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With the rapid development of human-friendly wearable devices, energy storage components are required to have skin-like stretchability or free-form to fit closer and more comfortably to the human body. This study introduces a hierarchically interpenetrated reentrant microcellular structure combined with 2D cellular graphene/MXene/carbon nanotubes (CNTs) and 3D cellular melamine foam. This composite structure works as a stretchable framework of lithium metal composite electrodes to provide stretchability for lithium metal electrodes, which are promising as next-generation energy storage systems. The interpenetrated but independent cellular structures successfully obtain stable structural deformability from the nonconductive and deformable melamine foam, while at the same time, high electrical conductivity, lithiophilicity, and mechanical stability of the graphene/CNT/MXene network serve as a lithium deposition support during the electrodeposition of lithium. The reentrant structure is fabricated by radial compressing the hierarchical cellular structures to take advantage of the structural stretchability of the accordion-like reentrant frameworks. The lithium-deposited composite electrodes exhibit much lower overpotential during Li stripping and plating than lithium metal foil anodes and show stable electrochemical performances under 30% of mechanical strain. The reentrant microcellular electrodes offer great potential for advanced designs of lithium metal electrodes for stretchable batteries with high energy density.
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Chiral metamaterials have received significant attention due to their strong chiroptical interactions with electromagnetic waves of incident light. However, the fabrication of large-area, hierarchically manufactured chiral plasmonic structures with high dissymmetry factors (g-factors) over a wide spectral range remains the key barrier to practical applications. Here we report a facile yet efficient method to fabricate hierarchical chiral nanostructures over a large area (>11.7 × 11.7 cm2) and with high g-factors (up to 0.07 in the visible region) by imparting extrinsic chirality to nanostructured polymer substrates through the simple exertion of mechanical force. We also demonstrate the application of our approach in the polarized emission of quantum dots and information encryption, including chiral quick response codes and anti-counterfeiting. This study thus paves the way for the rational design and fabrication of large-area chiral nanostructures and for their application in quantum communications and security-enhanced optical communications.
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Introduction: Deinoxanthin (DX), a carotenoid, has excellent antioxidant and anti-inflammatory properties. However, owing to its lipophilicity, it is unfavorably dispersed in water and has low stability, limiting its application in cosmetics, food, and pharmaceuticals. Therefore, it is necessary to study nanoparticles to increase the loading capacity and stability of DX. Methods: In this study, DX-loaded nanocapsules (DX@NCs) were prepared by nanoprecipitation by loading DX into nanocapsules. The size, polydispersity index, surface charge, and morphology of DX@NCs were confirmed through dynamic light scattering and transmission electron microscopy. The loading content and loading efficiency of DX in DX@NCs were analyzed using high-performance liquid chromatography. The antioxidant activity of DX@NCs was evaluated by DPPH assay and in vitro ROS. The biocompatibility of DX@NCs was evaluated using an in vitro MTT assay. In vitro NO analysis was performed to determine the effective anti-inflammatory efficacy of DX@NCs. Results: DX@NCs exhibited increased stability and antioxidant efficacy owing to the improved water solubility of DX. The in situ and in vitro antioxidant activity of DX@NCs was higher than that of unloaded DX. In addition, it showed a strong anti-inflammatory effect by regulating the NO level in an in vitro cell model. Conclusion: This study presents a nanocarrier to improve the water-soluble dispersion and stability of DX. These results demonstrate that DX@NC is a carrier with excellent stability and has a high potential for use in cosmetic and pharmaceutical applications owing to its antioxidant and anti-inflammatory effects.
