Conventional hyperspectral cameras cascade lenses and spectrometers to acquire the spectral datacube,which forms the fundamental framework for hyperspectral imaging.However,this cascading framework involves tradeoffs ...Conventional hyperspectral cameras cascade lenses and spectrometers to acquire the spectral datacube,which forms the fundamental framework for hyperspectral imaging.However,this cascading framework involves tradeoffs among spectral and imaging performances when the system is driven toward miniaturization.Here,we propose a spectral singlet lens that unifies optical imaging and computational spectrometry functions,enabling the creation of minimalist,miniaturized and high-performance hyperspectral cameras.As a paradigm,we capitalize on planar liquid crystal optics to implement the proposed framework,with each liquid-crystal unit cell acting as both phase modulator and electrically tunable spectral filter.Experiments with various targets show that the resulting millimeter-scale hyperspectral camera exhibits both high spectral fidelity(>95%)and high spatial resolutions(~1.7 times the diffraction limit).The proposed“two-in-one”framework can resolve the conflicts between spectral and imaging resolutions,which paves a practical pathway for advancing hyperspectral imaging systems toward miniaturization and portable applications.展开更多
Singlet oxygen(^(1)O_(2)),as the primary reactive oxygen species in photodynamic therapy,can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment.However,monitoring endog...Singlet oxygen(^(1)O_(2)),as the primary reactive oxygen species in photodynamic therapy,can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment.However,monitoring endogenous^(1)O_(2)is greatly challenging due to its extremely short lifetime and high reactivity in biological condition.Herein,we report an ultra-high signal-to-ratio near-infrared chemiluminescent probe(DCMCy)for the precise detection of endogenous^(1)O_(2)during photodynamic therapy(PDT).The methoxy moiety was removed from enolether unit in DCM-Cy to suppress the potential self-photooxidation reaction,thus greatly eliminating the photoinduced background signals during PDT.Additionally,the compact cyclobutane modification of DCM-Cy resulted in a significant 6-fold increase in cell permeability compared to conventional adamantane-dioxane probes.Therefore,our“step-by-step”strategy for DCM-Cy addressed the limitations of traditional chemiluminescent(CL)probes for^(1)O_(2),enabling effectively tracking of endogenous^(1)O_(2)level changes in living cells,pathogenic bacteria and mice in PDT.展开更多
Different from reversible agonist-stimulated receptor activation,singlet oxygen oxidation activates permanently G protein-coupled receptor(GPCR)cholecystokinin 1(CCK1R)in type II photodynamic action,with soluble photo...Different from reversible agonist-stimulated receptor activation,singlet oxygen oxidation activates permanently G protein-coupled receptor(GPCR)cholecystokinin 1(CCK1R)in type II photodynamic action,with soluble photosensitizer dyes(sulphonated aluminum phthalocyanine,λmax 675 nm)or genetically encoded protein photosensitizers(KillerRedλmax 585 nm;mini singlet oxygen generatorλmax 450 nm),together with a pulse of light(37 mW/cm2,1-2 minutes).Three lines of evidence shed light on the mechanism of GPCR activated by singlet oxygen(GPCR-ABSO):(1)CCK1R is quantitatively converted from dimer to monomer;(2)Transmembrane domain 3,a pharmacophore for permanent photodynamic CCK1R activation,can be transplanted to non-susceptible M3 acetylcholine receptor;and(3)Larger size of disordered region in intracellular loop 3 correlates with higher sensitivity to photodynamic CCK1R activation.GPCR-ABSO will add to the arsenal of engineered designer GPCR such as receptors activated solely by synthetic ligands and designer receptors exclusively activated by designer drugs,but show some clear advantages:Enhanced selectivity(double selectivity of localized photosensitizer and light illumination),long-lasting activation with no need for repeated drug administration,antagonist-binding site remains intact when needed,ease to apply to multiple GPCR.This type of permanent photodynamic activation may be applied to functional proteins other than GPCR.展开更多
Common activations of sulfite(S(Ⅳ))-based advanced oxidation processes(AOPs)utilized metal ions and oxides as catalysts,which are constrained by challenges in catalyst recovery,inadequate stability,and susceptibility...Common activations of sulfite(S(Ⅳ))-based advanced oxidation processes(AOPs)utilized metal ions and oxides as catalysts,which are constrained by challenges in catalyst recovery,inadequate stability,and susceptibility to secondary pollution in application.Calcium sulfite(CaSO_(3)),one of the byproducts of flue gas desulfurization,is of interest in AOPs because of its ability to slowly release S(Ⅳ),low toxicity,and costeffectiveness.Therefore,a heterogenous activator,molybdenum carbide(Mo_(2)C)was selected to stimulate Ca SO3for typical antibiotic elimination.Benefiting from the dissociation form of HSO_(3^(-))from CaSO_(3)and improved electron transfer of Mo_(2)C at pH 6,the simulated target metronidazole(MTZ)can be removed by 85.65%with rate constant of 0.02424 min^(-1)under near-neutral circumstance.The combining determinations of quenching test,electron spin resonance spectrum,and reactive species probe demonstrated singlet oxygen(^(1)O_(2))and sulfate radicals played leading role for MTZ decontamination.Characterization and theoretical calculation suggested the alteration of Mo valence state drove the activation of S(Ⅳ),and revealed that dissolved oxygen promoted the adsorption of HSO_(3^(-))on the surface of Mo_(2)C,then facilitating production of^(1)O_(2).The favorable stability and applicability for Mo_(2)C/CaSO_(3)process indicated an applied prospect in actual pharmaceutical wastewater.展开更多
Singlet oxygen(^(1)O_(2)),as an electrophilic oxidant,is essential for the selective water decontamination of pollutants from water.Herein,we showcase a high-performing electrocatalytic filtration system composed of c...Singlet oxygen(^(1)O_(2)),as an electrophilic oxidant,is essential for the selective water decontamination of pollutants from water.Herein,we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles(CoFeCNT)to selectively facilitate the electrochemical activation of O_(2)to^(1)O_(2).Benefiting from the prominently featured bimetal active sites of CoFeCNT,nearly complete production of^(1)O_(2)is achieved by the electrocatalytic activation of O_(2).Additionally,the proposed system exhibits a consistent pollutant removal efficiency>90%in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance,highlighting the dependable stability of the system for practical applications.The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor.This work provides a molecular level understanding of the oxygen reduction reaction,showing promising potential for the selective removal of emerging organic contaminants from water.展开更多
