Molecular Self-Assembly and Adsorption Structure of 2,2'-Dipyrimidyl Disulfides on Au(111) Surfaces.

The effects of solution concentration and pH on the formation and surface structure of 2-pyrimidinethiolate (2PymS) self-assembled monolayers (SAMs) on Au(111) via the adsorption of 2,2'-dipyrimidyl disulfide (DPymDS) were examined using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). STM observations revealed that the formation and structural order of 2PymS SAMs were markedly influenced by the solution concentration and pH. 2PymS SAMs formed in a 0.01 mM ethanol solution were mainly composed of a more uniform and ordered phase compared with those formed in 0.001 mM or 1 mM solutions. SAMs formed in a 0.01 mM solution at pH 2 were composed of a fully disordered phase with many irregular and bright aggregates, whereas SAMs formed at pH 7 had small ordered domains and many bright islands. As the solution pH increased from pH 7 to pH 12, the surface morphology of 2PymS SAMs remarkably changed from small ordered domains to large ordered domains, which can be described as a (4√2 × 3)R51° packing structure. XPS measurements clearly showed that the adsorption of DPymDS on Au(111) resulted in the formation of 2PymS (thiolate) SAMs via the cleavage of the disulfide (S-S) bond in DPymDS, and most N atoms in the pyrimidine rings existed in the deprotonated form. The results herein will provide a new insight into the molecular self-assembly behaviors and adsorption structures of DPymDS molecules on Au(111) depending on solution concentration and pH.

Juglone Suppresses LPS-induced Inflammatory Responses and NLRP3 Activation in Macrophages.

The NLRP3 (NACHT, LRR and PYD domains-containing protein 3) inflammasome has been implicated in a variety of diseases, including atherosclerosis, neurodegenerative diseases, and infectious diseases. Thus, inhibitors of NLRP3 inflammasome have emerged as promising approaches to treat inflammation-related diseases. The aim of this study was to explore the effects of juglone (5-hydroxyl-1,4-naphthoquinone) on NLRP3 inflammasome activation. The inhibitory effects of juglone on nitric oxide (NO) production were assessed in lipopolysaccharide (LPS)-stimulated J774.1 cells by Griess assay, while its effects on reactive oxygen species (ROS) and NLRP3 ATPase activity were assessed. The expression levels of NLRP3, caspase-1, and pro-inflammatory cytokines (IL-1ß, IL-18) and cytotoxicity of juglone in J774.1 cells were also determined. Juglone was non-toxic in J774.1 cells when used at 10 µM (p < 0.01). Juglone treatment inhibited the production of ROS and NO. The levels of NLRP3 and cleaved caspase-1, as well as the secretion of IL-1ß and IL-18, were decreased by treatment with juglone in a concentration-dependent manner. Juglone also inhibited the ATPase activities of NLRP3 in LPS/ATP-stimulated J774.1 macrophages. Our results suggested that juglone could inhibit inflammatory cytokine production and NLRP3 inflammasome activation in macrophages, and should be considered as a therapeutic strategy for inflammation-related diseases.

A Flexible High-Performance Photoimaging Device Based on Bioinspired Hierarchical Multiple-Patterned Plasmonic Nanostructures.

In insect eyes, ommatidia with hierarchical structured cornea play a critical role in amplifying and transferring visual signals to the brain through optic nerves, enabling the perception of various visual signals. Here, inspired by the structure and functions of insect ommatidia, a flexible photoimaging device is reported that can simultaneously detect and record incoming photonic signals by vertically stacking an organic photodiode and resistive memory device. A single-layered, hierarchical multiple-patterned back reflector that can exhibit various plasmonic effects is incorporated into the organic photodiode. The multiple-patterned flexible organic photodiodes exhibit greatly enhanced photoresponsivity due to the increased light absorption in comparison with the flat systems. Moreover, the flexible photoimaging device shows a well-resolved spatiotemporal mapping of optical signals with excellent operational and mechanical stabilities at low driving voltages below half of the flat systems. Theoretical calculation and scanning near-field optical microscopy analyses clearly reveal that multiple-patterned electrodes have much stronger surface plasmon coupling than flat and single-patterned systems. The developed methodology provides a versatile and effective route for realizing high-performance optoelectronic and photonic systems.

