One Stimulus In Situ Induces Two Sequential Luminescence Switchings in the Same Solvent‐Fuming Process: Anthracene Excimer as the Intermediate

Commonly, one stimulus only induces one luminescence switching in stimuli‐responsive experiment. Herein, it is reported that one stimulus in situ induces two luminescent switches, resulting from two phase transitions in a solvent‐fuming process. Two phase transitions are in situ composed of a first fast and a subsequent slow process, corresponding to the change of molecular packing from the amorphous state to the π–π dimer crystalline state to the cocrystalline state with the inclusion of solvents, accompanied with luminescent transformation from pure blue to green to deep blue. Theoretical and experimental results reveal that the staggered π–π dimer stacking of anthracenes serves as the intermediate state to bridge the two phase transitions. This finding expands a new horizon in the stimuli‐responsive field and inspires novel applications in information storage and security fields.     

Small‐Molecule‐Doped Organic Crystals with Long‐Persistent Luminescence

Traditional long‐persistent luminescence (LPL) materials, which are based on inorganic systems containing rare elements and with preparation temperatures of at least 1000 °C, exhibit afterglow times of more than 10 h and can be tuned for different applications. However, the development of this field is hindered due to the large thermal energy consumption and the need for nonrenewable resources. Thus, the development of a “green” design and preparation of LPL materials is of some importance. A doped‐crystalline material based on two metal‐free organic small molecules is easily prepared through ultrasonic crystallization at room temperature. It has a high‐quality, single‐crystalline structure, and visible LPL performance with a duration of more than 6 s upon low‐energy photoexcitation. A green, flexible, and convenient screen‐printing technology for controllable pattern anticounterfeiting is then developed from this purely organic material, which improves the prospects for commercial utilization in the future.     

Simultaneously Excited Downshifting/Upconversion Luminescence from Lanthanide‐Doped Core/Shell Fluoride Nanoparticles for Multimode Anticounterfeiting

This work presents a novel anticounterfeiting strategy based on a material changing its emission color in response to a change in the excitation sources—where a single ultraviolet (UV) or near‐infrared (NIR) light source are employed or simultaneously using two excitation sources (xenon lamp and NIR laser). Following this approach, various combinations of lanthanide (Ln³⁺)‐doped LiLuF₄/LiYF₄ core/shell nanoparticles are prepared, providing a promising route to design flexible nanomaterials, as well as already a small library of luminescent materials, which change color when varying the excitation source (UV, NIR or both UV and NIR). Aside from excitation source‐dependent color change, these materials additionally show excitation‐source power‐dependent color change. This work exploits the possibility of developing a new class of multimode anticounterfeit nanomaterials, with excellent performance, which would be almost impossible to mimic or replicate, providing a very high level of security.     

Shape‐Memory Microfluidics

Materials with embedded vascular networks afford rapid and enhanced control over bulk material properties including thermoregulation and distribution of active compounds such as healing agents or stimuli. Vascularized materials have a wide range of potential applications in self‐healing systems and tissue engineering constructs. Here, the application of vascularized materials for accelerated phase transitions in stimuli‐responsive microfluidic networks is reported. Poly(ester amide) elastomers are hygroscopic and exhibit thermo‐mechanical properties (T_g ≈ 37 °C) that enable heating or hydration to be used as stimuli to induce glassy‐rubbery transitions. Hydration‐dependent elasticity serves as the basis for stimuli‐responsive shape‐memory microfluidic networks. Recovery kinetics in shape‐memory microfluidics are measured under several operating modes. Perfusion‐assisted delivery of stimulus to the bulk volume of shape‐memory microfluidics dramatically accelerates shape recovery kinetics compared to devices that are not perfused. The recovery times are 4.2 ± 0.1 h and 8.0 ± 0.3 h in the perfused and non‐perfused cases, respectively. The recovery kinetics of the shape‐memory microfluidic devices operating in various modes of stimuli delivery can be accurately predicted through finite element simulations. This work demonstrates the utility of vascularized materials as a strategy to reduce the characteristic length scale for diffusion, thereby accelerating the actuation of stimuli‐responsive bulk materials.     