Harnessing the redox potential of biochar to activate airborne O_(2)for contaminant removal is challenging.In this study,ferrihydrite(Fh)modified the boron(B),nitrogen(N)co-doped biochars(BCs)composites(Fh/B(n)NC)were...Harnessing the redox potential of biochar to activate airborne O_(2)for contaminant removal is challenging.In this study,ferrihydrite(Fh)modified the boron(B),nitrogen(N)co-doped biochars(BCs)composites(Fh/B(n)NC)were developed for enhancing the degradation of a model pollutant,tetracycline(TC),merely by airborne O_(2).Fh/B(3)NC showed excellent O_(2)activation activity for efficient TC degradation with a apparent TC degradation rate of 5.54,6.88,and 22.15 times that of B(3)NC,Fh,and raw BCs,respectively,where 1O_(2)and H_(2)O_(2)were identified as the dominant ROS for TC degradation.The B incorporation into the carbon lattice of Fh/B(3)NC promoted the generation of electron donors,sp2 C and the reductive B species,hence boosting Fe(III)reduction and 1O_(2)generation.O_(2)adsorption was enhanced due to the positively charged adsorption sites(C-B+and N-C+).And 1O_(2)was generated via Fe(II)catalyzed low-efficient successive one-electron transfer(O_(2)→O_(2)·−→1O_(2),H_(2)O_(2)),as well as biochar catalyzed high-efficient two-electron transfer(O_(2)→H_(2)O_(2)→1O_(2))that does not involve.O_(2)−as the intermediate.Moreover,Fh/B,N co-doped biochar showed a wide pH range,remarkable anti-interference capabilities,and effective detoxification.These findings shed new light on the development of environmentally benign BCs materials capable of degradading organic pollutants.展开更多
The authors regret<During the submission process,Hongxiang Zhang and Honggen Peng served as the first and the second corresponding author,respectively.The original manuscript submitted for this paper also listed tw...The authors regret<During the submission process,Hongxiang Zhang and Honggen Peng served as the first and the second corresponding author,respectively.The original manuscript submitted for this paper also listed two co-corresponding authors(Hongxiang Zhang and Honggen Peng).But the corresponding author of Honggen Peng was omitted in the final published manuscript.So,we apply to designate Honggen Peng(penghonggen@ncu.edu.cn)as the second co-corresponding author and the corresponding unit is“a,b">.展开更多
Reactive oxygen species(ROS),including singlet oxygen(^(1)O_(2)),hydroxyl radicals(·OH),and superoxide anions(O_(2)^(·-)),are highly reactive molecules that play central roles in many chemical,biological,and...Reactive oxygen species(ROS),including singlet oxygen(^(1)O_(2)),hydroxyl radicals(·OH),and superoxide anions(O_(2)^(·-)),are highly reactive molecules that play central roles in many chemical,biological,and environmental processes due to their strong oxidative power[1].Generating ROS in a controlled manner under mild conditions is essential for achieving selective oxidation reactions.Light-driven methods are especially appealing for this purpose,as they offer precise control over where and when ROS are produced.展开更多
Switching the reaction routes in peroxymonosulfate(PMS)-based advanced oxidation processes have attracted much attention but remain challenging.Herein,a series of Co-N/C catalysts with different compositions and struc...Switching the reaction routes in peroxymonosulfate(PMS)-based advanced oxidation processes have attracted much attention but remain challenging.Herein,a series of Co-N/C catalysts with different compositions and structures were prepared by using bimetallic zeolitic imidazolate frameworks based on ZIF-8 and ZIF-67(x Zn/Co-ZIFs).Results show that Co doping amount could mediate the transformation of the activation pathway of PMS over CoN/C.When Co doping amount was less than 10%,the constructed x Co-N/C/PMS system(x≤10%)was singlet oxygen-dominated reaction;however further increasing Co doping amount would lead to the generation and coexistence of sulfate radicals and high-valent cobalt,besides singlet oxygen.Furthermore,the nitrogen-coordinated Co(Co-NX)sites could serve as main catalytically active sites to generate singlet oxygen.While excess Co doping amount caused the formation of Co nanoparticles from which leached Co ions were responsible for the generation of sulfate radicals and high-valent cobalt.Compared to undoped N/C,Co doping could significantly enhance the catalytic performance.The 0.5%Co-N/C could achieve the optimum degradation(0.488 min^(-1))and mineralization abilities(78.4%)of sulfamethoxazole among the investigated Co-N/C catalysts,which was superior to most of previously reported catalysts.In addition,the application prospects of the two systems in different environmental scenarios(pH,inorganic anions and natural organic matter)were assessed and showed different degradation behaviors.This study provides a strategy to regulate the reactive species in PMS-based advanced oxidation process.展开更多
Reactive oxygen species(ROSs)in Fenton process are of great importance in treating contaminants in wastewater.It is crucial to understand their chemical properties,formation,and reaction mechanisms with contaminants.T...Reactive oxygen species(ROSs)in Fenton process are of great importance in treating contaminants in wastewater.It is crucial to understand their chemical properties,formation,and reaction mechanisms with contaminants.This review summarizes the reactive oxygen species in Fenton process,including hydroxyl radical(·OH),superoxide radical(O_(2)·-),singlet oxygen(1O_(2)),hydroperoxyl radical(HO_(2)·),and high-valent iron.·OH shows a trend to react with chemistry groups with abundant electrons through H-atom abstraction,radical adduct formation and single electron transfer.Electron transfer is discovered to be an important pathway when1O_(2)degrades organic pollutants.Ring-opening andβ-scission are proposed to be the possible ways of1O_(2)to certain contaminants.Proton abstraction,nucleophilic substitution,and single electron transfer are proposed to explain how O_(2)·-degrade pollutants.As the conjugated acid of O_(2)·-,radical adduct formation and H-atom abstraction are reported for the reaction mechanisms of hydroperoxyl radical.High-valent iron in Fenton,namely Fe(IV),reacts with certain pollutants via single-or two-electron transfer.This review is important for researchers to understand the ROSs produced in Fenton and how they react with pollutants.展开更多
Advanced oxidation processes have been widely studied for organic pollutants treatment in water,but the degradation performance of radical-dominated pathway was severely inhibited by the side reactions between the ani...Advanced oxidation processes have been widely studied for organic pollutants treatment in water,but the degradation performance of radical-dominated pathway was severely inhibited by the side reactions between the anions and radicals,especially in high salinity conditions.Here,a singlet oxygen(^(1)O_(2))-dominated non-radical process was developed for organic pollutants degradation in high salinity wastewater,with layered crednerite(CuMnO_(2))as catalysts and peroxymonosulfate(PMS)as oxidant.Based on the experiments and density functional theory calculations,^(1)O_(2)was the dominating reactive species and the constructed Cu-O-Mn with electron-deficient Mn captured electron from PMS promoting the generation of^(1)O_(2).The rapid degradation of bisphenol A(BPA)was achieved by CuMnO_(2)/PMS system,which was 5-fold and 21-fold higher than that in Mn_(2)O_(3)/PMS system and Cu_(2)O/PMS system.The CuMnO_(2)/PMS system shown prominent BPA removal performance under high salinity conditions,prominent PMS utilization efficiency,outstanding total organic carbon removal rate,wide range of applicable pH and good stability.This work unveiled that the^(1)O_(2)-dominated non-radical process of CuMnO_(2)/PMS system overcame the inhibitory effect of anions in high salinity conditions,which provided a promising technique to remove organic pollutants from high saline wastewater.展开更多
