Uncovering the predictive pathways of lithium and sodium interchange in layered oxides.

Ion exchange is a powerful method to access metastable materials with advanced functionalities for energy storage applications. However, high concentrations and unfavourably large excesses of lithium are always used for synthesizing lithium cathodes from parent sodium material, and the reaction pathways remain elusive. Here, using layered oxides as model materials, we demonstrate that vacancy level and its corresponding lithium preference are critical in determining the accessible and inaccessible ion exchange pathways. Taking advantage of the strong lithium preference at the right vacancy level, we establish predictive compositional and structural evolution at extremely dilute and low excess lithium based on the phase equilibrium between Li0.94CoO2 and Na0.48CoO2. Such phase separation behaviour is general in both surface reaction-limited and diffusion-limited exchange conditions and is accomplished with the charge redistribution on transition metals. Guided by this understanding, we demonstrate the synthesis of NayCoO2 from the parent LixCoO2 and the synthesis of Li0.94CoO2 from NayCoO2 at 1-1,000 Li/Na (molar ratio) with an electrochemical assisted ion exchange method by mitigating the kinetic barriers. Our study opens new opportunities for ion exchange in predictive synthesis and separation applications.

Programmable and Pixelated Solute Concentration Fields Controlled by Three-Dimensionally Networked Microfluidic Source/Sink Arrays.

Membrane-integrated microfluidic platforms have played a pivotal role in understanding natural phenomena coupled with solute concentration gradients at the micro- and nanoscale, enabling on-chip microscopy in well-defined planar concentration fields. However, the standardized two-dimensional fabrication schemes in microfluidics have impeded the realization of more complex and diverse chemical environmental conditions due to the limited possible arrangements of source/sink conditions in a fluidic domain. In this study, we present a microfluidic platform with a three-dimensional microchannel network design, where discretized membranes can be integrated and individually controlled in a two-dimensional array format at any location within the entire quasi-two-dimensional solute concentration field. We elucidate the principles of the device to implement operations of the pixel-like sources/sinks and dynamically programmable control of various long-lasting solute concentration fields. Furthermore, we demonstrate the application of the generated solute concentration fields in manipulating the transport of micrometer or submicrometer particles with a high degree of freedom, surpassing conventionally available solute concentration fields. This work provides an experimental tool for investigating complex systems under high-order chemical environmental conditions, thereby facilitating the extensive development of higher-performance micro- and nanotechnologies.

Imaging supermolecular interactions of the pharmaceutical-cocrystal of apigenin-nicotinamide binding with serum albumin.

In this paper, a new pharmaceutical cocrystal was synthesized using apigenin (AP) and pharmaceutically acceptable conformer nicotinamide (Nico), and the drug delivery between AP-Nico pharmaceutical cocrystal and human serum albumin (HSA) in vivo was studied at atomic scale. The pharmaceutical cocrystal was characterized using Fourier-transform infrared (FTIR) spectroscopy, 1H NMR spectroscopy, differential scanning calorimetry (DSC), and powder X-ray diffraction (PXRD), and the self-assembling mechanism was explored. The dissolution and cumulative release in vitro were investigated. Molecular dynamic (MD) simulation combined with fluorescence spectroscopy was used to study the delivery mechanism of AP-Nico to HSA. The results showed that AP was pharmaceutically cocrystallized with Nico, which formed a pharmaceutical cocrystal mainly through hydrogen interaction between the -OH groups of AP and -NH2 groups of Nico. The solubility of the AP-Nico was 3 times higher than raw AP and the cumulative release rate was 71%. The fluorescence spectroscopy results showed that the AP-Nico pharmaceutical cocrystal bind with Sudlow's site I inside the HSA molecule with hydrogen-bond interaction as the main force. The Sudlow's site I of HSA conjugated with AP-Nico explains the conformational changes of HSA in-silico. This study provided a useful reference for synthesizing flavonoid pharmaceutical cocrystal to improve solubility and exploring the interaction mechanism while understanding its delivery mechanism in vivo.

