In this article, the fabrication of an active organic-inorganic one-dimensional photonic crystal structure to offer electrothermal fluorescence switching is described. The film is obtained by spin-coating of liquid crystal elastomers (LCEs) and TiO2 nanoparticles alternatively. By utilizing the property of LCEs that can change their size and shape reversibly under external thermal stimulations, the λmax of the photonic band gap of these films is tuned by voltage through electrothermal conversion. The shifted photonic band gap further changes the matching degree between the photonic band gap of the film and the emission spectrum of organic dye mounting on the film. With rhodamine B as an example, the enhancement factor of its fluorescence emission is controlled by varying the matching degree. Thus, the fluorescence intensity is actively switched by voltage applied on the system, in a fast, adjustable, and reversible manner. The control chain of using the electrothermal stimulus to adjust fluorescence intensity via controlling the photonic band gap is proved by a scanning electron microscope (SEM) and UV-vis reflectance. This mechanism also corresponded to the results from the finite-difference time-domain (FDTD) simulation. The comprehensive usage of photonic crystals and liquid crystal elastomers opened a new possibility for active optical devices.

Rationally and efficiently controlling chemical composition, microstructure, and morphology of carbon nanomaterials plays a crucial role in significantly enhancing their functional properties and expending their applications. In this work, a novel strategy for simultaneously controlling these structural parameters was developed on the base of a multifunctional precursor approach, in which the precursor not only serves as carbon source and structure-directing agent, but also contains two heteroatom doping sites. As exemplified by using pyrrole-terminated ionic liquid surfactant as such precursor, in conjunction with sol-gel chemistry this strategy allows for efficiently producing well-defined hollow carbon spheres with controlled microstructure and chemical compositions. Remarkably, the dual-doping sites in confined silica channels provide an exciting opportunity and flexibility to access various doped carbons through simply anion exchange or altering the used oxidative polymerization agent, especially the multispecies codoped materials by combination of the two doping modes. All the results indicate that the described strategy may open up a new avenue for efficiently synthesizing functional carbon materials with highly controllable capability.

The efficient synthesis of free-standing mesostructured two-dimensional (2D) nanofilms with high-yield as well as good control of composite, mesophase structure, orientation of the pore channel and thickness represents a big challenge. In this work, it was serendipitously found that microemulsion droplets of tetraethylorthosilicate (TEOS) could serve as a novel dynamic interface for continuous growth of nanofilms. Based on this finding, a general, efficient strategy for the direct and large-scale synthesis of free-standing mesoporous silica films (FSMSFs) was developed. Remarkably, with the careful control of the synthesis conditions, the FSMSFs with high-yield as well as good control of composite, mesophase structure, orientation of the pore channel and thickness could be efficiently achievable. More importantly, by using polymerizable surfactants the preorganized monomers in the nanochannels of the resultant silica films could be further converted into 2D polymers and carbon nanomaterials as well as metal particle-decorated forms, as exemplified by using pyrrole-terminated surfactants, demonstrating a powerful method to create 2D inorganic, organic or hybrid functional nanomaterials.

The synergetic combination of the distinct properties of azobenzene and bile acid could afford stable tweezer-like conformation with tunable hydrophilic and hydrophobic channels, thus increasing their antimicrobial activity toward both Gram-positive and Gram-negative bacteria, which can be conveniently switched off when the conformation turn back to the extended state. (C) 2016 Elsevier Ltd. All rights reserved.

The broad class of explosives includes nitro aromatics as well as challenging aliphatic nitro-organics whose detection is important from counter-terrorism and national security perspectives. Here we report a turn-on fluorescent sensor array based on aggregation-induced emission (AIE) fluorophores as receptors. To achieve a good sensing system with fast response, good sensitivity and low detection limit, three receptors with abundant chemical diversities for target analytes were synthesized. The turn-on response of the individual receptor showed highly variable and cross-reactive analyte-dependent changes in fluorescence. The excellent ability to identify a variety of explosives, especially the challenging aliphatic nitro-organics (2,3-dimethyl-2,3-dinitrobutane (DMNB), 1,3,5-trinitro-1,3,5-triazinane (RDX), cyclotetramethylene tetranitramine (HMX) and entaerythritol tetranitrate (PETN)), was demonstrated in qualitative and quantitative analyses with 100% accuracy. The fluorescence signal amplification in the presence of explosives allows for application of these receptors in a sensor microarray suitable for high-throughput screening. These results suggested that the cross-reactive sensor array based on AIE fluorophores could find a wide range of applications for sensing various analytes or complex mixtures.

