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Biochemistry and a large part of atmospheric chemistry occur in aqueous environments or at aqueous interfaces, where (photo)chemical reaction rates can be increased by up to several orders of magnitude. The key to understanding the chemistry and photoresponse of molecules in and "on" water lies in their valence electronic structure, with a sensitive probe being photoelectron spectroscopy. This work reports velocity-map photoelectron imaging of submicrometer-sized aqueous phenol droplets in the valence region after nonresonant (288 nm) and resonance-enhanced (274 nm) two-photon ionization with femtosecond ultraviolet light, complementing previous liquid microjet studies. For nonresonant photoionization, our concentration-dependent study reveals a systematic decrease in the vertical binding energy (VBE) of aqueous phenol from 8.0 ± 0.1 eV at low concentration (0.01 M) to 7.6 ± 0.1 eV at high concentration (0.8 M). We attribute this shift to a systematic lowering of the energy of the lowest cationic state with increasing concentration caused by the phenol dimer and aggregate formation at the droplet surface. Contrary to nonresonant photoionization, no significant concentration dependence of the VBE was observed for resonance-enhanced photoionization. We explain the concentration-independent VBE of ∼8.1 eV observed upon resonant ionization by ultrafast intermediate state relaxation and changes in the accessible Franck-Condon region as a consequence of the lowering of the intermediate state potential energy due to the formation of phenol excimers and excited phenol aggregates. Correcting for the influence of electron transport scattering in the droplets reduced the measured VBEs by 0.1-0.2 eV.

Macroporous polymers have gained significant attention due to their unique mass transport and size-selective properties. In this study, we focused on Polyimide (PI), a high-performance polymer, as an ideal candidate for macroporous structures. Despite various attempts to create macroporous PI (Macro PI) using emulsion templates, challenges remained, including limited chemical diversity and poor control over pore size and porosity. To address these issues, we systematically investigated the role of poly(amic acid) salt (PAAS) polymers as macrosurfactants and matrices. By designing 12 different PAAS polymers with diverse chemical structures, we achieved stable high internal phase emulsions (HIPEs) with >80 vol % internal volume. The resulting Macro PIs exhibited exceptional porosity (>99 vol %) after thermal imidization. We explored the structure-property relationships of these Macro PIs, emphasizing the importance of controlling pore size distribution. Furthermore, our study demonstrated the utility of these Macro PIs as separators in Li-metal batteries, providing stable charging-discharging cycles. Our findings not only enhance the understanding of emulsion-based macroporous polymers but also pave the way for their applications in advanced energy storage systems and beyond., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Evaluation of the insulating properties of polymers, such as the dielectric constant and dissipation factor, is crucial in electronic devices, including field-effect transistors and wireless communication applications. This study applies density functional theory (DFT) to predict the dielectric constant of soluble polyimides (SPIs). Various SPIs containing trifluoromethyl groups in the backbone with different pendant types, numbers, and symmetries are successfully synthesized, and their dielectric constants are evaluated and compared with the DFT-estimated values. Two types of DFT-optimized SPIs, single-chain and stacked-chain models, are used to describe the local geometries of the SPIs. In addition, to reveal the relationship between the molecular structure and dielectric constant, further investigations are conducted by considering the dielectric constant of composing ionic and electronic components. The DFT-estimated static dielectric constant of the single-chain model accurately reproduces the corresponding experimental value with at least 80% accuracy. Our approach provides a rational and accelerated strategy to evaluate polymer insulators for electronic devices based on cost-effective DFT calculations.

Here, we present the synthesis and characterization of a novel 2D crystalline framework, named C 2 O , which mainly consists of carbon and oxygen in a 2:1 molar ratio and features crown ether holes in its skeletal structure. The covalent-frameworked 2D crown ether can be synthesized on a gram-scale and exhibits fine chemical stability in various environments, including acid, base, and different organic solvents. The C 2 O efficiently activates KI through the strong coordination of K + with crown ether holes in a rigid framework, which enhances the nucleophilicity of I - and significantly improves its catalytic activity for CO 2 fixation with epoxides. The presence of C 2 O with KI results in remarkable increases in CO 2 conversion from 5.7% to 99.9% and from 2.9% to 74.2% for epichlorohydrin and allyl glycidyl ether, respectively. Moreover, C 2 O possesses both electrophilic and nucleophilic sites at the edge of its framework, allowing for the customization of physicochemical properties by a diverse range of chemical modifications. Specifically, incorporating allyl glycidyl ether (AGE) as an electrophile or ethoxyethylamine (EEA) as a nucleophile into C 2 O enables the synthesis of C 2 O-AGE or C 2 O-EEA , respectively. These modified frameworks exhibit improved conversions of 97.2% and 99.9% for CO 2 fixation with allyl glycidyl ether, outperforming unmodified C 2 O showing a conversion of 74.2%. This newly developed scalable, durable, and customizable covalent framework holds tremendous potential for the design and preparation of outstanding materials with versatile functionalities, rendering them highly attractive for a wide range of applications.

Electrolyte-gated transistors (EGTs) are promising candidates as artificial synapses owing to their precise conductance controllability, quick response times, and especially their low operating voltages resulting from ion-assisted signal transmission. However, it is still vague how ion-related physiochemical elements and working mechanisms impact synaptic performance. Here, to address the unclear correlations, we suggest a methodical approach based on electrochemical analysis using poly(ethylene oxide) EGTs with three alkali ions: Li + , Na + , and K + . Cyclic voltammetry is employed to identify the kind of electrochemical reactions taking place at the channel/electrolyte interface, which determines the nonvolatile memory functionality of the EGTs. Additionally, using electrochemical impedance spectroscopy and qualitative analysis of electrolytes, we confirm that the intrinsic properties of electrolytes (such as crystallinity, solubility, and ion conductivity) and ion dynamics ultimately define the linearity/symmetricity of conductance modulation. Through simple but systematic electrochemical analysis, these results offer useful insights for the selection of components for high-performing artificial synapses.

The prompt visual response is considered to be a highly intuitive tenet among sensors. Therefore, plasmomechanical strain sensors, which exhibit dynamic structural color changes, have recently been developed by using mechanical stimulus-based elastomeric substrates for wearable sensors. However, the reported plasmomechanical strain sensors either lack directional sensitivity or require complex signal processing and device design strategies to ensure anisotropic optical responses. To the best of our knowledge, there have been no reports on utilizing anisotropic mechanical substrates to obtain directional optical responses. Herein, we propose an anisotropic plasmomechanical sensor to distinguish between the applied force direction and the force magnitude. We employ a simple strain-engineered topological elastomer to mechanically transform closely packed metallic nanoparticles (NPs) into anisotropic directional rearrangements depending on the applied force direction. The proposed structure consists of a heterogeneous-modulus elastomer that exhibits a highly direction-dependent Poisson effect owing to the periodically line-patterned local strain redistribution occurring due to the same magnitude of applied external force. Consequently, the reorientation of the self-assembled gold (Au)-NP array manifests dual anisotropy, i.e., force- and polarization-direction-dependent plasmonic coupling. The cost-effectiveness and simple design of our proposed heterogeneous-modulus platform pave the way for numerous optical applications based on dynamic transformation and topological inhomogeneities.

