Zero-dimensional(0D)organic-inorganic metal halide perovskite is one of the hot research topics in the field of optoelectronic materials.Their structure generally consists of discrete metal halide octahedra entirely i...Zero-dimensional(0D)organic-inorganic metal halide perovskite is one of the hot research topics in the field of optoelectronic materials.Their structure generally consists of discrete metal halide octahedra entirely isolated by surrounding organic cations,forming independent luminescent centers[1,2].Such a configuration results in high exciton binding energy and exceptional luminescence efficiency,due to strong quantum confinement[3,4].展开更多
The controlled self-assembly of colloidal nanocrystals(NCs)is a fundamental research challenge in nanoscale materials science,aimed at constructing artificially engineered superlattices capable of rivaling or even exc...The controlled self-assembly of colloidal nanocrystals(NCs)is a fundamental research challenge in nanoscale materials science,aimed at constructing artificially engineered superlattices capable of rivaling or even exceeding the structural complexity in natural crystalline materials[1,2].Significantly,such precisely engineered superlattice architecture may exhibit intriguing optical,electronic,and catalytic functionalities stemming from both the individual NCs and the long-range ordered superlattice matrix[3,4].展开更多
It remained challenging to fabricate Tb^(3+)-doped lanthanide nanocrystals(NCs)to simultaneously acquire strong energy migration upconversion(EMU)emissions of Tb^(3+)while suppressing the Tm3+UV upconversion emissions...It remained challenging to fabricate Tb^(3+)-doped lanthanide nanocrystals(NCs)to simultaneously acquire strong energy migration upconversion(EMU)emissions of Tb^(3+)while suppressing the Tm3+UV upconversion emissions that cause background biofluorescence issues in bioapplications based on Tb^(3+)-doped EMU NCs.Herein,we report a novel sandwich structured core@shell@shell scheme for the design of EMU NCs,for example,NaLuF4∶Yb/Gd@NaGdF4∶Tm@NaLuF4∶Tb NCs,wherein Yb^(3+),Tm^(3+),and Tb^(3+)are incorporated separately into the inner core,middle shell,and outer shell,respectively.We found that in the sandwich structured NCs,the effective inter-shell energy transfer from Gd^(3+)in the middle shell to Tb^(3+)in the outer shell accelerated the Yb^(3+)-Tm^(3+)five-photon upconversion and the subsequent Tm^(3+)to Gd^(3+)energy transfer processes,which could eventually lead to almost complete inhibition of Tm^(3+)UV upconversion emissions,concurrent with the strong EMU emissions of Tb^(3+).Our findings might stimulate new concepts for manipulating upconversion emissions of lanthanide NCs.展开更多
Optical probes hold great promise for temperature sensing owing to their attractive properties including rapid response,high spatial resolution,and remote non-invasive detection.However,the exploration of thermometric...Optical probes hold great promise for temperature sensing owing to their attractive properties including rapid response,high spatial resolution,and remote non-invasive detection.However,the exploration of thermometric probes is hindered by their low relative sensitivity(Sr)or poor structural stability in water.Herein,we propose the first example of organic-inorganic metal halides based on TPP_(3)Cu_(2)Br_(2)(TPP=triphenylphosphine)that simultaneously present excellent water resistance and sensitive temperature-dependent photoluminescence lifetime in water.Benefiting from the soft lattice induced by the organic molecule of TPP,giant thermal expansion and great lattice distortion were achieved with increasing temperature.As such,the self-trapped exciton luminescence lifetime of TPP_(3)Cu_(2)Br_(2)can be shortened to 1.9%of the initial value from 280 to 380 K,resulting in the highest Sr of 12.82%K−1 among the undoped metal halides based luminescent thermometers.Significantly,TPP_(3)Cu_(2)Br_(2)displayed extraordinary water stability with emission intensity remaining nearly unchanged after immersing in water for 15 days.Moreover,high-precision luminescence lifetime based thermal sensing in water environment was successfully conducted,which proved to be inert to the detection depth in water with a small read-out error.This work offers new routes in the exploration of novel metal halides for highly sensitive thermometric probes toward versatile application scenarios.展开更多
The ultrasensitive detection of prostate-specific antigen(PSA)remains challenging for therapeutic evaluation and management of prostate cancer,particularly in monitoring post-prostatectomy recurrence.Current immunoass...The ultrasensitive detection of prostate-specific antigen(PSA)remains challenging for therapeutic evaluation and management of prostate cancer,particularly in monitoring post-prostatectomy recurrence.Current immunoassays,however,lack the sensitivity and robustness necessary for detecting trace-level PSA in clinical samples.To address this limitation,we develop a triplet energy transfer(TET)-sensitized downshifting luminescence immunosorbent assay(TET-DLISA)platform by utilizing size-optimized NaGdF4:Yb^(3+)/Er^(3+)downshifting nanoparticles(DSNPs)functionalized with a carboxylated near-infrared dye(Cypate)as signal reporters,for background-free NIR-Ⅱ detection.Under 808-nm excitation,efficient TET from Cypate to Yb^(3+)amplifies the NIR-Ⅱ emission of Er^(3+)by 284 times in 5.8-nm DSNPs,achieving a highly enhanced intersystem crossing efficiency(82.8%)while minimizing interfacial energy loss.By introducing DSNP@Cypate as an NIR-II signal reporter,the proposed TET-DLISA enables ultrasensitive PSA quantification via alkaline phosphatase(ALP)-catalyzed phosphate displacement of Cypate,yielding an outstanding signal-to-background ratio(SBR)of 273 and a detection limit of 98 fg mL^(-1),which is three orders of magnitude more sensitive than the corresponding ALP-based ELISA.Clinical validation with patient sera confirms a strong correlation with the results from commercial kits,demonstrating the platform’s clinical utility for post-surgical monitoring.This TET-DLISA platform provides a transformative paradigm for ultrasensitive biomarker detection,addressing unmet needs in precision diagnostics.展开更多
