Photosensitizing supramolecular assemblies based on a phenazine derivative(PPA)have been developed,which show a strong affinity toward Pd2+ions to generate supramolecular ensemble PPA@Pd nanoparticles(NPs).The PPA@Pd ...Photosensitizing supramolecular assemblies based on a phenazine derivative(PPA)have been developed,which show a strong affinity toward Pd2+ions to generate supramolecular ensemble PPA@Pd nanoparticles(NPs).The PPA@Pd NPs catalyse the Suzuki cross-coupled reaction under mild conditions(aerial conditions,mixed aqueous media,and visible light radiations).Although PPA@Pd NPs exhibit a strong affinity for arylboronic acid and could catalyse homocoupling of arylboronic acid,the preference of PPA assemblies for aryl halide directed the course of reactions toward the formation of cross-coupled products.The electron-rich PPA assemblies not only facilitate the oxidative addition step through photoinduced electron transfer to Pd^(2+)ions but also bring the reactants closer to the catalytic sites by selective interactions with aryl halides in the presence of arylboronic acid under visible light irradiation.The efficiency of PPA@Pd NPs to catalyse the Suzuki crosscoupled reaction has been demonstrated for the synthesis of unsymmetrically substituted terphenyl derivatives.展开更多
Photocatalytic hydrogen evolution reaction(HER)represents one of the most promising technologies for sus-tainable development.Even though metal-organic framework(MOF),comprising rich topologies and tunable functionali...Photocatalytic hydrogen evolution reaction(HER)represents one of the most promising technologies for sus-tainable development.Even though metal-organic framework(MOF),comprising rich topologies and tunable functionalities,is getting attention as a new generation of photocatalyst,a majority of them only provide unclear active sites along with the use of external noble-metal based photosensitizers and environmentally unfriendly scavengers.Therefore,it is urged to develop MOFs possessing structurally unambiguous active sites along with inherent photosensitizing units and execute photocatalytic HER with greener sacrificial reagents.Herein,we report a UiO-66-type framework,namely UiO-66-dcbdt-Cd(dcbdt^(2-)=1,4-dicarboxylatebenzene-2,3-dithiol),bearing Cd-thiocatecholato moieties as intrinsic photosensitizing units and structurally well-defined active sites for photocatalytic HER in H_(2)O.UiO-66-dcbdt-Cd gave the best HER yield of 5.29 mmol g^(-1)and rate of 1.32 mmol g^(-1)h^(-1),outperforming the negligible HER performance of pristine metal-free UiO-66-dcbdt.This work provides insight to manipulation of thhiocatecholate functionalities inside MOFs to construct inherent photosensitizing units as well as stable structurally unambiguous active sites for sustainable photocatalytic applications.展开更多
Strong acceptor-weak acceptor system FN-TPy has been designed and synthesized,which undergoes solvent dependent self-assembly in mixed aqueous media to generate through space intermolecular charge transfer assemblies....Strong acceptor-weak acceptor system FN-TPy has been designed and synthesized,which undergoes solvent dependent self-assembly in mixed aqueous media to generate through space intermolecular charge transfer assemblies.The as-prepared entropically favoured assemblies of FN-TPy exhibit excellent photostability and photosensitizing properties in the assembled state to activate aerial oxygen for efficient generation of reactive oxygen species through Type-I and Type-II pathways.The FN-TPy exhibits excellent potential for regulated oxidation of alcohols and aldehydes under mild reaction conditions(visible light irradiation,aqueous media,room temperature)using aerial oxygen as the‘oxidant’.The present study demonstrates the potential of FN-TPy assemblies to catalyse controlled oxidation of benzyl alcohol to benzoic acid.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
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
Pt(Ⅱ)-salophen complexes(S-1~S-4) and 9,10-diphenylanthracene(DPA) tethering pillar[5]arene derivatives(A-1 and A-2) were synthesized to act as sensitizers and annihilators for triplet-triplet annihilation upconversi...Pt(Ⅱ)-salophen complexes(S-1~S-4) and 9,10-diphenylanthracene(DPA) tethering pillar[5]arene derivatives(A-1 and A-2) were synthesized to act as sensitizers and annihilators for triplet-triplet annihilation upconversion(TTA-UC), respectively. It turned out that the pyridine cation served as a mask for the excited state of the sensitizer, the triplet states of S-2 and S-3 were significantly quenched by photo-induced electron transfer(PET) with phosphorescence quantum yield quenched from 24.4% for S-4 to 9.3% for S-3,and therefore, both S-2 and S-3 led to negligible UC emissions when traditional annihilator DPA was used as the annihilator. Delightfully, when supramolecular annihilator A-1 and A-2 were employed to include the pyridine cation, PET was significantly inhibited and the triplet states of the sensitizers were activated,TTA-UC emission was therefore boosted. The UC quantum yield of A-2/S-3 system was up to 130 times higher than that of DPA/S-3 system, and the UC emission was switchable by the addition of competitive vips.展开更多
