Design Of Multifunctional Materials Research Articles

Implications of coordination chemistry to cationic interactions in honeycomb layered nickel tellurates

Honeycomb layered tellurates represent a burgeoning class of multi-functional materials with fascinating crystal-structural versatility and a rich composition space. Despite their multifold capabilities, their compositional diversity remains underexplored due to complexities in experimental design and syntheses. Thus, in a bid to expand this frontier and derive relevant insights into allowed metastable compositions, we employ a density functional theory (DFT) approach to predict in silico the crystal structures of new honeycomb layered tellurates embodied by the composition, A2Ni2TeO6 (A = alkali, hydrogen or coinage-metal cations). Here, alkali-metal atoms with vastly larger radii than K (for instance, Rb and Cs) are found to engender a prismatic coordination with the oxygen atoms from the honeycomb slabs whilst coinage-metal atoms (such as Ag, Au and Cu) display a propensity for linear coordination. Further, H2Ni2TeO6 is found to also render a linear coordination wherein the hydrogen atom preferentially establishes a stronger coordination with one of the oxygen atoms to form hydroxyl groups. All A cations in the studied A2Ni2TeO6 compositions form a honeycomb lattice. Conclusions on the possibility of a monolayer-bilayer phase transition in coinage metal atom tellurates can be drawn by considering the implications of conformal symmetry of the cation honeycomb lattice and metallophilicity. This work not only propounds new honeycomb layered tellurate compositions but also provides novel insight into the rational design of multifunctional materials for applications ranging from energy storage, catalysis and optics to analogue condensed matter systems of gravity.

Synergistic synthesis of hydrophilic hollow zirconium organic frameworks for simultaneous recognition and capture of phosphorylated and glycosylated peptides

Highly efficient extraction of phospho- and glycopeptides from complicated biological samples is extremely crucial for comprehensive characterization of protein phosphorylation and glycosylation based on mass spectrometry (MS). In this work, a new synergistic strategy that combined surface covalent modification and alkaline etching was developed to synthesize hydrophilic hollow zirconium-organic frameworks (HHZr-MOFs) for simultaneous recognition and capture of phospho- and N-glycopeptides. The unique properties including high specific surface area, mesoporous shell and hollow cavity endowed HHZr-MOFs with facilitated mass transport and abundant accessible active sites. Benefited from the maltose modified on the external surface and Zr–O clusters retained on the internal surface, HHZr-MOFs could act as a highly efficient bifunctional probe for simultaneous enrichment of phospho- and N-glycopeptides based on hydrophilic interaction chromatography (HILIC) and metal oxide affinity chromatography (MOAC), respectively. Finally, a total of 98 endogenous phosphopeptides and 216 endogenous N-glycopeptides were simultaneously captured by HHZr-MOFs from saliva samples of patients with oral inflammation, and several phospho- and glycoproteins related with coagulation, bacterial defense and immune response for oral inflammation were identified by Gene ontology (GO) analyses, confirming the great potential of HHZr-MOFs in rapid detection of clinical biomarkers and comprehensive profiling of phosphoproteomic and glycoproteomic for complex biological samples. This work not only provides an alternative method to precisely design and synthesize sophisticated hollow MOFs with multifunctionalities, but also offers a novel concept of multifunctional material design for bioseparation and analysis in modification-specific proteomics.

Synthesis and optical spectroscopy of Na3Y(VO4)2:Eu3+ phosphors for thermometry and display applications.

A new Na3Y(VO4)2:Eu3+ (NYVO:Eu3+) phosphor was prepared using the sol–gel method. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to evaluate phase purity and particle size, respectively. The optical properties were investigated by UV-visible absorption, PL, and PLE spectroscopies. The absorption measurements show the formation of the vanadate host by the presence of its characteristic band in the visible region related to VO43− groups. The experimental results show that the NYVO:Eu3+ phosphors exhibit high-brightness and thermally stable emission. Under near-ultraviolet (UV) excitation, both the broadband emission from VO43− groups and the sharp peak emissions from Eu3+ ions are observed. The highest luminescence intensity was achieved for an optimal europium concentration of 15 mol%. The study of the chromaticity parameters of these compounds gives a thermally stable hot emission in the red domain, with a color purity of about 85%, which qualifies the NYVO:Eu3+ compound as a potential phosphor for light-emitting diode (LED) applications. Thermal sensing using NYVO:Eu3+ phosphors are based on monitoring the luminescence intensity ratio between the NYVO host emission and Eu3+ luminescence lines. Notably, the optical thermometry of NYVO:Eu3+ was characterized based on the fluorescence intensity ratio of VO43− and Eu3+ emissions in the 298–440 K range, with maximum absolute and relative sensitivities of 3.4% K−1 and 0.0032 K−1 respectively and a temperature uncertainty of 0.01. NYVO:Eu3+ can then be considered as a potential red phosphor for application in ultraviolet-pumped white light-emitting diodes and as a potential optical thermometer. It provides new possibilities for the design of multifunctional materials for red light-emitting diodes and for non-contact thermometry.