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Antioxidantes , Nanocápsulas , Antioxidantes/farmacología , Nanocápsulas/química , Carotenoides , Antiinflamatorios/farmacologíaRESUMEN
The growth of lithium (Li) dendrites reduces the lifespan of Li-metal batteries and causes safety issues. Herein, hierarchically porous aramid nanofiber separators capable of effectively suppressing the Li dendrite growth while maintaining highly stable cycle performances at high charge/discharge rates are reported. A two-step solvent exchange process combined with reprotonation-mediated self-assembly is utilized to control the bimodal porous structure of the separators. In particular, when ethanol and water are used sequentially, aramid nanofibers form hierarchical porous structures containing nanopores in macroporous polymer frameworks to yield a mechanically robust membrane with high porosity of 97% or more. The optimized samples exhibit high ionic conductivities of 1.87-4.04 mS cm-1 and high Li-ion transference numbers of 0.77-0.84 because of the ultrahigh porosity and selective affinity to anions. Li-metal symmetric cells do not show any noticeable presence of dendrites after 100 cycles, and they operate stably for more than 1500 cycles even under extreme conditions with a high current density of >20 mA cm-2 . In addition, the LiFePO4 /Li full cell retains 86.3% of its capacity after 1000 cycles at a charge rate of 30 C.
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Hydrogels have diverse chemical properties and can exhibit reversibly large mechanical deformations in response to external stimuli; these characteristics suggest that hydrogels are promising materials for soft robots. However, reported actuators based on hydrogels generally suffer from slow response speed and/or poor controllability due to intrinsic material limitations and electrode fabrication technologies. Here, we report a hydrogel actuator that operates at low voltages (<3 volts) with high performance (strain > 50%, energy density > 7 × 105 joules per cubic meter, and power density > 3 × 104 watts per cubic meter), surpassing existing hydrogel actuators and other types of electroactive soft actuators. The enhanced performance of our actuator is due to the formation of wrinkled nanomembrane electrodes that exhibit high conductivity and excellent mechanical deformation through capillary-assisted assembly of metal nanoparticles and deswelling-induced wrinkled structures. By applying an electric potential through the wrinkled nanomembrane electrodes that sandwich the hydrogel, we were able to trigger a reversible and substantial electroosmotic water flow inside a hydrogel film, which drove the controlled swelling of the hydrogel. The high energy efficiency and power density of our wrinkled nanomembrane electrode-induced actuator enabled the fabrication of an untethered insect-scale aquabot integrated with an on-board control unit demonstrating maneuverability with fast locomotion speed (1.02 body length per second), which occupies only 2% of the total mass of the robot.
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Hidrogeles , Agua , Animales , Hidrogeles/química , Electrodos , Conductividad Eléctrica , InsectosRESUMEN
Cell chirality plays a critical role in the linkage between molecular chirality and the asymmetrical biological functions of body organs. However, enantioselective interactions between cell chirality and the extracellular environment are not yet fully understood. In this study, we investigated the effects of structurally chiral extracellular microenvironments on cellular alignments and differentiations. Twisted wrinkle-shaped chiral micropatterns were prepared using biaxial and asymmetric buckling methods, wherein structural handedness was determined from the orientation of the tilt angle between the first and second microwrinkles. Myoblasts were separately cultured on two enantiomeric chiral micropatterns in a mirror-reflected shape. Cells cultured on the left-handed chiral micropatterns preferred alignments along the direction of the second microwrinkle, with a relatively deeper valley than that of the first microwrinkle. The aligned cells on the left-handed pattern showed higher differentiation rates, as assessed by fusion indices and marker protein expression levels, than those cultured on right-handed chiral micropatterns. These results suggest that myoblasts exhibit enantioselective recognition of structurally chiral microenvironments, which can promote cellular alignments and differentiation.
