Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O...Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O)]·DMA}n(1)and{[Cd(hfdp)(ndc)(H_(2)O)]·DMA}_(n)(2),respectively(DMA=N,N‑dimethylacetamide).Single‑crystal X‑ray diffraction analyses showed that both complexes 1 and 2 contain similar structures.Topological analysis indicates that complexes 1 and 2 have a{44·62}planar structure.In addition,both complexes reveal good thermal stability and fluorescence sensing performance.They exhibited good sensitivity and selectivity towards 2,4,6‑trinitrophenol(TNP)by fluorescent quenching.The limits of detection of 1 and 2 for TNP were 0.107 and 0.327μmol·L^(-1),respectively.CCDC:2475515,1;2475516,2.展开更多
In this study,using 3,5‑di(3′,5′‑dicarboxylphenyl)‑1H‑1,2,4‑triazole(H4L)as ligands,a gadolinia‑based organic framework complex{[GdNa(L)(H_(2)O)3]·2H_(2)O}_(n)(Gd‑Na‑MOF)was successfully designed and synthesize...In this study,using 3,5‑di(3′,5′‑dicarboxylphenyl)‑1H‑1,2,4‑triazole(H4L)as ligands,a gadolinia‑based organic framework complex{[GdNa(L)(H_(2)O)3]·2H_(2)O}_(n)(Gd‑Na‑MOF)was successfully designed and synthesized by hydrothermal method.The structure and properties were systematically characterized and tested by techniques such as single‑crystal X‑ray diffraction,powder X‑ray diffraction,thermogravimetric analysis,infrared spectroscopy,and fluorescence spectroscopy.The results indicate that this complex has a unique 3D structure,excellent thermal stability,and outstanding luminescent performance.Based on its luminescent properties,a polymer‑embedding method was employed to fabricate the Gd‑Na‑MOF into a flexible,washable composite fluorescent film,Gd‑Na‑MOF@PMMA/BMA(PMMA=polymethyl methacrylate,BMA=butyl methacrylate).This fluorescent film exhibited highly sensitive recognition capability for tyramine,with a low detection limit of 1.66μmol·L^(-1).It was used for the detection of tyramine in bananas,with a recovery rate of 96.92%‑100.26%.CCDC:2466949.展开更多
Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'...Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'-bipyridine]were successfully synthesized by the volatilization of the solution at room temperature.The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology.The results showed that the complexes all have a binuclear structure,and the structures contain free ethanol molecules.Moreover,the coordination number of the central metal of each structural unit is eight.Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures.After conducting a systematic study on the luminescence properties of complexes 1-4,their emission and excitation spectra were obtained.Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms,respectively.The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system,and their corre sponding luminescent regions cover the yellow light,red light,green light,and orange-red light bands,respectively.Within the temperature range of 299.15-1300 K,the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology.The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas,3D infrared spectroscopy,and ion fragment information detected by mass spectrometry.The specific decomposition path is as follows:firstly,free ethanol molecules and neutral ligands are removed,and finally,acidic ligands are released;the final product is the corresponding metal oxide.CCDC:2430420,1;2430422,2;2430419,3;2430424,4;2430421,5;2430423,6.展开更多
Herein,antibacterial silver‑doped fluorescent carbon dots(Ag‑CDs)were synthesized through a stepwise hydrothermal method,with polyethyleneimine(PEI),citric acid(CA),and silver nitrate(AgNO3)serving as precursors.The a...Herein,antibacterial silver‑doped fluorescent carbon dots(Ag‑CDs)were synthesized through a stepwise hydrothermal method,with polyethyleneimine(PEI),citric acid(CA),and silver nitrate(AgNO3)serving as precursors.The applicability and antimicrobial efficacy of these nanomaterials were systematically investigated for metal ion sensing.Experimental evidence demonstrated that the Ag‑CDs exhibited a pronounced fluorescence quenching response toward ferric ions(Fe^(3+)),enabling their quantitative determination via a linear concentration‑dependent relationship.These Ag‑CDs exhibited significant inhibitory effects on biofilm growth and disruption for both Escherichia coli and Staphylococcus aureus.Mechanism investigations indicate that Ag‑CDs induced the death of Escherichia coli and Pseudomonas aeruginosa by disrupting their bacterial morphology and structure,triggering the generation of intracellular reactive oxygen species(ROS),and impairing their antioxidant defense system.展开更多
A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescenc...A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.展开更多
While biomaterials are endowed with sophisticated functions by the temporal dynamics and autonomy derived from non-equilibrium assemblies in biological systems,fabricating advanced materials counterparts with these fe...While biomaterials are endowed with sophisticated functions by the temporal dynamics and autonomy derived from non-equilibrium assemblies in biological systems,fabricating advanced materials counterparts with these features through kinetic control remains rare.Herein,we report a non-equilibrium hydrogel that exhibits autonomous time-dependent ultrabright fluorescence(quantum yield 0.90),achieved through the kinetically controlled incorporation of thermodynamic equilibrium host-vip complexes into a poly(2-hydroxyethyl methacrylate)(PHEMA)network.Transient complexes are programmed by coupling rapid assembly kinetics with the slow competitive binding of the polymer matrix.This kinetic mismatch converts a thermodynamic equilibrium supramolecular system into a non-equilibrium state,generating temporally dynamic fluorescence that cyclically shifts from yellow to green and self-reverts.The programmed temporal dynamics endow the hydrogel with high potential for information encryption applications.展开更多
Highlights By conjugating the same anti-N monoclonal antibody(mAb4-mAb1)with colloidal gold or fluorescent microspheres,this study developed two rapid point-of-care antigen immunochromatographic strips for the detecti...Highlights By conjugating the same anti-N monoclonal antibody(mAb4-mAb1)with colloidal gold or fluorescent microspheres,this study developed two rapid point-of-care antigen immunochromatographic strips for the detection of porcine deltacoronavirus.The fluorescent microsphere-based lateral flow test strip demonstrated a sensitivity of 10^(1.7)TCID_(50)/0.1 mL,which is fourfold higher than that of the colloidal gold-based assay.Porcine deltacoronavirus(PDCoV)is a recently identified enteric coronavirus that causes an acute infectious disease in piglets,leading to diarrhea,vomiting,dehydration,and mortality(Hu et al.2015).展开更多