Obesity is a well-established risk factor for cancer, significantly impacting both cancer incidence and mortality. However, the intricate molecular mechanisms connecting adipose tissue to cancer cell metabolism are not fully understood. This Review explores the historical context of tumor energy metabolism research, tracing its origins to Otto Warburg's pioneering work in 1920. Warburg's discovery of the "Warburg effect", wherein cancer cells prefer anaerobic glycolysis even in the presence of oxygen, laid the foundation for understanding cancer metabolism. Building upon this foundation, the "reverse Warburg effect" emerged in 2009, elucidating the role of aerobic glycolysis in cancer-associated fibroblasts (CAFs) and its contribution to lactate accumulation in the tumor microenvironment, subsequently serving as a metabolic substrate for cancer cells. In contrast, within high-adiposity contexts, cancer cells exhibit a unique metabolic shift termed the "inversion of the Warburg effect". This phenomenon, distinct from the stromal-dependent reverse Warburg effect, relies on increased nutrient abundance in obesity environments, leading to the generation of glucose from lactate as a metabolic substrate. This Review underscores the heightened tumor proliferation and aggressiveness associated with obesity, introducing the "inversion of the Warburg effect" as a novel mechanism rooted in the altered metabolic landscape within an obese milieu. The insights presented here open promising avenues for therapeutic exploration, offering fresh perspectives and opportunities for the development of innovative cancer treatment strategies., Competing Interests: The authors declare no competing financial interest., (© 2024 American Chemical Society.)

Multivalued logic (MVL) technology is a promising solution for improving data density and reducing power consumption in comparison to complementary metal-oxide-semiconductor (CMOS) technology. Currently, heterojunction transistors (TRs) with negative differential transconductance (NDT) characteristics, which play an important role in the function of MVL circuits, adopt organic or 2D semiconductors as active layers, but it is still difficult to apply conventional CMOS processes. Herein, we demonstrate an oxide semiconductor (OS) heterojunction TR with NDT characteristics composed of p-type copper(I) oxide (Cu 2 O) and n-type indium gallium zinc oxide (IGZO) using the conventional CMOS manufacturing processes. The electrical characteristics of the fabricated device exhibit a high I on / I off ratio (∼3 × 10 3 ), wide NDT ranges (∼29 V), and high peak-to-valley current ratios (PVCR ≈ 25). The electrical properties of 15 devices were measured, confirming uniform performance in the PVCR, NDT range, and I on / I off ratio. We analyze the device operation by varying the source/drain (S/D) position and changing the device geometry and the thickness of the Cu 2 O layer. Additionally, we demonstrate heterojunction ambipolar TR to elucidate the transport mechanism of NDT devices at a high gate voltage ( V GS ). To confirm the feasibility of the MVL circuit, we present a ternary inverter with three clearly expressed logic states that have a long intermediate state and greater margin of error induced by wide NDT regions and high PVCR.

The commercialization of lithium-sulfur (Li-S) batteries has been hampered by diverse challenges, including the shuttle phenomenon and low electrical/ionic conductivity of lithium sulfide and sulfur. To address these issues, extensive research has been devoted to developing multifunctional interlayers. However, interlayers capable of simultaneously suppressing the polysulfide (PS) shuttle and ensuring stable electrical and ionic conductivity are relatively uncommon. Moreover, the use of thick and heavy interlayers results in an unavoidable decline in the energy density of Li-S batteries. We developed an ultrathin (750 nm), lightweight (0.182 mg cm -2 ) interlayer that facilitates mixed ionic-electronic conduction using the solution shearing technique. The interlayer, composed of carbon nanotube (CNT)/Nafion/poly-3,4-ethylenedioxythiophene:tetracyanoborate (PEDOT:TCB), effectively suppresses the shuttle phenomenon through the synergistic segregation and adsorption effects on PSs by Nafion and CNT/PEDOT, respectively. Furthermore, the electrical/ionic conductivity of the interlayer can be improved via counterion exchange and homogeneous Li + ion flux/good wettability from SO 3 - functional group of Nafion, respectively. Enhanced sulfur utilization and reaction kinetics through polysulfide shuttle inhibition and facilitated electron/ion transfer by interlayer enable a high discharge capacity of 1029 mA h g -1 in the Li-S pouch cell under a high sulfur loading of 5.3 mg cm -2 and low electrolyte/sulfur ratio of 5 μL mg -1 .

In live cells, the plasma membrane is composed of lipid domains separated by hundreds of nanometers in dynamic equilibrium. Lipid phase separation regulates the trafficking and spatiotemporal organization of membrane molecules that promote signal transduction. However, visualizing domains with adequate spatiotemporal accuracy remains challenging because of their subdiffraction limit size and highly dynamic properties. Here, we present a single lipid-molecular motion analysis pipeline (lipid-MAP) for analyzing the phase heterogeneity of lipid membranes by detecting the instantaneous velocity change of a single lipid molecule using the excellent optical properties of nanoparticles, high spatial localization accuracy of single-molecule localization microscopy, and separation capability of the diffusion state of the hidden Markov model algorithm. Using lipid-MAP, individual lipid molecules were found to be in dynamic equilibrium between two statistically distinguishable phases, leading to the formation of small (∼170 nm), viscous (2.5× more viscous than surrounding areas), and transient domains in live cells. Moreover, our findings provide an understanding of how membrane compositional changes, i.e., cholesterol and phospholipids, affect domain formation. This imaging method can contribute to an improved understanding of spatiotemporal-controlled membrane dynamics at the molecular level.

In the present study, we fabricated hollow cubic Cu x O nanoparticles (∼23 nm) incorporated with CNF (HC-Cu x O/CNF) through controlled thermal oxidation of solid cubic Cu 2 O nanoparticles (∼21 nm) supported on carbon nanofibers (SC-Cu 2 O/CNF) under airflow, exploiting the nanoscale Kirkendall effect. These hollow Cu x O nanocubes with increased surface areas exhibited outstanding catalytic activity for unsymmetrical chalcogenide synthesis under ligand-free conditions.

