ANO1-downregulation induced by schisandrathera D: a novel therapeutic target for the treatment of prostate and oral cancers.

Anoctamin 1 (ANO1), a drug target for various cancers, including prostate and oral cancers, is an intracellular calcium-activated chloride ion channel that plays various physiopathological roles, especially in the induction of cancer growth and metastasis. In this study, we tested a novel compound isolated from Schisandra sphenanthera, known as schisandrathera D, for its inhibitory effect on ANO1. Schisandrathera D dose-dependently suppressed the ANO1 activation-mediated decrease in fluorescence of yellow fluorescent protein; however, it did not affect the adenosine triphosphate-induced increase in the intracellular calcium concentration or forskolin-induced cystic fibrosis transmembrane conductance regulator activity. Specifically, schisandrathera D gradually decreased the levels of ANO1 protein and significantly reduced the cell viability in ANO1-expressing cells when compared to those in ANO1-knockout cells. These effects could be attributed to the fact that schisandrathera D displayed better binding capacity to ANO1 protein than the previously known ANO1 inhibitor, Ani9. Finally, schisandrathera D increased the levels of caspase-3 and cleaved poly (ADP-ribose) polymerase 1, thereby indicating that its anticancer effect is mediated through apoptosis. Thus, this study highlights that schisandrathera D, which reduces ANO1 protein levels, has apoptosis-mediated anticancer effects in prostate and oral cancers, and thus, can be further developed into an anticancer agent.

Hemicyanine-Based Near-Infrared Fluorescence Off-On Probes for Imaging Intracellular and In Vivo Nitroreductase Activity.

Nitroreductase (NTR) has the ability to activate nitro group-containing prodrugs and decompose explosives; thus, the evaluation of NTR activity is specifically important in pharmaceutical and environmental areas. Numerous studies have verified effective fluorescent methods to detect and image NTR activity; however, near-infrared (NIR) fluorescence probes for biological applications are lacking. Thus, in this study, we synthesized novel NIR probes (NIR-HCy-NO2 1-3) by introducing a nitro group to the hemicyanine skeleton to obtain fluorescence images of NTR activity. Additionally, this study was also designed to propose a different water solubility and investigate the catalytic efficiency of NTR. NIR-HCy-NO2 inherently exhibited a low fluorescence background due to the interference of intramolecular charge transfer (ICT) by the nitro group. The conversion from the nitro to amine group by NTR induced a change in the absorbance spectra and lead to the intense enhancement of the fluorescence spectra. When assessing the catalytic efficiency and the limit of detection (LOD), including NTR activity imaging, it was demonstrated that NIR-HCy-NO2 1 was superior to the other two probes. Moreover, we found that NIR-HCy-NO2 1 reacted with type I mitochondrial NTR in live cell imaging. Conclusively, NIR-HCy-NO2 demonstrated a great potential for application in various NTR-related fields, including NTR activity for cell imaging in vivo.

Diboronic-Acid-Based Electrochemical Sensor for Enzyme-Free Selective and Sensitive Glucose Detection.

A diboronic acid anthracene-based fluorescent system for detecting blood glucose could be used for 180 days. However, there has not yet been a boronic acid immobilized electrode to selectively detect glucose in a signal-increased way. Considering malfunctions of sensors at high sugar levels, the electrochemical signal should be increased proportionally to the glucose concentration. Therefore, we synthesized a new diboronic acid derivative and fabricated the derivative-immobilized electrodes for the selective detection of glucose. We performed cyclic voltammetry and electrochemical impedance spectroscopy with an Fe(CN)63-/4- redox pair for detecting glucose in the range of 0-500 mg/dL. The analysis revealed increased electron-transfer kinetics such as increased peak current and decreased semicircle radius of Nyquist plots as the glucose concentration increased. The cyclic voltammetry and impedance spectroscopy showed that the linear detection range of glucose was 40 to 500 mg/dL with limits of detection of 31.2 mg/dL and 21.5 mg/dL, respectively. We applied the fabricated electrode to detect glucose in artificial sweat and obtained 90% of the performance of the electrodes in PBS. Cyclic voltammetry measurements of other sugars such as galactose, fructose, and mannitol also showed linear increased peak currents proportional to the concentrations of the tested sugars. However, the slopes of the sugars were lower than that of glucose, indicating selectivity for glucose. These results proved the newly synthesized diboronic acid is a promising synthetic receptor for developing a long-term usable electrochemical sensor system.

