Two novel thieno-[3,4-b]-pyrazine-based molecules, TP-E and TP-O, were designed and synthesized for potential application as red fluorescent emitters. The bulky tetraphenylethylene groups were attached at the peripher...Two novel thieno-[3,4-b]-pyrazine-based molecules, TP-E and TP-O, were designed and synthesized for potential application as red fluorescent emitters. The bulky tetraphenylethylene groups were attached at the periphery of the thieno-[3,4-b]-pyrazine core to form the non-planar molecules, as efficient solid- state emitting materials. The peripheral groups were grafted to the emissive core through either a conjugated acetylene bond, or a non-conjugated ether bond. These molecules exhibit strnng red fluorescence in both dilute solutions and in thin films with large Stokes shifts of over 100 nm. The cyclic voltammetry measurements showed the reversible oxidation and reduction behavior for both compounds. All these properties indicate the two compounds are possible functional materials for use in ontoelectronic devices.展开更多
Organic fluorescentmaterials(OFMs),characterized by their unique molecular structures and exceptional optical properties,have demonstrated significant potential in diverse applications such as bioimaging,sensors,and d...Organic fluorescentmaterials(OFMs),characterized by their unique molecular structures and exceptional optical properties,have demonstrated significant potential in diverse applications such as bioimaging,sensors,and display technologies.Nevertheless,the reliance on chemists’intuition and experience in the traditional design of OFMs,coupled with the high cost and lack of scalability of conventional methods such as fluorescence detection and Density Functional Theory(DFT)calculations,makes it difficult to keep up with the rapid development of the field.The advent ofmachine learning(ML)has introduced transformative possibilities,enabling data-driven exploration of the intricate relationships between molecular structures and fluorescence properties.Herein,we review the applications of ML in the innovative design of OFMs with an emphasis on the workflow of modeling,optical property prediction,and OFM design.We also discuss the critical role of data curation and feature engineering in enhancing model performance.Our review provides an overview of commonly used models and assesses their efficacy.We critically examine key challenges such as database construction,model interpretability,and generalization ability,trying to provide a comprehensive framework that advances the integration of ML in the research of organic fluorescentmaterials,thereby facilitating the development of next-generation materials.展开更多
Comprehensive Summary Fluorescent silk has potential application in many fields such as bioimaging,tissue engineering scaffolds,luminescent marks,and dazzling fabrics.Among the methods to endow natural silk with fluor...Comprehensive Summary Fluorescent silk has potential application in many fields such as bioimaging,tissue engineering scaffolds,luminescent marks,and dazzling fabrics.Among the methods to endow natural silk with fluorescent properties,feeding silkworms with fluorescent additives is facile,low-cost and environment friendly,which has the prospect of large-scale production.In this paper,we reviewed the research progress for this aim in the past ten years,and summarized the unified characteristics for the substances that can enter the silk gland by digestive tract of silkworms.The advantages and disadvantages of various fluorescent materials for this application are compared in detail.And the future research directions are suggested to overcome the shortcomings of the present research.展开更多
The ionothermal reaction between CuCl_(2),1,4-bis(1,2,4-triazol-1-ylmethyl)benzene(BBTZ),and(NH_(4))_(6)Mo_(7)O_(24) in 1-ethyl-3-methylimidazolium bromide((Emim)Br)led to a new octamolybdate-based coordination polyme...The ionothermal reaction between CuCl_(2),1,4-bis(1,2,4-triazol-1-ylmethyl)benzene(BBTZ),and(NH_(4))_(6)Mo_(7)O_(24) in 1-ethyl-3-methylimidazolium bromide((Emim)Br)led to a new octamolybdate-based coordination polymer(Emim)2[Cu(BBTZ)_(2)(β-Mo_(8)O_(26))](Mo_(8)-CP).Mo_(8)-CP was characterized by elemental analysis,thermogravime-try,IR,powder X-ray diffraction,and single-crystal X-ray diffraction.In Mo_(8)-CP,structural analysis reveals that Cu coordinates with BBTZ ligands to form an interlocked 1D chain.These chains are further bridged by(β-Mo_(8)O_(26))^(4-)to construct a 3D coordination polymer.Notably,(Emim)^(+)acts as a structure-directing agent,occupying the channels of the 3D coordination polymer.Based on this unique structure,the ion exchange properties of Mo_(8)-CP toward rare-earth ions were investigated.It has been found that the luminescent color of the material can be successfully regulat-ed by introducing Eu^(3+)or Tb^(3+)through ion exchange.CCDC:2475110,Mo_(8)-CP.展开更多
During past few years,the construction of fluorescent metallacycles featuring the fluorescenceresonance energy transfer behavior has attracted extensive attention due to their diverse applications such as real-time mo...During past few years,the construction of fluorescent metallacycles featuring the fluorescenceresonance energy transfer behavior has attracted extensive attention due to their diverse applications such as real-time monitoring the dynamics of coordination-driven self-assembly,photoswitching fluorescence-resonance energy transfer,and light-controlled generation of singlet oxygen for cancer therapy.This review focuses on the recent advances on the design principles,preparation methods,optical properties,and the wide applications of fluorescent metallacycles with the FRET property.展开更多