The rapid emergence of drug-resistant bacterial strains undermines the efficacy of conventional antibiotics,necessitating the development of alternative therapies.Antimicrobial photodynamic therapy(PDT)is a promising ...The rapid emergence of drug-resistant bacterial strains undermines the efficacy of conventional antibiotics,necessitating the development of alternative therapies.Antimicrobial photodynamic therapy(PDT)is a promising approach,but its effectiveness is often limited by the suboptimal photocatalytic activity of photosensitizers.In this study,we introduce a novel photoresponsive carbon-based antibacterial agent,Ce6/g-C_(3)N_(4),which combines the photocatalytic properties of graphite-phase carbon nitride(g-C_(3)N_(4))with the photodynamic attributes of chlorin e6(Ce6).This agent,with an average particle size of 250.7 nm,demonstrates significantly enhanced photocatalytic activity.Additionally,the strong affinity of Ce6/g-C_(3)N_(4)for bacteria and efficient delivery of Ce6 result in an inhibition rate exceeding 99%against Gram-positive bacteria and excellent biofilm eradication under light irradiation.In vivo experiments reveal that Ce6/gC_(3)N_(4)effectively inhibits bacterial growth on wounds,and promotes wound healing post-light treatment,while maintaining good biocompatibility.Overall,the Ce6/g-C_(3)N_(4)antibacterial agent synergizes photodynamic and photocatalytic mechanisms,offering a new avenue for the photo-mediated,multi-strategic treatment of bacterial infections and wound healing.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
Photodynamic therapy (PDT) is undoubtedly a cutting-edge strategy for precise tumor therapy because of its unprecedented superiorities, such as negligible long-lasting adverse effects, high spatial and temporal select...Photodynamic therapy (PDT) is undoubtedly a cutting-edge strategy for precise tumor therapy because of its unprecedented superiorities, such as negligible long-lasting adverse effects, high spatial and temporal selectivity, and inappreciable drug resistance. While the operation wavelengths of the commonly used photosensitizers (PSs) are located in visible or first near-infrared (NIR-I, 650–900 nm) region. The lights in these regions possess relatively low penetration depth, which makes PDT unsuitable for deep-tissue treatment. Near-infrared-II (NIR-II, 1000–1700 nm) light with high tissue penetration ability can be employed as excitation source for PDT, which provides a promising alternative for precision therapy of deep-seated tumors. However, designing NIR-II activated PSs is in its infancy, and still faces many challenges, such as severe nonradiative relaxation and difficulties in adjusting energy levels. This paper reviews the therapeutic mechanisms of PDT and recent strategies for designing NIR-II activated inorganic PSs. The inorganic NIR-II PSs are classified based on their functions (such as type II PSs, type I PSs, and PSs with specific properties), and their applications for effective and precision deep-tissue treatment are summarized comprehensively. Furthermore, the major issues of applying these PSs in clinical practices are also discussed.展开更多
Innovative anti-cancer therapies that activate the immune system show promise in combating cancers resistant to conventional treatments.Photodynamic therapy(PDT)is one such treatment,which not only directly eliminates...Innovative anti-cancer therapies that activate the immune system show promise in combating cancers resistant to conventional treatments.Photodynamic therapy(PDT)is one such treatment,which not only directly eliminates tumor cells but also functions as an in situ tumor vaccine by enhancing tumor immunogenicity and triggering anti-tumor immune responses through immunogenic cell death(ICD).However,the effectiveness of PDT in enhancing immune responses is influenced by factors,such as photosensitizers and the tumor microenvironment,particularly hypoxia.Current clinically used PDT heavily relies on oxygen(O_(2))availability and can be limited by tumor hypoxia.Additionally,the tumor immunosuppressive microenvironment induced by hypoxia affects the anti-tumor immunity of tumor-infiltrating effector T cells.Meanwhile,the immunosuppressive myeloid-lineage cells are recruited to the hypoxic tumor tissue and exhibit higher immunosuppressive capabilities under hypoxia conditions.Consequently,numerous strategies have been developed to modulate tumor hypoxia or to create hypoxia-compatible PDT,aiming to reduce the effects of tumor hypoxia on PDT-driven immunotherapy.This review investigates these strategies,including approaches to alleviate,exploit,and disregard tumor hypoxia within the context of PDT/immunotherapy.It also emphasizes the role of advanced nanomedicine and its benefits in these strategies,while outlining current challenges and future prospects in the field.展开更多
Currently,it is still a challenge to develop an organic photosensitizer(PS)with outstanding near-infrared absorption,low O2dependence,precise tumor targeting and rapid clearance through the kidney to improve the overa...Currently,it is still a challenge to develop an organic photosensitizer(PS)with outstanding near-infrared absorption,low O2dependence,precise tumor targeting and rapid clearance through the kidney to improve the overall outcome of phototherapy.In this study,we have designed an organic PS(Nc PB)with an excellent near-infrared light absorption through a refined molecular strategy.Meanwhile,Nc PB was assembled into nanoparticles with different sizes(Nano Nc PB-1 and Nano Nc PB-0)by a supramolecular modulation strategy.As the results,the nanoparticle with an ultra-small size(Nano Nc PB-1)generated a large number of superoxide anion(O_(2)^(·-))in a low-O_(2)-dependent manner and release plenty of heat.Furthermore,the results of in vivo experiments demonstrated that Nano Nc PB-1 actively accumulated in tumor tissues and showed a 92%tumor inhibition after photodynamic and photothermal combination therapy.More importantly,Nano Nc PB-1 could be rapidly cleared from the body of mice via the renal pathway,which alleviates potential side effects of prolonged retention of PS in the circulation.展开更多
