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Ferric ion (Fe3+) is a biologically abundant and important metal ion. We developed several cyclometalated iridium complex-based molecular sensors (1, ppy-1, 1-phen, 1a, and 1-OMe) for the detection of Fe3+ using an acetal moiety as the reaction site. The acetal moiety in iridium complexes undergoes Fe3+-catalyzed hydrolysis and subsequent formation of a formyl group, resulting in turn-off photoluminescent and electrochemiluminescent responses. Sensor 1 showed excellent selectivity toward Fe3+ over other biologically important metal ions. Furthermore, we compared the performance of the sensors based on the structural differences of the iridium complexes, and revealed a relationship between the structure and chemical properties through electrochemical experiments and computational calculations., (© 2024 Wiley‐VCH GmbH.)

Azobenzene, while relevant, has faced constraints in biological system applications due to its suboptimal quantum yield and short-wavelength emission. This study presents a pioneering strategy for fabricating organic microdots by coupling foldamer-linked azobenzene, resulting in robust fluorescence intensity and stability, especially in aggregated states, thereby showing promise for bioimaging applications. Comprehensive experimental and computational examinations elucidate the mechanisms underpinning enhanced photostability and fluorescence efficacy. In vitro and in vivo evaluations disclose that the external layer of cis-azo-foldamer microdots performs a self-sacrificial function during photo-bleaching. Consequently, these red-fluorescent microdots demonstrate extraordinary structural and photochemical stabilities over extended periods. The conjugation of a β-peptide foldamer to the azobenzene chromophore through a glycine linker instigates a blue-shifted and amplified π * -n transition. Molecular dynamics simulations reveal that the aggregated state of cis-azo-foldamers fortifies the stability of cis isomers, thereby augmenting fluorescence efficiency. This investigation furnishes crucial insights into conceptualizing novel, biologically inspired materials, promising stable and enduring imaging applications, and carries implications for diverse arenas such as medical diagnostics, drug delivery, and sensing technologies., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Organ-selective drug delivery is expected to maximize the efficacy of various therapeutic modalities while minimizing their systemic toxicity. Lipid nanoparticles and polymersomes can direct the organ-selective delivery of mRNAs or gene editing machineries, but their delivery is limited to mostly liver, spleen, and lung. A platform that enables delivery to these and other target organs is urgently needed. Here, a library of glycocalyx-mimicking nanoparticles (GlyNPs) comprising five randomly combined sugar moieties is generated, and direct in vivo library screening is used to identify GlyNPs with preferential biodistribution in liver, spleen, lung, kidneys, heart, and brain. Each organ-targeting GlyNP hit show cellular tropism within the organ. Liver, kidney, and spleen-targeting GlyNP hits equipped with therapeutics effectively can alleviate the symptoms of acetaminophen-induced liver injury, cisplatin-induced kidney injury, and immune thrombocytopenia in mice, respectively. Furthermore, the differential organ targeting of GlyNP hits is influenced not by the protein corona but by the sugar moieties displayed on their surface. It is envisioned that the GlyNP-based platform may enable the organ- and cell-targeted delivery of therapeutic cargoes., (© 2024 Wiley‐VCH GmbH.)

Atopic dermatitis (AD) is a widespread, recurrent, and chronic inflammatory skin condition that imposes a major burden on patients. Conventional treatments, such as corticosteroids, are associated with various side effects, underscoring the need for innovative therapeutic approaches. In this study, the possibility of using indole-3-acetic acid-loaded layered double hydroxides (IAA-LDHs) is evaluated as a novel treatment for AD. IAA is an auxin-class plant hormone with antioxidant and anti-inflammatory effects. Following the synthesis of IAA-LDH nanohybrids, their ability to induce M2-like macrophage polarization in macrophages obtained from mouse bone marrow is assessed. The antioxidant activity of IAA-LDH is quantified by assessing the decrease in intracellular reactive oxygen species levels. The anti-inflammatory and anti-atopic characteristics of IAA-LDH are evaluated in a mouse model of AD by examining the cutaneous tissues, immunological organs, and cells. The findings suggest that IAA-LDH has great therapeutic potential as a candidate for AD treatment based on its in vitro and in vivo modulation of AD immunology, enhancement of macrophage polarization, and antioxidant activity. This inorganic drug delivery technology represents a promising new avenue for the development of safe and effective AD treatments., (© 2023 Wiley‐VCH GmbH.)

Owing to the limited electrochemical stability window of carbonate electrolytes, the initial formation of a solid electrolyte interphase and surface film on the negative and positive electrode surfaces by the decomposition of the electrolyte component is inevitable for the operation of lithium secondary batteries. The deposited film on the surface of the active material is vital for reducing further electrochemical side reactions at the surface; hence, the manipulation of this formation process is necessary for the appropriate operation of the assembled battery system. In this study, the thermal decomposition of LiPF 6 salt is used as a surface passivation agent, which is autocatalytically formed during high-temperature storage. The thermally formed difluorophosphoric acid is subsequently oxidized on the partially charged high-Ni positive electrode surface, which improves the cycleability of lithium metal cells via phosphorus- and fluorine-based surface film formation. Moreover, the improvement in the high-temperature cycleability is demonstrated by controlling the formation process in the lithium-ion pouch cell with a short period of high-temperature storage before battery usage., (© 2023 Wiley-VCH GmbH.)

