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Establishing a platform for the bioconversion of waste resources into value-added compounds is critical for achieving a sustainable and eco-friendly economy. Herein, we produced polyhydroxyalkanoate via microbial fermentation using cabbage waste as a feedstock and metabolically engineered Escherichia coli . For this, the hydrolysis conditions of cabbage waste were optimized by focusing on parameters such as substrate and enzyme concentrations to enhance the saccharification efficiency. The phaABC operon, which encodes key enzymes responsible for polyhydroxyalkanoate biosynthesis in Ralstonia eutropha H16, was overexpressed in E. coli . Using cabbage hydrolysate as the feedstock, this engineered E. coli strain could produce poly(3-hydroxybutyrate) with a polymer content of 26.0 wt % of dry cell weight. Moreover, malic acid in cabbage hydrolysate significantly enhanced poly(3-hydroxybutyrate) production; the addition of 0.5 g/L malic acid markedly increased poly(3-hydroxybutyrate) content by 59.9%. This study demonstrates the potential of cabbage waste as a promising raw material for the microbial production of polyhydroxyalkanoate.

RNA nanotechnology, including rolling circle transcription (RCT), has gained increasing interest as a fascinating siRNA delivery nanoplatform for biostable and tumor-targetable RNA-based therapies. However, due to the lack of fine-tuning technologies for RNA nanostructures, the relationship between physicochemical properties and siRNA efficacy of polymeric siRNA nanoparticles (PRNs) with different sizes has not yet been fully elucidated. Herein, we scrutinized the effects of size/surface chemistry-tuned PRNs on the biological and physiological interactions with tumors. PRNs with adjusted size and surface properties were prepared using sequential engineering processes: RCT, condensation, and nanolayer deposition of functional biopolymers. Through the RCT process, nanoparticles of three sizes with a diameter of 50-200 nm were fabricated and terminated with three types of biopolymers: poly-l-lysine (PLL), poly-l-glutamate (PLG), and hyaluronic acid (HA) for different surface properties. Among the PRNs, HA-layered nanoparticles with a diameter of ∼200 nm exhibited the most effective systemic delivery, resulting in superior anticancer effects in an orthotopic breast tumor model due to the CD44 receptor targeting and optimized nanosized structure. Depending on the type of PRNs, the in vivo siRNA delivery with protein expression inhibition differed by up to approximately 20-fold. These findings indicate that the types of layered biopolymers and the PRNs size mediate efficient polymeric siRNA delivery to the targeted tumors, resulting in high RNAi-induced therapeutic efficacy. This RNA-nanotechnology-based size/surface editing can overcome the limitations of siRNA therapeutics and represents a potent built-in module method to design RNA therapeutics tailored for targeted cancer therapy.

Triple-negative breast cancer (TNBC) presents treatment challenges due to a lack of detectable surface receptors. Natural killer (NK) cell-based adaptive immunotherapy is a promising treatment because of the characteristic anticancer effects of killing malignant cells directly by secreting cytokines and lytic granules. To maximize the cancer recognition ability of NK cells, biomaterial-mediated ex vivo cell surface engineering has been developed for sufficient cell membrane immobilization of tumor-targeting ligands via hydrophobic anchoring. In this study, we optimized amphiphilic balances of NK cell coating materials composed of CD44-targeting hyaluronic acid (HA)-poly(ethylene glycol) (PEG)-lipid to improve TNBC recognition and the anticancer effect. Changes in the modular design of our material by differentiating hydrophilic PEG length and incorporating lipid amount into HA backbones precisely regulated the amphiphilic nature of HA-PEG-lipid conjugates. The optimized biomaterial demonstrated improved anchoring into NK cell membranes and facilitating the surface presentation level of HA onto NK cell surfaces. This led to enhanced cancer targeting via increasing the formation of immune synapse, thereby augmenting the anticancer capability of NK cells specifically toward CD44-positive TNBC cells. Our approach addresses targeting ability of NK cell to solid tumors with a deficiency of surface tumor-specific antigens while offering a valuable material design strategy using amphiphilic balance in immune cell surface engineering techniques.

Phenylboronic acid (PBA) has been highly acknowledged as a significant cancer recognition moiety in sialic acid-overexpressing cancer cells. In this investigation, lipid-mediated biomaterial integrated PBA molecules onto the surface of natural killer (NK) cells to make a receptor-mediated immune cell therapeutic module. Therefore, a 1,2-distearoyl- sn -glycero-3-phosphorylethanolamine (DSPE) lipid-conjugated di-PEG-PBA (DSPE PEG -di(PEG-PBA) biomaterial was synthesized. The DSPE PEG -di(PEG-PBA) biomaterial exhibited a high affinity for sialic acid (SA), confirmed by fluorescence spectroscopy at pH 6.5 and 7.4. DSPE PEG -di(PEG-PBA) was successfully anchored onto NK cell surfaces (PBA-NK), and this biomaterial maintains intrinsic properties such as viability, ligand availability (FasL & TRAIL), and cytokine secretion response to LPS. The anticancer efficacy of PBA-NK cells was evaluated against 2D cancer cells (MDA-MB-231, HepG2, and HCT-116) and 3D tumor spheroids of MDA-MB-231 cells. PBA-NK cells exhibited greatly enhanced anticancer effects against SA-overexpressing cancer cells. Thus, PBA-NK cells represent a new anticancer strategy for cancer immunotherapy.