Over the past ten years,numerous papers have been published on the use of indocyanine green(ICG)fluorescence in liver surgery for hepatocellular carcinoma(HCC).There are many different applications.The first involves ...Over the past ten years,numerous papers have been published on the use of indocyanine green(ICG)fluorescence in liver surgery for hepatocellular carcinoma(HCC).There are many different applications.The first involves targeting superficial tumors in patients with macronodular cirrhosis and an irregular liver surface.In a minimally invasive setting,the lack of tactile feedback on the hepatic surface makes detecting subcapsular HCC with ultrasound alone challenging.ICG fusion images can mimic the tactile feedback of the hand and act as an ultrasound booster.ICG fluorescence can be used to evaluate tumor residues after minimally invasive thermal ablation.ICG fluorescence imaging can also be used to identify the grade of HCC early on and evaluate the microinvasive component.展开更多
Sulfur dioxide(SO_(2)) and its derivatives have been recognized as harmful environmental pollutants.However,they are often produced during the processing of traditional Chinese medicines,potentially compromising the q...Sulfur dioxide(SO_(2)) and its derivatives have been recognized as harmful environmental pollutants.However,they are often produced during the processing of traditional Chinese medicines,potentially compromising the quality of these medicinal materials and contributing to various health issues.Due to a lack of effective monitoring and imaging tools,the physiological effects of excessive SO_(2) residues in traditional Chinese medicine remain unclear.Therefore,developing a rapid and effective tool for detecting SO_(2) is crucial for understanding its metabolic pathways and effects in vivo.In this study,we developed a near infrared(NIR) and ratiometric fluorescent probe,NIR-RS,which exhibits high sensitivity,selectivity,and rapid response for SO_(2) detection.Notably,NIR-RS accurately quantifies SO_(2) contents in Pinelliae rhizoma(P.rhizoma) samples,with recovery rates from 98.46 % to 102.40 %,and relative standard deviations(RSDs)< 5.0 %.For bioimaging applications,NIR-RS has low cytotoxicity and good mitochondrial-targeting ability,making it suitable for imaging exogenous and endogenous SO_(2) in mitochondria.Additionally,NIR-RS was successfully applied to image SO_(2) content of P.rhizoma samples within cells,revealing that high SO_(2) residue elevated mitochondria adenosine triphosphate(ATP) content,these findings reveal that P.rhizoma with excessive SO_(2) can affect the organism's growth mechanisms through alterations in ATP pathways.In vivo,SO_(2) was found to predominantly accumulate in the liver following gavage with P.rhizoma solution,with accumulation levels increasing in proportion to SO_(2) residue concentration.High SO_(2) concentrations in P.rhizoma can cause pulmonary fibrosis and gastric mucosal damage.This work provides a valuable tool for regulating SO_(2) content in P.rhizoma and may help researcher better understand the metabolism of SO_(2) derivatives and explore their physiological roles in biological systems.展开更多
Cyclo[n]Thiophenes(CnTs)are a distinctive class ofπ-conjugated macrocyclic molecules that have attracted growing attention owing to their structural aesthetics and organic electronic characteristics.However,the devel...Cyclo[n]Thiophenes(CnTs)are a distinctive class ofπ-conjugated macrocyclic molecules that have attracted growing attention owing to their structural aesthetics and organic electronic characteristics.However,the development of CnTs has been largely impeded by inefficient synthetic route.In this work,we employ a bridge strategy using bipyridine as bridge to link two quaterthiophene units resulting in-shaped bicyclosystem.This strain-retaining approach improves the synthesis efficiency of the macrocycles.Two new macrocyclic molecules,(4T-2hexyl-2Me)_(2)-DPBP and(4T-2hexyl)_(2)-DPBP,were successfully synthesized in total yield 17%and 16%,respectively.Single-crystal structure of(4T-2hexyl-2Me)_(2)-DPBP reveals that the bipyridine bridge is orthogonally strapped by two quaterthiophene units.Notably,both compounds exhibit aggregation-induced emission enhancement(AIEE)behavior-an unprecedented feature among CnT-based macrocycles.Theoretical calculations reveal that this AIE phenomenon originates from the restriction of intramolecular motion(RIM)in the aggregated state,which suppresses the non-radiative decay channels.These results demonstrate a generalized strategy for the synthesis of functionalπ-conjugated macrocyclic molecules based fluorescent materials.展开更多
Schizophrenia(SCZ) is a severe mental disorder with an unclear pathogenesis.Increasing evidence suggests that oxidative stress(OS) may contribute to the neuropathological processes underlying SCZ.Biothiols,key endogen...Schizophrenia(SCZ) is a severe mental disorder with an unclear pathogenesis.Increasing evidence suggests that oxidative stress(OS) may contribute to the neuropathological processes underlying SCZ.Biothiols,key endogenous antioxidants,have been proposed as potential biomarkers for the disease.However,due to the presence of the blood-brain barrier(BBB),fluorescent probes are rarely used to image biothiols in the brain of SCZ models.In this study,a series of fluorescent probes for biothiols were developed using dicyanoisophorone derivatives as fluorophores known for their excellent optical properties,and carboxylic esters as recognition units.A parallel synthesis and rapid screening strategy was employed to construct and optimize these probes.By introducing trifluoromethyl and benzothiazole groups into the fluorophore,the emission wavelength was successfully shifted into the near-infrared region.Additionally,various trifluoromethyl-substituted aromatic and nitrogen heterocyclic compounds were incorporated to optimize the carboxylic esters,thereby improving the probes' reactivity and lipophilicity.Systematic evaluation of the physicochemical characteristics,and optical performance led to the identification of DCIBT-11 as the most promising candidate.DCI-BT-11 demonstrated excellent BBB permeability and a good response to biothiols both in vitro and in vivo.Notably,DCI-BT-11 was used for the first time to visualize biothiol flux and assess the therapeutic effects of the antioxidant N-acetylcysteine(NAC) in the brains of SCZ mouse models,offering new insights into the role of OS in the pathogenesis and treatment of SCZ.展开更多