Here, we proposed an eco-friendly synthetic method for synthesizing hybrid composites with ultralow dielectric properties at high frequencies up to 28 GHz for true 5G communication from aqueous aromatic polyimide (PI) polymers and dual-porous silica nanoparticles (DPS). The "one-step" water-based emulsion template method was used to synthesize the macroporous silica nanoparticles (MPS). A substantially negative ζ potential was produced along the surface of MPS by the poly(vinylpyrrolidone)-based chemical functionalization, enabling excellent aqueous dispersion stability. The water-soluble poly(amic acid) (PAA), as a precursor to PI, was also "one-step" polymerized in an aqueous solution. The MPS were dispersed in a water-soluble PAA matrix to create the hybrid composite films using an entirely water-based approach. The compatibility between the PAA matrix and MPS was elucidated by investigating relatively diverse end-terminated PAAs (with either amine or carboxyl group). It was also discovered that, during a thermally activated imidization reaction, the MPS are in situ converted into the DPS with macro- and microporous structures (with a surface area of 1522.4 m 2 /g). The thermal, dielectric, mechanical, and morphological characteristics of each composite film were examined, while the amount of DPS in the PI matrix varied from 1 to 20 wt %. With the addition of 5 wt % DPS as an optimum condition, it showed ultralow dielectric properties, with the D k and D f being 1.615 and 0.003 at a frequency of 28 GHz, respectively, and compatible mechanical properties, with the tensile strength and elastic modulus being 78.2 MPa and 0.32 GPa, respectively. These results can comprehensively satisfy various physical properties required as a substrate material for 5G communication devices.

Conventional two-dimensional materials either have natural layered structures or are produced, with large surface areas, via physical or chemical synthesis. However, to form a two-dimensional material from a non-layered material, a method different from the existing ones is required. In this study, a surfactant-assisted method was utilized to synthesize Zn(OH) 2 (a nonlayered transition metal oxide) nanosheets. This study described the synthesis of Zn(OH) 2 nanosheets using an anionic sulfate layer and demonstrated a method of controlling the thickness and shape of the synthesized nanosheets by varying the surfactant concentration. Further, the characteristics of oxygen evolution reaction using ZnO/Zn(OH) 2 nanosheets, obtained by annealing the synthesized sheets, as catalysts were studied., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Mass-correlated rotational alignment spectroscopy resolved the rotational Raman spectra for 5 benzene isotopologues with unprecedented resolution. 13-C isotopologues were characterized at natural abundance. Fitted rotational constants allowed the analysis of effective and equilibrium bond lengths for benzene with sub-mÅ uncertainties. We found that previously reported experimental structures were wrong by multiple mÅ, due to unrecognized H/D isotope effects. Our results also refute recent experimental and theoretical literature claims of identical effective C-H and C-D bond lengths in benzene and reveal an isotope effect similar to that in other small molecules.

γ-Aminobutyrate (GABA) is an important chemical by itself and can be further used for the production of monomer used for the synthesis of biodegradable polyamides. Until now, GABA production using Corynebacterium glutamicum harboring glutamate decarboxylases (GADs) has been limited due to the discrepancy between optimal pH for GAD activity (pH 4.0) and cell growth (pH 7.0). In this study, we developed recombinant C. glutamicum strains expressing mutated GAD from Escherichia coli (EcGADmut) and GADs from Lactococcus lactis CICC20209 (LlGAD) and Lactobacillus senmaizukei (LsGAD), all of which showed enhanced pH stability and adaptability at a pH of approximately 7.0. In shake flask cultivations, the GABA productions of C. glutamicum H36EcGADmut, C. glutamicum H36LsGAD, and C. glutamicum H36LlGAD were examined at pH 5.0, 6.0, and 7.0, respectively. Finally, C. glutamicum H36EcGADmut (40.3 and 39.3 g L -1 ), H36LlGAD (42.5 and 41.1 g L -1 ), and H36LsGAD (41.6 and 40.2 g L -1 ) produced improved GABA titers and yields in batch fermentation at pH 6.0 and pH 7.0, respectively, from 100 g L -1 glucose. The recombinant strains developed in this study could be used for the establishment of sustainable direct fermentative GABA production from renewable resources under mild culture conditions, thus increasing the availability of various GADs., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

SiO x ( x ≈ 1) is one of the most promising anode materials for application in secondary lithium-ion batteries because of its high theoretical capacity. Despite this merit, SiO x has a poor initial Coulombic efficiency, which impedes its widespread use. To overcome this limitation, in this work, we successfully demonstrate a novel synthesis of Mg-doped SiO x via a mass-producible physical vapor deposition method. The solid-state reaction between Mg and SiO x produces Si and electrochemically inert magnesium silicate, thus increasing the initial Coulombic efficiency. The Mg doping concentration determines the phase of the magnesium silicate domains, the size of the Si domains, and the heterogeneity of these two domains. Detailed electron microscopy and synchrotron-based analysis revealed that the nanoscale homogeneity of magnesium silicates driven by cycling significantly affected the lifetime. We found that 8 wt % Mg is the most optimized concentration for enhanced cyclability because MgSiO 3 , which is the dominant magnesium silicate composition, can be homogeneously mixed with silicon clusters, preventing their aggregation during cycling and suppressing void formation.

Intercalation in black phosphorus (BP) can induce and modulate a variety of the properties including superconductivity like other two-dimensional (2D) materials. In this perspective, spatially controlled intercalation has the possibility to incorporate different properties into a single crystal of BP. We demonstrate anisotropic angstrom-wide (∼4.3 Å) Cu intercalation in BP, where Cu atoms are intercalated along a zigzag direction of BP because of its inherent anisotropy. With atomic structure, its microstructural effects, arising from the angstrom-wide Cu intercalation, were investigated and extended to relation with macrostructure. As the intercalation mechanism, it was revealed by in situ transmission electron microscopy and theoretical calculation that Cu atoms are intercalated through top-down direction of BP. The Cu intercalation anisotropically induces transition of angstrom-wide electronic channels from semiconductor to semimetal in BP. Our findings throw light on the fundamental relationship between microstructure changes and properties in intercalated BP, and tailoring anisotropic 2D materials at angstrom scale.

The increasing demand for solution-processed and flexible organic electronics has promoted the fabrication of integrated logic circuits using organic field-effect transistors (OFETs) instead of fundamental unit devices. This has been made possible through the rapid development of materials and processes in the past few decades. It is important for the p- and n-type OFETs using different organic semiconductors (OSCs) to have complementarily matched electrical characteristics, which significantly improve the performance of organic logic circuits. In this study, an efficient strategy to optimize the performance of flexible organic electronics, such as OFETs and complementary inverters, is proposed using a combination of polymer insulators tailored to each OSC type. Photopatternable soluble copolyimides (S co PIs), which exhibit excellent insulating properties and chemical resistance, are synthesized and applied as gate dielectric layers in the OFETs. The material and electrical properties are systematically investigated by varying the molecular ratio of S co PIs to determine the optimal conditions for each OFET type. As a result, complementary inverters report 1.67 times higher integration density compared to the conventional ones while maintaining gain, switching threshold, and static noise margin of 23.7 V/V, 22.1 V, and 12.1 V, respectively, at a supply voltage of 40 V. The flexible complementary inverters are successfully demonstrated by fully exploiting the advantages of S co PIs.