Phospholes are emerging as distinctive conjugated scaffolds for organic fluorescent materials owing to their unique structural characteristics that are different from many commonly studied heterocyclic frameworks.Rece...Phospholes are emerging as distinctive conjugated scaffolds for organic fluorescent materials owing to their unique structural characteristics that are different from many commonly studied heterocyclic frameworks.Recently,phosphole-derived skeletons have garnered significant attention as a remarkable electron-accepting moiety,which has achieved substantial advance-ments in the application of fluorescent biomaterials because of their physicochemical traits,especially in the aspects of stability and versatility.In this context,this review summarizes the progress in phosphole-based fluorescent biomaterials over the past decade(2015-2024).It begins with an overview of the currently developed phosphole-based scaffolds specifically designed for biological applications,illustrating their unique structures and favorable properties.Representative examples are then showcased to demonstrate their potential in various biological scenarios with a primary focus on bioimaging and therapy.Last,challenges and prospects in this field are presented.This review could serve as a consolidated and valuable reference for the future exploration and innovation of bioimaging and therapy platforms.展开更多
Optical imaging plays an important role in biomedical research being extremely useful for early detection, screening and image-guided therapy. Lanthanide-doped up-converting nanoparticles were ideally suited for bioim...Optical imaging plays an important role in biomedical research being extremely useful for early detection, screening and image-guided therapy. Lanthanide-doped up-converting nanoparticles were ideally suited for bioimaging because they could be ex- cited in near infrared （NIR） and emit in NIR or visible （VIS）. Here, we compared lanthanide doped up-converting NaYF4 and organic fluorophores for application in deep-tissue imaging. For that purpose - tissue phantoms mimicking the natural properties of light scat- tering by living tissues were prepared. The studies allowed to quantitatively compare optical resolution of different fluorescent com- pounds, revealing that the NIR photoexcitation was favorable over conventional UV photoexcitation.展开更多
Here,we demonstrate the assembly of a new stable lanthanide-based metal-organic framework(MOF),Eu(HDPB)(phen)(1)(HDPB=(1,1’:3’,1’’-terphenyl)-3,3’’,5,5’’-tetracarboxylic acid,phen=1,10-phenanthroline),with a t...Here,we demonstrate the assembly of a new stable lanthanide-based metal-organic framework(MOF),Eu(HDPB)(phen)(1)(HDPB=(1,1’:3’,1’’-terphenyl)-3,3’’,5,5’’-tetracarboxylic acid,phen=1,10-phenanthroline),with a three-dimensional framework under solvothermal conditions.1 showed strong red fluorescence emission at room temperature and could be used as a selective and sensitive chemical sensor for pH and folic acid(FA)detection.Moreover,1 could also be applied as a fluorescent material for the visible identification of fingerprints.Then,using 1 as a filler,two mixed-matrix membranes(MMMs),1@poly(ε-caprolactone)(PCL)and 1@poly(vinylidene difluoride)(PVDF),have been fabricated.Notably,owing to the hydrophobic protection provided by the polymer matrix of the MOF particles,these two MMMs also exhibited fluorescence emission comparable to that of 1 and could be used for FA sensing with good selectivity and remarkable recyclability.More importantly,this is the first time that Eu-MOF-based MMMs have been employed in FA detection.The fabrication of MOF-based MMMs not only provides a facile method for sensing biomarkers,but it also enhances the recyclability of sensors.展开更多
Benzo-21-crown-7(B21 C7)is one of the most important crown ethers,which not only shows excellent physicochemical properties but also exhibits promising binding capability with dialkylammonium salts.In this paper,we de...Benzo-21-crown-7(B21 C7)is one of the most important crown ethers,which not only shows excellent physicochemical properties but also exhibits promising binding capability with dialkylammonium salts.In this paper,we designed and synthesized a fixed-tetraphenylethylene(FTPE)motif bridged ditopic benzo-21-crown-7 molecule(H).The fixed tetraphenylethylene motif endows H with aggregation induced emission(AIE)prope rty.In the presence of a ditopic dialkylammonium salt vip molecule(G),a fluorescent supramolecular polymer with golden luminescent property could be fabricated.This B21 C7-based host-vip supramolecular polymer with golden fluorescence may have potential application in dynamic luminescent materials.展开更多
Under hydrothermal environment,we synthesized lanthanide ions doped sodium yttrium fluoride(NaYF4:Er,Tm@NaYF4:Ce,Tb) luminescent microcrystals via an epitaxial growth technique.The structure and morphology of these mi...Under hydrothermal environment,we synthesized lanthanide ions doped sodium yttrium fluoride(NaYF4:Er,Tm@NaYF4:Ce,Tb) luminescent microcrystals via an epitaxial growth technique.The structure and morphology of these microcrystals were examined by SEM,TEM,EDS and XRD measurements.These particles show dual-mode emissions with red upconversion(UC) and green down conversion(DC) as single particles level.The mean length and diameter of these microparticles increase from 0.43 to2.26 μm and from 1.33 to 1.86 μm,respectively.Most interestingly,the photoluminescence properties of NaYF4:Er,Tm@NaYF4:Ce,Tb phosphor crystals are highly dependent on the crystallite size.The microcrystals fluoresce emit dual-mode emissions when they are solid or dispersed in solvents.Benefiting its intensive fluorescence and uniform morphology,these materials hold great potential for security and anti-counterfeiting applications.展开更多
Fluorescence material of Sm doped Si-Ca-Mg system was synthesized by using the method of solid phase reaction at high temperature. The phase composition and crystal structure of this material were analyzed with XRD me...Fluorescence material of Sm doped Si-Ca-Mg system was synthesized by using the method of solid phase reaction at high temperature. The phase composition and crystal structure of this material were analyzed with XRD method for its composition and the existence form of Sm atom. We aimed to exactly determine the phase composition of this fluorescence material and the doping position and environment of rare-earth Sm atom in the system because these factors have significant effects on the properties. The analytical results show that the Sm atoms dope in Ca2O26Si6Sm8 lattice in the form of atomic site-occupation in three different space positions with different occupancy rates. Therefore, based on the XRD analytical results, the fluorescence material of Sm doped Si-Ca-Mg system with high performance can be synthesized.展开更多