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Mioblastos , Diferenciación Celular , Mioblastos/metabolismo , EstereoisomerismoRESUMEN
Ionogels are emerging materials for advanced electrochemical devices; however, their mechanical instability to external stresses has raised concerns about their safety. This study reports aligned bacterial nanocellulose (BC) ionogel films swelled with the model ionic liquid (IL) of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) for an unprecedented combination of high stiffness and high energy dissipation without significant loss of ionic conductivity. The aligned BC ionogel films are prepared through wet-state stretching methods, followed by drying and swelling by ILs. The aligned ionogel films exhibit significantly improved dynamic mechanical properties, overcoming the mechanical conventional limit of traditional materials by 2.0 times at 25 °C and by a maximum of 4.0 times at 0 °C. Additionally, the same samples exhibit relatively high ionic conductivities of 0.16 mS cm-1 at 20 °C and 0.45 mS cm-1 at 60 °C with storage moduli over 10 GPa. The synergistic effect of the mechanical reinforcements by alignment of the BC nanofibers and the plasticizing effects by ILs could be attributed to the significant enhancement of dynamic mechanical properties and the retention of ionic conductivities. These results will lead to a deeper understanding of the material design for mechanically superior ionogel systems with increasing demands for advanced electronic and electrochemical devices.
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For next-generation wearable and implantable devices, energy storage devices should be soft and mechanically deformable and easily printable on any substrate or active devices. Herein, we introduce a fully stretchable lithium-ion battery system for free-form configurations in which all components, including electrodes, current collectors, separators, and encapsulants, are intrinsically stretchable and printable. The stretchable electrode acquires intrinsic stretchability and improved interfacial adhesion with the active materials via a functionalized physically cross-linked organogel as a stretchable binder and separator. Intrinsically stretchable current collectors are fabricated in the form of nanocomposites consisting of a matrix with excellent barrier properties without swelling in organic electrolytes and nanostructure-controlled multimodal conductive fillers. Due to structural and materials freedoms, we successfully fabricate several types of stretchable lithium-ion battery that reliably operates under various stretch deformations with capacity and rate capability comparable with a nonstretchable battery over 2.5 mWh cm-2 at 0.5 C, even under high mass loading conditions over 10 mg cm-2, including stacked configuration, direct integration on both sides of a stretch fabric, and application of various electrode materials and electrolytes. Especially, our stretchable battery printed on a stretch fabric also exhibits high performance and stretch/long-term stabilities in the air even with wearing and pulling.
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Research on the chiral magneto-optical properties of inorganic nanomaterials has enabled novel applications in advanced optical and electronic devices. However, the corresponding chiral magneto-optical responses have only been studied under strong magnetic fields of ≥1 T, which limits the wider application of these novel materials. In this paper, we report on the enhanced chiral magneto-optical activity of supra-assembled Fe3O4 magnetite nanoparticles in the visible range at weak magnetic fields of 1.5 mT. The spherical supra-assembled particles with a diameter of â¼90 nm prepared by solvothermal synthesis had single-crystal-like structures, which resulted from the oriented attachment of nanograins. They exhibited superparamagnetic behavior even with a relatively large supraparticle diameter that exceeded the size limit for superparamagnetism. This can be attributed to the small size of nanograins with a diameter of â¼12 nm that constitute the suprastructured particles. Magnetic circular dichroism (MCD) measurements at magnetic fields of 1.5 mT showed distinct chiral magneto-optical activity from charge transfer transitions of magnetite in the visible range. For the supraparticles with lower crystallinity, the MCD peaks in the 250-550 nm range assigned as the ligand-to-metal charge transfer (LMCT) and the inter-sublattice charge transfer (ISCT) show increased intensities in comparison to those with higher crystallinity samples. On the contrary, the higher crystallinity sample shows higher MCD intensities near 600-700 nm for the intervalence charge transfer (IVCT) transition. The differences in MCD responses can be attributed to the crystallinity determined by the reaction time, lattice distortion near grain boundaries of the constituent nanocrystals, and dipolar interactions in the supra-assembled structures.