This work was carried out with the aim of contributing to the treatment of cancer. Cancer is one of the most common causes of death. It constitutes a public health problem. Photodynamic therapy (PDT) is one treatment ...This work was carried out with the aim of contributing to the treatment of cancer. Cancer is one of the most common causes of death. It constitutes a public health problem. Photodynamic therapy (PDT) is one treatment option. This study contributes to the search for photosensitizing molecules used in PDT. Makaluvamines have shown interesting properties in the treatment of several human cancer cell lines. The present study analyzes the ultraviolet and visible absorption spectroscopic properties of a few Makaluvamines. These have been listed in the literature and can be in neutral or charged states (protonated and methylated). The investigation is based on quantum chemical calculations. Molecular geometries and vibrational frequencies have been calculated at the B3LYP/6-311++G(d,p) level. Absorption properties in the visible and ultraviolet spectral range are measured on optimized structures using time-dependent density functional theory (TD-DFT). The absorption spectra are obtained using the “Chemissian” software. The results of our calculations have allowed us to determine the absorption zones of the molecules studied, the energy gaps of the frontier orbitals, the main transitions associated with the absorption process, and their lifetimes. They have also identified four Makaluvamines (E, G, M, and L) that absorb in the therapeutic domain and may have photosensitizer properties.展开更多
This study is based on wireless optogenetic technology,utilizing the CRY2/CIB1 photosensitive system to achieve spatiotemporal control of PD-L1 expression.In vitro experiments showed that the surface PD-L1 positivity ...This study is based on wireless optogenetic technology,utilizing the CRY2/CIB1 photosensitive system to achieve spatiotemporal control of PD-L1 expression.In vitro experiments showed that the surface PD-L1 positivity rate of cells increased from 28.6±3.1%to 67.3±5.4%(P<0.001).In animal experiments,the terminal tumor volume in the light exposure group was 450±90 mm3,with a tumor inhibition rate of approximately 49.4%(P<0.001),and the median survival was extended to 32 days(compared to 24 days in the control group,P=0.004).Immunological tests revealed a significant increase in CD8+T cell infiltration(112±18 vs 52±10 cells/HPF,P<0.01),a 30%decrease in the proportion of Tregs(P<0.05),and an increase in the M1/M2 macrophage ratio to 1.8.The results suggest that the wireless optogenetic system can not only precisely regulate PD-L1 but also remodel the tumor immune microenvironment,providing a new approach for precise immunotherapy of GBM.展开更多
Artificial multisensory devices play a key role in human-computer interaction in the field of artificial intelligence(AI).In this work,we have designed and constructed a novel olfactory-visual bimodal neuromorphic car...Artificial multisensory devices play a key role in human-computer interaction in the field of artificial intelligence(AI).In this work,we have designed and constructed a novel olfactory-visual bimodal neuromorphic carbon nanotube thin film transistor(TFT)arrays for artificial olfactory-visual multisensory synergy recognition with a very low power consumption of 25 aJ for a single pulse,employing semiconducting single-walled carbon nanotubes(sc-SWCNTs)as channel materials and gas sensitive materials,and poly[[4,8-bis[5-(2-ethylhexyl)-2-thienyl]benzo[1,2-b:4,5-b0]dithiophene-2,6-diyl]-2,5-thiophenediyl-[5,7-bis(2-ethylhexyl)-4,8-dioxo-4H,8H-benzo[1,2-c:4,5-c0]dithio-phene-1,3-diyl]](PBDB-T)as the photosensitive material.It is noted that it is the first time to realize the simulation of olfactory and visual senses(from 280 nm to 650 nm)with the wide operating temperature range(0-150℃)in a single SWCNT TFT device and successfully simulate the recovery of olfactory senses after COVID-19 by olfactory-visual synergy.Furthermore,our SWCNT neuromorphic TFT devices with a high IOn/IOff ratio(up to 10^(6))at a low operating voltage(−2 to 0.5 V)can mimic not only the basic biological synaptic functions of olfaction and vision(such as paired-pulse facilitation,short-term plasticity,and long-term plasticity),but also optical wireless communication by Morse code.The proposed multisensory,broadband light-responsive,low-power synaptic devices provide great potential for developing AI robots to face complex external environments.展开更多
Zinc phthalocyanines(ZnPc)are widely recognized as efficient triplet photosensitizers in photodynamic therapy and photocatalysis,owing to their intense absorption in the visible range and long triplet-state lifetimes....Zinc phthalocyanines(ZnPc)are widely recognized as efficient triplet photosensitizers in photodynamic therapy and photocatalysis,owing to their intense absorption in the visible range and long triplet-state lifetimes.However,their application in triplet-triplet annihilation(TTA)upconversion is lacking to date.In this study,we synthesized a new ZnPc photosensitizer,4I-ZnPc,and composed a TTA upconversion system using rubrene as the energy acceptor.Upon photoexcitation at 663 nm,yellow fluorescence from rubrene was observed in deoxygenated dichloromethane,demonstrating TTA upconversion with an anti-Stokes shift of 0.331 eV and a quantum yield of 1.82%(out of the 50%maximum).Using nanosecond transient absorption spectroscopy,we determined the triplet lifetime of 4I-ZnPc,the triplet-triplet energy transfer efficiency,and the fluorescence quantum yield.These measurements provide critical insights into the photophysical processes governing the TTA upconversion system.Our results highlight the potential advantages and limitations of ZnPc as a triplet photosensitizer for TTA upconversion.展开更多
