A Novel Cross Tetrachiral Honeycomb Metamaterial with Designable Static and Dynamic Performances.

A novel cross tetrachiral honeycomb metamaterial is proposed, which not only possesses the negative Poisson's ratio property, but also has a wide-frequency bandgap. The effective elastic parameters of the cross tetrachiral honeycomb are first theoretically analyzed; then, its designable performances for negative Poisson's ratio and elastic modulus are studied by varying geometric parameters. The dynamic properties of the cross tetrachiral honeycomb metamaterial are investigated by analyzing the band structure. It is shown that without the addition of external mass to the structure, a designable wide bandgap can be generated to isolate the in-plane waves effectively by selecting the ligament angles and the radius of central cylinder. In addition, an effective approach is proposed for tuning the bandwidth without changing the geometric parameters of the structure. Compared to classical negative Poisson's ratio metamaterials, the proposed cross tetrachiral honeycomb metamaterial is designable and tunable for achieving a specific static or dynamic performance, and has potential applications in engineering practice.

Nanoscale Pickering emulsion food preservative films/coatings: Compositions, preparations, influencing factors, and applications.

Pickering emulsion (PE) technology effectively addresses the issues of poor compatibility and low retention of hydrophobic active ingredients in food packaging. Nonetheless, it is important to recognize that each stage of the preparation process for PE films/coatings (PEFCs) can significantly influence their functional properties. With the fundamental considerations of environmental friendliness and human safety, this review extensively explores the potential of raw materials for PEFC and introduces the preparation methods of nanoparticles, emulsification technology, and film-forming techniques. The critical factors that impact the performance of PEFC during the preparation process are analyzed to enhance food preservation effectiveness. Moreover, the latest advancements in PE packaging across diverse food applications are summarized, along with prospects for innovative food packaging materials. Finally, the preservation mechanism and application safety have been systematically elucidated. The study revealed that the PEFCs provide structural flexibility, where designable nanoparticles offer unique functional properties for intelligent control over active ingredient release. The selection of the dispersed and continuous phases, along with component proportions, can be customized for specific food characteristics and storage conditions. By employing suitable preparation and emulsification techniques, the stability of the emulsion can be improved, thereby enhancing the effectiveness of the films/coatings in preserving food. Including additional substances broadens the functionality of degradable materials. The PE packaging technology provides a safe and innovative solution for extending the shelf life and enhancing the quality of food products by protecting and releasing active components.

Charge-Assisted Ionic Hydrogen-Bonded Organic Frameworks: Designable and Stabilized Multifunctional Materials.

Hydrogen-bonded organic frameworks (HOFs) are a class of crystalline framework materials assembled by hydrogen bonds. HOFs have the advantages of high crystallinity, mild reaction conditions, good solution processability, and reproducibility. Coupled with the reversibility and flexibility of hydrogen bonds, HOFs can be assembled into a wide diversity of crystalline structures. Since the bonding energy of hydrogen bonds is lower than that of ligand and covalent bonds, the framework of HOFs is prone to collapse after desolventisation and the stability is not high, which limits the development and application of HOFs. In recent years, numerous stable and functional HOFs have been developed by π-π stacking, highly interpenetrated networks, charge-assisted, ligand-bond-assisted, molecular weaving, and covalent cross-linking. Charge-assisted ionic HOFs introduce electrostatic attraction into HOFs to improve stability while enriching structural diversity and functionality. In this paper, we review the development, the principles of rational design and assembly of charge-assisted ionic HOFs, and introduces the different building block construction modes of charge-assisted ionic HOFs. Highlight the applications of charge-assisted ionic HOFs in gas adsorption and separation, proton conduction, biological applications, etc., and prospects for the diverse design of charge-assisted ionic HOFs structures and multifunctional applications.

Laser Direct Writing of Sol-Gel-Derived Vacancy-Rich Functional Oxide Semiconductors.

Fabricating micro/nanostructures of oxide semiconductors with oxygen vacancies (OVs) is crucial for advancing miniaturized functional devices. However, traditional methods for the synthesis of semiconductor metal oxides (SMOs) with OVs usually involve thermal treatment, such as annealing or sintering, under anaerobic conditions. Herein, a multiphoton-induced femtosecond laser (fs) additive manufacturing method is reported for directly writing micropatterns with high resolution (∼1 µm) and abundant OVs in an atmospheric environment at room temperature (25 °C). The interdigitated functional devices fabricated by these micropatterns exhibit both photosensitivity and gas sensitivity. Additionally, this method can be applied to flexible and rigid substrates. The proposed method realizes the high-precision fabrication of SMOs with OVs, enabling the future heterogeneous integration of oxide semiconductors on various substrates, especially flexible substrates, for various device applications, such as soft and wearable electronics/optoelectronics.

