Light-Triggered Reversible Swelling of Azobenzene-Containing Block Copolymer Worms via Confined Deformation Prepared by Polymerization-Induced Self-Assembly.

Stimuli-responsive block copolymer nanoparticles (NPs) have received close attention in recent years owing to their tremendous application potential in smart materials. Azobenzene-containing NPs are widely studied due to the advantages of light as a stimulus and fast reversible trans-cis isomerization of azobenzene chromophores. However, the inefficient preparation process and difficult reversible transformation of morphologies limit their development. Herein it is demonstrated that the light-triggered reversible swelling behavior of wormlike NPs with high azobenzene content could be realized via confined deformation. These worms are prepared in large quantities via polymerization-induced self-assembly based on the copolymerization of 11-(4-(4-butylphenylazo)phenoxy)undecyl methacrylate (MAAz) and N-(methacryloxy)succinimide (NMAS) monomers. Upon UV/visible light irradiation, the reversible deformation of worms is achieved when the feed molar ratio of NMAS/MAAz is relatively high or via crosslinking using diamines, which leads to the reduction of the photoisomerization efficiency. The diameter variation of the worms is influenced by the amount and types of crosslinkers. Moreover, the scalability of this strategy is further proved by the fabrication of photo- and reductant-responsive crosslinked worms. It is expected that this study not only provides a new route to affording reversible photoresponsive NPs but also offers a unique insight into the reversible photodeformation mechanism of azobenzene-containing NPs.

Skin-Friendly Flexible Ultraviolet Detectors Based on Reversibly Deformable Worm-Like Polymer Nanoparticles.

Flexible ultraviolet (UV) light detection technology has important applications in wearable devices, smart sensors, and other fields and attracts much attention in recent years. However, for most semiconductor-based UV detectors, the elastic modulus between rigid semiconductors and flexible substrates is mismatched, which makes it difficult to fabricate UV detectors that meet the needs of wearable devices. Herein, a fully flexible, large-scale, skin-friendly UV photodetector component centered on photo-responsive worm-like polymer nanoparticles (NPs) is developed, and the resulting device can quantitatively detect UV illumination. Skin-friendly poly(vinyl alcohol) (PVA), amphiphilic azobenzene-containing polymer NPs (AzNPs), and water-soluble ionic liquids (IL) are formed into (AzNPs-IL)/PVA fabrics by electrospinning. There are interactions such as hydrogen bonding among PVA, AzNPs, and IL, which make the material system stable. The UV detector made of the fabric realizes UV sensing through the illuminance-mechanical stress-electrical signal conversion mechanism. It is capable of achieving a response time of 9 s, a detection range of 10-150 mW cm-2, and stability for 1000 cycle tests upon 365 nm UV irradiation. Moreover, it has good skin affinity, and the water contact angle of the fabric is only 23.57°, which holds great promise for wearable smart devices.

Federated Graph Neural Networks: Overview, Techniques, and Challenges.

Graph neural networks (GNNs) have attracted extensive research attention in recent years due to their capability to progress with graph data and have been widely used in practical applications. As societies become increasingly concerned with the need for data privacy protection, GNNs face the need to adapt to this new normal. Besides, as clients in federated learning (FL) may have relationships, more powerful tools are required to utilize such implicit information to boost performance. This has led to the rapid development of the emerging research field of federated GNNs (FedGNNs). This promising interdisciplinary field is highly challenging for interested researchers to grasp. The lack of an insightful survey on this topic further exacerbates the entry difficulty. In this article, we bridge this gap by offering a comprehensive survey of this emerging field. We propose a 2-D taxonomy of the FedGNN literature: 1) the main taxonomy provides a clear perspective on the integration of GNNs and FL by analyzing how GNNs enhance FL training as well as how FL assists GNN training and 2) the auxiliary taxonomy provides a view on how FedGNNs deal with heterogeneity across FL clients. Through discussions of key ideas, challenges, and limitations of existing works, we envision future research directions that can help build more robust, explainable, efficient, fair, inductive, and comprehensive FedGNNs.

Azobenzene-Containing Liquid Crystalline Twisted Ribbons via Polymerization-Induced Hierarchical Self-Assembly.

Polymerization-induced self-assembly incorporating liquid crystallization, as a polymerization-induced hierarchical self-assembly (PIHSA) method to produce polymeric particles with anisotropic morphologies facilely and efficiently, has drawn wide attention recently. However, the means of regulating the morphologies of liquid crystalline (LC) polymer assemblies still need to be explored. Herein, a route is presented to fabricate the twisted ribbons via PIHSA containing azobenzene based on poor reversible addition-fragmentation chain transfer (RAFT) control, called poorly controlled PIHSA. Cyano-4-(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid-2-(2-pyridyldithio) ethyl ester is used as the RAFT agent with poor controllability, and the morphological evolution from ribbons to twisted ribbons can be observed in the corresponding PIHSA system. The formation mechanism of the twisted ribbons is studied systematically and the broad molecular weight distribution is considered to be the decisive factor. Moreover, the supramolecular chirality induced by symmetry breaking is also related to the twist of the ribbons. This study enriches the methods of controlling the morphologies of LC polymer particles and is helpful for further clarifying the mechanism of PIHSA.

Light-Triggered Reversible Swelling of Polymeric Spheres via Surfactant-Free RAFT Emulsion Polymerization-Induced Self-Assembly.