Recent Development of Liquid Metal‐Based Functional Materials Combined with Common Transition Metals

AbstractGallium‐based liquid metals (LMs) are a group of metal materials that are in liquid state at room temperature. Their unique physiochemical properties such as fluidity, conductivity, and interfacial properties with other materials have presented great potentials and wide applications. Specifically, the interactions between gallium‐based LMs and some common but important transition metals (TMs) have not only enabled a series of intriguing phenomena but also provided valuable strategies or functional materials in soft robotics, devices, flexible electronics, addictive manufacturing, biomedical engineering and therapies, and other fields. The chemical mechanisms including the galvanic corrosion, infiltration, intermetallic compound formation should play vital roles within these interactions. Hereby the combining the LMs and TMs by alloying or physically mixing may offer a platform to develop novel and multifunctional materials system. To acquire a comprehensive understanding of those interactions as well as to inspire the researches for multifunctional materials design and applications, this article reviews the researches on the combination of LMs and TMs, discusses the characteristics, the mechanisms, and their applications especially in electronics, smart materials, and biomedicine. The main challenges and future research outlook are also discussed.

Biodegradable L-lysine-modified amino black phosphorus/poly(l-lactide-coε-caprolactone) nanofibers with enhancements in hydrophilicity, shape recovery and osteodifferentiation properties

Biodegradable poly-(lactide-coε-caprolactone) (PLCL) scaffolds have opened new perspectives for tissue engineering due to their nontoxic and fascinating functionality. Herein, a black phosphorus-based biodegradable material with a combination of promising enhanced hydrophilicity, shape recovery and osteodifferentiation properties was proposed. First, amino black phosphorous (BP-NH2) was prepared by a simple ball milling method. Then, L-lysine-modified black phosphorous (L-NH-BP) was formed by hydrogen bonding between L-lysine and amino BP and integrated into PLCL to form PLCL/L-NH-BP composite fibers. The scaffolds had excellent shape recovery and shape fixity properties. Moreover, based on gene expression and protein level assessment, the scaffolds could enhance the expression of alkaline phosphatase (ALP) and bone morphogenetic protein 2 (BMP2), simultaneously improving the mineralization ability of bone mesenchymal stem cells. Specifically, this new composite material was experimentally verified to be degradable under mild conditions. This strategy provided new insight into the design of multifunctional materials for diverse applications.

Supramolecular Association between γ-Cyclodextrin and Preyssler-Type Polyoxotungstate.

The development of hybrid materials based on polyoxometalates constitutes a strategy for the design of multifunctional materials. The slow evaporation of an aqueous solution of [NaP5W30O110]14− in the presence of γ-Cyclodextrin (γ-CD) led to the crystallization of a K6Na8{[NaP5W30O110]•(C48H80O40)}•23H2O (NaP5W30•1CD) supramolecular compound, which was characterized by single-crystal X-ray diffraction, IR-spectroscopy, thermogravimetric and elemental analyses. Structural analysis revealed the formation of 1:1 {[NaP5W30O110]•[γ-CD]}14− adduct in the solid state. Studies in solution by cyclic voltammetry, electrochemical impedance spectroscopy, 1H NMR spectroscopy, and 31P DOSY, have demonstrated weak interactions between the inorganic anion and the macrocyclic organic molecule.

2020 Timoshenko Medal Acceptance Lecture: Mechanics: Evergreen and Forever New

2020 Timoshenko Medal Acceptance Lecture: Mechanics: Evergreen and Forever New

Dual-functional 3D multi-wall carbon nanotubes/graphene/silicone rubber elastomer: Thermal management and electromagnetic interference shielding

To address overheating and electromagnetic interference of integrated electronics, the design of multi-functional materials with high out-of-plane thermal conductivity and excellent electromagnetic interference shielding effectiveness is desirable. In this contribution, an anisotropy graphene/multi-walled carbon nanotubes with 3D continuous network is fabricated by KOH induced hydrothermal reaction and subsequent graphitization at 2800 °C. When the graphene oxide to multi-walled carbon nanotubes ratio is 1:3, the balance between the decline of sp2 crystallite size in horizontal direction and the enhancement of turbostratic-stacking is achieved, which facilities the phonon transfer and electron transport. The optimal thermal conductivity of composites reaches up to 1.30 W m−1 K−1 at a low loading of 2.77 wt%, which is 465% higher than that of pure silicon rubber (0.23 W m−1 K−1). Meanwhile, the composite exhibits the maximum electric conductivity and electromagnetic interference shielding effectiveness of 42 dB in K-band. Moreover, it still retains the flexibility of matrix. This work paves the way of lightweight dual-function integrated materials.

