With the rapid development of holographic technology,metasurface-based holographic communication schemes have demonstrated immense potential for electromagnetic(EM)multifunctionality.However,traditional passive metasu...With the rapid development of holographic technology,metasurface-based holographic communication schemes have demonstrated immense potential for electromagnetic(EM)multifunctionality.However,traditional passive metasurfaces are severely limited by their lack of reconfigurability,hindering the realization of versatile holographic applications.Origami,an art form that mechanically induces spatial deformations,serves as a platform for multifunctional devices and has garnered significant attention in optics,physics,and materials science.The Miura-ori folding paradigm,characterized by its continuous reconfigurability in folded states,remains unexplored in the context of holographic imaging.Herein,we integrate the principles of Rosenfeld with L-and D-metal chiral enantiomers on a Miura-ori surface to tailor the aperture distribution.Leveraging the continuously tunable nature of the Miura-ori's folded states,the chiral response of the metallic structures varies across different folding configurations,enabling distinct EM holographic imaging functionalities.In the planar state,holographic encryption is achieved.Under specific folding conditions and driven by spin circularly polarized(CP)waves at a particular frequency,multiplexed holographic images can be reconstructed on designated focal planes with CP selectivity.Notably,the fabricated origami metasurface exhibits a large negative Poisson ratio,facilitating portability and deployment and offering novel avenues for spin-selective systems,camouflage,and information encryption.展开更多
Ln-containing polyoxoniobates(PONbs)have appealing applications in luminescence,information encryption and magnetic fields,but the synthesis of PONbs containing high-nuclearity Ln-O clusters is challenging due to the ...Ln-containing polyoxoniobates(PONbs)have appealing applications in luminescence,information encryption and magnetic fields,but the synthesis of PONbs containing high-nuclearity Ln-O clusters is challenging due to the easy hydrolysis of Ln^(3+)ions in alkaline environments.In this paper,we are able to integrate CO_(3)^(2-)and high-nuclearity Ln-O clusters into PONb to construct an inorganic giant Eu_(19)-embedded PONb H_(49)K_(16)Na_(13)(H_(2)O)_(63)[Eu_(21)O_(2)(OH)_(7)(H_(2)O)_(5)(Nb_(7)O_(22))_(10)(Nb_(2)O_(6))_(2)(CO_(3))_(18)]·91H_(2)O(1),which contains the highest nuclearity Eu-O clusters and the largest number of Eu^(3+)ions among PONbs.In addition,the film that was prepared by mixing 1 with gelatin and glycerol,exhibits reversible luminescence switching behavior under acid/alkali stimulation and has been used to create a fluorescence-encoded information approach.This work paves a feasible strategy for the construction of high-nuclearity Ln-O cluster-containing PONbs and the expansion of the application of Ln-containing PONbs in information encryption.展开更多
Photoswitchable fluorescent polymeric nanoparticles were widely concerned because of their excellent features including the flexible design,easy preparation and functionalization,and thus exhibited great application p...Photoswitchable fluorescent polymeric nanoparticles were widely concerned because of their excellent features including the flexible design,easy preparation and functionalization,and thus exhibited great application potential in information encryption,anti-counterfeiting,but remained challenging in improving the security.Herein,we described a self-erased time-resolved information encryption via using photoswitchable dual-color fluorescent polymeric nanoparticles(PDFPNs)containing two fluorescence dyes(blue and red)and photochromic spiroxazine derivatives.In view of the different thermo-induced isomerization rates of photochromic spiroxazine derivatives in different flexible substrates,the decoloration rate of PDFPNs can be programmatically tuned by regulating ratio between rigid polymer and flexible polymer.Therefore,after ultraviolet light(UV)irradiation,correct information could only be recognized in preestablished time during the self-erased process.Our results indicated that PDFPNs exhibited fast photo-responsibility(2 min),high fluorescence contrast,well-pleasing photo-reversibility(>20 times),and programmable thermo-responsiveness(24 s-6 h).We thus demonstrated their application in the selferased time-resolved information encryption and anti-counterfeiting with high security.展开更多
Due to the wide and adjustable emission range,Ce^(3+)is an indispensable luminous center for full spectrum lighting.However,it needs to be sintered at high temperature in a reducing atmosphere,resulting in difficulty ...Due to the wide and adjustable emission range,Ce^(3+)is an indispensable luminous center for full spectrum lighting.However,it needs to be sintered at high temperature in a reducing atmosphere,resulting in difficulty to coexisting with other multivalent activated ions(such as Eu^(3+),Tm^(3+)),which greatly hinders the formation of full spectrum.In this study,a calcium vacancy enhanced self-reduction of Ce^(4+)is realized in CaNaSb_(2)O_(6)F(CNSOF)host under air atmosphere sintering,through which Ce^(3+),Tm^(3+)and Eu^(3+)coexisting in a single-phase full spectrum phosphor was prepared.Notably,the artificial introduction of a calcium vacancy was designed to verify this self-reduction mechanism.Moreover,the energy transfer kinetics among Tm^(3+),Ce^(3+)and Eu^(3+)were explored.Finally,combined with a 340 nm UV chip,a full spectrum phosphor-converted light-emitting diode(pc-LED)was fabricated,showing a broad emission range from 400 to 750 nm,Commission Internationale de I'Edairage(CIE)of(0.3485,0.3673),Ra of 92 and correlated color temperature(CCT)of 4933 K.Utilizing the variation in emission colors of this phosphor under different UV wavelengths,a dual encryption method combining point character code and fluorescent encryption technique is proposed.This work provides an effective path for Ce^(4+)self-reduction to apply in full spectrum pc-LED and information encryption.展开更多
Luminescent nanoclusters(NCs)have attracted much attention because of their superior photophysical properties;however,the design of dynamic NCs with reversible structural change is highly challenging.Herein,we synthes...Luminescent nanoclusters(NCs)have attracted much attention because of their superior photophysical properties;however,the design of dynamic NCs with reversible structural change is highly challenging.Herein,we synthesize a kind of dynamic luminescent NCs through Schiff base crosslinking between triethylenetetramine(TETA)and tannic acid at room temperature.The proposed NCs have an excitation-independent blue emission,and the maximum emission is available at about 458 nm with two excitation centers.Furthermore,the crosslinking degree of the NCs can be effectively adjusted by TETA and their formation is a kineticcontrol process.Most importantly,the proposed NCs show a property of pHcontrolled reversible depolymerization and polymerization,accompanied by a cyclic“on-off-on”photoswitching,which is directly attributed to pH-stimulated reversible C=N bond cleavage and re-formation.Because of the reversible structure change properties,the dynamic NCs have been well used in reversible information encryption.This new finding provides not only us with a powerful strategy to study the structure–properties relationship of luminescent NCs but also a design idea for constructing smart optical nanomaterials.展开更多
