Mechanotropic Elastomers

Liquid crystal elastomers (LCEs) are anisotropic polymeric materials. When subjected to an applied stress, liquid crystalline (LC) mesogens within the elastomeric polymer network (re)orient to the loading direction. The (re)orientation during deformation results in nonlinear stress‐strain dependence (referred to as soft elasticity). Here, we uniquely explore mechanotropic phase transitions in elastomers with appreciable mesogenic content and compare these responses to LCEs in the polydomain orientation. The isotropic (amorphous) elastomers undergo significant directional orientation upon loading, evident in strong birefringence and x‐ray diffraction. Functionally, the mechanotropic displacement of the elastomers to load is also nonlinear. However, unlike the analogous polydomain LCE compositions examined here, the isotropic elastomers rapidly recover after deformation. The mechanotropic orientation of the mesogens in these materials increase the toughness of these thiol‐ene photopolymers by nearly 1300 % relative to a chemically similar elastomer prepared from wholly isotropic precursors.     

Mechanotropic Elastomers

Liquid crystal elastomers (LCEs) are anisotropic polymeric materials. When subjected to an applied stress, liquid crystalline (LC) mesogens within the elastomeric polymer network (re)orient to the loading direction. The (re)orientation during deformation results in nonlinear stress‐strain dependence (referred to as soft elasticity). Here, we uniquely explore mechanotropic phase transitions in elastomers with appreciable mesogenic content and compare these responses to LCEs in the polydomain orientation. The isotropic (amorphous) elastomers undergo significant directional orientation upon loading, evident in strong birefringence and x‐ray diffraction. Functionally, the mechanotropic displacement of the elastomers to load is also nonlinear. However, unlike the analogous polydomain LCE compositions examined here, the isotropic elastomers rapidly recover after deformation. The mechanotropic orientation of the mesogens in these materials increase the toughness of these thiol‐ene photopolymers by nearly 1300 % relative to a chemically similar elastomer prepared from wholly isotropic precursors.     

Shape memory effect exhibited by smectic-C liquid crystalline elastomers

It was long expected and recently shown that main-chain liquid crystalline elastomers (MC-LCEs) may serve as high performance soft actuators due to a coupling of their intrinsic characteristics of high, yet labile, ordering and network strain. Here, we present the synthesis of new siloxane-based smectic MC-LCEs. These new materials exhibit a unique thermomechanical behavior known as the shape memory effect, which has never been observed before in such LCEs. To achieve targeted transition temperatures required for facile actuation at low temperatures, specifically temperatures ranging from 15 to 65 degrees C, we have designed and prepared such elastomers incorporating two distinct mesogenic groups, termed 5H and 5tB, coupled with hydride-terminated poly(dimethylsiloxane) spacers.     

Photoswitchable and Reversible Fluorescent Eutectogels for Conformal Information Encryption

Smart fluorescent materials that can respond to environmental stimuli are of great importance in the fields of information encryption and anti-counterfeiting. However, traditional fluorescent materials usually face problems such as lack of tunable fluorescence and insufficient surface-adaptive adhesion, hindering their practical applications. Herein, inspired by the glowing sucker octopus, we present a novel strategy to fabricate a reversible fluorescent eutectogel with high transparency, adhesive and self-healing performance for conformal information encryption and anti-counterfeiting. Using anthracene as luminescent unit, the eutectogel exhibits photoswitchable fluorescence and can therefore be reversibly written/erased with patterns by non-contact stimulation. Additionally, different from mechanically irreversible adhesion via glue, the eutectogel can adhere to various irregular substrates over a wide temperature range (−20 to 65 °C) and conformally deform more than 1000 times without peeling off. Furthermore, by exploiting surface-adaptive adhesion, high transparency and good stretchability of the eutectogel, dual encryption can be achieved under UV and stretching conditions to further improve the security level. This study should provide a promising strategy for the future development of advanced intelligent anti-counterfeiting materials.     