Dendrimer-conjugated isotretinoin for controlled transdermal drug delivery.

BACKGROUND: In the present study, we aimed to develop a novel isotretinoin delivery model for treating skin diseases, revealing its potential advantages in drug delivery and targeted therapy. Using a self-assembly strategy, we grafted a dendrimer, based on a well-defined branched structure for nanomedical devices, with a well-defined nanoarchitecture, yielding spherical, highly homogeneous molecules with multiple surface functionalities. Accordingly, a self-assembled dendrimer-conjugated system was developed to achieve the transdermal delivery of isotretinoin (13cRA-D). RESULTS: Herein, 13cRA-D showed remarkable controlled release, characterized by slow release in normal tissues but accelerated release in tissues with low pH, such as sites of inflammation. These release characteristics could abrogate the nonteratogenic side effects of isotretinoin and allow efficient skin permeation. Moreover, 13cRA-D exhibited high therapeutic efficacy in acne models. Based on in vitro and in vivo experimental results, 13cRA-D afforded better skin penetration than isotretinoin and allowed lesion targeting. Additionally, 13cRA-D induced minimal skin irritation. CONCLUSION: Our findings suggest that 13cRA-D is a safe and effective isotretinoin formulation for treating patients with skin disorders.

A Scalable Microstructure Photonic Coating Fabricated by Roll-to-Roll "Defects" for Daytime Subambient Passive Radiative Cooling.

The deep space's coldness (∼4 K) provides a ubiquitous and inexhaustible thermodynamic resource to suppress the cooling energy consumption. However, it is nontrivial to achieve subambient radiative cooling during daytime under strong direct sunlight, which requires rational and delicate photonic design for simultaneous high solar reflectivity (>94%) and thermal emissivity. A great challenge arises when trying to meet such strict photonic microstructure requirements while maintaining manufacturing scalability. Herein, we demonstrate a rapid, low-cost, template-free roll-to-roll method to fabricate spike microstructured photonic nanocomposite coatings with Al2O3 and TiO2 nanoparticles embedded that possess 96.0% of solar reflectivity and 97.0% of thermal emissivity. When facing direct sunlight in the spring of Chicago (average 699 W/m2 solar intensity), the coatings show a radiative cooling power of 39.1 W/m2. Combined with the coatings' superhydrophobic and contamination resistance merits, the potential 14.4% cooling energy-saving capability is numerically demonstrated across the United States.

Fabricating and Laminating Films with Through-Holes and Engraved/Protruding Structures for 3D Micro/Nanofluidic Platforms.

Micro/nanofluidic devices have become popular for delicately processing biological, material, and chemical samples. However, their reliance on 2D fabrication schemes has hindered further innovation. Here, a 3D manufacturing method is proposed through the innovation of laminated object manufacturing (LOM), which involves the selection of building materials as well as the development of molding and lamination techniques. Fabrication of interlayer films is demonstrated with both multi-layered micro-/nanostructures and through-holes, using an injection molding approach and establishing strategic principles of film design. Utilization of the multi-layered through-hole films in LOM allows reducing the number of alignments and laminations by at least two times compared to conventional LOM. Using a dual-curing resin for film fabrication, a surface-treatment-free and collapse-free lamination technique is shown for constructing 3D multiscale micro/nanofluidic devices with ultralow aspect ratio nanochannels. The 3D manufacturing method enables the development of a nanochannel-based attoliter droplet generator capable of 3D parallelization for mass production, which implies the remarkable potential to extend numerous existing 2D micro/nanofluidic platforms into a 3D framework.

Minoxidil delivered via a stem cell membrane delivery controlled release system promotes hair growth in C57BL/6J mice.