With increasing drug resistance,Candida infections have posed serious threats to public health.Photodynamic therapy harnesses light to destroy pathomycete,providing a smart strategy for combating of Candida infections...With increasing drug resistance,Candida infections have posed serious threats to public health.Photodynamic therapy harnesses light to destroy pathomycete,providing a smart strategy for combating of Candida infections.However,due to lack of organelle targeting ability and bad extracellular polymeric substances penetrability,current photosensitizers(PSs)are far from desirable to clean biofilms and fight against drug resistance.Herein,a mitochondrion targeting aggregationinduced emission PS,LIQ-TPA-TZ,was developed for the efficient photodynamic treatment of oral Candida infection.LIQ-TPA-TZ has good singlet oxygen and hydroxyl radical generation ability,which can efficiently kill the Candida guilliermondii(C.guilliermondii)and eradicate the biofilm.It not only causes mitochondrial damage by disruption of mitochondrial respiratory chain and oxidative stress-related gene but also inhibits fungal adhesion and filamentous growth to prevent Candida colonization,mycelia growth and biofilm formation,which is favorable for eliminating the potential drug resistance.In the mouse oropharyngeal Candida biofilm infection model,LIQ-TPA-TZ significantly eliminates infection,alleviates inflammation,and accelerates mucosal defect healing.This study provides a favorable strategy for confronting drug resistance,which may be a potential Candidate for the treatment of Candida infection.展开更多
Brown carbon(BrC)has attracted widespread attention because of its strong absorption of solar radiation in the ultraviolet-visible wavelength range,which causes adverse impacts on human health.Originally,BrC was a phy...Brown carbon(BrC)has attracted widespread attention because of its strong absorption of solar radiation in the ultraviolet-visible wavelength range,which causes adverse impacts on human health.Originally,BrC was a physically defined class of substances.However,current research has gradually shifted towards the identification of its chemical groups,because its light-absorbing capability,chemical properties and health effects mainly depend on the chemical composition of its chromophores.Therefore,this review mainly focuses on the chemical understanding of BrC based on chromophores,and the secondary formation mechanism of chromophores,photosensitized reactions,and human health effects of BrC were detailly summarized.Firstly,BrC chromophores are divided into five categories:nitrogen-heterocycles,nitrogen-chain,aromatic species,oligomers and sulfur-containing organic compounds.Different chromophore precursor species exhibit variations,and their formation mechanisms are also distinct.Secondly,BrC can trigger the production of secondary organic aerosol(SOA)precursors or cause SOA growth because BrC is an important component of light-absorbing particles formed during incomplete combustion of biomass and fossil fuels,potentially exerting adverse effects on human health.Finally,developing sufficiently separated methods for BrC and refining algorithms and machine learning can lead to a more effective understanding of the chemical composition of chromophores,thus enabling better evaluation of the atmospheric effects and health impacts of BrC.In all,this review provides new insights into the categories of BrC chromophores and new advance in secondary formation mechanisms,photosensitized reactions,and human health effects on the basis of chemical structures.展开更多
We compared a range of BODIPY dimer derivatives without installing blocking groups by optimizing geometry structures and analyzing energies,frontier mo-lecular orbitals,Chole&Cele map,electron density difference,s...We compared a range of BODIPY dimer derivatives without installing blocking groups by optimizing geometry structures and analyzing energies,frontier mo-lecular orbitals,Chole&Cele map,electron density difference,spin-orbit coupling(SOC)matrix and decay rate constants from excited states.The dihedral angles of theβ-β-linked BODIPY dimer and theα-α-linked BODIPY dimer tend to flatten in the T_(1)state,which is detrimental to the occurrence of the intersystem crossing(ISC).Conversely,the dihedral angle of the meso-β-linked BODIPY dimer,the meso-meso-linked BODIPY dimer andα-γ-linked BODIPY dimer is within the range of 125°-143°in the T_(1)state,facilitating ISC and the generation of singlet oxygen.Notably,the transition from S1 to S0 involving lowest unoccupied mo-lecular orbital to highest occupied molecular orbital with long-wavelength emis-sion and moderate oscillator strength underpins the remarkable long emission peaks observed experimentally forα-γ-linked BODIPY dimer.Moreover,the apparent SOC matrix enhances the ISC process,resulting in a respectable effi-ciency in generating singlet oxygen for this dimer.In meso-β-linked BODIPY,meso-meso-linked BODIPY,andα-γ-linked BODIPY,the S_(1)→T_(1)process is characterized by a significant charge transfer,specifically transitioning from the^(1)CT state to the^(3)LE state,indicative of a spin-orbit charge transfer ISC(SOCTISC)mechanism.The ability to regulate the photosensitivity of BODIPY dimers by adjusting the dihedral angle between the two units in the T_(1)state unveils new avenues for designing high-performance photosensitizers for both therapeutic and imaging applications.展开更多
基金SERB,New Delhi,Grant/Award Number:CRG/2018/001274SERB Power fellowship,Grant/Award Number:SPF/2021/000019+2 种基金CSIR,New Delhi,Grant/Award Number:02(0358/19/EMR-II)RUSA2.0(Component-4)DST for support under FIST and PURSE programme。
文摘Photosensitizing supramolecular assemblies based on a phenazine derivative(PPA)have been developed,which show a strong affinity toward Pd2+ions to generate supramolecular ensemble PPA@Pd nanoparticles(NPs).The PPA@Pd NPs catalyse the Suzuki cross-coupled reaction under mild conditions(aerial conditions,mixed aqueous media,and visible light radiations).Although PPA@Pd NPs exhibit a strong affinity for arylboronic acid and could catalyse homocoupling of arylboronic acid,the preference of PPA assemblies for aryl halide directed the course of reactions toward the formation of cross-coupled products.The electron-rich PPA assemblies not only facilitate the oxidative addition step through photoinduced electron transfer to Pd^(2+)ions but also bring the reactants closer to the catalytic sites by selective interactions with aryl halides in the presence of arylboronic acid under visible light irradiation.The efficiency of PPA@Pd NPs to catalyse the Suzuki crosscoupled reaction has been demonstrated for the synthesis of unsymmetrically substituted terphenyl derivatives.