Instant Locking of Molecular Ordering in Liquid Crystal Elastomers by Oxygen‐Mediated Thiol–Acrylate Click Reactions

Liquid crystal elastomers (LCEs) with intrinsic anisotropic strains are reversible shape‐memory polymers of interest in sensor, actuator, and soft robotics applications. Rapid gelation of LCEs is required to fix molecular ordering within the elastomer network, which is essential for directed shape transformation. A highly efficient photo‐cross‐linking chemistry, based on two‐step oxygen‐mediated thiol–acrylate click reactions, allows for nearly instant gelation of the main‐chain LCE network upon exposure to UV light. Molecular orientation from the pre‐aligned liquid crystal oligomers can be faithfully transferred to the LCE films, allowing for preprogrammed shape morphing from two to three dimensions by origami‐ (folding‐only) and kirigami‐like (folding with cutting) mechanisms. The new LCE chemistry also enables widely tunable physical properties, including nematic‐to‐ isotropic phase‐transition temperatures (T_N‐I), glassy transition temperatures (T_g), and mechanical strains, without disrupting the LC ordering.     

Time-dependent Phosphorescence Color of Carbon Dots in Binary Salt Matrices through Activations by Structural Confinement and Defects for Dynamic Information Encryption

The emergence of time-dependent phosphorescence color (TDPC) materials has taken information encryption to high-security levels. However, due to the only path of exciton transfer, it is almost impossible to obtain TDPC for chromophores with a single emission center. Theoretically, in inorganic-organic composites, the exciton transfer of organic chromophores depends on the inorganic structure. Here, we assign two structural effects to inorganic NaCl by metal (Mg²⁺ or Ca²⁺ or Ba²⁺) doping, which triggers the TDPC performance of carbon dots (CDs) with a single emission center. The resulting material is used for multi-level dynamic phosphorescence color 3D coding to achieve information encryption. The structural confinement activates the green phosphorescence of CDs; while the structural defect activates tunneling-related yellow phosphorescence. Such simply doped inorganic matrices can be synthesized using the periodic table of metal cations, endowing chromophores with tremendous control over TDPC properties. This demonstration extends the design view of dynamic luminescent materials.     

A Novel Side‐Chain Liquid Crystal Elastomer Exhibiting Anomalous Reversible Shape Change

Liquid crystalline elastomers (LCEs) have been actively investigated as stimuli‐controlled actuators and soft robots. The basis of these applications is the ability of LCEs to undergo a reversible shape change upon a liquid crystalline (LC)‐isotropic phase transition. Herein, we report the synthesis of a novel LCE based on a side‐chain liquid crystalline polymer (SCLCP). In contrast to known LCEs, this LCE exhibits a striking anomalous shape change. Subjecting a mechanically stretched monodomain strip to LC‐disorder phase transition, both the length and width of the strip contract in isotropic phase, and both elongate in LC phase. This thermally induced behaviour is the result of a subtle interplay between the relaxation of polymer main chain oriented along the stretching direction and the disordering of side‐group mesogens oriented perpendicularly to the stretching direction. This finding points out potential design of LCEs of this peculiar type and possible applications to exploit.     

Thiol‐acrylate main‐chain liquid‐crystalline elastomers with tunable thermomechanical properties and actuation strain

The purpose of this study was to investigate the influence of cross‐linking on the thermomechanical behavior of liquid‐crystalline elastomers (LCEs). Main‐chain LCE networks were synthesized via a thiol‐acrylate Michael addition reaction. The robust nature of this reaction allowed for tailoring of the behavior of the LCEs by varying the concentration and functionality of the cross‐linker. The isotropic rubbery modulus, glass transition temperature, and strain‐to‐failure showed strong dependence on cross‐linker concentration and ranged from 0.9 MPa, 3 °C, and 105% to 3.2 MPa, 25 °C, and 853%, respectively. The isotropic transition temperature (T_i) was shown to be influenced by the functionality of the cross‐linker, ranging from 70 °C to 80 °C for tri‐ and tetra‐functional cross‐linkers. The magnitude of actuation can be tailored by controlling the amount of cross‐linker and applied stress. Actuation increased with increased applied stress and decreased with greater amounts of cross‐linking. The maximum strain actuation achieved was 296% under 100 kPa of bias stress, which resulted in work capacity of 296 kJ/m³ for the lowest cross‐linked networks. Overall, the experimental results provide a fundamental insight linking thermomechanical properties and actuation to a homogenous polydomain nematic LCE networks with order parameters of 0.80 when stretched. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 157–168     