The thoracic duct(TD),the largest lymphatic vessel in the human body,plays a critical role in returning lymph to the circulatory system.However,its dynamic,distensible nature and concealed anatomical location make int...The thoracic duct(TD),the largest lymphatic vessel in the human body,plays a critical role in returning lymph to the circulatory system.However,its dynamic,distensible nature and concealed anatomical location make intraoperative visualization critically challenging and increase the risk of injury.Real-time,high-resolution assessment of TD leaks remains an urgent clinical need.Here,we present a breakthrough molecular engineering strategy that leverages an intestinally lipophilic fluorescent formulation for dynamic in vivo TD imaging.Our rationally designed cyanine derivative IR790+,known for its rapid membrane permeability and endoplasmic reticulum(ER)targeting localization,demonstrates unprecedented chylomicron affinity,which subsequently transports the dye through the lymphatic system to the TD.Notably,dynamic,high-contrast intraoperative TD imaging is achieved from rat models to swine models.Administered orally as near-infrared(NIR)fluorescent contrast agent,this ultra-stable IR790+@oil formulation,engineered via flash nanoprecipitation,surpasses conventional counterparts by enabling non-invasive,real-time identification of TD.Intriguingly,this first-reported ER-targeting NIR formulation,delivered orally,represents a paradigm shift in fluorescence-guided surgery,significantly improving intraoperative accuracy.展开更多
Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species(RSSs) in the thiol-dependent redox systems are crucial in ferroptosis.This makes the simultaneous detection of...Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species(RSSs) in the thiol-dependent redox systems are crucial in ferroptosis.This makes the simultaneous detection of multiple RSSs significant for evaluating ferroptosis therapy.However,the traditional techniques,including fluorescent(FL) imaging and electrospray ionization-based mass spectrometry(MS) detection,cannot achieve the discrimination of different RSSs.Herein,simultaneous MS detection of multiple RSSs,including cysteine(Cys),homocysteine(Hcy),glutathione(GSH) and hydrogen sulfide(H_(2)S),was obtained upon enhancing ionization efficiency by a fluorescent probe(NBD-O-1).Based on the interaction between NBD-O-1 and RSSs,the complex of RSSs with a fragment of NBD-O-1 can be generated,which can be easily ionized for MS detection in the negative mode.Therefore,the intracellular RSSs can be well detected upon the incubation of He La cells with the probe of NBD-O-1,exhibiting the total RSS levels by the FL imaging and further providing expression of each RSS by enhanced MS detection.Furthermore,the RSSs during ferroptosis in He La cells have been evaluated using the present strategy,demonstrating the potential for ferroptosis examinations.This work has made an unconventional application of a fluorescent probe to enhance the detection of multiple RSSs by MS,providing significant molecular information for addressing the ferroptosis mechanism.展开更多
Thermally activated delayed fluorescence(TADF) emitters show great potential in photodynamic therapy(PDT) and bioimaging,leveraging their structural adaptability,efficient reverse intersystem crossing(RISC),robust pho...Thermally activated delayed fluorescence(TADF) emitters show great potential in photodynamic therapy(PDT) and bioimaging,leveraging their structural adaptability,efficient reverse intersystem crossing(RISC),robust photosensitizing capability,and high photoluminescence quantum yields(PLQYs).Herein,we developed a new class of donor-acceptor-donor(D-A-D)-type TADF materials by connecting the highly twisted indolizine-benzophenone electron acceptors with a series of electron donors including phenoxazine,phenothiazine and 9,9-dimethyl-9,10-dihydroacridine.These materials exhibit enhanced TADF properties,aggregation-induced emission(AIE),alongside high reactive oxygen species(ROS) generation efficiency,effectively mitigating aggregation-caused quenching observed in traditional fluorophores.Among them,IDP-p-PXZ,incorporating the phenoxazine donor,stands out with the smallest singlet-triplet splitting energy(ΔE_(ST)) and the highest spin-orbit coupling matrix elements(SOCMEs).Upon encapsulation into 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000](DSPE-PEG2000) nanoparticles(NPs),IDP-p-PXZ demonstrates extended delayed fluorescence lifetimes in air,an exceptionally fast intersystem crossing(ISC) rate constant(k_(ISC)) of 3.4×10^(7)s^(-1),and a radiative rate constant(k_(r)) of 5.05×10^(6)s^(-1).These NPs exhibit superior biocompatibility,efficient cellular internalization,and potent ROS production,enabling effective simultaneous PDT and confocal fluorescence imaging in HeLa cells.展开更多
The study of target proteins is crucial for understanding molecular interactions and developing analytical platforms,therapeutic agents and functional tools.Herein,we present a novel nanoplatform activated by near-inf...The study of target proteins is crucial for understanding molecular interactions and developing analytical platforms,therapeutic agents and functional tools.Herein,we present a novel nanoplatform activated by near-infrared(NIR) light for triple-modal proteins study,which enabling target protein labeling,enrichment and visualization.Azido-naphthalimide-coated upconversion nanoparticles(UCNPs) serve as NIR light-responsive nanoplatforms,showing promising applications in studying interactions between various bioactive molecules and proteins in living systems.Under NIR light irradiation,azido-naphthalimides are activated by ultraviolet(UV) and blue light emitted from UCNPs and the resulting amino-naphthalimides intermediate not only crosslink nearby target proteins but also enable imaging performance.We demonstrate that this nanoplatform is capable of selective protein labeling and imaging in complex protein environments,achieving specific labeling and imaging of both intracellular and extracellular proteins in mammalian cells as well as bacteria.Furthermore,in vivo protein labeling has been achieved using this novel NIR light-activatable nanoplatform.This technique will open new avenues for discoveries and mechanistic interrogation in chemical biology.展开更多
Although lead(Pb)-based perovskite solar cells(PSCs)have garnered intense attention for their remarkable photovoltaic conversion efficiency,their commercial process is urgently in need of an effective damage-evaluatio...Although lead(Pb)-based perovskite solar cells(PSCs)have garnered intense attention for their remarkable photovoltaic conversion efficiency,their commercial process is urgently in need of an effective damage-evaluation system for the early diagnosis of faulty PSCs.The main cause of microdamage in perovskite films is the outflow of Pb,which significantly impacts device performance.However,no reliable correlation has been established between classical damage detection techniques and Pb detection,resulting in limited detection sensitivity.Here,we report an in situ visual microdamage evaluation method of PSCs by coating the device surface with a silica gel encapsulation layer containing porphyrin molecules.This detection technology enables high selectivity and sensitivity based on the strong complexation between the porphyrin ring and trace Pb outflow from degraded PSCs.By establishing the linear relationship between the fluorescence intensity and Pb concentration in PSCs,trace Pb outflow is pinpointed and quantified with a low detection limit of 0.65μg cm^(-2).An applet is developed for the insitu visual fluorescence detection method to facilitate the continuous real-time monitoring of series-type PSCs,thereby enabling the prompt identification and replacement of damaged PSCs and ensuring the swift restoration of high efficiency.展开更多
