Photodynamic therapy(PDT)brings new hope for the treatment of breast cancer due to few side effects and highly effective cell killing;however,the low bioavailability of traditional photosensitizers(PSs)and their depen...Photodynamic therapy(PDT)brings new hope for the treatment of breast cancer due to few side effects and highly effective cell killing;however,the low bioavailability of traditional photosensitizers(PSs)and their dependence on oxygen severely limits their application.Aggregation-induced emission(AIE)PSs can dramatically facilitate the photosensitization effect,which can have positive impacts on tumor PDT.To-date,most AIE PSs lack tumor targeting capability and possess poor cell delivery,resulting in their use in large quantities that are harmful to healthy tissues.In this study,a series of AIE PSs based on pyridinium-substituted triphenylamine salts(TTPAs 1-6)with different alkyl chain lengths are synthesized.Results reveal that TTPAs 1-6 promote the generation of type I and II ROS,including·OH and 1O_(2).In particular,the membrane permeability and targeting of TTPAs 4-6 bearing C8-C10 side-chains are higher than TTPAs 1-3 bearing shorter alkyl chains.Additionally,they can assemble with albumin,thereby forming nanoparticles(TTPA 4-6 NPs)in situ in blood,which significantly facilitates mitochondrial-targeting and strong ROS generation ability.Moreover,the TTPA 4-6 NPs are pH-responsive,allowing for increased accumulation or endocytosis of the tumor and enhancing the imaging or therapeutic effect.Therefore,the in vivo distributions of TTPA 4-6 NPs are visually enriched in tumor sites and exhibited excellent PDT efficacy.This work demonstrates a novel strategy for AIE PDT and has the potential to play an essential role in clinical applications using nano-delivery systems.展开更多
The development of simple and effective strategies to prepare electrocatalysts,which possess unique and stable structures comprised of metal/nonmetallic atoms for oxygen reduction reaction(ORR)and oxygen evolution rea...The development of simple and effective strategies to prepare electrocatalysts,which possess unique and stable structures comprised of metal/nonmetallic atoms for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),is currently an urgent issue.Herein,an efficient bifunctional electrocatalyst featured by ultralong N,S-doped carbon nano-hollow-sphere chains about 1300 nm with encapsulated Co nanoparticles(Co-CNHSCs)is developed.The multifunctional catalytic properties of Co together with the heteroatom-induced charge redistribution(i.e.,modulating the electronic structure of the active site)result in superior catalytic activities toward OER and ORR in alkaline media.The optimized catalyst Co-CNHSC-3 displays an outstanding electrocatalytic ability for ORR and OER,a high specific capacity of 1023.6 mAh gZn^(-1),and excellent reversibility after 80 h at 10mA cm^(-2)in a Zn-air battery system.This work presents a new strategy for the design and synthesis of efficient multifunctional carbon-based catalysts for energy storage and conversion devices.展开更多
A series of nickel halides bearing 2,4-di-t-butyl-6-（quinolin-8-yliminomethyl） phenolate ligands was synthesized and characterized by IR spectroscopy and elemental analysis. Molecular structures of C1 （R = H, X = B...A series of nickel halides bearing 2,4-di-t-butyl-6-（quinolin-8-yliminomethyl） phenolate ligands was synthesized and characterized by IR spectroscopy and elemental analysis. Molecular structures of C1 （R = H, X = Br） and C2 （R = H, X = C1） were further confirmed by single-crystal X-ray crystallographic studies, and revealed a distorted square planar geometry at nickel. Upon activation with diethylaluminum chloride （Et2AlCl）, all nickel pre-catalysts displayed good catalytic activity [up to 9.3 × 10^5 g mol-1（Ni） h-1] for ethylene oligomerization with major dimerization. In the presence of methylaluminoxane （MAO）, the nickel complex C1 was capable of ethylene polymerization under 3 MPa, and produced polyethylene products with narrow polydispersity （1.16-1.73） and molecular weights in the range of 2.6-4.95 kg/mol.展开更多
