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Pursuing high-performance conductive hydrogels is still hot topic in development of advanced flexible wearable devices. Herein, a tough, self-healing, adhesive double network (DN) conductive hydrogel (named as OSA-(Gelatin/PAM)-Ca, O-(G/P)-Ca) was prepared by bridging gelatin and polyacrylamide network with functionalized polysaccharide (oxidized sodium alginate, OSA) through Schiff base reaction. Thanks to the presence of multiple interactions (Schiff base bond, hydrogen bond, and metal coordination) within the network, the prepared hydrogel showed outstanding mechanical properties (tensile strain of 2800 % and stress of 630 kPa), high conductivity (0.72 S/m), repeatable adhesion performance and excellent self-healing ability (83.6 %/79.0 % of the original tensile strain/stress after self-healing). Moreover, the hydrogel-based sensor exhibited high strain sensitivity (GF = 3.66) and fast response time (<0.5 s), which can be used to monitor a wide range of human physiological signals. Based on this, excellent compression sensitivity (GF = 0.41 kPa-1 in the range of 90-120 kPa), a three-dimensional (3D) array of flexible sensor was designed to monitor the intensity of pressure and spatial force distribution. In addition, a gel-based wearable sensor was accurately classified and recognized ten types of gestures, achieving an accuracy rate of >96.33 % both before and after self-healing under three machine learning models (the decision tree, SVM, and KNN). This paper provides a simple method to prepare tough and self-healing conductive hydrogel as flexible multifunctional sensor devices for versatile applications in fields such as healthcare monitoring, human-computer interaction, and artificial intelligence.
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The layer-by-layer stacked van der Waals structures (termed vdW hetero/homostructures) offer a new paradigm for materials design-their physical properties can be tuned by the vertical stacking sequence as well as by adding a mechanical twist, stretch, and hydrostatic pressure to the atomic structure. In particular, simple twisting and stacking of two layers of graphene can form a uniform and ordered Moiré superlattice, which can effectively modulate the electrons of graphene layers and lead to the discovery of unconventional superconductivity and strong correlations. However, the twist angle of twisted bilayer graphene (tBLG) is almost unchangeable once the interlayer stacking is determined, while applying mechanical elastic strain provides an alternative way to deeply regulate the electronic structure by controlling the lattice spacing and symmetry. In this review, diverse experimental advances are introduced in straining tBLG by in-plane and out-of-plane modes, followed by the characterizations and calculations toward quantitatively tuning the strain-engineered electronic structures. It is further discussed that the structural relaxation in strained Moiré superlattice and its influence on electronic structures. Finally, the conclusion entails prospects for opportunities of strained twisted 2D materials, discussions on existing challenges, and an outlook on the intriguing emerging field, namely "strain-twistronics".
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Twin boundaries (TBs) in transition metal dichalcogenides (TMDs) constitute distinctive one-dimensional electronic systems, exhibiting intriguing physical and chemical properties that have garnered significant attention in the fields of quantum physics and electrocatalysis. However, the controlled manipulation of TBs in terms of density and specific atomic configurations remains a formidable challenge. In this study, we present a non-epitaxial growth approach that enables the controlled and large-scale fabrication of homogeneous catalytically active TBs in monolayer TMDs on arbitrary substrates. Notably, the density achieved using this strategy is six times higher than that observed in convention chemical vapor deposition (CVD)-grown samples. Through rigorous experimental analysis and multigrain Wulff construction simulations, we elucidate the role of regulating the metal source diffusion process, which serves as the key factor for inducing the self-oriented growth of TMD grains and the formation of unified TBs. Furthermore, we demonstrate that this novel growth mode can be readily incorporated into the conventional CVD growth method by making a simple modification of the growth temperature profile, thereby offering a universal approach for engineering of grain boundaries in two-dimensional materials.