Lactic acid bacteria produce various bioactive compounds widely used in human healthcare. However, studies on cryoprotective agents for the efficient storage of lactic acid bacteria after freeze-drying are still lacking. Here, we report the shelf-life extension effects of a highly efficient and eco-friendly cryoprotective agent and a cold adaptation method on Lactobacillus sakei WiKim31. Cold adaptation of L. sakei WiKim31 increased exopolysaccharide expression in response to abiotic stress. As a possible cryoprotective agent, the citrus byproduct (CP) contains a variety of sugars, amino acids, and cations, exhibiting high antioxidant activity. L. sakei WiKim31 powders formulated with CP or a mixture of soy powder (SP) and CP exhibited high cell viability at 58.3 and 76.3%, respectively, after 56 days of storage. These results indicate that CP can be efficiently used as a novel cryoprotective agent either alone or in combination with SP to improve the storage conditions of L. sakei WiKim31 and preserve it longer., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

In electronic bipolar resistive switching (eBRS), the electron trapping and detrapping at the defect sites within the switching layer, such as the highly defective TiO 1.7 in this study, constitute the switching mechanism. It is an appealing candidate solution to the nonuniformity issue of resistive switching memory. However, TiO 1.7 -based eBRS has suffered from a lack of endurance and retention. In this study, a 7 nm-thick stoichiometric TiO 2 layer is interposed between an Al bottom electrode and a 50 nm-thick TiO 1.7 layer, which is in contact with an Al top electrode. Despite the minimal structural modification, improvements in the electrical performance were substantial. The off-to-on state resistance ratio of 20 and the resistance values could be retained up to 30 000 direct current sweep cycles and 10 6 alternating current pulse switching cycles. Data retention also significantly improves. Moreover, the device is electroforming-free and shows fully area-type switching characteristics. Such notable improvements are attributed to the favorable energy band structure of the Al/TiO 1.7 /TiO 2 /Al structure. The device shows almost linear potentiation and depression characteristics after the repeated pulse voltage applications, which significantly improves the accuracy of the neural network, the synapses of which are composed of the Al/TiO 1.7 /TiO 2 /Al memory cells.

Thermal oxidation resistance is an important property in printed electronics for sustaining electrical conductivity for long time and/or under harsh environments such as high temperature. This study reports the fabrication of copper nanoparticles (CuNPs)-based conductive tracks using large pulsed electron beam (LPEB) by irradiation on CuNPs to be sintered. With an acceleration voltage of 11 kV, the LPEB irradiation induced deep-sintering of CuNPs so that the sintered CuNPs exhibited bulk-like electrical conductivity. Consequently, the sintered Cu tracks maintained high electrical conductivity at 220 °C without using any thermal oxidation protection additive, such as silver, carbon nanotube, and graphene. In contrast, the films irradiated with an acceleration voltage of 8 kV and irradiated by intense pulsed light (IPL) showed fast oxidation characteristics and a corresponding reduction of electrical conductivities under high temperatures owing to a thin sintered layer. The performance of highly thermal oxidation-resistant Cu films sintered by LPEB irradiations was demonstrated through the device performance of a Joule heater., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Bacterial exopolysaccharides (EPSs) are important alternatives to plant polysaccharides in fermented products and exhibit antioxidant activity, which is particularly desirable for functional foods. This study evaluated the use of spent media wastewater (SMW) derived from kimchi fermentation for the production of an EPS and analyzed the characterization and antioxidant activity of the resulting EPS. The EPS concentration and conversion yields of sequential purification were 7.7-9.0 g/L and 38.6-45.1%, respectively. Fourier transform infrared spectra and NMR spectra indicated that the EPS was a linear glucan with α-(1 → 6) linkages. The EPS also exhibited thermal tolerance to high temperatures. In vitro antioxidant activity analyses indicated the scavenging activity on 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals, thiobarbituric acid reactance (TBAR), and ferric ion reducing antioxidant power (FRAP) values of 71.6-79.1, 28.2-33.0%, and 0.04-0.05 mM FeCl 3 , respectively. These results reveal that the EPS extracted from SMW has potential as a thermally tolerant, nontoxic, and natural antioxidant for industrial applications., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Organic semiconductor (OSC)-based gas detection has attracted considerable attention due to the facile manufacturing process and effective contact with target chemicals at room temperature. However, OSCs intrinsically suffer from inferior sensing and recovery capability due to lack of functional sites and deep gas penetration into the film. Here, we describe an interpenetrating polymer semiconductor nanonetwork (IPSN) channel possessing unreacted silanol (Si-OH) groups on its surface to overcome bottlenecks that come from OSC-based chemodetection. On the top of the IPSN, moreover, we introduced electron-donating amine (NH 2 ) groups as a chemical receptor because they strongly interact with the electron-withdrawing nature of NO 2 gas. The NH 2 -IPSN-based field-effect transistor exhibited high-performance chemodetection such as ultrasensitivity (990% ppm -1 at 5 ppm) and excellent NO 2 selectivity against other toxic gases. Impressively, the gas recovery was significantly improved because the NH 2 chemical receptors anchored on the surface of the IPSN suppress deep gas penetration into the film. This work demonstrates that our NO 2 chemodetection is expected to provide inspiration and guideline for realization of practical gas sensors in various industries and daily life.

