Deep-learning-based gas identification by time-variant illumination of a single micro-LED-embedded gas sensor.

Electronic nose (e-nose) technology for selectively identifying a target gas through chemoresistive sensors has gained much attention for various applications, such as smart factory and personal health monitoring. To overcome the cross-reactivity problem of chemoresistive sensors to various gas species, herein, we propose a novel sensing strategy based on a single micro-LED (µLED)-embedded photoactivated (µLP) gas sensor, utilizing the time-variant illumination for identifying the species and concentrations of various target gases. A fast-changing pseudorandom voltage input is applied to the µLED to generate forced transient sensor responses. A deep neural network is employed to analyze the obtained complex transient signals for gas detection and concentration estimation. The proposed sensor system achieves high classification (~96.99%) and quantification (mean absolute percentage error ~ 31.99%) accuracies for various toxic gases (methanol, ethanol, acetone, and nitrogen dioxide) with a single gas sensor consuming 0.53 mW. The proposed method may significantly improve the efficiency of e-nose technology in terms of cost, space, and power consumption.

Nanowatt-Level Photoactivated Gas Sensor Based on Fully-Integrated Visible MicroLED and Plasmonic Nanomaterials.

Photoactivated gas sensors that are fully integrated with micro light-emitting diodes (µLED) have shown great potential to substitute conventional micro/nano-electromechanical (M/NEMS) gas sensors owing to their low power consumption, high mechanical stability, and mass-producibility. Previous photoactivated gas sensors mostly have utilized ultra-violet (UV) light (250-400 nm) for activating high-bandgap metal oxides, although energy conversion efficiencies of gallium nitride (GaN) LEDs are maximized in the blue range (430-470 nm). This study presents a more advanced monolithic photoactivated gas sensor based on a nanowatt-level, ultra-low-power blue (λpeak  = 435 nm) µLED platform (µLP). To promote the blue light absorbance of the sensing material, plasmonic silver (Ag) nanoparticles (NPs) are uniformly coated on porous indium oxide (In2 O3 ) thin films. By the plasmonic effect, Ag NPs absorb the blue light and spontaneously transfer excited hot electrons to the surface of In2 O3 . Consequently, high external quantum efficiency (EQE, ≈17.3%) and sensor response (ΔR/R0 (%) = 1319%) to 1 ppm NO2 gas can be achieved with a small power consumption of 63 nW. Therefore, it is highly expected to realize various practical applications of mobile gas sensors such as personal environmental monitoring devices, smart factories, farms, and home appliances.

New insights into surface behavior of dimethylated arsenicals on montmorillonite using X-ray absorption spectroscopy.

Although recent studies have revealed the occurrence of dimethylated arsenicals, little is known about their behavior in environment. This study investigates the adsorption behavior of dimethylarsinic acid (DMAV), dimethyldithioarsinic acid (DMDTAV), and dimethylmonothioarsinic acid (DMMTAV) on montmorillonite. Complicated transformations among arsenicals under normal environmental conditions were also considered. Our results clearly demonstrate that DMDTAV was oxidized to DMMTAV, which was relatively stable but partially transformed to DMAV when exposed to air during adsorption. The transformed DMAV exhibited high adsorption affinities for montmorillonite, while DMMTAV and DMDTAV were not appreciably retained by montmorillonite for 48 h. This is the first study to provide insights into DMDTAV oxidation under environmental conditions. X-ray absorption near edge structure and extended X-ray absorption fine structure studies confirmed that most of the adsorbed arsenicals on montmorillonite were DMAV. The significantly different bonding characteristics of each adsorbed DMAV provide direct evidence for the transformation of DMAV from DMDTAV and DMMTAV. Our study suggests the importance of incorporating the DMMTAV in the realistic risk management for soil environments because it is highly toxic, easily transformed from DMDTAV, and stable in the environment.

Nanogap Formation Using a Chromium Oxide Film and Its Application as a Palladium Hydrogen Switch.

Developing high response hydrogen sensors manufacturable in a large scale is desirable in hydrogen industry. In this study, a chromium oxidation-based nanogap formation process was developed to fabricate a hydrogen switch with suspended palladium and gold films having a tens of nanometer-sized gap. The nanogap was formed by using oxidized chromium as a self-alignment shadow mask. The hydrogen switch operates by the principle of volume expansion of palladium upon exposure to the hydrogen gas and the current reading by closing of a nanogap formed between suspended palladium and gold films. Further improvement of the sensor performance was achieved by optimizing the design parameters such as suspended film lengths and thicknesses. The fabricated palladium nanogap hydrogen sensor showed an ultrahigh sensitivity of ΔI/I0 > 108 with a fast response time (22 s) to 4% hydrogen. The complementary metal-oxide-semiconductor-compatible fabrication of the hydrogen switch is easily scalable with low manufacturing cost.