Manganese(Mn)-based halide perovskites have attracted tremendous attention due to their low-cost and environment-friendlycharacteristics.Nevertheless,their applications are hindered by limited photoluminescence(PL)eff...Manganese(Mn)-based halide perovskites have attracted tremendous attention due to their low-cost and environment-friendlycharacteristics.Nevertheless,their applications are hindered by limited photoluminescence(PL)efficiency and insufficientstability.Dimensional engineering offers a viable pathway to modulate their photophysical properties and enhance theirrobustness.Herein,we design 2D@3D perovskites based on the dimensional reduction of CsMnCl_(3)⋅2H_(2)O_(3)D perovskites viaalternating cation interactions(ACIs)by employing chitosan as a polymeric spacer cation.ACI effectively stabilized the 2D@3Dperovskite and passivated surface defects through enriched H-bonding.As such,the PL intensity can be boosted by 50 times witha PL quantum yield(PLQY)of 18.1%.Intriguingly,2D@3D perovskites experienced valence transition(VT:Mn^(2+)→Mn^(4+))at hightemperatures,resulting in NH_(4)CsMnCl_(6)perovskite.Density functional theory calculations indicated that an interfacial orbitalhybridization-driven reaction mechanism triggered VT,which was initiated by the synergistic effect of octahedral distortion andACI within 2D@3D perovskite.Notably,the proposed VT perovskites exhibited narrowband emission of Mn^(4+)with remarkableair-,photo-,and thermally stability,achieving a PLQY up to 80.7%.This approach paves the way for exploring organic-inorganicinteractions in designing highly luminescent Mn-based perovskites.展开更多
Luminescent biosensing in the second nearinfrared(NIR-II) region is featured with superior spatial resolution and high penetration depth by virtue of the suppressed scattering of long-wavelength photons. Hitherto, the...Luminescent biosensing in the second nearinfrared(NIR-II) region is featured with superior spatial resolution and high penetration depth by virtue of the suppressed scattering of long-wavelength photons. Hitherto, the reported NIR-II nanoprobes are mostly based on carbon nanotubes, organic fluorophores or semiconducting quantum dots. As an alternative, trivalent lanthanide ions(Ln3+) doped nanoparticles have been emerging as a novel class of promising nanoprobes. In this review, we highlight the recent progress in the design of highly efficient Ln3+-doped NIR-II nanoparticles towards their emerging bioapplications, with an emphasis on autofluorescence-free bioimaging, sensitive bioassay, and accurate temperature sensing. Moreover, some efforts and challenges towards this rapidly expanding field are envisioned.展开更多
The accurate detection of blood glucose is of critical importance in the diagnosis and management of diabetes and its complications. Herein, we report a novel strategy based on an upconversion nanoparticles-polydopami...The accurate detection of blood glucose is of critical importance in the diagnosis and management of diabetes and its complications. Herein, we report a novel strategy based on an upconversion nanoparticles-polydopamine （UCNPs-PDA） nanosystem for the accurate detection of glucose in human serum and whole blood through a simple blending of test samples with ligand-free UCNPs, dopamine, and glucose oxidase （GOx）. Owing to the high affinity of lanthanide ions exposed on the surface of ligand-free UCNPs, dopamine monomers could spontaneously attach to the UCNPs and further polymerize to form a PDA shell resulting in a remarkable upconversion luminescence （UCL） quenching （97.4%） of UCNPs under 980-nm excitation. Such UCL quenching can be effectively inhibited by H2O2 produced from the GOx/glucose enzymatic reaction, thus enabling the detection of H2O2 or glucose based on the UCL quenching/inhibition bioassay. Owing to the highly sensitive UCL response and background-free interference of the UCNPs-PDA nanosystem, we achieved a sensitive, selective, and high-throughput bioassay for glucose in human serum and whole blood, thereby revealing the great potential of the UCNPs-PDA nanosystem for the accurate detection of blood glucose or other HRO2-generated biomolecules in clinical bioassays.展开更多
Sensitive detection of cancer biomarker microRNAs （miRNAs） is of vital importance for cancer diagnosis and treatment. Nonetheless, the detection sensitivity in the existing miRNA bioassays is severely limited by the...Sensitive detection of cancer biomarker microRNAs （miRNAs） is of vital importance for cancer diagnosis and treatment. Nonetheless, the detection sensitivity in the existing miRNA bioassays is severely limited by the structural characteristics of miRNA （including small length and high sequence homology） because most of these methods are based on target amplification. Herein, we report a novel approach to sensitive and specific detection of low-abundance miRNA via a unique strategy of nanoprobe dissolution-enhanced fluorescence amplification, in which a capture probe featuring molecular beacon structure is designed. By means of this strategy, miRNA-21 was detected in a linear range from 10 fM to 100 pM with a detection limit as low as 1.38 fM. High selectivity of the newly developed biosensor was demonstrated by the good discrimination against a target with a single-base mismatch. Furthermore, this assay was used for the detection of miRNA-21 added into fetal bovine serum samples with the recovery in the range of 90.2%--108% and coefficients of variation below 10.1%, indicating its promising applications to RNA immunoassays and early cancer diagnosis.展开更多
Multiplexed intracellular detection is desirable in biomedical sciences for its higher eficiency and accuracy compared to the single-analyte detection.However,it is very challenging to construct nanoprobes that posses...Multiplexed intracellular detection is desirable in biomedical sciences for its higher eficiency and accuracy compared to the single-analyte detection.However,it is very challenging to construct nanoprobes that possess multiple fluorescent signals to recognize the different intracellular species synchronously.Herein,we proposed a novel dual-excitation/dual-emission upconversion strategy for multiplexed detection through the design of upconversion nanoparticles(UCNP)loaded with two dyes for sensitization and quenching of the upconversion luminescence(UCL),respectively.Based on the two independent energy transfer processes of near-infrared(NIR)dye IR845 to UCNP and UCNP to visible dye PAPS-Zn,CIO-and Zn2+were simultaneously detected with a limit of detection(LOD)of41.4 and 10.5 nM,respectively.By tilizing a purpose built 830/980 nm dual-laser confocal microscope,both intrinsic and exogenous CIO and Zn2+in live MCF-7 cells have been accurately quantified.Such dual-excitation/dual-emission ratiometric UCL detection mode enables not only monitoring multiple intracellular analytes but also eliminating the detection deviation caused by inhomogeneous probe distribution in cells.Through modulation of NIR dye and visible dye with other reactive groups,the nanoprobes can be extended to analyze various intraellular species,which provides a promising tool to study the biological activities in live cells and diagnose diseases.展开更多
