The development of highly effective photosensitizers(PSs)based on supramolecular coordination complexes(SCCs)is highly appealing in supramolecular chemistry,materials science,and biology.SCCs offer promising platforms...The development of highly effective photosensitizers(PSs)based on supramolecular coordination complexes(SCCs)is highly appealing in supramolecular chemistry,materials science,and biology.SCCs offer promising platforms for incorporating multiple PSs and other functional units into their well-defined structures,allowing for precise control over the number and distribution of these components.In this study,we present an efficient and straightforward method for modulating the photosensitization process of PSs derived from a family of BF_(2)-chelated dipyrromethene(BODIPY)-containing Pt(Ⅱ)metallacycles by varying pre-designed Pt(Ⅱ)acceptors.By utilizing different Pt(Ⅱ)acceptors with varying Pt atom configurations and degrees ofπ-conjugated organic moieties,we observed tunable characteristics in the photosensitization process and singlet oxygen(^(1)O_(2))generation efficiency of these targeted metallacycles.Furthermore,we successfully conducted the visible-light-driven oxidative coupling of various amines to imines,catalyzed by the prepared metallacycle PSs.This study offers a novel approach for fabricating efficient PSs based on SCCs,featuring tunable photosensitization efficiency and excellent photocatalytic reactivity,while providing new insights into the preparation of effective PSs.展开更多
The fabrication of highly effective photosensitizers has received considerable attention because of their attractive functions and applications in the fields of photodynamic therapy, photosynthesis, photocatalysis, et...The fabrication of highly effective photosensitizers has received considerable attention because of their attractive functions and applications in the fields of photodynamic therapy, photosynthesis, photocatalysis, etc. Thus, it is highly desirable to develop a new approach to enhance photosensitization efficiency.Herein, through coordination-driven self-assembly, a series of metallacycles with efficient fluorescence resonance energy transfer(FRET) were effectively constructed, which displayed higher photosensitization efficiency and photocatalytic activity than their model metallacycles without FRET due to broadband absorption and singlet energy transfer from the energy acceptor to the energy donor. Moreover, iodization of fluorophores induced a significant enhancement of the photosensitization efficiency and photocatalytic activity of the metallacycles. This research provides an efficient strategy for improving photosensitization efficiency and a promising platform for the preparation of effective photosensitizers and photocatalysts.展开更多
Singlet oxygen(^(1)O_(2))is a highly reactive oxygen species involved in numerous chemical and photochemical reactions in diferent biological systems and in particular,in photodynamic therapy(PDT).However,the quantifc...Singlet oxygen(^(1)O_(2))is a highly reactive oxygen species involved in numerous chemical and photochemical reactions in diferent biological systems and in particular,in photodynamic therapy(PDT).However,the quantifcation of^(1)O_(2) generation during in vitro and in vivo pho-tosensitization is still technically challenging.To address this problem,indirect and direct methods for^(1)O_(2)detection have been intensively studied.This review presents the available methods currently in use or under development for detecting and quantifying^(1)O_(2) generation during photosensitization.The advantages and limitations of each method will be presented.Moreover,the future trends in developing PDT-^(1)O_(2) dosimetry will be briefly discussed.展开更多
Using heavy-atom-containing xanthene dyes,benzoins can be quanti- tatively prepared by photosensitized reduction from benzils with triethyla- mine.It is an important supplement to'benzoin condensation',asp.for...Using heavy-atom-containing xanthene dyes,benzoins can be quanti- tatively prepared by photosensitized reduction from benzils with triethyla- mine.It is an important supplement to'benzoin condensation',asp.for those benzoins with electron-donating substituents.展开更多
The reaction of triplet fusion,also named triplet-triplet annihilation,has attracted a lot of research interests because of its wide applications in photocatalytic,solar cells,and bioimaging.As for the singlet oxygen ...The reaction of triplet fusion,also named triplet-triplet annihilation,has attracted a lot of research interests because of its wide applications in photocatalytic,solar cells,and bioimaging.As for the singlet oxygen photosensitization,the reactive singlet oxygen species are generated through the energy transfers from photosensitizer(PS)to ground triplet oxygen molecule.In this work,we computed the electronic coupling for singlet oxygen photosensitization using the nonadiabatic coupling from the quantum chemical calculation.Then we utilized the molecular orbital(MO)overlaps to approximate it,where the MOs were computed from isolated single molecules.As demonstrated with quantitative results,this approach well describes the distribution of the coupling strength as the function of the intermolecular distance between the sensitizer and O_(2),providing us a simple but effective way to predict the coupling of triplet fusion reactions.展开更多