Many researchers have studied the photocatalytic oxidation of trace levels of benzene,toluene and xy-lene in air over titania photocatalysts.However,atthe moment,the effectiveness of the photocatalytic oxidation is li...Many researchers have studied the photocatalytic oxidation of trace levels of benzene,toluene and xy-lene in air over titania photocatalysts.However,atthe moment,the effectiveness of the photocatalytic oxidation is limited by the deactivation of photocata-lysts.展开更多
Metallacycles hold great promise for fluorescence-based sensing due to their synthetic advantages and unique physicochemical properties. However, it remains highly challenging to develop a versatile methodology for co...Metallacycles hold great promise for fluorescence-based sensing due to their synthetic advantages and unique physicochemical properties. However, it remains highly challenging to develop a versatile methodology for constructing highly emissive metallacycles with targeted functionalities and therefore soughtafter properties. Herein, we report a general strategy to construct a series of highly emissive perylene diimide-based metallacycles via the self-assembly of perylene diimide-based tetrapyridyl ligand with different dicarboxylic ligands featuring fixed angles and cis-Pt(PEt_(3))_(2)(OTf)_(2). Single crystal X-ray diffraction analyses verify the formation of bowtie-like metallacycles with two triangular cavities. Notably, the fluorescence quantum yields of most assemblies exceed 98%, amongst the highest values for metallacycles.Additionally, such metallacycles exhibit sensitive fluorescence responses toward picric acid with a detection limit of 2.8 × 10^(-6)mol/L. This study not only provides a rational strategy for preparing highly emissive bowtie-shaped metallacycles, but also sheds light on their usage in the detection of picric acid and associated compounds.展开更多
Dynamic fluorescent materials capable of stimulus-responsive emission modulation have emerged as pivotal components in next-generation information security systems.This study presents a novel photoresponsive fluoresce...Dynamic fluorescent materials capable of stimulus-responsive emission modulation have emerged as pivotal components in next-generation information security systems.This study presents a novel photoresponsive fluorescent composite system in which spiropyran(SP)was covalently grafted onto naphthalimide-functionalized silica aerogel matrices.These architectures exhibit reversible fluorescence resonance energy transfer between the naphthalimide donors and merocyanine-form of SP acceptors under ultraviolet irradiation,enabling dynamic emission shifting from green(blue)to red.The aggregation-induced emission characteristics of SP were used to engineer a smart material system that can reversibly regulate its distinct red fluorescence by precisely controlling the dispersion of amino groups on naphthalimide-functionalized silica aerogels.This spatial manipulation directly governs the molecular packing state of SP,enabling dynamic fluorescence modulation.A programmable control over the fluorescence chromatic transitions in the composite material was achieved by systematically adjusting the SP grafting densities(1%,2%,and 3%w/w).A unique mode of dynamic information encryption technology was developed by utilizing dynamic fluorescence variations.These materials can substantially enhance information encryption levels due to their precisely adjustable fluorescence properties in response to external stimuli over time.This makes the encryption process even more unpredictable and complex,thereby exponentially increasing the difficulty for unauthorized parties to replicate or decode the encrypted information.展开更多
Since Tang and Van Slyke’s seminal 1987 discovery[1],organic light-emitting diodes(OLEDs)have evolved into display technology mainstays[2].Nevertheless,developing blue OLEDs that simultaneously satisfy the stringent ...Since Tang and Van Slyke’s seminal 1987 discovery[1],organic light-emitting diodes(OLEDs)have evolved into display technology mainstays[2].Nevertheless,developing blue OLEDs that simultaneously satisfy the stringent demands for efficiency,operational lifetime,and color purity remains a critical hurdle[3,4].Thermally activated delayed fluorescence(TADF)materials emerged as a promising solution,enabling 100%exciton utilization without noble metals while offering exceptional molecular tunability[5,6].展开更多
Latent fingerprints are extremely vital for personal identification and criminalinvestigation,and potential information recognition techniques have been widelyused in the fields of information and communication electr...Latent fingerprints are extremely vital for personal identification and criminalinvestigation,and potential information recognition techniques have been widelyused in the fields of information and communication electronics.Although physicalpowder dusting methods have been frequently employed to develop latent fingerprintsand most of them are carried out by using single component powders ofmicron-sized fluorescent particles,magnetic powders,or metal particles,there isstill an enormous challenge in producing high-resolution image of latent fingerprintsat different backgrounds or substrates.Herein,a novel and effectivenanoimpregnation method is developed to synthesize bifunctional magnetic fluorescentmesoporous microspheres for latent fingerprints visualization by growthof mesoporous silica(mesoSiO_(2))on magical Fe_(3)O_(4) core and then deposition offluorescent YVO4:Eu^(3+)nanoparticles in the mesopores.The obtainedFe_(3)O_(4)@mesoSiO_(2)@YVO4:Eu^(3+)microspheres possess spatially isolated magneticcore and fluorescent shell which were insulated by mesoporous silica layer.Dueto their small particle size of submicrometer scale,high magnetization and lowmagnetic remanence as well as the combined magnetic and fluorescent properties,the microspheres show superior performance in visual latent fingerprint recognitionwith high contrast,high anti-interference,and sensitivity as well as goodretention on multifarious substrates regardless of surface permeability,roughness,refraction,colorfulness,and background fluorescence interference,and it makesthem ideal candidates for practical application in fingerprint visualization andeven magneto-optic information storage.展开更多