Pine wilt disease, caused by Bursaphelenchus xylophilus (pine wood nematode), leads to severe environmental and economic damage. Here, we report the results of experiments on the biological control of pine wilt disease through termination of the insect vector of the nematode and the mechanism of the insecticidal action of Metarhizium anisopliae JEF-279 against Monochamus alternatus (Japanese pine sawyer). A combined treatment with a fungal conidia suspension and a fungal protease-containing culture filtrate caused 75.8% mortality of the insect vector. Additionally, the presence of destruxins was confirmed in the dead Japanese pine sawyer adults, and half of the 10 protein spots in proteomic analysis were identified as an actin related to muscle contraction. Based on proteomic and microscopic analyses, the infection cycle of the Japanese pine sawyer by M. anisopliae JEF-279 was inferred to proceed in the following sequence: (1) host adhesion and germination, (2) epicuticle degradation, (3) growth as blastospore, (4) killing by various fungal toxins (insecticidal metabolites), (5) immune response as defense mechanism, and (6) hyphal extrusion and conidiation. Consequently, the combined fungal conidia suspension and protease-containing culture filtrate treatment may be applied as an insecticidal agent, and flaccid paralysis is likely a major mechanism underlying the insecticidal action of M. anisopliae JEF-279 on host insects., Competing Interests: The authors declare no competing financial interest.

The biorefining of agricultural waste into green chemicals has clear potential for improving global environmental sustainability. In this study, we evaluated the potential of acetic acid production from carbohydrate feedstock (onion waste, OW) as a more environmentally friendly source than feedstock produced from natural gas. In particular, OW is an ideal feedstock for the biorefining process as it contains a sufficient amount of carbohydrates (69.7%). Five days of the simultaneous saccharification and two-step fermentation (SSTF) process produced acetic acid from OW more efficiently than the simultaneous saccharification and cofermentation (SSCF) process. SSTF produced 19.3 g/L acetic acid and recorded the highest conversion yield (90.5%) from OW (6% substrate loading, w/v). These results suggested that acetic acid can be efficiently and sustainably produced from OW by the SSTF process., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Recent studies have found discordant mechanosensitive outcomes when comparing 2D and 3D, highlighting the need for tools to study mechanotransduction in 3D across a wide spectrum of stiffness. A gelatin methacryloyl (GelMA) hydrogel with a continuous stiffness gradient ranging from 5 to 38 kPa was developed to recapitulate physiological stiffness conditions. Adipose-derived stem cells (ASCs) were encapsulated in this hydrogel, and their morphological characteristics and expression of both mechanosensitive proteins (Lamin A, YAP, and MRTFa) and differentiation markers (PPARγ and RUNX2) were analyzed. Low-stiffness regions (∼8 kPa) permitted increased cellular and nuclear volume and enhanced mechanosensitive protein localization in the nucleus. This trend was reversed in high stiffness regions (∼30 kPa), where decreased cellular and nuclear volumes and reduced mechanosensitive protein nuclear localization were observed. Interestingly, cells in soft regions exhibited enhanced osteogenic RUNX2 expression, while those in stiff regions upregulated the adipogenic regulator PPARγ, suggesting that volume, not substrate stiffness, is sufficient to drive 3D stem cell differentiation. Inhibition of myosin II (Blebbistatin) and ROCK (Y-27632), both key drivers of actomyosin contractility, resulted in reduced cell volume, especially in low-stiffness regions, causing a decorrelation between volume expansion and mechanosensitive protein localization. Constitutively active and inactive forms of the canonical downstream mechanotransduction effector TAZ were stably transfected into ASCs. Activated TAZ resulted in higher cellular volume despite increasing stiffness and a consistent, stiffness-independent translocation of YAP and MRTFa into the nucleus. Thus, volume adaptation as a function of 3D matrix stiffness can control stem cell mechanotransduction and differentiation.