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Chiral-structured nanoscale materials exhibit chiroptical properties with preferential absorptions of circularly polarized light. The distinctive optical responses of chiral materials have great potential for advanced optical and biomedical applications. However, the fabrication of three-dimensional structures with mirrored nanoscale geometry is still challenging. This study introduces chiral plasmonic nanopatterns in wavy shapes based on the unidirectional alignment of block copolymer thin films and their tilted transfer, combined with buckling processes. The cylindrical nanodomains of polystyrene-block-poly(2-vinylpyridine) thin films were unidirectionally aligned over a large area by the shear-rolling process. The aligned block copolymer thin films were transferred onto uniaxially prestrained polydimethylsiloxane films at certain angles relative to the stretching directions. The strain was then released to induce buckling. The aligned nanopatterns across the axis of the formed microwrinkles were selectively infiltrated with gold ions. After reduction by plasma treatment, chiral plasmonic nanowave patterns were fabricated with the presence of mirror-reflected circular dichroism spectra. This fabrication method does not require any lithography processing or innately chiral biomaterials, which can be advantageous over other conventional fabrication methods for artificial nanoscale chiral materials.
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Oro , Oro/química , Dicroismo CircularRESUMEN
Layer-by-layer (LbL) assembly is a widely used method of nanofilm coating in various technology applications; however, the coating process is typically time-consuming and labor-intensive. This study presents a microfluidic platform that performs LbL assembly in a fast, parallel, preprogrammed manner, with only water-head pressure as the driving force. The platform generates periodic sequential outflows with four solutions (TiO2 and SiO2 nanoparticle solutions and two washing solutions), and simultaneously applies 12 different conditions of coating period (0.6-4 min) and shear stress (0.7-15 dyn cm-2) for anti-reflection coating in the visual spectrum. The thickness and roughness of the coated films are well regulated at the nanoscale using shear stress, coating period, and the number of bilayers. In this way, our study reveals the substantial influence of shear stress on the relative composition of the nanoparticles and void volume in the films, thereby varying the film transmittance with a maximum value of 98%. Compared to the conventional immersive coating method, the coating duration of our method was 15 times faster. This parallel coating method is highly effective for determining optimized coating conditions.
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Microfluídica , Nanopartículas , Dióxido de SilicioRESUMEN
Shear alignment of the block copolymer (BCP) thin film is one of the promising directed self-assembly (DSA) methodologies for the unidirectional alignment of sub-10 nm microdomains of BCPs for next-generation nanolithography and nanowire-grid polarizers. However, because of the differences in the surface/interfacial energies at the top surface/bottom interface, the shear-induced ordering of BCP nanopatterns has been restricted to BCPs with spherical and cylindrical nanopatterns and cannot be realized for high-aspect-ratio perpendicular lamellar structures, which is essential for practical application to semiconductor pattern processes. It is still a difficult challenge to fabricate the unidirectional alignment in a short time over a large area. In this study, we propose an approach for combining the shear-rolling process with the filtered plasma treatment of BCP films for the fabrication of unidirectionally aligned and perpendicularly oriented lamellar nanostructures. This approach enables fabrication within 1 min on a 4 in scale. We treated filtered plasma on the BCP film for perpendicular orientation and executed the hot-rolling process with different roller and stage speeds. Large-scale shear was generated only at the location where the BCP film was in contact with both the roller and stage, effectively applying shear stress to a large area of the BCP film within a short time. The repeated application of this shear-rolling process can achieve a higher level of unidirectional alignment. Our aligned BCP vertical lamellae were used to fabricate a high-aspect-ratio sub-10-nm-wide metallic nanowire array via dry/wet processes. In addition, shear-rolling with chemoepitaxy patterns can achieve higher orientational order and lower defectivity.
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Electrical conductivity, mechanical flexibility, and large electroactive surface areas are the most important factors in determining the performance of various flexible electrodes in energy storage devices. Herein, a layer-by-layer (LbL) assembly-induced metal electrodeposition approach is introduced to prepare a variety of highly porous 3D-current collectors with high flexibility, metallic conductivity, and large surface area. In this study, a few metal nanoparticle (NP) layers are LbL-assembled onto insulating paper for the preparation of conductive paper. Subsequent Ni electroplating of the metal NP-coated substrates reduces the sheet resistance from ≈103 to <0.1 Ω sq-1 while maintaining the porous structure of the pristine paper. Particularly, this approach is completely compatible with commercial electroplating processes, and thus can be directly extended to electroplating applications using a variety of other metals in addition to Ni. After depositing high-energy MnO NPs onto Ni-electroplated papers, the areal capacitance increases from 68 to 811 mF cm-2 as the mass loading of MnO NPs increases from 0.16 to 4.31 mg cm-2 . When metal NPs are periodically LbL-assembled with the MnO NPs, the areal capacitance increases to 1710 mF cm-2 .