Responsive photonic crystals (RPCs) assembled by monodisperse colloidal particles have attracted enormous interest recently due to their tremendous applications in smart devices. Their structural colors can be determined by particle sizes. However, the lack of a reliable way to tune the sizes in situ limits their development. Herein, we present an efficient route to solve this problem through the fabrication of spherical polymeric particles with light-triggered reversible swelling behavior via surfactant-free reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization-induced self-assembly (PISA). Amphiphilic macro-RAFT agents containing azobenzene groups were synthesized and subsequently employed to mediate the polymerization of methyl methacrylate. Uniform submicron spheres were obtained by modulating solid contents and other parameters. Benefiting from the photoisomerization of azobenzene moieties, the particle sizes expanded and contracted upon alternative ultraviolet/visible-light irradiation accordingly. This strategy will be a supplement to the emulsion PISA and especially give aid to the progress of the RPC materials.

Rationally Structured Triboelectric Nanogenerator Arrays for Harvesting Water-Current Energy and Self-Powered Sensing.

Water-current energy is an enormous and widely distributed clean energy in nature, with different scales from large ocean flow to small local turbulence. However, few effective technologies have been proposed to make use of different forms of water currents as a power source. Here, high-performance paired triboelectric nanogenerators (P-TENGs) capable of integrating massively into a thin flexible layer as a structured triboelectric surface (STS) are demonstrated for harvesting water-current energy. Novel gas packet exchange structure and rigid-flexible coupling deformation mechanism are introduced to ensure that the device can work very effectively even in deep water under high water pressure. The rationally designed TENG array in the STS enables highly efficient power take-off from the flow. Typically, the STS demonstrates a high-frequency output up to 57 Hz, largely superior to current TENG devices, and the power density is improved by over 100 times for triboelectric devices harvesting current energy. The flexible STS is capable of attaching to various surfaces or applying independently for self-powered sensing and underwater power supply, showing great potential for water-current energy utilization. Moreover, the work also initiates universal strategies to fabricate high-frequency devices under large environment pressure, which may profoundly enrich the design of TENGs.

Synergistic antibacterial photocatalytic and photothermal properties over bowl-shaped TiO2 nanostructures on Ti-19Zr-10Nb-1Fe alloy.

As implant substitutes are increasingly applied to the clinic, the infection caused by implants has become one of the most common complications, and the modification of the antibacterial function of the implant can reduce such complications. In this work, a well-defined bowl-shaped nanostructure coating with photocatalytic and photothermal synergistic antibacterial properties was prepared on Ti-19Zr-10Nb-1Fe (TZNF) alloy. The coating is obtained by spin-coating and sintering TiO2 precursors templated from self-assembled microspheres of polystyrene-poly(4-vinylpyridine) (PS-P4VP) amphiphilic block polymer on TZNF alloy. PS-P4VP provides the bowl-shaped TiO2 nanostructures doped with C, N elements, reducing the band-gap of TiO2, which can absorb near-infrared (NIR) light to release reactive oxygen species and produce photothermal conversion. The bowl structure is expected to enhance the utilization of light via the reflection in the confined space. The bowl-shaped surface has 100% antibacterial rates after 30 min of NIR light irradiation. In addition to antibacterial properties, the bowl-shaped surface has better hydrophilicity and protein adsorption capacity. The amount of protein adsorbed on TZNF with the bowl-shaped structures was six times that of TZNF. Hence, the bowl-shaped nanostructure can promote the proliferation and adhesion of osteoblasts, the cell proliferation rate was increased by 10-30%.

Enhancement of diatom growth and phytoplankton productivity with reduced O2 availability is moderated by rising CO2.

Many marine organisms are exposed to decreasing O2 levels due to warming-induced expansion of hypoxic zones and ocean deoxygenation (DeO2). Nevertheless, effects of DeO2 on phytoplankton have been neglected due to technical bottlenecks on examining O2 effects on O2-producing organisms. Here we show that lowered O2 levels increased primary productivity of a coastal phytoplankton assemblage, and enhanced photosynthesis and growth in the coastal diatom Thalassiosira weissflogii. Mechanistically, reduced O2 suppressed mitochondrial respiration and photorespiration of T. weissflogii, but increased the efficiency of their CO2 concentrating mechanisms (CCMs), effective quantum yield and improved light use efficiency, which was apparent under both ambient and elevated CO2 concentrations leading to ocean acidification (OA). While the elevated CO2 treatment partially counteracted the effect of low O2 in terms of CCMs activity, reduced levels of O2 still strongly enhanced phytoplankton primary productivity. This implies that decreased availability of O2 with progressive DeO2 could boost re-oxygenation by diatom-dominated phytoplankton communities, especially in hypoxic areas, with potentially profound consequences for marine ecosystem services in coastal and pelagic oceans.

Light-Triggered Reversible Slimming of Azobenzene-Containing Wormlike Nanoparticles Synthesized by Polymerization-Induced Self-Assembly for Nanofiltration Switches.

Photoresponsive wormlike block copolymer nanoparticles (NPs) have potential applications in versatile fields, but their preparation suffers from narrow worm phase region and tedious approaches. In this work, azobenzene-containing wormlike NPs based on poly(methylacrylic acid)-b-poly(4-((4-butylphenyl)diazenyl)phenyl methacrylate) are prepared via polymerization-induced self-assembly at high solids concentration in ethanol. The pure wormlike NPs occupy a remarkably broad region in the morphological phase diagram because of the rigid nature of the core-forming block. These wormlike NPs expand resulting from trans-cis transformation upon UV irradiation, and slim near to the original state via visible light irradiation. The diameter and its variation amplitude of worms increase with the chain length of core-forming block. Moreover, a nanofiltration switch for rhodamine B is assembled to illustrate one of its potential applications by remote trigger using light.