Nanoporous Silicon Thin Film-Based Hydrogen Sensor Using Metal-Assisted Chemical Etching with Annealed Palladium Nanoparticles.

This article reports a nanoporous silicon (Si) thin-film-based high-performance and low-power hydrogen (H2) sensor fabricated by metal-assisted chemical etching (MaCE). The nanoporous Si thin film treated with Pd-based MaCE showed improvement over a flat Si thin film sensor in H2 response (ΔI/I0 = 4.36% → 12.4% for 0.1% H2). Furthermore, it was verified that the combination of thermal annealing of Pd and subsequent MaCE on the Si thin film synergistically enhances the H2 sensitivity of the sensor by 65 times as compared to the flat Si thin film sensor (ΔI/I0 = 4.36% → 285% for 0.1% H2). This sensor also showed a very low operating power of 1.62 µW. After the thermal treatment, densely packed Pd nanoparticles agglomerate due to dewetting, which results in a higher surface-to-volume ratio by well-defined etched holes, leading to an increase in sensor response.

Two Distinct Mechanisms of Inhibition of LpxA Acyltransferase Essential for Lipopolysaccharide Biosynthesis.

The lipopolysaccharide biosynthesis pathway is considered an attractive drug target against the rising threat of multi-drug-resistant Gram-negative bacteria. Here, we report two novel small-molecule inhibitors (compounds 1 and 2) of the acyltransferase LpxA, the first enzyme in the lipopolysaccharide biosynthesis pathway. We show genetically that the antibacterial activities of the compounds against efflux-deficient Escherichia coli are mediated by LpxA inhibition. Consistently, the compounds inhibited the LpxA enzymatic reaction in vitro. Intriguingly, using biochemical, biophysical, and structural characterization, we reveal two distinct mechanisms of LpxA inhibition; compound 1 is a substrate-competitive inhibitor targeting apo LpxA, and compound 2 is an uncompetitive inhibitor targeting the LpxA/product complex. Compound 2 exhibited more favorable biological and physicochemical properties than compound 1 and was optimized using structural information to achieve improved antibacterial activity against wild-type E. coli. These results show that LpxA is a promising antibacterial target and imply the advantages of targeting enzyme/product complexes in drug discovery.

Monolithic Micro Light-Emitting Diode/Metal Oxide Nanowire Gas Sensor with Microwatt-Level Power Consumption.

High-performance, monolithic photoactivated gas sensors based on the integration of gas-sensitive semiconductor metal oxide nanowires on micro light-emitting diodes (µLEDs) are introduced. The µLEDs showed improved irradiance and energy conversion efficiency (i.e., external quantum efficiency, EQE), as the size of LEDs was reduced from 200 × 200 µm2 (irradiance of 46.5 W/cm2 and EQE of 4%) to 30 × 30 µm2 (irradiance of 822.4 W/cm2 and EQE of 9%). Gas-sensitive zinc oxide (ZnO) nanowires were directly synthesized on top of the µLED through a hydrothermal reaction. The direct contact between the sensing component and µLED sensor platform leads to high light coupling efficiency, minimizing power consumption of the sensor. Furthermore, the sensing performance (i.e., sensitivity) at optimal operating power was improved as the LED size was reduced. The smallest fabricated gas sensor (active area = 30 × 30 µm2) showed excellent NO2 sensitivity (ΔR/R0 = 605% to 1 ppm NO2) at the optimal operating power (∼184 µW). In addition, the sensor showed a low limit of detection (∼14.9 ppb) and robustness to high humidity conditions, which demonstrate its potential for practical applications in mobile internet of things (IoT) devices.

Adsorption properties of advanced functional materials against gaseous formaldehyde.