Monolayer transition metal dichalcogenides (TMDs) are promising for optoelectronics because of their high optical quantum yield and strong light-matter interaction. In particular, the van der Waals (vdW) heterostructures consisting of monolayer TMDs sandwiched by large gap hexagonal boron nitride have shown great potential for novel optoelectronic devices. However, a complicated stacking process limits scalability and practical applications. Furthermore, even though lots of efforts, such as fabrication of vdW heterointerfaces, modification of the surface, and structural phase transition, have been devoted to preserve or modulate the properties of TMDs, high environmental sensitivity and damage-prone characteristics of TMDs make it difficult to achieve a controllable technique for surface/interface engineering. Here, we demonstrate a novel way to fabricate multiple two-dimensional (2D) vdW heterostructures consisting of alternately stacked MoS 2 and MoO x with enhanced photoluminescence (PL). We directly oxidized multilayer MoS 2 to a MoO x /1 L-MoS 2 heterostructure with atomic layer precision through a customized oxygen plasma system. The monolayer MoS 2 covered by MoO x showed an enhanced PL intensity 3.2 and 6.5 times higher in average than the as-exfoliated 1 L- and 2 L-MoS 2 because of preserved crystallinity and compensated dedoping by MoO x . By using layer-by-layer oxidation and transfer processes, we fabricated the heterostructures of MoO x /MoS 2 /MoO x /MoS 2 , where the MoS 2 monolayers are separated by MoO x . The heterostructures showed the multiplied PL intensity as the number of embedded MoS 2 layers increases because of suppression of the nonradiative trion formation and interlayer decoupling between stacked MoS 2 layers. Our work shows a novel way toward the fabrication of 2D material-based multiple vdW heterostructures and our layer-by-layer oxidation process is beneficial for the fabrication of high performance 2D optoelectronic devices.

In general, lignin exhibits unpredictable and nonuniform thermal properties due to the structural variations caused by the extraction processes. Therefore, a systematic understanding of the correlation between the extraction conditions, structural characteristics, and properties is indispensable for the commercial utilization of lignin. In this study, the effect of extraction conditions on the structural characteristics of ethanol organosolv lignin (EOL) was investigated by response surface methodology. The structural characteristics of EOL (molecular weight, hydroxyl content, and intramolecular coupling structure) were significantly affected by the extraction conditions (temperature, sulfuric acid concentration, and ethanol concentration). In addition, the correlation between the structural characteristics and thermal properties of the extracted EOLs was estimated. The relevant correlations between the structural characteristics and thermal properties were determined. In particular, EOLs that had a low molecular weight, high phenolic hydroxyl content, and low aryl-ether linkage content exhibited prominent thermal properties in terms of their initial decomposition rate and a high glass transition temperature, T g . Correspondingly, EOL-PLA blends prepared using three EOL types exhibited improved thermal properties (starting point of thermal decomposition and maximum decomposition temperature) compared to neat PLA and had thermal decomposition behaviors coincident with the thermal properties of the constituent EOLs., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Visualizing the oxygen vacancy distributions is highly desirable for understanding the atomistic oxygen diffusion mechanisms in perovskites. In particular, the direct observation of the one-dimensional oxygen vacancy channels has not yet been achieved in perovskites with dual ion (i.e., cation and anion) ordering. Here, we perform atomic-resolution imaging of the one-dimensional oxygen vacancy channels and their structural dynamics in a NdBaCo 2 O 5.5 double perovskite oxide. An in situ heating transmission electron microscopy investigation reveals the disordering of oxygen vacancy channels by local rearrangement of oxygen vacancies at the specific temperature. A density functional theory calculation suggests that the possible pathway of oxygen vacancy migration is a multistep route via Co-O and Nd-O v (oxygen vacancy) sites. These findings could provide robust guidance for understanding the static and dynamic behaviors of oxygen vacancies in perovskite oxides.

The work presented in this report demonstrates that amphiphilic polysaccharide-clasped self-assembly (Amp-SA) with nanometer size, encapsulating hydrophobic nanoparticles (NPs) can be generated via electrohydrodynamic spraying. It is observed that the formation of hydrophobic NP-encapsulated Amp-SA is dependent on the surface chemistry of NPs. The citrate-coated magnetic NPs (MNPs-Cit) were also prepared and compared. The hydrophobic magnetic NP-encapsulated Amp-SA (Amp-SA-M) exhibited around 2.7-2.8-fold higher values in r 2 relaxivity than that of MNPs-Cit. In addition, the resulting Amp-SA-M achieved ∼17.2-fold higher values in r 2 / r 1 ratios than MNPs-Cit. The enhanced performances in magnetic transverse ( r 2 ) relaxivity and r 2 / r 1 ratio as well as the in vivo behavior of Amp-SA-M suggest the potential of Amp-SA-M as a promising MRI nanoprobe. This approach based on the nature-originated amphiphilic biopolymers may provide a novel insight into electrohydrodynamic techniques that have the ability to create various nanostructures, encapsulating high-quality hydrophobic nanomaterials for applications in diverse biotechnology.

An unsaturated polymer's cis / trans -olefin content has a significant influence on its properties. For polymers obtained by ring-opening metathesis polymerization (ROMP), the cis / trans -olefin content can be tuned by using specific catalysts. However, cis -selective ROMP has suffered from narrow monomer scope and lack of control over the polymerization (giving polymers with broad molecular weight distributions and prohibiting the synthesis of block copolymers). Herein, we report the versatile cis -selective controlled living ROMP of various endo -tricyclo[4.2.2.0 2,5 ]deca-3,9-diene and various norbornene derivatives using a fast-initiating dithiolate-chelated Ru catalyst. Polymers with cis -olefin content as high as 99% could be obtained with high molecular weight (up to M n of 105.1 kDa) and narrow dispersity (<1.4). The living nature of the polymerization was also exploited to prepare block copolymers with high cis -olefin content for the first time. Furthermore, owing to the successful control over the stereochemistry and narrow dispersity, we could compare cis - and trans -rich polynorbornene and found the former to have enhanced resistance to shear degradation.

A bioinspired three-dimensional (3D) fibrous structure possesses biomimicry, valuable functionality, and performance to scaffolding in tissue engineering. In particular, an electrospun fibrous mesh has been studied as a scaffold material in various tissue regeneration applications. We produced a low-density 3D polycaprolactone/lactic acid (LA) fibrous mesh (3D-PCLS) via the novel lactic-assisted 3D electrospinning technique exploiting the catalytic properties of LA as we reported previously. In the study, we demonstrated a strategy of recycling the LA component to synthesize the osteoinductive biomolecules in situ, calcium lactate (CaL), thereby forming a 3D bioactive PCL/CaL fibrous scaffold (3D-SCaL) for bone tissue engineering. The fiber morphology of 3D-PCLS and its packing degree could have been tailored by modifying the spinning solution and the collector design. 3D-SCaL demonstrated successful conversion of CaL from LA and exhibited the significantly enhanced biomineralization capacity, cell infiltration and proliferation rate, and osteoblastic differentiation in vitro with two different cell lines, MC3T3-e1 and bone marrow stem cells. In conclusion, 3D-SCaL proves to be a highly practical and accessible strategy using a variety of polymers to produce 3D fibers as a potential candidate for future regenerative medicine and tissue engineering applications.