An environment-stable hydrogel with skin-matchable performance for human-machine interface

Ionic hydrogel-based sensors have shined a spotlight on wearable electronics. However, the sensitivity and reliability of hydrogel devices are significantly hampered by the weak adhesion of skin-sensor interface as well as inferior temperature tolerance. Here, inspired by the structure and composition of dermis, a novel skin-attachable and environment-stable hydrogel was designed by integrating collagen into the LiCl-containing chemically cross-linked polyacrylamide hydrogel. The hydrogel exhibited skin-like mechanical properties of low modulus, superior stretchability as well as excellent elasticity. Furthermore, the introduction of collagen endowed the hydrogel with robust and seamless interfaces with diverse materials, including the curved skin. As a result, the hydrogel is capable of serving as a human-machine interface for collecting reliable electrocardiography (ECG) signals and discerning various human motions, with high sensitivity (gauge factor = 10.7), fast response, negligible hysteresis as well as extensive monitoring range. Notably, the hydrogel that can mimick the temperature-tolerant mechanism of most organisms possesses persistent stabilization of adhesive, conductive, sensory and mechanical performances at subzero or ambient conditions. The skin-inspired strategy paves an effective way for the design of multifunctional materials with potential applications in next-generation electronics.

Modular multifunctional Janus-structure film offering multiple anisotropic conduction, polychromatic luminescence and tuned magnetism

The microstructure and macrostructure design of multifunctional materials is a key to greatly reduce negative influences among different functional materials. Here, modular Janus-structure film (MJF) offering multiple anisotropic conduction, polychromatic luminescence and tuned magnetism is assembled using electro-spinning. {PMMA/PANI//PMMA/Eu(BA)3phen} Janus-structure nanoribbon, {PMMA/Fe3O4//PMMA/Tb(BA)3phen} Janus-structure nanoribbon and PMMA/Tb(BA)3phen/Eu(BA)3phen composite microfiber are, respectively, used as microconstruction units to manufacture various functional modules, including conduction-red luminescence module (C-RL module (down)) in down layer of MJF, conduction-red luminescence module (C-RL module (up), orange luminescence module (OL module) and magnetism-green luminescence module (M-GL module) in up layer of MJF. The structure, multiple anisotropic conduction, polychromatic luminescence and tuned magnetism of MJF are systematically studied. Micro-Janus-structure nanoribbon and macromodular structure, respectively, realize the micro- and macropartitions to avoid the adverse interferences among different functions. Such special structure, novel design philosophy and technology provide a new way for the construction of other multifunctional materials. The multiple anisotropic conduction of material expands the variety of anisotropic conductive materials and extends the application range, and further realizes the flexible applications of materials according to the specific requirements. The constructed new nanomaterials will have extensive applications in nanodevices and nanotechnology.

Facile Synthesis of Nickel Phosphate Nanorods as Biomimetic Enzyme with Excellent Electrocatalytic Activity for Highly Sensitive Detection of Superoxide Anion Released from Living Cells

In this work, the SOD biomimetic enzyme based on nickel phosphate nanorods [Ni(PO 4 )NRs] was prepared by a simple and eco-friendly hydrothermal method. After combined with MWCNTs, the Ni(PO 4 )NRs/C-MWCNTs nanocomposites were utilized as the novel electrode materials to construct the electrochemical O 2 •− biosensor with excellent electrical conductivity and unprecedented catalytic performance. The morphology of Ni(PO 4 )NRs/C-MWCNTs nanocomposite was examined by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman microscope, respectively. Under the optimum conditions, the proposed sensor exhibits high sensitivity (4.68×10 4 μAmM -1 cm -2 ), low detection limit (0.170 μM at S/N=3) and good selectivity to O 2 •− . In addition, the sensor can monitor the release of O 2 •− by MCF-7 cells with satisfactory results, which provides a great opportunity to apply in the field of fundamental research and clinic diagnostics. Our results would accelerate Ni(PO 4 )NRs as the SOD biomimetic enzyme for design biosening platforms and provide insights into design of multifunctional materials as biomimetic enzyme for various applications in biocatalysis and bioanalysis.