Intense efforts have been made to eliminate toxic volatile organic compounds (VOCs) in indoor environments, especially formaldehyde (FA). In this study, the removal performances of gaseous FA using two metal-organic frameworks, MOF-5 and UiO-66-NH2, and two covalent-organic polymers, CBAP-1 (EDA) and CBAP-1 (DETA), along with activated carbon as a conventional reference material, were evaluated. To assess the removal capacity of FA under near-ambient conditions, a series of adsorption experiments were conducted at its concentrations/partial pressures of both low (0.1-0.5 ppm/0.01-0.05 Pa) and high ranges (5-25 ppm/0.5-2.5 Pa). Among all tested materials at the high-pressure region ㅐ (e.g., at 2.5 ppm FA), a maximum adsorption capacity of 69.7 mg g-1 was recorded by UiO-66-NH2. Moreover, UiO-66-NH2 also displayed the best 10% breakthrough volume (BTV10) of 534 L g-1 (0.5 ppm FA) to 2963 L g-1 (0.1 ppm FA). In contrast, at the high concentration test (at 5, 10, and 25 ppm FA), the maximum BTV10 values were observed as: 137 (UiO-66-NH2), 144 (CBAP-1 (DETA)), and 36.8 L g-1 (CBAP-1 (EDA)), respectively. The Langmuir isotherm model was observed to be a better fit of the adsorption data than the Freundlich model under most of the tested conditions. The superiority of UiO-66-NH2 was attributed to the van der Waals interactions between the linkers (framework) and the hydrocarbon "tail" (FA) coupled with interactions between its open metal sites and the FA carbonyl groups. This study demonstrated the good potential of these advanced functional materials toward the practical removal of gaseous FA in indoor environments.

Biomimetic Turbinate-like Artificial Nose for Hydrogen Detection Based on 3D Porous Laser-Induced Graphene.

Inspired by the turbinate structure in the olfaction system of a dog, a biomimetic artificial nose based on 3D porous laser-induced graphene (LIG) decorated with palladium (Pd) nanoparticles (NPs) has been developed for room-temperature hydrogen (H2) detection. A 3D porous biomimetic turbinate-like network of graphene was synthesized by simply irradiating an infrared laser beam onto a polyimide substrate, which could further be transferred onto another flexible substrate such as polyethylene terephthalate (PET) to broaden its application. The sensing mechanism is based on the catalytic effect of the Pd NPs on the crystal defect of the biomimetic LIG turbinate-like microstructure, which allows facile adsorption and desorption of the nonpolar H2 molecules. The sensor demonstrated an approximately linear sensing response to H2 concentration. Compared to chemical vapor-deposited (CVD) graphene-based gas sensors, the biomimetic turbinate-like microstructure LIG-gas sensor showed ∼1 time higher sensing performance with much simpler and lower-cost fabrication. Furthermore, to expand the potential applications of the biomimetic sensor, we modulated the resistance of the biomimetic LIG sensor by varying laser sweeping gaps and also demonstrated a well-transferred LIG layer onto transparent substrates. Moreover, the LIG sensor showed good mechanical flexibility and robustness for potential wearable and flexible device applications.

Half-Pipe Palladium Nanotube-Based Hydrogen Sensor Using a Suspended Nanofiber Scaffold.

A half-pipe palladium nanotube network (H-PdNTN) structure was developed for high-performance hydrogen (H2) sensor applications. To fabricate the sensor, suspended poly(vinyl alcohol) (PVA) nanofiber bundles were electrospun on a conductive substrate, followed by a palladium (Pd) deposition on top of the PVA nanofiber bundles. Then, Pd-deposited PVA nanofibers were transferred to a host substrate, and the PVA nanofiber templates were selectively removed. Various material analyses confirmed that the PVA nanofibers were successfully dissolved leaving a half-pipe-shaped Pd nanotube network. The fabricated Pd nanotube-based sensors were tested for H2 responses with different gas concentrations. The 4 nm thick sensor showed the highest response (Δ R/ R0) to H2 gas. Platinum (Pt) decoration of the sensor showed an improved response speed compared to that of the pristine sensor via the catalytic function of Pt. Additionally, the sensor exhibited good H2 selectivity against other interfering gases. The H-PdNTN H2 sensor provides a facile and cost-effective way to fabricate high-performance H2 sensors.

Zinc Oxide-Enhanced Piezoelectret Polypropylene Microfiber for Mechanical Energy Harvesting.