Reactive oxygen species are essential in photocatalytic water treatment.In this paper,Gd doped carbon nitride(CN)photocatalysts were prepared by simple thermal polymerization for the photocatalytic degradation of tetr...Reactive oxygen species are essential in photocatalytic water treatment.In this paper,Gd doped carbon nitride(CN)photocatalysts were prepared by simple thermal polymerization for the photocatalytic degradation of tetracycline under visible light irradiation.The photodegradation rate of 1.OGdCN is as high as 95%in 18 min,and the photocatalytic performance is much higher than that of CN.The improvement of photocatalytic performance is mainly attributed to the fact that Gd ion implantation directly provides active sites for oxygen activation and induces the formation of N vacancies.The results of characterizations show that the introduction of Gd in CN can improve the conversion ability of activated oxygen,carrier separation and energy band structure adjustment.Therefore,1.0GdCN photocatalyst can be employed for efficient photocatalytic synthesis of tetracycline.Furthermore,three ways of photocatalytic degradation of tetracycline were revealed by high performance liquid chromatographymass spectrometry.This work provides insights into the doping strategy of CN to improve the production of reactive oxygen species for environmental remediation.展开更多
Spin-orbit,charge-transfer intersystem crossing(SOCT-ISC)can directly overcome the disadvantages of the traditional heavy-atom effect and improve the generation efficiency of reactive oxygen species(ROS).Since orthogo...Spin-orbit,charge-transfer intersystem crossing(SOCT-ISC)can directly overcome the disadvantages of the traditional heavy-atom effect and improve the generation efficiency of reactive oxygen species(ROS).Since orthogonal molecular orbitals of donor-acceptor(D-A)pairs favor the SOCT-ISC transition,herein aza-borondipyrromethenes(aza-BODIPYs)with 1,7-di-anthracyl groups(An-azaBDP)was successfully prepared,owing to steric hindrance to produce a big dihedral angle between the two molecular orbital(MO)planes.Moreover,according to density functional theory(DFT)and time-dependent density functional theory(TDDFT),the energy difference between the S1-T1orbitals of An-aza BDP is small and more inclined towards ISC.An-aza BDP can effectively generate singlet oxygen under light irradiation.An-aza BDP with light irradiation can induce apoptosis in SW620 cells,and can serve as a potential candidate for the treatment of cancer cells and tumors.展开更多
Using hydrogen-bonded organic frameworks(HOFs)as photosensitizers to perform photocatalytic oxidation reactions under green and mild conditions is still a challenge for the application of HOFs materials.This study pre...Using hydrogen-bonded organic frameworks(HOFs)as photosensitizers to perform photocatalytic oxidation reactions under green and mild conditions is still a challenge for the application of HOFs materials.This study presents a novel approach that exploits HOFs to enhance the efficiency of photocatalytic oxidation for achieving visible light catalytic oxidation of styrene and its derivatives in the aqueous environment.By using 1,3,6,8-tetrakis(p-benzoic acid)pyrene(H_(4)TBAPy)as the monomer,a pyrene-based hydrogen-bonded organic framework(PFC-1)with a microporous structure was successfully prepared.Compared with monomer H_(4)TBAPy,due to the exciton effect and the interlayer confinement of HOFs,the singlet oxygen(1O_(2))production efficiency is significantly improved,which has great potential in photocatalytic oxidation reactions.Subsequently,the practicality of PFC-1 as a photocatalyst was studied,and the photocatalytic oxidation of styrene and its derivatives in aqueous solution was achieved under visible light with high catalytic efficiency,indicating that PFC-1 has significant potential to promote photocatalytic oxidation reactions under mild conditions.The utilization of HOFs as photosensitizers in this straightforward approach enables the attainment of green photocatalytic oxidation,hence expanding the potential applications of HOFs materials within the realm of photocatalysis.展开更多
Efficient yield of^(1)O_(2)determines the photocatalytic degradation rate of antibiotics,but the regulatory mechanism for^(1)O_(2)selective generation in O_(2)activation is still lacking exploration.Herein,oxygen vaca...Efficient yield of^(1)O_(2)determines the photocatalytic degradation rate of antibiotics,but the regulatory mechanism for^(1)O_(2)selective generation in O_(2)activation is still lacking exploration.Herein,oxygen vacancy(OV)modification strategy of MIL-125 was successfully practiced to promote the selective generation of^(1)O_(2).Multiple characterizations including extended X-ray absorption fine structure(EXAFS)and electron paramagnetic resonance spectra(EPR)confirmed the formation of oxygen vacancy in OV-MIL-125.The synthesized OV-MIL-125 exhibited greatly enhanced^(1)O_(2)selective(~90%)and antibiotics removal rate in water with high mineralization rate.Dynamics analysis of excitons by transient-steady state fluorescence and phosphorescence,transient absorption spectra(TAS)revealed that oxygen vacancy greatly enhanced the intersystem crossing(ISC)of singlet exciton,promoting triplet exciton generation.Density functional theoretical(DFT)calculation also proved the reduced gap of intersystem(ΔE_(ST))and the modulated highest occupied molecular orbital(HOMO)-lowest unoccupied molecular orbital(LUMO)population which was conducive to intersystem crossing process.Calculation of transition state further confirmed the lower energy barrier forπ^(*)orbital spin flip of O_(2)adsorbed on OV-MIL-125.The Dexter energy transfer involving triplet annihilation dominated the O_(2)activation mechanism to generate^(1)O_(2)instead of the charge transfer to generate O_(2)^(·-)which happened in MIL-125.This study provides new thinking for photocatalytic activation of molecular oxygen and is expected to guide the design of MOF-based catalysts for water treatment.展开更多
The development of supramolecular hosts which can efficiently encapsulate photosensitizers to improve the photodynamic efficacy holds great promise for cancer therapy.Here,we report two perylene diimide-based metallac...The development of supramolecular hosts which can efficiently encapsulate photosensitizers to improve the photodynamic efficacy holds great promise for cancer therapy.Here,we report two perylene diimide-based metallacages that can form stable host–vip complexes with planar conjugated molecules including polycyclic aromatic hydrocarbons and photosensitizers(hypocrellin A).Such host–vip complexation not only prevents the aggregation of photosensitizers in aqueous environments,but also offers fluorescence resonance energy transfer(FRET)from the metallacage to the photosensitizers to further improve the singlet oxygen generation(Φ_(Δ)=0.66).The complexes are further assembled with amphiphilic polymers,forming nanoparticles with improved stability for anticancer study.Both in vitro and in vivo studies indicate that the nanoparticles display excellent anticancer activities upon light irradiation,showing great potential for cancer photodynamic therapy.This study provides a straightforward and effective approach for enhancing the photosensitivity of conventional photosensitizers via host–vip complexation-based FRET,which will open a new avenue for host–vip chemistry-based supramolecular theranostics.展开更多