Perovskite solar cells integrated with blue cut-off filters for mitigating light-induced degradation.

The stability of methylammonium (MA)-based perovskite solar cells (PSCs) remains one of the most urgent issues that need to be addressed. Inherent weak binding forces between MAs and halides cause the perovskite structure to become unstable under exposure to various external environmental factors such as moisture, oxygen, ultraviolet radiation, and heat. In particular, the degradation of perovskite films under light exposure accelerates the deterioration of the device, mainly due to the migration of halide ions. In this study, we investigated the effect of light energy on the degradation of inverted PSCs by introducing red ( = 610-800 nm), green (500-590 nm), and blue (300-500 nm) light-pass filters. After 30 h, the inverted PSCs of blue-light-induced devices retained a power conversion efficiency (PCE) of 70%, while those of the green and red light-induced devices retained PCEs of 85% and 90%, respectively. Direct evidence of light-induced degradation was obtained by investigating morphological changes in the perovskite films and the amount of ion accumulation on the Ag electrode. This evidence highlights the varying effect of light with different energies on device degradation. Furthermore, to minimize light-induced device degradation, we designed two types of blue cut-off filters that can selectively block light ranging from = 400 to 500 nm, comprising a multilayered inorganic metasurface. An optical simulation was used to optimize the performance of the designed filters. By investigating the changes in the photovoltaic parameters and the amount of ion accumulation on the Ag electrode, we confirmed that integrating blue cut-off filters into PSCs greatly improved the operational lifetime of the devices.

Functionalized N-Heterocyclic Carbene Monolayers on Gold for Surface-Initiated Polymerizations.

Although N-heterocyclic carbenes (NHCs) are superior to thiol adsorbates in that they form remarkably stable bonds with gold, the generation of NHC-based self-assembled monolayers (SAMs) typically requires a strong base and an inert atmosphere, which limits the utility of such films in many applications. Herein, we report the development and use of bench-stable NHC adsorbates, benzimidazolium methanesulfonates, for the direct formation of NHC films on gold surfaces under an ambient atmosphere at room temperature without the need for extraordinary precautions. The generated NHC SAMs were fully characterized using ellipsometry, X-ray photoelectron spectroscopy (XPS), polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS), and contact angle measurements, and they were compared to analogous SAMs generated from an NHC bicarbonate adsorbate. Based on these findings, a unique radical initiator α,ω-bidentate azo-terminated NHC adsorbate, NHC15AZO[OMs], was designed and synthesized for the preparation of SAMs on gold surfaces with both NHC headgroups bound to the surface. The adsorbate molecules in NHC15AZO SAMs can exist in a hairpin or a linear conformation depending on the concentration of the adsorbate solution used to prepare the SAM. These conformations were studied by a combination of ellipsometry, XPS, PM-IRRAS, and scanning electron microscopy using gold nanoparticles (AuNPs) as a tag material. Moreover, the potential utility of these unique radical-initiating NHC films as surface-initiated polymerization platforms was demonstrated by controlling the thickness of polystyrene brush films grown from azo-terminated NHC monolayer surfaces simply by adjusting the reaction time of the photoinitiated radical polymer growth process.

Open-Bandgap Graphene-Based Field-Effect Transistor Using Oligo(phenylene-ethynylene) Interfacial Chemistry.

Organic interfacial compounds (OICs) are required as linkers for the highly stable and efficient immobilization of bioprobes in nanobiosensors using 2D nanomaterials such as graphene. Herein, we first demonstrated the fabrication of a field-effect transistor (FET) via a microelectromechanical system process after covalent functionalization on large-scale graphene by introducing oligo(phenylene-ethynylene)amine (OPE). OPE was compared to various OICs by density functional theory simulations and was confirmed to have a higher binding energy with graphene and a lower band gap than other OICs. OPE can improve the immobilization efficiency of a bioprobe by forming a self-assembly monolayer via anion-based reaction. Using this technology, Magainin I-conjugated OGMFET (MOGMFET) showed a high sensitivity, high selectivity, with a limit of detection of 100  cfu mL-1 . These results indicate that the OPE OIC can be applied for stable and comfortable interfacing technology for biosensor fabrication.