This paper reports zinc oxide (ZnO)-coated piezoelectret polypropylene (PP) microfibers with a structure of two opposite arc-shaped braces for enhanced mechanical energy harvesting. The ZnO film was coated onto PP microfibers via magnetron sputtering to form a ZnO/PP compound structure. Triboelectric Nanogenerator (TENG) based on ZnO/PP microfiber compound film was carefully designed with two opposite arc-shaped braces. The results of this study demonstrated that the mechanical energy collection efficiency of TENG based on piezoelectret PP microfiber was greatly enhanced by the coated ZnO and high-voltage corona charging method. We found that, with the step-increased distance of traveling for the movable carbon black electrode, an electrical power with an approximately quadratic function of distance was generated by this mechanical-electrical energy conversion, because more PP microfibers were connected to the electrode. Further, with a full contact condition, the peak of the generated voltage, current, and charges based on the ZnO/PP microfibers by this mechanical-electrical energy conversion with 1 m/s2 reached 120 V, 3 µA, and 49 nC, respectively. Moreover, a finger-tapping test was used to demonstrate that the ZnO/PP microfiber TENG is capable of lighting eight light-emitting diodes.

High-Sensitivity and Low-Power Flexible Schottky Hydrogen Sensor Based on Silicon Nanomembrane.

High-performance and low-power flexible Schottky diode-based hydrogen sensor was developed. The sensor was fabricated by releasing Si nanomembrane (SiNM) and transferring onto a plastic substrate. After the transfer, palladium (Pd) and aluminum (Al) were selectively deposited as a sensing material and an electrode, respectively. The top-down fabrication process of flexible Pd/SiNM diode H2 sensor is facile compared to other existing bottom-up fabricated flexible gas sensors while showing excellent H2 sensitivity (Δ I/ I0 > 700-0.5% H2 concentrations) and fast response time (τ10-90 = 22 s) at room temperature. In addition, selectivity, humidity, and mechanical tests verify that the sensor has excellent reliability and robustness under various environments. The operating power consumption of the sensor is only in the nanowatt range, which indicates its potential applications in low-power portable and wearable electronics.

Palladium-Decorated Silicon Nanomesh Fabricated by Nanosphere Lithography for High Performance, Room Temperature Hydrogen Sensing.

A hydrogen (H2 ) gas sensor based on a silicon (Si) nanomesh structure decorated with palladium (Pd) nanoparticles is fabricated via polystyrene nanosphere lithography and top-down fabrication processes. The gas sensor shows dramatically improved H2 gas sensitivity compared with an Si thin film sensor without nanopatterns. Furthermore, a buffered oxide etchant treatment of the Si nanomesh structure results in an additional performance improvement. The final sensor device shows fast H2 response and high selectivity to H2 gas among other gases. The sensing performance is stable and shows repeatable responses in both dry and high humidity ambient environments. The sensor also shows high stability without noticeable performance degradation after one month. This approach allows the facile fabrication of high performance H2 sensors via a cost-effective, complementary metal-oxide-semiconductor (CMOS) compatible, and scalable nanopatterning method.

Elucidation of a four-site allosteric network in fibroblast growth factor receptor tyrosine kinases.

Receptor tyrosine kinase (RTK) signaling is tightly regulated by protein allostery within the intracellular tyrosine kinase domains. Yet the molecular determinants of allosteric connectivity in tyrosine kinase domain are incompletely understood. By means of structural (X-ray and NMR) and functional characterization of pathogenic gain-of-function mutations affecting the FGF receptor (FGFR) tyrosine kinase domain, we elucidated a long-distance allosteric network composed of four interconnected sites termed the 'molecular brake', 'DFG latch', 'A-loop plug', and 'αC tether'. The first three sites repress the kinase from adopting an active conformation, whereas the αC tether promotes the active conformation. The skewed design of this four-site allosteric network imposes tight autoinhibition and accounts for the incomplete mimicry of the activated conformation by pathogenic mutations targeting a single site. Based on the structural similarity shared among RTKs, we propose that this allosteric model for FGFR kinases is applicable to other RTKs.

A Miniature Protein Stabilized by a Cation-π Interaction Network.

The design of folded miniature proteins is predicated on establishing noncovalent interactions that direct the self-assembly of discrete thermostable tertiary structures. In this work, we describe how a network of cation-π interactions present in proteins containing "WSXWS motifs" can be emulated to stabilize the core of a miniature protein. This 19-residue protein sequence recapitulates a set of interdigitated arginine and tryptophan residues that stabilize a distinctive ß-strand:loop:PPII-helix topology. Validation of the compact fold determined by NMR was carried out by mutagenesis of the cation-π network and by comparison to the corresponding disulfide-bridged structure. These results support the involvement of a coordinated set of cation-π interactions that stabilize the tertiary structure.

The rhodopsin-arrestin-1 interaction in bicelles.