CuInS2 semiconductor nanocrystals (NCs) exhibit large absorption coefficient, size-dependent photoluminescence and low toxicity, making them excellent candidates in a variety of bioapplications. However, precise contr...CuInS2 semiconductor nanocrystals (NCs) exhibit large absorption coefficient, size-dependent photoluminescence and low toxicity, making them excellent candidates in a variety of bioapplications. However, precise control of both their composition and morphology to improve the luminescent efficiency remains a great challenge via conventional direct synthesis. Herein, we present a novel low-temperature template synthesis of highly efficient luminescent CuInS2 nanoprobes from In2S3 NCs via a facile cation exchange strategy. The proposed strategy enables synthesis of a series of CuInS2 NCs with broad size tunability from 2.2 to 29.6 nm. Through rationally manipulating the stoichiometry of Cu/In, highly efficient luminescence of CuInS2 with the maximum quantum yield of 28.6% has been achieved, which is about one order of magnitude improvement relative to that of directly synthesized NCs. By virtue of the intense emission of CuInS2 nanoprobes, we exemplify their application in sensitive homogeneous biodetection for an important biomolecule of adenosine triphosphate (ATP) with the limit of detection down to 49.3 nM. Moreover, the CuInS2 nanoprobes are explored for ATP-targeted cancer cell imaging, thus revealing their great potentials in the field of cancer diagnosis and prognosis.展开更多
Polarized upconversion luminescence(UCL)of lanthanide-doped micro/nano-crystals has shown great promise in single-particle tracking and super-resolution bioimaging.However,because of the spectral line broadening and m...Polarized upconversion luminescence(UCL)of lanthanide-doped micro/nano-crystals has shown great promise in single-particle tracking and super-resolution bioimaging.However,because of the spectral line broadening and multiple sites of lanthanide in upconversion particles(UCPs),the crystal-field(CF)polarization components of UCL are usually undistinguishable.Herein,we report the linearly polarized UCL in LiLuF_(4):Yb^(3+)/Er^(3+) single microcrystals with resolvable CF transition lines and a polarization degree up to 0.82.The CF levels and CF transition lines of Er^(3+),as well as their emission polarization anisotropy,are unraveled for the first time through low-temperature and high-resolution photoluminescence(PL)and UCL spectroscopies.By taking advantage of the well-resolved and highly-polarized CF transition lines of Er^(3+),we demonstrate the application of LiLuF_(4):Yb^(3+)/Er^(3+) single microcrystals as anisotropic UCL probes for orientation tracking.These findings provide fundamental insights into the polarization anisotropy of UCL in lanthanide-doped single particles,thus laying a foundation for the future design of anisotropic luminescent probes towards versatile applications.展开更多
Lanthanide-based luminescent anti-counterfeiting materials are widely used in various kinds of products.However,the emission color of traditional lanthanide-based luminescent materials usually remains nearly unaltered...Lanthanide-based luminescent anti-counterfeiting materials are widely used in various kinds of products.However,the emission color of traditional lanthanide-based luminescent materials usually remains nearly unaltered upon different excitation lights,which may only work for single-level anti-counterfeiting.Herein,the NaYbF4∶2%Er@NaYF4 core/shell nanoplates (NPs) with "chameleon-like" optical behavior are developed.These NPs display single-band red or green downshifting (DS) emission upon excitation at 377 or 490 nm,respectively.Upon 980 nm excitation,the color of upconversion (UC) emission can be finely tuned from green to yellow,and to red with increasing the excitation power density from 0.1 to 4.0 W/cm^2.The proposed materials readily integrate the advantages of excitation wavelength-dependent DS single-band emissions and sensitive excitation power-dependent UC multicolor emissions in one and the same material,which has never been reported before.Particularly,the proposed NPs exhibit excellent performance as security labels on trademark tag and security ink on painting,thus revealing the great potential of these lanthanide-doped fluoride NPs in multilevel anti-counterfeiting applications.展开更多
Rattle structure is a topic of great interest in design and application of nano- materials due to the unique core@void@shell architecture and the integration of functions. Herein, we developed a novel ＂ship-in-a-bot...Rattle structure is a topic of great interest in design and application of nano- materials due to the unique core@void@shell architecture and the integration of functions. Herein, we developed a novel ＂ship-in-a-bottle＂ method to fabricate upconverting （UC） luminescent nanorattles by incorporating lanthanide-doped fluorides into hollow mesoporous silica. The size of nanorattles and the filling amount of fluorides can be well controlled. In addition, the modification of silica shell （with phenylene and amine groups） and the variation of efficient UC fluorides （NaYF4：Yb, Er, NaLuF4：Yb, Er, NaGdF4：Yb, Er and LiYF4：Yb, Er） were readily achieved. The resulting nanorattles exhibited a high capacity and pH-dependent release of the anti-cancer drug doxorubicin （DOX）. Furthermore, we employed these nanorattles in proof-of-concept UC-monitoring drug release by utilizing the energy transfer process from UC fluorides to DOX, thus revealing the great potential of the nanorattles as efficient cancer theranostic agent.展开更多
Tremendous progress in nanomaterial and nanotechnology has been made in recent years,which greatly contributes to the development of inorganic nanoparticles(NPs)as luminescent probes in diverse biomedical applications...Tremendous progress in nanomaterial and nanotechnology has been made in recent years,which greatly contributes to the development of inorganic nanoparticles(NPs)as luminescent probes in diverse biomedical applications.In particular,these luminescent nanoprobes are widely employed for sensitive assays of biomarkers like disease markers.Generally,the luminescent bioassay technologies mainly rely on conventional molecular probes such as lanthanide(Ln3+)chelates or organic dyes,which suffer from inferior photochemical stability,low photobleaching,potential long-term toxicity,or high background noise.In contrast,Ln3+-doped NPs possess distinct physicochemical properties including better photostability,lower toxicity,and superior optical properties like long photoluminescent(PL)lifetime,narrow