Multilevel Anti-Counterfeiting Based on Covert Structural Features Embedded in Femtosecond-Laser-Treated Gold Nanocluster/Graphene Hybrid Layer.

The conventional nanoscale anti-counterfeiting scheme, exhibiting limited encoding capacity, faces growing challenges of being falsified with the advent of advanced high-resolution equipment. In this study, we propose a multilevel anti-counterfeiting device based on a femtosecond laser (fs-laser) treated plasmonic gold nanocluster/graphene (AuNC/Gr) hybrid structure integrated with a resonant cavity. The covert structural features encoded in random colored patterns, optical reflection spectra, and Raman spectra constitute three classes of anti-counterfeiting signatures, which originate from the AuNC-covered Gr, which initiates plasmonic and thermal couplings. The attendant inverted thermal distribution is presumed to confine the structural features to the AuNC-Gr interface while leaving no detectable traces on the surface of AuNC/Gr even under advanced high-resolution equipment. Therefore, the proposed approach achieves multilevel anti-counterfeiting accomplishing physically unclonable functions in the form of random colored patterns, reflection spectra, and Raman spectra. As the first report for realizing remarkable optical modulation (i.e., random colored patterns) without any surface trace or damage via fs-laser-AuNC/Gr interaction, our study also discloses the outstanding performance of Gr in fs-laser-induced optothermoplasmonic lithography on near-percolation metal films. Simultaneously, the demonstrated fs-laser-processed plasmonic hybrid structure in conjunction with a resonant cavity is anticipated to expand the encoding capabilities for nanoscale anti-counterfeiting while avoiding the risk of being imitated because of the covert structural features.

Nanoparticulate Photoluminescent Probes for Bioimaging: Small Molecules and Polymers.

Recent interest in research on photoluminescent molecules due to their unique properties has played an important role in advancing the bioimaging field. In particular, small molecules and organic dots as probes have great potential for the achievement of bioimaging because of their desirable properties. In this review, we provide an introduction of probes consisting of fluorescent small molecules and polymers that emit light across the ultraviolet and near-infrared wavelength ranges, along with a brief summary of the most recent techniques for bioimaging. Since photoluminescence probes emitting light in different ranges have different goals and targets, their respective strategies also differ. Diverse and novel strategies using photoluminescence probes against targets have gradually been introduced in the related literature. Among recent papers (published within the last 5 years) on the topic, we here concentrate on the photophysical properties and strategies for the design of molecular probes, with key examples of in vivo photoluminescence research for practical applications. More in-depth studies on these probes will provide key insights into how to control the molecular structure and size/shape of organic probes for expanded bioimaging research and applications.

In situ, real-time, colorimetric detection of γ-hydroxybutyric acid (GHB) using self-protection products coated with chemical receptor-embedded hydrogel.

Due to the increase in drug-facilitated sexual assault (DFSA) enabled by the illegal use of drugs, there have been constant demands for simple methods that can be used to protect oneself against crime in real life. γ-Hydroxybutyric acid (GHB), a central nervous system depressant, is one of the most dangerous drugs for use in DFSA because it is colorless and has slow physiological effects, which pose challenges for developing in situ, real-time GHB monitoring techniques. In this study, we developed a method for in situ colorimetric GHB detection using various self-protection products (SPPs) coated with 2-(3-bromo-4-hydroxystyryl)-3-ethylbenzothiazol-3-ium iodide (BHEI) as a chemical receptor embedded in hydrogels. Additionally, smartphone-based detection offers enhanced colorimetric sensitivity compared to that of the naked eye. The developed SPPs will help address drug-facilitated social problems.

Nanoencapsulated Phase-Change Materials: Versatile and Air-Tolerant Platforms for Triplet-Triplet Annihilation Upconversion.

