Author Correction: Layered nanocomposites by shear-flow-induced alignment of nanosheets.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Layered nanocomposites by shear-flow-induced alignment of nanosheets.

Biological materials, such as bones, teeth and mollusc shells, are well known for their excellent strength, modulus and toughness1-3. Such properties are attributed to the elaborate layered microstructure of inorganic reinforcing nanofillers, especially two-dimensional nanosheets or nanoplatelets, within a ductile organic matrix4-6. Inspired by these biological structures, several assembly strategies-including layer-by-layer4,7,8, casting9,10, vacuum filtration11-13 and use of magnetic fields14,15-have been used to develop layered nanocomposites. However, how to produce ultrastrong layered nanocomposites in a universal, viable and scalable manner remains an open issue. Here we present a strategy to produce nanocomposites with highly ordered layered structures using shear-flow-induced alignment of two-dimensional nanosheets at an immiscible hydrogel/oil interface. For example, nanocomposites based on nanosheets of graphene oxide and clay exhibit a tensile strength of up to 1,215 ± 80 megapascals and a Young's modulus of 198.8 ± 6.5 gigapascals, which are 9.0 and 2.8 times higher, respectively, than those of natural nacre (mother of pearl). When nanosheets of clay are used, the toughness of the resulting nanocomposite can reach 36.7 ± 3.0 megajoules per cubic metre, which is 20.4 times higher than that of natural nacre; meanwhile, the tensile strength is 1,195 ± 60 megapascals. Quantitative analysis indicates that the well aligned nanosheets form a critical interphase, and this results in the observed mechanical properties. We consider that our strategy, which could be readily extended to align a variety of two-dimensional nanofillers, could be applied to a wide range of structural composites and lead to the development of high-performance composites.

Chemical Design of Supramolecular Reversible Adhesives for Promising Applications.

Supramolecular reversible adhesives have garnered significant attention due to their potential applications in various fields. These adhesives exhibit remarkable properties such as reversible adhesion, self-healing, and high flexibility. This concept aims to present a comprehensive overview of the current research progress in developing supramolecular reversible adhesives. Firstly, the fundamentals of supramolecular chemistry and the principles underlying the design and synthesis of reversible adhesive systems are discussed. Next, the concept focuses on characterizing the reversible adhesion strength of supramolecular adhesive systems that have been developed. The adhesion performance of supramolecular reversible adhesives is summarized, highlighting their unique characteristics and promising applications. Finally, the challenges and future perspectives in the field of supramolecular reversible adhesives are discussed. The comprehensive overview provided in this concept aims to inspire further research and innovation in this exciting field.

Facile synthesis of Ag lattice doped mesoporous In2O3 nanocubes for high performance ethanol sensing.

Ag lattice doped In2O3 with a mesoporous structure was synthesized through a combination of hydrothermal and calcination methods. The structural and morphological characteristics were assessed using XRD, SEM, TEM, TGA, BET, and XPS analyses. Gas sensing measurements revealed that the 7.0 mol% Ag-doped In2O3 sensor displayed a response of 420 towards 100 ppm ethanol at 140 °C, which was 19 times higher than that of the pure In2O3 gas sensor. Density functional theory calculations indicated that Ag-doped In2O3 exhibited enhanced adsorption performance, higher adsorption energy, and electron transfer, resulting in higher sensitivity to ethanol. These findings were also supported by the electronic band structure, work function, and DOS analyses. These results indicated that the Ag doped mesoporous In2O3 has high potential for the preparation of high-performance ethanol sensors in practical applications.

Visible-light-driven catalyst-free C-S cross-coupling of thiol derivatives and aryl halides.

A mild, scalable, and high-yielding visible-light-promoted C-S cross-coupling between alkyl thiol derivatives and (hetero)aryl halides without the need for metals, ligands, or photocatalysts is reported, offering advantages over traditional C-S bond forming strategies. The formation of an electron donor-acceptor (EDA) complex is supported by experimental and computational mechanistic studies, which undergoes visible-light-induced charge transfer to initiate C-S bond formation in the absence of a photoredox catalyst.