We demonstrate an ionic polymer artificial mechanotransducer (i-PAM) capable of simultaneously yielding an efficient wide bandwidth and a blocking force to maximize human tactile recognition in soft tactile feedback. The unique methodology in the i-PAM relies on an ionic interpenetrating nanofibrillar network that is formed at the interface of (i) an ionic thermoplastic polyurethane nanofibrillar matrix with an ionic liquid of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM] + [TFSI] - ) and (ii) ionic poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) conducting polymer electrodes with dimethyl sulfoxide and [EMIM] + [TFSI] - as additives. The i-PAM-based actuator with the ionic PEDOT:PSS exhibits a stable operation up to 200 Hz at low voltage as well as a blocking force of 0.4 mN, which can be potentially adapted to soft tactile feedback. Furthermore, on the basis of this fast i-PAM, we realized alphabet tactile rendering by using a 3 × 3 i-PAM array stimulated by a dc input of 2 V. We believe that our proposed approach can provide a rational guide to the human-machine soft haptic interface.

Anti-icing materials that can efficiently limit ice formation have a strong potential to replace existing anti-icing techniques, such as Joule heating, chemical release, or mechanical removal, which are usually inefficient, expensive, and environmentally harmful. In this study, an anti-icing material based on a magnetically responsive hierarchical hair array that can actively modulate drop bouncing dynamics is presented. The magnetically responsive hair array exhibits an immediate and reversible structural bending motion in response to an external magnetic field. The array also exhibits superhydrophobicity, regardless of its tilt angle, due to the tapered geometry of the hairs and the multiscale surface roughness of the array. Due to its dynamic structure and water-repellent characteristics, the array can induce distinct multiple modes of drop bouncing behavior by adjusting its structural bending state in a reversible fashion. Three different types of bouncing behavior, namely, quasi-pancake bouncing, directional bouncing, and macrotexture-induced droplet fragmentation, can be obtained with the vertical, tilted, and fully bent hair arrays, respectively. We demonstrate that the dynamically controllable drop bouncing behavior of the magnetically responsive hierarchical array enables the efficient and robust prevention of ice formation and accumulation.

Thermotherapy is a widespread technique that provides relief for muscle spasms and joint injuries. A great deal of energy is used to heat the surrounding environment, and heat emitted by the human body is wasted on our surroundings. Herein, a woven Kevlar fiber (WKF)-based personal thermal management device was fabricated by directly growing vertical copper-nickel (Cu-Ni) nanowires (NWs) on the WKF surface using a hydrothermal method. The treated WKF was combined with reduced graphene oxide (rGO) dispersed in polydimethylsiloxane (PDMS) to form composites using vacuum-assisted resin transfer molding (VARTM). This WKF-based personal thermal management system contained a conductive network of metallic NWs and rGO that promoted effective Joule heating and reflected back the infrared (IR) radiation emitted by the human body. It thus behaved as a type of thermal insulation. The Cu-Ni NWs were synthesized with a tunable Ni layer on Cu core NWs to enhance the oxidation resistance of the Cu NWs. The combined effect of the NW networks and rGO enabled a surface temperature of 70 °C to be attained on application of 1.5 V to the composites. The Cu 3 Ni 1 -WKF/PDMS provided 43% more thermal insulation and higher IR reflectance than bare WKF/PDMS. The absorbed impact energy and tensile strength was highest for the Cu 1 Ni 3 - and rGO-integrated WKF/PDMS samples. Those Cu-Ni NWs having higher Ni contents displayed better mechanical properties and those with higher Cu contents showed higher Joule heating performance and IR reflectivity at a given rGO loading. The composite shows sufficient breathability and very high durability. The high flexibility of the composites and their ability to generate sufficient heat during various human motions ensures their suitability for wearable applications.

Interests in nanoscale integrated ferroelectric devices using doped HfO 2 -based thin films are actively reviving in academia and industry. The main driving force for the formation of the metastable non-centrosymmetric ferroelectric phase is considered to be the interface/grain boundary energy effect of the small grains in polycrystalline configuration. These small grains, however, can invoke unfavorable material properties, such as nonuniform switching performance. This study provides an in-depth understanding of such aspects of this material through careful measurement and modeling of the ferroelectric switching kinetics. Various previous switching models developed for conventional ferroelectric thin-film capacitors cannot fully account for the observed time- and voltage-dependent switching current evolution. The accurate fitting of the experimental results required careful consideration of the inhomogeneous field distribution across the electrode area, which could be acquired by an appropriate mathematical formulation of polarization as a function of electric field and time. Compared with the conventional polycrystalline Pb(Zr,Ti)O 3 film, the statistical distribution of the local field was found to be three times wider. The activation field and characteristic time for domain switching were larger by more than 1 order of magnitude. It indicates that doped HfO 2 is inhomogeneous and "hard" ferroelectric material compared with conventional perovskite-based ferroelectrics.