Objective: Umbilical cord-derived mesenchymal stem cell membrane-loaded minoxidil (MXD) nanoparticles (STCM-MXD-NPs) were prepared to investigate their effects on hair growth in C57BL/6J mice. Methods: STCM-MXD-NPs were obtained by freeze-thawing and differential centrifugation, and their effects on hair growth were evaluated using C57BL/6J mice. The mRNA and protein expression levels of vascular endothelial growth factor (VEGF) and insulin-like growth factor-1 (IGF-1) were detected by real-time polymerase chain reaction and enzyme-linked immunosorbent assays, respectively. Protein expression levels of marker of proliferation Ki-67 (MKI67) and ß-catenin (CTNNB) in skin tissue were detected by immunohistochemistry. Results: STCM-MXD-NPs improved MXD solubility. They released the drug slowly, increasing its transdermal properties, accumulation in the skin, and content in the hair bulb tissues with a better efficacy than that of ordinary MXD. Moreover, STCM-MXD-NPs significantly upregulated the mRNA and protein levels of VEGF and IGF-1 and promoted the protein expression of MKI67 and CTNNB in mouse skin tissues, promoting mouse hair growth. Conclusion: Stem cell membrane-loaded MXD nanoparticles with slow-release properties increased MXD accumulation in the skin by improving its transdermal properties, increasing VEGF, IGF-1, MKI67, and CTNNB expression levels and promoting hair growth in C57BL/6J mice.

Spray-Coated Superhydrophobic Overlayer with Photothermal and Electrothermal Functionalities for All-Weather De/anti-icing Applications.

High-performance de/anti-icing overlayers which can be deposited on diverse surfaces offer great potential in many industrial settings and daily life, yet a versatile overlayer applicable to all-weather conditions (high humidity, low temperature, raining, snowing, etc.) is in high demand for practical applications. This study presents the fabrication and application of a superhydrophobic overlayer with a bioinspired hierarchical surface which additionally possesses photothermal and electrothermal functionalities, so it can operate as a de/anti-icing layer in extreme environments. The overlayer, with a papilla-like microstructure similar to that of a lotus leaf, features polydopamine-decorated layered basic zinc acetate microparticles distributed in the framework of multiwalled carbon nanotubes. Specifically, the overlayer is superhydrophobic, and its capability of suppressing the condensation of water droplets and growth of ice crystals is verified by both in situ environmental scanning electron microscopy observations and freezing experiments. Moreover, the overlayer can be warmed up to 74 and 105 °C under the excitation of sunlight and direct current bias, respectively, which is sufficiently high for deicing in severe weather. It is worth mentioning that the overlayer is produced by a spray-coating technique; therefore, it is suitable for large-scale deployment on arbitrary substrate materials. The findings provide insights into a new strategy for engineering multifunctional overlayers and can lead to expanding applications of composite coatings.

Recent advances in hydrogels-based osteosarcoma therapy.

Osteosarcoma (OS), as a typical kind of bone tumors, has a high incidence among adolescents. Traditional tumor eradication avenues for OS such as chemotherapy, surgical therapy and radiation therapy usually have their own drawbacks including recurrence and metastasis. In addition, another serious issue in the treatment of OS is bone repair because the bone after tumor invasion usually has difficulty in repairing itself. Hydrogels, as a synthetic or natural platform with a porous three-dimensional structure, can be applied as desirable platforms for OS treatment. They can not only be used as carriers for tumor therapeutic drugs but mimic the extracellular matrix for the growth and differentiation of mesenchymal stem cells (MSCs), thus providing tumor treatment and enhancing bone regeneration at the same time. This review focuses the application of hydrogels in OS suppression and bone regeneration, and give some suggests on future development.

Full-Fiber Auxetic-Interlaced Yarn Sensor for Sign-Language Translation Glove Assisted by Artificial Neural Network.