The macrocyclic family comprising pillar[n]arenes and cucurbit[n]urils have received much attention recently. However, studies on the construction of supramolecular complexes formed directly with derivatized pillar[n]...The macrocyclic family comprising pillar[n]arenes and cucurbit[n]urils have received much attention recently. However, studies on the construction of supramolecular complexes formed directly with derivatized pillar[n]arenes and cucurbit[n]urils are scant. Given the interest in such systems, herein we have synthesized a new type of naphthalene-derivatized pillar[n]arene NTP5 and selected Q[10] as the host molecule. The 4-[2-(1-naphthalenyl)ethenyl]pyridine of NTP5 is encapsulated by Q[10] and formed a hostvip complex in water-acetic acid(1:1) solution accompanied by enhanced fluorescence, which changed the morphology of NTP5 from a sphere to a porous form. In addition, the fluorescence of Q[10]-NTP5 can be quenched by the addition of the highly toxic pesticide paraquat(PQ), and the mechanism was shown to be the formation of a new charge transfer ternary system of Q[10]-NTP5-PQ. This work provides new ideas for the contribution of supramolecular assemblies based on derivatized pillar[n]arenes and their combination with cucurbit[n]urils and reveals their potential applications.展开更多
The binding interactions between 4-aminopyridine(4-AP) and a series of cucurbit[n]urils(Q[5], Q[6],TMe Q[6], Q[7], Q[8]) have been studied using1H NMR spectroscopy, UV–vis absorption spectroscopy,isothermal titration...The binding interactions between 4-aminopyridine(4-AP) and a series of cucurbit[n]urils(Q[5], Q[6],TMe Q[6], Q[7], Q[8]) have been studied using1H NMR spectroscopy, UV–vis absorption spectroscopy,isothermal titration calorimetry(ITC) and X-ray crystallography. The data indicates that the Q[5]@4-AP complex exhibits exo binding, which is not observed in the other four host-vip complexes. Furthermore,X-ray crystallography clearly reveals how the Q[n]s bind with 4-AP to form complexes, for example Q[5]forms an outer-surface complex, whilst Q[6], TMe Q[6] and Q[7] formed 1:1 host and vip type complexes, and Q[8] formed a stable 1:2 ternary complex due to its large cavity, which can accommodate two 4-AP molecules.展开更多
Three new deep blue light emitters,bearing quinoxaline with different substituents(biphenyl/pyrene)at the 1-or 2-position,were synthesized by a Pd-catalysed coupling reaction in high yields,and were fully characterize...Three new deep blue light emitters,bearing quinoxaline with different substituents(biphenyl/pyrene)at the 1-or 2-position,were synthesized by a Pd-catalysed coupling reaction in high yields,and were fully characterized by 1H/13C NMR spectroscopy,single crystal X-ray diffraction,and high-resolution mass spectrometry(HRMS).展开更多
基金supported by the National Natural Science Foundation of China (81860543,32360237)Guizhou Provincial Science and Technology Projects (ZK[2023]+4 种基金Key Project 041,ZK[2021]076,[2019]2792 and[2018]5779-14)Guizhou Provincial Department of Education Foundation (KY[2022]229)Cultivation program of the Affiliated Hospital of Guizhou Medical University (gyfynsfc-2022-39)Cultivation program of the Guizhou Medical University (20NSP012)CR thanks the University of Hull for support
文摘Photodynamic therapy(PDT)brings new hope for the treatment of breast cancer due to few side effects and highly effective cell killing;however,the low bioavailability of traditional photosensitizers(PSs)and their dependence on oxygen severely limits their application.Aggregation-induced emission(AIE)PSs can dramatically facilitate the photosensitization effect,which can have positive impacts on tumor PDT.To-date,most AIE PSs lack tumor targeting capability and possess poor cell delivery,resulting in their use in large quantities that are harmful to healthy tissues.In this study,a series of AIE PSs based on pyridinium-substituted triphenylamine salts(TTPAs 1-6)with different alkyl chain lengths are synthesized.Results reveal that TTPAs 1-6 promote the generation of type I and II ROS,including·OH and 1O_(2).In particular,the membrane permeability and targeting of TTPAs 4-6 bearing C8-C10 side-chains are higher than TTPAs 1-3 bearing shorter alkyl chains.Additionally,they can assemble with albumin,thereby forming nanoparticles(TTPA 4-6 NPs)in situ in blood,which significantly facilitates mitochondrial-targeting and strong ROS generation ability.Moreover,the TTPA 4-6 NPs are pH-responsive,allowing for increased accumulation or endocytosis of the tumor and enhancing the imaging or therapeutic effect.Therefore,the in vivo distributions of TTPA 4-6 NPs are visually enriched in tumor sites and exhibited excellent PDT efficacy.This work demonstrates a novel strategy for AIE PDT and has the potential to play an essential role in clinical applications using nano-delivery systems.