Dynamic fluorescent materials play a crucial role in secure inks for data encryption;however,they are still plagued by issues such as photodegradation,poor latency,and susceptibility to unauthorized access.Herein,we p...Dynamic fluorescent materials play a crucial role in secure inks for data encryption;however,they are still plagued by issues such as photodegradation,poor latency,and susceptibility to unauthorized access.Herein,we propose a photochemically modulated dynamic fluorescent encryption system based on^(1)O_(2)sensitization of fluorescent composites,comprising a^(1)O_(2)-sensitive fluorophore(F2)and non-emissive polymers.After UV irradiation,in-situ generated^(1)O_(2)from the polymer effectively binds with F2 to form endoperoxides(F2EPO),resulting in a significant redshift in emission,up to 150 nm.The^(1)O_(2)concentration is closely related to the irradiation time,rendering different fluorescent colors in a time-gated fashion.Moreover,the emission of F2EPO can be regulated by polymer chemical structure,molecular weight,and crosslinking density.Relying on these merits,we develop a dynamic data encryption method with various non-emissive polymers as the data storage media,UV light irradiation as the data encoder,and F2 as the data decoder.UV light irradiation of diverse polymer solutions generates^(1)O_(2)at different concentrations,effectively encoding the data,which remains invisible under both UV and natural lights.The addition of F2 to these irradiated polymer solutions produces different redshifted fluorescence,enabling secure data decryption.Attributing to the non-emissive nature of the polymers,time-gated readout fashion,excellent latency of^(1)O_(2),and subtle interactions between^(1)O_(2)and F2,this data encryption is nearly undecipherable.This work offers an advantage data encryption approach beyond the reach of conventional fluorophores.展开更多
Here,multimodal fluorescent materials of Ca_(3)Al_(2)Ge_(3)O_(12):Mn^(2+),Cr^(3+)were synthesized by the traditional high-temperature solid-state reaction method.In this garnet Ca_(3)Al_(2)Ge_(3)O_(12) structure,Mn^(2...Here,multimodal fluorescent materials of Ca_(3)Al_(2)Ge_(3)O_(12):Mn^(2+),Cr^(3+)were synthesized by the traditional high-temperature solid-state reaction method.In this garnet Ca_(3)Al_(2)Ge_(3)O_(12) structure,Mn^(2+)and Cr^(3+)ions occupy dodecahedral sites(Ca sites)and hexahedral sites(Al sites),and can produce dynamic colortunable persistent luminescence at different concentrations,different excitations,and different temperatures;in particular,continuous luminescence with temperature(300 K–473 K)shows a color change from green to deep red.Through detailed pyrolysis studies and theoretical calculations,it is demonstrated that the double-trap structure existing in the host makes the persistent luminescence color temperaturedependent.Anti-counterfeiting and industrial inspection molds were successfully accomplished,which means Ca_(3)Al_(2)Ge_(3)O_(12):Mn^(2+),Cr^(3+)may be used in anti-counterfeiting and industrial inspection.展开更多
Traditional fluorescent materials are easy to counterfeit because of their static and single signal output.Photofluorochromic materials with highly efficient luminescence and color-changing behavior increase the infor...Traditional fluorescent materials are easy to counterfeit because of their static and single signal output.Photofluorochromic materials with highly efficient luminescence and color-changing behavior increase the information encryption level,but it is challenging to regulate their fluorescent quenching rate after photoinduced electron transfer(PET),therefore photofluorochromic materials have been rarely reported.This work proposes that improving theπ-conjugation effect of luminescent units and avoiding Förster resonance energy transfer(FRET)during photochromic processes are effective strategies to construct photofluorochromic materials.Accordingly,three novel organic supramolecular compounds with different photofluorochromic properties were prepared and their application in information encryption and multiple dynamic anticounterfeiting was evaluated.The findings of this work demonstrate an effective strategy for the design of photofluorochromic molecules with higher security requirements for multiple dynamic anticounterfeiting.展开更多
It is attractive and encouraging to develop new fluorescent carbon dots(CDs)with excellent optical properties and promising applications prospects.Herein,highly-efficient green emissive CDs(m-CDs)with a high quantum y...It is attractive and encouraging to develop new fluorescent carbon dots(CDs)with excellent optical properties and promising applications prospects.Herein,highly-efficient green emissive CDs(m-CDs)with a high quantum yield(QY)of 71.7%in water are prepared through a facile solvothermal method.Interestingly,the m-CDs exhibit excellent fluorescence stability in the pH range of 1–9.However,the fluorescence intensity of the m-CDs is almost completely quenched as the pH is increased from 9 to 10.The mechanism of the unique pH-responsive behavior is discussed in detail and a plausible mechanism is proposed.Owing to the unique pH-responsive behavior,the m-CDs are used as a on-off fluorescent probe for water quality identification.By combining the reversible pH-ultrasensitive optical properties of the m-CDs in the pH range of 9–10 with the glucose oxidase-mimicking(GOx-mimicking)ability of Au nanoparticles(AuNPs),glucose can be quantitatively detected.Finally,two environment-friendly starch-based solid-state fluorescence materials(powder and film)are developed through green preparation routes.展开更多
基金the National Natural Science Foundation of China(Nos.21274016 and 21072026)Fundamental Research Funds for the Central Universities(No.DUT13LK06)for financial support to this work
文摘Two novel thieno-[3,4-b]-pyrazine-based molecules, TP-E and TP-O, were designed and synthesized for potential application as red fluorescent emitters. The bulky tetraphenylethylene groups were attached at the periphery of the thieno-[3,4-b]-pyrazine core to form the non-planar molecules, as efficient solid- state emitting materials. The peripheral groups were grafted to the emissive core through either a conjugated acetylene bond, or a non-conjugated ether bond. These molecules exhibit strnng red fluorescence in both dilute solutions and in thin films with large Stokes shifts of over 100 nm. The cyclic voltammetry measurements showed the reversible oxidation and reduction behavior for both compounds. All these properties indicate the two compounds are possible functional materials for use in ontoelectronic devices.