Yarn sensors have shown promising application prospects in wearable electronics owing to their shape adaptability, good flexibility, and weavability. However, it is still a critical challenge to develop simultaneously structure stable, fast response, body conformal, mechanical robust yarn sensor using full microfibers in an industrial-scalable manner. Herein, a full-fiber auxetic-interlaced yarn sensor (AIYS) with negative Poisson's ratio is designed and fabricated using a continuous, mass-producible, structure-programmable, and low-cost spinning technology. Based on the unique microfiber interlaced architecture, AIYS simultaneously achieves a Poisson's ratio of-1.5, a robust mechanical property (0.6 cN/dtex), and a fast train-resistance responsiveness (0.025 s), which enhances conformality with the human body and quickly transduce human joint bending and/or stretching into electrical signals. Moreover, AIYS shows good flexibility, washability, weavability, and high repeatability. Furtherly, with the AIYS array, an ultrafast full-letter sign-language translation glove is developed using artificial neural network. The sign-language translation glove achieves an accuracy of 99.8% for all letters of the English alphabet within a short time of 0.25 s. Furthermore, owing to excellent full letter-recognition ability, real-time translation of daily dialogues and complex sentences is also demonstrated. The smart glove exhibits a remarkable potential in eliminating the communication barriers between signers and non-signers.

From Mesoscopic Functionalization of Silk Fibroin to Smart Fiber Devices for Textile Electronics and Photonics.

Bombyx mori silk fibers exhibit significant potential for applications in smart textiles, such as fiber sensors, fiber actuators, optical fibers, and energy harvester. Silk fibroin (SF) from B. mori silkworm fibers can be reconstructed/functionalized at the mesoscopic scale during refolding from the solution state into fibers. This facilitates the mesoscopic functionalization by engaging functional seeds in the refolding of unfolded SF molecules. In particular, SF solutions can be self-assembled into regenerated fiber devices by artificial spinning technologies, such as wet spinning, dry spinning, microfluidic spinning, electrospinning, and direct writing. Meso-functionalization manipulates the SF property from the mesoscopic scale, transforming the original silk fibers into smart fiber devices with smart functionalities, such as sensors, actuators, optical fibers, luminous fibers, and energy harvesters. In this review, the progress of mesoscopic structural construction from SF materials to fiber electronics/photonics is comprehensively summarized, along with the spinning technologies and fiber structure characterization methods. The applications, prospects, and challenges of smart silk fibers in textile devices for wearable personalized healthcare, self-propelled exoskeletons, optical and luminous fibers, and sustainable energy harvesters are also discussed.

New Silk Road: From Mesoscopic Reconstruction/Functionalization to Flexible Meso-Electronics/Photonics Based on Cocoon Silk Materials.

Two of the key questions to be addressed are whether and how one can turn cocoon silk into fascinating materials with different electronic and optical functions so as to fabricate the flexible devices. In this review, a comprehensive overview of the unique strategy of mesoscopic functionalization starting from silk fibroin (SF) materials to the fabrication of various meso flexible SF devices is presented. Notably, SF materials with novel and enhanced properties can be achieved by mesoscopically reconstructing the hierarchical structures of SF materials. This is based on rerouting the refolding process of SF molecules by meso-nucleation templating. As-acquired functionalized SF materials can be applied to fabricate bio-compatible/degradable flexible/implantable meso-optical/electronic devices of various types. Consequently, functionalized SF can be fabricated into optical elements, that is, nonlinear photonic and fluorescent components, and make it possible to construct silk meso-electronics with high-performance. These advances enable the applications of SF-material based devices in the areas of physical and biochemical sensing, meso-memristors, transistors, brain electrodes, and energy generation/storage, applicable to on-skin long-term monitoring of human physiological conditions, and in-body sensing, information processing, and storage.

Direct Single-Step Printing of Conductive Grids on Curved Surfaces Using Template-Guided Foaming.

Advanced transparent conductors have been studied intensively in the aspects of materials, structures, and printing methods. The material and structural advancements have been successfully accomplished with various conductive nanomaterials and spring-like structures for better electrical conductivity and high mechanical flexibility of the transparent conductors. However, the capability to print submicrometer conductive patterns directly and conformally on curved surfaces with low processing cost and high throughput remains a technological challenge to achieve, primarily because of the original two-dimensional (2D) nature of conventional lithography processes. In our study, we exploit a liquid-mediated patterning approach in the development of flexible templates, enabling printing of curvilinear silver grids in a single-step and strain-free manner at a submicrometer resolution within several minutes with minimum loss of noble metals. The template can guide arrays of receding liquid-air interfaces on curved substrates during liquid evaporation, thereby generating ordered 2D foam structures that can confine and assemble silver nanoparticles in grid patterns. The printed silver grids exhibit suitable optical, electrical, and Joule-heating performances, enabling their application in transparent heaters. Our technique has the potential to extend the existing 2D micro/nanofluidic liquid-mediated patterning approach to three-dimensional (3D) control of liquid-air interfaces for low-cost all-liquid-processed functional 3D optoelectronics in the future.