Asymmetric Janus materials are of wide‐spread interest due to their unique anisotropic and directional features. In our work, through a simple combination of nanosphere lithography at the solution interface and dopamine chemistry, a new approach for the facile synthesis of large, asymmetric, free‐standing, 2D photonic Janus films with a highly tunable Janus balance and multiple functionalities is developed. Herein we rationally exploit the unique properties (reducibility, self‐adhesive nature, and post‐modification ability) of the polydopamine (PDA) layer and the good deformation and dissolution ability of polystyrene (PS). The precisely controllable chemical compositions on the PDA layer and the multi‐variable morphologies from the PS part offer us a great chance to tune the Janus balance of the film in different dimensions. As a demonstration of the resultant Janus films for potential applications, femtoliter cup arrays are achieved after the removal of PS, which are used for confined crystallization. Good surface‐enhanced Raman scattering (SERS) enhancement of the Ag‐metallic Janus film is shown, which confirms this excellent platform for creating new functional materials. Our study not only bridges dopamine chemistry with 2D photonic crystals but also opens up new avenues for artificially designed Janus nanoarchitectures with multi­ple functions.

Recently, it has been demonstrated that the combination of periodic dielectric structures with metallic structures provides an efficient means to yield a synergetic optical response or functionality in the resultant hybrid plasmonic-photonic systems. In this work, a new hybrid plasmonic-photonic structure of 2D-ordered dielectric sub-micron bowls on a flat gold surface was proposed, prepared, and theoretically and experimentally characterized. This hybrid structure supports two types of modes: surface plasmon polaritons bound at the metallic surface and waveguided mode of light confined in the cavity of bowls. Optical responses of this hybrid structure as well as the spatial electric field distribution of each mode are found to be strongly dependent on the structural parameters of this system, and thus could be widely modified on demand. Importantly, compared to the widely studied hybrid systems, namely the flat metallic surface coated with a monolayer array of latex spheres, the waveguided mode with strong field enhancement appearing in the cavities of bowls is more facilely accessible and thus suitable for practical use. For demonstration, a 2D-ordered silica sub-micron bowl array deposited on a flat gold surface was fabricated and used as a regenerable platform for fluorescence enhancement by simply accommodating emitters in bowls. All the simulation and experiment results indicate that the 2D-ordered dielectric sub-micron bowls on a metal surface should be a useful hybrid plasmonic-photonic system with great potential for applications such as sensors or tunable emitting devices if appropriate periods and materials are employed.

Exploiting "chaperone molecule" to navigate the successful assembly energy landscapes has been extensively used in biological systems, whereas in artifical supramolecular systems the "chaperone-assisted" assembly strategy to be used for the synthesis of materials with novel structures or the structures to be hardly prepared by "conventional" methods are still far from realizing the potential functions. In this work, we present a new example of small organic molecule acting as "chaperone molecule" in the facile formation of organic molecular porous materials. This porous material is composed of pure cucurbit[8]uril (CB[8]) macrocycle and possesses a honeycomb-like structure with an isolated and relatively large one-dimensional (1D) nanochannel. Moreover, it has good chemical and thermal stability, and shows a good adsorption capability for large molecule loading. Importantly, with the assistance of chaperone molecules, pure CB[8] could also be recycled even from a complex aqueous solution, demonstrating a powerful purification method of CB[8] from complex systems.

Effective deposition of MOFs on "inert" solid surfaces is very challenging. In this work, we found that polydopamine, which can be facilely and tightly formed on any types as well as any forms of solid surfaces, could be used as an effective nucleation center for MOF deposition. Based on this finding, various MOFs were successfully deposited onto nanofibrous polymer membranes, especially the commercially available "inert" ones, affording hierarchically structured porous films.

A series of tetraphenylethylene (TPE)-bile acid conjugates was described. It was found that the synergetic combination of the distinct properties of TPE and bile acid units could directly afford uniform fluorescent vesicles with amphiphilic binding pockets in the membrane. This structural features of such vesicles provides a unique opportunity for facile construction of functional chemical systems through host-guest chemistry.