Sulfide oxidation under aerobic conditions can produce active oxygen for the transformation of organic pollutants in aquatic environments.However,the catalytic performance of transition metal-supported carbon material...Sulfide oxidation under aerobic conditions can produce active oxygen for the transformation of organic pollutants in aquatic environments.However,the catalytic performance of transition metal-supported carbon material on this process is poor understood.This study found that Co-loaded carbon nanotubes(CNTs)was able to realize the efficient aerobic transformation of antibiotic ciprofloxacin(CIP)by sulfide,with the pseudo-first order reaction rate constant improved from 0.013 h^(-1)without catalyst to 0.44–0.71 h^(-1)with 100 mg/L Co-loaded CNTs.Singlet oxygen(^(1)O_(2))was the main active specie playing key roles in the process of CIP aerobic transformation with presence of Co-loaded CNTs.Mechanism studies indicated that the excellent electron transfer ability of Co-loaded CNTs might play an important role to promote the electron transfer and facilitate the formation of intermediate H_(2)O_(2)and^(1)O_(2).Additionally,the Co-loaded CNTs/sulfide system effectively reduced the acute toxicity of organic pollutant,and Co-loaded CNTs showed remarkable cycling stability and negligible leaching.This study gives a better understanding for the Co-loaded CNTs mediated aerobic antibiotics transformation by sulfide,and provide a reference for the application of Co-loaded carbon materials on organics aerobic transformation by sulfide.展开更多
To overcome the conflict between the long-wavelength excitation and high singlet oxygen quantum yield of photosensitizers,we conjugated a two-photon fluorophore,tetrahydroquinoxaline coumarin(TQ),and an efficient phot...To overcome the conflict between the long-wavelength excitation and high singlet oxygen quantum yield of photosensitizers,we conjugated a two-photon fluorophore,tetrahydroquinoxaline coumarin(TQ),and an efficient photodynamic therapeutic agent,benzo[a]phenothiazinium(NBS-NH_(2)),through a hexamethylene linker to build a two-photon photosensitizer,TQ-NBS.In TQ-NBS,TQ served as an energy donor and NBS-NH_(2) acted as an energy acceptor;and TQ-NBS was a F?rster resonance energy transfer(FRET)cassette with a 92.8%efficiency.The large two-photon absorption cross-section of TQ allowed photosensitizer TQ-NBS to work in a 900 nm two-photon excitation(TPE)mode,which greatly benefited the deep tissue penetration in PDT treatment.Meanwhile,the excellent phototoxicity and near-infrared fluorescence of NBS-NH2was kept in TQ-NBS under a TPE mode via a FRET process.Photosensitizer TQ-NBS exhibited a high phototoxic efficacy in living cells and tumor-bearing mice.展开更多
X-ray excited photodynamic therapy(X-PDT)is the bravo answer of photodynamic therapy(PDT)for deep-seated tumors,as it employs X-ray as the irradiation source to overcome the limitation of light penetration depth.Howev...X-ray excited photodynamic therapy(X-PDT)is the bravo answer of photodynamic therapy(PDT)for deep-seated tumors,as it employs X-ray as the irradiation source to overcome the limitation of light penetration depth.However,high X-ray irradiation dose caused organ lesions and side effects became the major barrier to X-PDT application.To address this issue,this work employed a classic-al co-precipitation reaction to synthesize NaLuF_(4):15%Tb^(3+)(NLF)with an average particle size of(23.48±0.91)nm,which was then coupled with the photosensitizer merocyanine 540(MC540)to form the X-PDT system NLF-MC540 with high production of singlet oxygen.The system could induce antitumor efficacy to about 24%in relative low dose X-ray irradiation range(0.1-0.3 Gy).In vivo,when NLF-MC540 irradiated by 0.1 Gy X-ray,the tumor inhibition percentage reached 89.5%±5.7%.The therapeutic mechanism of low dose X-PDT was found.A significant increase of neutrophils in serum was found on the third day after X-PDT.By immunohistochemical staining of tumor sections,the Ly6G^(+),CD8^(+),and CD11c^(+)cells infiltrated in the tumor microenvironment were studied.Utilizing the bilat-eral tumor model,the NLF-MC540 with 0.1 Gy X-ray irradiation could inhibit both the primary tumor and the distant tumor growth.De-tected by enzyme linked immunosorbent assay(ELISA),two cytokines IFN-γand TNF-αin serum were upregulated 7 and 6 times than negative control,respectively.Detected by enzyme linked immune spot assay(ELISPOT),the number of immune cells attributable to the IFN-γand TNF-αlevels in the group of low dose X-PDT were 14 and 6 times greater than that in the negative control group,respectively.Thus,it conclude that low dose X-PDT system could successfully upregulate the levels of immune cells,stimulate the secretion of cy-tokines(especially IFN-γand TNF-α),activate antitumor immunity,and finally inhibit colon tumor growth.展开更多
Photodynamic therapy(PDT)has been increasingly used in the clinical treatment of neoplastic,inflammatory and infectious skin diseases.However,the generation of reactive oxygen species(ROS)may induce undesired side eff...Photodynamic therapy(PDT)has been increasingly used in the clinical treatment of neoplastic,inflammatory and infectious skin diseases.However,the generation of reactive oxygen species(ROS)may induce undesired side effects in normal tissue surrounding the treatment lesion,which is a big challenge for the clinical application of PDT.To date,(–)-Epigallocatechin gallate(EGCG)has been widely proposed as an antiangiogenic and antitumor agent for the protection of normal tissue from ROS-mediated oxidative damage.This study evaluates the regulation ability of EGCG for photodynamic damage of blood vessels during hematoporphyrin monomethyl ether(Hemoporfin)-mediated PDT.The quenching rate constants of EGCG for the triplet-state Hemoporfin and photosensitized 1O2 generation are determined to be 6.8×10^(8)M^(−1)S^(−1),respectively.The vasoconstriction of blood vessels in the protected region treated with EGCG hydrogel after PDT is lower than that of the control region treated with pure hydrogel,suggesting an efficiently reduced photodamage of Hemoporfin for blood vessels treated with EGCG.This study indicates that EGCG is an efficient quencher for triplet-state Hemoporfin and 1O2,and EGCG could be potentially used to reduce the undesired photodamage of normal tissue in clinical PDT.展开更多
基金supported by the National Key Research and Development Program of China(Grant Nos.2023YFB2804700,2021YFA1202000 and 2021YFE0205800)National Natural Science Foundation of China(Grant Nos.12174292,62222507,and 62175101)+1 种基金Natural Science Foundation of Jiangsu Province(No.BK20212004)Fundamental Research Funds for the Central Universities(2042024kf1005).