In optoelectronic devices based on two-dimensional (2D) semiconductor heterojunctions, the efficient charge transport of photogenerated carriers across the interface is a critical factor to determine the device performances. Here, we report an unexplored approach to boost the optoelectronic device performances of the WSe 2 -MoS 2 p - n heterojunctions via the monolithic-oxidation-induced doping and resultant modulation of the interface band alignment. In the proposed device, the atomically thin WO x layer, which is directly formed by layer-by-layer oxidation of WSe 2 , is used as a charge transport layer for promoting hole extraction. The use of the ultrathin oxide layer significantly enhanced the photoresponsivity of the WSe 2 -MoS 2 p - n junction devices, and the power conversion efficiency increased from 0.7 to 5.0%, maintaining the response time. The enhanced characteristics can be understood by the formation of the low Schottky barrier and favorable interface band alignment, as confirmed by band alignment analyses and first-principle calculations. Our work suggests a new route to achieve interface contact engineering in the heterostructures toward realizing high-performance 2D optoelectronics.

Cascade metathesis and metallotropy (M&M) polymerization, which involves sequential olefin metathesis and metallotropic 1,3-shift reactions specifically from multiyne monomers, is the only method reported so far to prepare conjugated polyenynes via the chain-growth mechanism. Using this method, various conjugated polyenynes containing cyclopentene units in the backbone could be synthesized via exclusive α-addition by using the third-generation Grubbs catalyst. Herein, we demonstrate the complete switch of regioselectivity toward β-addition using a Ru carbene containing a dithiolate ligand, and thus, synthesized unique conjugated polyenynes having alternating cyclohexene and cyclopentene units in the backbone. Furthermore, detailed in situ NMR studies revealed an interesting phenomenon that the adjacent triple bond strongly chelates to the propagating Ru carbene during the polymerization.

Aromatic soluble polyimides (PIs) have been widely used in organic field-effect transistors (OFETs) as gate dielectric layers due to their promising features such as outstanding chemical resistance, thermal stability, low-temperature processability, and mechanical flexibility. However, the molecular structures of soluble PIs on the electrical characteristics of OFETs are not yet fully understood. In this work, the material, dielectric, and electrical properties are evaluated to systematically investigate the chemical structure effect of aromatic dianhydride and diamine monomers on the device performance. Four soluble PIs based on 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 5-(2,5-Dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, in which the monomeric precursors contain different backbones, side groups, and linkages, were employed to compare the chemical structure impact. The dielectric properties, which significantly affect the charge transport and crystallinity of OSC thin films, clearly depended on the soluble PI types as well as the surface energy and the thermal stability. Furthermore, the electrical characteristic measurement and parameter extraction of OFETs based on TIPS-pentacene revealed that the 6FDA-based soluble PIs, which lead to high field-effect mobility, near-zero threshold electric field, and outstanding electrical stability under bias stress, are the most promising gate dielectric candidates. Finally, low-temperature solution-processed OFETs are successfully integrated with ultrathin flexible substrates, and they exhibit no significant electrical performance loss after mechanical flexibility tests. This work presents a step forward in the development of soluble PI gate dielectrics for flexible electronic devices with high device performance.

Polysaccharide-nanoparticle (NP) hybrid nanoclusters have great potential to revitalize diverse bioapplications; however, fabricating polysaccharide-based hybrid nanoclusters composed of high-quality NPs generated in the organic phase remains a challenge. Here, using calcium alginate as a polysaccharide/tetramethylammonium hydroxide (TMAOH) combination, we report a novel approach to the design of alginate-hydrophobic magnetic-plasmonic core-shell (MPCS) NP hybrid nanoclusters (A-MPCS HNCs). Furthermore, we observe the dependence of the formation of A-MPCS HNCs on the TMAOH concentration. The enhanced performance in both magnetic resonance r 2 relaxivity and photoacoustic (PA) signals and the biocompatibility/bioactivity as well as the in vivo performance of A-MPCS HNCs shows them to be a promising magnetic resonance/photoacoustic dual-mode imaging agent. Our strategy could open doors to the use of other precious high-quality nanomaterials created in the organic phase via well-established synthetic chemistry in the design of alginate-hydrophobic nanomaterial hybrid nanoclusters, giving rise to novel and multifarious bioapplications.

Achieving high emission efficiency in solid-state quantum dots (QDs) is an essential requirement for high-performance QD optoelectronics. However, most QD films suffer from insufficient excitation and light extraction efficiencies, along with nonradiative energy transfer between closely adjacent QDs. Herein, we suggest a highly effective strategy to enhance the photoluminescence (PL) of QD composite films through an assembly of QDs and poly(styrene- b -4-vinylpyridine)) (PS- b -P4VP) block copolymer (BCP). A BCP matrix casted under controlled humidity provides multiscale phase-separation features based on (1) submicrometer-scale spinodal decomposition between polymer-rich and water-rich phases and (2) sub-10 nm-scale microphase separation between polymer blocks. The BCP-QD composite containing bicontinuous random pores achieves significant enhancement of both light absorption and extraction efficiencies via effective random light scattering. Moreover, the microphase-separated morphology substantially reduces the Förster resonance energy transfer efficiency from 53% (pure QD film) to 22% (BCP-QD composite), collectively achieving an unprecedented 21-fold enhanced PL over a broad spectral range.

Here, a polymerizable lithium salt, lithium (trifluoromethanesulfonyl)(vinylsulfonyl)imide, was synthesized and used to prepare cross-linked gel polymer electrolyte systems with poly(ethylene glycol) methyl ether methacrylate as an ion-conducting moiety, poly(ethylene glycol) dimethacrylate as a cross-linker, and propylene carbonate as a liquid electrolyte without adding any conventional inorganic lithium salt. The gel polymer electrolytes prepared in this study exhibited a reasonably high ionic conductivity (6.7 × 10 -4 S cm -1 at 25 °C and 1.8 × 10 -3 S cm -1 at 60 °C) and lithium-ion transference number (0.52), and the lithium battery prepared using the gel polymer electrolyte showed a stable cycling performance over 50 cycles.

An array of amorphous tin oxide (a-SnO x ) nanohelixes (NHs) was fabricated on copper foil as an electrode for Na-ion batteries via the oblique angle deposition method, a solution- and surfactant-free process. The combination of the amorphous phase SnO x with a low oxidation number and its vertically aligned NH geometry with a large surface area and high porosity, which facilitate Na-ion dynamics and accommodate the volume changes, enabled a reversible capacity of up to 915 mA h g -1 after 50 cycles, fast rate capability with 48.1% retention at 2 A g -1 , and high stability, which are superior to those of crystalline nanoparticle-based electrodes.