A novel strategy for highly sensitive detection and discrimination of explosives is developed based on the metal–organic polyhedra (MOP)‐decorated plasmonic substrate. It is found that the careful selection of the geometric and electronic characteristics of the assembly units (organic ligands and unsaturated metals sites) embedded within the MOP cage allows for the integration of multiple weak molecular interactions in a controllable fashion and thus the MOP cage can serve as an excellent receptor for selective uptake and binding of explosives. By further grafting of the MOP cage onto a plasmonic substrate with good surface‐enhanced Raman scattering enhancement factor, the resulting sensor shows a good sensing capability to various groups of ultratrace explosives, especially the challenging aliphatic nitro‐organics.

Anisotropic photonic crystal materials have long been pursued for their broad applications. A novel method for creating chemically patterned inverse opals is proposed here. The patterning technique is based on selective photolysis of a photolabile polymer together with postmodification on released amine groups. The patterning method allows regioselective modification within an inverse opal structure, taking advantage of selective chemical reaction. Moreover, combined with the unique signal self-reporting feature of the photonic crystal, the fabricated structure is capable of various applications, including gradient photonic bandgap and dynamic chemical patterns. The proposed method provides the ability to extend the structural and chemical complexity of the photonic crystal, as well as its potential applications.

Molecularly imprinted photonic polymers can serve as ideal sensing elements for efficiently creating cross-reactive sensor arrays. Based on this concept, a new method for sensitive and label-free detection of challenging PBDEs was developed, by which the direct detection and discrimination of trace levels of PBDEs against a high-background of interferents was achieved with 100% accuracy.

Based on the fascinating properties of polydopamine (PDA), a simple strategy was developed for facilely and efficiently fabricating plasmonic substrate with nanohybrid structure (PDA/Metal NPs/PDA). Because of the good reductive ability of PDA, metal nanoparticles such as Ag, Au, or Ag/Au hybrid particles with the good control of size and distribution on plasmonic substrate could be easily achieved. Also, owing to the exceptional self-adhesive nature, the presynthesized monodisperse metal NPs can be directly adsorbed to the surface to enrich plasmon response. Moreover, by carefully tuning the dopamine immersion time, the formed nanohybrid structure PDA/metal NPs/PDA enabled the distance-dependent MEF phenomenon where the distance could be controlled with a resolution of approximately 1 nm. In particular, the covalent (Michael addition or Schiff-base reaction) binding enabled us an easy but efficient way to immobilize a large diverse fluorophores or biomolecules on plasmonic substrate. All these above properties indicated the promising PDA-based plasmonic substrate for fluorescence enhancement. As a demonstration of the good fluorescence enhancement property, thiol-based dye was used. The ca. 5-fold fluorescence intensity enhancement on the plasmonic substrate with pattern structure clearly proved that PDA-based plasmonic substrate was indeed a good reactive platform for fluorescence enhancement. With the assistance of FDTD, the electromagnetic near-field distributions and the radiative power emitted by fluorophores on the substrate were found to be significantly improved, further helpful for explaining our experimental observations. Finally, the optimal set calculations guided us that based on the careful selection of fluorophore and space distance, a better fluorescence enhancement could be achieved for further optical and biological applications. These performed experiments suggested that the PDA-based fabricating protocol is indeed a powerful strategy for creating plasmon substrate that could find a wide range of applications.

Assays for acetylcholinesterase (AChE) with high sensitivity and high selectivity as well as facile manipulation have been urgently required in various fields. In this work, a reaction-based photonic strategy was developed for the efficient assay of AChE activity and inhibition based on the synergetic combination of the specific thiol-maleimide addition reaction with photonic porous structure. It was found that various applications including detection of AChE activity, measurement of the related enzymatic kinetics, and screening of inhibitors could be efficiently implemented using such strategy. Remarkably, the unique photonic nanostructure endows the constructed sensing platform with high sensitivity with a limit of detection (LOD) of 5 mU/mL for AChE activity, high selectivity, and self-reporting signaling. Moreover, the label-free solid film-based sensing approach described here has advantages of facile manipulation and bare-eye readout, compared with conventional liquid-phase methods, exhibiting promising potential in practical application for the AChE assay.

Here we report on the use of a self-assembled organic object to template the first example of a nanoscale metal–organic framework (MOF) with a helical morphology.