emission band,and tunable spectral range from the ultraviolet to the second near-infrared(NIR-II),which make them extremely ideal as luminescent nanoprobes.As such,enormous research enthusiasm has been invested in this fascinating field of Ln3+-doped luminescent nanoprobes in recent years.Accordingly,background-free luminescent bioassays with high signal-to-noise have been achieved by employing Ln3+-doped NPs on the basis of their downshifting luminescence(DSL)with a long PL lifetime,NIR-II luminescence with long-wavelength emissions,or upconverting luminescence(UCL)upon NIR excitation.However,there are still key challenges for Ln3+-doped nanoprobes owing to their low brightness and quantum yield,which restrict their biomedical applications.During the past decade,we have explored efficient approaches for the synthesis and design of highly efficient Ln3+-doped nanoprobes toward ultrasensitive luminescent bioassay of disease markers.In this Account,we summarize our most recent endeavors toward the development of inorganic Ln3+-doped NPs as sensitive nanoprobes for luminescent bioassays.First,we overview the approaches of controlled synthesis and optical manipulation to obtain highly efficient Ln3+-doped NPs with desirable optical properties.Second,we survey the design of Ln3+-doped nanoprobes with outstanding water dispersibility and excellent biocompatibility through surface functional bioconjugation of NPs.By employing these nanoprobes,we propose and exemplify several background-free luminescent bioassay strategies in an effort to suppress the interference of background noise from scattered lights and autofluorescence from biological samples.Third,we highlight the ultrasensitive bioassay of disease markers such as the time-resolved luminescent bioassay,NIR-II luminescent bioassay,and UCL bioassay.Finally,the major challenges,promising emerging trends,and future perspectives on this attractive field are discussed.Through this Account,we aim to offer a series of effective approaches to luminescent bioassay with high sensitivity and excellent specificity based on Ln3+-doped nanoprobes,which may broaden the roadway for clinical bioassays and accelerate the exploration of novel nanoprobes in versatile biomedical applications.展开更多
Near-infrared(NIR)light,which has ignorable tissue scattering/absorption,minimal photodamage,and no autofluorescence interference,is highly favorable for bioapplications.NIR dye and lanthanide-doped nanoparticle(LnNP)...Near-infrared(NIR)light,which has ignorable tissue scattering/absorption,minimal photodamage,and no autofluorescence interference,is highly favorable for bioapplications.NIR dye and lanthanide-doped nanoparticle(LnNP),as representative NIR-excited luminescence probes,have attracted increasing interest due to their unique optical property and low biological toxicity.Design of luminescence probes based on NIR dye/LnNP nanocomposites cannot only integrate the advantages but also achieve additional functions via regulating internal energy transfer pathways.In this review,we focus on the most recent advances in the development of NIR dye/LnNP nanocomposites as potential bioprobes,which cover from their fundamental photophysics to bioapplications,including energy transfer mechanisms,interface engineering(involving binding interaction,distance,and aggregation as key factors),and their applications for dye-sensitized upconversion/downshifting luminescent bioimaging,detection of biomolecules,and NIR-triggered diagnosis and therapy.Some future prospects and efforts toward this active research field are also envisioned.展开更多
Hybrid composites made of metal-organic frameworks(MOFs)and lanthanide-doped upconversion nanoparticles(UCNPs)have attracted considerable interest for their synergistically enhanced functions in various applications s...Hybrid composites made of metal-organic frameworks(MOFs)and lanthanide-doped upconversion nanoparticles(UCNPs)have attracted considerable interest for their synergistically enhanced functions in various applications such as chemical sensing,photocatalysis,anticounterfeiting and nanomedicine.However,precise assembly of MOF/UCNP hybrid composites with tunable morphologies remains a challenge due to the lack of effective synthetic methods and fundamental understanding of the growth mechanisms.Herein,we propose a modulator-directed assembly strategy to synthesize a series of ZIF-8@UCNP composites(ZIF-8=zeolitic imidazolate framework-8).The UCNPs densely paved on the surface of ZIF-8 microcrystals and endowed the composites with intense upconversion blue emission,which were verified by steady-state/transient photoluminescence(PL)spectroscopy and single-particle imaging.Ethylenediamine(EDA)was firstly used as a modulator to fine-tune the predominant MOF facets and realized distinct morphologies of the composites.By adjusting the concentration of EDA from 0 to 25 mmol/L,the morphology of the ZIF-8@UCNP composites was tuned from rhombic dodecahedron(RD)to truncated rhombic dodecahedron(TRD),cube with truncated edges(CTE),cube,and finally a unique form of interpenetration twins(IT).The nucleation and growth process of the ZIF-8@UCNP composites was monitored by time-dependent scanning electron microscopy(SEM)images and the formation mechanism was thoroughly revealed.Furthermore,we demonstrated that the strategy for assembly of morphology-controllable ZIF-8@UCNP composites was generally applicable to various UCNPs with different sizes and shapes.The proposed strategy is expected to open up new avenues for the controllable synthesis of MOF/UCNP composites toward diverse applications.展开更多
Over the past decade,near-infrared(NIR)luminescent materials have emerged as a frontier in photonics and material science,finding diverse applications in bioimaging,encryption,and photodetection[1].Particularly,NIR na...Over the past decade,near-infrared(NIR)luminescent materials have emerged as a frontier in photonics and material science,finding diverse applications in bioimaging,encryption,and photodetection[1].Particularly,NIR nanoprobes are widely utilized in life science and clinical medicine because of their high spatial resolution,deep tissue penetration,low optical absorption and scattering,and minimal autofluorescence[2,3].展开更多
文摘Zero-dimensional(0D)organic-inorganic metal halide perovskite is one of the hot research topics in the field of optoelectronic materials.Their structure generally consists of discrete metal halide octahedra entirely isolated by surrounding organic cations,forming independent luminescent centers[1,2].Such a configuration results in high exciton binding energy and exceptional luminescence efficiency,due to strong quantum confinement[3,4].