Subtle structure tailoring of metal-free triazine luminogens for highly efficient ultralong organic phosphorescence

Highly efficient ultralong organic phosphorescence (UOP) based on a series of metal-free triazine luminogens was achieved via subtly structural tailoring of bromine substituted positions.Impressively,p-BrAT in solid state displayed high phosphorescence efficiency up to 9.7% with a long lifetime of 386 ms,which was one of the highest efficient UOP materials reported so far in metal-free compounds.     

Subtle structure tailoring of metal-free triazine luminogens for highly efficient ultralong organic phosphorescence

Ultralong organic phosphorescent materials have invoked considerable attention for their great potential in sensing, data encryption, information anti-counterfeiting and so forth. However, effective ways to achieve highly efficient ultralong organic phosphorescence (UOP) in metal-free organic materials remain a great challenge. Herein, we designed three isomers based on asymmetric triazines with various bromine substituted positions. Impressively, phosphorescence efficiency of p-BrAT in solid state can reach up to 9.7% with a long lifetime of 386 ms, which was one of the highest efficient UOP materials reported so far. Theoretical calculations further demonstrated that para-substitution exhibited the most effective radiative transition for triplet excitons. These results will provide an effective approach to achieving highly efficient UOP materials.     

Carbon Dots with Dual‐Emissive,Robust, and Aggregation‐Induced Room‐Temperature Phosphorescence Characteristics

Carbon dots (CDs) with dual‐emissive, robust, and aggregation‐induced RTP characteristics are reported for the first time. The TA‐CDs are prepared via hydrothermal treatment of trimellitic acid and exhibit unique white prompt and yellow RTP emissions in solid state under UV excitation (365 nm) on and off, respectively. The yellow RTP emission of TA‐CDs powder should be resulted from the formation of a new excited triplet state due to their aggregation, and the white prompt emission is due to their blue fluorescence and yellow RTP dual‐emissive nature. The RTP emission of TA‐CDs powder was highly stable under grinding, which is very rare amongst traditional pure organic RTP materials. To employ the unique characteristics of TA‐CDs, advanced anti‐counterfeiting and information encryption methodologies (water‐stimuli‐response producing RTP) were preliminarily investigated.     

Programmable and Self-Healable Liquid Crystal Elastomer Actuators Based on Halogen Bonding

Shape-changing polymeric materials have gained significant attention in the field of bioinspired soft robotics. However, challenges remain in versatilizing the shape-morphing process to suit different tasks and environments, and in designing systems that combine reversible actuation and self-healing ability. Here, we report halogen-bonded liquid crystal elastomers (LCEs) that can be arbitrarily shape-programmed and that self-heal under mild thermal or photothermal stimulation. We incorporate halogen-bond-donating diiodotetrafluorobenzene molecules as dynamic supramolecular crosslinks into the LCEs and show that these relatively weak crosslinks are pertinent for their mechanical programming and self-healing. Utilizing the halogen-bonded LCEs, we demonstrate proof-of-concept soft robotic motions such as crawling and rolling with programmed velocities. Our results showcase halogen bonding as a promising, yet unexplored tool for the preparation of smart supramolecular constructs for the development of advanced soft actuators.     