Efficient and long-term stable triplet-triplet annihilation upconversion (TTA-UC) can be achieved by effectively protecting the excited organic triplet ensembles from photoinduced oxygen quenching, and discovery of a new material platform that promotes TTA-UC in ambient conditions is of paramount importance for practical applications. In this study, we present the first demonstration of an organic nonparaffin phase-change material (PCM) as an air-tolerant medium for TTA-UC with a unique solid-liquid phase transition in response to temperature variation. For the proposed concept, 2,4-hexadien-1-ol is used and extensively characterized with several key features, including good solvation capacity, mild melting point (30.5 °C), and exclusive antioxidant property, enabling a high-efficiency, low-threshold, and photostable TTA-UC system without energy-intensive degassing processes. In-depth characterization reveals that the triplet diffusion among the transient species, i.e., 3sensitizer* and 3acceptor*, is efficient and well protected from oxygen quenching in both aerated liquid- and solid-phase 2,4-hexadien-1-ol. We also propose a new strategy for the nanoencapsulation of PCM by employing hollow mesoporous silica nanoparticles as vehicles. This scheme is applicable to both aqueous- and solid-phase TTA-UC systems as well as suitable for various applications, such as thermal energy storage and smart drug delivery.

In-situ food spoilage monitoring using a wireless chemical receptor-conjugated graphene electronic nose.

Monitoring food spoilage is one of the most effective methods for preventing food poisoning caused by biogenic amines or microbes. Therefore, various analytical techniques have been introduced to detect low concentrations of cadaverine (CV) and putrescine (PT), which are representative biogenic polyamines involved in food spoilage (5-8 ppm at the stage of initial decomposition after storage for 5 days at 5 °C and 17-186 ppm at the stage of advanced decomposition after storage for 7 days at 5 °C). Although previous methods showed selective CV and PT detection even at low concentrations, the use of these methods remains challenging in research areas that require in-situ, real-time, on-site monitoring. In this study, we demonstrated for the first time an in-situ high-performance chemical receptor-conjugated graphene electronic nose (CRGE-nose) whose limits of detection (LODs), 27.04 and 7.29 ppb, for CV and PT are up to 102 times more sensitive than those of conventional biogenic amine sensors. Specifically, the novel chemical receptors 2,7-bis(3-morpholinopropyl)benzo[lmn][3,8] phenanthroline-1,3,6,8(2H,7H)-tetraone (NaPhdiMor (NPM)) and 2,7-bis(2-((3-morpholinopropyl)amino)ethyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NaPhdiEtAmMor (NPEAM)) were designed on the basis of density functional theory (DFT) calculations, and their interaction mechanism was characterized by a DFT 3D simulation. Interestingly, the CRGE-nose was connected on a micro sim chip substrate via wire bonding and then integrated into wireless portable devices, resulting in a cost-effective, high-performance prototype CRGE-nose device capable of on-site detection. The portable CRGE-nose can be used for in-situ monitoring of CV and PT concentration changes as low as 27.04 and 7.29 ppb in real meats such as pork, beef, lamb and chicken.

Feasibility study on transcutaneous auricular vagus nerve stimulation using millimeter waves.

Objective. Electrical stimulation of the auricular vagus nerve is a non-invasive neuromodulation technique that has been used for various conditions, including depression, epilepsy, headaches, and cerebral ischemia. However, unwanted non-vagal nerve stimulations can occur because of diffused stimulations. The objective of this study is to develop a region-specific non-invasive vagus nerve stimulation (VNS) technique using the millimeter wave (MMW) as a stimulus for the auricular branch of the vagus nerve (ABVN).Approach. A numerical simulation was conducted to ascertain whether the MMW could excite the ABVN in the human outer-ear with a millimeter-scale spatial resolution. Additionally, MMW-induced neuronal responses in seven mice were evaluated. Transcutaneous auricular VNS (ta-VNS) was applied to the cymba conchae innervated by the AVBN using a 60-GHz continuous wave (CW). As a control, the auricle's exterior margin was stimulated and referred to as transcutaneous auricular non-vagus nerve stimulation (ta-nonVNS). During stimulation, the local field potential (LFP) in the nucleus tractus solitarii (NTS), an afferent vagal projection site, was recorded simultaneously.Main results. The ta-VNS with a stimulus level of 13 dBm showed a significant increase in the LFP power in the NTS. The mean increases in power (n = 7) in the gamma high and gamma very high bands were 8.6 ± 2.0% and 18.2 ± 5.9%, respectively. However, the ta-nonVNS with a stimulus level of 13 dBm showed a significant decrease in the LFP power in the NTS. The mean decreases in power in the beta and gamma low bands were 11.0 ± 4.4% and 10.8 ± 2.8%, respectively. These findings suggested that MMW stimulation clearly induced a different response according to the presence of ABVN.Significance. Selective auricular VNS is feasible using the MMW. This study provides the basis for the development of a new clinical treatment option using the stimulation of the ta-VNS with a square millimeter spatial resolution.