文摘Conventional hyperspectral cameras cascade lenses and spectrometers to acquire the spectral datacube,which forms the fundamental framework for hyperspectral imaging.However,this cascading framework involves tradeoffs among spectral and imaging performances when the system is driven toward miniaturization.Here,we propose a spectral singlet lens that unifies optical imaging and computational spectrometry functions,enabling the creation of minimalist,miniaturized and high-performance hyperspectral cameras.As a paradigm,we capitalize on planar liquid crystal optics to implement the proposed framework,with each liquid-crystal unit cell acting as both phase modulator and electrically tunable spectral filter.Experiments with various targets show that the resulting millimeter-scale hyperspectral camera exhibits both high spectral fidelity(>95%)and high spatial resolutions(~1.7 times the diffraction limit).The proposed“two-in-one”framework can resolve the conflicts between spectral and imaging resolutions,which paves a practical pathway for advancing hyperspectral imaging systems toward miniaturization and portable applications.
基金supported by National Natural Science Foundation of China(Nos.32121005,22225805,22308101,and 32394001)Shanghai Science and Technology Innovation Action Plan(No.23J21901600)+2 种基金Innovation Program of Shanghai Municipal Education Commission,Shanghai Frontier Science Research Base of Optogenetic Techniques for Cell Metabolism(Shanghai Municipal Education Commission,No.2021 Sci&Tech 03-28)the China Postdoctoral Science Foundation(No.2021M701199)Natural Science Foundation of Shanghai(No.23ZR1416600).
文摘Singlet oxygen(^(1)O_(2)),as the primary reactive oxygen species in photodynamic therapy,can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment.However,monitoring endogenous^(1)O_(2)is greatly challenging due to its extremely short lifetime and high reactivity in biological condition.Herein,we report an ultra-high signal-to-ratio near-infrared chemiluminescent probe(DCMCy)for the precise detection of endogenous^(1)O_(2)during photodynamic therapy(PDT).The methoxy moiety was removed from enolether unit in DCM-Cy to suppress the potential self-photooxidation reaction,thus greatly eliminating the photoinduced background signals during PDT.Additionally,the compact cyclobutane modification of DCM-Cy resulted in a significant 6-fold increase in cell permeability compared to conventional adamantane-dioxane probes.Therefore,our“step-by-step”strategy for DCM-Cy addressed the limitations of traditional chemiluminescent(CL)probes for^(1)O_(2),enabling effectively tracking of endogenous^(1)O_(2)level changes in living cells,pathogenic bacteria and mice in PDT.
基金Supported by the National Natural Science Foundation of China,No.32271278 and No.31971170.
文摘Different from reversible agonist-stimulated receptor activation,singlet oxygen oxidation activates permanently G protein-coupled receptor(GPCR)cholecystokinin 1(CCK1R)in type II photodynamic action,with soluble photosensitizer dyes(sulphonated aluminum phthalocyanine,λmax 675 nm)or genetically encoded protein photosensitizers(KillerRedλmax 585 nm;mini singlet oxygen generatorλmax 450 nm),together with a pulse of light(37 mW/cm2,1-2 minutes).Three lines of evidence shed light on the mechanism of GPCR activated by singlet oxygen(GPCR-ABSO):(1)CCK1R is quantitatively converted from dimer to monomer;(2)Transmembrane domain 3,a pharmacophore for permanent photodynamic CCK1R activation,can be transplanted to non-susceptible M3 acetylcholine receptor;and(3)Larger size of disordered region in intracellular loop 3 correlates with higher sensitivity to photodynamic CCK1R activation.GPCR-ABSO will add to the arsenal of engineered designer GPCR such as receptors activated solely by synthetic ligands and designer receptors exclusively activated by designer drugs,but show some clear advantages:Enhanced selectivity(double selectivity of localized photosensitizer and light illumination),long-lasting activation with no need for repeated drug administration,antagonist-binding site remains intact when needed,ease to apply to multiple GPCR.This type of permanent photodynamic activation may be applied to functional proteins other than GPCR.
基金the support received from the National Natural Science Foundation of China(No.51908485)the Central Guidance on Local Science and Technology Development Fund of Hebei Province(Nos.246Z3603G and 226Z3603G)。
文摘Common activations of sulfite(S(Ⅳ))-based advanced oxidation processes(AOPs)utilized metal ions and oxides as catalysts,which are constrained by challenges in catalyst recovery,inadequate stability,and susceptibility to secondary pollution in application.Calcium sulfite(CaSO_(3)),one of the byproducts of flue gas desulfurization,is of interest in AOPs because of its ability to slowly release S(Ⅳ),low toxicity,and costeffectiveness.Therefore,a heterogenous activator,molybdenum carbide(Mo_(2)C)was selected to stimulate Ca SO3for typical antibiotic elimination.Benefiting from the dissociation form of HSO_(3^(-))from CaSO_(3)and improved electron transfer of Mo_(2)C at pH 6,the simulated target metronidazole(MTZ)can be removed by 85.65%with rate constant of 0.02424 min^(-1)under near-neutral circumstance.The combining determinations of quenching test,electron spin resonance spectrum,and reactive species probe demonstrated singlet oxygen(^(1)O_(2))and sulfate radicals played leading role for MTZ decontamination.Characterization and theoretical calculation suggested the alteration of Mo valence state drove the activation of S(Ⅳ),and revealed that dissolved oxygen promoted the adsorption of HSO_(3^(-))on the surface of Mo_(2)C,then facilitating production of^(1)O_(2).The favorable stability and applicability for Mo_(2)C/CaSO_(3)process indicated an applied prospect in actual pharmaceutical wastewater.
基金supported by the Natural Science Foundation of Shanghai(No.23ZR1401300)the National Natural Science Foundation of China(No.52170068).
文摘Singlet oxygen(^(1)O_(2)),as an electrophilic oxidant,is essential for the selective water decontamination of pollutants from water.Herein,we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles(CoFeCNT)to selectively facilitate the electrochemical activation of O_(2)to^(1)O_(2).Benefiting from the prominently featured bimetal active sites of CoFeCNT,nearly complete production of^(1)O_(2)is achieved by the electrocatalytic activation of O_(2).Additionally,the proposed system exhibits a consistent pollutant removal efficiency>90%in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance,highlighting the dependable stability of the system for practical applications.The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor.This work provides a molecular level understanding of the oxygen reduction reaction,showing promising potential for the selective removal of emerging organic contaminants from water.
基金supported by the National Natural Science Foundation of China(No.U21A20293).