Dynamic assembly on time scale is common in biological systems but rare for artificial materials,especially for smart luminescent materials.Programming molecular assembly in a spatio-temporal manner and resulting in w...Dynamic assembly on time scale is common in biological systems but rare for artificial materials,especially for smart luminescent materials.Programming molecular assembly in a spatio-temporal manner and resulting in white-light-including multicolor fluorescence with time-dynamic features remains challenging.Herein,controlling molecular assembly on time scale is achieved by integrating a pH-responsive motif to a transient alkaline solution which is fabricated by activators(NaOH)and deactivators(esters),leading to automatic assembly on time scale and time-dependent multicolor fluorescence changing from blue to white and yellow.The kinetics of the assembly process is dependent on the ester hydrolysis process,which can be controlled by varying ester concentrations,temperature,initial pH,stirring rate and ester structures.This dynamic fluorescent system can be further developed for intelligent fluorescent materials such as fluorescent ink,three-dimension(3D)codes and even four-dimension(4D)codes,exhibiting a promising potential for information encryption.展开更多
Crystal polymers or liquid crystal elastomers undergo a phase transition that results in a change in the corresponding optical properties,which has the potential to be applied in areas such as information encryption a...Crystal polymers or liquid crystal elastomers undergo a phase transition that results in a change in the corresponding optical properties,which has the potential to be applied in areas such as information encryption and anti-counterfeiting.The utilization of these materials for patterning purposes requires different phase transition temperatures.However,once prepared,altering the phase transition temperature of them presents significant challenges.Herein,a poly(oxime-ester)(POE)network is developed to achieve high-resolution and multilevel patterning by photo-induced isomerization.The as-prepared POE exhibits the ability to transition from an opaque state to a transparent state under temperature stimuli,with the transition temperature and kinetics dependent on UV light exposure time.Thus,complex patterns and information can be encrypted through different selective regional exposure time and decrypted under specific temperature or cooling time.Furthermore,we illustrate an example of temporal communication,where cooling time or temperature serves as the encoded information.This research expands the application scope of advanced encryption materials,showcasing the potential of POE in dynamic information encryption and decryption processes.展开更多
A novel self-recoverable mechanoluminescent phosphor Ca_(5)Ga_(6)O_(14)∶Eu^(3+) was developed by the high-tem-perature solid-state reaction method,and its luminescence properties were investigated.Ca_(5)Ga_(6)O_(14)...A novel self-recoverable mechanoluminescent phosphor Ca_(5)Ga_(6)O_(14)∶Eu^(3+) was developed by the high-tem-perature solid-state reaction method,and its luminescence properties were investigated.Ca_(5)Ga_(6)O_(14)∶Eu^(3+)can produce red mechanoluminescence,and importantly,it shows good repeatability.The mechanoluminescence of Ca_(5)Ga_(6)O_(14)∶Eu^(3+) results from the piezoelectric field generated inside the material under stress,rather than the charge carriers stored in the traps,which can be confirmed by the multiple cycles of mechanoluminescence tests and heat treatment tests.The mechanoluminescence color can be turned from red to green by co-doping varied concentrations of Tb^(3+),which may be meaningful for encrypted letter writing.The encryption scheme for secure communication was devised by harnessing mechanoluminescence patterns in diverse shapes and ASCII codes,which shows good encryption performance.The results suggest that the mechanoluminescence phosphor Ca_(5)Ga_(6)O_(14)∶Eu^(3+),Tb^(3+)may be applied to the optical information encryption.展开更多
Mimicking tactile perception is critical to the development of advanced interactive neuromorphic platforms.Inspired by cutaneous perceptual functions,a bionic tactile perceptual platform is proposed.PDMS-based tactile...Mimicking tactile perception is critical to the development of advanced interactive neuromorphic platforms.Inspired by cutaneous perceptual functions,a bionic tactile perceptual platform is proposed.PDMS-based tactile sensors act as bionic skin touch receptors.Flexible indium tin oxide neuromorphic transistors fabricated with a single-step mask pro-cessing act as artificial synapses.Thus,the tactile perceptual platform possesses the ability of information processing.Interestingly,the flexible tactile perception platform can find applications in information encryption and decryption.With adoption of cipher,signal transmitted by the perception platform is encrypted.Thus,the security of information transmis-sion is effectively improved.The flexible tactile perceptual platform would have potentials in cognitive wearable devices,advanced human-machine interaction system,and intelligent bionic robots.展开更多
Information security has attracted broad attention in today’s information age,and information encryption on paper has been widely studied since paper is still the most important information carrier.Fluorescent inks a...Information security has attracted broad attention in today’s information age,and information encryption on paper has been widely studied since paper is still the most important information carrier.Fluorescent inks are commonly used in information encryption on paper,but they suffer from background fluorescence interference.Herein,we develop a background-free and easy-to-perform method for information encryption based on the inkjet printing of upconversion nanoparticles(UCNPs).The UCNPs can efficiently eliminate background fluorescence interference since phosphors in paper cannot be activated by near-infrared(NIR)light.Moreover,owing to their small size,excellent dispersibility and good stability,UCNP inks can be directly applied to commercial inkjet printers for convenient and high-throughput information encryption on paper.Information was easily printed on different kinds of paper substrates and the information can only be visualized under NIR light excitation.Furthermore,a novel information encryption strategy was designed by utilizing UCNPs with different excitation wavelengths.Only excitation at the defined wavelength can obtain the correct information.This proposed information encryption strategy can completely avoid background fluorescence interference,and it also features easy operation,high throughput as well as low costs,indicating its good promise to serve as a household encryption method in our daily life.展开更多