Augmented reality (AR) is a computer graphics technique that creates a seamless interface between the real and virtual worlds. AR usage rapidly spreads across diverse areas, such as healthcare, education, and entertainment. Despite its immense potential, AR interface controls rely on an external joystick, a smartphone, or a fixed camera system susceptible to lighting. Here, an AR-integrated soft wearable electronic system that detects the gestures of a subject for more intuitive, accurate, and direct control of external systems is introduced. Specifically, a soft, all-in-one wearable device includes a scalable electrode array and integrated wireless system to measure electromyograms for real-time continuous recognition of hand gestures. An advanced machine learning algorithm embedded in the system enables the classification of ten different classes with an accuracy of 96.08%. Compared to the conventional rigid wearables, the multi-channel soft wearable system offers an enhanced signal-to-noise ratio and consistency over multiple uses due to skin conformality. The demonstration of the AR-integrated soft wearable system for drone control captures the potential of the platform technology to offer numerous human-machine interface opportunities for users to interact remotely with external hardware and software., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Designing chiral channels in organic frameworks presents an ongoing challenge due to the intricate control of size, shape, and functionality required. A novel approach is presented, which crafts enantiomeric chiral channels in metal-peptide networks (MPNs) by integrating short foldamer ligands with CuI clusters. The MPN structure serves as a 3D blueprint for host-guest chemistry, fostering modular substitution to refine chiral channel properties at the atomic scale. Incorporating hydrogen bond networks augments guest molecule interactions with the channel surface. This approach expedites enantiomer discrimination in racemic mixtures and incites adaptable guest molecules to take on specific axially chiral conformations. Distinct from traditional metal-organic frameworks (MOFs) and conventional reticular architectures, this foldamer-based methodology provides a predictable and customizable host-guest interaction system within a 3D topology. This innovation sets the stage for multifunctional materials that merge host-guest interaction systems with metal-complex properties, opening up potential applications in catalysis, sensing, and drug delivery., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Relaxor ferroelectrics (RFEs) are being actively investigated for energy-storage applications due to their large electric-field-induced polarization with slim hysteresis and fast energy charging-discharging capability. Here, a novel nanograin engineering approach based upon high kinetic energy deposition is reported, for mechanically inducing the RFE behavior in a normal ferroelectric Pb(Zr 0.52 Ti 0.48 )O 3 (PZT), which results in simultaneous enhancement in the dielectric breakdown strength (E DBS ) and polarization. Mechanically transformed relaxor thick films with 4 µm thickness exhibit an exceptional E DBS of 540 MV m -1 and reduced hysteresis with large unsaturated polarization (103.6 µC cm -2 ), resulting in a record high energy-storage density of 124.1 J cm -3 and a power density of 64.5 MW cm -3 . This fundamental advancement is correlated with the generalized nanostructure design that comprises nanocrystalline phases embedded within the amorphous matrix. Microstructure-tailored ferroelectric behavior overcomes the limitations imposed by traditional compositional design methods and provides a feasible pathway for realization of high-performance energy-storage materials., (© 2023 Wiley-VCH GmbH.)

We introduce a novel cyclic β-amino acid, trans-(3S,4R)-4-aminotetrahydrothiophene-3-carboxylic acid (ATTC), as a versatile building block for designing peptide foldamers with controlled secondary structures. We synthesized and characterized a series of β-peptide hexamers containing ATTC using various techniques, including X-ray crystallography, circular dichroism, and NMR spectroscopy. Our findings reveal that ATTC-containing foldamers can adopt 12-helical conformations similar to their isosteres and offer the possibility of fine-tuning their properties via post-synthetic modifications. In particular, chemoselective conjugation strategies demonstrate that ATTC provides unique post-synthetic modification opportunities, which expand their potential applications across diverse research areas. Collectively, our study highlights the versatility and utility of ATTC as an alternative to previously reported cyclic β-amino acid building blocks in both structural and functional aspects, paving the way for future research in the realm of peptide foldamers and beyond., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Deoxyribonuclease-I (DNase-I), a representative endonuclease, is an important biomarker for the diagnosis of infectious diseases and cancer progression. However, enzymatic activity decreases rapidly ex vivo, which highlights the need for precise on-site detection of DNase-I. Here, a localized surface plasmon resonance (LSPR) biosensor that enables the simple and rapid detection of DNase-I is reported. Moreover, a novel technique named electrochemical deposition and mild thermal annealing (EDMIT) is applied to overcome signal variations. By taking advantage of the low adhesion of gold clusters on indium tin oxide substrates, both the uniformity and sphericity of gold nanoparticles are increased under mild thermal annealing conditions via coalescence and Ostwald ripening. This ultimately results in an approximately 15-fold decrease in LSPR signal variations. The linear range of the fabricated sensor is 20-1000 ng mL -1 with a limit of detection (LOD) of 127.25 pg mL -1 , as demonstrated by spectral absorbance analyses. The fabricated LSPR sensor stably measured DNase-I concentrations from samples collected from both an inflammatory bowel disease (IBD) mouse model, as well as human patients with severe COVID-19 symptoms. Therefore, the proposed LSPR sensor fabricated via the EDMIT method can be used for early diagnosis of other infectious diseases., (© 2023 Wiley-VCH GmbH.)