We report a new class of metal-organic framework (MOF) inks with a water-repellent, photocurable fluoropolymer (PFPE) having up to 90 wt % MOF loading. These MOF inks are enabled to process various MOFs through spray coating, pen writing, stencil printing, and molding at room temperature. Upon UV curing, the hydrophobic PFPE matrix efficiently blocks water permeation but allows accessibility of chemicals into the MOF pores, thereby freeing the MOF to perform its unique function. Moreover, by introducing functional MOFs we successfully demonstrated a water-tolerant chemosensor for a class of aromatic pollutants in water and a chemical-resistant thermosensor for visualizing temperature image. This approach would open up innumerable opportunities for those MOFs that are otherwise dormant.

On the basis of a combined experimental and computational study, a novel method for preparing fully conjugated polyenynes via cascade metathesis and metallotropy (M&M) polymerization of various multialkynes is developed. DFT calculations elucidate the detailed mechanism of the metallotropic 1,3-shift, which is a key process of M&M polymerization. An α,β-(C,C,C)-agostic interaction stabilizing the metallacyclobutadiene transition state is found to be critically important for the successful polymerization with excellent specificity. The polymerization efficiency displayed by the tetrayne monomer is controlled by the steric demands of its substituents, and more complex hexayne monomers can be successfully polymerized to give access to highly conjugated polyenynes via a series of intramolecular metathesis and metallotropic shift cascade reactions. Furthermore, living polymerization led to the synthesis of block copolymers consisting of fully conjugated polyenyne backbones. The implementation of pentayne monomers provides polyenynes with successive C-C triple bonds via consecutive metallotropic 1,3-shift. In short, the design of multialkynes enables the preparation of diverse conjugated polyenyne motifs via selective M&M cascade reactions.

Despite the advance of on-skin sensors over the last decade, a sensor that solves simultaneously the critical issues for using in everyday life, such as stable performance in various environments, use over a long period of time, and repeated use by easy handling, has not yet been achieved. Here, we introduce an auxetic hygroscopic sensor that simultaneously meets all of the conditions. The auxetic structure with a negative Poisson's ratio matches with deformation of the skin in ankles; hence, a conformal contact between the sensor and the skin could be maintained during repeated movements. Sweat was absorbed in the auxetic electrode made of a hydrogel pattern coated with Ag nanowires and evaporated quickly; such hygroscopic characteristic led to excellent breathability. An electrocardiogram sensor and a haptic device were fabricated according to the proposed design for a sensor electrode. The sensors provide stable detecting performance in various environments, such as exercising, submersion in water, exposure to concentrated salt water, and continuous wearing for long time (7 days). Also, the sensors could be manually attached repeatedly without degrading the performance. This study provides new structural insights for on-skin sensors and presents future research directions.

Chalcone derivatives have been investigated as therapeutic agents for the anticancer, antioxidant, and anti-inflammatory fields. In this study, we have synthesized four different types of chalcone derivatives and demonstrated in vitro bioactivities. We divided these derivatives into two groups of chalcones on the basis of similar substituents on the aromatic rings, and we tested cell viability and proliferation potentials, which indicated that the methoxy substituent on the A ring could enhance cytotoxicity and antiproliferation potential depending on the chalcone concentration. We also investigated osteogenic differentiation of C2C12 cells by ALP staining, the early marker for osteogenesis, which demonstrated that the chalcones could not only induce activity of BMP-2 but also inhibit the activity of noggin, a BMP antagonist. In addition, chalcone bearing hydroxyl groups at the 2-, 4-, and 6-position on the A ring inhibited treptococcus mutans growth, a major causative agent of dental caries. Therefore, we concluded that the chalcone derivatives synthesized in this research can be good candidates for therapeutic agents promoting bone differentiation, with an expectation of inhibiting S. mutans, in dentistry.

Relaxivity tuning of nanomaterials with the intrinsic T 1 - T 2 dual-contrast ability has great potential for MRI applications. Until now, the relaxivity tuning of T 1 and T 2 dual-modal MRI nanoprobes has been accomplished through the dopant, size, and morphology of the nanoprobes, leaving room for bioapplications. However, a surface engineering method for the relaxivity tuning was seldom reported. Here, we report the novel relaxivity tuning method based on the surface engineering of dual-mode T 1 - T 2 MRI nanoprobes (DMNPs), along with protein interaction monitoring with the DMNPs as a potential biosensor application. Core nanoparticles (NPs) of europium-doped iron oxide (EuIO) are prepared by a thermal decomposition method. As surface materials, citrate (Cit), alendronate (Ale), and poly(maleic anhydride- alt-1-octadecene)/poly(ethylene glycol) (PP) are employed for the relaxivity tuning of the NPs based on surface engineering, resulting in EuIO-Cit, EuIO-Ale, and EuIO-PP, respectively. The key achievement of the current study is that the surface materials of the DMNP have significant impacts on the r 1 and r 2 relaxivities. The correlation between the hydrophobicity of the surface material and longitudinal relaxivity ( r 1 ) of EuIO NPs presents an exponential decay feature. The r 1 relaxivity of EuIO-Cit is 13.2-fold higher than that of EuIO-PP. EuIO can act as T 1 - T 2 dual-modal (EuIO-Cit) or T 2 -dominated MRI contrast agents (EuIO-PP) depending on the surface engineering. The feasibility of using the resulting nanosystem as a sensor for environmental changes, such as albumin interaction, was also explored. The albumin interaction on the DMNP shows both T 1 and T 2 relaxation time changes as mutually confirmative information. The relaxivity tuning approach based on the surface engineering may provide an insightful strategy for bioapplications of DMNPs and give a fresh impetus for the development of novel stimuli-responsive MRI nanoplatforms with T 1 and T 2 dual-modality for various biomedical applications.

Graphene oxide decorated with oxygen functional groups is a promising candidate as an active layer in resistive switching devices due to its controllable physical-chemical properties, high flexibility, and transparency. However, the origin of conductive channels and their growth dynamics remain a major challenge. We use in situ transmission electron microscopy techniques to demonstrate that nanoscale graphene oxide sheets bonded with oxygen dynamically change their physical and chemical structures upon an applied electric field. Artificially engineered bilayer reduced graphene oxide films with asymmetric oxygen content exhibit nonvolatile write-once-read-many memory behaviors without experiencing the bubble destruction due to the efficient migration of oxygen ions. We clearly observe that a conductive graphitic channel with a conical shape evolves from the upper oxygen-rich region to the lower oxygen-poor region. These findings provide fundamental guidance for understanding the oxygen motions of oxygen-containing carbon materials for future carbon-based nanoelectronics.

