Tunable Wettability of Graphene through Nondestructive Hydrogenation and Wettability-Based Patterning for Bioapplications.

The wettability of graphene has been extensively studied and successfully modified by chemical functionalization. Nevertheless, the unavoidable introduction of undesired defects and the absence of systematic and local control over wettability by previous methods have limited the use of graphene in applications. In addition, microscale patterning, according to wettability, has not been attempted. Here, we demonstrate that the wettability of graphene can be systematically controlled and surface patterned into microscale sections based on wettability without creating significant defects, possible by nondestructive hydrogen plasma. Hydrophobic graphene is progressively converted to hydrophilic hydrogenated graphene (H-Gr) that reaches superhydrophilicity. The great contrast in wettability between graphene and H-Gr makes it possible to selectively position and isolate human breast cancer cells on arrays of micropatterns since strong hydrophilicity facilitates the adsorption of the cells. We believe that our method will provide an essential technique for enabling surface and biological applications requiring microscale patterns with different wettability.

Analysis of Tertiary Interactions between SART3 and U6 Small Nuclear RNA Using Modified Nanocapillaries.

We employed modified glass nanocapillaries to investigate interactions between the RNA-binding protein, known as cell carcinoma antigen recognized by T cells-3 (SART3), and the noncoding spliceosome component, U6 small nuclear RNA (snRNA), at the single-molecule level. We functionalized the nanocapillaries with U6 snRNA fragments, which were hybridized to DNA molecules and then covalently attached to the nanocapillary surface. When transported through the modified nanocapillaries, two different SART3-derived constructs, HAT-RRM1-RRM2 and RRM1-RRM2, exhibited resistive ionic current pulses with different dwell times, which represented their different binding affinities to tethered U6 snRNAs. The dissociation constants (KD), estimated from the bias voltage dependence of translocation events, were approximately 1.9 µM and 201 µM for HAT-RRM1-RRM2 and RRM1-RRM2, respectively. These values were comparable to corresponding values obtained with isothermal titration calorimetry, demonstrating that the modified glass nanocapillaries are applicable to analyses of protein-ligand interactions at the single-molecule level.

Selective Detection of Single-Stranded DNA Molecules Using a Glass Nanocapillary Functionalized with DNA.

We describe glass nanocapillaries with single-stranded DNA molecules (ssDNA) covalently attached to the capillary surface. These DNA-functionalized nanocapillaries selectively facilitate the translocation of target ssDNA that is complementary to the probe ssDNA. In addition, the complementary target ssDNA exhibits an event duration time longer than that of the noncomplementary target ssDNA. The temperature dependence measurements of translocation events show that the longer duration time is a result of an interaction between probe and target ssDNA and is dependent on the base pair binding strength. These results demonstrate that single-base mismatch transport selectivity can be achieved using the DNA-functionalized nanocapillaries.

Macrophage Differentiation from Monocytes Is Influenced by the Lipid Oxidation Degree of Low Density Lipoprotein.

LDL plays an important role in atherosclerotic plaque formation and macrophage differentiation. However, there is no report regarding the oxidation degree of LDL and macrophage differentiation. Our study has shown that the differentiation into M1 or M2 macrophages is related to the lipid oxidation level of LDL. Based on the level of lipid peroxidation, LDL is classified into high-oxidized LDL (hi-oxLDL) and low-oxidized LDL (low-oxLDL). The differentiation profiles of macrophages were determined by surface receptor expression and cytokine secretion profiles. Low-oxLDL induced CD86 expression and production of TNF-α and IL-12p40 in THP-1 cells, indicating an M1 macrophage phenotype. Hi-oxLDL induced mannose receptor expression and production of IL-6 and monocyte chemoattractant protein-1, which mostly match the phenotype of M2 macrophages. Further supporting evidence for an M2 polarization by hi-oxLDL was the induction of LOX-1 in THP-1 cells treated with hi-oxLDL but not with low-oxLDL. Similar results were obtained in primary human monocytes. Therefore, our results strongly suggest that the oxidation degree of LDL influences the differentiation of monocytes into M1 or M2 macrophages and determines the inflammatory fate in early stages of atherosclerosis.

Hydrogen sensing under ambient conditions using SnO2 nanowires: synergetic effect of Pd/Sn codeposition.