文摘Harnessing the redox potential of biochar to activate airborne O_(2)for contaminant removal is challenging.In this study,ferrihydrite(Fh)modified the boron(B),nitrogen(N)co-doped biochars(BCs)composites(Fh/B(n)NC)were developed for enhancing the degradation of a model pollutant,tetracycline(TC),merely by airborne O_(2).Fh/B(3)NC showed excellent O_(2)activation activity for efficient TC degradation with a apparent TC degradation rate of 5.54,6.88,and 22.15 times that of B(3)NC,Fh,and raw BCs,respectively,where 1O_(2)and H_(2)O_(2)were identified as the dominant ROS for TC degradation.The B incorporation into the carbon lattice of Fh/B(3)NC promoted the generation of electron donors,sp2 C and the reductive B species,hence boosting Fe(III)reduction and 1O_(2)generation.O_(2)adsorption was enhanced due to the positively charged adsorption sites(C-B+and N-C+).And 1O_(2)was generated via Fe(II)catalyzed low-efficient successive one-electron transfer(O_(2)→O_(2)·−→1O_(2),H_(2)O_(2)),as well as biochar catalyzed high-efficient two-electron transfer(O_(2)→H_(2)O_(2)→1O_(2))that does not involve.O_(2)−as the intermediate.Moreover,Fh/B,N co-doped biochar showed a wide pH range,remarkable anti-interference capabilities,and effective detoxification.These findings shed new light on the development of environmentally benign BCs materials capable of degradading organic pollutants.
文摘The authors regret<During the submission process,Hongxiang Zhang and Honggen Peng served as the first and the second corresponding author,respectively.The original manuscript submitted for this paper also listed two co-corresponding authors(Hongxiang Zhang and Honggen Peng).But the corresponding author of Honggen Peng was omitted in the final published manuscript.So,we apply to designate Honggen Peng(penghonggen@ncu.edu.cn)as the second co-corresponding author and the corresponding unit is“a,b">.
文摘Reactive oxygen species(ROS),including singlet oxygen(^(1)O_(2)),hydroxyl radicals(·OH),and superoxide anions(O_(2)^(·-)),are highly reactive molecules that play central roles in many chemical,biological,and environmental processes due to their strong oxidative power[1].Generating ROS in a controlled manner under mild conditions is essential for achieving selective oxidation reactions.Light-driven methods are especially appealing for this purpose,as they offer precise control over where and when ROS are produced.
基金supported by the National Natural Science Foundation of China(Nos.52100081,51978178,and 51521006)the Department of Science and Technology of Guangdong Province of China(Nos.2021A1515011797,2023A1515012062,2019A1515012044,and 2022A1515010226)+4 种基金the Department of Education of Guangdong Province of China(No.2021KTSCX078)the Program for Innovative Research Teams of Guangdong Higher Education Institutes of China(No.2021KCXTD043)Maoming Municipal Department of Science and Technology of Guangdong Province of China(No.2018S0013)the Key Laboratory of Petrochemical Pollution Control of Guangdong Higher Education Institutes(No.2017KSYS004)the Startup Fund of GDUPT(Nos.2018rc63 and 2020rc041)。
文摘Switching the reaction routes in peroxymonosulfate(PMS)-based advanced oxidation processes have attracted much attention but remain challenging.Herein,a series of Co-N/C catalysts with different compositions and structures were prepared by using bimetallic zeolitic imidazolate frameworks based on ZIF-8 and ZIF-67(x Zn/Co-ZIFs).Results show that Co doping amount could mediate the transformation of the activation pathway of PMS over CoN/C.When Co doping amount was less than 10%,the constructed x Co-N/C/PMS system(x≤10%)was singlet oxygen-dominated reaction;however further increasing Co doping amount would lead to the generation and coexistence of sulfate radicals and high-valent cobalt,besides singlet oxygen.Furthermore,the nitrogen-coordinated Co(Co-NX)sites could serve as main catalytically active sites to generate singlet oxygen.While excess Co doping amount caused the formation of Co nanoparticles from which leached Co ions were responsible for the generation of sulfate radicals and high-valent cobalt.Compared to undoped N/C,Co doping could significantly enhance the catalytic performance.The 0.5%Co-N/C could achieve the optimum degradation(0.488 min^(-1))and mineralization abilities(78.4%)of sulfamethoxazole among the investigated Co-N/C catalysts,which was superior to most of previously reported catalysts.In addition,the application prospects of the two systems in different environmental scenarios(pH,inorganic anions and natural organic matter)were assessed and showed different degradation behaviors.This study provides a strategy to regulate the reactive species in PMS-based advanced oxidation process.
基金supported by the National Natural Science Foundation of China(Nos.22176102 and 21806081)Natural Science Foundation of Tianjin(No.19JCQNJC07900)+2 种基金Fundamental Research Funds for the Central UniversitiesNatural Science Foundation of Jiangsu Province in China(No.BK20230410)Natural Science Research of Jiangsu Higher Education Institution of China(No.23KJB610010)。
文摘Reactive oxygen species(ROSs)in Fenton process are of great importance in treating contaminants in wastewater.It is crucial to understand their chemical properties,formation,and reaction mechanisms with contaminants.This review summarizes the reactive oxygen species in Fenton process,including hydroxyl radical(·OH),superoxide radical(O_(2)·-),singlet oxygen(1O_(2)),hydroperoxyl radical(HO_(2)·),and high-valent iron.·OH shows a trend to react with chemistry groups with abundant electrons through H-atom abstraction,radical adduct formation and single electron transfer.Electron transfer is discovered to be an important pathway when1O_(2)degrades organic pollutants.Ring-opening andβ-scission are proposed to be the possible ways of1O_(2)to certain contaminants.Proton abstraction,nucleophilic substitution,and single electron transfer are proposed to explain how O_(2)·-degrade pollutants.As the conjugated acid of O_(2)·-,radical adduct formation and H-atom abstraction are reported for the reaction mechanisms of hydroperoxyl radical.High-valent iron in Fenton,namely Fe(IV),reacts with certain pollutants via single-or two-electron transfer.This review is important for researchers to understand the ROSs produced in Fenton and how they react with pollutants.
基金supported by the Open Fund of Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling (No.2020B121201003)the National Natural Science Foundation of China (Nos.21876099,22106088,and 22276110)+1 种基金the Key Research&Developmental Program of Shandong Province (No.2021CXGC011202)the Fundamental Research Funds of Shandong University (No.zy202102)。
文摘Advanced oxidation processes have been widely studied for organic pollutants treatment in water,but the degradation performance of radical-dominated pathway was severely inhibited by the side reactions between the anions and radicals,especially in high salinity conditions.Here,a singlet oxygen(^(1)O_(2))-dominated non-radical process was developed for organic pollutants degradation in high salinity wastewater,with layered crednerite(CuMnO_(2))as catalysts and peroxymonosulfate(PMS)as oxidant.Based on the experiments and density functional theory calculations,^(1)O_(2)was the dominating reactive species and the constructed Cu-O-Mn with electron-deficient Mn captured electron from PMS promoting the generation of^(1)O_(2).The rapid degradation of bisphenol A(BPA)was achieved by CuMnO_(2)/PMS system,which was 5-fold and 21-fold higher than that in Mn_(2)O_(3)/PMS system and Cu_(2)O/PMS system.The CuMnO_(2)/PMS system shown prominent BPA removal performance under high salinity conditions,prominent PMS utilization efficiency,outstanding total organic carbon removal rate,wide range of applicable pH and good stability.This work unveiled that the^(1)O_(2)-dominated non-radical process of CuMnO_(2)/PMS system overcame the inhibitory effect of anions in high salinity conditions,which provided a promising technique to remove organic pollutants from high saline wastewater.