Economic Separations of Organic Acidic or Basic Enantiomeric Mixtures-A Protocol Suggestion.

In this review, we aim to present new concepts for the revisited separation of enantiomers from racemic compounds and a protocol worth to be followed in designing the preparation of pure enantiomers. We have taken into account not only the influence of the properties (eutectic composition) and characteristics of the reactants (racemic compound, resolving agent), but also the behavior of the resulting diastereomers and the different conditions (e.g., crystallization time, solvents used, solvate-forming compounds, achiral additives, etc.). The examples discussed are resolutions developed by our research team, through which we will try to illustrate the impact of all these considerations, presenting the methodological investigations interpreting recent discoveries and observations. Some special solid-state analytical and structural investigations assisting us in the elucidation and invention design of the resolution processes of some active pharmaceutical ingredients, such as Tetramisole, tofisopam, and Amlodipine, are also shown.

Designable Guest-Molecule Encapsulation in Metal-Organic Frameworks for Proton Conductivity.

Metal-organic frameworks (MOFs), as a porous frame material, exhibit considerable electrical conductivity. In recent decades, research on the proton conductivity of MOFs has made gratifying progress. In this review, the designable guest molecules encapsulated into MOFs are summarized and generalized into four types in terms of promoting proton conductive performance, and then recent progress in the promotion of proton conductivity by MOFs encapsulating guest molecules is discussed. The existing challenges and prospects for the development of this strategy for promoting MOFs' proton conductivity are also listed.

Designable Ultratransparent and Superhydrophobic Surface of Embedded Artificial Compound Eye with Extremely Low Adhesion.

Real-world implementation of artificial compound eye (ACE) has been limited by its poor transparency and high requirement for the stable Cassie state. In general, the improvement of surface dewetting performance sacrifices the transparency of ACE. Herein, ACE was obtained by an integrated manufacturing technology that combined photolithography, microprinting, and chemical growth. Through skillful manipulation of the fabrication process, dewetting hairs were fabricated on the top of micropillars and around the microlens. The combination of nanohairs and micropillars resulted in outstanding superhydrophobicity (∼170°), pristine lotus effect with low sliding angle (∼1°), and contact angle hysteresis (∼2°). Moreover, the surface showed almost no adhesion under a preload of 4 mN, exhibiting excellent stable Cassie state and antiadhesion performance. Furthermore, dynamic impact showed that the impacting droplet was quickly detached from the surface (contact time ∼14.1 ms) without sticking for We = 60. The designed transparency resulted in high performance of optical unit (∼99%, bare glass for comparison). Moreover, ACE exhibited better focusing and imaging capability under larger aperture diameter than microlens without nanohairs. We envision that this research presents a significant advancement in imparting superhydrophobicity and transparency to a so-far inapplicable family of optical devices for many practical outdoor applications.

Facile Method To Prepare a Novel Biological HKUST-1@CMCS with Macroscopic Shape Control for the Long-Acting and Sustained Release.

We have developed a green and versatile method to prepare hierarchically porous Cu3(BTC)2@carboxymethyl chitosan (HKUST-1@CMCS) with a macroscopic shape control and designable performance via the cross-linking of Cu(II) ions with CMCS. Furthermore, atomic force microscopy, scanning electron microscopy, powder X-ray diffraction, Brunauer-Emmett-Teller, and X-ray photoelectron spectroscopy analyses showed that the morphology of HKUST-1 could be controlled and changed by tailoring the surface roughness ( Rq) of polymer matrix. For the ball-like, fiberlike, and membrane-like composites, the matrix Rq values were 887, 88.4, and 18.2 nm and the average sizes of HKUST-1 crystals were about 10.2, 5.9, and 1.7 µm, respectively. It was found that the larger the Rq of the polymer matrix, the higher the drug payload. The results of drug release showed that the release percentage of dimethyl fumarate from HKUST-1@CMCS was 66% in 326 h, whereas that of Cu@CMCS was only 12 h. Obviously, the HKUST-1@CMCS had a long-acting and sustained release property compared to that of Cu@CMCS due to its complementary advantages of metal-organic frameworks (MOFs) and polymers. Therefore, this study not only provided an interesting way to make up for the shortcomings of MOFs and natural polymer but also developed a long-acting delivery system for a huge potential application prospect.

Highly conductive, mechanically strong graphene monolith assembled by three-dimensional printing of large graphene oxide.