Semiconducting SnO2 nanowires deposited with Pd and Sn nanoparticles on their surface are shown to be a highly sensitive hydrogen sensor with fast response time at room temperature. Compared with the SnO2 nanowire deposited with Pd or Sn nanoparticles alone, the Pd/Sn-deposited SnO2 nanowire exhibits a significant improvement in the sensitivity and reversibility of sensing hydrogen gas in the air at room temperature. Our investigation indicates that two factors are responsible for the synergistic effect of Pd/Sn codeposition on SnO2 nanowires. One is that in the presence of Pd the oxidation of Sn nanoparticles on the surface of the SnO2 nanowire is incomplete leading only to suboxides SnOx (1 ≤ x < 2), and the other is that the surface of the Pd/Sn-deposited SnO2 nanowire is almost perfectly hydrophobic.

Glucose oxidase nanotube-based enzymatic biofuel cells with improved laccase biocathodes.

Glucose/O(2) biofuel cells (BFCs) with an improved power density and stability were developed, using glucose oxidase (GOD) nanotubes with polypyrrole (PPy)-carbon nanotubes (CNTs)-GOD layers deposited on their surface as an anode and a PPy-laccase-2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) film type cathode. The GOD nanotubes were fabricated within the nanopores of an anodized aluminum oxide membrane using a template-assisted layer-by-layer deposition method. These BFCs exhibited a higher volumetric power than the best performance reported previously; this was likely due to an increase in enzyme loading of GOD nanotubes and improved electrochemical properties of the PPy-CNTs-GOD layers. The stability of BFCs was closely related to the leakage of ABTS from the cathode. When the leakage of ABTS was suppressed, the power density of BFCs was nearly unchanged for at least 8 days under physiological conditions.

Funnel Devices Based on Asymmetrically Strained Transition Metal Dichalcogenides.

The strain applied to transition metal dichalcogenides (TMDs) reduces their energy bandgap, and local strains result in a funnel-like band structure in which funneled excitons move toward the most strained region. Herein, a funnel device based on asymmetrically strained WS2 and MoS2 is reported. Asymmetric strains are induced by transferring the TMD flakes onto a fork-shaped SU-8 microstructure. Raman and photoluminescence spectra peaks are shifted according to the morphology of the SU-8 microstructure, indicating the application of asymmetric strains to the TMDs. To investigate whether funneled excitons can be converted to electrical currents, various devices are constructed by depositing symmetric and asymmetric electrodes onto the strained TMDs. The scanning photocurrent mapping images follow a fork-shaped pattern, indicating probable conversion of the funneled excitons into electrical currents. In the case of the funnel devices with asymmetric Au and Al electrodes, short-circuit current (ISC ) of WS2 is enhanced by the strains, whereas ISC of MoS2 is suppressed because the Schottky barrier lowers with increasing strain for the MoS2 . These results demonstrate that the funnel devices can be implemented using asymmetrically strained TMDs and the effect of strains on the Schottky barrier is dependent on the TMD used.

Enhancement of triboelectricity based on fully organic composite films with a conducting polymer.

Triboelectric nanogenerators (TENGs) based on ferroelectric organic materials have advantages of high flexibility, biocompatibility, controllable ferroelectric properties, etc. However, this has limited the electrical output performance due to their lower ferroelectric characteristics than those of inorganic ferroelectric materials. A lot of effort has been made to improve the organic ferroelectric characteristics through composites, surface modifications, structures, etc. Herein, we report TENGs made of ferroelectric composite materials consisting of poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The composite was prepared by simply blending PVDF-TrFE and PEDOT:PSS with a weight ratio from 0% to 60%. When the ratio was 20%, the ferroelectric-crystalline phase was enhanced and the highest dielectric constant was observed. Accordingly, the TENGs consisting of 20% composite film and polyimide exhibited the best output performance: the maximum open circuit voltage and short circuit current were ∼15 V and ∼2.3 µA at 1 Hz oscillation, respectively. These results indicate that the ferroelectric characteristics of PVDF-TrFE can be enhanced by adding PEDOT:PSS as a nanofiller.

Photothermal inactivation of universal viral particles by localized surface plasmon resonance mediated heating filter membrane.