Protein/Polymer‐Based Dual‐Responsive Gold Nanoparticles with pH‐Dependent Thermal Sensitivity

This article presents the synthesis and physicochemical behavior of dual‐responsive plasmonic nanoparticles with reversible optical properties based on protein‐coated gold nanoparticles grafted with thermosensitive polymer brushes by means of surface‐initiated atom transfer radical polymerization (SI‐ATRP) that exhibit pH‐dependent thermo‐responsive behavior. Spherical gold NPs of two different sizes (15 nm and 60 nm) and with different stabilizing agents (citrate and cetyltrimethylammonium bromide (CTAB), respectively) were first capped with bovine serum albumin (BSA). The resulting BSA‐capped NPs (Au@BSA NPs) exhibited not only extremely high colloidal stability under physiological conditions, but also a reversible U‐shaped pH‐responsive behavior, similar to pure BSA. The ?‐amine of the L‐lysine in the protein coating was then used to covalently bind an ATRP‐initiator, allowing for the SI‐ATRP of thermosensitive polymer brushes of oligo(ethylene glycol) methacrylates with an LCST of 42 °C in pure water and around 37 °C under physiological conditions. Such protein coated nanoparticles grafted with thermosensitive polymers exhibit a smart pH‐dependent thermosensitive behavior.     

Stimuli‐Responsive Materials Based on Interpenetrating Polymer Liquid Crystal Hydrogels

Stimuli‐responsive materials based on interpenetrating liquid crystal‐hydrogel polymer networks are fabricated. These materials consist of a cholesteric liquid crystalline network that reflects color and an interwoven poly(acrylic acid) network that provides a humidity and pH response. The volume change in the cross‐linked hydrogel polymer results in a dimensional alteration in the cholesteric network as well, which, in turn, leads to a color change yielding a dual‐responsive photonic material. Furthermore a patterned coating having responsive and static interpenetrating polymer network areas is produced that changes both its surface topography and color.     

Hydrophilic Doped Quantum Dots “Ink” and Their Inkjet‐Printed Patterns for Dual Mode Anticounterfeiting by Reversible Cation Exchange Mechanism

Luminescent quantum dots (QDs) patterns have attracted great attention in anticounterfeiting applications because they can emit fluorescence upon excitation. Here, different from traditional luminescent patterns for anticounterfeiting purposes, a novel strategy based on the reversible cation exchange enabled Ag doped CdS quantum dots (CdS:Ag QDs) is reported to provide a higher security for anticounterfeiting. First, the reversibility of cation exchange enabled doped QDs crystal engineering have been revealed. The switch from nonluminescence to luminescence for several cycles by such a mechanism has been achieved. Second, the hydrophilic doped QDs “ink” can be prepared by surface modification, and then flexible bulk‐sized patterns can be printed on different substrates by inkjet printing technology, such as the parchment paper, PET foil, and paper currency substrates. Third, owing to the characteristic of stable crystal structure of CdS:Ag QDs, the patterns of such doped QDs on substrates can be switched by in situ cation exchange to achieve conversion of the disappearance and recovery of luminescent signals, from which a multiple dual mode anticounterfeiting verification can be provided.     

An Integrated Luminescent Information Encryption–Decryption and Anticounterfeiting Chip Based on Laser Induced Graphene

Visual optical information encryption–decryption and anti-counterfeiting (IEDAC) technology play a vital role in the field of information security. Recent luminescent information encryption technologies face the disadvantages of depending on external large-scale stimulus decryption equipment, inability to read out repeatedly, and information leakage, impeding the practical applications of luminescence encryption. Here, an integrated luminescent IEDAC chip is proposed, which provides a convenient approach to store and decipher pre-patterned luminescence information based on laser engraved template and film heater. The luminescent encryption chip contains a double-layer structure made up of long persistent phosphors based on SrCaGa₄O₈ host and a laser induced graphene heater, which makes it possible to decrypt information on a single chip. This design enables dual-mode (photoluminescence/long persistent luminescence), dual-color (blue/yellow-green), and multi-level IEDAC function, providing a novel insight and integrated strategy for implementing advanced IEDAC technologies.     

