Precisely controlled spatial distributions of artificial light-harvesting systems in aqueous media are of significant importance for mimicking natural light-harvesting systems;however,they are often restrained by the ...Precisely controlled spatial distributions of artificial light-harvesting systems in aqueous media are of significant importance for mimicking natural light-harvesting systems;however,they are often restrained by the solubility and the aggregation-caused quenching effect of the hydrophobic chromophores.Herein,we report one highly efficient artificial light-harvesting system based on peptoid nanotubes that mimic the hierarchical cylindrical structure of natural systems.The high crystallinity of these nanotubes enabled the organization of arrays of donor chromophores with precisely controlled spatial distributions,favoring an efficient Förster resonance energy transfer(FRET)process in aqueous media.This FRET system exhibits an extremely high efficiency of 98.6%with a fluorescence quantum yield of 40%and an antenna effect of 29.9.We further demonstrated the use of this artificial light-harvesting system for quantifying miR-210 within cancer cells.The fluorescence intensity ratio of donor to acceptor is linearly related to the concentration of intercellular miR-210 in the range of 3.3–156 copies/cell.Such high sensitivity in intracellular detection of miR-210 using this artificial light-harvesting system offers a great opportunity and pathways for biological imaging and detection,and for the further creation of microRNA(miRNA)toolbox for quantitative epigenetics and personalized medicine.展开更多
Near-infrared(NIR)laser-induced phototherapy through NIR agents has demonstrated the great potential for cancer therapy.However,insufficient tumor killing due to the nonuniform heat or cytotoxic singlet oxygen(1 O2)di...Near-infrared(NIR)laser-induced phototherapy through NIR agents has demonstrated the great potential for cancer therapy.However,insufficient tumor killing due to the nonuniform heat or cytotoxic singlet oxygen(1 O2)distribution over tumors from phototherapy results in tumor recurrence and inferior outcomes.To achieve high tumor killing efficacy,one of the solutions is to employ the combinational treatment of phototherapy with other modalities,especially with chemotherapeutic agents.In this paper,a simple and effective multimodal therapeutic system was designed via combining chemotherapy,photothermal therapy(PTT),and photodynamic therapy(PDT)to achieve the polytherapy of malignant glioma which is one of the most aggressive tumors in the brain.IR-780(IR780)dye-labeled tube-forming peptoids(PepIR)were synthesized and self-assembled into crystalline nanotubes(PepIR nanotubes).These PepIR nanotubes showed an excellent efficacy for PDT/PTT because the IR780 photosensitizers were effectively packed and separated from each other within crystalline nanotubes by tuning IR780 density;thus,a self-quenching of these IR780 molecules was significantly reduced.Moreover,the efficient DOX loading achieved due to the nanotube large surface area contributed to an efficient and synergistic chemotherapy against glioma cells.Given the unique properties of peptoids and peptoid nanotubes,we believe that the developed multimodal DOX-loaded PepIR nanotubes in this work offer great promises for future glioma therapy in clinic.展开更多
Peptoids(or poly-N-substituted glycines)are a promising class of bioinspired sequence-defined polymers due to their highly efficient synthesis,high chemical stability,enzyme hydrolysis resistance,and biocompatibility....Peptoids(or poly-N-substituted glycines)are a promising class of bioinspired sequence-defined polymers due to their highly efficient synthesis,high chemical stability,enzyme hydrolysis resistance,and biocompatibility.By tuning the side chain chemistry of peptoids,it allows for precise control over sequences and achieving a large side-chain diversity.Due to these unique features,in the last several years,many amphiphilic peptoids were designed as highly tunable building blocks for the preparation of biomimetic nanomaterials with well-defined hierarchical structures and desired functionalities.Herein,we provide an overview of the recent achievements in this area by dividing them into the following three aspects.First,mica-and silica-templated peptoid selfassembly are summarized.The presence of inorganic substrates provides the guarantee of investigating their selfassembly mechanisms and interactions between peptoids and substrates using nanoscale characterization techniques,particularly in situ atomic force microscopy(AFM)and AFMbased dynamic force spectroscopy(AFM-DFS).Second,solution-phase self-assembly of peptoids into nanotubes and nanosheets is presented,as well as their self-repair properties.Third,the applications of peptoid-based nanomaterials are outlined,including the construction of catalytic nanomaterials as a template and cytosolic delivery as cargoes.展开更多
基金supported by the U.S.Department of Energy,Office of Basic Energy Sciences,Division of Materials Science and Engineering under an award FWP 65357 at Pacific Northwest National Laboratory(PNNL)the Cougar Cage Fund for the work of biological imaging and detection of microRNA.Development of peptoid synthesis capabilities was supported by the Materials Synthesis and Simulation Across Scales(MS3)Initiative through the Laboratory Directed Research and Development(LDRD)program at PNNL.XRD work was conducted at the Advanced Light Source(ALS)of Lawrence Berkeley National Laboratory+1 种基金supported by the Office of Science(No.DE-AC02-05CH11231)PNNL is multi-program national laboratory operated for Department of Energy by Battelle(No.DE-AC05-76RL01830).