基金Project supported by the National Key Research and Development Program of China(2022YFF1100804)Natural Science Foundation of Xinjiang Uygur Auonomous Region(2022D01C456)+3 种基金Guangdong Basic and Applied Basic Research Foundation(2023A1515011736,2021A1515010671)Guangdong Province Scientific Research Platform Project(2022ZDZX4046,2023ZDZX4052,2020KTSCX135)Guangdong Province Specialized Scientific Research Fund Projects(20192019B121201004)High Level Talents Introduction Project of"Pearl River Talent Plan"in Guangdong Province(2019CX01L308)。
文摘Reactive oxygen species are essential in photocatalytic water treatment.In this paper,Gd doped carbon nitride(CN)photocatalysts were prepared by simple thermal polymerization for the photocatalytic degradation of tetracycline under visible light irradiation.The photodegradation rate of 1.OGdCN is as high as 95%in 18 min,and the photocatalytic performance is much higher than that of CN.The improvement of photocatalytic performance is mainly attributed to the fact that Gd ion implantation directly provides active sites for oxygen activation and induces the formation of N vacancies.The results of characterizations show that the introduction of Gd in CN can improve the conversion ability of activated oxygen,carrier separation and energy band structure adjustment.Therefore,1.0GdCN photocatalyst can be employed for efficient photocatalytic synthesis of tetracycline.Furthermore,three ways of photocatalytic degradation of tetracycline were revealed by high performance liquid chromatographymass spectrometry.This work provides insights into the doping strategy of CN to improve the production of reactive oxygen species for environmental remediation.
基金supported by the National Natural Science Foundation of China(Nos.22078201,U1908202)Liaoning&Shenyang Key Laboratory of Functional Dye and Pigment(Nos.2021JH13/10200018,21–104–0–23)。
文摘Spin-orbit,charge-transfer intersystem crossing(SOCT-ISC)can directly overcome the disadvantages of the traditional heavy-atom effect and improve the generation efficiency of reactive oxygen species(ROS).Since orthogonal molecular orbitals of donor-acceptor(D-A)pairs favor the SOCT-ISC transition,herein aza-borondipyrromethenes(aza-BODIPYs)with 1,7-di-anthracyl groups(An-azaBDP)was successfully prepared,owing to steric hindrance to produce a big dihedral angle between the two molecular orbital(MO)planes.Moreover,according to density functional theory(DFT)and time-dependent density functional theory(TDDFT),the energy difference between the S1-T1orbitals of An-aza BDP is small and more inclined towards ISC.An-aza BDP can effectively generate singlet oxygen under light irradiation.An-aza BDP with light irradiation can induce apoptosis in SW620 cells,and can serve as a potential candidate for the treatment of cancer cells and tumors.
基金financial support from the National Natural Science Foundation of China(No.52205210)the Natural Science Foundation of Shandong Province(Nos.ZR2020MB018,ZR2022QE033 and ZR2021QB049)。
文摘Using hydrogen-bonded organic frameworks(HOFs)as photosensitizers to perform photocatalytic oxidation reactions under green and mild conditions is still a challenge for the application of HOFs materials.This study presents a novel approach that exploits HOFs to enhance the efficiency of photocatalytic oxidation for achieving visible light catalytic oxidation of styrene and its derivatives in the aqueous environment.By using 1,3,6,8-tetrakis(p-benzoic acid)pyrene(H_(4)TBAPy)as the monomer,a pyrene-based hydrogen-bonded organic framework(PFC-1)with a microporous structure was successfully prepared.Compared with monomer H_(4)TBAPy,due to the exciton effect and the interlayer confinement of HOFs,the singlet oxygen(1O_(2))production efficiency is significantly improved,which has great potential in photocatalytic oxidation reactions.Subsequently,the practicality of PFC-1 as a photocatalyst was studied,and the photocatalytic oxidation of styrene and its derivatives in aqueous solution was achieved under visible light with high catalytic efficiency,indicating that PFC-1 has significant potential to promote photocatalytic oxidation reactions under mild conditions.The utilization of HOFs as photosensitizers in this straightforward approach enables the attainment of green photocatalytic oxidation,hence expanding the potential applications of HOFs materials within the realm of photocatalysis.
基金supported by the National Natural Science Foundation of China(Nos.22276086 and 21976078)the Natural Science Foundation of Jiangxi Province(Nos.20202ACB213001 and20232BAB213029)。
文摘Efficient yield of^(1)O_(2)determines the photocatalytic degradation rate of antibiotics,but the regulatory mechanism for^(1)O_(2)selective generation in O_(2)activation is still lacking exploration.Herein,oxygen vacancy(OV)modification strategy of MIL-125 was successfully practiced to promote the selective generation of^(1)O_(2).Multiple characterizations including extended X-ray absorption fine structure(EXAFS)and electron paramagnetic resonance spectra(EPR)confirmed the formation of oxygen vacancy in OV-MIL-125.The synthesized OV-MIL-125 exhibited greatly enhanced^(1)O_(2)selective(~90%)and antibiotics removal rate in water with high mineralization rate.Dynamics analysis of excitons by transient-steady state fluorescence and phosphorescence,transient absorption spectra(TAS)revealed that oxygen vacancy greatly enhanced the intersystem crossing(ISC)of singlet exciton,promoting triplet exciton generation.Density functional theoretical(DFT)calculation also proved the reduced gap of intersystem(ΔE_(ST))and the modulated highest occupied molecular orbital(HOMO)-lowest unoccupied molecular orbital(LUMO)population which was conducive to intersystem crossing process.Calculation of transition state further confirmed the lower energy barrier forπ^(*)orbital spin flip of O_(2)adsorbed on OV-MIL-125.The Dexter energy transfer involving triplet annihilation dominated the O_(2)activation mechanism to generate^(1)O_(2)instead of the charge transfer to generate O_(2)^(·-)which happened in MIL-125.This study provides new thinking for photocatalytic activation of molecular oxygen and is expected to guide the design of MOF-based catalysts for water treatment.
基金supported by the National Natural Science Foundation of China(22171219 and 22222112)Innovation Talent Promotion Plan of Shaanxi Province for Science and Technology Innovation Team(2023-CX-TD-51)+2 种基金Key Laboratory Fund for Plasma Physics(6142A04210108)the Interdisciplinary Training Program for Doctoral Candidate of Xi’an Jiaotong University(IDT2105)National Natural Science Foundation NSAF Joint Fund(U2230112).