In Vitro Activity of a Novel Siderophore-Cephalosporin LCB10-0200 (GT-1), and LCB10-0200/Avibactam, against Carbapenem-Resistant Escherichia coli, Klebsiella pneumoniae, Acinetobacter baumannii, and Pseudomonas aeruginosa Strains at a Tertiary Hospital in Korea.

The siderophore-antibiotic conjugate LCB10-0200 (a.k.a. GT-1) has been developed to combat multidrug-resistant Gram-negative bacteria. In this study, the in vitro activity of LCB10-0200 and LCB10-0200/avibactam (AVI) has been investigated against carbapenem-resistant Escherichia coli, Klebsiella pneumoniae, Acinetobacter baumannii, and Pseudomonas aeruginosa. Minimal inhibitory concentrations (MICs) of LCB10-0200, LCB10-0200/AVI, aztreonam, aztreonam/AVI, ceftazidime, ceftazidime/AVI, and meropenem were measured using the agar dilution method. Whole genome sequencing was performed using Illumina and the resistome was analyzed. LCB10-0200 displayed stronger activity than the comparator drugs in meropenem-resistant E. coli and K. pneumoniae, and the addition of AVI enhanced the LCB10-0200 activity to MIC ≤ 0.12 mg/L for 90.5% of isolates. In contrast, whereas LCB10-0200 alone showed potent activity against meropenem-resistant A. baumannii and P. aeruginosa at MIC ≤ 4 mg/L for 84.3% of isolates, the combination with AVI did not improve its activity. LCB10-0200/AVI was active against CTX-M-, SHV-, CMY-, and KPC- producing E. coli and K. pneumoniae, while LCB10-0200 alone was active against ADC-, OXA-, and VIM- producing A. baumannii and P. aeruginosa. Both LCB10-0200 and LCB10-0200/AVI displayed low activity against IMP- and NDM- producing strains. LCB10-0200 alone exhibited strong activity against selected strains. The addition of AVI significantly increased LCB10-0200 activity against carbapenem-resistant E. coli, K. pneumoniae.

Peroneal Tendon Subluxation and Dislocation in Calcaneus Fractures.

The present study investigated the relationship between type of calcaneal fractures and subluxation or dislocation of peroneal tendon. Also, we investigated clinical outcomes of patients with both calcaneal fractures and dislocations or subluxations of peroneal tendons in early surgical treatments (at the time of surgery for calcaneal fractures) and delayed surgical treatment (at the time of surgery for calcaneal plate removal) for dislocations or subluxations of peroneal tendons. We included 151 patients with calcaneal fractures who were followed for ≥2 years after surgery. Among them, 21 cases (13.9%) required reduction for peroneal tendon subluxation or dislocation. Reductions of peroneal tendons were performed at the time of surgery for calcaneal fractures in 11 cases, whereas the other 10 cases were performed during surgery for calcaneal implant removal. As classified by Essex-Lopresti, 94 cases (62.3%) were joint depression type and 17 (18.1%) were accompanied by dislocations or subluxations of peroneal tendons, whereas 57 (37.7%) were tongue type and 4 (7.0%) were accompanied by dislocations or subluxations of peroneal tendons. As classified by the Sanders system, 96 cases (63.6%) were Sanders A fracture lines, and 18 (18.8%) were accompanied by dislocations or subluxations of peroneal tendons. In 55 cases (36.4%) without Sanders A fracture lines, 3 (5.5%) were accompanied by dislocations or subluxations of peroneal tendons. In conclusion, calcaneal fractures with peroneal tendon dislocations are more common in joint depression type and Sander A type. Also, after a ≥2-year follow-up period, there were no significant differences in visual analog scale or foot and ankle outcome score whether reduction of peroneal tendons was done with reduction of fracture or removal of implant of calcaneus.