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Biocompatible chitosan-based hydrogels have attracted extensive attention in wound dressing due to their human skin-like tissue characteristics. However, it is a crucial challenge to fabricate chitosan-based hydrogels with versatile properties, including flexibility, stretchability, adhesivity, and antibacterial activity. In this work, a kind of chitosan-based hydrogels with integrated functionalities are facilely prepared by solution polymerization of acrylamide (AAm) and sodium p-styrene sulfonate (SS) in the presence of quaternized carboxymethyl chitosan (QCMCS). Due to the dual cross-linking between QCMCS and P(AAm-co-SS), the optimized QCMCS/P(AAm-co-SS) hydrogel exhibits tough mechanical properties (0.767 MPa tensile stress and 1100% fracture strain) and moderate tissue adhesion (11.4 kPa). Moreover, biological evaluation in vitro illustrated that as-prepared hydrogel possesses satisfactory biocompatibility, hemocompatibility, and excellent antibacterial ability (against S. aureus and E. coli are 98.8% and 97.3%, respectively). Then, the hydrogels are tested in a rat model for bacterial infection incision in vivo, and the results show that they can significantly accelerate epidermal regeneration and wound closure. This is due to their ability to reduce the inflammatory response, promote the formation of collagen deposition and granulation tissue. The proposed chitosan-based antibacterial hydrogels have the potential to be a highly effective wound dressing in clinical wound healing.
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Quitosano , Ratas , Animales , Humanos , Hidrogeles/farmacología , Adhesivos , Escherichia coli , Staphylococcus aureus , Antibacterianos/farmacología , VendajesRESUMEN
The emergence of protein hydrogel sensors has attracted intensive attention because of their biocompatibility and biodegradability, and potential application in wearable electronics. However, natural protein hydrogel sensors commonly exhibited low conductivity, weak mechanical strength, and unsatisfactory self-recovery performance. Herein, a fully physical crosslinked conductive BSA-MA-PPy/P(AM-co-AA)/Fe3+ hydrogel based on methacrylic anhydride (MA)-modified and polypyrrole (PPy)-functionalized bovine serum albumin (BSA) introduced into poly(acrylamide-co-acrylic acid) (P(AM-co-AA)) matrix was constructed. Due to the presence of the hydrogen bond complexation and the metal-ligand coordination between ferric ion (Fe3+) and the polymer chain, the as-prepared hydrogel showed outstanding mechanical strength (5.36 MPa tensile stress, 17.66 MJ/m3 toughness, and 1.61 MPa elastic modulus) and fast self-recovery performance (99.89 %/96.18 %/93.57 % stress/elastic modulus/dissipated energy within 10 min at room temperature). Meanwhile, the hydrogel exhibited outstanding conductivity (1.13 S/m) due to the presence of PPy and Fe3+ moieties, high strain sensitivity (GF = 4.98) and good biocompatibility without causing skin allergic reactions. Thus, the hydrogel can be fabricated into strain sensor to monitor the joint motion of the human body. Moreover, it can be used as soft electrode in electrocardiogram device to realize wireless heart-rate monitoring in the real-time conditions (relaxation and post-exercising), which exhibited excellent reusability, stability, and reliability simultaneously.
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Hidrogeles , Albúmina Sérica Bovina , Humanos , Polímeros , Reproducibilidad de los Resultados , Pirroles , Electrocardiografía , Anhídridos , Conductividad EléctricaRESUMEN
The coalescence of randomly distributed grains with different crystallographic orientations can result in pervasive grain boundaries (GBs) in 2D materials during their chemical synthesis. GBs not only are the inherent structural imperfection that causes influential impacts on structures and properties of 2D materials, but also have emerged as a platform for exploring unusual physics and functionalities stemming from dramatic changes in local atomic organization and even chemical makeup. Here, recent advances in studying the formation mechanism, atomic structures, and functional properties of GBs in a range of 2D materials are reviewed. By analyzing the growth mechanism and the competition between far-field strain and local chemical energies of dislocation cores, a complete understanding of the rich GB morphologies as well as their dependence on lattice misorientations and chemical compositions is presented. Mechanical, electronic, and chemical properties tied to GBs in different materials are then discussed, towards raising the concept of using GBs as a robust atomic-scale scaffold for realizing tailored functionalities, such as magnetism, luminescence, and catalysis. Finally, the future opportunities in retrieving GBs for making functional devices and the major challenges in the controlled formation of GB structures for designed applications are commented.