Flower-like CaMoO4: Eu3+/AgBr composites for nitroaromatic compounds sensing and its catalytic activity

In this work, bifunctional 3D flower-like CaMoO4: Eu3+/AgBr composites were successfully prepared using a two-step hydrothermal process. The as-prepared samples were characterized by SEM, XRD, FT-IR and EIS technologies, and their catalytic and photoluminescence properties were investigated in detail. The results showed that flower-like CaMoO4: Eu3+/AgBr composites exhibited high catalytic activity for 4-nitrophenol reduction. The reduction reaction can be completed within 5 min at room temperature, and the calculated apparent rate constant is 0.607 min−1. Furthermore, CaMoO4: Eu3+/AgBr composites could be developed as an inorganic sensor for nitroaromatic compound assay, due to the competitive adsorption mechanism. Thus, this work provided a new thought in the design of multifunctional materials for the monitoring and removal of organic pollutants.

Mechanochemistry enables optical-electrical multifunctional response and tunability in two-dimensional hybrid perovskites

Two-dimensional (2D) organic-inorganic hybrid perovskites (OIHPs) have attracted phenomenal attention because of their superior optoelectronic performances. The combination of their structural tunability and material stability offers an unprecedented opportunity to engineer materials with unique functionalities. However, developing a rapid and effective design method for introducing luminescence into dielectric switch and realizing controllable regulation has been an enormous challenge. Thus far, materials with tunable optoelectronic multichannel response have not been successfully implemented. In this study, we successfully developed a facile and effective mechanochemical method for realizing the integration and regulation of luminescence and dielectric switch in 2D perovskites, which is unprecedented for the design of dielectric switching materials. The mild external mechanical stimuli enabled the formation of Mn2+ ion-doped 2D hybrid perovskites (Cyclopropylammonium)2Pb1− x Mn x Br4 with excellent dielectric switch and rapidly controllable luminescence of highly efficient blue light, white light, pink light, and orange light. This work will provide a new perspective on the rapid and effective design of multifunctional materials and can inspire the future development of low-cost and high-efficiency electronics.

Effects of Different Counter Anions on Solid-State Electron Transfer in Viologen Compounds: Modulation of Color and Piezo- and Photochromic Properties.

Charge transfer (CT) and electron transfer (ET) underlie the various applications of viologen compounds. However, the CT and ET in solids are still insufficiently understood and difficult to control, which is challenging but fundamental to the design of multifunctional materials. Our strategy is to attempt a delicate control of CT and ET by subjecting model compounds to pressure. In this work, a series of viologens of the same cation with different anions show anion-dependent color and piezo-/photochromism due to ground-state CT and stimuli-induced ET; the ease of solid-state ET can be tuned in the order of Cl- > Br- > I-/BF4-/PF6-/ClO4-. With in situ high pressure UV-vis experiments, we also observed unexpectedly the pressure-induced solid-state ET in [H2bcpV]·I2 besides the pressure modulation of the CT absorption. It proves pressure is a more powerful stimulus than light in tuning solid-state CT and ET.

Physically Active Bioreactors for Tissue Engineering Applications.

Tissue engineering (TE) is a strongly expanding research area. TE approaches require biocompatible scaffolds, cells, and different applied stimuli, which altogether mimic the natural tissue microenvironment. Also, the extracellular matrix serves as a structural base for cells and as a source of growth factors and biophysical cues. The 3D characteristics of the microenvironment is one of the most recognized key factors for obtaining specific cell responses in vivo, being the physical cues increasingly investigated. Supporting those advances is the progress of smart and multifunctional materials design, whose properties improve the cell behavior control through the possibility of providing specific chemical and physical stimuli to the cellular environment. In this sense, a varying set of bioreactors that properly stimulate those materials and cells in vitro, creating an appropriate biomimetic microenvironment, is developed to obtain active bioreactors. This review provides a comprehensive overview on the important microenvironments of different cells and tissues, the smart materials type used for providing such microenvironments and the specific bioreactor technologies that allow subjecting the cells/tissues to the required biomimetic biochemical and biophysical cues. Further, it is shown that microfluidic bioreactors represent a growing and interesting field that hold great promise for achieving suitable TE strategies.