On-Site Detection of Aflatoxin B1 in Grains by a Palm-Sized Surface Plasmon Resonance Sensor.

Aflatoxins (AFs) are highly toxic compounds that can cause both acute and chronic toxicity in humans. Aflatoxin B1 (AFB1) is considered the most toxic of AFs. Therefore, the rapid and on-site detection of AFB1 is critical for food safety management. Here, we report the on-site detection of AFB1 in grains by a portable surface plasmon resonance (SPR) sensor. For the detection of AFB1, the surface of an SPR Au chip was sequentially modified by cysteine-protein G, AFB1 antibody, and bovine serum albumin (BSA). Then, the sample solution and AFB1-BSA conjugate were flowed onto the Au chip in serial order. In the absence of AFB1, the SPR response greatly increased due to the binding of AFB1-BSA on the Au chip. In the presence of AFB1, the SPR response showed little change because the small AFB1 molecule binds on the Au chip instead of the large AFB1-BSA molecule. By using this portable SPR-based competitive immunoassay, the sensor showed low limits of detection (2.51 ppb) and quantification (16.32 ppb). Furthermore, we successfully detected AFB1 in rice, peanut, and almond samples, which suggests that the proposed sensing method can potentially be applied to the on-site monitoring of mycotoxins in food.

Remarkably enhanced adhesion of coherently aligned catechol-terminated molecules on ultraclean ultraflat gold nanoplates.

We report the characterization and formation of catechol-terminated molecules immobilized on gold nanoplates (Au NPLs) using N-(3,4-dihydroxyphenethyl)-2-mercaptoacetamide (Cat-EAA-SH). Single-crystalline Au NPLs, synthesized using a one-step chemical vapor transport method, have ultraclean and ultraflat surfaces that make Cat-EAA-SH molecules aligned into a well-ordered network of a large-scale. Topographic study of the catechol-terminated molecules on Au NPLs using atomic force microscopy showed more orderly orientation and higher density, leading to significantly higher adhesion as observed from local force-distance curves than those on other Au surfaces. These coherently aligned catechol-terminated molecules on the atomically smooth gold surface led to significanty more reproducible and thus more physico-chemically meaningful measurements than was possible before by employing rough gold surfaces.

Ultra-specific zeptomole microRNA detection by plasmonic nanowire interstice sensor with Bi-temperature hybridization.

MicroRNAs (miRNAs) are emerging new biomarkers for many human diseases. To fully employ miRNAs as biomarkers for clinical diagnosis, it is most desirable to accurately determine the expression patterns of miRNAs. The optimum miRNA profiling method would feature 1) highest sensitivity with a wide dynamic range for accurate expression patterns, 2) supreme specificity to discriminate single nucleotide polymorphisms (SNPs), and 3) simple sensing processes to minimize measurement variation. Here, an ultra-specific detection method of miRNAs with zeptomole sensitivity is reported by applying bi-temperature hybridizations on single-crystalline plasmonic nanowire interstice (PNI) sensors. This method shows near-perfect accuracy of SNPs and a very low detection limit of 100 am (50 zeptomole) without any amplification or labeling steps. Furthermore, multiplex sensing capability and wide dynamic ranges (100 am-100 pm) of this method allows reliable observation of the expression patterns of miRNAs extracted from human tissues. The PNI sensor offers combination of ultra-specificity and zeptomole sensitivity while requiring two steps of hybridization between short oligonucleotides, which could present the best set of features for optimum miRNA sensing method.

Perovskite-Supramolecular Co-Assembly for Chiral Optoelectronics.