The level of glutathione(GSH)is significantly associated with numerous pathological processes,thus,real-time detection of the GSH level is of significance for early diagnosis of GSH-related diseases.Herein,we develope...The level of glutathione(GSH)is significantly associated with numerous pathological processes,thus,real-time detection of the GSH level is of significance for early diagnosis of GSH-related diseases.Herein,we developed in vivo second near-infrared(NIR-II)window fluorescence(FL)and ratiometric photoacoustic(RPA)dual-modality imaging of GSH using a GSH-activatable probe(LET-14).LET-14 was synthesized based on a rhodamine hybrid xanthene skeleton with a FL shielding 2,4-dinitrobenzene sulfonyl group that can be specifically cleaved by GSH,thus resulting in a markedly bathochromic-shift absorption,a 6.5-fold increase in NIR-II FL intensity(FL920)and a 13-fold increase in RPA signal(PA880/PA705)in vitro.Intriguingly,LET-14 exhibits good selectivity and sensitivity for NIR-II FL and RPA dual-modality imaging of GSH in 4T1 tumor-bearing mouse model.Our findings develop an in vivo detection tool of GSH,which has great potential in the field of cancer diagnosis.展开更多
Simultaneous identification and quantitative detection of phenylenediamine(PDA)isomers,including o-phenylenediamine(OPD),m-phenylenediamine(MPD),and p-phenylenediamine(PPD),are essential for environmental risk assessm...Simultaneous identification and quantitative detection of phenylenediamine(PDA)isomers,including o-phenylenediamine(OPD),m-phenylenediamine(MPD),and p-phenylenediamine(PPD),are essential for environmental risk assessment and human health protection.However,current visual detection methods can only distinguish individual PDA isomers and failed to identify binary or ternary mixtures.Herein,a highly active and ultrastable peroxidase(POD)-like CoPt graphitic nanozyme was used for naked-eye identification and colorimetric/fluorescent(FL)dual-mode quantitative detection of PDA isomers.The CoPt@G nanozyme effectively catalyzed the oxidation of OPD,MPD,PPD,OPD+PPD,OPD+MPD,MPD+PPD and OPD+MPD+PPD into yellow,colorless,lilac,yellow,yellow,wine red and reddish-brown products,respectively,in the presence of H_(2)O_(2).Thus,the MPD,PPD,MPD+PPD and OPD+MPD+PPD were easily identified based on the distinct color of their oxidation products,and the OPD,OPD+PPD,OPD+MPD could be further identified by the additional addition of MPD or PPD.Subsequently,CoPt@G/H_(2)O_(2)-,a 3,3′,5,5′-tetramethylbenzidine(TMB)/CoPt@G/H_(2)O_(2)-,and MPD/CoPt@G/H_(2)O_(2)-enabled colorimetric/FL dual-mode platforms for the quantitative detection of OPD,MPD and PPD were proposed.The experimental results illustrated that the constructed sensing platforms exhibit satisfactory sensitivity,comparable to that reported in previous studies.Finally,the evaluation of PDAs in water samples was realized,yielding satisfactory recoveries.This work expanded the application prospects of nanozymes in assessing environmental risks and protection of human security.展开更多
Precise heterometal doping or substitution of specific metal sites in isostructural metal clusters remains a formidable synthetic challenge,despite its transformative potential for modulating excited-state characteris...Precise heterometal doping or substitution of specific metal sites in isostructural metal clusters remains a formidable synthetic challenge,despite its transformative potential for modulating excited-state characteristics and customizing optical properties.In this work,we achieved the precise synthesis of isostructural alloy clusters R/S-Ag_(3)Cu([Ag_(3)Cu(tppm)(R/S-IPTT)]ClO_(4),R/S-IPTT=R/S-4-isopropylthiazolidine-2-thiolate,tppm=tris(diphenylphosphino)methane)in high yield(89%-91%)through selective doping of a Cu(Ⅰ)atom into chiral homometallic cluster enantiomers R/S-Ag_(4)([Ag_(4)(tppm)(R/S-IPTT)]ClO_(4)).In stark contrast to R/S-Ag_(4)(Φ_(em)<0.5%)that displays weak circularly polarized luminescence(CPL)with phosphorescence characteristic,R/S-Ag_(3)Cu(Φ_(em)≈70%)demonstrates strong CPL properties featured with thermally activated delay fluorescence(TADF)at ambient temperature.The selective substitution of the apical Ag(Ⅰ)atom in Ag_(4)triangular pyramid with a Cu(Ⅰ)atom not only gives rise to beyond 100-fold boosting of photoluminescence quantum yield(PLQY),but also leads to more pronounced optically chiral activity of alloy clusters in excited states in view of the larger photoluminescence dissymmetry factors(g_(PL))of R/S-Ag_(3)Cu(-3.5×10^(-3)/3.4×10^(-3))than that of R/S-Ag_(4)(-2.7×10^(-3)/2.6×10^(-3)).Furthermore,compared with chiral homometallic clusters R/S-Cu_(4)([Cu_(4)(tppm)(R/S-IPTT)]ClO_(4))with the same TADF characteristic at ambient temperature,R/S-Ag_(3)Cu manifests 1.7-fold PLQY and 6-fold g_(PL)due to faster reverse intersystem crossing(RISC)and more effective coupling of electric and magnetic transition moments in alloy clusters.This work not only presents a typical example of selective heterometal doping to modulate excited-state properties of isostructural metal clusters,but also gets deeper insight into the doping chemistry of dissimilar metals at the molecular level.展开更多
The detection of amino acid enantiomers holds significant importance in biomedical,chemical,food,and other fields.Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensit...The detection of amino acid enantiomers holds significant importance in biomedical,chemical,food,and other fields.Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes,which can compromise accuracy and repeatability.In this study,we report a novel fluorescent probe(R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths(>60 nm).This water-soluble probe(R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers,enabling reliable chiral detection of 14 natural amino acids.It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color.Additionally,a logic operation with two inputs and three outputs was constructed based on these optical properties.Notably,amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels.This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.展开更多
文摘Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O)]·DMA}n(1)and{[Cd(hfdp)(ndc)(H_(2)O)]·DMA}_(n)(2),respectively(DMA=N,N‑dimethylacetamide).Single‑crystal X‑ray diffraction analyses showed that both complexes 1 and 2 contain similar structures.Topological analysis indicates that complexes 1 and 2 have a{44·62}planar structure.In addition,both complexes reveal good thermal stability and fluorescence sensing performance.They exhibited good sensitivity and selectivity towards 2,4,6‑trinitrophenol(TNP)by fluorescent quenching.The limits of detection of 1 and 2 for TNP were 0.107 and 0.327μmol·L^(-1),respectively.CCDC:2475515,1;2475516,2.