Dual-functional aggregation-induced photosensitizers(AIE-PSs)with singlet oxygen generation(SOG)ability and bright fluorescence in aggregated state have received much attention in image-guided photodynamic therapy(PDT...Dual-functional aggregation-induced photosensitizers(AIE-PSs)with singlet oxygen generation(SOG)ability and bright fluorescence in aggregated state have received much attention in image-guided photodynamic therapy(PDT).However,designing an AIE-PS with both high SOG and intense fluorescence via molecular design is still challenging.In this work,we report a new nanohybrid consisting of gold nanostar(AuNS)and AIE-PS dots with enhanced fluorescence and photosensitization for theranostic applications.The spectral overlap between the extinction of AuNS and fluorescence emission of AIE-PS dots(665 nm)is carefully selected using five different AuNSs with distinct localized surface plasmon(LSPR)peaks.Results show that all the AuNS s can enhance the 1 O2 production of AIE-PS dots,among which the AuNS with LSPR peak at 585 nm exhibited the highest 1 O2 enhancement factor of15-fold with increased fluorescence brightness.To the best of our knowledge,this is the highest enhancement factor reported for the metalenhanced singlet oxygen generation systems.The Au585@AIE-PS nanodots were applied for simultaneous fluorescence imaging and photodynamic ablation of HeLa cancer cells with strongly enhanced PDT efficiency in vitro.This study provides a better understanding of the metal-enhanced AIE-PS nanohybrid systems,opening up new avenue towards advanced image-guided PDT with greatly improved efficacy.展开更多
By the use of the advanced ESR technique and through comparing with BHPD, the characteristic of YHPD photosensitization is discussed in this paper in the respect of the primary process of photosensitization. The exper...By the use of the advanced ESR technique and through comparing with BHPD, the characteristic of YHPD photosensitization is discussed in this paper in the respect of the primary process of photosensitization. The experiment results showed: (ⅰ) not only ~1O_2, but also free radicals(O_2· OH and YHPD)can be formed by the aid of YHPD; and (ⅱ) as to the ability of producing ~1O_2, YHPD<BHPD, while for generating O_2 and-OH, YHPD>BHPD. Two points are indicated: first, the photosensitized damage of YHPD is interrelated to not only ~1O_2, but also free radicals (O_2. OH and YHPD); second, although the photosensitized damage of YHPD is stronger than that of BHPD, yet the photosensitized damage is negatively correlated to the yield of ~1O_2 but positively correlated to those of O_2 and OH. Based on these two points, it is suggested that activated oxygen free radicals(O_2 and. OH) instead of ~1O_2 play the main role as instantaneously activated material in the photosensitized damage of YHPD.展开更多
In water, N,N′-diarylpyridinium thiazolo[5,4-d]thiazole vips(G1–G3) were encapsulated by cucurbit[8]uril(Q[8]) to construct Q[8]_(3)/G_(2) complexes, in which the encapsulated G molecules exist as an exact face-to...In water, N,N′-diarylpyridinium thiazolo[5,4-d]thiazole vips(G1–G3) were encapsulated by cucurbit[8]uril(Q[8]) to construct Q[8]_(3)/G_(2) complexes, in which the encapsulated G molecules exist as an exact face-to-face dimer. These complexation behaviors have been indicated by proton nuclear magnetic resonance(~1H NMR) spectroscopy and isothermal titration calorimetry(ITC),and have been confirmed by X-ray single crystal structural analysis of Q[8]_(3)/G2_(2). While free vips G1–G3 have no ability to sensitize singlet oxygen, they all become effective singlet oxygen sensitizers when complexed with Q[8]. By irradiation of white light, Q[8]_(3)/G_(2) complexes induced selective oxidation of aryl sulfide to aryl sulfoxide in good yields and selective oxidation of dimethyl sulfide(DMS) to dimethyl sulfoxide(DMSO) in excellent yields without over-oxidation to dimethyl sulfone(DMSO_(2))even for elongated irradiation. High-yield photo-oxidation of DMS to DMSO_(2) was only achieved by irradiation of blue light in the presence of Q[8]_(3)/G1_(2), which was also effective in photobleaching of Rhodamine B in water. The higher photo-oxidation power of Q[8]_(3)/G1_(2) has been ascribed to an additional generation of reactive oxygen species besides singlet oxygen.展开更多
Photosensitization,originated from the activation of triplet states,is the basis of many photodynamic applications,but often competes with a series of nonradiative processes.Herein,we communicate a new function of dou...Photosensitization,originated from the activation of triplet states,is the basis of many photodynamic applications,but often competes with a series of nonradiative processes.Herein,we communicate a new function of double-stranded DNA(dsDNA)for label-free photosensitization switching.Up to∼70-fold singlet oxygen generation boosting was observed for SYBR Green I(SG)upon binding with dsDNA.Detailed photophysical and theoretical studies have revealed the role of dsDNA as a matrix,which could efficiently suppress the nonradiative transitions of SG.展开更多
By kinetic methods, functional relation of TAN radical, produced in the process of TEMPONE trapping O2, vs. time during photosensitization was established. Accordingly relative rate constants of generating all kinds o...By kinetic methods, functional relation of TAN radical, produced in the process of TEMPONE trapping O2, vs. time during photosensitization was established. Accordingly relative rate constants of generating all kinds of active intermediates through types I and II mechanism of photosensitization can be calculated. Using the formula and experimental results, the relative rate constants of generating O2, O2 and PS2 of three kinds of perylenequinone photosensitizer: HA, HB and CP in DMF-H20 and DMSO-H2O system were calculated, and then the structure-activity relationship of perylenequinone photosensitizer and the relation between photosensitivity and solvent was studied.展开更多
Pheophorbide a (PPa), a decomposition product of chlorophyll a, is a photosensitizer. The photosensiti-zation mechanisms (Type Ⅰ and Type Ⅱ) of PPa in simple buffer solutions and in buffer solutions containing doubl...Pheophorbide a (PPa), a decomposition product of chlorophyll a, is a photosensitizer. The photosensiti-zation mechanisms (Type Ⅰ and Type Ⅱ) of PPa in simple buffer solutions and in buffer solutions containing double-layered DPPC liposomes have been studied using techniques of ESR, spin-trapping, spin-counteraction and laser flash photolysis . The results showed that adding DPPC liposomes to the buffer solution caused an increase of efficiency of generating 1O2 and PPa - by photoactivating PPa. The increase could be ascribed to the disaggregation of hydrophobic PPa caused by the addition of liposomes and the protective effect of liposomal media on the triplet state of PPa. It is concluded that the photosensitization of PPa in liposomal systems is different from that in simple aqueous solutions, and shows higher efficacy. The results will be useful to elucidating the mechanisms of photodynamic therapy of cancer.展开更多
