PROTAC nanoassemblies significantly accumulate in the tumor region across the disrupted blood-brain barrier(BBB),triggering a burst release of the photosensitizer and active PROTAC by Cat B-mediated enzymatic cleavage.Upon laser irradiation,photodynamic therapy(PDT)synergizes with PROTAC-mediated PTP1B proteolysis to induce potent immunogenic cell death(ICD)in tumor cells.Subsequently,persistent PTP1B degradation by nanoassemblies in Cat B-overexpressed intratumoral T cells downregulates exhaustion markers,reinvigorating their function-ality.These sequential processes of photodynamic PTP1B proteolysis ultimately augment T cellmediated antitumor immunity as well as protective immunity,completely eradicating the primary GBM and preventing its recurrence.Overall,our findings underscore the therapeutic potential of combining PDT with PROTAC activity for GBM immunotherapy.
基金supported by an intramural grant from KIST to YP,as well as grants from the National Research Foundation of Korea(NRF)funded by the Korean government(MSIT)(NRF-2020M3A9G7103935 and RS-2024-00338729 to HJ and RS-2024-00337093 to YP).
文摘Exhausted T(Tex)cells are a distinct subset of T cells that arise in response to prolonged antigen exposure during chronic infections or cancer.Although Tex cells exhibit reduced functionality,they still retain some protective abilities.Exhausted CD8+T cells are a heterogeneous group consisting of four subsets:progenitor,intermediate,effector,and terminally exhausted.Each subset is characterized by distinct transcriptional,epigenetic,and functional traits[1].Recent studies have indicated that the progenitor and intermediate Tex subsets are mainly responsible for the proliferative surge observed during anti-PD-1 immunotherapy,which results in the production of a large pool of functional effector cells,thereby sustaining the antitumor immune response[2].However,blocking the PD-1 pathway alone typically fails to achieve lasting disease control in most patients.Simultaneous blockade of PD-1 and other immune checkpoint receptors can enhance CD8+T-cell-mediated immunity,leading to more effective treatment outcomes.