基金funded by the Foundation of Basic and Applied Basic Research of Guangdong Province(2020B1515120024)Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01Z032)Science and Technology Program of Guangzhou(202201010244).
文摘Photocatalytic hydrogen evolution reaction(HER)represents one of the most promising technologies for sus-tainable development.Even though metal-organic framework(MOF),comprising rich topologies and tunable functionalities,is getting attention as a new generation of photocatalyst,a majority of them only provide unclear active sites along with the use of external noble-metal based photosensitizers and environmentally unfriendly scavengers.Therefore,it is urged to develop MOFs possessing structurally unambiguous active sites along with inherent photosensitizing units and execute photocatalytic HER with greener sacrificial reagents.Herein,we report a UiO-66-type framework,namely UiO-66-dcbdt-Cd(dcbdt^(2-)=1,4-dicarboxylatebenzene-2,3-dithiol),bearing Cd-thiocatecholato moieties as intrinsic photosensitizing units and structurally well-defined active sites for photocatalytic HER in H_(2)O.UiO-66-dcbdt-Cd gave the best HER yield of 5.29 mmol g^(-1)and rate of 1.32 mmol g^(-1)h^(-1),outperforming the negligible HER performance of pristine metal-free UiO-66-dcbdt.This work provides insight to manipulation of thhiocatecholate functionalities inside MOFs to construct inherent photosensitizing units as well as stable structurally unambiguous active sites for sustainable photocatalytic applications.
基金SERB,New Delhi,Grant/Award Number:CRG/2018/001274SERB Power fellowship,Grant/Award Number:SPF/2021/000019CSIR,New Delhi,Grant/Award Number:02(0358/19/EMR-II)。
文摘Strong acceptor-weak acceptor system FN-TPy has been designed and synthesized,which undergoes solvent dependent self-assembly in mixed aqueous media to generate through space intermolecular charge transfer assemblies.The as-prepared entropically favoured assemblies of FN-TPy exhibit excellent photostability and photosensitizing properties in the assembled state to activate aerial oxygen for efficient generation of reactive oxygen species through Type-I and Type-II pathways.The FN-TPy exhibits excellent potential for regulated oxidation of alcohols and aldehydes under mild reaction conditions(visible light irradiation,aqueous media,room temperature)using aerial oxygen as the‘oxidant’.The present study demonstrates the potential of FN-TPy assemblies to catalyse controlled oxidation of benzyl alcohol to benzoic acid.
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.
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 Natural Science Foundation of China (Nos. 22171194, 21971169, 92056116 and 21871194)the Fundamental Research Funds for the Central Universities (No. 20826041D4117)the Science & Technology Department of Sichuan Province (Nos. 2022YFH0095 and 2021ZYD0052)。
文摘Pt(Ⅱ)-salophen complexes(S-1~S-4) and 9,10-diphenylanthracene(DPA) tethering pillar[5]arene derivatives(A-1 and A-2) were synthesized to act as sensitizers and annihilators for triplet-triplet annihilation upconversion(TTA-UC), respectively. It turned out that the pyridine cation served as a mask for the excited state of the sensitizer, the triplet states of S-2 and S-3 were significantly quenched by photo-induced electron transfer(PET) with phosphorescence quantum yield quenched from 24.4% for S-4 to 9.3% for S-3,and therefore, both S-2 and S-3 led to negligible UC emissions when traditional annihilator DPA was used as the annihilator. Delightfully, when supramolecular annihilator A-1 and A-2 were employed to include the pyridine cation, PET was significantly inhibited and the triplet states of the sensitizers were activated,TTA-UC emission was therefore boosted. The UC quantum yield of A-2/S-3 system was up to 130 times higher than that of DPA/S-3 system, and the UC emission was switchable by the addition of competitive vips.