基金funded by the Joint Funds of the Zhejiang Provincial Natural Science Foundation of China(LQ23B020010)the Science Foundation of Zhejiang Sci-Tech University(22202010-Y).
文摘Organic fluorescentmaterials(OFMs),characterized by their unique molecular structures and exceptional optical properties,have demonstrated significant potential in diverse applications such as bioimaging,sensors,and display technologies.Nevertheless,the reliance on chemists’intuition and experience in the traditional design of OFMs,coupled with the high cost and lack of scalability of conventional methods such as fluorescence detection and Density Functional Theory(DFT)calculations,makes it difficult to keep up with the rapid development of the field.The advent ofmachine learning(ML)has introduced transformative possibilities,enabling data-driven exploration of the intricate relationships between molecular structures and fluorescence properties.Herein,we review the applications of ML in the innovative design of OFMs with an emphasis on the workflow of modeling,optical property prediction,and OFM design.We also discuss the critical role of data curation and feature engineering in enhancing model performance.Our review provides an overview of commonly used models and assesses their efficacy.We critically examine key challenges such as database construction,model interpretability,and generalization ability,trying to provide a comprehensive framework that advances the integration of ML in the research of organic fluorescentmaterials,thereby facilitating the development of next-generation materials.
基金by the National Natural Science Foundation of China(21975048,21771039)the Shanghai Science and Technology Committee(19Dz2270100).
文摘Comprehensive Summary Fluorescent silk has potential application in many fields such as bioimaging,tissue engineering scaffolds,luminescent marks,and dazzling fabrics.Among the methods to endow natural silk with fluorescent properties,feeding silkworms with fluorescent additives is facile,low-cost and environment friendly,which has the prospect of large-scale production.In this paper,we reviewed the research progress for this aim in the past ten years,and summarized the unified characteristics for the substances that can enter the silk gland by digestive tract of silkworms.The advantages and disadvantages of various fluorescent materials for this application are compared in detail.And the future research directions are suggested to overcome the shortcomings of the present research.
文摘The ionothermal reaction between CuCl_(2),1,4-bis(1,2,4-triazol-1-ylmethyl)benzene(BBTZ),and(NH_(4))_(6)Mo_(7)O_(24) in 1-ethyl-3-methylimidazolium bromide((Emim)Br)led to a new octamolybdate-based coordination polymer(Emim)2[Cu(BBTZ)_(2)(β-Mo_(8)O_(26))](Mo_(8)-CP).Mo_(8)-CP was characterized by elemental analysis,thermogravime-try,IR,powder X-ray diffraction,and single-crystal X-ray diffraction.In Mo_(8)-CP,structural analysis reveals that Cu coordinates with BBTZ ligands to form an interlocked 1D chain.These chains are further bridged by(β-Mo_(8)O_(26))^(4-)to construct a 3D coordination polymer.Notably,(Emim)^(+)acts as a structure-directing agent,occupying the channels of the 3D coordination polymer.Based on this unique structure,the ion exchange properties of Mo_(8)-CP toward rare-earth ions were investigated.It has been found that the luminescent color of the material can be successfully regulat-ed by introducing Eu^(3+)or Tb^(3+)through ion exchange.CCDC:2475110,Mo_(8)-CP.
基金the National Nature Science Foundation of China(Nos.21922506,21871092,21672070 and31702070)Shanghai Pujiang Program(No.18PJD015)+1 种基金the Fundamental Research Funds for the Central Universities,Shanghai Municipal Natural Science Foundation(No.19ZR1437900)the Opening Projects of Shanghai Key Laboratory of Green Chemistry and Chemical Processes,and State Key Laboratory of Fine Chemicals(No.KF 1801)。
文摘During past few years,the construction of fluorescent metallacycles featuring the fluorescenceresonance energy transfer behavior has attracted extensive attention due to their diverse applications such as real-time monitoring the dynamics of coordination-driven self-assembly,photoswitching fluorescence-resonance energy transfer,and light-controlled generation of singlet oxygen for cancer therapy.This review focuses on the recent advances on the design principles,preparation methods,optical properties,and the wide applications of fluorescent metallacycles with the FRET property.
基金supported by the National Natural Science Foundation of China(2375066 and U23A20594)the Guangdong Basic and Applied Basic Research Foundation(2023B1515040003).