文摘The controlled self-assembly of colloidal nanocrystals(NCs)is a fundamental research challenge in nanoscale materials science,aimed at constructing artificially engineered superlattices capable of rivaling or even exceeding the structural complexity in natural crystalline materials[1,2].Significantly,such precisely engineered superlattice architecture may exhibit intriguing optical,electronic,and catalytic functionalities stemming from both the individual NCs and the long-range ordered superlattice matrix[3,4].
基金supported by the Science and Technology Cooperation Fund between Chinese and Australian Governments(grant no.2017YFE0132300)the Strategic Priority Research Program of the CAS(grant no.XDB20000000)+1 种基金the National Natural Science Foundation of China(grant nos.21771185,U1805252,12074380,12074379,and 21975257)the CAS/SAFEA International Partnership Program for Creative Research Teams.
文摘It remained challenging to fabricate Tb^(3+)-doped lanthanide nanocrystals(NCs)to simultaneously acquire strong energy migration upconversion(EMU)emissions of Tb^(3+)while suppressing the Tm3+UV upconversion emissions that cause background biofluorescence issues in bioapplications based on Tb^(3+)-doped EMU NCs.Herein,we report a novel sandwich structured core@shell@shell scheme for the design of EMU NCs,for example,NaLuF4∶Yb/Gd@NaGdF4∶Tm@NaLuF4∶Tb NCs,wherein Yb^(3+),Tm^(3+),and Tb^(3+)are incorporated separately into the inner core,middle shell,and outer shell,respectively.We found that in the sandwich structured NCs,the effective inter-shell energy transfer from Gd^(3+)in the middle shell to Tb^(3+)in the outer shell accelerated the Yb^(3+)-Tm^(3+)five-photon upconversion and the subsequent Tm^(3+)to Gd^(3+)energy transfer processes,which could eventually lead to almost complete inhibition of Tm^(3+)UV upconversion emissions,concurrent with the strong EMU emissions of Tb^(3+).Our findings might stimulate new concepts for manipulating upconversion emissions of lanthanide NCs.
基金supported by the National Natural Science Foundation of China(Nos.22135008,22275188,U22A20398,12104455)Natural Science Foundation of Fujian Province(Nos.2023I0032,2022J05092).
文摘Optical probes hold great promise for temperature sensing owing to their attractive properties including rapid response,high spatial resolution,and remote non-invasive detection.However,the exploration of thermometric probes is hindered by their low relative sensitivity(Sr)or poor structural stability in water.Herein,we propose the first example of organic-inorganic metal halides based on TPP_(3)Cu_(2)Br_(2)(TPP=triphenylphosphine)that simultaneously present excellent water resistance and sensitive temperature-dependent photoluminescence lifetime in water.Benefiting from the soft lattice induced by the organic molecule of TPP,giant thermal expansion and great lattice distortion were achieved with increasing temperature.As such,the self-trapped exciton luminescence lifetime of TPP_(3)Cu_(2)Br_(2)can be shortened to 1.9%of the initial value from 280 to 380 K,resulting in the highest Sr of 12.82%K−1 among the undoped metal halides based luminescent thermometers.Significantly,TPP_(3)Cu_(2)Br_(2)displayed extraordinary water stability with emission intensity remaining nearly unchanged after immersing in water for 15 days.Moreover,high-precision luminescence lifetime based thermal sensing in water environment was successfully conducted,which proved to be inert to the detection depth in water with a small read-out error.This work offers new routes in the exploration of novel metal halides for highly sensitive thermometric probes toward versatile application scenarios.
基金supported by the National Key Research and Development Program of China(No.2022YFB3503700)the NSFC(Nos.U22A20398,22135008,12574475,22275190,and 51402294)+1 种基金NSF of Fujian Province(Nos.2025I0049 and 2023J01261)the Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(Nos.CXZX-2022-GH10 and CXZX-2022-GS01).
文摘The ultrasensitive detection of prostate-specific antigen(PSA)remains challenging for therapeutic evaluation and management of prostate cancer,particularly in monitoring post-prostatectomy recurrence.Current immunoassays,however,lack the sensitivity and robustness necessary for detecting trace-level PSA in clinical samples.To address this limitation,we develop a triplet energy transfer(TET)-sensitized downshifting luminescence immunosorbent assay(TET-DLISA)platform by utilizing size-optimized NaGdF4:Yb^(3+)/Er^(3+)downshifting nanoparticles(DSNPs)functionalized with a carboxylated near-infrared dye(Cypate)as signal reporters,for background-free NIR-Ⅱ detection.Under 808-nm excitation,efficient TET from Cypate to Yb^(3+)amplifies the NIR-Ⅱ emission of Er^(3+)by 284 times in 5.8-nm DSNPs,achieving a highly enhanced intersystem crossing efficiency(82.8%)while minimizing interfacial energy loss.By introducing DSNP@Cypate as an NIR-II signal reporter,the proposed TET-DLISA enables ultrasensitive PSA quantification via alkaline phosphatase(ALP)-catalyzed phosphate displacement of Cypate,yielding an outstanding signal-to-background ratio(SBR)of 273 and a detection limit of 98 fg mL^(-1),which is three orders of magnitude more sensitive than the corresponding ALP-based ELISA.Clinical validation with patient sera confirms a strong correlation with the results from commercial kits,demonstrating the platform’s clinical utility for post-surgical monitoring.This TET-DLISA platform provides a transformative paradigm for ultrasensitive biomarker detection,addressing unmet needs in precision diagnostics.
基金financial support from the CAS President’s International Fellowship Initiative(No.2023VMC0017)the National Natural Science Foundation of China(Nos.22135008,22275188,U22A20398,and 12374389).