Hybrid inorganic-organic perovskites with chiral response and outstanding optoelectronic characteristics are promising materials for next-generation spin-optoelectronics. In particular, two-dimensional (2D) perovskites are promising chiroptical candidates due to their unique ability to incorporate chiral organic cations into their crystal structure, which imparts chirality. To enable their practical applications in chiral optoelectronic devices, it is essential to achieve an anisotropy factor (gCD ∼ 2) in chiral 2D perovskites. Currently, chiral 2D perovskites exhibit a relatively low gCD of 3.1 × 10-3. Several approaches have been explored to improve the chiral response of chiral 2D perovskites, including tailoring the molecular structure of chiral cations and increasing the degree of octahedral tilting in the perovskite lattice. However, current methods for chiral amplification have only achieved a moderate enhancement of gCD by 2-fold and are often accompanied by undesirable shifts or inversion in the circular dichroism spectra. There is a need for a more efficient approach to enhancing the chirality in 2D perovskites. Here, we report an innovative coassembly process that allows us to seamlessly grow chiral 2D perovskites on supramolecular helical structures. We discover that the interactions between perovskites and chiral supramolecular structures promote crystal lattice distortion in perovskites, which improves the chirality of 2D perovskites. Additionally, the obtained hierarchical coassembly can effectively harness the structural chirality of the supramolecular helices. The multilevel chiral enhancement leads to an enhancement in gCD by 2.7-fold without compromising the circular dichroism spectra of 2D perovskites.

SARS-CoV2 mRNA vaccine intravenous administration induces myocarditis in chronic inflammation.

The current COVID-19 mRNA vaccines were developed and applied for pandemic-emergent conditions. These vaccines use a small piece of the virus's genetic material (mRNA) to stimulate an immune response against COVID-19. However, their potential effects on individuals with chronic inflammatory conditions and vaccination routes remain questionable. Therefore, we investigated the effects of mRNA vaccines in a mouse model of chronic inflammation, focusing on their cardiac toxicity and immunogenicity dependent on the injection route. mRNA vaccine intravenous administration with or without chronic inflammation exacerbated cardiac pericarditis and myocarditis; immunization induced mild inflammation and inflammatory cytokine IL-1beta and IL-6 production in the heart. Further, IV mRNA vaccination induced cardiac damage in LPS chronic inflammation, particularly serum troponin I (TnI), which dramatically increased. IV vaccine administration may induce more cardiotoxicity in chronic inflammation. These findings highlight the need for further research to understand the underlying mechanisms of mRNA vaccines with chronic inflammatory conditions dependent on injection routes.

Giant chiral amplification of chiral 2D perovskites via dynamic crystal reconstruction.

Chiral hybrid perovskites show promise for advanced spin-resolved optoelectronics due to their excellent polarization-sensitive properties. However, chiral perovskites developed to date rely solely on the interaction between chiral organic ligand cations exhibiting point chirality and an inorganic framework, leading to a poorly ordered short-range chiral system. Here, we report a powerful method to overcome this limitation using dynamic long-range organization of chiral perovskites guided by the incorporation of chiral dopants, which induces strong interactions between chiral dopants and chiral cations. The additional interplay of chiral cations with chiral dopants reorganizes the morphological and crystallographic properties of chiral perovskites, notably enhancing the asymmetric behavior of chiral 2D perovskites by more than 10-fold, along with the highest dissymmetry factor of photocurrent (gPh) of ~1.16 reported to date. Our findings present a pioneering approach to efficiently amplify the chiroptical response in chiral perovskites, opening avenues for exploring their potential in cutting-edge optoelectronic applications.

Photocatalytic activity of metal-inserted WO3 thin films prepared by RF magnetron sputtering.

Metal (Au,Pt)-inserted WO3 thin films were deposited on quartz glass using a radio frequency magnetron sputtering method. Their structural and optical properties were analyzed by scanning electron microscopy, X-ray diffractometry, absorption spectrometry, and photoluminescence spectrometry. The photocatalytic activities of the films were investigated by the measurement of photodecomposition of methylene blue under visible-ray irradiation. Metal-inserted WO3 films showed higher photocatalytic activity than WO3 film. Pt-inserted WO3 thin film showed the most effective decomposition efficiency, it is due to the high absorption and the suppression of recombination between photo-excited electrons and holes.