文摘Phospholes are emerging as distinctive conjugated scaffolds for organic fluorescent materials owing to their unique structural characteristics that are different from many commonly studied heterocyclic frameworks.Recently,phosphole-derived skeletons have garnered significant attention as a remarkable electron-accepting moiety,which has achieved substantial advance-ments in the application of fluorescent biomaterials because of their physicochemical traits,especially in the aspects of stability and versatility.In this context,this review summarizes the progress in phosphole-based fluorescent biomaterials over the past decade(2015-2024).It begins with an overview of the currently developed phosphole-based scaffolds specifically designed for biological applications,illustrating their unique structures and favorable properties.Representative examples are then showcased to demonstrate their potential in various biological scenarios with a primary focus on bioimaging and therapy.Last,challenges and prospects in this field are presented.This review could serve as a consolidated and valuable reference for the future exploration and innovation of bioimaging and therapy platforms.
基金Project supported by Wroclaw Research Centre EIT+within the project"The Application of Nanotechnology in Advanced Materials"-NanoMat(POIG.01.01.02-02-002/08)financed by the European Regional Development Fund(Operational Programme Innovative Economy,1.1.2)
文摘Optical imaging plays an important role in biomedical research being extremely useful for early detection, screening and image-guided therapy. Lanthanide-doped up-converting nanoparticles were ideally suited for bioimaging because they could be ex- cited in near infrared （NIR） and emit in NIR or visible （VIS）. Here, we compared lanthanide doped up-converting NaYF4 and organic fluorophores for application in deep-tissue imaging. For that purpose - tissue phantoms mimicking the natural properties of light scat- tering by living tissues were prepared. The studies allowed to quantitatively compare optical resolution of different fluorescent com- pounds, revealing that the NIR photoexcitation was favorable over conventional UV photoexcitation.
基金the National Science Foundation of China(No.52075218,51775232).
文摘Here,we demonstrate the assembly of a new stable lanthanide-based metal-organic framework(MOF),Eu(HDPB)(phen)(1)(HDPB=(1,1’:3’,1’’-terphenyl)-3,3’’,5,5’’-tetracarboxylic acid,phen=1,10-phenanthroline),with a three-dimensional framework under solvothermal conditions.1 showed strong red fluorescence emission at room temperature and could be used as a selective and sensitive chemical sensor for pH and folic acid(FA)detection.Moreover,1 could also be applied as a fluorescent material for the visible identification of fingerprints.Then,using 1 as a filler,two mixed-matrix membranes(MMMs),1@poly(ε-caprolactone)(PCL)and 1@poly(vinylidene difluoride)(PVDF),have been fabricated.Notably,owing to the hydrophobic protection provided by the polymer matrix of the MOF particles,these two MMMs also exhibited fluorescence emission comparable to that of 1 and could be used for FA sensing with good selectivity and remarkable recyclability.More importantly,this is the first time that Eu-MOF-based MMMs have been employed in FA detection.The fabrication of MOF-based MMMs not only provides a facile method for sensing biomarkers,but it also enhances the recyclability of sensors.
基金the financial support from the National Natural Science Foundation of China(No.21702020)。
文摘Benzo-21-crown-7(B21 C7)is one of the most important crown ethers,which not only shows excellent physicochemical properties but also exhibits promising binding capability with dialkylammonium salts.In this paper,we designed and synthesized a fixed-tetraphenylethylene(FTPE)motif bridged ditopic benzo-21-crown-7 molecule(H).The fixed tetraphenylethylene motif endows H with aggregation induced emission(AIE)prope rty.In the presence of a ditopic dialkylammonium salt vip molecule(G),a fluorescent supramolecular polymer with golden luminescent property could be fabricated.This B21 C7-based host-vip supramolecular polymer with golden fluorescence may have potential application in dynamic luminescent materials.
基金Project supported by the National Natural Science Foundation of China (21271074,51372091)the Teamwork Projects funded by the Guangdong Natural Science Foundation (S2013030012842)+1 种基金Guangdong Provincial Science&Technology Project (2015B090903074)Guangzhou Science&Technology Project (201605030005)。
文摘Under hydrothermal environment,we synthesized lanthanide ions doped sodium yttrium fluoride(NaYF4:Er,Tm@NaYF4:Ce,Tb) luminescent microcrystals via an epitaxial growth technique.The structure and morphology of these microcrystals were examined by SEM,TEM,EDS and XRD measurements.These particles show dual-mode emissions with red upconversion(UC) and green down conversion(DC) as single particles level.The mean length and diameter of these microparticles increase from 0.43 to2.26 μm and from 1.33 to 1.86 μm,respectively.Most interestingly,the photoluminescence properties of NaYF4:Er,Tm@NaYF4:Ce,Tb phosphor crystals are highly dependent on the crystallite size.The microcrystals fluoresce emit dual-mode emissions when they are solid or dispersed in solvents.Benefiting its intensive fluorescence and uniform morphology,these materials hold great potential for security and anti-counterfeiting applications.
基金National Natural Science Foundation of China 20671020
文摘Fluorescence material of Sm doped Si-Ca-Mg system was synthesized by using the method of solid phase reaction at high temperature. The phase composition and crystal structure of this material were analyzed with XRD method for its composition and the existence form of Sm atom. We aimed to exactly determine the phase composition of this fluorescence material and the doping position and environment of rare-earth Sm atom in the system because these factors have significant effects on the properties. The analytical results show that the Sm atoms dope in Ca2O26Si6Sm8 lattice in the form of atomic site-occupation in three different space positions with different occupancy rates. Therefore, based on the XRD analytical results, the fluorescence material of Sm doped Si-Ca-Mg system with high performance can be synthesized.