基金Collaborative Innovation Center of Suzhou Nano Science and TechnologyNational Natural Science Foundation of China,Grant/Award Numbers:21773163,22271203+3 种基金EPSRC for an Overseas Travel Grant,Grant/Award Number:EP/R023816/1State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry,Grant/Award Number:KF2021005Priority Academic Program Development of Jiangsu Higher Education InstitutionsProject of Scientific and Technologic Infrastructure of Suzhou,Grant/Award Number:SZS201905。
文摘The development of simple and effective strategies to prepare electrocatalysts,which possess unique and stable structures comprised of metal/nonmetallic atoms for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),is currently an urgent issue.Herein,an efficient bifunctional electrocatalyst featured by ultralong N,S-doped carbon nano-hollow-sphere chains about 1300 nm with encapsulated Co nanoparticles(Co-CNHSCs)is developed.The multifunctional catalytic properties of Co together with the heteroatom-induced charge redistribution(i.e.,modulating the electronic structure of the active site)result in superior catalytic activities toward OER and ORR in alkaline media.The optimized catalyst Co-CNHSC-3 displays an outstanding electrocatalytic ability for ORR and OER,a high specific capacity of 1023.6 mAh gZn^(-1),and excellent reversibility after 80 h at 10mA cm^(-2)in a Zn-air battery system.This work presents a new strategy for the design and synthesis of efficient multifunctional carbon-based catalysts for energy storage and conversion devices.
文摘A series of nickel halides bearing 2,4-di-t-butyl-6-（quinolin-8-yliminomethyl） phenolate ligands was synthesized and characterized by IR spectroscopy and elemental analysis. Molecular structures of C1 （R = H, X = Br） and C2 （R = H, X = C1） were further confirmed by single-crystal X-ray crystallographic studies, and revealed a distorted square planar geometry at nickel. Upon activation with diethylaluminum chloride （Et2AlCl）, all nickel pre-catalysts displayed good catalytic activity [up to 9.3 × 10^5 g mol-1（Ni） h-1] for ethylene oligomerization with major dimerization. In the presence of methylaluminoxane （MAO）, the nickel complex C1 was capable of ethylene polymerization under 3 MPa, and produced polyethylene products with narrow polydispersity （1.16-1.73） and molecular weights in the range of 2.6-4.95 kg/mol.
基金supported by the National Natural Science Foundation of China(No.21861011)the Innovation Program for Highlevel Talents of Guizhou Province(No.2016-5657)+1 种基金the Science and Technology Fund of Guizhou Province(No.[2020]-1Y046)University of Hull for support。
文摘The macrocyclic family comprising pillar[n]arenes and cucurbit[n]urils have received much attention recently. However, studies on the construction of supramolecular complexes formed directly with derivatized pillar[n]arenes and cucurbit[n]urils are scant. Given the interest in such systems, herein we have synthesized a new type of naphthalene-derivatized pillar[n]arene NTP5 and selected Q[10] as the host molecule. The 4-[2-(1-naphthalenyl)ethenyl]pyridine of NTP5 is encapsulated by Q[10] and formed a hostvip complex in water-acetic acid(1:1) solution accompanied by enhanced fluorescence, which changed the morphology of NTP5 from a sphere to a porous form. In addition, the fluorescence of Q[10]-NTP5 can be quenched by the addition of the highly toxic pesticide paraquat(PQ), and the mechanism was shown to be the formation of a new charge transfer ternary system of Q[10]-NTP5-PQ. This work provides new ideas for the contribution of supramolecular assemblies based on derivatized pillar[n]arenes and their combination with cucurbit[n]urils and reveals their potential applications.
基金supported by the Innovation Program for Highlevel Talents of Guizhou Province (No. 2016-5657)the University of Hull for support。
文摘The binding interactions between 4-aminopyridine(4-AP) and a series of cucurbit[n]urils(Q[5], Q[6],TMe Q[6], Q[7], Q[8]) have been studied using1H NMR spectroscopy, UV–vis absorption spectroscopy,isothermal titration calorimetry(ITC) and X-ray crystallography. The data indicates that the Q[5]@4-AP complex exhibits exo binding, which is not observed in the other four host-vip complexes. Furthermore,X-ray crystallography clearly reveals how the Q[n]s bind with 4-AP to form complexes, for example Q[5]forms an outer-surface complex, whilst Q[6], TMe Q[6] and Q[7] formed 1:1 host and vip type complexes, and Q[8] formed a stable 1:2 ternary complex due to its large cavity, which can accommodate two 4-AP molecules.
基金This work was supported by the National Natural Science Foundation of China(Nos.21975054 and 21602014)the Natural Science Foundation of Guangdong Provinee of China(No.2019A1515010925)+2 种基金the Guangdong Provincial Key Laboratory of Information Photonics Technology(No.2020B121201011)the"One Hundred Talents Program"of the Guangdong University of Technology(No.1108-220413205)the Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter of The Guang-dong University of Technology(No.220413205).
文摘Three new deep blue light emitters,bearing quinoxaline with different substituents(biphenyl/pyrene)at the 1-or 2-position,were synthesized by a Pd-catalysed coupling reaction in high yields,and were fully characterized by 1H/13C NMR spectroscopy,single crystal X-ray diffraction,and high-resolution mass spectrometry(HRMS).