CRISPR/Cas-Assisted Nanoneedle Sensor for Adenosine Triphosphate Detection in Living Cells.

The clustered regularly interspaced short palindromic repeats (CRISPR)-associated protein (Cas) (CRISPR/Cas) systems have recently emerged as powerful molecular biosensing tools based on their collateral cleavage activity due to their simplicity, sensitivity, specificity, and broad applicability. However, the direct application of the collateral cleavage activity for in situ intracellular detection is still challenging. Here, we debut a CRISPR/Cas-assisted nanoneedle sensor (nanoCRISPR) for intracellular adenosine triphosphate (ATP), which avoids the challenges associated with intracellular collateral cleavage by introducing a two-step process of intracellular target recognition, followed by extracellular transduction and detection. ATP recognition occurs by first presenting in the cell cytosol an aptamer-locked Cas12a activator conjugated to nanoneedles; the recognition event unlocks the activator immobilized on the nanoneedles. The nanoneedles are then removed from the cells and exposed to the Cas12a/crRNA complex, where the activator triggers the cleavage of an ssDNA fluorophore-quencher pair, generating a detectable fluorescence signal. NanoCRISPR has an ATP detection limit of 246 nM and a dynamic range from 1.56 to 50 µM. Importantly, nanoCRISPR can detect intracellular ATP in 30 min in live cells without impacting cell viability. We anticipate that the nanoCRISPR approach will contribute to broadening the biomedical applications of CRISPR/Cas sensors for the detection of diverse intracellular molecules in living systems.

Dual-Functional Solar-to-Steam Generation and SERS Detection Substrate Based on Plasmonic Nanostructure.

Solar-to-steam (STS) generation based on plasmonic materials has attracted significant attention as a green method for producing fresh water. Herein, a simple in situ method is introduced to fabricate Au nanoparticles (AuNPs) on cellulose filter papers as dual-functional substrates for STS generation and surface-enhanced Raman spectroscopy (SERS) sensing. The substrates exhibit 90% of broadband solar absorption between 350 and 1800 nm and achieve an evaporation rate of 0.96 kg·m-2·h-1 under 1-sun illumination, room temperature of 20 °C, and relative humidity of 40%. The STS generation of the substrate is stable during 30 h continuous operation. Enriched SERS hotspots between AuNPs endow the substrates with the ability to detect chemical contamination in water with ppb limits of detection for rhodamine 6G dye and melamine. To demonstrate dual-functional properties, the contaminated water was analyzed with SERS and purified by STS. The purified water was then analyzed with SERS to confirm its purity. The developed substrate can be an improved and suitable candidate for fresh water production and qualification.

Ultrasensitive Near-Infrared Circularly Polarized Light Detection Using 3D Perovskite Embedded with Chiral Plasmonic Nanoparticles.

Chiral organic ligand-incorporated low-dimensional metal-halide perovskites have received increasing attention for next-generation photodetectors because of the direct detection capability of circularly polarized light (CPL), which overcomes the requirement for subsidiary optical components in conventional CPL photodetectors. However, most chiral perovskites have been based on low-dimensional structures that confine chiroptical responses to the ultraviolet (UV) or short-wavelength visible region and limit photocurrent due to their wide bandgap and poor charge transport. Here, chiroptical properties of 3D Cs0.05 FA0.5 MA0.45 Pb0.5 Sn0.5 I3 polycrystalline films are achieved by incorporating chiral plasmonic gold nanoparticles (AuNPs) into the mixed PbSn perovskite, without sacrificing its original optoelectronic properties. CPL detectors fabricated using chiral AuNP-embedded perovskite films can operate without external power input; they exhibit remarkable chirality in the near-infrared (NIR) region with a high anisotropy factor of responsivity (gres ) of 0.55, via giant plasmon resonance shift of chiral plasmonic AuNPs. In addition, a CPL detector array fabricated on a plastic substrate demonstrates highly sensitive self-powered NIR detection with superior flexibility and durability.

Mammalian Cochlear Hair Cell Imaging Using Optical Coherence Tomography (OCT): A Preliminary Study.