文摘In this study,using 3,5‑di(3′,5′‑dicarboxylphenyl)‑1H‑1,2,4‑triazole(H4L)as ligands,a gadolinia‑based organic framework complex{[GdNa(L)(H_(2)O)3]·2H_(2)O}_(n)(Gd‑Na‑MOF)was successfully designed and synthesized by hydrothermal method.The structure and properties were systematically characterized and tested by techniques such as single‑crystal X‑ray diffraction,powder X‑ray diffraction,thermogravimetric analysis,infrared spectroscopy,and fluorescence spectroscopy.The results indicate that this complex has a unique 3D structure,excellent thermal stability,and outstanding luminescent performance.Based on its luminescent properties,a polymer‑embedding method was employed to fabricate the Gd‑Na‑MOF into a flexible,washable composite fluorescent film,Gd‑Na‑MOF@PMMA/BMA(PMMA=polymethyl methacrylate,BMA=butyl methacrylate).This fluorescent film exhibited highly sensitive recognition capability for tyramine,with a low detection limit of 1.66μmol·L^(-1).It was used for the detection of tyramine in bananas,with a recovery rate of 96.92%‑100.26%.CCDC:2466949.
文摘Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'-bipyridine]were successfully synthesized by the volatilization of the solution at room temperature.The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology.The results showed that the complexes all have a binuclear structure,and the structures contain free ethanol molecules.Moreover,the coordination number of the central metal of each structural unit is eight.Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures.After conducting a systematic study on the luminescence properties of complexes 1-4,their emission and excitation spectra were obtained.Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms,respectively.The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system,and their corre sponding luminescent regions cover the yellow light,red light,green light,and orange-red light bands,respectively.Within the temperature range of 299.15-1300 K,the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology.The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas,3D infrared spectroscopy,and ion fragment information detected by mass spectrometry.The specific decomposition path is as follows:firstly,free ethanol molecules and neutral ligands are removed,and finally,acidic ligands are released;the final product is the corresponding metal oxide.CCDC:2430420,1;2430422,2;2430419,3;2430424,4;2430421,5;2430423,6.
文摘Herein,antibacterial silver‑doped fluorescent carbon dots(Ag‑CDs)were synthesized through a stepwise hydrothermal method,with polyethyleneimine(PEI),citric acid(CA),and silver nitrate(AgNO3)serving as precursors.The applicability and antimicrobial efficacy of these nanomaterials were systematically investigated for metal ion sensing.Experimental evidence demonstrated that the Ag‑CDs exhibited a pronounced fluorescence quenching response toward ferric ions(Fe^(3+)),enabling their quantitative determination via a linear concentration‑dependent relationship.These Ag‑CDs exhibited significant inhibitory effects on biofilm growth and disruption for both Escherichia coli and Staphylococcus aureus.Mechanism investigations indicate that Ag‑CDs induced the death of Escherichia coli and Pseudomonas aeruginosa by disrupting their bacterial morphology and structure,triggering the generation of intracellular reactive oxygen species(ROS),and impairing their antioxidant defense system.
文摘A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.
基金supported by the National Natural Science Foundation of China(22025503,22220102004,22401093)the Science and Technology Commission of Shanghai Municipality(24DX1400200)+2 种基金the Innovation Program of Shanghai Municipal Education Commission(2023ZKZD40)the Programme of Introducing Talents of Discipline to Universities(B16017)the China Postdoctoral Science Foundation(2023M741167,GZB20230211,2024T170273)。
文摘While biomaterials are endowed with sophisticated functions by the temporal dynamics and autonomy derived from non-equilibrium assemblies in biological systems,fabricating advanced materials counterparts with these features through kinetic control remains rare.Herein,we report a non-equilibrium hydrogel that exhibits autonomous time-dependent ultrabright fluorescence(quantum yield 0.90),achieved through the kinetically controlled incorporation of thermodynamic equilibrium host-vip complexes into a poly(2-hydroxyethyl methacrylate)(PHEMA)network.Transient complexes are programmed by coupling rapid assembly kinetics with the slow competitive binding of the polymer matrix.This kinetic mismatch converts a thermodynamic equilibrium supramolecular system into a non-equilibrium state,generating temporally dynamic fluorescence that cyclically shifts from yellow to green and self-reverts.The programmed temporal dynamics endow the hydrogel with high potential for information encryption applications.
基金financially supported by the National Key Research and Development Program of China(2021YFF0703600)。
文摘Highlights By conjugating the same anti-N monoclonal antibody(mAb4-mAb1)with colloidal gold or fluorescent microspheres,this study developed two rapid point-of-care antigen immunochromatographic strips for the detection of porcine deltacoronavirus.The fluorescent microsphere-based lateral flow test strip demonstrated a sensitivity of 10^(1.7)TCID_(50)/0.1 mL,which is fourfold higher than that of the colloidal gold-based assay.Porcine deltacoronavirus(PDCoV)is a recently identified enteric coronavirus that causes an acute infectious disease in piglets,leading to diarrhea,vomiting,dehydration,and mortality(Hu et al.2015).
文摘Over the past ten years,numerous papers have been published on the use of indocyanine green(ICG)fluorescence in liver surgery for hepatocellular carcinoma(HCC).There are many different applications.The first involves targeting superficial tumors in patients with macronodular cirrhosis and an irregular liver surface.In a minimally invasive setting,the lack of tactile feedback on the hepatic surface makes detecting subcapsular HCC with ultrasound alone challenging.ICG fusion images can mimic the tactile feedback of the hand and act as an ultrasound booster.ICG fluorescence can be used to evaluate tumor residues after minimally invasive thermal ablation.ICG fluorescence imaging can also be used to identify the grade of HCC early on and evaluate the microinvasive component.