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Pharmacodynamic (PD) studies are an essential component of preclinical drug discovery. Current approaches for PD studies, including the analysis of novel kidney disease targeting therapeutic agents, are limited to animal models with unclear translatability to the human condition. To address this challenge, we developed a novel approach for PD studies using transplanted, perfused human kidney organoids. We performed pharmacokinetic (PK) studies with GFB-887, an investigational new drug now in phase 2 trials. Orally dosed GFB-887 to athymic rats that had undergone organoid transplantation resulted in measurable drug exposure in transplanted organoids. We established the efficacy of orally dosed GFB-887 in PD studies, where quantitative analysis showed significant protection of kidney filter cells in human organoids and endogenous rat host kidneys. This widely applicable approach demonstrates feasibility of using transplanted human organoids in preclinical PD studies with an investigational new drug, empowering organoids to revolutionize drug discovery.
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Enfermedades Renales , Organoides , Animales , Descubrimiento de Drogas , Drogas en Investigación , Humanos , Riñón , RatasRESUMEN
External photo-stimuli on heterojunctions commonly induce an electric potential gradient across the interface therein, such as photovoltaic effect, giving rise to various present-day technical devices. In contrast, in-plane potential gradient along the interface has been rarely observed. Here we show that scanning a light beam can induce a persistent in-plane photoelectric voltage along, instead of across, silicon-water interfaces. It is attributed to the following movement of a charge packet in the vicinity of the silicon surface, whose formation is driven by the light-induced potential change across the capacitive interface and a high permittivity of water with large polarity. Other polar liquids and hydrogel on silicon also allow the generation of the in-plane photovoltage, which is, however, negligible for nonpolar liquids. Based on the finding, a portable silicon-hydrogel array has been constructed for detecting the shadow path of a moving Cubaris. Our study opens a window for silicon-based photoelectronics through introducing semiconductor-water interfaces.
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Grain boundaries (GBs) are vital to crystal materials and their applications. Although GBs in bulk and two-dimensional materials have been extensively studied, the segmented GBs observed in transition metal dichalcogenide monolayers by a sequence of folded segments remain a mystery. We visualize the large-area distribution of the segmented GBs in MoSe2 monolayers and unravel their structural origin using ab initio calculations combined with high-resolution atomic characterizations. Unlike normal GBs in two-dimensional materials with commonly one type of dislocation cores, the segmented GBs consist of two basic elements-4|8 and 4|4|8 cores, whose alloying results in structural diversity and distinctly high stability due to relieved stress fields nearby. The defective polygons can uniquely migrate along the segmented GBs via the movement of single molybdenum atoms, unobtrusively endowing a given GB with variable appearances. Furthermore, the segmented GBs can achieve useful functionalities such as intrinsic magnetism and highly active electrocatalysis.
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Canonical transient receptor potential channels (TRPC) are involved in receptor-operated and/or store-operated Ca2+ signaling. Inhibition of TRPCs by small molecules was shown to be promising in treating renal diseases. In cells, the channels are regulated by calmodulin (CaM). Molecular details of both CaM and drug binding have remained elusive so far. Here, we report structures of TRPC4 in complex with three pyridazinone-based inhibitors and CaM. The structures reveal that all the inhibitors bind to the same cavity of the voltage-sensing-like domain and allow us to describe how structural changes from the ligand-binding site can be transmitted to the central ion-conducting pore of TRPC4. CaM binds to the rib helix of TRPC4, which results in the ordering of a previously disordered region, fixing the channel in its closed conformation. This represents a novel CaM-induced regulatory mechanism of canonical TRP channels.