Review of microfluidic approaches for fabricating intelligent fiber devices: importance of shape characteristics.

Shape characteristics, which include the physical dimensions (scale), apparent morphology, surface features, and structure, are essential factors of fibrous materials and determine many of their properties. Microfluidic technologies have recently been proposed as an approach for producing one-dimensional (1D) fibers with controllable shape characteristics and particle alignment, which impart specific functionality to the fiber. Moreover, superfine 1D fibers with a high surface area and ordered structure have many potential applications as they can be directly braided or woven into textiles, clothes, and tissues with two- or three-dimensional (2D or 3D) structures. Previous reviews of microfluidic spinning have not focus on the importance of the shape characteristic on fiber performance and their use in intelligent fiber design. Here, the latest achievements in microfluidic approaches for fiber-device fabrication are reviewed considering the underlying preparation principles, shape characteristics, and functionalization of the fibers. Additionally, intelligent fiber devices with shapes tailored by microfluidic approaches are discussed, including 1D sensors and actuators, luminous fibers, and devices for encoding, energy harvesting, water collection, and tissue engineering applications. Finally, recent progress, challenges, and future perspectives of the microfluidic approaches for fiber device fabrication are discussed.

Biomimetic Salinity Power Generation Based on Silk Fibroin Ion-Exchange Membranes.

Powering implanted medical devices (IMDs) is a long-term challenge since their use in biological environments requires a long-term and stable supply of power and a biocompatible and biodegradable battery system. Here, silk fibroin-based ion-exchange membranes are developed using bionics principles for reverse electrodialysis devices (REDs). Silk fibroin nanofibril (SNF) membranes are negatively and positively modified, resulting in strong cation and anion selectivity that regulates ion diffusion to generate electric power. These oppositely charged SNF membranes are assembled with Ag/AgCl electrodes into a multicompartment RED. By filling them with 10 and 0.001 mM NaCl solutions, a maximum output power density of 0.59 mW/m2 at an external loading resistance of 66 kΩ is obtained. In addition, 10 pairs of SNF membranes produce a considerable voltage of 1.58 V. This work is a proof of concept that key components of battery systems can be fabricated with protein materials. Combined with the emergence of water-based battery technologies, the findings in this study provide insights for the construction of tissue-integrated batteries for the next generation of IMDs.

A capacitive humidity sensor based on all-protein embedded with gold nanoparticles @ carbon composite for human respiration detection.

Wool and silk fiber are the most extensive resources of protein fibers and have been used in the textile field for many years. The extracted biocompatible proteins are more and more widely used in flexible devices, sensors, tissue engineering, etc. Here, a fully biomaterial based flexible humidity sensor has been successfully fabricated for the first time. Interdigital electrodes of humidity sensor are printed on a transparent sensor substrate made of silk protein by inkjet printing. The humidity sensitive material is gold nanoparticles hosted nitrogen doped carbon (AuNPs@NC), which is fabricated by in situ dispersion of gold nanoparticles in a wool keratin assisted porous carbon precursor. The best treatment condition of the sensitive materials is obtained by comparing the sensitivity of humidity response. Moreover, the as-prepared biocompatible flexible sensor was successfully used to detect human respiration.

Delivery Mechanism of the Pharmaceutical Complex of Genistein-Adenine Based on Spectroscopic and Molecular Modelling at Atomic Scale.