Light-driven diffraction grating based on a photothermal actuator incorporating femtosecond laser-induced GO/rGO.

A light-driven diffraction grating incorporating two grating patterns with different pitches atop a photothermal actuator (PTA) has been proposed. It is based on graphene oxide/reduced graphene oxide (GO/rGO) induced via femtosecond laser direct writing (FsLDW). The rGO, its controllable linewidth, and transmission support the formation of grating patterns; its noticeably small coefficient of thermal expansion (CTE), good flexibility, and thermal conductivity enable the fabrication of a PTA consisting of a polydimethylsiloxane layer with a relatively large CTE. Under different intensities of light stimuli, diffraction patterns can be efficiently tailored according to different gratings, which are selectively addressed by incident light beam hinging on the bending of the PTA. This is the first demonstration of combining gratings and PTA, wherein the GO plays the role of a bridge. The light-driven mechanism enables the contactless operation of the proposed device, which can be efficiently induced via FsLDW. The diffraction angle could be changed between 2° and 6° horizontally, and the deviation of side lobes from the main lobe could be altered vertically in a continuous range. The proposed device may provide powerful support for activating dynamic diffraction devices in photothermally contactless schemes.

Narrowband and flexible perfect absorber based on a thin-film nano-resonator incorporating a dielectric overlay.

We developed a flexible perfect absorber based on a thin-film nano-resonator, which consists of metal-dielectric-metal integrated with a dielectric overlay. The proposed perfect absorber exhibits a high quality (Q-)factor of ~ 33 with a narrow bandwidth of ~ 20 nm in the visible band. The resonance condition hinging on the adoption of a dielectric overlay was comprehensively explored by referring to the absorption spectra as a function of the wavelength and thicknesses of the overlay and metal. The results verified that utilizing a thicker metal layer improved the Q-factor and surface smoothness, while the presence of the overlay allowed for a relaxed tolerance during practical fabrication, in favor of high fidelity with the design. The origin of the perfect absorption pertaining to zero reflection was elucidated by referring to the optical admittance. We also explored a suite of perfect absorbers with varying thicknesses. An angle insensitive performance, which is integral to such a flexible optical device, was experimentally identified. Consequently, the proposed thin-film absorber featured an enhanced Q-factor in conjunction with a wide angle of acceptance. It is anticipated that our absorber can facilitate seminal applications encompassing advanced sensors and absorption filtering devices geared for smart camouflage and stealth.

Development of Colonic Organoids Containing Enteric Nerves or Blood Vessels from Human Embryonic Stem Cells.

The increased interest in organoid research in recent years has contributed to an improved understanding of diseases that are currently untreatable. Various organoids, including kidney, brain, retina, liver, and spinal cord, have been successfully developed and serve as potential sources for regenerative medicine studies. However, the application of organoids has been limited by their lack of tissue components such as nerve and blood vessels that are essential to organ physiology. In this study, we used three-dimensional co-culture methods to develop colonic organoids that contained enteric nerves and blood vessels. The development of enteric nerves and blood vessels was confirmed phenotypically and genetically by the use of immunofluorescent staining and Western blotting. Colonic organoids that contain essential tissue components could serve as a useful model for the study of colon diseases and help to overcome current bottlenecks in colon disease research.

High-performance portable graphene field-effect transistor device for detecting Gram-positive and -negative bacteria.