Ferroelectric (FE) capacitor is a critical electric component in microelectronic devices. Among many of its intriguing properties, the recent finding of voltage drop (V-drop) across the FE capacitor while the positive charges flow in is especially eye-catching. This finding was claimed to be direct evidence that the FE capacitor is in negative capacitance (NC) state, which must be useful for (infinitely) high capacitance and ultralow voltage operation of field-effect transistors. Nonetheless, the NC state corresponds to the maximum energy state of the FE material, so it has been widely accepted in the community that the material alleviates that state by forming ferroelectric domains. This work reports a similar V-drop effect from the 150 nm thick epitaxial BaTiO 3 ferroelectric thin film, but the interpretation was completely disparate; the V-drop can be precisely simulated by the reverse domain nucleation and propagation of which charge effect cannot be fully compensated for by the supplied charge from the external charge source. The disappearance of the V-drop effect was also observed by repeated FE switching only up to 10 cycles, which can hardly be explained by the involvement of the NC effect. The retained reverse domain nuclei even after the subsequent poling can explain such behavior.

Well-aligned NiCo 2 S 4 nanowires, synthesized hydrothermally on the surface of woven Kevlar fiber (WKF), were used to fabricate composites with reduced graphene oxide (rGO) dispersed in polyester resin (PES) by means of vacuum-assisted resin transfer molding. The NiCo 2 S 4 nanowires were synthesized with three precursor concentrations. Nanowire growth was characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Hierarchical and high growth density of the nanowires led to exceptional mechanical properties of the composites. Compared with bare WKF/PES, the tensile strength and absorbed impact energy were enhanced by 96.2% and 92.3%, respectively, for WKF/NiCo 2 S 4 /rGO (1.5%)/PES. The synergistic effect of NiCo 2 S 4 nanowires and rGO in the fabricated composites improved the electrical conductivity of insulating WKF/PES composites, reducing the resistance to ∼10 3 Ω. Joule heating performance depended strongly on the precursor concentration of the nanowires and the presence of rGO in the composite. A maximum surface temperature of 163 °C was obtained under low-voltage (5 V) application. The Joule heating performance of the composites was demonstrated in a surface deicing experiment; we observed that 17 g of ice melted from the surface of the composite in 14 min under an applied voltage of 5 V at -28 °C. The excellent performance of WKF/NiCo 2 S 4 /rGO/PES composites shows great potential for aerospace structural applications requiring outstanding mechanical properties and Joule heating capability for deicing of surfaces.

We report a novel solvent-free and direct photopatternable poly[(mercaptopropyl)methyl-siloxane] (PMMS) hybrid dielectric for flexible top-gate organic field-effect transistors (OFETs) utilizing a photoactivated thiol-ene reaction under UV irradiation of 254 nm to induce cross-linking, even in air and at low temperatures. In particular, a solvent-free PMMS-f dielectric film, for which an optimal cross-linking density is shown by a well-organized molar ratio between thiol and vinyl in the thiol-ene reaction, exhibited a high dielectric constant (5.4 @ 100 Hz) and a low leakage current (<1 nA mm -2 @ 2 MV cm -1 ). The excellent dielectric characteristics of the solvent-free PMMS-hybrid dielectrics, along with their other unique characteristics of a direct photopatternability for which UV-nanoimprint lithography is used and a high surface energy of 45.6 mJ m -2 , allowed the successful application of the dielectrics to flexible solvent-free top-gate OFETs with a high reliability against the radius of curvature (9.5, 7.0, and 5.5 mm) and repetitive bending cycles at the radius of curvature of 5.5 mm. This will eventually enable the proposed dielectric design to be used in a variety of applications such as flexible displays and soft organic sensors including chemical and tactile capability.

Mechanical properties of transparent electrodes, including flexibility, are important in flexible electronics for sustaining electrical conductivity under bending with small radius of curvature. Low contact resistance of junctions in metal nanowire percolation networks is the most important factor to produce electrodes with excellent optical, electrical and mechanical performance. Here, we report the fabrication of welded silver nanowire percolation networks using large pulsed electron beam (LPEB) irradiation as a welding process of silver nanowires (AgNWs). It results in modification of electrical and mechanical properties because of the low contact resistance at welded junctions. Consequently, the flexible and transparent AgNW electrodes fabricated by LPEB irradiation showed lower sheet resistance of 12.63 Ω sq(-1) at high transmittance of 93% (at 550 nm), and superb mechanical flexibility, compared with other AgNW electrodes prepared by thermal treatement and without any treatment. Polymer light-emitting diodes (PLEDs) using AgNWs by LPEB irradiation were fabricated to confirm that the AgNW electrode by LPEB irradiation was able to become alternative to indium tin oxide (ITO) and they showed good device performance as a maximum luminous efficiency of 7.37 cd A(-1), and excellent mechanical flexibility under bending with small radius of curvature.