Common medications for treating inflammatory bowel disease (IBD) have limited therapeutic efficacy and severe adverse effects. This underscores the urgent need for novel therapeutic approaches that can effectively target inflamed sites in the gastrointestinal tract upon oral administration, exerting potent therapeutic efficacy while minimizing systemic effects. Here, we report the construction and in vivo therapeutic evaluation of a library of anti-inflammatory glycocalyx-mimicking nanoparticles (designated GlyNPs) in a mouse model of IBD. The anti-inflammatory GlyNP library was created by attaching bilirubin (BR) to a library of glycopolymers composed of random combinations of the five most naturally abundant sugars. Direct in vivo screening of 31 BR-attached anti-inflammatory GlyNPs via oral administration into mice with acute colitis led to identification of a candidate GlyNP capable of targeting macrophages in the inflamed colon and effectively alleviating colitis symptoms. These findings suggest that the BR-attached GlyNP library can be used as a platform to identify anti-inflammatory nanomedicines for various inflammatory diseases., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Developing double boron-based emitters with extremely narrow band spectrum and high efficiency in organic light-emitting diodes (OLEDs) is crucial and challenging. Herein, we report two materials, NO-DBMR and Cz-DBMR, hinge on polycyclic heteraborin skeletons based on role-play of the highest occupied molecular orbital (HOMO) energy levels. The NO-DBMR contains an oxygen atom, whereas the Cz-DBMR has a carbazole core in the double boron-embedded ν-DABNA structure. The synthesized materials resulted in an unsymmetrical pattern for NO-DBMR and surprisingly a symmetrical pattern for Cz-DBMR. Consequently, both materials showed extremely narrow full width at half maximum (FWHM) of 14 nm in hypsochromic (pure blue) and bathochromic (Bluish green) shifted emission without losing their high color fidelity. Furthermore, both materials show high photoluminescence quantum yield (PLQY) of over 82 %, and an extremely small singlet-triplet energy gap (ΔE ST ) of 0.04 eV, resulting in high reverse intersystem crossing process (k RISC ) of 10 5  s -1 . Due to the efficient thermally activated delayed fluorescence (TADF) characteristics, the fabricated OLEDs based on these heteraborins manifested maximum external quantum efficiency (EQE max ) of 33.7 and 29.8 % for NO-DBMR and Cz-DBMR, respectively. This is the first work reported with this type of strategy for achieving an extremely narrow emission spectrum in hypsochromic and bathochromic shifted emissions with a similar molecular skeleton., (© 2023 Wiley-VCH GmbH.)

The uncontrollable dendritic growth of metallic lithium during repeated cycling in carbonate electrolytes is a crucial obstacle hindering the practical use of Li-metal batteries (LMBs). Among numerous approaches proposed to mitigate the intrinsic constraints of Li metal, the design of a functional separator is an attractive approach to effectively suppress the growth of Li dendrites because direct contact with both the Li metal surface and the electrolyte is maintained. Here, a newly designed all-in-one separator containing bifunctional CaCO 3 nanoparticles (CPP separator) is proposed to achieve the flattening of Li deposits on the Li electrode. Strong interactions between the highly polar CaCO 3 nanoparticles and the polar solvent reduces the ionic radius of the Li + -solvent complex, thus increasing the Li + transference number and leading to a reduced concentration overpotential in the electrolyte-filled separator. Furthermore, the integration of CaCO 3 nanoparticles into the separator induces the spontaneous formation of mechanically-strong and lithiophilic CaLi 2 at the Li/separator interface, which effectively decreases the nucleation overpotential toward Li plating. As a result, the Li deposits exhibit dendrite-free planar morphologies, thus enabling excellent cycling performance in LMBs configured with a high-Ni cathode in a carbonate electrolyte under practical operating conditions., (© 2023 Wiley-VCH GmbH.)