DFT study of electron donor-acceptor (EDA) complexes: mechanism exploration and theoretical prediction.

Organic synthesis methods initiated by visible light have received increasing attention from synthetic chemists. Reactions initiated by EDA complexes do not require the use of toxic or expensive photoredox catalysts, unlike traditional photoreaction processes. However, this kind of reaction requires a particular structure for the substrate, so it is important to study the detailed and systematic reaction mechanism for its design. EDA complexes of substituted 1H-indole and substituted benzyl bromide derivatives were studied by density functional theory (DFT). The difference between EDA complexes with substituents of different kinds and locations were compared by theoretical study and a new EDA complex was predicted.

CSF Susceptibility Variation in Patient With Intracranial Hemorrhage: Implications for Quantitative Susceptibility Mapping Reference Selection.

BACKGROUND: Quantitative susceptibility mapping (QSM) is an emerging MRI technique with multiple clinical applications. As tissue susceptibility cannot be directly measured using MRI, QSM imaging techniques must indirectly compute susceptibility values, requiring regularization methods. CSF is a popular choice for regularization due to its near water susceptibility in healthy controls. However, the impact of pus, elevated protein, or blood dissolved in CSF on QSM regularization is not well defined. OBJECTIVE: This study aimed to investigate the effects of intracranial hemorrhage (ICH) on selecting CSF as reference for QSM imaging. MATERIALS AND METHODS: A total of 87 subjects, 53 with ICH (5 intraventricular, 19 subarachnoid, 27 both, and 2 intraparenchymal only) and 37 without hemorrhage (27 with MS, 10 without MS), were included in this study. Imaging was performed using 3D multiecho gradient echo, FLAIR, and multiecho complex total field inversion (mcTFI) at 3 T. McTFI with and without CSF zero-referencing regularization was generated from the 3DMEGRE data and reviewed with FLAIR images. Regions of hemorrhagic (H+) and nonhemorrhagic (H-) CSF were manually selected in reference to head CT and FLAIR images by a PGY III diagnostic radiology resident and Certificate of Added Qualification-certified neuroradiologist with 10 years' experience. Paired Student t test and one-way ANOVA were used with post hoc multicomparisons. A P value <0.05 was considered statistically significant. RESULTS: Areas of H- CSF were noted to have higher regularized QSM values in subjects with ICH relative to subjects without. Unregularized H- QSM values were also noted to have a systematically higher value in ICH subjects relative to subjects without blood. Subjects with MS and without ICH did not show significant difference in H- CSF regularized or unregularized QSM values. CONCLUSIONS: QSM values of areas suggested to not have hemorrhage on other imaging showed significantly higher QSM values in ICH subjects relative to subjects without ICH. Additionally, areas of hemorrhage did not show significant QSM value difference between regularized and unregularized QSM images. These findings suggest that, in subjects with any area of ICH, QSM values for no-hemorrhagic areas may be significantly altered using CSF regularization relative to subjects without ICH, with implications for intra- and intersubject QSM value analysis.

Assembly and Utility of a Drawstring-Mimetic Supramolecular Complex.

Inspired by the drawstring structure in daily life, here we report the development of a drawstring-mimetic supramolecular complex at the molecular scale. This complex consists of a rigid figure-of-eight macrocyclic host molecule and a flexible linear guest molecule which could interact through three-point non-covalent binding to form a highly selective and efficient host-guest assembly. The complex not only resembles the drawstring structure, but also mimics the properties of a drawstring with regard to deformations under external forces. The supramolecular drawstring can be utilized as an interlocked crosslinker for poly(methyl acrylate), and the corresponding polymer samples exhibit comprehensive enhancement of macroscopic mechanical performance including stiffness, strength, and toughness.