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Calmodulina/metabolismo , Moduladores del Transporte de Membrana/farmacología , Piridazinas/farmacología , Canales Catiónicos TRPC/efectos de los fármacos , Proteínas de Pez Cebra/efectos de los fármacos , Animales , Sitios de Unión , Calmodulina/química , Calmodulina/genética , Células HEK293 , Humanos , Ligandos , Potenciales de la Membrana , Moduladores del Transporte de Membrana/química , Moduladores del Transporte de Membrana/metabolismo , Modelos Moleculares , Unión Proteica , Conformación Proteica , Piridazinas/química , Piridazinas/metabolismo , Células Sf9 , Relación Estructura-Actividad , Canales Catiónicos TRPC/química , Canales Catiónicos TRPC/genética , Canales Catiónicos TRPC/metabolismo , Xenopus , Proteínas de Pez Cebra/química , Proteínas de Pez Cebra/genética , Proteínas de Pez Cebra/metabolismoRESUMEN
Lateral heterostructures of two-dimensional transition metal dichalcogenides (TMDs) have offered great opportunities in the engineering of monolayer electronics, catalysis and optoelectronics. To explore the full potential of these materials, developing methods to precisely control the spatial scale of the heterostructure region is crucial. Here, we report the synthesis of ultra-long MoS2 nano-channels with several micrometer length and 2-30 nanometer width within the MoSe2 monolayers, based on intrinsic grain boundaries (GBs). First-principles calculations disclose that the strain fields near the GBs not only lead to the preferred substitution of selenium by sulfur but also drive coherent extension of the MoS2 channel from the GBs. Such a strain-driven synthesis mechanism is further shown applicable to other topological defects. We also demonstrate that the spontaneous strain of MoS2 nano-channels can further improve the hydrogen production activity of GBs, paving the way for designing GB based high-efficient TMDs in the catalytic application.
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The nonselective Ca2+-permeable transient receptor potential (TRP) channels play important roles in diverse cellular processes, including actin remodeling and cell migration. TRP channel subfamily C, member 5 (TRPC5) helps regulate a tight balance of cytoskeletal dynamics in podocytes and is suggested to be involved in the pathogenesis of proteinuric kidney diseases, such as focal segmental glomerulosclerosis (FSGS). As such, protection of podocytes by inhibition of TRPC5 mediated Ca2+ signaling may provide a novel therapeutic approach for the treatment of proteinuric kidney diseases. Herein, we describe the identification of a novel TRPC5 inhibitor, GFB-8438, by systematic optimization of a high-throughput screening hit, pyridazinone 1. GFB-8438 protects mouse podocytes from injury induced by protamine sulfate (PS) in vitro. It is also efficacious in a hypertensive deoxycorticosterone acetate (DOCA)-salt rat model of FSGS, significantly reducing both total protein and albumin concentrations in urine.
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Controllable synthesis of high-quality hexagonal boron nitride (h-BN) is desired toward the industrial application of 2D devices based on van der Waals heterostructures. Substantial efforts are devoted to synthesize h-BN on copper through chemical vapor deposition, which has been successfully applied to grow graphene. However, the progress in synthesizing h-BN has been significantly retarded, and it is still challenging to realize millimeter-scale domains and control their morphologies reliably. Here, the nucleation density of h-BN on Cu is successfully reduced by over two orders of magnitude by simply introducing a small amount of silicon, giving rise to large triangular domains with maximum 0.25 mm lateral size. Moreover, the domain morphologies can be modified from needles, tree patterns, and leaf darts to triangles through controlling the growth temperature. The presence of silicon alters the growth mechanism from attachment-limited mode to diffusion-limited mode, leading to dendrite domains that are rarely observed on pure Cu. A phase-field model is utilized to reveal the growing dynamics regarding B-N diffusion, desorption, flux, and reactivity variables, and explain the morphology evolution. The work sheds lights on the h-BN growth toward large single crystals and morphology probabilities.