Recently,persistent luminescence materials(PLMs)have attracted extensive attention in the anti-counterfeiting and information encryption fields.Unfortunately,single visible persistent luminescence(PersL)demonstrates l...Recently,persistent luminescence materials(PLMs)have attracted extensive attention in the anti-counterfeiting and information encryption fields.Unfortunately,single visible persistent luminescence(PersL)demonstrates limited information security because the changes in information coded by visible PersL can be observed by the human eyes.In this work,we develop a dual-mode PLM with ultraviolet(UV)and visible PersL.展开更多
In recent years,hydrogen-bonded organic frameworks(HOFs)have been used in fluorescence sensing and anti-counterfeiting applications because of their mild preparation conditions,excellent optical properties and biocomp...In recent years,hydrogen-bonded organic frameworks(HOFs)have been used in fluorescence sensing and anti-counterfeiting applications because of their mild preparation conditions,excellent optical properties and biocompatibility,but dual-functional HOFs based on the same response mechanism have rarely been reported.Methotrexate(MTX)is a broad-spectrum anti-tumor drug.展开更多
In this work,we report a facile and efficient supramolecular strategy for the construction of colortunable thermally activated delayed fluorescence polymeric materials(TADF PMs)through host–vip complexation.Consequ...In this work,we report a facile and efficient supramolecular strategy for the construction of colortunable thermally activated delayed fluorescence polymeric materials(TADF PMs)through host–vip complexation.Consequently,new kinds of TADF PMs exhibiting multicolor emissions were constructed conveniently by mixing a calix[3]acridan-modified polymer and various commercially available receptors.This emergent TADF property was attributed to the formation of the through-space charge transfer(TSCT)interactions between the macrocyclic donor in the polymer and the vip acceptors.Moreover,multicolor emission and high photoluminescence quantum yield(PLQY)of up to 40%were achieved readily by tailoring the vips with different electron-withdrawing abilities.Further,we found that the TADF PMs could be prepared readily on a large scale with good processability;thus,the approach could achieve potential application on rewritable advanced information encryption.Therefore,this work not only develops an efficient supramolecular strategy to design and construct color-tunable TADF PMs but also offers a new perspective for their practical applications in materials science.展开更多
Developing high-performance circularly polarized luminescence(CPL)materials with large luminescence dissymmetry factors(g_(lum))remains challenging.We demonstrate that covalently anchoring an anthraquinone(AQ)chromoph...Developing high-performance circularly polarized luminescence(CPL)materials with large luminescence dissymmetry factors(g_(lum))remains challenging.We demonstrate that covalently anchoring an anthraquinone(AQ)chromophore to a chiral LC network via a synergistic noncovalent-covalent approach,unlike the common strategy of noncovalent doping of luminophores into chiral liquid crystals(LCs)to enhance glum,can achieve an unprecedented glum value of up to 1.73.The predoped AQ chromophores are capable of undergoing a photoinduced topochemical addition reaction with the diarylacetylene component of SLC1717 LC,leading to the formation of covalently anchored emitters embedded in the LC network and the realization of boosted CPL signals.The structural similarity of the in-situ-generated emitters with LC components enabled satisfactory orientation within the original LC,contributing to nearly pure output of circularly polarized light through a selective reflection mechanism.The remarkable photochromism and CPL properties were subsequently harnessed to develop photopattern generation and,particularly,the design of Morse code multiple information encryption.This work introduces a brand-new strategy for the fabrication of CPL LC materials with extremely large g_(lum) values,opening up the possibility of covalent anchoring of chromophores to ordered chiral structures to design high performance CPL systems.展开更多
Self-healing polyurethane-elastomers are highly desired in various fields.However,there is often a trade-off between mechanical properties and dynamic self-healing due to the mutually exclusive mechanism.Herein,we dev...Self-healing polyurethane-elastomers are highly desired in various fields.However,there is often a trade-off between mechanical properties and dynamic self-healing due to the mutually exclusive mechanism.Herein,we develop a self-healable and mechanically robust poly(oxime-urethane)elastomer(Zn-DAPU)to circumvent this inherent trade-off by incorporating zincpyridinyl cross-links into the hydrogen bonding and dynamic oxime-urethane supramolecular-covalent hybrid network.Benefiting from the synergistic strengthening of H-bonding and coordinate interactions,Zn-DAPU network performs tunable toughness with metal ion concentration change,which improves 345.2%and reaches 82.2 MJ m^(-3),with robust tensile strength of 22.8 MPa,Young's modulus of 37.1 MPa,and satisfactory elongation of 815.7%.The healing efficiency can be reached at 91.7%with a restored toughness of 75.4 MJ m^(-3)at 80℃for 10 h.Furthermore,zinc-contained networks exhibit photolysis behavior due to the homolytic cleavage of N-O bonds in oxime-urethane moieties,which can be functionalized further with fluorescamine as the specific information encryption coating with quick response codes(QRs)upon polyester fabric.This work provides valuable guidance towards the development of high-performance self-healing polyurethane and wearable functional materials.展开更多
Dissipative self-assembly,which exploits energy inputs of chemical fuels to maintain the functional states far from equilibrium,is essential to living systems.Among a variety of fuels,carbon dioxide(CO_(2))gas has yet...Dissipative self-assembly,which exploits energy inputs of chemical fuels to maintain the functional states far from equilibrium,is essential to living systems.Among a variety of fuels,carbon dioxide(CO_(2))gas has yet to be introduced in artificial dissipative materials.Here we describe a CO_(2)-fueled non-equilibrium co-assembly system that couples with a C1 catalytic pathway to dissipate the fuel for function output.Using common frustrated Lewis pair(FLP)as precursors,CO_(2)can dynamically bridge between them to constitute metastable amphiphiles,which not only highly activate CO_(2)but also enable their co-assembly with substrates into a transient fibrillar gel.In turn,the backward pathway is realized by cooperative C1 catalysis of the substrate and activated CO_(2)species in the assembled state.This can boost the depletion of gas fuel and facilitate disassembly to the sol.Moreover,tailoring the intrinsic substrate/FLP chemistries,as well as external cues,to shift the catalytic activity is accessible to regulate the period and lifetime of sol-gel-sol transition over a wide range.Based on the tunability in phase transition on a time scale,we develop time-gated information encryption materials using the transient FLP array loaded gas-encoded substrates,and the correct information can be read only at a specified time window.This study provides inspiration for a new paradigm of fuel for dissipative systems and their intelligent materials applications.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