Wetting-Enabled Three-Dimensional Interfacial Polymerization (WET-DIP) for Bioinspired Anti-Dehydration Hydrogels.

Anti-dehydration hydrogels have attracted considerable attention due to their promising applications in stretchable sensors, flexible electronics, and soft robots. However, anti-dehydration hydrogels prepared by conventional strategies inevitably depend on additional chemicals or suffer from cumbersome preparation processes. Here, inspired by the succulent Fenestraria aurantiaca a one-step wetting-enabled three-dimensional interfacial polymerization (WET-DIP) strategy for constructing organogel-sealed anti-dehydration hydrogels is developed. By virtue of the preferential wetting on the hydrophobic-oleophilic substrate surfaces, the organogel precursor solution can spread on the three-dimensional (3D) surface and encapsulate the hydrogel precursor solution, forming anti-dehydration hydrogel with 3D shape after in situ interfacial polymerization. The WET-DIP strategy is simple and ingenious, and accessible to discretionary 3D-shaped anti-dehydration hydrogels with a controllable thickness of the organogel outer layer. Strain sensors based on this anti-dehydration hydrogel also exhibit long-term stability in signal monitoring. This WET-DIP strategy shows great potentialities for constructing hydrogel-based devices with long-term stability.

Dynamically Stabilized Electronic Regulation and Electrochemical Reconstruction in Co and S Atomic Pair Doped Fe3 O4 for Water Oxidation.

The electronic regulation and surface reconstruction of earth-abundant electrocatalysts are essential to efficient oxygen evolution reaction (OER). Here, an inverse-spinel Co,S atomic pair codoped Fe3 O4 grown on iron foam (Co,S-Fe3 O4 /IF) is fabricated as a cost-effective electrocatalyst for OER. This strategy of Co and S atomic pair directional codoping features accelerates surface reconstruction and dynamically stabilizes electronic regulation. CoS atomic pairs doped in the Fe3 O4 crystal favor controllable surface reconstruction via sulfur leaching, forming oxygen vacancies and Co doping on the surface of reconstructed FeOOH (Co-FeOOH-Ov /IF). Before and after surface reconstruction via in situ electrochemical process, the Fe sites with octahedral field dynamically maintains an appropriate electronic structure for OER intermediates, thus exhibiting consistently excellent OER performance. The electrochemically tuned Fe-based electrodes exhibit a low overpotential of 349 mV at a current density of 1000 mA cm-2 , a slight Tafel slope of 43.3 mV dec-1 , and exceptional long-term electrolysis stability of 200 h in an alkaline medium. Density functional theory calculations illustrate the electronic regulation of Fe sites, changes in Gibbs free energies, and the breaking of the restrictive scaling relation between OER intermediates. This work provides a promising directional codoping strategy for developing precatalysts for large-scale water-splitting systems.

Unperceivable motion mimicking hygroscopic geometric reshaping of pine cones.

The hygroscopic deformation of pine cones, featured by opening and closing their scales depending on the environmental humidity, is a well-known stimuli-responsive model system for artificial actuators. However, it has not been noted that the deformation of pine cones is an ultra-slow process. Here, we reveal that vascular bundles with unique parallelly arranged spring/square microtubular heterostructures dominate the hygroscopic movement, characterized as ultra-slow motion with the outer sclereids. The spring microtubes give a much larger hygroscopic deformation than that of the square microtubes along the longitudinal axis direction, which bends the vascular bundles and consequently drives the scales to move. The outer sclereids with good water retention enable the vascular-bundle-triggered deformation to proceed ultra-slowly. Drawing inspiration, we developed soft actuators enabling controllable yet unperceivable motion. The motion velocity is almost two orders of magnitude lower than that of the same-class actuators reported, which made the as-developed soft actuators applicable in camouflage and reconnaissance.

Achiral nanoparticle trapping and chiral nanoparticle separating with quasi-BIC metasurface.