The primary reaction of photosensitization of Hypocrellin A (HA) has been studied byusing techniques of ESR, spin-trapping and spin-counteraction. The experiments show thatHA is able to generate not only ~1O_2,but als...The primary reaction of photosensitization of Hypocrellin A (HA) has been studied byusing techniques of ESR, spin-trapping and spin-counteraction. The experiments show thatHA is able to generate not only ~1O_2,but also O_2^-·OH and HA^- which are observed for thefirst time. The conversion of generating active oxygen into generating nonoxygen free rad-ical is confirmed as well. Based on the characteristics of the primary reaction which gene-rates these active substances (transient products), it is proposed that the photosensitized dam-age for the biological system by HA is probably related to not only ~1O_2 itself, but also amultiple effect from ~1O_2 as well as O_2^-,·OH and HA^+ free radical.展开更多
Based on the characteristics of laser-induced surface ignition,energetic photosensitive films show promising potential to meet the ignition requirements of various energetic materials(EMs).In this study,DATNBI/ferric ...Based on the characteristics of laser-induced surface ignition,energetic photosensitive films show promising potential to meet the ignition requirements of various energetic materials(EMs).In this study,DATNBI/ferric alginate(DI/FeA),DI/cobalt alginate(DI/CoA),and DI/nickel alginate(DI/Ni A)films are fabricated by employing sodium alginate(SA)with a three-dimensional network structure as the film matrix,via ionic cross-linking of SA with Fe^(3+),Co^(2+),and Ni^(2+)ions.The study demonstrates that the ionic cross-linking enhances the hydrophobic performance of the films,with the water contact angle increasing from 82.1??to 123.5??.Concurrently,the films'near-infrared(NIR)light absorption improved.Furthermore,transition metal ions facilitate accelerated electron transfer,thereby catalyzing the thermal decomposition of DATNBI.Under 1064 nm laser irradiation,the DI/Fe A film exhibits exceptional combustion performance,with an ignition delay time as low as 76 ms.It successfully acts as an NIR laser ignition medium to initiate the self-sustained combustion of CL-20.This study demonstrates the synergistic realization of enhanced hydrophobicity,improved photosensitivity,and promoted catalytic decomposition through microstructural design of the material,providing new insights for the design of additive-free EMs in laser ignition applications.展开更多
Oxidative damage to cells leads to accumulated harmful wastes,which in turn aggravate the imbalance of reactive oxygen species(ROS)and related diseases.Therefore,provoking the cellular defense system against severe ox...Oxidative damage to cells leads to accumulated harmful wastes,which in turn aggravate the imbalance of reactive oxygen species(ROS)and related diseases.Therefore,provoking the cellular defense system against severe oxidation and maintaining ROS homeostasis are desired.Herein,we designed and synthesized a powerful mitochondria-targeting aggregation-induced emission photosensitizer(named DTCSPY)by maximal restriction of heat dissipation.It is demonstrated that taming ROS generation within mitochondria through photosensitization-triggered autophagy via DTCSPY achieved a better neuroprotective effect against oxidative damages than Nacety-L-cysteine and vitamin C.This work not only provides a new way to design high-performance photosensitizers by regulating the photophysical property,but also verifies the concept that taming ROS can be used for cell protection against destructive oxidation,thereby displaying broad prospects for alleviating oxidation-related diseases and promoting cell-based therapy.展开更多
Laser Raman spectroscopy was used to investigate the microcosmic and photosensitive damage of YHPD to lysozyme, of which the three-dimensional structure has been elucidated. The experimental results shown by various d...Laser Raman spectroscopy was used to investigate the microcosmic and photosensitive damage of YHPD to lysozyme, of which the three-dimensional structure has been elucidated. The experimental results shown by various damages of the main-chain and side-chain of lysozyme are as follows: (ⅰ) Phe and Cys are also damaged by photosensitization of YHPD, except for Trp, Tyr, Met, 1/2Cys and His; (ⅱ) the order of the photosensitized sensitivity of various groups of these amino acids have been described; (ⅲ) Trp and Tyr buried in the three-dimensional structure of the protein are damaged very greatly, and (ⅳ) the main-chain conformation of the protein has changed considerably, such as a decrease in orderly structure (α-helix, β-sheet and β-turn) and a simultaneous increase in random coil.展开更多
Nitrate renoxification significantly influences atmospheric nitrogen cycling and global OH budgets.Although numerous nitrite acid(HONO)formation pathways from nitrate photolysis have been widely reported,the influence...Nitrate renoxification significantly influences atmospheric nitrogen cycling and global OH budgets.Although numerous nitrite acid(HONO)formation pathways from nitrate photolysis have been widely reported,the influence of various environmental factors and aerosol properties on reactive nitrogen production remains largely unclear.In this work,we employed NaNO_(3)/humic acid(HA)as a model nitrate photosensitization system to investigate the crucial roles of aerosol acidity,organic fraction,and dissolved oxygen in the production of HONO,NO_(2),and NO_(2)^(-).The presence of HA at 10 mg/L resulted in a remarkable increase in HONO production rates by approximately 2–3 times and NO_(2)^(-) concentration by 3–6 times across a pH range of 5.2 to 2.0.Meanwhile,the molar fraction of gaseous HONO in total N(Ⅲ)production increased from4%to 69%as bulk-phase pH decreased from 5.2 to 2.0.The higher organic fraction(i.e.,20 and 50 mg/L HA concentration)instead inhibited HONO and NO_(2) release.The presence of dissolved oxygen was found to be adverse for reactive nitrogen production.This suggests that the HA photosensitizer promoted the secondary conversion of NO_(2) to HONO mainly via reduced ketyl radical intermediates,while superoxide radical formation might exert a negative effect.Our findings provide comprehensive insights into reactive nitrogen production from photosensitized nitrate photolysis mediated by various external and internal factors,potentially accounting for discrepancies between field observations and model simulations.展开更多