Genistein (GS) exhibits various biological activities, but its clinical application is limited because of the low bioavailability. In this study, a GS-adenine pharmaceutical complex was prepared through solvent evaporation to improve the bioavailability of GS, and a molecular model of a two-component supramolecular pharmacological transport mechanism was established. The structure of GS-adenine was characterized, in addition, interaction patterns between GS and adenine were investigated using density functional theory. The results showed that the solubility of GS-adenine was five times higher than that of GS, and the cumulative release rate of GS-adenine was 86 %. The results of fluorescence spectroscopy and molecular dynamic simulations showed that GS-adenine bound to the Sudlow's site I of HSA mainly through hydrophobic interactions. This study provides a useful reference for synthesizing pharmaceutical complexes to improve solubility and for exploring the mechanism of multiple pharmaceutical components in vivo.

Flexible and disposable gold nanoparticles-N-doped carbon-modified electrochemical sensor for simultaneous detection of dopamine and uric acid.

Catalytic and electrocatalytic applications of supported metal nanoparticles are hindered due to an aggregation of metal nanoparticles and catalytic leaching under harsh operations. Hence, stable and leaching free catalysts with high surface area are extremely desirable but also challenging. Here we report a gold nanoparticles-hosted mesoporous nitrogen doped carbon matrix, which is prepared using bovine serum albumin (BSA) through calcination. BSA plays three roles in this process as a reducing agent, capping agent and carbon precursor, hence the protocol exhibits economic and sustainable. Gold nanoparticles at N-doped BSA carbon (AuNPs@NBSAC)-modified three-electrode strip-based flexible sensor system has been developed, which displayed effective, sensitive and selective for simultaneous detection of uric acid (UA) and dopamine (DA). The AuNPs@NBSAC-modified sensor showed an excellent response toward DA with a linear response throughout the concentration range from 1 to 50 µM and a detection limit of 0.05 µM. It also exhibited an excellent response toward UA, with a wide detection range from 5 to 200 µM as well as a detection limit of 0.1 µM. The findings suggest that the AuNPs@NBSAC nanohybrid reveals promising applications and can be considered as potential electrode materials for development of electrochemical biosensors.

3D Upper Body Reconstruction with Sparse Soft Sensors.

Three-dimensional (3D) reconstruction of human body has wide applications, for example, for customized design of clothes and digital avatar production. Existing vision-based systems for 3D body reconstruction require users to wear minimal or extreme-tight clothes in front of cameras, and thus suffer from privacy problems. In this work, we explore a novel solution based on a sparse number of soft sensors on a standard garment, and use it for capturing 3D upper body shape. We utilize the maximal stretching range by modeling the nonlinear performance profile for individual sensors. The body shape can be dynamically reconstructed by analyzing the relationship between mesh deformation and sensor reading, with a learning-based approach. The wearability and flexibility of our prototype allow its use in indoor/outdoor environments and for long-term breath monitoring. Our prototype has been extensively evaluated by multiple users with different body sizes and the same user for multiple days. The results show that our garment prototype is comfortable to wear, and achieves the state-of-the-art reconstruction performance with the advantages in privacy projection and application scenarios.

Programing Performance of Silk Fibroin Superstrong Scaffolds by Mesoscopic Regulation among Hierarchical Structures.

To design higher-strength natural scaffold materials, wool keratin (WK) rich in α-helix structures is used as a well-defined foreign substrate, which induces the formation of ß-crystallites in silk fibroin (SF). Consequently, the macroscopic properties of silk materials (such as the rheological properties of SF hydrogels and the mechanical properties of stents) can be manipulated by governing the change in the hierarchical mesoscopic structure of silk materials. In this work, by monitoring the structure and morphology in the SF gel process, the mechanism of the effect of keratin on SF network formation was speculated, which was further used to design ultra-high-strength protein scaffolds. It has been confirmed that WK accelerates the gelation of SF by reducing the multistep nucleation barrier and increasing the primary nucleation sites, and then establishing a high-density SF domain network. The modulus of the protein composite scaffold prepared by this facile strategy can reach 11.55 MPa, and the MC-3T3 cells can grow well on the scaffold surface. The results suggest that freeze-dried biocompatible SF-based scaffolds are potential candidates for bone tissue engineering.