Here we show a simple and effective cross-linking method to prepare a high performance cross-linked sulfonated poly(arylene ether sulfone) (C-SPAES) membrane using bishydroxy perfluoropolyether (PFPE) as a cross-linker for fuel cell applications. The C-SPAES membrane shows much improved physicochemical stability due to the cross-linked structure and reasonably high proton conductivity compared to the non-cross-linked SPAES membrane due to the incorporation of flexible PFPE and the effective phase-separated morphology between the hydrocarbon and perfluorinated moieties forming well-connected networks. Under intermediate-temperature and low humidity conditions (90 °C, 50% RH, and 150 kPa), the membrane electrode assembly employing the C-SPAES membrane reveals an outstanding cell performance (1.17 W cm -2 at 0.65 V) ascribed to its reasonably high proton conductivity and enhanced interfacial compatibility between the perfluorinated moieties in the electrode and C-SPAES membrane. Furthermore, a hydration-dehydration cycling test result at 90 °C reveals that the C-SPAES membrane has notable durability against rigorous operating conditions.

As interest in electric vehicles and mass energy storage systems continues to grow, Li-O 2 batteries are attracting much attention as a candidate for next-generation energy storage systems owing to their high energy density. However, safety problems related to the use of lithium metal anodes have hampered the commercialization of Li-O 2 batteries. Herein, we introduced a quasi-solid polymer electrolyte with excellent electrochemical, chemical, and thermal stabilities into Li-O 2 batteries. The ion-conducting QSPE was prepared by gelling a polymer network matrix consisting of poly(ethylene glycol) methyl ether methacrylate, methacrylated tannic acid, lithium trifluoromethanesulfonate, and nanofumed silica with a small amount of liquid electrolyte. The quasi-solid-state Li-O 2 cell consisted of a lithium powder anode, a quasi-solid polymer electrolyte, and a Pd 3 Co/multiwalled carbon nanotube cathode, which enhanced the electrochemical performance of the cell. This cell, which exhibited improved safety owing to the suppression of lithium dendrite growth, achieved a lifetime of 125 cycles at room temperature. These results show that the introduction of a quasi-solid electrolyte is a potentially new alternative for the commercialization of solid-state Li-O 2 batteries.

Development of localized inflammatory environments by M1 macrophages in the cardiac infarction region exacerbates heart failure after myocardial infarction (MI). Therefore, the regulation of inflammation by M1 macrophages and their timely polarization toward regenerative M2 macrophages suggest an immunotherapy. Particularly, controlling cellular generation of reactive oxygen species (ROS), which cause M1 differentiation, and developing M2 macrophage phenotypes in macrophages propose a therapeutic approach. Previously, stem or dendritic cells were used in MI for their anti-inflammatory and cardioprotective potentials and showed inflammation modulation and M2 macrophage progression for cardiac repair. However, cell-based therapeutics are limited due to invasive cell isolation, time-consuming cell expansion, labor-intensive and costly ex vivo cell manipulation, and low grafting efficiency. Here, we report that graphene oxide (GO) can serve as an antioxidant and attenuate inflammation and inflammatory polarization of macrophages via reduction in intracellular ROS. In addition, GO functions as a carrier for interleukin-4 plasmid DNA (IL-4 pDNA) that propagates M2 macrophages. We synthesized a macrophage-targeting/polarizing GO complex (MGC) and demonstrated that MGC decreased ROS in immune-stimulated macrophages. Furthermore, DNA-functionalized MGC (MGC/IL-4 pDNA) polarized M1 to M2 macrophages and enhanced the secretion of cardiac repair-favorable cytokines. Accordingly, injection of MGC/IL-4 pDNA into mouse MI models attenuated inflammation, elicited early polarization toward M2 macrophages, mitigated fibrosis, and improved heart function. Taken together, the present study highlights a biological application of GO in timely modulation of the immune environment in MI for cardiac repair. Current therapy using off-the-shelf material GO may overcome the shortcomings of cell therapies for MI.

Na-ion batteries are attractive as an alternative to Li-ion batteries because of their lower cost. Organic compounds have been considered as promising electrode materials due to their environmental friendliness and molecular diversity. Herein, aluminum-coordinated poly(tetrahydroxybenzoquinone) (P(THBQ-Al)), one of the coordination polymers, is introduced for the first time as a promising cathode for Na-ion batteries. P(THBQ-Al) is synthesized through a facile coordination reaction between benzoquinonedihydroxydiolate (C 6 O 6 H 2 2- ) and Al 3+ as ligands and complex metal ions, respectively. Tetrahydroxybenzoquinone is environmentally sustainable, because it can be obtained from natural resources such as orange peels. Benzoquinonedihydroxydiolate also contributes to delivering high reversible capacity, because each benzoquinonedihydroxydiolate unit is capable of two electron reactions through the sodiation of its conjugated carbonyl groups. Electrochemically inactive Al 3+ improves the structural stability of P(THBQ-Al) during cycling because of a lack of a change in its oxidation state. Moreover, P(THBQ-Al) is thermally stable and insoluble in nonaqueous electrolytes. These result in excellent electrochemical performance including a high reversible capacity of 113 mA h g -1 and stable cycle performance with negligible capacity fading over 100 cycles. Moreover, the reaction mechanism of P(THBQ-Al) is clarified through ex situ XPS and IR analyses, in which the reversible sodiation of C═O into C-O-Na is observed.

The production of shape-controlled heterometallic nanoparticles (NPs) consisting of Pt and nonprecious metal oxides is crucial to demonstrate the composition-property relationship of NPs. Herein, we report a facile one-pot approach for the controlled synthesis of dumbbell-like Pt-Fe 3 O 4 -MnO x and dendritic Pt-MnO x NPs. The key to the success of this synthesis is in changing the quantity of Fe(CO) 5 additive to control the reaction kinetics. In the absence of Fe(CO) 5 , dendritic Pt-MnO x NPs were synthesized through the assembly of small seed NPs. On the other hand, dumbbell-like Pt-Fe 3 O 4 -MnO x NPs were obtained in the presence of Fe(CO) 5 through controlling the nucleation and growth of Fe and Mn on the Pt NPs, followed by air oxidation. Compared to a Pt/graphene oxide (GO) catalyst, dumbbell-like Pt-Fe 3 O 4 -MnO x NPs on GO showed an enhancement of specific activity toward the oxygen reduction reaction owing to the compressive-strain effect exerted on the Pt lattice., Competing Interests: The authors declare no competing financial interest.

In this study, the far-red-emitting fluorescence probe 1, containing a rhodamine derivative and a hydrazide reactive group, was developed for peroxynitrite detection and imaging. This probe, which is cell permeable and shows high sensitivity and selectivity in fluorometric detection of peroxynitrite over other ROS/RNS, was successfully utilized to detect exogenous and endogenous peroxynitrite in HeLa and RAW 264.7 cells, respectively. More importantly, 1 can also be used to detect endogenous peroxynitrite generated in Pseudomonas aeruginosa (PAO1)-infected mouse bone marrow-derived neutrophils. We anticipate that the new probe will serve as a powerful molecular imaging tool in investigations of the role(s) played by peroxynitrite in a variety of physiological and pathological contexts.