文摘Manganese(Mn)-based halide perovskites have attracted tremendous attention due to their low-cost and environment-friendlycharacteristics.Nevertheless,their applications are hindered by limited photoluminescence(PL)efficiency and insufficientstability.Dimensional engineering offers a viable pathway to modulate their photophysical properties and enhance theirrobustness.Herein,we design 2D@3D perovskites based on the dimensional reduction of CsMnCl_(3)⋅2H_(2)O_(3)D perovskites viaalternating cation interactions(ACIs)by employing chitosan as a polymeric spacer cation.ACI effectively stabilized the 2D@3Dperovskite and passivated surface defects through enriched H-bonding.As such,the PL intensity can be boosted by 50 times witha PL quantum yield(PLQY)of 18.1%.Intriguingly,2D@3D perovskites experienced valence transition(VT:Mn^(2+)→Mn^(4+))at hightemperatures,resulting in NH_(4)CsMnCl_(6)perovskite.Density functional theory calculations indicated that an interfacial orbitalhybridization-driven reaction mechanism triggered VT,which was initiated by the synergistic effect of octahedral distortion andACI within 2D@3D perovskite.Notably,the proposed VT perovskites exhibited narrowband emission of Mn^(4+)with remarkableair-,photo-,and thermally stability,achieving a PLQY up to 80.7%.This approach paves the way for exploring organic-inorganicinteractions in designing highly luminescent Mn-based perovskites.
基金supported by the Strategic Priority Research Program of the CAS(XDB20000000)the National Natural Science Foundation of China(21771185,11704380,51672272,21804134and U1805252)+1 种基金the CAS/SAFEA International Partnership Program for Creative Research Teamsthe Natural Science Foundation of Fujian Province(2017I0018)
文摘Luminescent biosensing in the second nearinfrared(NIR-II) region is featured with superior spatial resolution and high penetration depth by virtue of the suppressed scattering of long-wavelength photons. Hitherto, the reported NIR-II nanoprobes are mostly based on carbon nanotubes, organic fluorophores or semiconducting quantum dots. As an alternative, trivalent lanthanide ions(Ln3+) doped nanoparticles have been emerging as a novel class of promising nanoprobes. In this review, we highlight the recent progress in the design of highly efficient Ln3+-doped NIR-II nanoparticles towards their emerging bioapplications, with an emphasis on autofluorescence-free bioimaging, sensitive bioassay, and accurate temperature sensing. Moreover, some efforts and challenges towards this rapidly expanding field are envisioned.
文摘The accurate detection of blood glucose is of critical importance in the diagnosis and management of diabetes and its complications. Herein, we report a novel strategy based on an upconversion nanoparticles-polydopamine （UCNPs-PDA） nanosystem for the accurate detection of glucose in human serum and whole blood through a simple blending of test samples with ligand-free UCNPs, dopamine, and glucose oxidase （GOx）. Owing to the high affinity of lanthanide ions exposed on the surface of ligand-free UCNPs, dopamine monomers could spontaneously attach to the UCNPs and further polymerize to form a PDA shell resulting in a remarkable upconversion luminescence （UCL） quenching （97.4%） of UCNPs under 980-nm excitation. Such UCL quenching can be effectively inhibited by H2O2 produced from the GOx/glucose enzymatic reaction, thus enabling the detection of H2O2 or glucose based on the UCL quenching/inhibition bioassay. Owing to the highly sensitive UCL response and background-free interference of the UCNPs-PDA nanosystem, we achieved a sensitive, selective, and high-throughput bioassay for glucose in human serum and whole blood, thereby revealing the great potential of the UCNPs-PDA nanosystem for the accurate detection of blood glucose or other HRO2-generated biomolecules in clinical bioassays.
文摘Sensitive detection of cancer biomarker microRNAs （miRNAs） is of vital importance for cancer diagnosis and treatment. Nonetheless, the detection sensitivity in the existing miRNA bioassays is severely limited by the structural characteristics of miRNA （including small length and high sequence homology） because most of these methods are based on target amplification. Herein, we report a novel approach to sensitive and specific detection of low-abundance miRNA via a unique strategy of nanoprobe dissolution-enhanced fluorescence amplification, in which a capture probe featuring molecular beacon structure is designed. By means of this strategy, miRNA-21 was detected in a linear range from 10 fM to 100 pM with a detection limit as low as 1.38 fM. High selectivity of the newly developed biosensor was demonstrated by the good discrimination against a target with a single-base mismatch. Furthermore, this assay was used for the detection of miRNA-21 added into fetal bovine serum samples with the recovery in the range of 90.2%--108% and coefficients of variation below 10.1%, indicating its promising applications to RNA immunoassays and early cancer diagnosis.
基金the Science and Technology Cooperation Fund between Chinese and Australian Governments(No.2017YFE0132300)the Strategic Priority Research Program of the CAS(No.XDB20000000)+2 种基金the National Natural Science Foundation of China(Nos.51672272,21771185,21771178,and 21975257)Youth Innovation Promotion Association of CAS(No.2017347)the CAS/SAFEA International Partnership Program for Creative Research Teams.
文摘Multiplexed intracellular detection is desirable in biomedical sciences for its higher eficiency and accuracy compared to the single-analyte detection.However,it is very challenging to construct nanoprobes that possess multiple fluorescent signals to recognize the different intracellular species synchronously.Herein,we proposed a novel dual-excitation/dual-emission upconversion strategy for multiplexed detection through the design of upconversion nanoparticles(UCNP)loaded with two dyes for sensitization and quenching of the upconversion luminescence(UCL),respectively.Based on the two independent energy transfer processes of near-infrared(NIR)dye IR845 to UCNP and UCNP to visible dye PAPS-Zn,CIO-and Zn2+were simultaneously detected with a limit of detection(LOD)of41.4 and 10.5 nM,respectively.By tilizing a purpose built 830/980 nm dual-laser confocal microscope,both intrinsic and exogenous CIO and Zn2+in live MCF-7 cells have been accurately quantified.Such dual-excitation/dual-emission ratiometric UCL detection mode enables not only monitoring multiple intracellular analytes but also eliminating the detection deviation caused by inhomogeneous probe distribution in cells.Through modulation of NIR dye and visible dye with other reactive groups,the nanoprobes can be extended to analyze various intraellular species,which provides a promising tool to study the biological activities in live cells and diagnose diseases.