Environmental pollution and energy deficiency represent major problems for the sustainability of the modern world. Photocatalysis has recently emerged as an effective and environmentally friendly technique to address ...Environmental pollution and energy deficiency represent major problems for the sustainability of the modern world. Photocatalysis has recently emerged as an effective and environmentally friendly technique to address some of these sustainability issues,although the key to the success of this approach is dependent on the photocatalysts themselves. Based on their attractive physic chemical properties,including their ultrahigh surface areas,homogeneous active sites and tunable functionality,metal-organic frameworks（MOFs） have become interesting platforms for the development of solar energy conversion devices. Furthermore,MOFs have recently been used in a wide variety of applications,including heterogeneous photocatalysis for pollutant degradation,organic transformations,hydrogen production and CO2 reduction. In this review,we have highlighted recent progress towards the application of MOFs in all of these areas. We have collected numerous reported examples of the use of MOFs in these areas,as well as providing some analysis of the key factors influencing the efficiency of these systems. Moreover,we have provided a detailed discussion of new strategies that have been developed for enhancing the photocatalytic activity of MOFs. Finally,we have provided an outlook for this area in terms of the future challenges and potential prospects for MOFs in photocatalysis.展开更多
A nanomicelle(denoted as TPGS/Ppa)was fabricated via the coassembly of the amphiphilic D-α-tocopheryl polyethylene glycol 1000 succinate(TPGS)and the hydrophobic photosensitizer pyropheophorbide a(Ppa)for photodynami...A nanomicelle(denoted as TPGS/Ppa)was fabricated via the coassembly of the amphiphilic D-α-tocopheryl polyethylene glycol 1000 succinate(TPGS)and the hydrophobic photosensitizer pyropheophorbide a(Ppa)for photodynamic therapy(PDT).The obtained nanomicelle possessed a spherical structure with a diameter of(18.0±2.2)nm and a zeta potential of approximately -18 mV.Besides,the nanomicelle exhibited excellent photostability,biocompatibility,and phototoxicity,and could effectively reach the tumor region via the enhanced permeability and retention effect.Additionally,it could be found that the TPGS/Ppa nanomicelle exhibited higher phototoxicity against 4T1 murine mammary cancer cells than free Ppa.In the 4T1 tumor-bearing mouse model,the nanomicelle showed an excellent antitumor therapeutic effect.This study develops a new type of photodynamic nanomicelle TPGS/Ppa,which can increase the accumulation of drugs and prolong their tumor retention time,providing a feasible strategy for realizing the delivery of small-molecule hydrophobic drugs and tumor PDT.展开更多
Developing metal-free,purely organic photocatalysts with high recyclability and the ability to utilize red light to yield specific reactive oxygen species for aerobic photocatalysis is both crucial and challenging in ...Developing metal-free,purely organic photocatalysts with high recyclability and the ability to utilize red light to yield specific reactive oxygen species for aerobic photocatalysis is both crucial and challenging in current research.Herein,we first found that a type-I photosensitizer,EtNBS-H,can achieve red-light-driven aerobic photocatalysis with remarkable catalytic performance and facile recoverability.Upon irradiation with red light,EtNBS-H exclusively generates O2−•,enabling the efficient hydroxylation of arylboronic acids,and oxidization of thioethers and other substrates with conversion exceeding 99%.Significantly,EtNBS-H stands out for its simple recovery and reuse through a facile pH-tunable acid-base reaction.This allows for the attainment of high-purity products through extraction,and enables the retrieval of the photocatalyst from the reaction medium for subsequent reuse with an average recovery rate exceeding 94%.Moreover,utilizing EtNBS-H as a photocatalyst in the scale-up reaction,the gram-scale products with a yield of>95%and purity of>99%were obtained,highlighting its potential for the guidance of developing recyclable organic photocatalysts that harness red light.This work offers a promising approach for sustainable and large-scale photocatalytic organic synthesis.展开更多
This study investigates the intersystem crossing(ISC)mechanism in donor-acceptor(D-A)type distyryl-BODIPY photosensitizers,including previously reported M1(benzene donor),M2,M3(phenothiazine donors),and newly predicte...This study investigates the intersystem crossing(ISC)mechanism in donor-acceptor(D-A)type distyryl-BODIPY photosensitizers,including previously reported M1(benzene donor),M2,M3(phenothiazine donors),and newly predicted M4(triphenylamine donor),M5-M7(nitrogen-containing aliphatic rings with thiophene donors).Using computational chemistry,we analyzed their geometric configurations,spectral properties,spin-orbit coupling,and electron-hole orbitals.We found that S_(2) is a charge transfer singlet state(^(1)CT),T2is a locally excited triplet state(^(3)LE),and the S_(2)→T_(2)transition is the main ISC pathway in M2-M7,following the ^(1)CT→^(3)LE mechanism.M5-M7 show near-vertical dihedral angles between donor and acceptor in the S_(2) state relative to M2-M4,facilitating charge transfer.The strain energies in the nitrogen-containing rings of M5-M7 affect oxidation potentials and ISC.M5,with the highest strain energy,shows the lowest oxidation potential,smaller△_(ES2-T2),highest SOC,and fastest kisc,making it the most efficient predicted singlet oxygen producer.This research clarifies the structure-performance relationships of near-infrared D-A type distyryl-BODIPY photosensitizers and provides a theoretical foundation for developing heavy-atom-free photosensitizers with tuned fluorescence quantum yield and singlet oxygen quantum yield.展开更多