OBJECTIVES: This study aimed to investigate the feasibility of using optical coherence tomography (OCT) to provide information about cochlear microanatomy at a cellular level, specifically of cochlear hair cells in mammals. MATERIALS AND METHODS: A total of 10 Sprague-Dawley rats were divided into 2 experimental groups for comparing the arrangement of normal and damaged hair cells. Postnatal day 3 Sprague-Dawley rats were used to test the swept-source OCT system, and the images recorded were compared with fluorescence microscope images. RESULTS: Intracochlear structures (the inner hair cells, outer hair cells, and auditory nerve fibers) were clearly visualized at the individual cellular level. CONCLUSION: These images reflect the ability of OCT to provide images of the inner hair cells, outer hair cells, and auditory nerve fibers (ex vivo). OCT is a promising technology, and these findings could be used to encourage research in the area of cochlear microstructure imaging in the future.

Preclinical mouse model of optical coherence tomography for subcortical brain imaging without dissection.

The purpose of this study was to investigate the feasibility of using optical coherence tomography (OCT) to identify internal brain lesions, specifically intracerebral hemorrhage, without dissection. Mice with artificially injected brain hematomas were used to test the OCT system, and the recorded images were compared with microscopic images of the same mouse brains after hematoxylin and eosin staining. The intracranial structures surrounding the hematomas were clearly visualized by the OCT system without dissection. These images reflect the ability of OCT to determine the extent of a lesion in several planes. OCT is a useful technology, and these findings could be used as a starting point for future research in intraoperative imaging.

Development of 6E3 antibody-mediated SERS immunoassay for drug-resistant influenza virus.

Influenza viruses are responsible for several pandemics and seasonal epidemics and pose a major public health threat. Even after a major outbreak, the emergence of drug-resistant influenza viruses can pose disease control problems. Here we report a novel 6E3 monoclonal antibody capable of recognizing and binding to the H275Y neuraminidase (NA) mutation, which has been associated with reduced susceptibility of influenza viruses to NA inhibitors. The 6E3 antibody had a KD of 72.74 µM for wild-type NA and 32.76 pM for H275Y NA, suggesting that it can identify drug-resistant pandemic H1N1 (pH1N1) influenza virus. Molecular modeling studies also suggest the high-affinity binding of this antibody to pH1N1 H275Y NA. This antibody was also subject to dot-blot, enzyme-linked immunosorbent assay, bare-eye detection, and lateral flow assay to demonstrate its specificity to drug-resistant pH1N1. Furthermore, it was immobilized on Au nanoplate and nanoparticles, enabling surface-enhanced Raman scattering (SERS)-based detection of the H275Y mutant pH1N1. Using 6E3 antibody-mediated SERS immunoassay, the drug-resistant influenza virus can be detected at a low concentration of 102 plaque-forming units/mL. We also detected pH1N1 in human nasopharyngeal aspirate samples, suggesting that the 6E3-mediated SERS assay has the potential for diagnostic application. We anticipate that this newly developed antibody and SERS-based immunoassay will contribute to the diagnosis of drug-resistant influenza viruses and improve treatment strategies for influenza patients.

Au@ZIF-8 SERS paper for food spoilage detection.

Putrescine and cadaverine are important volatile indicators for the evaluation of food spoilage. In this study, a metal-organic framework (MOF)-coated surface-enhanced Raman scattering (SERS) paper platform for the detection of putrescine and cadaverine is developed. Au@ zeolite imidazolate framework-8 (ZIF-8) SERS paper is fabricated by the coating of ZIF-8 layer on a Au nanoparticle-impregnated paper that is prepared by dry plasma reduction. The Au@ZIF-8 SERS paper is characterized by scanning electron microscope, energy-dispersive X-ray spectroscopy, X-ray diffraction, and N2 sorption isotherm. The ZIF-8 layer enables the accumulation of gaseous molecules and also provides enhancement of SERS signals. The fluorescence, SERS, and simulation results prove the improved detection ability of the Au@ZIF-8 platform for the volatile molecules. For the selective detection of putrescine and cadaverine, the Au@ZIF-8 SERS paper is functionalized with 4-mercatobenzaldehyde (4-MBA). The 4-MBA molecule acts as a Raman reporter and also a specific receptor for the volatile amine molecules. Using the intensity ratiometric detection of 4-MBA-functionalized Au@ZIF-8 SERS paper, putrescine and cadaverine are quantitatively detected with detection limits of 76.99 and 115.88 parts per billion, respectively. Furthermore, the detection of volatile amine molecules released from spoiled salmon, chicken, beef, and pork samples is demonstrated. It is anticipated that the MOF-coated SERS paper platforms will be applicable not only in food safety but other applications including disease diagnosis and environmental monitoring.