基金supported by the Strategic Priority Research Program of the CAS (No.XDB20000000)the National Natural Science Foundation of China (Nos.U1805252, 21771185,21804134, 51672272, and 21771178)the CAS/SAFEA International Partnership Program for Creative Research Teams, and Natural Science Foundation of Fujian Province (No.201710018).
文摘CuInS2 semiconductor nanocrystals (NCs) exhibit large absorption coefficient, size-dependent photoluminescence and low toxicity, making them excellent candidates in a variety of bioapplications. However, precise control of both their composition and morphology to improve the luminescent efficiency remains a great challenge via conventional direct synthesis. Herein, we present a novel low-temperature template synthesis of highly efficient luminescent CuInS2 nanoprobes from In2S3 NCs via a facile cation exchange strategy. The proposed strategy enables synthesis of a series of CuInS2 NCs with broad size tunability from 2.2 to 29.6 nm. Through rationally manipulating the stoichiometry of Cu/In, highly efficient luminescence of CuInS2 with the maximum quantum yield of 28.6% has been achieved, which is about one order of magnitude improvement relative to that of directly synthesized NCs. By virtue of the intense emission of CuInS2 nanoprobes, we exemplify their application in sensitive homogeneous biodetection for an important biomolecule of adenosine triphosphate (ATP) with the limit of detection down to 49.3 nM. Moreover, the CuInS2 nanoprobes are explored for ATP-targeted cancer cell imaging, thus revealing their great potentials in the field of cancer diagnosis and prognosis.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(CAS,XDB20000000)the National Natural Science Foundation of China(U1805252,21875250,11774345,12074379,21771185,12074380,and 21975257)+1 种基金the Youth Innovation Promotion Association of the CAS(2020305)the Natural Science Foundation of Fujian Province(2020I0037).
文摘Polarized upconversion luminescence(UCL)of lanthanide-doped micro/nano-crystals has shown great promise in single-particle tracking and super-resolution bioimaging.However,because of the spectral line broadening and multiple sites of lanthanide in upconversion particles(UCPs),the crystal-field(CF)polarization components of UCL are usually undistinguishable.Herein,we report the linearly polarized UCL in LiLuF_(4):Yb^(3+)/Er^(3+) single microcrystals with resolvable CF transition lines and a polarization degree up to 0.82.The CF levels and CF transition lines of Er^(3+),as well as their emission polarization anisotropy,are unraveled for the first time through low-temperature and high-resolution photoluminescence(PL)and UCL spectroscopies.By taking advantage of the well-resolved and highly-polarized CF transition lines of Er^(3+),we demonstrate the application of LiLuF_(4):Yb^(3+)/Er^(3+) single microcrystals as anisotropic UCL probes for orientation tracking.These findings provide fundamental insights into the polarization anisotropy of UCL in lanthanide-doped single particles,thus laying a foundation for the future design of anisotropic luminescent probes towards versatile applications.
基金the National Natural Foundation of China (NSFC)(Nos.21771185,51672272,21650110462,and U1805252)the Strategic Priority Research Program of the CAS (No.XDB20000000)+1 种基金the CAS/SAFEA International Partnership Program for Creative Research TeamsNatural Science Foundation of Fujian Province (No. 201710018).
文摘Lanthanide-based luminescent anti-counterfeiting materials are widely used in various kinds of products.However,the emission color of traditional lanthanide-based luminescent materials usually remains nearly unaltered upon different excitation lights,which may only work for single-level anti-counterfeiting.Herein,the NaYbF4∶2%Er@NaYF4 core/shell nanoplates (NPs) with "chameleon-like" optical behavior are developed.These NPs display single-band red or green downshifting (DS) emission upon excitation at 377 or 490 nm,respectively.Upon 980 nm excitation,the color of upconversion (UC) emission can be finely tuned from green to yellow,and to red with increasing the excitation power density from 0.1 to 4.0 W/cm^2.The proposed materials readily integrate the advantages of excitation wavelength-dependent DS single-band emissions and sensitive excitation power-dependent UC multicolor emissions in one and the same material,which has never been reported before.Particularly,the proposed NPs exhibit excellent performance as security labels on trademark tag and security ink on painting,thus revealing the great potential of these lanthanide-doped fluoride NPs in multilevel anti-counterfeiting applications.
基金This work is supported by the National Basic Research Program of China （No. 2014CB845605）, Special Project of National Major Scientific Equipment Development of China （No. 2012YQ120060）, the National Natural Science Foundation of China （Nos. 21201163, 21401196, U1305244, and 21325104）, the CAS/SAFEA International Partnership Program for Creative Research Teams, and Strategic Priority Research Program of the CAS （No. XDA09030307）.
文摘Rattle structure is a topic of great interest in design and application of nano- materials due to the unique core@void@shell architecture and the integration of functions. Herein, we developed a novel ＂ship-in-a-bottle＂ method to fabricate upconverting （UC） luminescent nanorattles by incorporating lanthanide-doped fluorides into hollow mesoporous silica. The size of nanorattles and the filling amount of fluorides can be well controlled. In addition, the modification of silica shell （with phenylene and amine groups） and the variation of efficient UC fluorides （NaYF4：Yb, Er, NaLuF4：Yb, Er, NaGdF4：Yb, Er and LiYF4：Yb, Er） were readily achieved. The resulting nanorattles exhibited a high capacity and pH-dependent release of the anti-cancer drug doxorubicin （DOX）. Furthermore, we employed these nanorattles in proof-of-concept UC-monitoring drug release by utilizing the energy transfer process from UC fluorides to DOX, thus revealing the great potential of the nanorattles as efficient cancer theranostic agent.
基金supported by the National Key R&D Program of China(No.2022YFB3503700)the National Natural Science Foundation of China(Nos.21975257,22275188,22135008,U22A20398)the CAS/SAFEA International Partnership Program for Creative Research Teams,Natural Science Foundation of Fujian Province(No.2021L3024).