pH Switchable Nanoplatform for In Vivo Persistent Luminescence Imaging and Precise Photothermal Therapy of Bacterial Infection

Photothermal therapy (PTT) is one of the most promising approaches to combat multidrug‐resistant bacteria with less potential to induce resistance and systemic toxicity. However, uncontrollable distribution of photothermal agents leads to lethal temperatures for normal cells, and failure to offer timely and effective antibacterial stewardship. A pH switchable nanoplatform for persistent luminescence imaging‐guided precise PTT to selectively destroy only pathological cells while protecting nearby normal cells in bacterial infected microenvironment is shown. The PLNP@PANI‐GCS is fabricated by grafting polyaniline (PANI) and glycol chitosan (GCS) onto the surface of persistent luminescence nanoparticles (PLNPs). It takes advantage of the long persistent luminescence of PLNPs to realize autofluorescence‐free imaging, the pH‐dependent light–heat conversion property of PANI to get a stronger photothermal effect at pH 6.5 than pH 7.4, and the pH environment responsive surface charge transition of GCS. Consequently, PLNP@PANI‐GCS enables effective response to bacterial‐infected acid region and electrostatic bonding to bacteria in vivo, ensuring the spatial accuracy of near‐infrared light irradiation and specific heating directly to bacteria. In vivo imaging‐guided PTT to bacterial infection abscess shows effective treatment. PLNP@PANI‐GCS has great potential in treating multidrug‐resistant bacterial infection with low possibility of developing microbial drug resistance and little harm to normal cells.     

Plasmonic Color Filters as Dual‐State Nanopixels for High‐Density Microimage Encoding

Plasmonic color filtering has provided a range of new techniques for “printing” images at resolutions beyond the diffraction‐limit, significantly improving upon what can be achieved using traditional, dye‐based filtering methods. Here, a new approach to high‐density data encoding is demonstrated using full color, dual‐state plasmonic nanopixels, doubling the amount of information that can be stored in a unit‐area. This technique is used to encode two data sets into a single set of pixels for the first time, generating vivid, near‐full sRGB (standard Red Green Blue color space)color images and codes with polarization‐switchable information states. Using a standard optical microscope, the smallest “unit” that can be read relates to 2 × 2 nanopixels (370 nm × 370 nm). As a result, dual‐state nanopixels may prove significant for long‐term, high‐resolution optical image encoding, and counterfeit‐prevention measures.     

A Coupled Higher‐Order Nonlinear Schrödinger Equation Including Higher‐Order Bright and Dark Solitons

We suggest a generalized Lax pair on a Hermitian symmetric space to generate a new coupled higher‐order nonlinear Schrödinger equation of a dual type which contains both bright and dark soliton equations depending on parameters in the Lax pair. Through the generalized ways of reduction and the scaling transformation for the coupled higher‐order nonlinear Schrödinger equation, two integrable types of higher‐order dark soliton equations and their extensions to vector equations are newly derived in addition to the corresponding equations of the known higher‐order bright solitons. Analytical discussion on a general scalar solution of the higher‐order dark soliton equation is then made in detail.     

Molecularly‐Engineered, 4D‐Printed Liquid Crystal Elastomer Actuators

Three‐dimensional structures that undergo reversible shape changes in response to mild stimuli enable a wide range of smart devices, such as soft robots or implantable medical devices. Herein, a dual thiol‐ene reaction scheme is used to synthesize a class of liquid crystal (LC) elastomers that can be 3D printed into complex shapes and subsequently undergo controlled shape change. Through controlling the phase transition temperature of polymerizable LC inks, morphing 3D structures with tunable actuation temperature (28 ± 2 to 105 ± 1 °C) are fabricated. Finally, multiple LC inks are 3D printed into single structures to allow for the production of untethered, thermo‐responsive structures that sequentially and reversibly undergo multiple shape changes.     