Cholangiocarcinoma (CCA) is a fatal disease often detected late in unresectable stages. Currently, there are no effective diagnostic methods or biomarkers to detect CCA early with high confidence. Analysis of tumor-derived extracellular vesicles (tEVs) harvested from liquid biopsies can provide a new opportunity to achieve this goal. Here, an advanced nanoplasmonic sensing technology is reported, termed FLEX (fluorescence-amplified extracellular vesicle sensing technology), for sensitive and robust single EV analysis. In the FLEX assay, EVs are captured on a plasmonic gold nanowell surface and immunolabeled for cancer-associated biomarkers to identify tEVs. The underlying plasmonic gold nanowell structures then amplify EVs' fluorescence signals, an effective amplification process at the single EV level. The FLEX EV analysis revealed a wide heterogeneity of tEVs and their marker levels. FLEX also detected small tEVs not detected by conventional EV fluorescence imaging due to weak signals. Tumor markers (MUC1, EGFR, and EPCAM) are identified in CCA, and this marker combination is applied to detect tEVs in clinical bile samples. The FLEX assay detected CCA with an area under the curve of 0.93, significantly better than current clinical markers. The sensitive and accurate nanoplasmonic EV sensing technology can aid in early CCA diagnosis., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Defect states at the surface and grain boundaries of perovskite films have been known to be major determinants impairing the optoelectrical properties of perovskite films and the stability of perovskite solar cells (PeSCs). Herein, an n-type conjugated small-molecule additive based on fused-unit dithienothiophen[3,2-b]-pyrrolobenzothiadiazole-core (JY16) is developed for efficient and stable PeSCs, where JY16 possesses the same backbone as the widely used Y6 but with long-linear n-hexadecyl side chains rather than branched side chains. Upon introducing JY16 into the perovskite films, the electron-donating functional groups of JY16 passivate defect states in perovskite films and increase the grain size of perovskite films through Lewis acid-base interactions. Compared to Y6, JY16 exhibits superior charge mobility owing to its molecular packing ability and prevents decomposition of perovskite films under moisture conditions owing to their hydrophobic characteristics, improving the charge extraction ability and moisture stability of PeSCs. Consequently, the PeSC with JY16 shows a high power conversion efficiency of 21.35%, which is higher than those of the PeSC with Y6 (20.12%) and without any additive (18.12%), and outstanding moisture stability under 25% relative humidity, without encapsulation. The proposed organic semiconducting additive will prove to be crucial for achieving highly efficient and moisture stable PeSCs., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Cancer-targeting ligands used for nanomedicines have been limited mostly to antibodies, peptides, aptamers, and small molecules thus far. Here, a library of glycocalyx-mimicking nanoparticles as a platform to enable screening and identification of cancer-targeting nanomedicines is reported. Specifically, a library of 31 artificial glycopolymers composed of either homogeneous or heterogeneous display of five different sugar moieties (β-glucose, β-galactose, α-mannose, β-N-acetyl glucosamine, and β-N-acetyl galactosamine) is converted to a library of glyconanoparticles (GlyNPs). GlyNPs optimal for targeting CT26, DU145, A549, and PC3 tumors are systematically screened and identified. The cypate-conjugated GlyNP displaying α-mannose and β-N-acetyl glucosamine show selective targeting and potent photothermal therapeutic efficacy against A549 human lung tumors. The docetaxel-contained GlyNP displaying β-glucose, β-galactose, and α-mannose demonstrate targeted chemotherapy against DU145 human prostate tumors. The results presented herein collectively demonstrate that the GlyNP library is a versatile platform enabling the identification of cancer-targeting glyconanoparticles and suggest its potential applicability for targeting various diseased cells beyond cancer., (© 2022 Wiley-VCH GmbH.)

Light-emitting fibers have been intensively developed for the realization of textile displays and various lighting applications, as promising free-form electronics with outstanding interconnectivity. These advances in the fiber displays have been made possible by the successful implementation of the core technologies of conventional displays, including high optoelectronic performance and essential elements, in the fiber form-factor. However, although white organic light-emitting diodes (WOLEDs), as a fundamental core technology of displays, are essential for realizing full-color displays and solid-state lighting, fiber-based WOLEDs are still challenging due to structural issues and the lack of approaches to implementing WOLEDs on fiber. Herein, the first fiber WOLED is reported, exhibiting high optoelectronic performance and a reliable color index, comparable to those of conventional planar WOLEDs. As key features, it is found that WOLEDs can be successfully introduced on a cylindrical fiber using a dip-coatable single white-emission layer based on simulation and optimization of the white spectra. Furthermore, to ensure durability from usage, the fiber WOLED is encapsulated by an Al 2 O 3 /elastomer bilayer, showing stable operation under repetitive bending and pressure, and in water. This pioneering work is believed to provide building blocks for realizing complete textile display technologies by complementing the lack of the core technology., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Despite its abundance, water is not widely used as a medium for organic reactions. However, under geothermal conditions, water exhibits unique physicochemical properties, such as viscosity and a dielectric constant, and the ionic product become similar to those of common organic solvents. We have synthesized highly crystalline polyimide-based covalent organic frameworks (PICs) under geomimetic hydrothermal conditions. By exploiting triphenylene-2,3,6,7,10,11-hexacarboxylic acid in combination with various aromatic diamines, PICs with various pore dimensions and crystallinities were synthesized. XRD, FT-IR, and DFT calculations revealed that the solubility of the oligomeric intermediates under hydrothermal conditions affected the stacking structures of the crystalline PICs. Furthermore, the synthesized PICs demonstrate promising potential as an anode material in lithium-ion batteries owing to its unique redox-active properties and high surface area., (© 2021 Wiley-VCH GmbH.)