Current techniques for Gram-typing and for diagnosing a pathogen at the early infection stage rely on Gram stains, cultures, Enzyme linked immunosorbent assay (ELISA), polymerase chain reaction (PCR), and gene microarrays, which are labor-intensive and time-consuming approaches. In addition, a delayed or imprecise diagnosis of clinical pathogenic bacteria leads to a life-threatening emergency or overuse of antibiotics and a high-rate occurrence of antimicrobial-resistance microbes. Herein, we report high-performance antibiotics (as bioprobes) conjugated graphene micropattern field-effect transistors (ABX-GMFETs) to facilitate on-site Gram-typing and help in the detection of the presence or absence of Gram-negative and -positive bacteria in the samples. The ABX-GMFET platform, which consists of recognition probes and GM transistors conjugated with novel interfacing chemical compounds, was integrated into the microfluidics to minimize the required human intervention and facilitate automation. The mechanism of binding of ABX-GMFET was based on a charge or chemical moiety interaction between the bioprobes and target bacteria. Subsequently, ABX-GMFETs exhibited unprecedented high sensitivity with a limit of detection (LOD) of 100 CFU/mL (1-9 CFU/mL), real-time target specificity.

Anomalous restoration of sp2 hybridization in graphene functionalization.

The functionalization of nanocarbon materials such as graphene has attracted considerable attention over the past decades. In this work, we designed and synthesized a unique N-heterocyclic carbene compound with a pyrene tail group (NHCp) to investigate how carbene species can be used for the functionalization of graphene. Although the carbene moiety of NHCp has the ability to covalently bond to graphene, the pyrene tail can noncovalently interact with graphene and allows monitoring its surrounding microenvironment. The major characteristics of the resulting nanohybrids were highly dependent on the type of graphene and the NHCp-to-graphene weight ratio. Importantly, despite the covalent functionalization of graphene, an anomalous decrease in the intensity of the Raman D peak and improved conductivity were observed for the nanohybrids. It was found that the covalent bond of NHCp to the graphene edge may allow the hybridization of their orbitals, which affects electronic energy levels and alters the double resonance process that originates the D peak at the edge defect. Importantly, the NHCp compound can act as a π acceptor (not just as a σ donor) via the NHCp-graphene covalent bridge. This is the first report showing that the concept of π-backdonation can be realized in two-dimensional materials, such as graphene, and rationally designed carbene molecules can functionalize graphene without losing their beneficial sp2 hybridization characteristics.

High-Performance Conducting Polymer Nanotube-based Liquid-Ion Gated Field-Effect Transistor Aptasensor for Dopamine Exocytosis.

In this study, ultrasensitive and precise detection of a representative brain hormone, dopamine (DA), was demonstrated using functional conducting polymer nanotubes modified with aptamers. A high-performance aptasensor was composed of interdigitated microelectrodes (IMEs), carboxylated polypyrrole nanotubes (CPNTs) and DA-specific aptamers. The biosensors were constructed by sequential conjugation of CPNTs and aptamer molecules on the IMEs, and the substrate was integrated into a liquid-ion gating system surrounded by pH 7.4 buffer as an electrolyte. To confirm DA exocytosis based on aptasensors, DA sensitivity and selectivity were monitored using liquid-ion gated field-effect transistors (FETs). The minimum detection level (MDL; 100 pM) of the aptasensors was determined, and their MDL was optimized by controlling the diameter of the CPNTs owing to their different capacities for aptamer introduction. The MDL of CPNT aptasensors is sufficient for discriminating between healthy and unhealthy individuals because the total DA concentration in the blood of normal person is generally determined to be ca. 0.5 to 6.2 ng/mL (3.9 to 40.5 nM) by high-performance liquid chromatography (HPLC) (this information was obtained from a guidebook "Evidence-Based Medicine 2018 SCL " which was published by Seoul Clinical Laboratory). The CPNTs with the smaller diameters (CPNT2: ca. 120 nm) showed 100 times higher sensitivity and selectivity than the wider CPNTs (CPNT1: ca. 200 nm). Moreover, the aptasensors based on CPNTs had excellent DA discrimination in the presence of various neurotransmitters. Based on the excellent sensing properties of these aptasensors, the DA levels of exogeneous DA samples that were prepared from PC12 cells by a DA release assay were successfully measured by DA kits, and the aptasensor sensing properties were compared to those of standard DA reagents. Finally, the real-time response values to the various exogeneous DA release levels were similar to those of a standard DA aptasensor. Therefore, CPNT-based aptasensors provide efficient and rapid DA screening for neuron-mediated genetic diseases such as Parkinson's disease.