Effects of structural imperfections on the dynamic mechanical response of main-chain smectic elastomers

We examine the influence of structural imperfections on mechanical damping in polydomain smectic main-chain liquid crystalline elastomers (MCLCE) subjected to small strain oscillatory shear. The mechanical loss factor tan δ = G″(ω)/G′(ω) exhibits a strong maximum (tan δ ≈ 1.0) near the smectic-isotropic (clearing) transition. “Optimal” elastomers that exhibit minimal equilibrium swelling in a good solvent are compared with highly swelling “imperfect elastomers” that contain higher concentrations of structural imperfections such as pendant chains. For the imperfect elastomers, tan δ is markedly enhanced in the isotropic state because of relaxation of pendant chains and other imperfections. However, within the smectic state, the magnitude of tan δ and its temperature dependence are similar for optimal and imperfect elastomers at ω = 1 Hz. The prominent loss peak near the clearing transition arises from segment-level relaxations that are insensitive to the details of chain connectivity. Smectic MCLCE can be tailored for applications as vibration-damping materials by manipulating the clearing transition temperature through the backbone structure or by deliberate introduction of structural imperfections such as pendant chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3267–3276, 2007     

Invisible Security Ink Based on Water‐Soluble Graphitic Carbon Nitride Quantum Dots

Stimuli‐responsive photoluminescent (PL) materials have been widely used as fluorescent ink for data security applications. However, traditional fluorescent inks are limited in maintaining the secrecy of information because the inks are usually visible by naked eyes either under ambient light or UV‐light illumination. Here, we introduced metal‐free water‐soluble graphitic carbon nitride quantum dots (g‐CNQDs) as invisible security ink for information coding, encryption, and decryption. The information written by the g‐CNQDs is invisible in ambient light and UV light, but it can be readable by a fluorescence microplate reader. Moreover, the information can be encrypted and decrypted by using oxalic acid and sodium bicarbonate as encryption reagent and decryption reagent, respectively. Our findings provide new opportunities for high‐level information coding and protection by using water‐soluble g‐CNQDs as invisible security ink.     

An organic-inorganic hybrid thermochromic ferroelastic with multi-channel switches

Multifunctional switchable materials are attracting tremendous interest because of their great application potential in signal processing, information encryption, and smart devices. Here, we reported an organic-inorganic hybrid thermochromic ferroelastic crystal, [TMIm][CuCl₄] (TMIm = 1,1,3,3-tetramethylimidazolidinium), which undergoes two reversible phase transitions at 333 K and 419 K, respectively. Intriguingly, these three phases experience a remarkable ferroelastic-paraelastic-ferroelastic (2/m-mmm-2/m) transition, which remains relatively unexplored in ferroelastics. Moreover, the ferroelastic domains can be simultaneously switched under temperature and stress stimuli. Meanwhile, [TMIm][CuCl₄] exhibits thermochromic phenomenon, endowing it with extra spectral encryption possibilities during information processing. Combined with dielectric switching behavior, [TMIm][CuCl₄] are promising for practical applications in memory devices, next-generation sensors, and encryption technology.     

荧光传感方法检测爆炸物的研究进展

爆炸物检测是当前国际安全中迫切关注的问题之一。在过去的几十年中,大量的荧光传感材料用于荧光传感检测气态、液态和固态爆炸物见诸于报道。近年来,为了实现爆炸物的快速响应、高灵敏和高选择性的检测,研究工作者大力开发了各种新型荧光材料。这篇综述总结了近年来用于爆炸物检测的先进荧光材料,详尽、系统、重点地介绍了共轭聚合物、荧光小分子、超分子体系、具有聚集诱导发光效应的活性材料及静电纺丝纳米材料等各种荧光材料在爆炸物检测中的应用,展望了荧光传感方法在爆炸物检测领域的应用前景。     

Biocatalytic Feedback‐Driven Temporal Programming of Self‐Regulating Peptide Hydrogels