基金the financial support by the National Natural Science Foundation of China(Nos.22301081,22301269 and 22401096)China Postdoctoral Science Foundation(No.2023M731095)+4 种基金the Shanghai Frontiers Science Center for Molecular Intelligent Synthesesthe Fundamental Research Funds for the Central UniversitiesYoung Talent Fund of Association for Science and Technology in Shaanxi,China(No.20240628)Scientific Research Program Funded by Education Department of Shaanxi Provincial Government(No.23JK0752)Foundation of Yulin Association for Science and Technology(No.20230512)。
文摘The development of highly effective photosensitizers(PSs)based on supramolecular coordination complexes(SCCs)is highly appealing in supramolecular chemistry,materials science,and biology.SCCs offer promising platforms for incorporating multiple PSs and other functional units into their well-defined structures,allowing for precise control over the number and distribution of these components.In this study,we present an efficient and straightforward method for modulating the photosensitization process of PSs derived from a family of BF_(2)-chelated dipyrromethene(BODIPY)-containing Pt(Ⅱ)metallacycles by varying pre-designed Pt(Ⅱ)acceptors.By utilizing different Pt(Ⅱ)acceptors with varying Pt atom configurations and degrees ofπ-conjugated organic moieties,we observed tunable characteristics in the photosensitization process and singlet oxygen(^(1)O_(2))generation efficiency of these targeted metallacycles.Furthermore,we successfully conducted the visible-light-driven oxidative coupling of various amines to imines,catalyzed by the prepared metallacycle PSs.This study offers a novel approach for fabricating efficient PSs based on SCCs,featuring tunable photosensitization efficiency and excellent photocatalytic reactivity,while providing new insights into the preparation of effective PSs.
基金supported by the National Nature Science Foundation of China (No. 21871092)Program of Shanghai Outstanding Academic Leaders (No. 21XD1421200)+1 种基金the Fundamental Research Funds for the Central Universities2021 Academic Innovation Ability Enhancement Plan for Excellent Doctoral Students of East China Normal University (No. YBNLTS2021-025)。
文摘The fabrication of highly effective photosensitizers has received considerable attention because of their attractive functions and applications in the fields of photodynamic therapy, photosynthesis, photocatalysis, etc. Thus, it is highly desirable to develop a new approach to enhance photosensitization efficiency.Herein, through coordination-driven self-assembly, a series of metallacycles with efficient fluorescence resonance energy transfer(FRET) were effectively constructed, which displayed higher photosensitization efficiency and photocatalytic activity than their model metallacycles without FRET due to broadband absorption and singlet energy transfer from the energy acceptor to the energy donor. Moreover, iodization of fluorophores induced a significant enhancement of the photosensitization efficiency and photocatalytic activity of the metallacycles. This research provides an efficient strategy for improving photosensitization efficiency and a promising platform for the preparation of effective photosensitizers and photocatalysts.
基金supported by the National Natural Science Foundation of China(60978070,61036014,61175216)the Natural Science Foundation for Dis-tinguished Young Scholars of Fujian Province(2011J06022)+1 种基金the program for New Century Excel-lent Talents in University of China(NCET-10-0012)the Program for Changjiang Scholars and Inno-vative Research Team in University(IRT1115).
文摘Singlet oxygen(^(1)O_(2))is a highly reactive oxygen species involved in numerous chemical and photochemical reactions in diferent biological systems and in particular,in photodynamic therapy(PDT).However,the quantifcation of^(1)O_(2) generation during in vitro and in vivo pho-tosensitization is still technically challenging.To address this problem,indirect and direct methods for^(1)O_(2)detection have been intensively studied.This review presents the available methods currently in use or under development for detecting and quantifying^(1)O_(2) generation during photosensitization.The advantages and limitations of each method will be presented.Moreover,the future trends in developing PDT-^(1)O_(2) dosimetry will be briefly discussed.
文摘Using heavy-atom-containing xanthene dyes,benzoins can be quanti- tatively prepared by photosensitized reduction from benzils with triethyla- mine.It is an important supplement to'benzoin condensation',asp.for those benzoins with electron-donating substituents.
基金the supports from the Chinese Academy of Sciences(CAS)Institute of Chemistry,CAS+3 种基金the supports from the National Natural Science Foundation of China(No.21933011)the Beijing Municipal Science&Technology Commission(No.Z191100007219009)the K.C.Wong Education Foundationthe support from the National Natural Science Foundation of China(No.21773073)。
文摘The reaction of triplet fusion,also named triplet-triplet annihilation,has attracted a lot of research interests because of its wide applications in photocatalytic,solar cells,and bioimaging.As for the singlet oxygen photosensitization,the reactive singlet oxygen species are generated through the energy transfers from photosensitizer(PS)to ground triplet oxygen molecule.In this work,we computed the electronic coupling for singlet oxygen photosensitization using the nonadiabatic coupling from the quantum chemical calculation.Then we utilized the molecular orbital(MO)overlaps to approximate it,where the MOs were computed from isolated single molecules.As demonstrated with quantitative results,this approach well describes the distribution of the coupling strength as the function of the intermolecular distance between the sensitizer and O_(2),providing us a simple but effective way to predict the coupling of triplet fusion reactions.