Bioinspired super-tough and multifunctional soy protein-based material via a facile approach

With the increasing interest and demand for intelligent, multifunctional materials, a judicious and facile design is essential but still challenging in practical applications. Generally, biological materials perform multiple functions based on the perfect synergy and green methodology. Multifunctional, self-assembled lipid bilayers are excellent sources of inspiration for the effective design of multifunctional materials. Biomaterials possess biocompatibility and biodegradability, which are ideal options for intelligent materials. Herein, with an inspiration from lipid bilayers, a delicately designed soy protein-based material with multiple functions is reported. This material exhibits superior toughness (24.54 MJ/m3) and high stretchability (253.54%), and possesses an outstanding self-healing ability with a rapid healing time at ambient temperature. Its integrated toughness and self-healing ability are superior to those of most reported polymeric materials. In addition, the constructed lipid bilayer-like structure enables this soy protein-based material to act as a sensor that can detect various environmental stimuli (humidity or temperature) through electrical and optical responses. The responsive performance of the soy protein-based material is investigated, which has shown good sensitivity and long-term stability. This soy protein-based material with multiple intelligent functions is potentially applicable in bioengineering, wearable electronics, and smart coating.

Geo-inspired crystallization engineering: multifunctional materials design and fabrication at nanoscale and beyond

Crystallization engineering aims to design and develop solutions for the optimum conversion of natural resources for use by humans, by using crystallization. Crystallization is a cross-scale process, from atoms, ions and molecules in microscale to bulk crystals in macroscale. Fabricating nanomaterials with desired performances is an open issue with multiscale challenges during crystallization. For innovation in crystallization engineering, geology may provide various sources of inspiration such as structures, compositions and formation conditions, if mineral materials can be regarded as novel artificial materials. This review shows us some geo-inspirations that enable people to create and engineer novel materials with satisfactory performance.

Recent Developments on Multi-Functional Metal-Free Mechanochromic Luminescence and Thermally Activated Delayed Fluorescence Organic Materials

Metal-free organic compounds with highly ordered π-conjugated twisted skeletons are capable of generating brilliant multi-colored light. Additionally, the co-existence of numerous other multi-functional properties have endowed them with the potential to be a promising class of materials for several electronic and photonic applications and next-generation advanced luminescent material-based devices. This review highlights the recent developments made in this fascinating class of multi-property encompassing materials, involving a highly twisted donor-acceptor based single molecular platform with synchronized photophysical behavior such as thermally activated delayed fluorescence (TADF), mechanoresponsive (MR), room-temperature phosphorescence (RTP), and aggregation induced emission (AIE) with associated unique and inherently manifested structure-property relationship investigations. Furthermore, a brief summary of the optoelectronic behavior of TADF materials are also presented by correlating their performances in the organic light-emitting diodes (OLEDs) and corresponding EL devices. In addition to mechanochromic luminescence (MCL) with TADF behavior, new types of emitters are also being developed, with tunable color changes such as blue-green, yellow-orange, yellow-red, etc., with some emitters crossing the entire visible span to produce white OLEDs. These developments have enriched the library of fascinating organic materials in addition to providing new directions of multifunctional material design for solutions processed OLED and several other advanced devices.

Analytical transport network theory & structural mechanics: Towards computationally inexpensive multi-functional materials design

Analytical transport network (ATN) theory is extended to account for static, structural mechanics. The extension provides a consistent, computationally economical, and interpretable formalism for examining morphological/topological trade-offs relevant to the design of multi-functional materials. The approach is demonstrated through application to over 100,000 computationally-generated lattice structures consisting of non-uniform channels. It is orders of magnitude faster and less memory intensive than finite element analysis. This, along with its compact mathematical formalism, present the opportunity for future integration into multi-functional characterization/design frameworks (e.g., topology optimization and machine learning).

Electric and photoluminescence properties of Eu3+-doped PZN-9PT single crystal

Eu3+-doped 0.91Pb(Zn1/3Nb2/3)O3-0.09PbTiO3 (PZN-9PT: Eu) single crystals were grown by the flux technique. The phase structure, ferroelectric, dielectric, and photoluminescence properties of the crystal were investigated. The PZN-9PT: Eu crystal has a pure perovskite structure. The residual polarization Pr, coercive field Ec, total bipolar strain, and unipolar stain are 36.7664 μC/cm2, 11.0597 kV/cm, 0.35%, and 0.12%, respectively. The coercive field Ec of PZN-9PT: Eu crystal is three times higher than that of PZN-9PT crystal. The Curie temperature Tc of the PZN-9PT: Eu crystal is about 172 °C which is slightly higher than that of PZN-PT single crystal. Under the excitation of 464 nm laser, four broadband peaks appear around 593 nm, 613 nm, 657 nm, and 716 nm, corresponding to the 5D0 → 7FJ (J = 0, 1, 2, 3, 4) transition emission, respectively. The luminescence intensity of all the emission peaks decreases with increasing temperatures range from 298 to 393 K. Our results can provide a new way for the design of multifunctional materials used in optical-electrical devices.