Dielectric metasurfaces based on quasi-bound states in the continuum (quasi-BICs) are a promising approach for manipulating light-matter interactions. In this study, we numerically demonstrate the potential of silicon elliptical tetramer dielectric metasurfaces for achirality nanoparticle trapping and chiral nanoparticle separation. We first analyze a symmetric tetramer metasurface, which exhibits dual resonances (P1 and P2) with high electromagnetic field intensity enhancement and a high-quality factor (Q-factor). This metasurface can trap achiral nanoparticles with a maximum optical trapping force of 35 pN for 20 nm particles at an input intensity of 100 mW. We then investigate an asymmetric tetramer metasurface, which can identify and separate enantiomers under the excitation of left-handed circularly polarized (LCP) light. Results show that the chiral optical force can push one enantiomer towards regions of the quasi-BIC system while removing the other. In addition, the proposed asymmetric tetramer metasurface can provide multiple Fano resonances (ranging from R1 to R5) and high trap potential wells of up to 33 kBT. Our results demonstrate that the proposed all-dielectric metasurface has high performance in nanoparticle detection, with potential applications in biology, life science, and applied physics.

One-step assembly of a MacMillan catalyst-based phenolic-type polymer.

We report herein a "bottom-up" approach for the one-step assembly of a MacMillan catalyst-based phenolic-type polymer (Mac-CP). The resulting self-supported polymeric organocatalyst possesses homogeneously distributed and highly concentrated catalytic sites. Furthermore, Mac-CP is soluble in CH3CN but insoluble in hexane. This unique property can be used to employ the polymer as an efficient catalyst in homogeneous organocatalysis and heterogeneous recycling. As a result, Mac-CP possesses comparable catalytic activity and enantioselectivity to its homogeneous counterpart in the asymmetric Diels-Alder reaction (95% yield, 93% enantiomeric excess (ee) for endo and 92% ee for exo).

Visible-light induced C(sp3)-H arylation of glycine derivatives by cerium catalysis.

A Ce(III)-catalyzed, visible-light induced aerobic oxidative dehydrogenative coupling reaction between glycine derivatives and electron-rich arenes is disclosed. The protocol proceeds efficiently under mild conditions, providing an efficient method for the rapid synthesis of α-arylglycine derivatives without the need for an external photosensitizer and additional oxidant. Moreover, this protocol could be performed on a 5 mmol scale, without obvious reduction of the efficiency.

Synthesis of 3(2H)-furanone derivatives: p-TsOH/halotrimethylsilane promoted cycloketonization of γ-hydroxyl ynones.

A p-TsOH/halotrimethylsilane facilitated cycloketonization of γ-hydroxyl ynones is detailed. This methodology enables the one-step synthesis of polysubstituted 3(2H)-furanone products. It is remarkable that the reaction exhibits excellent regio- and chemoselectivity by the addition of very small quantities of p-toluenesulfonic acid and water.

Theoretical Study on Spectrum and Luminescence Mechanism of Cy5.5 and Cy7.5 Dye Based on Density Functional Theory (DFT).

Cy5.5 and 7.5 are the most commonly used NIR 2-region fluoresceins, which have good luminescence properties and important biomedical tracer applications. In this paper, their molecular non-covalent interactions, UV-Vis absorption spectra, main bond lengths, electrostatic potential distributions, frontier molecular orbitals (HOMO and LUMO) and energy gaps were calculated by density functional theory (DFT). We found that the differences in the luminescence properties and energy gaps of Cy5.5 and Cy7.5 molecules may be caused by the length of the conjugated chains between the two aromatic rings in the molecule. By calculating the relevant molecular characteristics, this paper can provide ideas and theoretical basis for the relevant modification and application, as well as the development of new fluorescent dyes.

Self-Pumping Janus Hydrogel with Aligned Channels for Accelerating Diabetic Wound Healing.