基金supported by the Institute of Materials Research and Engineering under Biomimetic and Biomedical Materials program(IMRE/00-1P1400)Newcastle University(RSA/CCEAMD5010)+1 种基金National University of Singapore(R279-000-482-133)The funding from NRF Investigatorship(R279-000-444-281)is also appreciated。
文摘Dual-functional aggregation-induced photosensitizers(AIE-PSs)with singlet oxygen generation(SOG)ability and bright fluorescence in aggregated state have received much attention in image-guided photodynamic therapy(PDT).However,designing an AIE-PS with both high SOG and intense fluorescence via molecular design is still challenging.In this work,we report a new nanohybrid consisting of gold nanostar(AuNS)and AIE-PS dots with enhanced fluorescence and photosensitization for theranostic applications.The spectral overlap between the extinction of AuNS and fluorescence emission of AIE-PS dots(665 nm)is carefully selected using five different AuNSs with distinct localized surface plasmon(LSPR)peaks.Results show that all the AuNS s can enhance the 1 O2 production of AIE-PS dots,among which the AuNS with LSPR peak at 585 nm exhibited the highest 1 O2 enhancement factor of15-fold with increased fluorescence brightness.To the best of our knowledge,this is the highest enhancement factor reported for the metalenhanced singlet oxygen generation systems.The Au585@AIE-PS nanodots were applied for simultaneous fluorescence imaging and photodynamic ablation of HeLa cancer cells with strongly enhanced PDT efficiency in vitro.This study provides a better understanding of the metal-enhanced AIE-PS nanohybrid systems,opening up new avenue towards advanced image-guided PDT with greatly improved efficacy.
基金Project supported by the National Natural Science Foundation of China
文摘By the use of the advanced ESR technique and through comparing with BHPD, the characteristic of YHPD photosensitization is discussed in this paper in the respect of the primary process of photosensitization. The experiment results showed: (ⅰ) not only ~1O_2, but also free radicals(O_2· OH and YHPD)can be formed by the aid of YHPD; and (ⅱ) as to the ability of producing ~1O_2, YHPD<BHPD, while for generating O_2 and-OH, YHPD>BHPD. Two points are indicated: first, the photosensitized damage of YHPD is interrelated to not only ~1O_2, but also free radicals (O_2. OH and YHPD); second, although the photosensitized damage of YHPD is stronger than that of BHPD, yet the photosensitized damage is negatively correlated to the yield of ~1O_2 but positively correlated to those of O_2 and OH. Based on these two points, it is suggested that activated oxygen free radicals(O_2 and. OH) instead of ~1O_2 play the main role as instantaneously activated material in the photosensitized damage of YHPD.
基金supported by the National Natural Science Foundation of China (22271090, 12204167)。
文摘In water, N,N′-diarylpyridinium thiazolo[5,4-d]thiazole vips(G1–G3) were encapsulated by cucurbit[8]uril(Q[8]) to construct Q[8]_(3)/G_(2) complexes, in which the encapsulated G molecules exist as an exact face-to-face dimer. These complexation behaviors have been indicated by proton nuclear magnetic resonance(~1H NMR) spectroscopy and isothermal titration calorimetry(ITC),and have been confirmed by X-ray single crystal structural analysis of Q[8]_(3)/G2_(2). While free vips G1–G3 have no ability to sensitize singlet oxygen, they all become effective singlet oxygen sensitizers when complexed with Q[8]. By irradiation of white light, Q[8]_(3)/G_(2) complexes induced selective oxidation of aryl sulfide to aryl sulfoxide in good yields and selective oxidation of dimethyl sulfide(DMS) to dimethyl sulfoxide(DMSO) in excellent yields without over-oxidation to dimethyl sulfone(DMSO_(2))even for elongated irradiation. High-yield photo-oxidation of DMS to DMSO_(2) was only achieved by irradiation of blue light in the presence of Q[8]_(3)/G1_(2), which was also effective in photobleaching of Rhodamine B in water. The higher photo-oxidation power of Q[8]_(3)/G1_(2) has been ascribed to an additional generation of reactive oxygen species besides singlet oxygen.
基金support from the National Natural Science Foundation of China(nos.21874093 and 21522505)the Fundamental Research Funds for the Central China Universities(no.2018SCUH0075).
文摘Photosensitization,originated from the activation of triplet states,is the basis of many photodynamic applications,but often competes with a series of nonradiative processes.Herein,we communicate a new function of double-stranded DNA(dsDNA)for label-free photosensitization switching.Up to∼70-fold singlet oxygen generation boosting was observed for SYBR Green I(SG)upon binding with dsDNA.Detailed photophysical and theoretical studies have revealed the role of dsDNA as a matrix,which could efficiently suppress the nonradiative transitions of SG.
基金Project supported by the National Natural Science Foundation of China.
文摘By kinetic methods, functional relation of TAN radical, produced in the process of TEMPONE trapping O2, vs. time during photosensitization was established. Accordingly relative rate constants of generating all kinds of active intermediates through types I and II mechanism of photosensitization can be calculated. Using the formula and experimental results, the relative rate constants of generating O2, O2 and PS2 of three kinds of perylenequinone photosensitizer: HA, HB and CP in DMF-H20 and DMSO-H2O system were calculated, and then the structure-activity relationship of perylenequinone photosensitizer and the relation between photosensitivity and solvent was studied.
基金Project supported by the National Natural Science Foundation of China (Grant No. 39830090)
文摘Pheophorbide a (PPa), a decomposition product of chlorophyll a, is a photosensitizer. The photosensiti-zation mechanisms (Type Ⅰ and Type Ⅱ) of PPa in simple buffer solutions and in buffer solutions containing double-layered DPPC liposomes have been studied using techniques of ESR, spin-trapping, spin-counteraction and laser flash photolysis . The results showed that adding DPPC liposomes to the buffer solution caused an increase of efficiency of generating 1O2 and PPa - by photoactivating PPa. The increase could be ascribed to the disaggregation of hydrophobic PPa caused by the addition of liposomes and the protective effect of liposomal media on the triplet state of PPa. It is concluded that the photosensitization of PPa in liposomal systems is different from that in simple aqueous solutions, and shows higher efficacy. The results will be useful to elucidating the mechanisms of photodynamic therapy of cancer.