文摘The development of supramolecular hosts which can efficiently encapsulate photosensitizers to improve the photodynamic efficacy holds great promise for cancer therapy.Here,we report two perylene diimide-based metallacages that can form stable host–vip complexes with planar conjugated molecules including polycyclic aromatic hydrocarbons and photosensitizers(hypocrellin A).Such host–vip complexation not only prevents the aggregation of photosensitizers in aqueous environments,but also offers fluorescence resonance energy transfer(FRET)from the metallacage to the photosensitizers to further improve the singlet oxygen generation(Φ_(Δ)=0.66).The complexes are further assembled with amphiphilic polymers,forming nanoparticles with improved stability for anticancer study.Both in vitro and in vivo studies indicate that the nanoparticles display excellent anticancer activities upon light irradiation,showing great potential for cancer photodynamic therapy.This study provides a straightforward and effective approach for enhancing the photosensitivity of conventional photosensitizers via host–vip complexation-based FRET,which will open a new avenue for host–vip chemistry-based supramolecular theranostics.
基金the National Natural Science Foundation of China(Nos.52200186,U19A20108,52025101 and 52070025)China Postdoctoral Science Foundation(No.2021M693720)Chongqing Municipal Education Commission(No.KJCX2020001)for financially supporting this study。
文摘Sulfide oxidation under aerobic conditions can produce active oxygen for the transformation of organic pollutants in aquatic environments.However,the catalytic performance of transition metal-supported carbon material on this process is poor understood.This study found that Co-loaded carbon nanotubes(CNTs)was able to realize the efficient aerobic transformation of antibiotic ciprofloxacin(CIP)by sulfide,with the pseudo-first order reaction rate constant improved from 0.013 h^(-1)without catalyst to 0.44–0.71 h^(-1)with 100 mg/L Co-loaded CNTs.Singlet oxygen(^(1)O_(2))was the main active specie playing key roles in the process of CIP aerobic transformation with presence of Co-loaded CNTs.Mechanism studies indicated that the excellent electron transfer ability of Co-loaded CNTs might play an important role to promote the electron transfer and facilitate the formation of intermediate H_(2)O_(2)and^(1)O_(2).Additionally,the Co-loaded CNTs/sulfide system effectively reduced the acute toxicity of organic pollutant,and Co-loaded CNTs showed remarkable cycling stability and negligible leaching.This study gives a better understanding for the Co-loaded CNTs mediated aerobic antibiotics transformation by sulfide,and provide a reference for the application of Co-loaded carbon materials on organics aerobic transformation by sulfide.
基金supported by National Key Research and Development Program of China(No.2022YFA1207600)National Natural Science Foundation of China(Nos.22178395,62175262 and 62005294)。
文摘To overcome the conflict between the long-wavelength excitation and high singlet oxygen quantum yield of photosensitizers,we conjugated a two-photon fluorophore,tetrahydroquinoxaline coumarin(TQ),and an efficient photodynamic therapeutic agent,benzo[a]phenothiazinium(NBS-NH_(2)),through a hexamethylene linker to build a two-photon photosensitizer,TQ-NBS.In TQ-NBS,TQ served as an energy donor and NBS-NH_(2) acted as an energy acceptor;and TQ-NBS was a F?rster resonance energy transfer(FRET)cassette with a 92.8%efficiency.The large two-photon absorption cross-section of TQ allowed photosensitizer TQ-NBS to work in a 900 nm two-photon excitation(TPE)mode,which greatly benefited the deep tissue penetration in PDT treatment.Meanwhile,the excellent phototoxicity and near-infrared fluorescence of NBS-NH2was kept in TQ-NBS under a TPE mode via a FRET process.Photosensitizer TQ-NBS exhibited a high phototoxic efficacy in living cells and tumor-bearing mice.
基金funded by the National Natural Science Foundation of China (Nos.81771972,52171243,and 52371256)the National Key Research and Development Program of China (No.2017YFC0107405).
文摘X-ray excited photodynamic therapy(X-PDT)is the bravo answer of photodynamic therapy(PDT)for deep-seated tumors,as it employs X-ray as the irradiation source to overcome the limitation of light penetration depth.However,high X-ray irradiation dose caused organ lesions and side effects became the major barrier to X-PDT application.To address this issue,this work employed a classic-al co-precipitation reaction to synthesize NaLuF_(4):15%Tb^(3+)(NLF)with an average particle size of(23.48±0.91)nm,which was then coupled with the photosensitizer merocyanine 540(MC540)to form the X-PDT system NLF-MC540 with high production of singlet oxygen.The system could induce antitumor efficacy to about 24%in relative low dose X-ray irradiation range(0.1-0.3 Gy).In vivo,when NLF-MC540 irradiated by 0.1 Gy X-ray,the tumor inhibition percentage reached 89.5%±5.7%.The therapeutic mechanism of low dose X-PDT was found.A significant increase of neutrophils in serum was found on the third day after X-PDT.By immunohistochemical staining of tumor sections,the Ly6G^(+),CD8^(+),and CD11c^(+)cells infiltrated in the tumor microenvironment were studied.Utilizing the bilat-eral tumor model,the NLF-MC540 with 0.1 Gy X-ray irradiation could inhibit both the primary tumor and the distant tumor growth.De-tected by enzyme linked immunosorbent assay(ELISA),two cytokines IFN-γand TNF-αin serum were upregulated 7 and 6 times than negative control,respectively.Detected by enzyme linked immune spot assay(ELISPOT),the number of immune cells attributable to the IFN-γand TNF-αlevels in the group of low dose X-PDT were 14 and 6 times greater than that in the negative control group,respectively.Thus,it conclude that low dose X-PDT system could successfully upregulate the levels of immune cells,stimulate the secretion of cy-tokines(especially IFN-γand TNF-α),activate antitumor immunity,and finally inhibit colon tumor growth.
基金supported by the National Natural Science Foundation of China(Grant Nos.61935004,62227823 and 61805040)the Beijing Institute of Technology Research Fund Program for Young Scholars(XSQD-202123001).
文摘Photodynamic therapy(PDT)has been increasingly used in the clinical treatment of neoplastic,inflammatory and infectious skin diseases.However,the generation of reactive oxygen species(ROS)may induce undesired side effects in normal tissue surrounding the treatment lesion,which is a big challenge for the clinical application of PDT.To date,(–)-Epigallocatechin gallate(EGCG)has been widely proposed as an antiangiogenic and antitumor agent for the protection of normal tissue from ROS-mediated oxidative damage.This study evaluates the regulation ability of EGCG for photodynamic damage of blood vessels during hematoporphyrin monomethyl ether(Hemoporfin)-mediated PDT.The quenching rate constants of EGCG for the triplet-state Hemoporfin and photosensitized 1O2 generation are determined to be 6.8×10^(8)M^(−1)S^(−1),respectively.The vasoconstriction of blood vessels in the protected region treated with EGCG hydrogel after PDT is lower than that of the control region treated with pure hydrogel,suggesting an efficiently reduced photodamage of Hemoporfin for blood vessels treated with EGCG.This study indicates that EGCG is an efficient quencher for triplet-state Hemoporfin and 1O2,and EGCG could be potentially used to reduce the undesired photodamage of normal tissue in clinical PDT.