基金supported by the Natural Science Foundation of Hubei Province (Nos.2023AFB376 and 2024AFD287)National Key Research and Development Program (No.2023YFC3503804)the National Natural Science Foundation of China (No.22077044)。
文摘Sulfur dioxide(SO_(2)) and its derivatives have been recognized as harmful environmental pollutants.However,they are often produced during the processing of traditional Chinese medicines,potentially compromising the quality of these medicinal materials and contributing to various health issues.Due to a lack of effective monitoring and imaging tools,the physiological effects of excessive SO_(2) residues in traditional Chinese medicine remain unclear.Therefore,developing a rapid and effective tool for detecting SO_(2) is crucial for understanding its metabolic pathways and effects in vivo.In this study,we developed a near infrared(NIR) and ratiometric fluorescent probe,NIR-RS,which exhibits high sensitivity,selectivity,and rapid response for SO_(2) detection.Notably,NIR-RS accurately quantifies SO_(2) contents in Pinelliae rhizoma(P.rhizoma) samples,with recovery rates from 98.46 % to 102.40 %,and relative standard deviations(RSDs)< 5.0 %.For bioimaging applications,NIR-RS has low cytotoxicity and good mitochondrial-targeting ability,making it suitable for imaging exogenous and endogenous SO_(2) in mitochondria.Additionally,NIR-RS was successfully applied to image SO_(2) content of P.rhizoma samples within cells,revealing that high SO_(2) residue elevated mitochondria adenosine triphosphate(ATP) content,these findings reveal that P.rhizoma with excessive SO_(2) can affect the organism's growth mechanisms through alterations in ATP pathways.In vivo,SO_(2) was found to predominantly accumulate in the liver following gavage with P.rhizoma solution,with accumulation levels increasing in proportion to SO_(2) residue concentration.High SO_(2) concentrations in P.rhizoma can cause pulmonary fibrosis and gastric mucosal damage.This work provides a valuable tool for regulating SO_(2) content in P.rhizoma and may help researcher better understand the metabolism of SO_(2) derivatives and explore their physiological roles in biological systems.
基金support from the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0520000)the National Key R&D Program of China(No.2022YFA1203200)+3 种基金National Natural Science Foundation of China(No.52273170)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2021030)Postdoctoral Fellowship Program of CPSF(No.GZC20232735)BMS Junior Fellow of Beijing National Laboratory For molecular Science(No.2023BMS20111).
文摘Cyclo[n]Thiophenes(CnTs)are a distinctive class ofπ-conjugated macrocyclic molecules that have attracted growing attention owing to their structural aesthetics and organic electronic characteristics.However,the development of CnTs has been largely impeded by inefficient synthetic route.In this work,we employ a bridge strategy using bipyridine as bridge to link two quaterthiophene units resulting in-shaped bicyclosystem.This strain-retaining approach improves the synthesis efficiency of the macrocycles.Two new macrocyclic molecules,(4T-2hexyl-2Me)_(2)-DPBP and(4T-2hexyl)_(2)-DPBP,were successfully synthesized in total yield 17%and 16%,respectively.Single-crystal structure of(4T-2hexyl-2Me)_(2)-DPBP reveals that the bipyridine bridge is orthogonally strapped by two quaterthiophene units.Notably,both compounds exhibit aggregation-induced emission enhancement(AIEE)behavior-an unprecedented feature among CnT-based macrocycles.Theoretical calculations reveal that this AIE phenomenon originates from the restriction of intramolecular motion(RIM)in the aggregated state,which suppresses the non-radiative decay channels.These results demonstrate a generalized strategy for the synthesis of functionalπ-conjugated macrocyclic molecules based fluorescent materials.
基金supported by the National Natural Science Foundation of China (Nos.22177025,21807021,22177026)the Science Fund for Creative Research Groups of the Natural Science Foundation of Hebei Province (No.B2021201038)+1 种基金the Foundation of Hebei University (No.050001-513300201004)the Director’s Foundation of the Key Laboratory of Medicinal Chemistry and Molecular Diagnosis,Ministry of Education,Hebei University (No.MCMDZR2024003)。
文摘Schizophrenia(SCZ) is a severe mental disorder with an unclear pathogenesis.Increasing evidence suggests that oxidative stress(OS) may contribute to the neuropathological processes underlying SCZ.Biothiols,key endogenous antioxidants,have been proposed as potential biomarkers for the disease.However,due to the presence of the blood-brain barrier(BBB),fluorescent probes are rarely used to image biothiols in the brain of SCZ models.In this study,a series of fluorescent probes for biothiols were developed using dicyanoisophorone derivatives as fluorophores known for their excellent optical properties,and carboxylic esters as recognition units.A parallel synthesis and rapid screening strategy was employed to construct and optimize these probes.By introducing trifluoromethyl and benzothiazole groups into the fluorophore,the emission wavelength was successfully shifted into the near-infrared region.Additionally,various trifluoromethyl-substituted aromatic and nitrogen heterocyclic compounds were incorporated to optimize the carboxylic esters,thereby improving the probes' reactivity and lipophilicity.Systematic evaluation of the physicochemical characteristics,and optical performance led to the identification of DCIBT-11 as the most promising candidate.DCI-BT-11 demonstrated excellent BBB permeability and a good response to biothiols both in vitro and in vivo.Notably,DCI-BT-11 was used for the first time to visualize biothiol flux and assess the therapeutic effects of the antioxidant N-acetylcysteine(NAC) in the brains of SCZ mouse models,offering new insights into the role of OS in the pathogenesis and treatment of SCZ.
基金supported by the National Natural Science Foundation of China(22225805,81400681,32394001,32121005)the Shanghai Science and Technology Innovation Action Plan(22Y11907200,23J21901600)the Innovation Program of Shanghai Municipal Education Commission,Shanghai Municipal Health Commission(2024ZZ2025)。
文摘The thoracic duct(TD),the largest lymphatic vessel in the human body,plays a critical role in returning lymph to the circulatory system.However,its dynamic,distensible nature and concealed anatomical location make intraoperative visualization critically challenging and increase the risk of injury.Real-time,high-resolution assessment of TD leaks remains an urgent clinical need.Here,we present a breakthrough molecular engineering strategy that leverages an intestinally lipophilic fluorescent formulation for dynamic in vivo TD imaging.Our rationally designed cyanine derivative IR790+,known for its rapid membrane permeability and endoplasmic reticulum(ER)targeting localization,demonstrates unprecedented chylomicron affinity,which subsequently transports the dye through the lymphatic system to the TD.Notably,dynamic,high-contrast intraoperative TD imaging is achieved from rat models to swine models.Administered orally as near-infrared(NIR)fluorescent contrast agent,this ultra-stable IR790+@oil formulation,engineered via flash nanoprecipitation,surpasses conventional counterparts by enabling non-invasive,real-time identification of TD.Intriguingly,this first-reported ER-targeting NIR formulation,delivered orally,represents a paradigm shift in fluorescence-guided surgery,significantly improving intraoperative accuracy.