基金the National Natural Science Foundation of China.
文摘The primary reaction of photosensitization of Hypocrellin A (HA) has been studied byusing techniques of ESR, spin-trapping and spin-counteraction. The experiments show thatHA is able to generate not only ~1O_2,but also O_2^-·OH and HA^- which are observed for thefirst time. The conversion of generating active oxygen into generating nonoxygen free rad-ical is confirmed as well. Based on the characteristics of the primary reaction which gene-rates these active substances (transient products), it is proposed that the photosensitized dam-age for the biological system by HA is probably related to not only ~1O_2 itself, but also amultiple effect from ~1O_2 as well as O_2^-,·OH and HA^+ free radical.
基金supported by Research Fund of SWUST for PhD(Grant No.22zx7175)Sichuan Science and Technology Program(Grant No.2024NSFSC1097)。
文摘Based on the characteristics of laser-induced surface ignition,energetic photosensitive films show promising potential to meet the ignition requirements of various energetic materials(EMs).In this study,DATNBI/ferric alginate(DI/FeA),DI/cobalt alginate(DI/CoA),and DI/nickel alginate(DI/Ni A)films are fabricated by employing sodium alginate(SA)with a three-dimensional network structure as the film matrix,via ionic cross-linking of SA with Fe^(3+),Co^(2+),and Ni^(2+)ions.The study demonstrates that the ionic cross-linking enhances the hydrophobic performance of the films,with the water contact angle increasing from 82.1??to 123.5??.Concurrently,the films'near-infrared(NIR)light absorption improved.Furthermore,transition metal ions facilitate accelerated electron transfer,thereby catalyzing the thermal decomposition of DATNBI.Under 1064 nm laser irradiation,the DI/Fe A film exhibits exceptional combustion performance,with an ignition delay time as low as 76 ms.It successfully acts as an NIR laser ignition medium to initiate the self-sustained combustion of CL-20.This study demonstrates the synergistic realization of enhanced hydrophobicity,improved photosensitivity,and promoted catalytic decomposition through microstructural design of the material,providing new insights for the design of additive-free EMs in laser ignition applications.
基金financially supported by the National Science Foundation of China(nos.21788102,51873092,and 51961160730)the Research Grants Council of Hong Kong(nos.16305518,16305618,N-HKUST609/19,AHKUST605/16,and C6009-17G)+2 种基金the Innovation and Technology Commission(nos.ITC-CNERC14SC01 and ITCPD/17-9)Ming Wai Lau Centre for Reparative Medicine Associate Member Program(no.MWLC19SC02)the National Key Research and Development Program of China(no.2017YFE0132200).
文摘Oxidative damage to cells leads to accumulated harmful wastes,which in turn aggravate the imbalance of reactive oxygen species(ROS)and related diseases.Therefore,provoking the cellular defense system against severe oxidation and maintaining ROS homeostasis are desired.Herein,we designed and synthesized a powerful mitochondria-targeting aggregation-induced emission photosensitizer(named DTCSPY)by maximal restriction of heat dissipation.It is demonstrated that taming ROS generation within mitochondria through photosensitization-triggered autophagy via DTCSPY achieved a better neuroprotective effect against oxidative damages than Nacety-L-cysteine and vitamin C.This work not only provides a new way to design high-performance photosensitizers by regulating the photophysical property,but also verifies the concept that taming ROS can be used for cell protection against destructive oxidation,thereby displaying broad prospects for alleviating oxidation-related diseases and promoting cell-based therapy.
基金Project supported by the National Natural Science Foundation of China.
文摘Laser Raman spectroscopy was used to investigate the microcosmic and photosensitive damage of YHPD to lysozyme, of which the three-dimensional structure has been elucidated. The experimental results shown by various damages of the main-chain and side-chain of lysozyme are as follows: (ⅰ) Phe and Cys are also damaged by photosensitization of YHPD, except for Trp, Tyr, Met, 1/2Cys and His; (ⅱ) the order of the photosensitized sensitivity of various groups of these amino acids have been described; (ⅲ) Trp and Tyr buried in the three-dimensional structure of the protein are damaged very greatly, and (ⅳ) the main-chain conformation of the protein has changed considerably, such as a decrease in orderly structure (α-helix, β-sheet and β-turn) and a simultaneous increase in random coil.
基金supported by the National Key R&D Program of China(No.2022YFC3701102)the National Natural Science Foundation of China(Nos.22376029,22176038,91744205 and 21777025)the Natural Science Foundation of Shanghai City(No.22ZR1404700).
文摘Nitrate renoxification significantly influences atmospheric nitrogen cycling and global OH budgets.Although numerous nitrite acid(HONO)formation pathways from nitrate photolysis have been widely reported,the influence of various environmental factors and aerosol properties on reactive nitrogen production remains largely unclear.In this work,we employed NaNO_(3)/humic acid(HA)as a model nitrate photosensitization system to investigate the crucial roles of aerosol acidity,organic fraction,and dissolved oxygen in the production of HONO,NO_(2),and NO_(2)^(-).The presence of HA at 10 mg/L resulted in a remarkable increase in HONO production rates by approximately 2–3 times and NO_(2)^(-) concentration by 3–6 times across a pH range of 5.2 to 2.0.Meanwhile,the molar fraction of gaseous HONO in total N(Ⅲ)production increased from4%to 69%as bulk-phase pH decreased from 5.2 to 2.0.The higher organic fraction(i.e.,20 and 50 mg/L HA concentration)instead inhibited HONO and NO_(2) release.The presence of dissolved oxygen was found to be adverse for reactive nitrogen production.This suggests that the HA photosensitizer promoted the secondary conversion of NO_(2) to HONO mainly via reduced ketyl radical intermediates,while superoxide radical formation might exert a negative effect.Our findings provide comprehensive insights into reactive nitrogen production from photosensitized nitrate photolysis mediated by various external and internal factors,potentially accounting for discrepancies between field observations and model simulations.