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Ga-based two-dimensional transition-metal trichalcogenides with tunable ferromagnetic semiconducting properties are explored by first-principles calculations. It is found that the CrGaTe3 monolayer is an intrinsic ferromagnetic semiconductor with an indirect bandgap of 0.3 eV and exhibits strong dynamical, thermal and mechanical stabilities in the free-standing form. Its Curie temperature of 71 K estimated by Monte Carlo simulations can be significantly enhanced up to near room-temperature (263 K) by 5% biaxial tensile strain at which its structure still remains dynamically stable, while compressive strain can turn the monolayer from a ferromagnetic semiconductor to an antiferromagnetic semiconductor and finally to a ferromagnetic metal with a Curie temperature of 473 K at -5% strain. It is revealed that the pronounced strain tunability originates from the competition between a variety of magnetic exchange interactions. The CrGaSe3 monolayer is found to exhibit similar intrinsic ferromagnetic semiconducting properties and strain tunability. The exceptional properties render Ga-based transition-metal trichalcogenides promising candidates for spintronic applications.
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The development of effective method for monitoring of endogenous hypochlorous acid (HClO) in vivo is of great significance for early diagnosis of lipopolysaccharide (LPS) induced acute liver injury. Herein, we report a polymer micelles-based ratiometric fluorescent probe (PM) based on the combination of intramolecular charge transfer (ICT) mechanism and fluorescence resonance energy transfer (FRET) principle for selective visualization of endogenous HClO in vivo. Upon the reaction of PM with HClO, the electron-donating thiourea moiety is oxidized and transformed into imidazoline moiety (electron-withdrawing group), resulting in a dramatic blue shift (Ë100nm) in the fluorescence emission. The as-prepared PM shows good water dispersibility (100% aqueous media), fast response (<40s), high sensitivity (a detection limit of 1.75nM), and outstanding selectivity toward HClO over other ROS/RNS (50 equiv.). In addition, the vivo imaging experiments demonstrate that PM facilitates the visualization of endogenous HClO generation with LPS induced acute liver injury in zebrafish model.
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Lesión Pulmonar Aguda/diagnóstico , Técnicas Biosensibles , Ácido Hipocloroso/aislamiento & purificación , Lesión Pulmonar Aguda/inducido químicamente , Animales , Transferencia Resonante de Energía de Fluorescencia , Colorantes Fluorescentes/química , Ácido Hipocloroso/química , Límite de Detección , Lipopolisacáridos/toxicidad , Hígado/diagnóstico por imagen , Hígado/patología , Micelas , Polímeros/química , Pez CebraRESUMEN
6,7-Dihydro-5H-2,1-benzisoxazol-4-one analogs are potent inhibitors of aldosterone synthase (CYP11B2) with selectivity over the highly homologous enzyme cortisol synthase (CYP11B1). These compounds are unique among inhibitors of CYP11B2 in their lack of a strong-heme binding group such as a pyridine or imidazole. Poor metabolic stability in hepatocyte incubations was found to proceed via a reduction of the isoxazole ring. While the enzyme responsible for the reductive metabolism remains unknown, the rate of metabolism could be attenuated by the addition of polar functionality. The in vitro CYP11B2 potency and selectivity were confirmed in vivo in a cynomolgus monkey model by the inhibition of ACTH stimulated aldosterone production without impacting plasma cortisol concentrations.