文摘Many researchers have studied the photocatalytic oxidation of trace levels of benzene,toluene and xy-lene in air over titania photocatalysts.However,atthe moment,the effectiveness of the photocatalytic oxidation is limited by the deactivation of photocata-lysts.
基金supported by the National Natural Science Foundation of China (No. 22171219)the Fundamental Research Funds for the Central Universities (No. xzy022021004)。
文摘Metallacycles hold great promise for fluorescence-based sensing due to their synthetic advantages and unique physicochemical properties. However, it remains highly challenging to develop a versatile methodology for constructing highly emissive metallacycles with targeted functionalities and therefore soughtafter properties. Herein, we report a general strategy to construct a series of highly emissive perylene diimide-based metallacycles via the self-assembly of perylene diimide-based tetrapyridyl ligand with different dicarboxylic ligands featuring fixed angles and cis-Pt(PEt_(3))_(2)(OTf)_(2). Single crystal X-ray diffraction analyses verify the formation of bowtie-like metallacycles with two triangular cavities. Notably, the fluorescence quantum yields of most assemblies exceed 98%, amongst the highest values for metallacycles.Additionally, such metallacycles exhibit sensitive fluorescence responses toward picric acid with a detection limit of 2.8 × 10^(-6)mol/L. This study not only provides a rational strategy for preparing highly emissive bowtie-shaped metallacycles, but also sheds light on their usage in the detection of picric acid and associated compounds.
基金supported by the Zhejiang Sci-Tech University Shengzhou Innovation Research Institute(SYY2.023C000005)the National Natural Science Foundation of China(51803184)。
文摘Dynamic fluorescent materials capable of stimulus-responsive emission modulation have emerged as pivotal components in next-generation information security systems.This study presents a novel photoresponsive fluorescent composite system in which spiropyran(SP)was covalently grafted onto naphthalimide-functionalized silica aerogel matrices.These architectures exhibit reversible fluorescence resonance energy transfer between the naphthalimide donors and merocyanine-form of SP acceptors under ultraviolet irradiation,enabling dynamic emission shifting from green(blue)to red.The aggregation-induced emission characteristics of SP were used to engineer a smart material system that can reversibly regulate its distinct red fluorescence by precisely controlling the dispersion of amino groups on naphthalimide-functionalized silica aerogels.This spatial manipulation directly governs the molecular packing state of SP,enabling dynamic fluorescence modulation.A programmable control over the fluorescence chromatic transitions in the composite material was achieved by systematically adjusting the SP grafting densities(1%,2%,and 3%w/w).A unique mode of dynamic information encryption technology was developed by utilizing dynamic fluorescence variations.These materials can substantially enhance information encryption levels due to their precisely adjustable fluorescence properties in response to external stimuli over time.This makes the encryption process even more unpredictable and complex,thereby exponentially increasing the difficulty for unauthorized parties to replicate or decode the encrypted information.
基金supported by the National Natural Science Foundation of China(52222308)the Open Project Program of Wuhan National Laboratory for Optoelectronics(2023WNLOKF010)。
文摘Since Tang and Van Slyke’s seminal 1987 discovery[1],organic light-emitting diodes(OLEDs)have evolved into display technology mainstays[2].Nevertheless,developing blue OLEDs that simultaneously satisfy the stringent demands for efficiency,operational lifetime,and color purity remains a critical hurdle[3,4].Thermally activated delayed fluorescence(TADF)materials emerged as a promising solution,enabling 100%exciton utilization without noble metals while offering exceptional molecular tunability[5,6].
基金China Postdoctoral Science Foundation,Grant/Award Numbers:2021M690660,2021TQ0066Key Basic Research Program of Science and Technology Commission of Shanghai Municipality,Grant/Award Number:20JC1415300+1 种基金National Natural Science Foundation of China,Grant/Award Numbers:21701153,21875044Program of Shanghai Academic Research Leader,Grant/Award Number:19XD1420300。
文摘Latent fingerprints are extremely vital for personal identification and criminalinvestigation,and potential information recognition techniques have been widelyused in the fields of information and communication electronics.Although physicalpowder dusting methods have been frequently employed to develop latent fingerprintsand most of them are carried out by using single component powders ofmicron-sized fluorescent particles,magnetic powders,or metal particles,there isstill an enormous challenge in producing high-resolution image of latent fingerprintsat different backgrounds or substrates.Herein,a novel and effectivenanoimpregnation method is developed to synthesize bifunctional magnetic fluorescentmesoporous microspheres for latent fingerprints visualization by growthof mesoporous silica(mesoSiO_(2))on magical Fe_(3)O_(4) core and then deposition offluorescent YVO4:Eu^(3+)nanoparticles in the mesopores.The obtainedFe_(3)O_(4)@mesoSiO_(2)@YVO4:Eu^(3+)microspheres possess spatially isolated magneticcore and fluorescent shell which were insulated by mesoporous silica layer.Dueto their small particle size of submicrometer scale,high magnetization and lowmagnetic remanence as well as the combined magnetic and fluorescent properties,the microspheres show superior performance in visual latent fingerprint recognitionwith high contrast,high anti-interference,and sensitivity as well as goodretention on multifarious substrates regardless of surface permeability,roughness,refraction,colorfulness,and background fluorescence interference,and it makesthem ideal candidates for practical application in fingerprint visualization andeven magneto-optic information storage.