Stimuli responsive phosphors with photoluminescence and thermoresponsive luminescence are intriguing for information encryption applications.Herein,two solvent-mediated,stimuli responsive phosphors based on phosphine-...Stimuli responsive phosphors with photoluminescence and thermoresponsive luminescence are intriguing for information encryption applications.Herein,two solvent-mediated,stimuli responsive phosphors based on phosphine-copper(I)iodide complexes 1 and 2 are reported.Complex 1 exhibited temperature-and excitation-wavelength-dependent dual-emission characteristics,displaying high energy(HE)and low energy(LE)bands with the quantum yield(QY)of 38.5%under 365 nm irradiation;but complex 2 exhibited no emission.The LE emission can be attributed to a triplet halide-to-metal charge transfer(^(3)XMCT)and copper-centered 4d→3s,3p transitions,whereas the HE emission originates from a triplet halide-to-ligand charge-transfer(^(3)XLCT).Importantly,in complex 2,the strong C—H∙∙∙Cl interaction in the supramolecular crystal lattice annihilated the sensitive cluster centered(3CC)excited state.Intriguingly,only the HE emission band of complex 2 can be successfully activated by high-energy excitation or changing the temperature.Nevertheless,the QY of complex 2 is 15.6%under 310 nm irradiation,which is smaller than that of complex 1 of 49.8%.This behavior was further confirmed by heating,where both complexes show HE emission.The reversible crystal transformation between complexes 1 and 2 was achieved.Furthermore,the reversible excitation-wavelength-dependent dual-emission and thermoresponsive properties make these phosphors suitable candidates for anti-counterfeiting and information encryption applications.展开更多
The exploration of solvent-driven reversible structural transformation in clusters is crucial for advanced stimulus-responsive optical applications and understanding of structure-property relationships.Herein,we repor...The exploration of solvent-driven reversible structural transformation in clusters is crucial for advanced stimulus-responsive optical applications and understanding of structure-property relationships.Herein,we report a solvent-driven reversible trans-formation between two copper(I)clusters:[Cu(totp)(CH_(3)CN)_(3)][Cu_(2)I_(3)(totp)(DPPPy)]·CH_(3)CN 1 and Cu_(4)I_(4)(DPPPy)_(2)·0.5CH_(2)Cl_(2)2(totp=tri-o-tolylphosphine,DPPPy=2-[diphenylphosphino]pyridine).X-ray radioluminescence and encryption applications were studied based on structure-dependent photophysical properties difference.The noncovalent interaction-mediated space charge transition between isolated ion units of 1 enables more efficient thermally activated delayed fluorescence by reverse intersystem crossing,accounting for structure-dependent luminescence.Notably,compared to 2,1 exhibits a higher scintillation light yield of 14832 photons MeV^(-1),exceeding that of the commercial scintillator Bi_(4)Ge_(3)O_(12)(8000 photons MeV^(-1)),and a low X-ray detection limit of 22.49 nGy s^(-1),far below the typical diagnostic dose(5.5μGy s^(-1)).Furthermore,scintillating film fabricated by 1 achieves X-ray imaging with a high spatial resolution of 16 lp/mm.The reversible structural interconversion enables solvent-responsive luminescent switches,and thus,the dynamic encryption system capable of multistage decryption was developed.This work not only offers new insight into solvent-regulated clusters transformations but also provides a promising strategy for developing high-performance copper(I)clusters-based scintillators and stimulus-responsive optical devices.展开更多
Carbon dots(CDs)with aggregation-induced emission(AIE)have sparked significant interest in multidimensional anti-counterfeiting due to their exceptional fluorescence properties.However,the preparation of AIE CDs with ...Carbon dots(CDs)with aggregation-induced emission(AIE)have sparked significant interest in multidimensional anti-counterfeiting due to their exceptional fluorescence properties.However,the preparation of AIE CDs with multicolor solid-state fluorescence remains a formidable challenge due to its complicated construction.In the present work,a novel class of multicolor AIE CDs(M-CDs)were fabricated using selected precursor(salicylic acid,thiosalicylic acid,and 2,2'-dithiodibenzoic acid),with an eco-friendly,low-cost one-pot solvothermal method.In the dilute organic solution,M-CDs manifested blue emission,but upon aggregation in the presence of water,the red,yellow,green,and blue emissions were displayed due to the AIE effect.Structural analysis,coupled with theoretical calculations,revealed that the increase in the size of sp2 domains would lower the Eg and cause a red-shift emission wavelength.Significantly,the continuous emission of M-CDs from blue to red can be utilized as ink for multimode printing,enabling the creation of a variety of school badges and quick response codes.These findings hold promising implications for multi-information encryption applications.展开更多
基金financial supports from National Key Research and Development Program of China(No.2022YFB3806200)。
文摘With the rapid development of holographic technology,metasurface-based holographic communication schemes have demonstrated immense potential for electromagnetic(EM)multifunctionality.However,traditional passive metasurfaces are severely limited by their lack of reconfigurability,hindering the realization of versatile holographic applications.Origami,an art form that mechanically induces spatial deformations,serves as a platform for multifunctional devices and has garnered significant attention in optics,physics,and materials science.The Miura-ori folding paradigm,characterized by its continuous reconfigurability in folded states,remains unexplored in the context of holographic imaging.Herein,we integrate the principles of Rosenfeld with L-and D-metal chiral enantiomers on a Miura-ori surface to tailor the aperture distribution.Leveraging the continuously tunable nature of the Miura-ori's folded states,the chiral response of the metallic structures varies across different folding configurations,enabling distinct EM holographic imaging functionalities.In the planar state,holographic encryption is achieved.Under specific folding conditions and driven by spin circularly polarized(CP)waves at a particular frequency,multiplexed holographic images can be reconstructed on designated focal planes with CP selectivity.Notably,the fabricated origami metasurface exhibits a large negative Poisson ratio,facilitating portability and deployment and offering novel avenues for spin-selective systems,camouflage,and information encryption.