基金supported by the National Natural Science Foundation of China(2127303621177024)+1 种基金the National Basic Research Program of China(973 Program2014CB239303)~~
文摘Environmental pollution and energy deficiency represent major problems for the sustainability of the modern world. Photocatalysis has recently emerged as an effective and environmentally friendly technique to address some of these sustainability issues,although the key to the success of this approach is dependent on the photocatalysts themselves. Based on their attractive physic chemical properties,including their ultrahigh surface areas,homogeneous active sites and tunable functionality,metal-organic frameworks（MOFs） have become interesting platforms for the development of solar energy conversion devices. Furthermore,MOFs have recently been used in a wide variety of applications,including heterogeneous photocatalysis for pollutant degradation,organic transformations,hydrogen production and CO2 reduction. In this review,we have highlighted recent progress towards the application of MOFs in all of these areas. We have collected numerous reported examples of the use of MOFs in these areas,as well as providing some analysis of the key factors influencing the efficiency of these systems. Moreover,we have provided a detailed discussion of new strategies that have been developed for enhancing the photocatalytic activity of MOFs. Finally,we have provided an outlook for this area in terms of the future challenges and potential prospects for MOFs in photocatalysis.
文摘A nanomicelle(denoted as TPGS/Ppa)was fabricated via the coassembly of the amphiphilic D-α-tocopheryl polyethylene glycol 1000 succinate(TPGS)and the hydrophobic photosensitizer pyropheophorbide a(Ppa)for photodynamic therapy(PDT).The obtained nanomicelle possessed a spherical structure with a diameter of(18.0±2.2)nm and a zeta potential of approximately -18 mV.Besides,the nanomicelle exhibited excellent photostability,biocompatibility,and phototoxicity,and could effectively reach the tumor region via the enhanced permeability and retention effect.Additionally,it could be found that the TPGS/Ppa nanomicelle exhibited higher phototoxicity against 4T1 murine mammary cancer cells than free Ppa.In the 4T1 tumor-bearing mouse model,the nanomicelle showed an excellent antitumor therapeutic effect.This study develops a new type of photodynamic nanomicelle TPGS/Ppa,which can increase the accumulation of drugs and prolong their tumor retention time,providing a feasible strategy for realizing the delivery of small-molecule hydrophobic drugs and tumor PDT.
基金supported by the National Key Research and Development Program of China(2022YFA1505900)the National Natural Science Foundation of China(22105016,22275010 and 52002015).
文摘Developing metal-free,purely organic photocatalysts with high recyclability and the ability to utilize red light to yield specific reactive oxygen species for aerobic photocatalysis is both crucial and challenging in current research.Herein,we first found that a type-I photosensitizer,EtNBS-H,can achieve red-light-driven aerobic photocatalysis with remarkable catalytic performance and facile recoverability.Upon irradiation with red light,EtNBS-H exclusively generates O2−•,enabling the efficient hydroxylation of arylboronic acids,and oxidization of thioethers and other substrates with conversion exceeding 99%.Significantly,EtNBS-H stands out for its simple recovery and reuse through a facile pH-tunable acid-base reaction.This allows for the attainment of high-purity products through extraction,and enables the retrieval of the photocatalyst from the reaction medium for subsequent reuse with an average recovery rate exceeding 94%.Moreover,utilizing EtNBS-H as a photocatalyst in the scale-up reaction,the gram-scale products with a yield of>95%and purity of>99%were obtained,highlighting its potential for the guidance of developing recyclable organic photocatalysts that harness red light.This work offers a promising approach for sustainable and large-scale photocatalytic organic synthesis.
基金financially supported by the Fundamental Research Funds for the Central Universities(No.DUT20RC(3)076)Natural Science Foundation of Liaoning Province(No.2020-MS293)。
文摘This study investigates the intersystem crossing(ISC)mechanism in donor-acceptor(D-A)type distyryl-BODIPY photosensitizers,including previously reported M1(benzene donor),M2,M3(phenothiazine donors),and newly predicted M4(triphenylamine donor),M5-M7(nitrogen-containing aliphatic rings with thiophene donors).Using computational chemistry,we analyzed their geometric configurations,spectral properties,spin-orbit coupling,and electron-hole orbitals.We found that S_(2) is a charge transfer singlet state(^(1)CT),T2is a locally excited triplet state(^(3)LE),and the S_(2)→T_(2)transition is the main ISC pathway in M2-M7,following the ^(1)CT→^(3)LE mechanism.M5-M7 show near-vertical dihedral angles between donor and acceptor in the S_(2) state relative to M2-M4,facilitating charge transfer.The strain energies in the nitrogen-containing rings of M5-M7 affect oxidation potentials and ISC.M5,with the highest strain energy,shows the lowest oxidation potential,smaller△_(ES2-T2),highest SOC,and fastest kisc,making it the most efficient predicted singlet oxygen producer.This research clarifies the structure-performance relationships of near-infrared D-A type distyryl-BODIPY photosensitizers and provides a theoretical foundation for developing heavy-atom-free photosensitizers with tuned fluorescence quantum yield and singlet oxygen quantum yield.