基金supported by the Natural Science Foundation of the Jiangsu Higher Education Institutes of China(No.22KJB530006)Hainan Provincial Natural Science Foundation of China(No.824QN267)。
文摘The rapid emergence of drug-resistant bacterial strains undermines the efficacy of conventional antibiotics,necessitating the development of alternative therapies.Antimicrobial photodynamic therapy(PDT)is a promising approach,but its effectiveness is often limited by the suboptimal photocatalytic activity of photosensitizers.In this study,we introduce a novel photoresponsive carbon-based antibacterial agent,Ce6/g-C_(3)N_(4),which combines the photocatalytic properties of graphite-phase carbon nitride(g-C_(3)N_(4))with the photodynamic attributes of chlorin e6(Ce6).This agent,with an average particle size of 250.7 nm,demonstrates significantly enhanced photocatalytic activity.Additionally,the strong affinity of Ce6/g-C_(3)N_(4)for bacteria and efficient delivery of Ce6 result in an inhibition rate exceeding 99%against Gram-positive bacteria and excellent biofilm eradication under light irradiation.In vivo experiments reveal that Ce6/gC_(3)N_(4)effectively inhibits bacterial growth on wounds,and promotes wound healing post-light treatment,while maintaining good biocompatibility.Overall,the Ce6/g-C_(3)N_(4)antibacterial agent synergizes photodynamic and photocatalytic mechanisms,offering a new avenue for the photo-mediated,multi-strategic treatment of bacterial infections and wound healing.
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(Nos.22175098,52373142)the Jiangsu Planned Projects for Postdoctoral Research Funds(No.2021K114B)the Huali Talents Program of Nanjing University of Posts and Telecommunications,the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX23_0984)。
文摘Photodynamic therapy (PDT) is undoubtedly a cutting-edge strategy for precise tumor therapy because of its unprecedented superiorities, such as negligible long-lasting adverse effects, high spatial and temporal selectivity, and inappreciable drug resistance. While the operation wavelengths of the commonly used photosensitizers (PSs) are located in visible or first near-infrared (NIR-I, 650–900 nm) region. The lights in these regions possess relatively low penetration depth, which makes PDT unsuitable for deep-tissue treatment. Near-infrared-II (NIR-II, 1000–1700 nm) light with high tissue penetration ability can be employed as excitation source for PDT, which provides a promising alternative for precision therapy of deep-seated tumors. However, designing NIR-II activated PSs is in its infancy, and still faces many challenges, such as severe nonradiative relaxation and difficulties in adjusting energy levels. This paper reviews the therapeutic mechanisms of PDT and recent strategies for designing NIR-II activated inorganic PSs. The inorganic NIR-II PSs are classified based on their functions (such as type II PSs, type I PSs, and PSs with specific properties), and their applications for effective and precision deep-tissue treatment are summarized comprehensively. Furthermore, the major issues of applying these PSs in clinical practices are also discussed.
基金supported by the Qin Chuangyuan Traditional Chinese Medicine(TCM)and Innovation Research and Development Project of Shaanxi Provincial Administration of TCM(No.2022-QCYZH-017)Natural Science Foundation of Zhejiang Province(No.LY24E030010)+5 种基金Natural Science Foundation of Shaanxi Province(Nos.2022JM183,2024JC-YBMS-272)the Shaanxi Fundamental Science Research Project for Chemistry&Biology(No.22JHQ072)Shaanxi Provincial Key R&D Program(No.2022SF-342HZ)the Fundamental Research Funds for the Central Universities(Nos.xzy012022037,xzy012023002)the Postdoctoral Science Foundation of Shaanxi Province(No.2023BSHYDZZ05)Foundation by Shaanxi Provincial Administration of TCM(No.2021-ZZ-JC032)。
文摘Innovative anti-cancer therapies that activate the immune system show promise in combating cancers resistant to conventional treatments.Photodynamic therapy(PDT)is one such treatment,which not only directly eliminates tumor cells but also functions as an in situ tumor vaccine by enhancing tumor immunogenicity and triggering anti-tumor immune responses through immunogenic cell death(ICD).However,the effectiveness of PDT in enhancing immune responses is influenced by factors,such as photosensitizers and the tumor microenvironment,particularly hypoxia.Current clinically used PDT heavily relies on oxygen(O_(2))availability and can be limited by tumor hypoxia.Additionally,the tumor immunosuppressive microenvironment induced by hypoxia affects the anti-tumor immunity of tumor-infiltrating effector T cells.Meanwhile,the immunosuppressive myeloid-lineage cells are recruited to the hypoxic tumor tissue and exhibit higher immunosuppressive capabilities under hypoxia conditions.Consequently,numerous strategies have been developed to modulate tumor hypoxia or to create hypoxia-compatible PDT,aiming to reduce the effects of tumor hypoxia on PDT-driven immunotherapy.This review investigates these strategies,including approaches to alleviate,exploit,and disregard tumor hypoxia within the context of PDT/immunotherapy.It also emphasizes the role of advanced nanomedicine and its benefits in these strategies,while outlining current challenges and future prospects in the field.
基金the National Natural Science Foundation of China(Nos.T2322004 and 22078066)。
文摘Currently,it is still a challenge to develop an organic photosensitizer(PS)with outstanding near-infrared absorption,low O2dependence,precise tumor targeting and rapid clearance through the kidney to improve the overall outcome of phototherapy.In this study,we have designed an organic PS(Nc PB)with an excellent near-infrared light absorption through a refined molecular strategy.Meanwhile,Nc PB was assembled into nanoparticles with different sizes(Nano Nc PB-1 and Nano Nc PB-0)by a supramolecular modulation strategy.As the results,the nanoparticle with an ultra-small size(Nano Nc PB-1)generated a large number of superoxide anion(O_(2)^(·-))in a low-O_(2)-dependent manner and release plenty of heat.Furthermore,the results of in vivo experiments demonstrated that Nano Nc PB-1 actively accumulated in tumor tissues and showed a 92%tumor inhibition after photodynamic and photothermal combination therapy.More importantly,Nano Nc PB-1 could be rapidly cleared from the body of mice via the renal pathway,which alleviates potential side effects of prolonged retention of PS in the circulation.