Improved Quantum Yield and Excellent Luminescence Stability of Europium‐Incorporated Polymeric Hydrogen‐Bonded Heptazine Frameworks Due to an Efficient Hydrogen‐Bonding Effect

Two of the most persistent challenges for the high‐end application of luminescent lanthanide (Ln) compounds are a low quantum yield and luminescence quenching caused by a liquid medium. In this work, a type of polymeric hydrogen‐bonded heptazine framework is developed incorporating trivalent europium ions (P‐HHF‐Eu) via a low‐cost and facile low‐temperature thermal condensation reaction. Structural characterization clearly reveals that the solid‐phase pyrolyzation reaction results in the formation of P‐HHF‐Eu. Using time‐resolved and steady state photoluminescence (PL) spectroscopies, the photophysics and photochemistry of P‐HHF‐Eu at different hydration degrees are investigated and the role of hydrogen bonding in the significant enhancement of the emission properties is demonstrated. Furthermore, the P‐HHF‐Eu particles suspended in polyvinyl alcohol hydrogel exhibit excellent luminescence stability with a high PL quantum yield of up to ≈46% and wavelength responsive color‐tunable emission, which holds potential for security applications.     

Self‐Protective Room‐Temperature Phosphorescence of Fluorine and Nitrogen Codoped Carbon Dots

The unstable triplet excited state is a core problem when developing self‐protective room temperature phosphorescence (RTP) in carbon dots (CDs). Here, fluorine and nitrogen codoped carbon dots (FNCDs) with long‐lived triplet excited states, emitting pH‐stabilized blue fluorescence and pH‐responsive green self‐protective RTP, are reported for the first time. The self‐protective RTP of FNCDs arises from n–π * electron transitions for C? N/C?N bonds with a small energy gap between singlet and triplet states at room temperature. Moreover, the interdot/intradot hydrogen bonds and steric protection of C? F bonds reduce quenching of RTP by oxygen at room temperature. The RTP emission of FNCDs shows outstanding reversibility, while the blue fluorescence emission has good pH stability. Based on these FNCDs, a data encoding/reading strategy for advanced anticounterfeiting is proposed via time‐resolved luminescence imaging techniques, as well as steganography of complex patterns.     

基于暗原色与逆暗原色融合的含明亮区域图像去雾

针对暗原色先验模型对于图像明亮区域不适应,暗原色估计偏大,导致透射率估计偏小,出现色彩失真现象,本文介绍一种新的暗原色修正方法。提出一种逆暗原色概念,将雾化图像的暗原色与逆暗原色进行融合处理得到一种新的修正暗原色,从而获得比较真实的明亮区域透射率,有效消除了明亮区域的色彩失真。以有效细节强度、色调还原程度、结构信息及综合测评作为图像质量评价指标,与目前流行算法进行对比实验,本文算法的色调还原程度指标平均值提高41.1%,综合测评指标平均值提高48.7%。实验结果表明,本文算法在改善明亮区域色彩失真及提高去雾图像总体质量方面优于目前流行算法。     

A Dual‐Functional Persistently Luminescent Nanocomposite Enables Engineering of Mesenchymal Stem Cells for Homing and Gene Therapy of Glioblastoma

Therapeutically engineered mesenchymal stem cells (MSC) have shown promising capability for glioblastoma (GBM) therapy; however, simultaneous tracking of their migration and long‐term fate is urgently needed for clinical application. This study shows the design and fabrication of a dual‐functional persistent luminescence nanocomposite (LPLNP‐PPT/TRAIL) for effective therapeutic engineering and tracking of MSC in the meantime. LPLNP‐PPT/TRAIL shows low‐toxicity, near‐infrared persistent luminescence emitting without in situ excitation, and superior in vivo deep brain tissue imaging, which can efficiently track the tumortropic migration of the therapeutic engineered MSC. Both in vitro and in vivo findings demonstrate the feasibility of LPLNP‐PPT/TRAIL engineered MSC for inducing apoptosis of glioblastoma cells. This work first establishes an LPLNP‐based dual‐functional platform for cell engineering and provides us implications for GBM‐related diagnosis and therapy.     