Here, we report on a simple and high-rate oxidization method for producing solution-based compound mixtures of indium zinc oxide (IZO) and indium gallium zinc oxide (IGZO) metal-oxide semiconductors (MOS) for thin-film transistor (TFT) applications. One of the issues for solution-based MOS fabrication is how to sufficiently oxidize the precursor in order to achieve high performance. As the oxidation rate of solution processing is lower than vacuum-based deposition such as sputtering, devices using solution-processed MOS exhibit relatively poorer performance. Therefore, we propose a method to prepare the metal-oxide precursor upon exposure to saturated water vapor in a closed volume for increasing the oxidization efficiency without requiring additional oxidizing agent. We found that the hydroxide rate of the MOS film exposed to water vapor is lower than when unexposed (≤18%). Hence, we successfully fabricated oxide TFTs with high electron mobility (27.9 cm(2)/V·s) and established a rapid process (annealing at 400 °C for 5 min) that is much shorter than the conventional as-deposited long-duration annealing (at 400 °C for 1 h) whose corresponding mobility is even lower (19.2 cm(2)/V·s).

Advanced morphology of intertwined core-corona structured bifunctional catalyst (IT-CCBC) is introduced where perovskite lanthanum nickel oxide nanoparticles (LaNiO3 NP) are encapsulated by high surface area network of nitrogen-doped carbon nanotubes (NCNT) to produce highly active and durable bifunctional catalyst for rechargeable metal-air battery applications. The unique composite morphology of IT-CCBC not only enhances the charge transport property by providing rapid electron-conduction pathway but also facilitates in diffusion of hydroxyl and oxygen reactants through the highly porous framework. Confirmed by electrochemical half-cell testing, IT-CCBC in fact exhibits very strong synergy between LaNiO3 NP and NCNT demonstrating bifunctionality with significantly improved catalytic activities of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Furthermore, when compared to the state-of-art catalysts, IT-CCBC outperforms Pt/C and Ir/C in terms of ORR and OER, respectively, and shows improved electrochemical stability compared to them after cycle degradation testing. The practicality of the catalyst is corroborated by testing in a realistic rechargeable zinc-air battery utilizing atmospheric air in ambient conditions, where IT-CCBC demonstrates superior charge and discharge voltages and long-term cycle stability with virtually no battery voltage fading. These improved electrochemical properties of the catalyst are attributed to the nanosized dimensions of LaNiO3 NP controlled by simple hydrothermal technique, which enables prolific growth of and encapsulation by highly porous NCNT network. The excellent electrochemical results presented in this study highlight IT-CCBC as highly efficient and commercially viable bifunctional catalyst for rechargeable metal-air battery applications.

Polyaniline (PANI) is one of the most widely investigated conducting polymers and is considered to be of practical use for many future applications. Here, we first demonstrate that the anisotropic growth of PANI at the nanometer scale can be kinetically controlled by employing a polymeric stabilizer, poly(N-vinylpyrrolidone). The polymerization rate became slower in the presence of the stabilizer (the rate constants calculated at the initial stage decreased with increasing concentration of the stabilizer), yielding PANI nanostructures with lower aspect ratios. Therefore, it is believed that the stabilizer sterically restricts the directional fiber growth mechanism governing PANI chain growth in aqueous solution. Three PANI nanostructures, specifically nanospheres, nanorods, and nanofibers, were fabricated and their oxidation/protonation levels were investigated systematically. It was found that the nanofibers had the most outstanding oxidation/protonation level accompanied by structural ordering (note that the only difference between the polymerization conditions in each case was the concentration of the stabilizer). We also examine the electrochemical properties of PANI nanostructure electrodes in three-electrode and two-electrode (actual capacitor cell) configurations. The intrinsic charge-transport ability of individual nanostructures strongly affected the electrochemical properties of the electrodes. Briefly, the nanofiber electrode had faster electrode kinetics and better capacitance than the nanorods and nanospheres. Lastly, an extrinsic factor, the interparticle contact resistance, also turned out to noticeably influence the capacitances of the electrodes.

It has been reported that the surface pressure-area isotherm of poly(D,L-lactic acid-ran-glycolic acid) (PLGA) at the air-water interface exhibits several interesting features: (1) a plateau at intermediate compression levels, (2) a sharp rise in surface pressure upon further compression, and (3) marked surface pressure-area hysteresis during compression-expansion cycles. To investigate the molecular origin of this behavior, we conducted an extensive set of surface pressure and AFM imaging measurements with PLGA materials having several different molecular weights and also a poly(D,L-lactic acid-ran-glycolic acid-ran-caprolactone) (PLGACL) material in which the caprolactone monomers were incorporated as a plasticizing component. The results suggest that (i) the plateau in the surface pressure-area isotherm of PLGA (or PLGACL) occurs because of the formation (and collapse) of a continuous monolayer of the polymer under continuous compression; (ii) the PLGA monolayer becomes significantly resistant to compression at high compression because under that condition the collapsed domains become large enough to become glassy (such behavior was not observed in the nonglassy PLGACL sample); and (iii) the isotherm hysteresis is due to a coarsening of the collapsed domains that occurs under high-compression conditions. We also investigated the monolayer properties of PEG-PLGA and PEG-PLGACL diblock copolymers. The results demonstrate that the tendency of PLGA (or PLGACL) to spread on water allows the polymer to be used as an anchoring block to form a smooth biodegradable monolayer of block copolymers at the air-water interface. These diblock copolymer monolayers exhibit protein resistance.