基金supported by the National Key Research and Development Program of China (No.2024YFA1509600)National Natural Science Foundation of China (Nos.22474010 and 22274012)the Fundamental Research Funds for the Central Universities (No.2233300007)。
文摘Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species(RSSs) in the thiol-dependent redox systems are crucial in ferroptosis.This makes the simultaneous detection of multiple RSSs significant for evaluating ferroptosis therapy.However,the traditional techniques,including fluorescent(FL) imaging and electrospray ionization-based mass spectrometry(MS) detection,cannot achieve the discrimination of different RSSs.Herein,simultaneous MS detection of multiple RSSs,including cysteine(Cys),homocysteine(Hcy),glutathione(GSH) and hydrogen sulfide(H_(2)S),was obtained upon enhancing ionization efficiency by a fluorescent probe(NBD-O-1).Based on the interaction between NBD-O-1 and RSSs,the complex of RSSs with a fragment of NBD-O-1 can be generated,which can be easily ionized for MS detection in the negative mode.Therefore,the intracellular RSSs can be well detected upon the incubation of He La cells with the probe of NBD-O-1,exhibiting the total RSS levels by the FL imaging and further providing expression of each RSS by enhanced MS detection.Furthermore,the RSSs during ferroptosis in He La cells have been evaluated using the present strategy,demonstrating the potential for ferroptosis examinations.This work has made an unconventional application of a fluorescent probe to enhance the detection of multiple RSSs by MS,providing significant molecular information for addressing the ferroptosis mechanism.
基金supported by the National Natural Science Foundation of China (No.22405062)the Guangdong Basic and Applied Basic Research Foundation (No.2021A1515110869)+2 种基金the Shenzhen Science and Technology Program (No.ZDSYS20210623091813040)Innovation Program of Zhanjiang (No.2020LHJH005)Funds for Ph.D.researchers of Guangdong Medical University in 2025 (No.4SG25007G)。
文摘Thermally activated delayed fluorescence(TADF) emitters show great potential in photodynamic therapy(PDT) and bioimaging,leveraging their structural adaptability,efficient reverse intersystem crossing(RISC),robust photosensitizing capability,and high photoluminescence quantum yields(PLQYs).Herein,we developed a new class of donor-acceptor-donor(D-A-D)-type TADF materials by connecting the highly twisted indolizine-benzophenone electron acceptors with a series of electron donors including phenoxazine,phenothiazine and 9,9-dimethyl-9,10-dihydroacridine.These materials exhibit enhanced TADF properties,aggregation-induced emission(AIE),alongside high reactive oxygen species(ROS) generation efficiency,effectively mitigating aggregation-caused quenching observed in traditional fluorophores.Among them,IDP-p-PXZ,incorporating the phenoxazine donor,stands out with the smallest singlet-triplet splitting energy(ΔE_(ST)) and the highest spin-orbit coupling matrix elements(SOCMEs).Upon encapsulation into 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000](DSPE-PEG2000) nanoparticles(NPs),IDP-p-PXZ demonstrates extended delayed fluorescence lifetimes in air,an exceptionally fast intersystem crossing(ISC) rate constant(k_(ISC)) of 3.4×10^(7)s^(-1),and a radiative rate constant(k_(r)) of 5.05×10^(6)s^(-1).These NPs exhibit superior biocompatibility,efficient cellular internalization,and potent ROS production,enabling effective simultaneous PDT and confocal fluorescence imaging in HeLa cells.
基金supported by the National Natural Science Foundation of China (No.22007008)the LiaoNing Revitalization Talents Program (No.XLYC1907021)the Fundamental Research Funds for the Central Universities (Nos.DUT23YG120,DUT19RC(3)009)。
文摘The study of target proteins is crucial for understanding molecular interactions and developing analytical platforms,therapeutic agents and functional tools.Herein,we present a novel nanoplatform activated by near-infrared(NIR) light for triple-modal proteins study,which enabling target protein labeling,enrichment and visualization.Azido-naphthalimide-coated upconversion nanoparticles(UCNPs) serve as NIR light-responsive nanoplatforms,showing promising applications in studying interactions between various bioactive molecules and proteins in living systems.Under NIR light irradiation,azido-naphthalimides are activated by ultraviolet(UV) and blue light emitted from UCNPs and the resulting amino-naphthalimides intermediate not only crosslink nearby target proteins but also enable imaging performance.We demonstrate that this nanoplatform is capable of selective protein labeling and imaging in complex protein environments,achieving specific labeling and imaging of both intracellular and extracellular proteins in mammalian cells as well as bacteria.Furthermore,in vivo protein labeling has been achieved using this novel NIR light-activatable nanoplatform.This technique will open new avenues for discoveries and mechanistic interrogation in chemical biology.
基金financial support from the Shccig-Qinling Program(SMYJY202300294C)the Science,Technology,and Innovation Commission of Shenzhen Municipality(GJHZ20220913143204008,JCYJ20220818103417036)+1 种基金the National Natural Science Foundation of China(22261142666,52172237,52372225)the Shaanxi Science Fund for Distinguished Young Scholars(2022JC-21)。
文摘Although lead(Pb)-based perovskite solar cells(PSCs)have garnered intense attention for their remarkable photovoltaic conversion efficiency,their commercial process is urgently in need of an effective damage-evaluation system for the early diagnosis of faulty PSCs.The main cause of microdamage in perovskite films is the outflow of Pb,which significantly impacts device performance.However,no reliable correlation has been established between classical damage detection techniques and Pb detection,resulting in limited detection sensitivity.Here,we report an in situ visual microdamage evaluation method of PSCs by coating the device surface with a silica gel encapsulation layer containing porphyrin molecules.This detection technology enables high selectivity and sensitivity based on the strong complexation between the porphyrin ring and trace Pb outflow from degraded PSCs.By establishing the linear relationship between the fluorescence intensity and Pb concentration in PSCs,trace Pb outflow is pinpointed and quantified with a low detection limit of 0.65μg cm^(-2).An applet is developed for the insitu visual fluorescence detection method to facilitate the continuous real-time monitoring of series-type PSCs,thereby enabling the prompt identification and replacement of damaged PSCs and ensuring the swift restoration of high efficiency.