基金supported by the National Natural Science Foundation of China(22275193 and 52303355)the Natural Science Foundation of Fujian Province(2021J06034)+2 种基金Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Science,CXZX-2022-GH09(E255KF0101)Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences(E055AJ01)the STS Project of Fujian-CAS(Grant No.:2023T3027).
文摘Dynamic fluorescent materials play a crucial role in secure inks for data encryption;however,they are still plagued by issues such as photodegradation,poor latency,and susceptibility to unauthorized access.Herein,we propose a photochemically modulated dynamic fluorescent encryption system based on^(1)O_(2)sensitization of fluorescent composites,comprising a^(1)O_(2)-sensitive fluorophore(F2)and non-emissive polymers.After UV irradiation,in-situ generated^(1)O_(2)from the polymer effectively binds with F2 to form endoperoxides(F2EPO),resulting in a significant redshift in emission,up to 150 nm.The^(1)O_(2)concentration is closely related to the irradiation time,rendering different fluorescent colors in a time-gated fashion.Moreover,the emission of F2EPO can be regulated by polymer chemical structure,molecular weight,and crosslinking density.Relying on these merits,we develop a dynamic data encryption method with various non-emissive polymers as the data storage media,UV light irradiation as the data encoder,and F2 as the data decoder.UV light irradiation of diverse polymer solutions generates^(1)O_(2)at different concentrations,effectively encoding the data,which remains invisible under both UV and natural lights.The addition of F2 to these irradiated polymer solutions produces different redshifted fluorescence,enabling secure data decryption.Attributing to the non-emissive nature of the polymers,time-gated readout fashion,excellent latency of^(1)O_(2),and subtle interactions between^(1)O_(2)and F2,this data encryption is nearly undecipherable.This work offers an advantage data encryption approach beyond the reach of conventional fluorophores.
基金supported by the National Natural Science Foundation of China(No.51902080)the central government to guide local scientific and Technological Development(No.206Z1102G and 216Z1101G)Post-graduate’s Innovation Fund Project of Hebei University(HBU2022bs014).
文摘Here,multimodal fluorescent materials of Ca_(3)Al_(2)Ge_(3)O_(12):Mn^(2+),Cr^(3+)were synthesized by the traditional high-temperature solid-state reaction method.In this garnet Ca_(3)Al_(2)Ge_(3)O_(12) structure,Mn^(2+)and Cr^(3+)ions occupy dodecahedral sites(Ca sites)and hexahedral sites(Al sites),and can produce dynamic colortunable persistent luminescence at different concentrations,different excitations,and different temperatures;in particular,continuous luminescence with temperature(300 K–473 K)shows a color change from green to deep red.Through detailed pyrolysis studies and theoretical calculations,it is demonstrated that the double-trap structure existing in the host makes the persistent luminescence color temperaturedependent.Anti-counterfeiting and industrial inspection molds were successfully accomplished,which means Ca_(3)Al_(2)Ge_(3)O_(12):Mn^(2+),Cr^(3+)may be used in anti-counterfeiting and industrial inspection.
基金support from the National Natural Science Foundation of China(grant no.21571032)the Natural Science Foundation of Jilin Province,China(grant no.2021220002000715)the Analysis and Testing Foundation of Northeast Normal University.
文摘Traditional fluorescent materials are easy to counterfeit because of their static and single signal output.Photofluorochromic materials with highly efficient luminescence and color-changing behavior increase the information encryption level,but it is challenging to regulate their fluorescent quenching rate after photoinduced electron transfer(PET),therefore photofluorochromic materials have been rarely reported.This work proposes that improving theπ-conjugation effect of luminescent units and avoiding Förster resonance energy transfer(FRET)during photochromic processes are effective strategies to construct photofluorochromic materials.Accordingly,three novel organic supramolecular compounds with different photofluorochromic properties were prepared and their application in information encryption and multiple dynamic anticounterfeiting was evaluated.The findings of this work demonstrate an effective strategy for the design of photofluorochromic molecules with higher security requirements for multiple dynamic anticounterfeiting.
基金supported by the National Natural Science Foundation of China(Nos.21375123,21675151,and 21721003)the Ministry of Science and Technology of China(No.2016YFA0203203).
文摘It is attractive and encouraging to develop new fluorescent carbon dots(CDs)with excellent optical properties and promising applications prospects.Herein,highly-efficient green emissive CDs(m-CDs)with a high quantum yield(QY)of 71.7%in water are prepared through a facile solvothermal method.Interestingly,the m-CDs exhibit excellent fluorescence stability in the pH range of 1–9.However,the fluorescence intensity of the m-CDs is almost completely quenched as the pH is increased from 9 to 10.The mechanism of the unique pH-responsive behavior is discussed in detail and a plausible mechanism is proposed.Owing to the unique pH-responsive behavior,the m-CDs are used as a on-off fluorescent probe for water quality identification.By combining the reversible pH-ultrasensitive optical properties of the m-CDs in the pH range of 9–10 with the glucose oxidase-mimicking(GOx-mimicking)ability of Au nanoparticles(AuNPs),glucose can be quantitatively detected.Finally,two environment-friendly starch-based solid-state fluorescence materials(powder and film)are developed through green preparation routes.