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Radioactive Cs ions are extremely harmful to the human body, causing cancers and other diseases. Treatments were performed on radioactive Cs present in wastewater after use in industrial or medical fields. Prussian blue (PB) has been widely used for the removal of Cs ions from water but its colloidal structure hinders reuse, making it problematic for practical use. To solve this problem, we used a commercial macroporous polymer resin as a PB matrix. To provide an efficient anchor for PB, the surface of the polymer resin was decorated with sodium dodecylbenzenesulfonate to produce a negatively charged surface. The successful chemical binding between the polymer resin and PB prevented leakage of the latter during adsorption and crosslinked structure of the matrix provided regeneration of the adsorbent. The adsorbent maintained its removal efficiency after five repeats of the regeneration process. The PB-based, Cs ion-exchange resin showed excellent selectivity toward Cs ions and good reusability, maintaining its high adsorption capacity.
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Bencenosulfonatos/química , Cesio/química , Ferrocianuros/química , Resinas de Intercambio Iónico/química , Contaminantes Químicos del Agua/química , Adsorción , Humanos , Aguas Residuales/química , Purificación del AguaRESUMEN
For the development of wearable electronics, the replacement of rigid, metallic components with fully elastomeric materials is crucial. However, current elastomeric electrodes suffer from low electrical conductivity and poor electrical stability. Herein, a metal-like conductive elastomer with exceptional electrical performance and stability is presented, which is used to fabricate fully elastomeric electronics. The key feature of this material is its wrinkled structure, which is induced by in situ cooperation of solvent swelling and densely packed nanoparticle assembly. Specifically, layer-by-layer assembly of metal nanoparticles and small-molecule linkers on elastomers generates the hierarchical wrinkled elastomer. The elastomer demonstrates remarkable electrical conductivity (170 000 and 11 000 S cm-1 at 0% and 100% strain, respectively), outperforming previously reported elastomeric electrodes based on nanomaterials. Furthermore, a fully elastomeric triboelectric nanogenerator based on wrinkled elastomeric electrode exhibits excellent electric power generation performance due to the compressible, large contact area of the wrinkled surface during periodic contact and separation.
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Transfer methods to displace active functional layers onto desired surfaces have been developed for the fabrication of nanostructured thin film devices. However, multiple transfers with highly polar surfaces were not yet fully demonstrated presumably due to difficulty in the control of the competitive adhesions at interfaces. In this study, we present adhesion-assisted multiple transfer methods for the fabrication of highly ordered nanolaminated structures with layer-by-layer (LbL) assembled films composed of various functional nanomaterials. The interfacial adhesions were controlled with adhesive layers having a thickness of only 2.5 nm for the successful transfer of the LbL nanofunctional films from the donor substrates to the receiver substrates, which was determined mainly by the major functional moieties at the contact surfaces. The root-mean-square roughness should be lower than 200 nm for conformal contact in the transfer. The versatility of the proposed method was demonstrated with various functional Au, silica, ZnO, and TiO2 nanoparticles as constituent materials and various types of substrates including Si wafer, glass, and polyethylene terephthalate surfaces. The fabricated films with periodic depositions of two different materials could exhibit photoreflective properties with high-order reflection peaks, which were simply tunable by adjusting the order in the multiple transfer. This transfer method could effectively reduce the cost and time in the nanofabrication as it did not require costly equipment, harsh synthesis conditions, and hazardous solvents.