Only limited information is available on the design and synthesis of functional materials for preventing corrosion of metal nanostructures. In the nanometer regime, even noble metals are subject to chemical attack. Here, the corrosion behavior of noble metal nanoparticles coated with a conjugated polymer nanolayer was explored for the first time. Specifically, electrochemical corrosion and sulfur tarnishing behaviors were examined for Ag-polypyrrole (PPy) core-shell nanoparticles using potentiodynamic polarization and spectrophotometric analysis, respectively. First, the Ag-PPy nanoparticles exhibited enhanced resistance to electrochemically induced corrosion compared to their exposed silver counterparts. Briefly, a neutral PPy shell provided the highest protection efficiency (75.5%), followed by sulfate ion- (61.3%) and dodecylbenzenesulfonate ion- (53.6%) doped PPy shells. However, the doping of the PPy shell with chloride ion induced an adverse effect (protection efficiency, -120%). Second, upon exposure to sulfide ions, the Ag-PPy nanoparticles preserved their morphology and colloidal stability while the bare silver analog underwent significant structural deformation. To further understand the function of the PPy shell as a protection layer for the silver core, the catalytic activity of the nanostructures was also evaluated. Using the reduction of 4-nitrophenol as a representative example of a catalytic reaction, the rate constant for that reduction using the PPy encased Ag nanoparticles was found to be 1.1 × 10(-3) s(-1), which is approximately 33% less than that determined for the parent silver. These results demonstrate that PPy can serve as both an electrical and chemical barrier for mitigating undesirable chemical degradation in corrosive environments, as well as provide a simple physical barrier to corrosive substances under appropriate conditions.

A model poly(ethylene oxide) (PEO) brush system, prepared by spreading a poly(ethylene oxide)-poly(n-butyl acrylate) (PEO-PnBA) amphiphilic diblock copolymer onto an air-water interface, was investigated under various grafting density conditions by using the X-ray reflectivity (XR) technique. The overall electron density profiles of the PEO-PnBA monolayer in the direction normal to the air-water interface were determined from the XR data. From this analysis, it was found that inside of the PEO brush, the water density is significantly lower than that of bulk water, in particular, in the region close to the PnBA-water interface. Separate XR measurements with a PnBA homopolymer monolayer confirm that the reduced water density within the PEO-PnBA monolayer is not due to unfavorable contacts between the PnBA surface and water. The above result, therefore, lends support to the notion that PEO chains provide a hydrophobic environment for the surrounding water molecules when they exist as polymer brush chains.

Tailoring the morphology of materials in the nanometer regime is vital to realizing enhanced device performance. Here, we demonstrate flexible nerve agent sensors, based on hydroxylated poly(3,4-ethylenedioxythiophene) (PEDOT) nanotubes (HPNTs) with surface substructures such as nanonodules (NNs) and nanorods (NRs). The surface substructures can be grown on a nanofiber surface by controlling critical synthetic conditions during vapor deposition polymerization (VDP) on the polymer nanotemplate, leading to the formation of multidimensional conducting polymer nanostructures. Hydroxyl groups are found to interact with the nerve agents. Representatively, the sensing response of dimethyl methylphosphonate (DMMP) as a simulant for sarin is highly sensitive and reversible from the aligned nanotubes. The minimum detection limit is as low as 10 ppt. Additionally, the sensor had excellent mechanical bendability and durability.

Recent studies have suggested the existence of a small subset of cancer cells called cancer stem cells (CSCs), which possess the ability to initiate malignancies, promote tumor formation, drive metastasis, and evade conventional chemotherapies. Elucidation of the specific signaling pathway and mechanism underlying the action of CSCs might improve the efficacy of cancer treatments. In this study, we analyzed differentially expressed proteins between tumerigenic and nontumorigenic cells isolated from the human hepatocellular carcinoma (HCC) cell line, Huh7, via proteomic analysis to identify proteins correlated with specific features of CSCs. The expression level of Transgelin was 25-fold higher in tumorigenic cells than nontumorigenic cells. Similar results were also observed in tumorigenic cells derived from colorectal adenocarcinoma and prostate carcinoma. More importantly, the elevated levels of Transgelin significantly increased the invasiveness of tumorigenic cells, whereas reduced levels decreased the invasive potential. Moreover, in tumors derived from Huh7-induced xenografts, Transgelin was also co-expressed with CXCR4, which is responsible for tumor invasion. Taken together, these results indicate that the metastatic potential of CSCs arises from highly expressed Transgelin.