Metal-coordinated frameworks derived from small peptidic ligands have received much attention thanks to peptides' vast structural and functional diversity. Various peptides with partial conformational preferences have been used to build metal-peptide frameworks, however, the use of conformationally constrained β-peptide foldamers has not been explored yet. Herein we report the first metal-coordination-mediated assembly of β-peptide foldamers with 12-helical folding propensity. The coordination of Ag + to the terminal pyridyl moieties afforded a set of metal-peptide frameworks with unique entangled topologies. Interestingly, formation of the network structures was accompanied by notable conformational distortions of the foldamer ligands. As the first demonstration of new metal-peptide frameworks built from modular β-peptide foldamers, we anticipate that this work will be an important benchmark for further structural evolution and mechanistic investigation., (© 2021 Wiley-VCH GmbH.)

The highly strained bowl-shaped pentacyclic structure of herquline A has rendered it one of the most difficult problems in organic synthesis yet to be solved. The challenges associated with the synthesis of herquline A have been well documented in four Ph.D. dissertations and in multiple reports regarding syntheses of its structurally simpler congeners. Herein, we report the construction of the pentacyclic core of herquline A that contains both N10-C2 and C3-C3' bonds. The key for success was the development of the tandem aza-Michael addition/enolate capture protocol that set the stage for subsequent palladium catalyzed C3(sp 2 )-C3'(sp 2 ) coupling reaction. Ensuing oxidative dearomatization of the left aryl ring allowed the formation of the pentacyclic diketone core of herquline A., (© 2021 Wiley-VCH GmbH.)

The synthesis of morphologically well-defined peptidic materials via self-assembly is challenging but demanding for biocompatible functional materials. Moreover, switching morphology from a given shape to other predictable forms by molecular modification of the identical building block is an even more complicated subject because the self-assembly of flexible peptides is prone to diverge upon subtle structural change. To accomplish controllable morphology transformation, systematic self-assembly studies are performed using congener short β-peptide foldamers to find a minimal structural change that alters the self-assembled morphology. Introduction of oxygen-containing β-amino acid (ATFC) for subtle electronic perturbation on hydrophobic foldamer induces a previously inaccessible solid-state conformational split to generate the most susceptible modification site for morphology transformation of the foldamer assemblies. The site-dependent morphological switching power of ATFC is further demonstrated by dual substitution experiments and proven by crystallographic analyses. Stepwise morphology transformation is shown by modifying an identical foldamer scaffold. This study will guide in designing peptidic molecules from scratch to create complex and biofunctional assemblies with nonspherical shapes., (© 2021 The Authors. Small published by Wiley-VCH GmbH.)

The current outbreak of the beta-coronavirus (beta-Cov) severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) began in December 2019. No specific antiviral treatments or vaccines are currently available. A recent study has reported that coronavirus disease 2019 (COVID-19), the disease caused by SARS-CoV-2 infection, is associated with neutrophil-specific plasma membrane rupture, and release excessive neutrophil extracellular traps (NETs) and extracellular DNAs (eDNAs). This mechanism involves the activation of NETosis, a neutrophil-specific programmed cell death, which is believed to play a crucial role in COVID-19 pathogenesis. Further progression of the disease can cause uncontrolled inflammation, leading to the initiation of cytokine storms, acute respiratory distress syndrome (ARDS), and sepsis. Herein, it is reported that DNase-I-coated melanin-like nanospheres (DNase-I pMNSs) mitigate sepsis-associated NETosis dysregulation, thereby preventing further progression of the disease. Recombinant DNase-I and poly(ethylene glycol) (PEG) are used as coatings to promote the lengthy circulation and dissolution of NET structure. The data indicate that the application of bioinspired DNase-I pMNSs reduce neutrophil counts and NETosis-related factors in the plasma of SARS-CoV-2 sepsis patients, alleviates systemic inflammation, and attenuates mortality in a septic mouse model. Altogether, the findings suggest that these nanoparticles have potential applications in the treatment of SARS-CoV-2-related illnesses and other beta-CoV-related diseases., Competing Interests: The authors declare no conflict of interest., (© 2020 The Authors. Published by Wiley‐VCH GmbH.)