G-protein-coupled receptors (GPCRs) are essential mediators of information transfer in eukaryotic cells. Interactions between GPCRs and their binding partners modulate the signaling process. For example, the interaction between GPCR and cognate G protein initiates the signal, while the interaction with cognate arrestin terminates G-protein-mediated signaling. In visual signal transduction, arrestin-1 selectively binds to the phosphorylated light-activated GPCR rhodopsin to terminate rhodopsin signaling. Under physiological conditions, the rhodopsin-arrestin-1 interaction occurs in highly specialized disk membrane in which rhodopsin resides. This membrane is replaced with mimetics when working with purified proteins. While detergents are commonly used as membrane mimetics, most detergents denature arrestin-1, preventing biochemical studies of this interaction. In contrast, bicelles provide a suitable alternative medium. An advantage of bicelles is that they contain lipids, which have been shown to be necessary for normal rhodopsin-arrestin-1 interaction. Here we describe how to reconstitute rhodopsin into bicelles, and how bicelle properties affect the rhodopsin-arrestin-1 interaction.

A structured loop modulates coupling between the substrate-binding and dimerization domains in the multidrug resistance transporter EmrE.

Secondary active transporters undergo large conformational changes to facilitate the efflux of substrates across the lipid bilayer. Among the smallest known transport proteins are members of the small multidrug resistance (SMR) family that are composed of four transmembrane (TM) domains and assemble into dimers. An unanswered question in the SMR field is how the dimerization domain (TM4) is coupled with the substrate-binding chamber (TM1-3). To provide insight for this essential aspect of ion-coupled transport, we carried out a structure-function study on the SMR protein EmrE using solid-state NMR spectroscopy in lipid bilayers and resistance assays in Escherichia coli. The chemical shifts for EmrE were consistent with ß-strand secondary structure for the loop connecting TM3 and TM4. Based on these structural results, EmrE mutants were created to ascertain whether a specific loop length and composition were necessary for function. A linker encompassing six extra Gly residues relative to wild-type EmrE failed to give resistance; however, the number of residues in the loop was not the only criterion for a functional efflux pump. Replacement of the central hydrophobic residue with Gly (L83G) also conferred no ethidium resistance phenotype, which supported the conclusion that the structure and length of the loop were both essential for ion-coupled transport. Taken together with a bioinformatics analysis, a structured linker is likely conserved across the SMR family to play an active role in mediating the conformational switch between inward-open and outward-open states necessary for drug efflux. These findings underscore the important role loops can play in mediating efflux.

Intrinsic conformational plasticity of native EmrE provides a pathway for multidrug resistance.

EmrE is a multidrug resistance efflux pump with specificity to a wide range of antibiotics and antiseptics. To obtain atomic-scale insight into the attributes of the native state that encodes the broad specificity, we used a hybrid of solution and solid-state NMR methods in lipid bilayers and bicelles. Our results indicate that the native EmrE dimer oscillates between inward and outward facing structural conformations at an exchange rate (k(ex)) of ~300 s(-1) at 37 °C (millisecond motions), which is ~50-fold faster relative to the tetraphenylphosphonium (TPP(+)) substrate-bound form of the protein. These observables provide quantitative evidence that the rate-limiting step in the TPP(+) transport cycle is not the outward-inward conformational change in the absence of drug. In addition, using differential scanning calorimetry, we found that the width of the gel-to-liquid crystalline phase transition was 2 °C broader in the absence of the TPP(+) substrate versus its presence, which suggested that changes in transporter dynamics can impact the phase properties of the membrane. Interestingly, experiments with cross-linked EmrE showed that the millisecond inward-open to outward-open dynamics was not the culprit of the broadening. Instead, the calorimetry and NMR data supported the conclusion that faster time scale structural dynamics (nanosecond-microsecond) were the source and therefore impart the conformationally plastic character of native EmrE capable of binding structurally diverse substrates. These findings provide a clear example how differences in membrane protein transporter structural dynamics between drug-free and bound states can have a direct impact on the physical properties of the lipid bilayer in an allosteric fashion.

The quiet renaissance of protein nuclear magnetic resonance.

From roughly 1985 through the start of the new millennium, the cutting edge of solution protein nuclear magnetic resonance (NMR) spectroscopy was to a significant extent driven by the aspiration to determine structures. Here we survey recent advances in protein NMR that herald a renaissance in which a number of its most important applications reflect the broad problem-solving capability displayed by this method during its classical era during the 1970s and early 1980s.