This study introduces localized surface plasmon resonance (L-SPR) mediated heating filter membrane (HFM) for inactivating universal viral particles by using the photothermal effect of plasmonic metal nanoparticles (NPs). Plasmonic metal NPs were coated onto filter membrane via a conventional spray-coating method. The surface temperature of the HFM could be controlled to approximately 40-60 °C at room temperature, owing to the photothermal effect of the gold (Au) NPs coated on them, under irradiation by visible light-emitting diodes. Due to the photothermal effect of the HFMs, the virus titer of H1Npdm09 was reduced by > 99.9%, the full inactivation time being < 10 min, confirming the 50% tissue culture infective dose (TCID50) assay. Crystal violet staining showed that the infectious samples with photothermal inactivation lost their infectivity against Mardin-Darby Canine Kidney cells. Moreover, photothermal inactivation could also be applied to reduce the infectivity of SARS-CoV-2, showing reduction rate of 99%. We used quantitative reverse transcription polymerase chain reaction (qRT-PCR) techniques to confirm the existence of viral genes on the surface of the HFM. The results of the TCID50 assay, crystal violet staining method, and qRT-PCR showed that the effective and immediate reduction in viral infectivity possibly originated from the denaturation or deformation of membrane proteins and components. This study provides a new, simple, and effective method to inactivate viral infectivity, leading to its potential application in various fields of indoor air quality control and medical science.

Magnetic nanoparticle-based separation of metallic and semiconducting carbon nanotubes.

We report a simple and scalable method for the separation of semiconducting single-walled carbon nanotubes (SWNTs) from metallic SWNTs using magnetic nanoparticles (MNPs) functionalized with polycationic tri-aminated polysorbate 80 (TP80). MNPs-TP80 are selectively adsorbed on acid-treated semiconducting SWNTs, which makes the semiconducting SWNTs be highly concentrated to over 95% under a magnetic field. Almost all the field effect transistor network devices, which were fabricated using separated semiconducting SWNTs, exhibited a p-type semiconducting behavior with an on/off ratio of higher than 10(4).

Carbon nanotube-based dual-mode biosensor for electrical and surface plasmon resonance measurements.

We have developed carbon nanotube-based dual-mode biosensors with a metal semiconductor field effect transistor structure on a quartz substrate. DNA hybridization occurring on the Au top gate can be detected by simultaneously measuring the change in the electrical conductance and the surface plasmon resonance (SPR). Since electrical and SPR measurements offer high sensitivity and reliability, respectively, this dual-mode biosensor is expected to provide both of these features.

Rectifying optoelectronic memory based on WSe2/graphene heterostructures.

van der Waals heterostructures composed of two-dimensional materials vertically stacked have been extensively studied to develop various multifunctional devices. Here, we report WSe2/graphene heterostructure devices with a top floating gate that can serve as multifunctional devices. They exhibit gate-controlled rectification inversion, rectified nonvolatile memory effects, and multilevel optoelectronic memory effects. Depending on the polarity of the gate voltage pulses (V Gp), electrons or holes can be trapped in the floating gate, resulting in rectified nonvolatile memory properties. Furthermore, upon repeated illumination with laser pulses, positive or negative staircase photoconductivity is observed depending on the history of V Gp, which is ascribed to the tunneling of electrons or holes between the WSe2 channel and the floating gate. These multifunctional devices can be used to emulate excitatory and inhibitory synapses that have different neurotransmitters. Various synaptic functions, such as potentiation/depression curves and spike-timing-dependent plasticity, have been also implemented using these devices. In particular, 128 optoelectronic memory states with nonlinearity less than 1 can be achieved by controlling applied laser pulses and V Gp, suggesting that the WSe2/graphene heterostructure devices with a top floating gate can be applied to optoelectronic synapse devices.

Collective dynamics of neuronal activities in various modular networks.

Modularity is a key feature of structural and functional brain networks. However, the association between the structure and function of modular brain networks has not been revealed. We constructed three types of modular cortical networks in vitro and investigated their neuronal activities. The modular networks comprising 4, 3, or 2 modules were constructed using polydimethylsiloxane (PDMS) microstructures fabricated directly on a multi-electrode array (MEA) without transfer. The 4-module network had the strongest modular connectivity, followed by the 3-module and 2-module networks. To investigate how neuronal activities were affected by the modular network structure, spontaneous neuronal activities were recorded on different days in vitro and analyzed based on spike amplitudes, network bursts, and the propagation properties of individual spikes. Different characteristics were observed depending on the network topology and modular connectivity. Moreover, when an electrode was stimulated by biphasic voltage pulses, bursts were elicited for the 4-module network, whereas spikes were elicited for the 3-module and 2-module networks. Direct fabrication of the PDMS microstructures on the MEA without transfer allows microscale construction of modular networks and high-density functional recording; therefore, the technique utilizing the PDMS microstructures can be applied to the systematic study of the dynamics of modular neuronal networks in vitro.