基金supported by the National Natural Science Foundation of China(Nos.82372116,U23A2097)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515010620)+2 种基金Shenzhen Medical Research Fund(Nos.B2302047,A2302047)Shenzhen Science and Technology Program(No.JCYJ20220818095806014)Research Team Cultivation Program of Shenzhen University(No.2023QNT019).
文摘The level of glutathione(GSH)is significantly associated with numerous pathological processes,thus,real-time detection of the GSH level is of significance for early diagnosis of GSH-related diseases.Herein,we developed in vivo second near-infrared(NIR-II)window fluorescence(FL)and ratiometric photoacoustic(RPA)dual-modality imaging of GSH using a GSH-activatable probe(LET-14).LET-14 was synthesized based on a rhodamine hybrid xanthene skeleton with a FL shielding 2,4-dinitrobenzene sulfonyl group that can be specifically cleaved by GSH,thus resulting in a markedly bathochromic-shift absorption,a 6.5-fold increase in NIR-II FL intensity(FL920)and a 13-fold increase in RPA signal(PA880/PA705)in vitro.Intriguingly,LET-14 exhibits good selectivity and sensitivity for NIR-II FL and RPA dual-modality imaging of GSH in 4T1 tumor-bearing mouse model.Our findings develop an in vivo detection tool of GSH,which has great potential in the field of cancer diagnosis.
基金supported by the National Key Research and Development Program of China(No.2022YFC2403500)the National Natural Science Foundation of China(No.22225401)+1 种基金the Science and Technology Innovation Program of Hunan Province(No.2020RC4017)the Guizhou Provincial Science and Technology Projects(No.ZK[2023]293).
文摘Simultaneous identification and quantitative detection of phenylenediamine(PDA)isomers,including o-phenylenediamine(OPD),m-phenylenediamine(MPD),and p-phenylenediamine(PPD),are essential for environmental risk assessment and human health protection.However,current visual detection methods can only distinguish individual PDA isomers and failed to identify binary or ternary mixtures.Herein,a highly active and ultrastable peroxidase(POD)-like CoPt graphitic nanozyme was used for naked-eye identification and colorimetric/fluorescent(FL)dual-mode quantitative detection of PDA isomers.The CoPt@G nanozyme effectively catalyzed the oxidation of OPD,MPD,PPD,OPD+PPD,OPD+MPD,MPD+PPD and OPD+MPD+PPD into yellow,colorless,lilac,yellow,yellow,wine red and reddish-brown products,respectively,in the presence of H_(2)O_(2).Thus,the MPD,PPD,MPD+PPD and OPD+MPD+PPD were easily identified based on the distinct color of their oxidation products,and the OPD,OPD+PPD,OPD+MPD could be further identified by the additional addition of MPD or PPD.Subsequently,CoPt@G/H_(2)O_(2)-,a 3,3′,5,5′-tetramethylbenzidine(TMB)/CoPt@G/H_(2)O_(2)-,and MPD/CoPt@G/H_(2)O_(2)-enabled colorimetric/FL dual-mode platforms for the quantitative detection of OPD,MPD and PPD were proposed.The experimental results illustrated that the constructed sensing platforms exhibit satisfactory sensitivity,comparable to that reported in previous studies.Finally,the evaluation of PDAs in water samples was realized,yielding satisfactory recoveries.This work expanded the application prospects of nanozymes in assessing environmental risks and protection of human security.
基金supported by the National Natural Science Foundation of China(92061202,21531008,22175181)the Fujian Province Science and Technology Project Program(2022H0041)the Self-deployment Project Research Program of Haixi Institute,Chinese Academy of Sciences(CXZX-2022-GH11)。
文摘Precise heterometal doping or substitution of specific metal sites in isostructural metal clusters remains a formidable synthetic challenge,despite its transformative potential for modulating excited-state characteristics and customizing optical properties.In this work,we achieved the precise synthesis of isostructural alloy clusters R/S-Ag_(3)Cu([Ag_(3)Cu(tppm)(R/S-IPTT)]ClO_(4),R/S-IPTT=R/S-4-isopropylthiazolidine-2-thiolate,tppm=tris(diphenylphosphino)methane)in high yield(89%-91%)through selective doping of a Cu(Ⅰ)atom into chiral homometallic cluster enantiomers R/S-Ag_(4)([Ag_(4)(tppm)(R/S-IPTT)]ClO_(4)).In stark contrast to R/S-Ag_(4)(Φ_(em)<0.5%)that displays weak circularly polarized luminescence(CPL)with phosphorescence characteristic,R/S-Ag_(3)Cu(Φ_(em)≈70%)demonstrates strong CPL properties featured with thermally activated delay fluorescence(TADF)at ambient temperature.The selective substitution of the apical Ag(Ⅰ)atom in Ag_(4)triangular pyramid with a Cu(Ⅰ)atom not only gives rise to beyond 100-fold boosting of photoluminescence quantum yield(PLQY),but also leads to more pronounced optically chiral activity of alloy clusters in excited states in view of the larger photoluminescence dissymmetry factors(g_(PL))of R/S-Ag_(3)Cu(-3.5×10^(-3)/3.4×10^(-3))than that of R/S-Ag_(4)(-2.7×10^(-3)/2.6×10^(-3)).Furthermore,compared with chiral homometallic clusters R/S-Cu_(4)([Cu_(4)(tppm)(R/S-IPTT)]ClO_(4))with the same TADF characteristic at ambient temperature,R/S-Ag_(3)Cu manifests 1.7-fold PLQY and 6-fold g_(PL)due to faster reverse intersystem crossing(RISC)and more effective coupling of electric and magnetic transition moments in alloy clusters.This work not only presents a typical example of selective heterometal doping to modulate excited-state properties of isostructural metal clusters,but also gets deeper insight into the doping chemistry of dissimilar metals at the molecular level.
基金the financial support from the National Natural Science Foundation of China(Nos.22377097,22307036,22074114)Natural Science Foundation of Hubei Province of China(Nos.2020CFB623,2021CFB556)Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education(No.LCX202305)。
文摘The detection of amino acid enantiomers holds significant importance in biomedical,chemical,food,and other fields.Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes,which can compromise accuracy and repeatability.In this study,we report a novel fluorescent probe(R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths(>60 nm).This water-soluble probe(R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers,enabling reliable chiral detection of 14 natural amino acids.It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color.Additionally,a logic operation with two inputs and three outputs was constructed based on these optical properties.Notably,amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels.This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.