Flexible piezoelectric acoustic sensors have been developed to generate multiple sound signals with high sensitivity, shifting the paradigm of future voice technologies. Speech recognition based on advanced acoustic sensors and optimized machine learning software will play an innovative interface for artificial intelligence (AI) services. Collaboration and novel approaches between both smart sensors and speech algorithms should be attempted to realize a hyperconnected society, which can offer personalized services such as biometric authentication, AI secretaries, and home appliances. Here, representative developments in speech recognition are reviewed in terms of flexible piezoelectric materials, self-powered sensors, machine learning algorithms, and speaker recognition., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Advances in material science and nanotechnology have fostered the miniaturization of devices. Over the past two decades, the form-factor of these devices has evolved from 3D rigid, volumetric devices through 2D film-based flexible electronics, finally to 1D fiber electronics (fibertronics). In this regard, fibertronic strategies toward wearable applications (e.g., electronic textiles (e-textiles)) have attracted considerable attention thanks to their capability to impart various functions into textiles with retaining textiles' intrinsic properties as well as imperceptible irritation by foreign matters. In recent years, extensive research has been carried out to develop various functional devices in the fiber form. Among various features, lighting and display features are the highly desirable functions in wearable electronics. This article discusses the recent progress of materials, architectural designs, and new fabrication technologies of fiber-shaped lighting devices and the current challenges corresponding to each device's operating mechanism. Moreover, opportunities and applications that the revolutionary convergence between the state-of-the-art fibertronic technology and age-long textile industry will bring in the future are also discussed., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Flash photothermal treatment via Xenon lamp with a broad wavelength spectrum can effectively remove oxygen functionalities and restore sp 2 domains at graphitic carbon materials. The chemical composition and relevant structure formation of flash reduced graphene oxide liquid crystal (GOLC) fibers are investigated in accordance with flash irradiation conditions. Owing to the spatial controllability of reduction level via anisotropic flash irradiation, the mechanical properties and electrical conductivity of graphene fibers can be delicately counterbalanced to attain desired properties. High sensitivity humidity sensors can be fabricated from the flash reduced fibers demonstrating notably higher sensitivity over the thermally reduced counterparts. This ultrafast flash reduction holds great promise for multidimensional macroscopic GO based structures, enabling a wide range of potential applications, including textile electronics and wearable sensors., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