Large field-of-view nanometer-sectioning microscopy by using metal-induced energy transfer and biexponential lifetime analysis.

Total internal reflection fluorescence (TIRF) microscopy, which has about 100-nm axial excitation depth, is the method of choice for nanometer-sectioning imaging for decades. Lately, several new imaging techniques, such as variable angle TIRF microscopy, supercritical-angle fluorescence microscopy, and metal-induced energy transfer imaging, have been proposed to enhance the axial resolution of TIRF. However, all of these methods use high numerical aperture (NA) objectives, and measured images inevitably have small field-of-views (FOVs). Small-FOV can be a serious limitation when multiple cells need to be observed. We propose large-FOV nanometer-sectioning microscopy, which breaks the complementary relations between the depth of focus and axial sectioning by using MIET. Large-FOV imaging is achieved with a low-magnification objective, while nanometer-sectioning is realized utilizing metal-induced energy transfer and biexponential fluorescence lifetime analysis. The feasibility of our proposed method was demonstrated by imaging nanometer-scale distances between the basal membrane of human aortic endothelial cells and a substrate.

Chemical and thermal stability of Pt nanocubes synthesized with various surface-capping agents.

Pt nanocubes with a size of below 10 nm were synthesized by using various surface-capping agents of polyvinylpyrrolidone (PVP), tetradecyltrimethylammonium bromide (TTAB), and oleylamine with high shape purity. TGA and XPS data revealed the amount and characteristics of the residual organic molecules on the surface of Pt nanocubes. Chemical and thermal stability of these nanoparticles were examined by observing the change of cubic shape upon heating under different chemical environments of N2, H2 and air. The shape change such as rounding of the vertexes or aggregation depended on the type of surface-capping agent and chemical environments. The cubic shape generally started to deform at 200 degrees C and the nanoparticles were mostly fused together at 300 degrees C. The thermal treatment under air produced more PtO layer on the surface with less shape deformation or aggregation when compared with H2 or N2 treatments. Among three surface-capping agents used in this study, oleylamine-capped Pt nanocubes show the highest shape stability with no shape change or aggregation even at 300 degrees C under air.

Electrical antimicrobial susceptibility testing based on aptamer-functionalized capacitance sensor array for clinical isolates.

To prescribe effective antibiotics to patients with bacterial infections in a timely manner and to avoid the misuse of antibiotics, a rapid antimicrobial susceptibility test (AST) is essential. However, conventional AST methods require more than 16 h to provide results; thus, we developed an electrical AST (e-AST) system, which provides results within 6 h. The proposed e-AST is based on an array of 60 aptamer-functionalized capacitance sensors that are comparable to currently available AST panels and a pattern-matching algorithm. The performance of the e-AST was evaluated in comparison with that of broth microdilution as the reference test for clinical strains isolated from septic patients. A total of 4,554 tests using e-AST showed a categorical agreement of 97% with a minor error of 2.2%, major error of 0.38%, and very major error of 0.38%. We expect that the proposed e-AST could potentially aid antimicrobial stewardship efforts and lead to improved patient outcomes.

Methotrexate-loaded multifunctional nanoparticles with near-infrared irradiation for the treatment of rheumatoid arthritis.