基金the financial support from the National Natural Science Foundation of China(Nos.21971040,22171045,and 22371046)。
文摘Ln-containing polyoxoniobates(PONbs)have appealing applications in luminescence,information encryption and magnetic fields,but the synthesis of PONbs containing high-nuclearity Ln-O clusters is challenging due to the easy hydrolysis of Ln^(3+)ions in alkaline environments.In this paper,we are able to integrate CO_(3)^(2-)and high-nuclearity Ln-O clusters into PONb to construct an inorganic giant Eu_(19)-embedded PONb H_(49)K_(16)Na_(13)(H_(2)O)_(63)[Eu_(21)O_(2)(OH)_(7)(H_(2)O)_(5)(Nb_(7)O_(22))_(10)(Nb_(2)O_(6))_(2)(CO_(3))_(18)]·91H_(2)O(1),which contains the highest nuclearity Eu-O clusters and the largest number of Eu^(3+)ions among PONbs.In addition,the film that was prepared by mixing 1 with gelatin and glycerol,exhibits reversible luminescence switching behavior under acid/alkali stimulation and has been used to create a fluorescence-encoded information approach.This work paves a feasible strategy for the construction of high-nuclearity Ln-O cluster-containing PONbs and the expansion of the application of Ln-containing PONbs in information encryption.
基金financially supported by the National Key R&D Program of China(Nos.2023YFB3812400,2023YFB3812403)National Natural Foundation of China(Nos.52273206,52350233)+1 种基金Hunan Provincial Natural Science Foundation(No.2021JJ10029)Huxiang High-level Talent Gathering Project(No.2022RC4039).
文摘Photoswitchable fluorescent polymeric nanoparticles were widely concerned because of their excellent features including the flexible design,easy preparation and functionalization,and thus exhibited great application potential in information encryption,anti-counterfeiting,but remained challenging in improving the security.Herein,we described a self-erased time-resolved information encryption via using photoswitchable dual-color fluorescent polymeric nanoparticles(PDFPNs)containing two fluorescence dyes(blue and red)and photochromic spiroxazine derivatives.In view of the different thermo-induced isomerization rates of photochromic spiroxazine derivatives in different flexible substrates,the decoloration rate of PDFPNs can be programmatically tuned by regulating ratio between rigid polymer and flexible polymer.Therefore,after ultraviolet light(UV)irradiation,correct information could only be recognized in preestablished time during the self-erased process.Our results indicated that PDFPNs exhibited fast photo-responsibility(2 min),high fluorescence contrast,well-pleasing photo-reversibility(>20 times),and programmable thermo-responsiveness(24 s-6 h).We thus demonstrated their application in the selferased time-resolved information encryption and anti-counterfeiting with high security.
基金Project supported by National Natural Science Foundation of China(62075203,12304460)Zhejiang Provincial Natural Science Foundation of China(LQ23A040007)Basic Public Welfare Research Program of Zhejiang Province(LDT23F05013F05)。
文摘Due to the wide and adjustable emission range,Ce^(3+)is an indispensable luminous center for full spectrum lighting.However,it needs to be sintered at high temperature in a reducing atmosphere,resulting in difficulty to coexisting with other multivalent activated ions(such as Eu^(3+),Tm^(3+)),which greatly hinders the formation of full spectrum.In this study,a calcium vacancy enhanced self-reduction of Ce^(4+)is realized in CaNaSb_(2)O_(6)F(CNSOF)host under air atmosphere sintering,through which Ce^(3+),Tm^(3+)and Eu^(3+)coexisting in a single-phase full spectrum phosphor was prepared.Notably,the artificial introduction of a calcium vacancy was designed to verify this self-reduction mechanism.Moreover,the energy transfer kinetics among Tm^(3+),Ce^(3+)and Eu^(3+)were explored.Finally,combined with a 340 nm UV chip,a full spectrum phosphor-converted light-emitting diode(pc-LED)was fabricated,showing a broad emission range from 400 to 750 nm,Commission Internationale de I'Edairage(CIE)of(0.3485,0.3673),Ra of 92 and correlated color temperature(CCT)of 4933 K.Utilizing the variation in emission colors of this phosphor under different UV wavelengths,a dual encryption method combining point character code and fluorescent encryption technique is proposed.This work provides an effective path for Ce^(4+)self-reduction to apply in full spectrum pc-LED and information encryption.
基金supported by the National Natural Science Foundation of China(52273197 and 52333007)Shenzhen Key Laboratory of Functional Aggregate Materials(ZDSYS20211021111400001)+2 种基金the Science and Technology Plan of Shenzhen(JCYJ2021324134613038,JCYJ20220818103007014,KQTD20210811090142053,GJHZ20210705141810031)the Innovation and Technology Commission(ITC-CNERC14SC01)Tianjin Key Medical Discipline(Specialty)Construction Project.