There is a rapidly increasing interest in developing stimuli-responsive nanomaterials for treating a variety of diseases. By enabling the activation of function locally at the sites of interest, it is possible to increase therapeutic efficacy significantly while simultaneously reducing adverse side effects. While there are many sophisticated nanomaterials available, they are often highly complex and not easily transferrable to industrial scales and clinical settings. However, nanomaterials based on hyaluronic acid offer a compelling strategy for reducing their complexity while retaining several desirable benefits such as active targeting and stimuli-responsive degradation. Herein, the basic properties of hyaluronic acid, its binding partners, and natural routes for degradation by hyaluronidases-hyaluronic-acid-degrading enzymes-and oxidative stresses are discussed. Recent advances in designing hyaluronic acid-based, actively targeted, hyaluronidase- or reactive-oxygen-species-responsive nanomaterials for both diagnostic imaging and therapeutic delivery, which go beyond merely the classical targeting of CD44, are summarized., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We present the formation of a nanobelt by self-assembly of β-benzyl GABA (γ-aminobutyric acid). This simple γ-amino acid building block self-assembled to form a well-defined nanobelt in chloroform. The nanobelt showed distinct optical properties due to π-π interactions. This new-generation self-assembled single amino acid may serve as a template for functional nanomaterials., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The effect of a small ionic surfactant, cetyltrimethylammonium bromide (CTAB), on the self-assembly of a β-peptide has been systematically studied by using scanning electron microscopy, X-ray diffraction, selected area electron diffraction, and molecular dynamics (MD) simulations. The latter study suggested that the formation of asymmetric microcrystals may be due to the preferential adsorption of CTAB on {011} and (001) crystal faces. This work provides a plausible rationale for the characteristic 3D morphogenesis of foldectures and elucidates the interaction between the surfactant and organic building block molecules., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The rational design of self-assembling organic materials is extremely challenging due to the difficulty in precisely predicting solid-state architectures from first principles, especially if synthons are conformationally flexible. A tractable model system to study self-assembly was constructed by appending cyclopropanoyl caps to the N termini of helical α/β-peptide foldamers, designed to form both N-H⋅⋅⋅O and C α -H⋅⋅⋅O hydrogen bonds, which then rapidly self-assembled to form foldectures (foldamer architectures). Through a combined analytical and computational investigation, cyclopropanoyl capping was observed to markedly enhance self-assembly in recalcitrant substrates and direct the formation of a single intermolecular N-H⋅⋅⋅O/C α -H⋅⋅⋅O bonding motif in single crystals, regardless of peptide sequence or foldamer conformation. In contrast to previous studies, foldamer constituents of single crystals and foldectures assumed different secondary structures and different molecular packing modes, despite a conserved N-H⋅⋅⋅O/C α -H⋅⋅⋅O bonding motif. DFT calculations validated the experimental results by showing that the N-H⋅⋅⋅O/C α -H⋅⋅⋅O interaction created by the cap was sufficiently attractive to influence self-assembly. This versatile strategy to harness secondary noncovalent interactions in the rational design of self-assembling organic materials will allow for the exploration of new substrates and speed up the development of novel applications within this increasingly important class of materials., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A strategy of materials synthesis, characteristic evaluations, and manufacturing process for a mechanically elastic, biologically safe silicon-based dopamine detector that is designed to be completely transient, i.e., dissolved in water and/or biofluids, potentially in the brain after a desired period of operation, is introduced. Use of inexpensive, bioresorbable iron (Fe)-based nanoparticles (NPs) is one of the attractive choices for efficient catalytic oxidation of dopamine as an alternative for noble, nontransient platinum (Pt) nanoparticles, based on extensive studies of synthesized materials and catalytic reactions. Arrays of transient dopamine sensors validate electrochemical functionality to determine physiological levels of dopamine and to selectively sense dopamine in a variety of neurotransmitters, illuminating feasibilities for a higher level of soft, transient electronic implants integrated with other components of overall system., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Current diagnostic markers for gastric cancer are not sufficiently specific or sensitive for use in clinical practice. The aims of this study are to compare the proteomes of serum samples from patients with gastric cancers and normal controls, and to develop useful tumor markers of gastric cancer by quantitative proteomic analysis. We identified a total of 388 proteins with a ≤1% FDR and with at least two unique peptides from the sera of each group. Among them, 215, 251, and 260 proteins were identified in serum samples of patients in an advanced cancer group, early cancer group, and normal control group, respectively. We selected differentially expressed proteins in cancer patients compared with those of normal controls via semiquantitative analyses comparing the spectral counts of identified proteins. These differentially expressed proteins were successfully verified using an MS-based quantitative assay, multiple reactions monitoring analysis. Four proteins (vitronectin, clusterin isoform 1, thrombospondin 1, and tyrosine-protein kinase SRMS) were shown to have significant changes between the cancer groups and the normal control group. These four serum proteins were able to discriminate gastric cancer patients from normal controls with sufficient specificity and selectivity., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The first total synthesis of inostamycin A is described. With efficient and stereoselective synthetic routes to aldehyde 3 and ketone 4 developed through asymmetric aldol reactions, addition reactions and reduction, and with chiral building blocks, the two large fragments were coupled with remarkable anti stereoselectivity and efficiency by aldol condensation. The coupling reaction provided the complete carbon skeleton with all the requisite functional groups and stereogenic centers for inostamycin A. The two quaternary carbons at C20 and C16 of ketone 4 were elaborated in a highly stereocontrolled manner by addition reactions of the transmetallated 5 to ethyl ketone 6 and the transmetallated 7 to methyl ketone 8, respectively, in which the use of LaCl3 for transmetallation was critical for high coupling efficiency., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The creation of self-assembling microscale architectures that possess new and useful physical properties remains a significant challenge. Herein we report that an 11-helical foldamer self-assembles in a controlled manner to form a series of 3D foldectures with unusual three-fold symmetrical shapes that are distinct from those generated from 12-helical foldamers. The foldamer packing motif was revealed by powder X-ray diffraction technique, and provides an important link between the molecular-level symmetry and the microscale morphologies. The utility of foldectures with hollow interiors as robust and well-defined supramolecular hosts was demonstrated for inorganic, organic, and even protein guests. This work will pave the way for the design of functional foldectures with greater 3D shape diversity and for the development of biocompatible delivery vehicles and containment vessels., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Microbial microencapsulation not only protects microorganisms from harmful environments by physically isolating them from the outside media but also has the potential to tailor the release profile of the encapsulated cells. However, the microbial release has not yet been controlled tightly, leading to undesired detrimental exposure of microorganisms to the outside. In this work, we suggest a simple method for controlling the cell release by suppressing the microbial growth in the microbeads. Alginate microbeads, encapsulating yeast cells, were coated with ultrathin but robust polydopamine shells, and the resulting core/shell structures effectively reduced the growth rate, while maintaining the cell viability., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Bioreducible carboxymethyl dextran (CMD) derivatives are synthesized by the chemical modification of CMD with lithocholic acid (LCA) through a disulfide linkage. The hydrophobic nature of LCA allows the conjugates (CMD-SS-LCAs) to form self-assembled nanoparticles in aqueous conditions. Depending on the degree of LCA substitution, the particle diameters range from 163 to 242 nm. Doxorubicin (DOX), chosen as a model anticancer drug, is effectively encapsulated into the nanoparticles with high loading efficiency (>70%). In vitro optical imaging tests reveal that the fluorescence signal of DOX quenched in the bioreducible nanoparticles is highly recovered in the presence of glutathione (GSH), a tripeptide capable of reducing disulfide bonds in the intracellular compartments. Bioreducible nanoparticles rapidly release DOX when they are incubated with 10 mm GSH, whereas the drug release is greatly retarded in physiological buffer (pH 7.4). DOX-loaded bioreducible nanoparticles exhibit higher toxicity to SCC7 cancer cells than DOX-loaded nanoparticles without the disulfide bond. Confocal laser scanning microscopy observation demonstrate that bioreducible nanoparticles can effectively deliver DOX into the nuclei of SCC7 cells. In vivo biodistribution study indicates that Cy5.5-labeled CMD-SS-LCAs selectively accumulate at tumor sites after systemic administration into tumor-bearing mice. Notably, DOX-loaded bioreducible nanoparticles exhibit higher antitumor efficacy than reduction-insensitive control nanoparticles. Overall, it is evident that bioreducible CMD-SS-LCA nanoparticles are useful as a drug carrier for cancer therapy., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The lithiation/de-lithiation behavior of a ternary oxide (Li2MO3, where M = Mo or Ru) is examined. In the first lithiation, the metal oxide (MO2) component in Li2MO3 is lithiated by a conversion reaction to generate nano-sized metal (M) particles and two equivalents of Li2O. As a result, one idling Li2O equivalent is generated from Li2MO3. In the de-lithiation period, three equivalents of Li2O react with M to generate MO3. The first-cycle Coulombic efficiency is theoretically 150% since the initial Li2MO3 takes four Li(+) ions and four electrons per formula unit, whereas the M component is oxidized to MO3 by releasing six Li(+) ions and six electrons. In practice, the first-cycle Coulombic efficiency is less than 150% owing to an irreversible charge consumption for electrolyte decomposition. The as-generated MO3 is lithiated/de-lithiated from the second cycle with excellent cycle performance and rate capability., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nanoporous Pt hollow nanostructures with octahedral and hexagonal frame-like morphologies were prepared by a novel one-pot self-templating route with no assistance from a preformed template or shape-directing agent. The hexagonal frame-like Pt hollow structures exhibited significantly enhanced catalytic activity toward CO oxidation reaction compared to the octahedral Pt hollow nanostructures due to the higher oxidation state of Pt., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Mesoporous CuO particles threaded with carbon nanotubes are suggested as a novel class of nanocomposite material for a high-performance anode in the lithium-ion batteries. The nanocomposite electrode exhibits a highly reversible capacity (650 mA h g(-1) at 0.1 C rate) and an excellent C rate capability (580 mA h g(-1) at 5 C, and 500 mA h g(-1) at 10 C)., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Recently, substantial attention has been focused on the association between obesity and chronic inflammation. The aim of the present study was to investigate whether high-fat diet (HFD)-induced obesity induces the activation of the IL-1 type I receptor (IL-1RI)-mediated inflammatory signaling cascade in the skeletal muscle of mice. Male C57BL/6J mice were fed either an HFD or a normal diet (ND) for 12 wk. Compared with the results in mice receiving the ND, the HFD increased the expression of IL-1RI and downstream signaling proteins, such as myeloid differentiation primary response gene 88 (MyD88), IL-1R-associated kinase 4 and phospho-transforming growth factor-activated kinase 1 in the skeletal muscle. Additionally, activities of both inhibitor of kappaB kinase beta and inhibitor of kappaB degradation were significantly elevated in the skeletal muscle of mice fed with an HFD compared with mice receiving an ND. In contrast, the levels of other downstream transcription factors, such as activator protein-1 and INF regulatory factor 5, were not affected by the HFD. These results suggest that the IL-1RI-MyD88-nuclear factor kappaB signaling pathway might be involved in the induction of the inflammatory response in the skeletal muscle of mice fed with an HFD.