文摘Tremendous progress in nanomaterial and nanotechnology has been made in recent years,which greatly contributes to the development of inorganic nanoparticles(NPs)as luminescent probes in diverse biomedical applications.In particular,these luminescent nanoprobes are widely employed for sensitive assays of biomarkers like disease markers.Generally,the luminescent bioassay technologies mainly rely on conventional molecular probes such as lanthanide(Ln3+)chelates or organic dyes,which suffer from inferior photochemical stability,low photobleaching,potential long-term toxicity,or high background noise.In contrast,Ln3+-doped NPs possess distinct physicochemical properties including better photostability,lower toxicity,and superior optical properties like long photoluminescent(PL)lifetime,narrow emission band,and tunable spectral range from the ultraviolet to the second near-infrared(NIR-II),which make them extremely ideal as luminescent nanoprobes.As such,enormous research enthusiasm has been invested in this fascinating field of Ln3+-doped luminescent nanoprobes in recent years.Accordingly,background-free luminescent bioassays with high signal-to-noise have been achieved by employing Ln3+-doped NPs on the basis of their downshifting luminescence(DSL)with a long PL lifetime,NIR-II luminescence with long-wavelength emissions,or upconverting luminescence(UCL)upon NIR excitation.However,there are still key challenges for Ln3+-doped nanoprobes owing to their low brightness and quantum yield,which restrict their biomedical applications.During the past decade,we have explored efficient approaches for the synthesis and design of highly efficient Ln3+-doped nanoprobes toward ultrasensitive luminescent bioassay of disease markers.In this Account,we summarize our most recent endeavors toward the development of inorganic Ln3+-doped NPs as sensitive nanoprobes for luminescent bioassays.First,we overview the approaches of controlled synthesis and optical manipulation to obtain highly efficient Ln3+-doped NPs with desirable optical properties.Second,we survey the design of Ln3+-doped nanoprobes with outstanding water dispersibility and excellent biocompatibility through surface functional bioconjugation of NPs.By employing these nanoprobes,we propose and exemplify several background-free luminescent bioassay strategies in an effort to suppress the interference of background noise from scattered lights and autofluorescence from biological samples.Third,we highlight the ultrasensitive bioassay of disease markers such as the time-resolved luminescent bioassay,NIR-II luminescent bioassay,and UCL bioassay.Finally,the major challenges,promising emerging trends,and future perspectives on this attractive field are discussed.Through this Account,we aim to offer a series of effective approaches to luminescent bioassay with high sensitivity and excellent specificity based on Ln3+-doped nanoprobes,which may broaden the roadway for clinical bioassays and accelerate the exploration of novel nanoprobes in versatile biomedical applications.
基金Science andTechnologyCooperation Fund between Chinese and AustralianGovernments,Grant/Award Number:2017YFE0132300Strategic Priority Research Program of the CAS,Grant/Award Number:XDB20000000+1 种基金NSFC,Grant/Award Numbers:51672272,21771185,21771178,21975257,12074380Youth Innovation Promotion Association of CAS,Grant/Award Number:2017347。
文摘Near-infrared(NIR)light,which has ignorable tissue scattering/absorption,minimal photodamage,and no autofluorescence interference,is highly favorable for bioapplications.NIR dye and lanthanide-doped nanoparticle(LnNP),as representative NIR-excited luminescence probes,have attracted increasing interest due to their unique optical property and low biological toxicity.Design of luminescence probes based on NIR dye/LnNP nanocomposites cannot only integrate the advantages but also achieve additional functions via regulating internal energy transfer pathways.In this review,we focus on the most recent advances in the development of NIR dye/LnNP nanocomposites as potential bioprobes,which cover from their fundamental photophysics to bioapplications,including energy transfer mechanisms,interface engineering(involving binding interaction,distance,and aggregation as key factors),and their applications for dye-sensitized upconversion/downshifting luminescent bioimaging,detection of biomolecules,and NIR-triggered diagnosis and therapy.Some future prospects and efforts toward this active research field are also envisioned.
基金This work was supported by the National Natural Science Foundation of China(NSFC)(Nos.U1805252,22175179,22135008,12174392,21975257,and 12104456)NSF of Fujian Province(Nos.2021I0040,2021L3024)the Chinese Academy of Sciences/State Administration of Foreign Experts Affairs(CAS/SAFEA)International Partnership Program for Creative Research Teams.
文摘Hybrid composites made of metal-organic frameworks(MOFs)and lanthanide-doped upconversion nanoparticles(UCNPs)have attracted considerable interest for their synergistically enhanced functions in various applications such as chemical sensing,photocatalysis,anticounterfeiting and nanomedicine.However,precise assembly of MOF/UCNP hybrid composites with tunable morphologies remains a challenge due to the lack of effective synthetic methods and fundamental understanding of the growth mechanisms.Herein,we propose a modulator-directed assembly strategy to synthesize a series of ZIF-8@UCNP composites(ZIF-8=zeolitic imidazolate framework-8).The UCNPs densely paved on the surface of ZIF-8 microcrystals and endowed the composites with intense upconversion blue emission,which were verified by steady-state/transient photoluminescence(PL)spectroscopy and single-particle imaging.Ethylenediamine(EDA)was firstly used as a modulator to fine-tune the predominant MOF facets and realized distinct morphologies of the composites.By adjusting the concentration of EDA from 0 to 25 mmol/L,the morphology of the ZIF-8@UCNP composites was tuned from rhombic dodecahedron(RD)to truncated rhombic dodecahedron(TRD),cube with truncated edges(CTE),cube,and finally a unique form of interpenetration twins(IT).The nucleation and growth process of the ZIF-8@UCNP composites was monitored by time-dependent scanning electron microscopy(SEM)images and the formation mechanism was thoroughly revealed.Furthermore,we demonstrated that the strategy for assembly of morphology-controllable ZIF-8@UCNP composites was generally applicable to various UCNPs with different sizes and shapes.The proposed strategy is expected to open up new avenues for the controllable synthesis of MOF/UCNP composites toward diverse applications.
文摘Over the past decade,near-infrared(NIR)luminescent materials have emerged as a frontier in photonics and material science,finding diverse applications in bioimaging,encryption,and photodetection[1].Particularly,NIR nanoprobes are widely utilized in life science and clinical medicine because of their high spatial resolution,deep tissue penetration,low optical absorption and scattering,and minimal autofluorescence[2,3].