文摘Luminescent nanoclusters(NCs)have attracted much attention because of their superior photophysical properties;however,the design of dynamic NCs with reversible structural change is highly challenging.Herein,we synthesize a kind of dynamic luminescent NCs through Schiff base crosslinking between triethylenetetramine(TETA)and tannic acid at room temperature.The proposed NCs have an excitation-independent blue emission,and the maximum emission is available at about 458 nm with two excitation centers.Furthermore,the crosslinking degree of the NCs can be effectively adjusted by TETA and their formation is a kineticcontrol process.Most importantly,the proposed NCs show a property of pHcontrolled reversible depolymerization and polymerization,accompanied by a cyclic“on-off-on”photoswitching,which is directly attributed to pH-stimulated reversible C=N bond cleavage and re-formation.Because of the reversible structure change properties,the dynamic NCs have been well used in reversible information encryption.This new finding provides not only us with a powerful strategy to study the structure–properties relationship of luminescent NCs but also a design idea for constructing smart optical nanomaterials.
基金supported by the National Natural Science Foundation of China(Nos.22220102004,22025503)Shanghai Municipal Science and Technology Major Project(No.2018SHZDZX03)+4 种基金the Innovation Program of Shanghai Municipal Education Commission(No.2023ZKZD40)the Fundamental Research Funds for the Central Universitiesthe Programme of Introducing Talents of Discipline to Universities(No.B16017)Science and Technology Commission of Shanghai Municipality(No.21JC1401700)the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(No.SN-ZJU-SIAS-006)。
文摘Dynamic assembly on time scale is common in biological systems but rare for artificial materials,especially for smart luminescent materials.Programming molecular assembly in a spatio-temporal manner and resulting in white-light-including multicolor fluorescence with time-dynamic features remains challenging.Herein,controlling molecular assembly on time scale is achieved by integrating a pH-responsive motif to a transient alkaline solution which is fabricated by activators(NaOH)and deactivators(esters),leading to automatic assembly on time scale and time-dependent multicolor fluorescence changing from blue to white and yellow.The kinetics of the assembly process is dependent on the ester hydrolysis process,which can be controlled by varying ester concentrations,temperature,initial pH,stirring rate and ester structures.This dynamic fluorescent system can be further developed for intelligent fluorescent materials such as fluorescent ink,three-dimension(3D)codes and even four-dimension(4D)codes,exhibiting a promising potential for information encryption.
基金supported by the National Natural Science Foundation of China(No.22005061)the Natural Science Foundation of Jiangxi Province(No.20224BAB214009).
文摘Crystal polymers or liquid crystal elastomers undergo a phase transition that results in a change in the corresponding optical properties,which has the potential to be applied in areas such as information encryption and anti-counterfeiting.The utilization of these materials for patterning purposes requires different phase transition temperatures.However,once prepared,altering the phase transition temperature of them presents significant challenges.Herein,a poly(oxime-ester)(POE)network is developed to achieve high-resolution and multilevel patterning by photo-induced isomerization.The as-prepared POE exhibits the ability to transition from an opaque state to a transparent state under temperature stimuli,with the transition temperature and kinetics dependent on UV light exposure time.Thus,complex patterns and information can be encrypted through different selective regional exposure time and decrypted under specific temperature or cooling time.Furthermore,we illustrate an example of temporal communication,where cooling time or temperature serves as the encoded information.This research expands the application scope of advanced encryption materials,showcasing the potential of POE in dynamic information encryption and decryption processes.
文摘A novel self-recoverable mechanoluminescent phosphor Ca_(5)Ga_(6)O_(14)∶Eu^(3+) was developed by the high-tem-perature solid-state reaction method,and its luminescence properties were investigated.Ca_(5)Ga_(6)O_(14)∶Eu^(3+)can produce red mechanoluminescence,and importantly,it shows good repeatability.The mechanoluminescence of Ca_(5)Ga_(6)O_(14)∶Eu^(3+) results from the piezoelectric field generated inside the material under stress,rather than the charge carriers stored in the traps,which can be confirmed by the multiple cycles of mechanoluminescence tests and heat treatment tests.The mechanoluminescence color can be turned from red to green by co-doping varied concentrations of Tb^(3+),which may be meaningful for encrypted letter writing.The encryption scheme for secure communication was devised by harnessing mechanoluminescence patterns in diverse shapes and ASCII codes,which shows good encryption performance.The results suggest that the mechanoluminescence phosphor Ca_(5)Ga_(6)O_(14)∶Eu^(3+),Tb^(3+)may be applied to the optical information encryption.
基金Project supported by the National Natural Science Foundation of China(Grant No.51972316)Ningbo Key Scientific and Technological Project(Grant No.2021Z116).
文摘Mimicking tactile perception is critical to the development of advanced interactive neuromorphic platforms.Inspired by cutaneous perceptual functions,a bionic tactile perceptual platform is proposed.PDMS-based tactile sensors act as bionic skin touch receptors.Flexible indium tin oxide neuromorphic transistors fabricated with a single-step mask pro-cessing act as artificial synapses.Thus,the tactile perceptual platform possesses the ability of information processing.Interestingly,the flexible tactile perception platform can find applications in information encryption and decryption.With adoption of cipher,signal transmitted by the perception platform is encrypted.Thus,the security of information transmis-sion is effectively improved.The flexible tactile perceptual platform would have potentials in cognitive wearable devices,advanced human-machine interaction system,and intelligent bionic robots.
基金supported by the National Natural Science Foundation of China(21422105,21675120)the Ten Thousand Talents Program for Young Talents.