Graphene oxide (GO) is considered a comparatively recent biomaterial with enormous potential because of its nontoxicity, high dispersity, and enhanced interaction with biomolecules. These characteristics of GO can promote the interactions between the substrates and cell surfaces. In this study, we incorporated GO in a cryogel-based scaffold system to observe their influence on the osteogenic responses of human tonsil-derived mesenchymal stem cells (hTMSCs). Compared to polyethylene glycol (PEG)-based cryogel scaffold, GO-embedded PEG-based (PEGDA-GO) cryogels not only showed improved cell attachment and focal adhesion kinase (FAK) signaling activation but also enhanced cell viability. Taken together, we demonstrated that PEGDA-GO cryogels can stimulate osteogenic differentiation under an osteoinductive condition and enhance osteogenic phenotypes compared to the control group. In summary, we demonstrate that GO embedded in cryogels system is an effective biofunctionalizing scaffold to control osteogenic commitment of stem cells.

A new methodology for fabrication of inorganic-organic hybrid ionogels and scaffolds is developed through facile cross-linking and solution extraction of a newly developed ionic polyhedral oligomeric silsesquioxane with inorganic core. Through design of various cationic tertiary amines, as well as cross-linkable functional groups on each arm of the inorganic core, high-performance ionogels are fabricated with excellent electrochemical stability and unique ion conduction behavior, giving superior lithium ion battery performance. Moreover, through solvent extraction of the liquid components, hybrid scaffolds with well-defined, interconnected mesopores are utilized as heterogeneous catalysts for the CO 2 -catalyzed cycloaddition of epoxides. Excellent catalytic performance, as well as highly efficient recyclability are observed when compared to other previous literature materials.

Gel polymer electrolytes (GPEs) based on semi-interpenetrating polymer network (IPN) structure for lithium-ion batteries were prepared by mixing boron-containing cross-linker (BC) composed of ethylene oxide (EO) chains, cross-linkable methacrylate group, and anion-trapping boron moiety with poly(vinylidene fluoride) (PVDF) followed by ultraviolet light-induced curing process. Various physical and electrochemical properties of the GPEs were systematically investigated by varying the EO chain length and boron content. Dimensional stability at high temperature without thermal shrinkage, if any, was observed due to the presence of thermally stable PVDF in the GPEs. GPE having 80 wt % of BC and 20 wt % of PVDF exhibited an ionic conductivity of 4.2 mS cm -1 at 30 °C which is 1 order of magnitude larger than that of the liquid electrolyte system containing the commercial Celgard separator (0.4 mS cm -1 ) owing to the facile electrolyte uptake ability of EO chain and anion-trapping ability of the boron moiety. As a result, the lithium-ion battery cell prepared using the GPE with BC showed an excellent cycle performance at 1.0 C maintaining 87% of capacity during 100 cycles.

The adhesion of blood clots to blood vessels, such as through the adhesion of fibrin, is essential in hemostasis. While numerous strategies for initiating clot formation and preventing clot lysis are being developed to create improved hemostatic agents, strategies for enhancing clot adhesion have not been widely explored. Here, we show that adhesion of blood clots can be increased by adding a previously characterized synthetic polymer that is crosslinked by coagulation factor XIIIa during clotting. Addition of the polymer to normal plasma increased the adhesive strength of clots by 2-fold. It also recovered the adhesive strength of nonadhesive fibrinogen-deficient whole blood clots from <0.06 kPa to 1.9 ± 0.14 kPa, which is similar to the adhesive strength of a fibrinogen-rich clot (1.8 ± 0.64 kPa). The polymer also enabled plasma clots to remain adhered under fibrinolytic conditions. By demonstrating that the adhesive strength of clots can be increased with a synthetic material, this provides a potential strategy for creating advanced hemostatic materials, such as treatments for fibrinogen deficiency in trauma-induced coagulopathy.

The reliability and durability of energy storage devices are as important as their essential characteristics (e.g., energy and power density) for stable power output and long lifespan and thus much more crucial under harsh conditions. However, energy storage under extreme conditions is still a big challenge because of unavoidable performance decays and the inevitable damage of components. Here, we report high-temperature operating, flexible supercapacitors (f-SCs) that can provide reliable power output and extreme durability under severe electrochemical, mechanical, and thermal conditions. The outstanding capacitive features (e.g., ∼40% enhancement of the rate capability and a maximum capacitances of 170 F g(-1) and 18.7 mF cm(-2) at 160 °C) are attributed to facilitated ion transport at elevated temperatures. Under high-temperature operation and/or a flexibility test in both static and dynamic modes at elevated temperatures >100 °C, the f-SCs showed extreme long-term stability of 100000 cycles (>93% of initial capacitance value) and mechanical durability after hundreds of bending cycles (at bend angles of 60-180°). Even at 120 °C, the versatile design of tandem serial and parallel f-SCs was demonstrated to provide both desirable energy and power requirements at high temperatures.

Histone deacetylase inhibitors (HDACi) target abnormal epigenetic states associated with a variety of pathologies, including cancer. Here, the development of a prodrug of the canonical broad-spectrum HDACi suberoylanilide hydroxamic acid (SAHA) is described. Although hydroxamic acids are utilized universally in the development of metalloenzyme inhibitors, they are considered to be poor pharmacophores with reduced activity in vivo. We developed a prodrug of SAHA by appending a promoiety, sensitive to thiols, to the hydroxamic acid warhead (termed SAHA-TAP). After incubation of SAHA-TAP with an HDAC, the thiol of a conserved HDAC cysteine residue becomes covalently tagged with the promoiety, initiating a cascade reaction that leads to the release of SAHA. Mass spectrometry and enzyme kinetics experiments validate that the cysteine residue is covalently appended with the TAP promoiety. SAHA-TAP demonstrates cytotoxicity activity against various cancer cell lines. This strategy represents an original prodrug design with a dual mode of action for HDAC inhibition.

Core-shell silica particles with ion-conducting poly(ethylene glycol) and anion-trapping boron moiety in the shell layer were prepared to be used as fillers for polymer composite electrolytes based on organic/inorganic hybrid branched copolymer as polymer matrix for all-solid-state lithium-ion battery applications. The core-shell silica particles were found to improve mechanical strength and thermal stability of the polymer matrix and poly(ethylene glycol) and boron moiety in the shell layer increase compatibility between filler and polymer matrix. Furthermore, boron moiety in the shell layer increases both ionic conductivity and lithium transference number of the polymer matrix because lithium salt can be more easily dissociated by the anion-trapping boron. Interfacial compatibility with lithium metal anode is also improved because well-dispersed silica particles serve as protective layer against interfacial side reactions. As a result, all-solid-state battery performance was found to be enhanced when the copolymer having core-shell silica particles with the boron moiety was used as solid polymer electrolyte.