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Sub-10 nm patterns prepared by directed self-assembly (DSA) of block copolymer (BCP) thin films offer a breakthrough method to overcome the limitations of photolithography. Perpendicular orientation of the BCP nanostructures is essential for lithographic applications, but dissimilar surface/interfacial energies of two blocks generally favour parallel orientations, so that the perpendicular orientation could only be obtained under very limited conditions. Here, we introduce a generalized method for creating perpendicular orientations by filtered plasma treatment of the BCP films. By cross-linking the surface of disordered BCP films using only physical collisions of neutral species without ion bombardment or UV irradiation, neutral layers consistent with the BCP volume fraction are produced that promote the perpendicular orientations. This method works with BCPs of various types, volume fractions, and molecular weights individually at the top and bottom interfaces, so it was applied to orientation-controlled 3D multilayer structures and DSA processes for sub-10 nm line-spacing patterns.
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Interconnectivity of components in three-dimensional networks (3DNs) is essential for stress transfer in hydrogels, aerogels, and composites. Entanglement of nanoscale components in the network relies on weak short-range intermolecular interactions. The intrinsic stiffness and rod-like geometry of nanoscale components limit the cohesive energy of the physical crosslinks in 3DN materials. Nature realizes networked gels differently using components with extensive branching. Branched aramid nanofibers (BANFs) mimicking polymeric components of biological gels were synthesized to produce 3DNs with high efficiency stress transfer. Individual BANFs are flexible, with the number of branches controlled by base strength in the hydrolysis process. The extensive connectivity of the BANFs allows them to form hydro- and aerogel monoliths with an order of magnitude less solid content than rod-like nanocomponents. Branching of nanofibers also leads to improved mechanics of gels and nanocomposites.
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Nanofibras/química , Polímeros/química , Celulosa/química , Geles/química , Enlace de Hidrógeno , Microscopía de Fuerza Atómica , Microscopía Electrónica de Rastreo , Microscopía Electrónica de Transmisión , Nanocompuestos/química , Resistencia al Corte , Espectroscopía Infrarroja por Transformada de FourierRESUMEN
Fabrication of chiroptical materials with broadband response in the visible light region is vital to fully realize their potential applications. One way to achieve broadband chiroptical activity is to fabricate chiral nanostructures from materials that exhibit broadband absorption in the visible light region. However, the compounds used for chiroptical materials have predominantly been limited to materials with narrowband spectral response. Here, we synthesize Ag2S-based nanohelices derived from helical coordination polymers. The right- and left-handed coordination helices used as precursors are prepared from l- and d-glutathione with Ag+ and a small amount of Cu2+. The pyrolysis of the coordination helices yields right- and left-handed helices of Cu0.12Ag1.94S/C, which exhibit chiroptical activity spanning the entire visible light region. Finite element method simulations substantiate that the broadband chiroptical activity is attributed to synergistic broadband light absorption and light scattering. Furthermore, another series of Cu0.10Ag1.90S/C nanohelices are synthesized by choosing the l- or d-Glu-Cys as starting materials. The pitch length of nanohelicies is controlled by changing the peptides, which alters their chiroptical properties. The pyrolysis of coordination helices enables one to fabricate helical Ag2S-based materials that enable broadband chiroptical activity but have not been explored owing to the lack of synthetic routes.
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Chiral nanomaterials are characterized by handedness morphology on the nanoscale, manifested as preferential interaction with circularly polarized light. However, the origin of this light-matter interaction remains elusive. Here we simulated a model of chiral helical arrays of plasmonic nanoparticles with central anisotropic nanopillars to examine the effect of birefringence on the collective chiroptical response. Contrary to typical assumptions in previous works, we varied the biaxial refractive indices of the central nanopillars and observed a significant modulation of optical activity by calculating and characterizing circular dichroism (CD) spectra. The chiroptical response exhibited a sign change compared with that of the isotropic condition in a specific parametric range of negative birefringence. In addition, the CD peak increased by 3 to 16 as the ordinary refractive index increased from 1.5 to 3.0. These results are likely to be useful for designing chiral nanomaterials for applications in metamaterials, biosensors, and optoelectrical devices.