文摘Precisely controlled spatial distributions of artificial light-harvesting systems in aqueous media are of significant importance for mimicking natural light-harvesting systems;however,they are often restrained by the solubility and the aggregation-caused quenching effect of the hydrophobic chromophores.Herein,we report one highly efficient artificial light-harvesting system based on peptoid nanotubes that mimic the hierarchical cylindrical structure of natural systems.The high crystallinity of these nanotubes enabled the organization of arrays of donor chromophores with precisely controlled spatial distributions,favoring an efficient Förster resonance energy transfer(FRET)process in aqueous media.This FRET system exhibits an extremely high efficiency of 98.6%with a fluorescence quantum yield of 40%and an antenna effect of 29.9.We further demonstrated the use of this artificial light-harvesting system for quantifying miR-210 within cancer cells.The fluorescence intensity ratio of donor to acceptor is linearly related to the concentration of intercellular miR-210 in the range of 3.3–156 copies/cell.Such high sensitivity in intracellular detection of miR-210 using this artificial light-harvesting system offers a great opportunity and pathways for biological imaging and detection,and for the further creation of microRNA(miRNA)toolbox for quantitative epigenetics and personalized medicine.
基金supported by Washington State University(WSU)start-up fund.Peptoid synthesis work was supported by the Materials Synthesis and Simulation Across Scales(MS3)Initiative through the LDRD fund at Pacific Northwest National Laboratory(PNNL)Assembly of peptoid nanotubes and their structural characterizations were supported by the U.S.Department of Energy,Office of Basic Energy Sciences,Biomolecular Materials Program at PNNL+1 种基金the Advanced Light Source with support from the Molecular Foundry,at Lawrence Berkeley National Laboratory,both of which are supported by the Office of Science,under Contract No.DE-AC02-05CH11231PNNL is a multiprogram national laboratory operated for Department of Energy by Battelle under Contract No.DE-AC05-76RL01830.
文摘Near-infrared(NIR)laser-induced phototherapy through NIR agents has demonstrated the great potential for cancer therapy.However,insufficient tumor killing due to the nonuniform heat or cytotoxic singlet oxygen(1 O2)distribution over tumors from phototherapy results in tumor recurrence and inferior outcomes.To achieve high tumor killing efficacy,one of the solutions is to employ the combinational treatment of phototherapy with other modalities,especially with chemotherapeutic agents.In this paper,a simple and effective multimodal therapeutic system was designed via combining chemotherapy,photothermal therapy(PTT),and photodynamic therapy(PDT)to achieve the polytherapy of malignant glioma which is one of the most aggressive tumors in the brain.IR-780(IR780)dye-labeled tube-forming peptoids(PepIR)were synthesized and self-assembled into crystalline nanotubes(PepIR nanotubes).These PepIR nanotubes showed an excellent efficacy for PDT/PTT because the IR780 photosensitizers were effectively packed and separated from each other within crystalline nanotubes by tuning IR780 density;thus,a self-quenching of these IR780 molecules was significantly reduced.Moreover,the efficient DOX loading achieved due to the nanotube large surface area contributed to an efficient and synergistic chemotherapy against glioma cells.Given the unique properties of peptoids and peptoid nanotubes,we believe that the developed multimodal DOX-loaded PepIR nanotubes in this work offer great promises for future glioma therapy in clinic.
基金supported by the Startup Research Fund of Dongguan University of Technology(KCYKYQD2017015)the US Department of Energy,Office of Science,Office of Basic Energy Sciences,as part of the Energy Frontier Research Centers program:CSSAS—The Center for the Science of Synthesis Across Scales(DESC0019288)。
文摘Peptoids(or poly-N-substituted glycines)are a promising class of bioinspired sequence-defined polymers due to their highly efficient synthesis,high chemical stability,enzyme hydrolysis resistance,and biocompatibility.By tuning the side chain chemistry of peptoids,it allows for precise control over sequences and achieving a large side-chain diversity.Due to these unique features,in the last several years,many amphiphilic peptoids were designed as highly tunable building blocks for the preparation of biomimetic nanomaterials with well-defined hierarchical structures and desired functionalities.Herein,we provide an overview of the recent achievements in this area by dividing them into the following three aspects.First,mica-and silica-templated peptoid selfassembly are summarized.The presence of inorganic substrates provides the guarantee of investigating their selfassembly mechanisms and interactions between peptoids and substrates using nanoscale characterization techniques,particularly in situ atomic force microscopy(AFM)and AFMbased dynamic force spectroscopy(AFM-DFS).Second,solution-phase self-assembly of peptoids into nanotubes and nanosheets is presented,as well as their self-repair properties.Third,the applications of peptoid-based nanomaterials are outlined,including the construction of catalytic nanomaterials as a template and cytosolic delivery as cargoes.