The manufacturing of three-dimensional (3D) graphene monolith with high mechanical and electrical performance has become an urgent issue in view of their potential applications in energy and electronics fields. Due to the structure rigidity and poor liquid-phase processing capability of graphene sheets, it is challenging to fabricate 3D graphene monolith with high mechanical performance, including strength, toughness and resiliency. Graphene oxide (GO) shows an improved dispersibility and reduction-restorable conductivity, which enables it to effectively balance the processing and comprehensive performances of graphene monolith. Here, we demonstrate a strategy to fabricate high-performance, shape-designable 3D graphene monolith through a 3D printing method based on large-sized graphene oxide (LGO) fluid ink. The concentration of the LGO ink for printing is as low as 20 mg/mL. The resulting monolith exhibits low density (12.8 mg/cm3), high electrical conductivity (41.1 S/m), high specific strength (10.7 × 103 N·m/Kg) and compressibility (up to 80% compressive strain). Such a 3D printing technique enables plenty of complicated monolith structures and broadens the application range of graphene.

Liquid-Metal-Based Super-Stretchable and Structure-Designable Triboelectric Nanogenerator for Wearable Electronics.

The rapid advancement of intelligent wearable electronics imposes the emergent requirement for power sources that are deformable, compliant, and stretchable. Power sources with these characteristics are difficult and challenging to achieve. The use of liquid metals as electrodes may provide a viable strategy to produce such power sources. In this work, we propose a liquid-metal-based triboelectric nanogenerator (LM-TENG) by employing Galinstan as the electrode and silicone rubber as the triboelectric and encapsulation layer. The small Young's modulus of the liquid metal ensures the electrode remains continuously conductive under deformations, stretching to a strain as large as ∼300%. The surface oxide layer of Galinstan effectively prevents the liquid Galinstan electrode from further oxidization and permeation into silicone rubber, yielding outstanding device stability. Operating in the single-electrode mode at 3 Hz, the LM-TENG with an area of 6 × 3 cm2 produces an open-circuit voltage of 354.5 V, transferred short-circuit charge of 123.2 nC, short-circuit current of 15.6 µA, and average power density of 8.43 mW/m2, which represent outstanding performance values for TENGs. Further, the LM-TENG maintains stable performance under various deformations, such as stretching, folding, and twisting. LM-TENGs in different forms, such as bulk-shaped, bracelet-like, and textile-like, are all able to harvest mechanical energy from human walking, arm shaking, or hand patting to sustainably drive wearable electronic devices.

Salt-bridge networks within globular and disordered proteins: characterizing trends for designable interactions.

There has been considerable debate about the contribution of salt bridges to the stabilization of protein folds, in spite of their participation in crucial protein functions. Salt bridges appear to contribute to the activity-stability trade-off within proteins by bringing high-entropy charged amino acids into close contacts during the course of their functions. The current study analyzes the modes of association of salt bridges (in terms of networks) within globular proteins and at protein-protein interfaces. While the most common and trivial type of salt bridge is the isolated salt bridge, bifurcated salt bridge appears to be a distinct salt-bridge motif having a special topology and geometry. Bifurcated salt bridges are found ubiquitously in proteins and interprotein complexes. Interesting and attractive examples presenting different modes of interaction are highlighted. Bifurcated salt bridges appear to function as molecular clips that are used to stitch together large surface contours at interacting protein interfaces. The present work also emphasizes the key role of salt-bridge-mediated interactions in the partial folding of proteins containing long stretches of disordered regions. Salt-bridge-mediated interactions seem to be pivotal to the promotion of "disorder-to-order" transitions in small disordered protein fragments and their stabilization upon binding. The results obtained in this work should help to guide efforts to elucidate the modus operandi of these partially disordered proteins, and to conceptualize how these proteins manage to maintain the required amount of disorder even in their bound forms. This work could also potentially facilitate explorations of geometrically specific designable salt bridges through the characterization of composite salt-bridge networks. Graphical abstract ᅟ.

High strength, biocompatible hydrogels with designable shapes and special hollow-formed character using chitosan and gelatin.

Hydrogels with good mechanical properties, excellent biocompatibility and designable shapes are of great importance for their biomedical applications. Herein, a series of high strength, biocompatible hydrogels have been synthesized by integrating sodium citrate into the thermally reversible chitosan/gelatin to form multiple physically crosslinking networks. Besides the ideal formability, a thermal etching or welding method has been developed to program the surface morphology and fabricate hydrogels with complicated shapes freely. More impressively, the special hollow "cup-shaped and tubular" structure has also been constructed by applying an interrupted gelation process in controlled ion crosslinking time and the subsequent dissolving process at 37°C in deionized water. The high strength, biocompatible hydrogels with special internal and external shape adjustable characters, potentially useful in vascular repair and substitutes of cartilage, may further broaden our understanding of the plasticity of the hydrogels.