文摘Information security has attracted broad attention in today’s information age,and information encryption on paper has been widely studied since paper is still the most important information carrier.Fluorescent inks are commonly used in information encryption on paper,but they suffer from background fluorescence interference.Herein,we develop a background-free and easy-to-perform method for information encryption based on the inkjet printing of upconversion nanoparticles(UCNPs).The UCNPs can efficiently eliminate background fluorescence interference since phosphors in paper cannot be activated by near-infrared(NIR)light.Moreover,owing to their small size,excellent dispersibility and good stability,UCNP inks can be directly applied to commercial inkjet printers for convenient and high-throughput information encryption on paper.Information was easily printed on different kinds of paper substrates and the information can only be visualized under NIR light excitation.Furthermore,a novel information encryption strategy was designed by utilizing UCNPs with different excitation wavelengths.Only excitation at the defined wavelength can obtain the correct information.This proposed information encryption strategy can completely avoid background fluorescence interference,and it also features easy operation,high throughput as well as low costs,indicating its good promise to serve as a household encryption method in our daily life.
基金supported by the National Natural Science Foundation of China(61705228 and 62105333)the Key Research Program of the Chinese Academy of Sciences(No.ZDRW-CN-2021-3)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2020ZZ114).
文摘Recently,persistent luminescence materials(PLMs)have attracted extensive attention in the anti-counterfeiting and information encryption fields.Unfortunately,single visible persistent luminescence(PersL)demonstrates limited information security because the changes in information coded by visible PersL can be observed by the human eyes.In this work,we develop a dual-mode PLM with ultraviolet(UV)and visible PersL.
基金supported by the National Natural Science Foundation of China(21971194)the Developing Science Funds of Tongji University.
文摘In recent years,hydrogen-bonded organic frameworks(HOFs)have been used in fluorescence sensing and anti-counterfeiting applications because of their mild preparation conditions,excellent optical properties and biocompatibility,but dual-functional HOFs based on the same response mechanism have rarely been reported.Methotrexate(MTX)is a broad-spectrum anti-tumor drug.
基金supported by the National Natural Science Foundation of China(grant nos.22371277,22171272,and 22031010)the Strategic Priority Research Program of the Chinese Academy of Sciences(CAS+1 种基金grant no.XDB0520302)the Youth Innovation Promotion Association CAS(grant no.2021035).
文摘In this work,we report a facile and efficient supramolecular strategy for the construction of colortunable thermally activated delayed fluorescence polymeric materials(TADF PMs)through host–vip complexation.Consequently,new kinds of TADF PMs exhibiting multicolor emissions were constructed conveniently by mixing a calix[3]acridan-modified polymer and various commercially available receptors.This emergent TADF property was attributed to the formation of the through-space charge transfer(TSCT)interactions between the macrocyclic donor in the polymer and the vip acceptors.Moreover,multicolor emission and high photoluminescence quantum yield(PLQY)of up to 40%were achieved readily by tailoring the vips with different electron-withdrawing abilities.Further,we found that the TADF PMs could be prepared readily on a large scale with good processability;thus,the approach could achieve potential application on rewritable advanced information encryption.Therefore,this work not only develops an efficient supramolecular strategy to design and construct color-tunable TADF PMs but also offers a new perspective for their practical applications in materials science.
基金supported by the National Natural Science Foundation of China(grant nos.22322207,92356307,and 52321006)the National Key Research and Development Program of China(grant no.2022YFA1204402)+1 种基金the Beijing Nova Program(grant no.20220484071)the Strategic Priority Research Program of the Chinese Academy of Sciences(grant no.XDB0520201).
文摘Developing high-performance circularly polarized luminescence(CPL)materials with large luminescence dissymmetry factors(g_(lum))remains challenging.We demonstrate that covalently anchoring an anthraquinone(AQ)chromophore to a chiral LC network via a synergistic noncovalent-covalent approach,unlike the common strategy of noncovalent doping of luminophores into chiral liquid crystals(LCs)to enhance glum,can achieve an unprecedented glum value of up to 1.73.The predoped AQ chromophores are capable of undergoing a photoinduced topochemical addition reaction with the diarylacetylene component of SLC1717 LC,leading to the formation of covalently anchored emitters embedded in the LC network and the realization of boosted CPL signals.The structural similarity of the in-situ-generated emitters with LC components enabled satisfactory orientation within the original LC,contributing to nearly pure output of circularly polarized light through a selective reflection mechanism.The remarkable photochromism and CPL properties were subsequently harnessed to develop photopattern generation and,particularly,the design of Morse code multiple information encryption.This work introduces a brand-new strategy for the fabrication of CPL LC materials with extremely large g_(lum) values,opening up the possibility of covalent anchoring of chromophores to ordered chiral structures to design high performance CPL systems.
基金supported by the National Natural Science Foundation of China(21975107)the Natural Science Foundation of Jiangsu Province(BK2019020945)financial support from the PolyU Departmental General Research Fund(P0046213)。
文摘Self-healing polyurethane-elastomers are highly desired in various fields.However,there is often a trade-off between mechanical properties and dynamic self-healing due to the mutually exclusive mechanism.Herein,we develop a self-healable and mechanically robust poly(oxime-urethane)elastomer(Zn-DAPU)to circumvent this inherent trade-off by incorporating zincpyridinyl cross-links into the hydrogen bonding and dynamic oxime-urethane supramolecular-covalent hybrid network.Benefiting from the synergistic strengthening of H-bonding and coordinate interactions,Zn-DAPU network performs tunable toughness with metal ion concentration change,which improves 345.2%and reaches 82.2 MJ m^(-3),with robust tensile strength of 22.8 MPa,Young's modulus of 37.1 MPa,and satisfactory elongation of 815.7%.The healing efficiency can be reached at 91.7%with a restored toughness of 75.4 MJ m^(-3)at 80℃for 10 h.Furthermore,zinc-contained networks exhibit photolysis behavior due to the homolytic cleavage of N-O bonds in oxime-urethane moieties,which can be functionalized further with fluorescamine as the specific information encryption coating with quick response codes(QRs)upon polyester fabric.This work provides valuable guidance towards the development of high-performance self-healing polyurethane and wearable functional materials.