Phototunable Full‐Color Emission of Cellulose‐Based Dynamic Fluorescent Materials

An iridescent chameleon‐like material that can change its colors under different circumstances is always desired in color‐on‐demand applications. Herein, a strategy based on trichromacy and the dynamically tunable fluorescence resonance energy transfer (FRET) process to design and prepare these chameleon‐like fluorescent materials is proposed. A set of trichromic (red, green, and blue), solid fluorescent materials are synthesized by covalently attaching spiropyran, fluorescein, and pyrene onto cellulose chains independently. After simply mixing them together, a full range of color is realized. The chameleon‐like nature of these materials is based on the dynamic tunable FRET process between donors (green and blue) and acceptors (red) in which the energy transfer efficiency can be finely tuned by irradiation. Ultimately, the reversible and nonlinear regulation of fluorescence properties, including color and intensity, is achieved on a timescale recognizable by the naked eye. Benefited by the excellent processability inherited from the cellulose derivatives, the as‐prepared materials are feasibly transformed into different forms. Particularly, a fluorescent ink with the complicated fluorescent input–output dependence suggests more than a proof‐of‐concept; indeed, it suggests a unique method of information encryption, security printing, and dynamic anticounterfeiting.     

Photoluminescence Tuning in Stretchable PDMS Film Grafted Doped Core/Multishell Quantum Dots for Anticounterfeiting

The development of new luminescent materials for anticounterfeiting is of great importance, owing to their unique physical, chemical, and optical properties. The authors report the use of color‐tunable colloidal CdS/ZnS/ZnS:Mn²⁺/ZnS core/multishell quantum dots (QDs)‐functionalized luminescent polydimethylsiloxane film (LPF) for anticounterfeiting applications. Both luminescent QDs and as‐fabricated, stretchable, and transparent LPF show blue and orange emission simultaneously, which are ascribed to CdS band‐edge emission and the ⁴T₁ → ⁶A₁ transition of Mn²⁺, respectively; their emission intensity ratios are dependent on the power‐density of a single‐wavelength excitation source. Additionally, photoluminescence tuning of CdS/ZnS/ZnS:Mn²⁺/ZnS QDs in hexane or embedded in LPF can also be realized under fixed excitation power due to a resonance energy transfer effect. Tunable photoluminescence of these flexible LPF grafted doped core/shell QDs can be finely controlled and easily realized, depending on outer excitation power and intrinsic QD concentration, which is intriguing and inspires the fabrication of many novel applications.     

Carbazole–Dibenzofuran Dyads as Metal‐Free Single‐Component White‐Color Photoemitters

White‐color light emitters from single organic molecule without heavy metals are valuable for practical applications in organic light‐emitting devices. In this study, carbazole (Cz)–dibenzofuran (DBF) donor–acceptor dyads are designed for white‐color light emitters. Originally, these molecules show photoluminescence (PL) in near ultraviolet region. However, upon successive ultraviolet (UV) irradiation, white‐color PL appears, comprising dual‐color phosphorescence from the amorphous and crystalline state of the dyad. A continuous UV irradiation makes the twisting angle between the Cz and DBF planes flatten through the triplet‐excited state, which proceeds crystallization. Thermal annealing and UV irradiation can switch the blue‐ and white‐color phosphorescences from the dyad. Furthermore, charge injection generates white‐color electroluminescence. The materials with PL color modulation ability by UV‐light irradiation and heating can be applicable as light‐ and thermo‐sensors.     

Intercalation‐Induced Tunable Stimuli‐Responsive Color‐Change Properties of Crystalline Organic Layered Compound

Layered structures accommodate guest molecules and ions in the interlayer space through intercalation. Organic layered compounds, such as layered polymers, have both intercalation and dynamic properties. Here intercalation‐induced tunable temperature‐ and mechanical‐stress‐responsive color‐change properties of crystalline layered polydiacetylene (PDA) as an organic layered compound are reported. In general, organic materials with stimuli responsivity are developed by molecular design and synthesis. In the present work, intercalation of guest metal cations in the layered PDA directs tuning of the stimuli‐responsive color‐change properties, such as color, responsivity, and reversibility. Whereas PDA without intercalation of metal ions distinctly changes the color from blue to red at the threshold temperature, the PDA with intercalation of the divalent metal ions (PDA‐M²⁺) shows a variety of color‐change properties. The present study indicates that intercalation has versatile potentials for functionalization of organic layered compounds.