BACKGROUNDS: Despite the advances of rheumatoid arthritis (RA) therapeutics, several patients do not receive adequate treatment due to the toxicity and/or insufficient response of drugs. The aim of this study is to design photothermally controlled drug release from multifunctional nanoparticles (MNPs) at a near-infrared (NIR) irradiated site to improve therapeutic efficacy for RA and reduce side effects. METHODS: Au film was deposited onto methotrexate (MTX)-loaded poly(ethylene glycol)-poly(lactic-co-glycolic acid) (PLGA) nanoparticles, resulting in MTX-loaded MNPs. The synergistic effects of MTX-loaded MNPs with NIR irradiation were investigated using RA fibroblast-like synoviocytes (FLSs) and collagen-induced arthritis (CIA) mice. RESULTS: Upon NIR irradiation, NIR resonance of the Au half-shell generated heat locally, accelerating MTX release from PLGA nanoparticles. In vivo NIR images of MTX-loaded MNPs indicated effective delivery of the MNPs to the inflamed joints. Moreover, in collagen-induced arthritis mice, MTX-loaded MNPs containing 1/1400 of MTX solution (repeated-dose administration) had therapeutic effects comparable to conventional treatment with MTX solution. In vitro experiments showed higher therapeutic efficacy of MTX-loaded MNPs with NIR irradiation than that of chemotherapy alone. CONCLUSIONS: A combination therapy of MTX-loaded MNP and NIR irradiation showed durable and good treatment efficacy for the suppression of arthritis in a single administration of small dose of MTX. Our results demonstrate that the treatment modality using drug-loaded MNP with NIR irradiation may be a promising therapeutic strategy for the treatment of RA and allow in vivo NIR optical imaging.

Vertical capacitance aptasensors for real-time monitoring of bacterial growth and antibiotic susceptibility in blood.

For the treatment of bacteremia, early diagnosis and rapid antibiotic susceptibility tests (ASTs) are necessary because survival chances decrease significantly if the proper antibiotic administration is delayed. However, conventional methods require several days from blood collection to AST as it requires three overnight cultures, including blood culture, subculture, and AST culture. Herein, we report a more rapid method of sensing bacterial growth and AST in blood based on a vertical capacitance sensor functionalized with aptamers. Owing to their vertical structure, the influence of blood cells sunk by gravity on capacitance measurements were minimized. Thus, bacterial growth in blood at 100-103 CFU/mL was monitored in real-time by measuring changes in capacitance at f = 10 kHz. Moreover, real-time capacitance measurements at f = 0.5 kHz provided information on biofilm formation induced during blood cultures. Bacterial growth and biofilm formation are inhibited above the minimal inhibitory concentration of antibiotics; therefore, we also demonstrated that vertical capacitance aptasensors could be applied to rapid AST from positive blood cultures without a need for the subculture process.

Multilevel MoS2 Optical Memory with Photoresponsive Top Floating Gates.

Optoelectronic memory devices, whose states can be controlled using electrical optical signals, are receiving much attention for their potential applications in image sensing and parallel data transmission and processes. Here, we report MoS2-based devices with top floating gates of Au, graphene, and MoS2. Unlike conventional floating gate memory devices, our devices have the photoresponsive floating gate at the top, acting as a charge trapping layer. Stable and reliable switching with an on/off ratio of ∼106 and a retention time of >104 s is achieved by illumination with 405 nm light pulses as well as application of gate voltage pulses. However, upon illumination with 532 or 635 nm light pulses, multilevel optical memory effects are observed, which are dependent on the wavelength and the optical exposure dosage. In addition, compared to the device employing a graphene floating gate, the device with an MoS2 floating gate is more sensitive to light, suggesting that the multilevel optical memory properties originate from photoexcited carriers in the top floating gate and can be modulated by adjusting the top floating gate materials. The structure of the top floating gate may open up a new way to novel optoelectronic memory devices.

Enhanced output performance on LbL multilayer PVDF-TrFE piezoelectric films for charging supercapacitor.

The piezoelectric nanogenerator (PENG) has the potential to become a promising power supply for monitoring and sensors in Internet of Things (IoT) systems through wireless networks. In order to further increase the utilization of energy harvesters in an IoT system, we introduce a novel approach that greatly enhances the piezoelectric output performances by employing the layer-by-layer (LbL) method. Poly(vinylidenefluoride-co-trifluoroethylene) (PVDF-TrFE) polymer film, which has piezoelectric properties and mechanical flexibility, was used for the active layer in PENG. The maximum open-circuit voltage and closed-circuit current of the LbL multilayer PENG reached 34 V and 100 nA, respectively. In particular, the closed-circuit current of the LbL multilayer PENG was dramatically improved to be five times higher than that of the single-layer PENG. Furthermore, a supercapacitor was employed to investigate the energy storage capability of PENGs using different methods. The proposed LbL multilayer PENG is expected to be a candidate for a promising power supply for self-powered systems in the IoT system.