A nanolithographic approach based on hierarchical peptide self-assembly is presented. An aromatic peptide of N-(t-Boc)-terminated triphenylalanine is designed from a structural motif for the beta-amyloid associated with Alzheimer's disease. This peptide adopts a turnlike conformation with three phenyl rings oriented outward, which mediate intermolecular pi-pi stacking interactions and eventually facilitate highly crystalline bionanosphere assembly with both thermal and chemical stability. The self-assembled bionanospheres spontaneously pack into a hexagonal monolayer at the evaporating solvent edge, constituting evaporation-induced hierarchical self-assembly. Metal nanoparticle arrays or embossed Si nanoposts could be successfully created from the hexagonal bionanosphere array masks in conjunction with a conventional metal-evaporation or etching process. Our approach represents a bionanofabrication concept that biomolecular self-assembly is hierarchically directed to establish a straightforward nanolithography compatible with conventional device-fabrication processes.

A novel series of boronated porphyrins for potential use in boron neutron capture therapy (BNCT) and photodynamic therapy (PDT) for tumor suppression is described. Protoporphyrin IX {i.e., bis(alpha-methyl-beta-pentylethylether)protoporphyrin IX, and bis(alpha-methyl-beta-dodecanylethylether)protoporphyrin IX} bearing polyhedral borane anions (B(12)H(11)SH(2-), B(12)H(11)NH(3) (-), or B(12)H(11)OH(2-)) were synthesized with reasonable yields. Modification of the protoporphyrin IX structure was achieved by variation of the lengths of the alkyl chains (pentyl and dodecanyl) attached through ether linkages to the former vinyl groups. The goal of this modification was to develop boronated porphyrins with chemical and physical properties that differed from those of protoporphyrin IX. Performance of an MTT assay with each derivative revealed that the synthesized boronated porphyrins showed low cytotoxicities in a variety of cancer cells. Of these compounds, B(12)H(11)NH(2) (2-)-conjugated porphyrin induced a significant increase in the level of boron accumulation and PDT efficacy against HeLa cells.