A phase diagram was constructed for a polystyrene-block-polyisoprene (PS-b-PI, M(W) = 32 700, f(PI) = 0.670) in thin films on Si wafer as a function of film thickness over the range of 150-2410 nm (7-107L(0) (L(0): domain spacing)). The PS-b-PI exhibits a variety of ordered phases from hexagonally perforated lamellar (HPL) via double gyroid (DG) to hexagonally packed cylinder (HEX) before going to the disordered (DIS) phase upon heating. The morphology of the PS-b-PI in thin film was investigated by grazing incidence small-angle X-ray scattering, transmission electron microscopy, and transmission electron microtomography. In thin film, the phase transition temperature is difficult to be determined unequivocally with in situ heating processes since the phase transition is slow and two phases coexist over a wide temperature range. Therefore, in an effort to find an "equilibrium" phase, we determined the long-term stable phase formed after cooling the film from the DIS phase to a target temperature and annealing for 24 h at the temperature. The temperature windows of stable ordered phases are strongly influenced by the film thickness. As the film thickness decreases, the temperature window of layer-like structures such as HPL and HEX becomes wider, whereas that of the DG stable region decreases. For the films thinner than 160 nm (8L(0)), only the HPL phase was found. In the films exhibiting DG phase, a perforated layer structure at the free surface was found, which gradually converts to the internal DG structure. The relief of interfacial tension by preferential wetting appears to play an important role in controlling the morphology in very thin films.

The metabolism of cancer cells is altered to support rapid proliferation. Pharmacological activators of a tumor cell specific pyruvate kinase isozyme (PKM2) may be an approach for altering the classic Warburg effect characteristic of aberrant metabolism in cancer cells yielding a novel antiproliferation strategy. In this manuscript, we detail the discovery of a series of substituted N,N'-diarylsulfonamides as activators of PKM2. The synthesis of numerous analogues and the evaluation of structure-activity relationships are presented as well as assessments of mechanism and selectivity. Several agents are found that have good potencies and appropriate solubility for use as chemical probes of PKM2 including 55 (AC(50) = 43 nM, maximum response = 84%; solubility = 7.3 microg/mL), 56 (AC(50) = 99 nM, maximum response = 84%; solubility = 5.7 microg/mL), and 58 (AC(50) = 38 nM, maximum response = 82%; solubility = 51.2 microg/mL). The small molecules described here represent first-in-class activators of PKM2.

We investigated the epitaxial phase transition from double gyroid (DG) to hexagonally packed cylinder (HEX) phases of a polystyrene-b-polyisoprene diblock copolymer in a thin film on a Si wafer substrate. The internal structure of the thin film was investigated by grazing incidence small-angle X-ray scattering, transmission electron microscopy, and transmission electron microtomography (TEMT). TEMT allows observation of the 3D-image of coexisting DG and HEX directly. Good domain orientation in the thin film and direct 3D-imaging of TEMT made it possible to observe the coexisting phase of DG and HEX, and a new epitaxial transition path from DG to HEX was found.

We report the synthesis of atypical nanoparticles in donut shape with or without additional spherical nanoparticles attached on them by using the donut-like nanostructure formed in a thin film of triblock copolymers. In a high-humidity condition, a spin-coated film of triblock copolymer had donut-like holes consisting of the periphery and the center. By selective coordination of precursors of nanoparticles to the periphery of the holes, donut-like oxide nanoparticles were synthesized by oxygen plasma treatment on the film. Moreover, we were able to attach spherical nanoparticles on the donut-like nanoparticles by incorporating the other type of precursors to the center of the holes. Thus, beyond the synthesis of typical spherical nanoparticles, the results here extend potentials of the block copolymer approach to control the shape and complexity of nanoparticles.

The crystal structures of gyceraldehyde 3-phosphate dehydrogenase (GAPDH) from Escherichia coli have been determined in three different enzymatic states, NAD(+)-free, NAD(+)-bound, and hemiacetal intermediate. The NAD(+)-free structure reported here has been determined from monoclinic and tetragonal crystal forms. The conformational changes in GAPDH induced by cofactor binding are limited to the residues that bind the adenine moiety of NAD(+). Glyceraldehyde 3-phosphate (GAP), the substrate of GAPDH, binds to the enzyme with its C3 phosphate in a hydrophilic pocket, called the "new P(i)" site, which is different from the originally proposed binding site for inorganic phosphate. This observed location of the C3 phosphate is consistent with the flip-flop model proposed for the enzyme mechanism [Skarzynski, T., Moody, P. C., and Wonacott, A. J. (1987) J. Mol. Biol. 193, 171-187]. Via incorporation of the new P(i) site in this model, it is now proposed that the C3 phosphate of GAP initially binds at the new P(i) site and then flips to the P(s) site before hydride transfer. A superposition of NAD(+)-bound and hemiacetal intermediate structures reveals an interaction between the hydroxyl oxygen at the hemiacetal C1 of GAP and the nicotinamide ring. This finding suggests that the cofactor NAD(+) may stabilize the transition state oxyanion of the hemiacetal intermediate in support of the flip-flop model for GAP binding.