Excessive exudate secreted from diabetic wounds often results in skin overhydration, severe infections, and secondary damage upon dressing changes. However, conventional wound dressings are difficult to synchronously realize the non-maceration of wound sites and rapid exudate transport due to their random porous structure. Herein, a self-pumping Janus hydrogel with aligned channels (JHA) composed of hydrophilic poly (ethylene glycol) diacrylate (PEGDA) hydrogel layer and hydrophobic polyurethane (PU)/graphene oxide (GO)/polytetrafluoroethylene (PTFE) layer is designed to rapidly export exudate and accelerate diabetic wound healing. In the design, the ice-templating process endows the hydrophilic hydrogel layer with superior liquid transport ability and mechanical strength due to the formation of aligned channel structure. The hydrophobic layer with controlled thickness functions as an effective barrier to prevent exudate from wetting the skin surface. Experiments in diabetic rat model show that JHA can significantly promote re-epithelialization and collagen deposition, shorten the inflammation phase, and accelerate wound healing. This unique JHA dressing may have great potential for real-life usage in clinical patients.

Strong Anchoring of Hydrogels through Superwetting-Assisted High-Density Interfacial Grafting.

Strong adhesion of hydrogels on solids plays an important role in stable working for various practical applications. However, current hydrogel adhesion suffers from poor interfacial bonding with solid surfaces. Here, we propose a general superwetting-assisted interfacial polymerization (SAIP) strategy to robustly anchor hydrogels onto solids by forming high-density interfacial covalent bonds. The key of our strategy is to make the initiator fully contact solid surfaces via a superwetting way for enhancing the interfacial grafting efficiency. The designed anchored hydrogels show strong bulk failure with a high breaking strength of ≈1.37 MPa, different from weak interfacial failure that occurs in traditional strategies. The strong interfacial adhesion greatly enhances the stability of hydrogels against swelling destruction. This work opens up new inspirations for designing strongly anchored hydrogels from an interfacial chemistry perspective.

Prediction of the Lotus Effect on Solid Surfaces by Machine Learning.

Superhydrophobic surfaces with the "lotus effect" have wide applications in daily life and industry, such as self-cleaning, anti-freezing, and anti-corrosion. However, it is difficult to reliably predict whether a designed superhydrophobic surface has the "lotus effect" by traditional theoretical models due to complex surface topographies. Here, a reliable machine learning (ML) model to accurately predict the "lotus effect" of solid surfaces by designing a set of descriptors about nano-scale roughness and micro-scale topographies in addition to the surface hydrophobic modification is demonstrated. Geometrical and mathematical descriptors combined with gray level cooccurrence matrices (GLCM) offer a feasible solution to the puzzle of accurate descriptions of complex topographies. Furthermore, the "black box" is opened by feature importance and Shapley-additive-explanations (SHAP) analysis to extract waterdrop adhesion trends on superhydrophobic surfaces. The accurate prediction on as-fabricated superhydrophobic surfaces strongly affirms the extensionality of the ML model. This approach can be easily generalized to screen solid surfaces with other properties.

Topological photonic crystal biosensor with valley edge modes based on a silicon-on-insulator slab.

In the development of integrated sensing, how to reduce losses and improve robustness has always been one of the key problems to be solved. The topological photonic crystal structure based on the quantum Hall effect has gradually attracted the attention of researchers due to its unique immune defect performance and anti-scattering performance. Here, we have successfully applied the valley photonic crystal structures to topologically manipulate the light within the band gap of 252 THz-317 THz in a silicon-on-insulator platform. We experimentally demonstrated that satisfactory transmission performance can be obtained using the valley-dependent topological edge states below light cone, even if there are structure defects such as lattice missing and lattice mistake near the interface between two kinds VPCs. Based on the features of topological protection, a triangular cavity consisting of three 10×a-length sides is proposed, and the Q factor value reaches 1.83×105 with little influence from defects. Finally, based on drying etching technology, a biosensor with cavity-coupled waveguide structure was prepared, and the RI sensitivity was 1228 nm/RIU.