基金supported by the National Natural Science Foundation of China(22371053,21674022,223B2103,51703034)the National Defense Science and Technology Innovation Zone(166 Program)the Outstanding Young Scholar Program。
文摘Dissipative self-assembly,which exploits energy inputs of chemical fuels to maintain the functional states far from equilibrium,is essential to living systems.Among a variety of fuels,carbon dioxide(CO_(2))gas has yet to be introduced in artificial dissipative materials.Here we describe a CO_(2)-fueled non-equilibrium co-assembly system that couples with a C1 catalytic pathway to dissipate the fuel for function output.Using common frustrated Lewis pair(FLP)as precursors,CO_(2)can dynamically bridge between them to constitute metastable amphiphiles,which not only highly activate CO_(2)but also enable their co-assembly with substrates into a transient fibrillar gel.In turn,the backward pathway is realized by cooperative C1 catalysis of the substrate and activated CO_(2)species in the assembled state.This can boost the depletion of gas fuel and facilitate disassembly to the sol.Moreover,tailoring the intrinsic substrate/FLP chemistries,as well as external cues,to shift the catalytic activity is accessible to regulate the period and lifetime of sol-gel-sol transition over a wide range.Based on the tunability in phase transition on a time scale,we develop time-gated information encryption materials using the transient FLP array loaded gas-encoded substrates,and the correct information can be read only at a specified time window.This study provides inspiration for a new paradigm of fuel for dissipative systems and their intelligent materials applications.
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(Nos.22475195 and 22101263)Postdoctoral Science Foundation of China(No.2024M762981)Zhengzhou University.
文摘Stimuli responsive phosphors with photoluminescence and thermoresponsive luminescence are intriguing for information encryption applications.Herein,two solvent-mediated,stimuli responsive phosphors based on phosphine-copper(I)iodide complexes 1 and 2 are reported.Complex 1 exhibited temperature-and excitation-wavelength-dependent dual-emission characteristics,displaying high energy(HE)and low energy(LE)bands with the quantum yield(QY)of 38.5%under 365 nm irradiation;but complex 2 exhibited no emission.The LE emission can be attributed to a triplet halide-to-metal charge transfer(^(3)XMCT)and copper-centered 4d→3s,3p transitions,whereas the HE emission originates from a triplet halide-to-ligand charge-transfer(^(3)XLCT).Importantly,in complex 2,the strong C—H∙∙∙Cl interaction in the supramolecular crystal lattice annihilated the sensitive cluster centered(3CC)excited state.Intriguingly,only the HE emission band of complex 2 can be successfully activated by high-energy excitation or changing the temperature.Nevertheless,the QY of complex 2 is 15.6%under 310 nm irradiation,which is smaller than that of complex 1 of 49.8%.This behavior was further confirmed by heating,where both complexes show HE emission.The reversible crystal transformation between complexes 1 and 2 was achieved.Furthermore,the reversible excitation-wavelength-dependent dual-emission and thermoresponsive properties make these phosphors suitable candidates for anti-counterfeiting and information encryption applications.
基金supported by the National Natural Science Foundation of China(21971240 and 22271283)the Natural Science Foundation of Shandong Province(ZR2025QC1361)。
文摘The exploration of solvent-driven reversible structural transformation in clusters is crucial for advanced stimulus-responsive optical applications and understanding of structure-property relationships.Herein,we report a solvent-driven reversible trans-formation between two copper(I)clusters:[Cu(totp)(CH_(3)CN)_(3)][Cu_(2)I_(3)(totp)(DPPPy)]·CH_(3)CN 1 and Cu_(4)I_(4)(DPPPy)_(2)·0.5CH_(2)Cl_(2)2(totp=tri-o-tolylphosphine,DPPPy=2-[diphenylphosphino]pyridine).X-ray radioluminescence and encryption applications were studied based on structure-dependent photophysical properties difference.The noncovalent interaction-mediated space charge transition between isolated ion units of 1 enables more efficient thermally activated delayed fluorescence by reverse intersystem crossing,accounting for structure-dependent luminescence.Notably,compared to 2,1 exhibits a higher scintillation light yield of 14832 photons MeV^(-1),exceeding that of the commercial scintillator Bi_(4)Ge_(3)O_(12)(8000 photons MeV^(-1)),and a low X-ray detection limit of 22.49 nGy s^(-1),far below the typical diagnostic dose(5.5μGy s^(-1)).Furthermore,scintillating film fabricated by 1 achieves X-ray imaging with a high spatial resolution of 16 lp/mm.The reversible structural interconversion enables solvent-responsive luminescent switches,and thus,the dynamic encryption system capable of multistage decryption was developed.This work not only offers new insight into solvent-regulated clusters transformations but also provides a promising strategy for developing high-performance copper(I)clusters-based scintillators and stimulus-responsive optical devices.
基金the National Natural Science Foundation of China(No.21807085)the Natural Science Foundation Research Project of Shaanxi Province(No.2023-JCYB-087)+2 种基金the Technology Innovation Leading Program of Shaanxi(No.2020QFY07-05)the Innovation Capability Support Program of Shaanxi(No.2022KJXX-88)the fund of Education Department of Shaanxi Province(Program No.Z20230071).
文摘Carbon dots(CDs)with aggregation-induced emission(AIE)have sparked significant interest in multidimensional anti-counterfeiting due to their exceptional fluorescence properties.However,the preparation of AIE CDs with multicolor solid-state fluorescence remains a formidable challenge due to its complicated construction.In the present work,a novel class of multicolor AIE CDs(M-CDs)were fabricated using selected precursor(salicylic acid,thiosalicylic acid,and 2,2'-dithiodibenzoic acid),with an eco-friendly,low-cost one-pot solvothermal method.In the dilute organic solution,M-CDs manifested blue emission,but upon aggregation in the presence of water,the red,yellow,green,and blue emissions were displayed due to the AIE effect.Structural analysis,coupled with theoretical calculations,revealed that the increase in the size of sp2 domains would lower the Eg and cause a red-shift emission wavelength.Significantly,the continuous emission of M-CDs from blue to red can be utilized as ink for multimode printing,enabling the creation of a variety of school badges and quick response codes.These findings hold promising implications for multi-information encryption applications.