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Citocromo P-450 CYP11B2/antagonistas & inhibidores , Inhibidores Enzimáticos/farmacología , Isoxazoles/farmacología , Citocromo P-450 CYP11B2/metabolismo , Relación Dosis-Respuesta a Droga , Inhibidores Enzimáticos/síntesis química , Inhibidores Enzimáticos/química , Humanos , Isoxazoles/síntesis química , Isoxazoles/química , Estructura Molecular , Relación Estructura-ActividadRESUMEN
In this study, amphiphilic diblock copolymers were designed and synthesized via the incorporation of reversible addition-fragmentation chain transfer radical polymerization (RAFT) and a subsequent grafting technique. Subsequently, Hg2+-sensitive water-soluble fluorescent polymeric micelles (FNs) were prepared by a reprecipitation strategy. The spectroscopic characteristics demonstrate that the fluorescein isothiocyanate (FITC) was successfully linked into the polymer. Due to the promoted reaction of desulfurization cyclization by Hg2+, the fluorescence of fluorescein in FNs was obviously quenched. The as-prepared FNs showed admirable Hg2+-sensitivity (detection limit: 54 nM), excellent water-solubility and high selectivity. In addition, FNs were successfully used to determine Hg2+ in blood serum. We expected that the as-prepared FNs could perform potential applications in imaging, sensing, and bioanalytic chemistry.
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Colorantes Fluorescentes/química , Mercurio/análisis , Polímeros/química , Agua Potable/química , Colorantes Fluorescentes/síntesis química , Humanos , Micelas , Estructura Molecular , Polímeros/síntesis química , Solubilidad , Agua/químicaRESUMEN
The design of effective tools for detecting copper ion (Cu2+) and sulfide anion (S2-) is of great importance due to the abnormal level of Cu2+ and S2- has been associated with an increase in risk of many diseases. Herein, we report on the fabrication of fluorescence resonance energy transfer (FRET) based fluorescent probe PF (PEI-FITC) for detecting Cu2+ and S2- in 100% aqueous media via a facile one-pot method by covalent linking fluorescein isothiocyanate (FITC) with branched-polyethylenimine (b-PEI). PF could selectively coordinate with Cu2+ among 10 metal ions to form PF-Cu2+ complex, resulting in fluorescence quenching through FRET mechanism. Furthermore, the in situ generated PF-Cu2+ complex can be used to selectively detect S2- based on the displacement approach, resulting in an off-on type sensing. There is no obvious interference from other anions, such as Cl-, NO3-, ClO4-, SO42-, HCO3-, CO32-, Br-, HPO42-, F- and S2O32-. In addition, PF was successfully used to determine Cu2+ and S2- in human serum and tap water samples. Therefore, the FRET-based probe PF may provide a new method for selective detection of multifarious analysts in biological and environmental applications, and even hold promise for application in more complicated systems.
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Cobre/análisis , Transferencia Resonante de Energía de Fluorescencia/métodos , Colorantes Fluorescentes/química , Sulfuros/análisis , Agua/química , Aniones , Cobre/sangre , Humanos , Concentración de Iones de Hidrógeno , Sulfuros/sangreRESUMEN
2-Ureido-4(1H)-pyrimidinone-bridged ferrocene-fullerene assembly I is designed and synthesized for elaborating the photoinduced electron-transfer processes in self-complementary quadruply hydrogen-bonded modules. Unexpectedly, steady-state and time-resolved spectroscopy reveal an inefficient electron-transfer process from the ferrocene to the singlet or triplet excited state of the fullerene, although the electron-transfer reactions are thermodynamically feasible. Instead, an effective intra-assembly triplet-triplet energy-transfer process is found to be operative in assembly I with a rate constant of 9.2×10(5) s(-1) and an efficiency of 73% in CH(2)Cl(2) at room temperature.
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The total synthesis of the marine alkaloid halichlorine is described, based on an approach that involves constructing the fully substituted asymmetric center at an early stage. The five-membered ring is formed by 5-exo-trig radical cyclization and the unsaturated six-membered ring by a process that formally represents a sequential combination of conjugate addition and S(N)2' displacement-a method that is general for making bicyclic compounds with nitrogen at a ring fusion position. A formal synthesis of (+)-halichlorine is also reported, based on the development of a general method for preparing optically pure piperidines. The key step of this method, which was used to make one of our intermediates, is the Claisen rearrangement of a 4-vinyloxy-3,4-dihydro-2H-pyridine-1-carboxylic acid benzyl ester. Such O-vinyl compounds are easily generated in situ from the corresponding alcohols, which are themselves readily assembled from serine and terminal acetylenes.