文摘This work was carried out with the aim of contributing to the treatment of cancer. Cancer is one of the most common causes of death. It constitutes a public health problem. Photodynamic therapy (PDT) is one treatment option. This study contributes to the search for photosensitizing molecules used in PDT. Makaluvamines have shown interesting properties in the treatment of several human cancer cell lines. The present study analyzes the ultraviolet and visible absorption spectroscopic properties of a few Makaluvamines. These have been listed in the literature and can be in neutral or charged states (protonated and methylated). The investigation is based on quantum chemical calculations. Molecular geometries and vibrational frequencies have been calculated at the B3LYP/6-311++G(d,p) level. Absorption properties in the visible and ultraviolet spectral range are measured on optimized structures using time-dependent density functional theory (TD-DFT). The absorption spectra are obtained using the “Chemissian” software. The results of our calculations have allowed us to determine the absorption zones of the molecules studied, the energy gaps of the frontier orbitals, the main transitions associated with the absorption process, and their lifetimes. They have also identified four Makaluvamines (E, G, M, and L) that absorb in the therapeutic domain and may have photosensitizer properties.
文摘This study is based on wireless optogenetic technology,utilizing the CRY2/CIB1 photosensitive system to achieve spatiotemporal control of PD-L1 expression.In vitro experiments showed that the surface PD-L1 positivity rate of cells increased from 28.6±3.1%to 67.3±5.4%(P<0.001).In animal experiments,the terminal tumor volume in the light exposure group was 450±90 mm3,with a tumor inhibition rate of approximately 49.4%(P<0.001),and the median survival was extended to 32 days(compared to 24 days in the control group,P=0.004).Immunological tests revealed a significant increase in CD8+T cell infiltration(112±18 vs 52±10 cells/HPF,P<0.01),a 30%decrease in the proportion of Tregs(P<0.05),and an increase in the M1/M2 macrophage ratio to 1.8.The results suggest that the wireless optogenetic system can not only precisely regulate PD-L1 but also remodel the tumor immune microenvironment,providing a new approach for precise immunotherapy of GBM.
基金supported by the National Key Research and Development Program of China(2020YFA0714700)Natural Science Foundation of China(62274174)+3 种基金Key Research and Development Program of Jiangsu Province(BK20232009)a fellowship from the China Postdoctoral Science Foundation(NO:2023M742559)the Cooperation Project of Vacuum Interconnect Research Facility(NANO-X)of Suzhou Institute of Nano-Tech and Nano-Bionics,Chinese Academy of Sciences(F2208)the technical support for Nano-X from Suzhou Institute of Nano-Tech and Nano-Bionics,Chinese Academy of Sciences(SINANO)。
文摘Artificial multisensory devices play a key role in human-computer interaction in the field of artificial intelligence(AI).In this work,we have designed and constructed a novel olfactory-visual bimodal neuromorphic carbon nanotube thin film transistor(TFT)arrays for artificial olfactory-visual multisensory synergy recognition with a very low power consumption of 25 aJ for a single pulse,employing semiconducting single-walled carbon nanotubes(sc-SWCNTs)as channel materials and gas sensitive materials,and poly[[4,8-bis[5-(2-ethylhexyl)-2-thienyl]benzo[1,2-b:4,5-b0]dithiophene-2,6-diyl]-2,5-thiophenediyl-[5,7-bis(2-ethylhexyl)-4,8-dioxo-4H,8H-benzo[1,2-c:4,5-c0]dithio-phene-1,3-diyl]](PBDB-T)as the photosensitive material.It is noted that it is the first time to realize the simulation of olfactory and visual senses(from 280 nm to 650 nm)with the wide operating temperature range(0-150℃)in a single SWCNT TFT device and successfully simulate the recovery of olfactory senses after COVID-19 by olfactory-visual synergy.Furthermore,our SWCNT neuromorphic TFT devices with a high IOn/IOff ratio(up to 10^(6))at a low operating voltage(−2 to 0.5 V)can mimic not only the basic biological synaptic functions of olfaction and vision(such as paired-pulse facilitation,short-term plasticity,and long-term plasticity),but also optical wireless communication by Morse code.The proposed multisensory,broadband light-responsive,low-power synaptic devices provide great potential for developing AI robots to face complex external environments.
基金supported by the National Natural Science Foundation of China(Nos.22473104 and 22403086)support of the China Postdoctoral Science Foundation(No.2023M733378).