Switchable self‐assemblies respond to external stimuli with a transition between near‐equilibrium states. Although being a key to present‐day advanced materials, these systems respond rather passively, and do not display autonomous dynamics. For autonomous behavior, approaches must be found to orchestrate the time domain of self‐assemblies, which would lead to new generations of dynamic and self‐regulating materials. Herein, we demonstrate catalytic control of the time domain of pH‐responsive peptide hydrogelators in a closed system. We program transient acidic pH states by combining a fast acidic activator with the slow, enzymatic, feedback‐driven generation of a base (dormant deactivator). This transient state can be programmed over orders of magnitude in time. It is coupled to dipeptides to create autonomously self‐regulating, dynamic gels with programmed lifetimes, which are used for fluidic guidance, burst release, and self‐erasing rapid prototyping.     

Comparison of the transient stress–strain response of rubber to its linear dynamic behavior

Master curves of the small strain and dynamic shear modulus are compared with the transient mechanical response of rubbers stretched at ambient temperature over a seven‐decade range of strain rates (10^?4 to 10³ s^?1). The experiments were carried out on 1,4‐ and 1,2‐polybutadienes and a styrene–butadiene copolymer. These rubbers have respective glass transition temperatures, T_g, equal to ?93.0, 0.5, and 4.1 °C, so that the room temperature measurements probed the rubbery plateau, the glass transition zone, and the onset of the glassy state. For the 1,4‐polybutadiene, in accord with previous results, strain and strain rate effects were decoupled (additive). For the other two materials, encroachment of the segmental dynamics precluded separation of the effects of strain and rate. These results show that for rubbery polymers near T_g the use of linear dynamic data to predict stresses, strain energies, and other mechanical properties at higher strain rates entails large error. For example, the strain rate associated with an upturn in the modulus due to onset of the glass transition was three orders of magnitude higher for large tensile strains than for linear oscillatory shear strains. © 2011 Wiley Periodicals, Inc.* J Polym Sci Part B: Polym Phys, 2011     

Modulating Photo‐ and Electroluminescence in a Stimuli‐Responsive π‐Conjugated Donor–Acceptor Molecular System

Functional organic materials that display reversible changes in fluorescence in response to external stimuli are of immense interest owing to their potential applications in sensors, probes, and security links. While earlier studies mainly focused on changes in photoluminescence (PL) color in response to external stimuli, stimuli‐responsive electroluminescence (EL) has not yet been explored for color‐tunable emitters in organic light‐emitting diodes (OLEDs). Here a stimuli‐responsive fluorophoric molecular system is reported that is capable of switching its emission color between green and orange in the solid state upon grinding, heating, and exposure to chemical vapor. A mechanistic study combining X‐ray diffraction analysis and quantum chemical calculations reveals that the tunable green/orange emissions originate from the fluorophore's alternating excited‐state conformers formed in the crystalline and amorphous phases. By taking advantage of this stimuli‐responsive fluorescence behavior, two‐color emissive OLEDs were produced using the same fluorophore in different solid phases.     

An amphiphilic molecule with a single fluorophore exhibits multiple stimuli-responsive behavior

Fluorescent materials that respond to multiple stimuli have broad applications ranging from sensing and bioimaging to information encryption. Herein, we report the design and synthesis of a single-fluorophore-based amphiphile DCSO, which shows temperature-, solvent-, humidity-, and radiation-dependent fluorescence. DCSO consists of a dicyanostilbene (DCS) group as a rigid hydrophobic core with oligo(ethylene glycol) (OEG) chains at both ends as a flexible hydrophilic periphery. The DCS group acts as a highly efficient fluorophore, while the OEG chain endows the molecule with thermo-responsiveness. Fluorescent colors can vary from blue to green to yellow in response to external stimuli. On the basis of light radiation, we demonstrate that this system can be applied to time-dependent information encryption, in which the correct information can only be read at a specific time under irradiation. This work further demonstrates the usefulness and application of single-fluorophore-based luminescent materials with multiple stimuli-responsive functions.