The controlled formation of MOF-based superstructures with well-defined nanoscale sizes and exquisite morphologies represents a big challenge, but can trigger a new set of properties distinct from their bulk counterparts. Here we report on the use of a self-assembled organic object to template the first example of a nanoscale metal-organic framework (MOF) with a helical morphology. Two prototypical MOFs (HKUST-1 and MIL-100) were used to exemplify the growth of such materials on supramolecular assemblies. Interestingly, it was found that, dependent on the nature of the precursors, not only could well-defined helical MOF nanotubes be facilely fabricated, but novel helical bundle nanostructures could also be formed. These resultant MOF superstructures show additional optical properties and could be used as precursors for the preparation of chiral nanocarbons.

With prospects for application in much scientific research, wrinkle patterns have attracted much attention. Several delicate methods, including a pre-patterning process and a controlled stress release procedure, have been developed to fabricate well-controlled wrinkle patterns. In this work, we discovered accidentally that unsophisticated mechanical scratching can also lead to ordered wrinkle structures. Combining experiment results and theoretical models as well as the folding properties of bile acid derivatives, it is revealed that ordered spring-like structures and their organized aggregates (multi-lamellar membranes), which are all based on unique amphiphilicity and rigid steroid skeletons, play a crucial role in the formation of well-organized wrinkle patterns. As far as we know, this is the first attempt to explain polymer wrinkle phenomena on a molecular level. Furthermore, due to their excellent biocompatibility, these polymers may serve as new wrinkling materials and exhibit potential uses in the field of bioengineering.

In this work, maleimide-containing polymer inverse opals have been successfully prepared by utilization of an acrylate monomer bearing a masked (protected) maleimide unit. As an ideal clickable functional group, maleimide can promote the Michael addition of thiol-containing molecules and the thermoreversible Diels–Alder reaction of furan derivatives, providing tremendous opportunities to produce various functional materials from one maleimide-containing polymer. As a demonstration, four chemical systems were facilely evolved from the prepared maleimide-containing inverse opal. By exploiting the nucleophilic thiol–ene reaction of maleimide, the zwitterionic pH-responsive inverse opal and electroactive inverse opal were first fabricated by reacting with cysteine and thiol-containing ferrocene derivatives, respectively. Based on the same reaction, it was also found that the maleimide-containing inverse opal could serve as a self-reporting sensing platform to sensitively detect the reduction of oxidized glutathione by specific enzymes. On the other hand, the thermoreversible nature of the Diels–Alder reaction of the maleimide groups made it possible to construct a dynamic molecule gating system by reacting with alkyl-chain-substituted furan derivatives from the prepared interconnected macroporous film. In fact, due to the unlimited variety provided by the two kinds of reactions mentioned above, the described photonic material exhibits a significant extendibility and could be easily post-modified for special purposes with maintenance of the opaline structure. Thus, this novel clickable maleimide-containing polymer inverse opal could serve as a reactive platform for producing a variety of functional photonic materials.

Active photonic crystals (PC) or photonic crystal heterostructures have many applications such as chemical and biological sensors, active colour displays, structural colour printing and fluorescence enhancement. However, photonic crystal structures with the different functions mentioned above require different preparation methods, and some of them require sophisticated instruments for specific production processes. Thus, development of a simple way or a useful platform for conveniently fabricating specific photonic crystal structures with different functions is highly desirable and significant. Herein, by exploiting the self-polymerization of dopamine, we successfully introduced polydopamine (PDA) into silica opaline templates and produced PDA photonic crystal structures. Based on the utilization of the unique properties of PDA such as reactivity, reductive ability, powerful adhesive capability as well as carbonizable feature, PDA-based photonic crystal structures provide a very useful platform for further convenient fabrication of multifunctional photonic crystal structures with a variety of potential applications. Due to the virtually unlimited variety provided by the active secondary reactions of PDA, the post-modification of PDA-based photonic crystals can readily afford photonic crystal based chemical or biological sensors. The reductive as well as adhesive ability of PDA provides another tremendous opportunity to produce photonic crystal heterostructures with various metals, metal oxides, polymer or semiconductor nanoparticles. As a demonstration, PDA/Ag/PDA and PDA/Pt/PDA opaline structures were prepared by PDA-assisted metallization or adsorption, respectively, which could find promising application in fluorescence enhancement of organic dyes or chemical solvent sensors. More importantly, the carbonizable feature of PDA allows for efficiently producing carbon inverse opaline films as well as metal particle doped carbon inverse opaline films by carbonizing the corresponding PDA, PDA/Ag/PDA or PDA/Pt/PDA photonic structures, which may show various potential applications in catalysis and energy conversion.