文摘Zinc phthalocyanines(ZnPc)are widely recognized as efficient triplet photosensitizers in photodynamic therapy and photocatalysis,owing to their intense absorption in the visible range and long triplet-state lifetimes.However,their application in triplet-triplet annihilation(TTA)upconversion is lacking to date.In this study,we synthesized a new ZnPc photosensitizer,4I-ZnPc,and composed a TTA upconversion system using rubrene as the energy acceptor.Upon photoexcitation at 663 nm,yellow fluorescence from rubrene was observed in deoxygenated dichloromethane,demonstrating TTA upconversion with an anti-Stokes shift of 0.331 eV and a quantum yield of 1.82%(out of the 50%maximum).Using nanosecond transient absorption spectroscopy,we determined the triplet lifetime of 4I-ZnPc,the triplet-triplet energy transfer efficiency,and the fluorescence quantum yield.These measurements provide critical insights into the photophysical processes governing the TTA upconversion system.Our results highlight the potential advantages and limitations of ZnPc as a triplet photosensitizer for TTA upconversion.
基金supported by the National Natural Science Foundation of China(22177094)the Fundamental Research Funds for the Central Universities(YJ202419).
文摘With increasing drug resistance,Candida infections have posed serious threats to public health.Photodynamic therapy harnesses light to destroy pathomycete,providing a smart strategy for combating of Candida infections.However,due to lack of organelle targeting ability and bad extracellular polymeric substances penetrability,current photosensitizers(PSs)are far from desirable to clean biofilms and fight against drug resistance.Herein,a mitochondrion targeting aggregationinduced emission PS,LIQ-TPA-TZ,was developed for the efficient photodynamic treatment of oral Candida infection.LIQ-TPA-TZ has good singlet oxygen and hydroxyl radical generation ability,which can efficiently kill the Candida guilliermondii(C.guilliermondii)and eradicate the biofilm.It not only causes mitochondrial damage by disruption of mitochondrial respiratory chain and oxidative stress-related gene but also inhibits fungal adhesion and filamentous growth to prevent Candida colonization,mycelia growth and biofilm formation,which is favorable for eliminating the potential drug resistance.In the mouse oropharyngeal Candida biofilm infection model,LIQ-TPA-TZ significantly eliminates infection,alleviates inflammation,and accelerates mucosal defect healing.This study provides a favorable strategy for confronting drug resistance,which may be a potential Candidate for the treatment of Candida infection.
基金supported by the National Natural Science Foundation of China(Nos.42020104001,42327806 and 42177354).
文摘Brown carbon(BrC)has attracted widespread attention because of its strong absorption of solar radiation in the ultraviolet-visible wavelength range,which causes adverse impacts on human health.Originally,BrC was a physically defined class of substances.However,current research has gradually shifted towards the identification of its chemical groups,because its light-absorbing capability,chemical properties and health effects mainly depend on the chemical composition of its chromophores.Therefore,this review mainly focuses on the chemical understanding of BrC based on chromophores,and the secondary formation mechanism of chromophores,photosensitized reactions,and human health effects of BrC were detailly summarized.Firstly,BrC chromophores are divided into five categories:nitrogen-heterocycles,nitrogen-chain,aromatic species,oligomers and sulfur-containing organic compounds.Different chromophore precursor species exhibit variations,and their formation mechanisms are also distinct.Secondly,BrC can trigger the production of secondary organic aerosol(SOA)precursors or cause SOA growth because BrC is an important component of light-absorbing particles formed during incomplete combustion of biomass and fossil fuels,potentially exerting adverse effects on human health.Finally,developing sufficiently separated methods for BrC and refining algorithms and machine learning can lead to a more effective understanding of the chemical composition of chromophores,thus enabling better evaluation of the atmospheric effects and health impacts of BrC.In all,this review provides new insights into the categories of BrC chromophores and new advance in secondary formation mechanisms,photosensitized reactions,and human health effects on the basis of chemical structures.
基金financially supported by the Fundamental Research Funds for the Central Universities(DUT20RC(3)076)Natural Science Foundation of Liaoning Province(2020-MS-293).Thanks Shuoqi Sun from HZWTECH for help and discussions regarding this study.
文摘We compared a range of BODIPY dimer derivatives without installing blocking groups by optimizing geometry structures and analyzing energies,frontier mo-lecular orbitals,Chole&Cele map,electron density difference,spin-orbit coupling(SOC)matrix and decay rate constants from excited states.The dihedral angles of theβ-β-linked BODIPY dimer and theα-α-linked BODIPY dimer tend to flatten in the T_(1)state,which is detrimental to the occurrence of the intersystem crossing(ISC).Conversely,the dihedral angle of the meso-β-linked BODIPY dimer,the meso-meso-linked BODIPY dimer andα-γ-linked BODIPY dimer is within the range of 125°-143°in the T_(1)state,facilitating ISC and the generation of singlet oxygen.Notably,the transition from S1 to S0 involving lowest unoccupied mo-lecular orbital to highest occupied molecular orbital with long-wavelength emis-sion and moderate oscillator strength underpins the remarkable long emission peaks observed experimentally forα-γ-linked BODIPY dimer.Moreover,the apparent SOC matrix enhances the ISC process,resulting in a respectable effi-ciency in generating singlet oxygen for this dimer.In meso-β-linked BODIPY,meso-meso-linked BODIPY,andα-γ-linked BODIPY,the S_(1)→T_(1)process is characterized by a significant charge transfer,specifically transitioning from the^(1)CT state to the^(3)LE state,indicative of a spin-orbit charge transfer ISC(SOCTISC)mechanism.The ability to regulate the photosensitivity of BODIPY dimers by adjusting the dihedral angle between the two units in the T_(1)state unveils new avenues for designing high-performance photosensitizers for both therapeutic and imaging applications.