Relation between work function and structural properties of triangular defects in 4H-SiC epitaxial layer: Kelvin probe force microscopic and spectroscopic analyses.

To understand the relationship between the work function and structural properties of sufficiently expanded triangular defects (size: ∼250 µm) in the 4H-SiC epitaxial layer, Kelvin probe force microscopy (KPFM) and spectroscopic [micro-Raman spectroscopy and photoluminescence (PL)] analyses were performed. Spectroscopic analysis demonstrated that the triangular defects mostly comprise the 3C polytypes and that it experiences internal stress, defects, and defect-induced carrier generation. The distinguishable areas in the triangular defects had surface potential values different from those of the 4H-SiC matrix; this could be explained by the work function difference, which arises from variations in the electron affinity of the 3C polytype as well as the positional variations of the Fermi energy level in terms of electron concentration. In addition, tensile-stress-induced surface disorder leading to variations in electron affinity was discussed. The mechanical properties of the triangular defects measured by a nanoindenter were significantly deteriorated because of many dislocation arrays and stacking faults with many broken and/or strained bonds.

Extratympanic Observation of Middle and Inner Ear Structures in Rodents Using Optical Coherence Tomography.

OBJECTIVES: This study aimed to investigate whether optical coherence tomography (OCT) provides useful information about the microstructures of the middle and inner ear via extratympanic approach and thereby could be utilized as an alternative diagnostic technology in ear imaging. METHODS: Five rats and mice were included, and the swept-source OCT system was applied to confirm the extent of visibility of the middle and inner ear and measure the length or thickness of the microstructures in the ear. The cochlea was subsequently dissected following OCT and histologically evaluated to compare with the OCT images. RESULTS: The middle ear microstructures such as ossicles, stapedial artery and oval window through the tympanic membrane with the OCT could be confirmed in both rats and mice. It was also possible to obtain the inner ear images such as each compartment of the cochlea in the mice, but the bone covering bulla needed to be removed to visualize the inner ear structures in the rats which had thicker bulla. The bony thickness covering the cochlea could be measured, which showed no significant differences between OCT and histologic image at all turns of cochlea. CONCLUSION: OCT has been shown a promising technology to assess real-time middle and inner ear microstructures noninvasively with a high-resolution in the animal model. Therefore, OCT could be utilized to provide additional diagnostic information about the diseases of the middle and inner ear.

Visualization of left ventricular Purkinje fiber distribution using widefield optical coherence microscopy.

BACKGROUND: The distribution and connection of ventricular Purkinje fibers are known to be associated with idiopathic left ventricular arrhythmias. Unusual anatomy is one of the important factors associated with catheter ablation success rate. With the widefield high-speed, swept-source optical coherence microscopy (OCM) and light microscope, we visualized the left ventricular Purkinje fiber distribution. METHODS: Left ventricular walls of five adult ovine hearts were incised from the mitral annulus to the apex. Using the widefield OCM technique and light microscopy, we observed the distribution, direction, depth, and dividing patterns of the Purkinje network with multiple tangential angles and without tissue destruction. RESULTS: Widefield OCM was used to characterize the ovine heart Purkinje network system in a 4 × 4 mm2 field. Left ventricular Purkinje fibers traveled in the sub-endocardial area near the left-sided peri-membranous septal area and ran like a wide hair bundle. The distal branching fibers penetrated to the endocardium and connected to the contractile muscle. In this distal area, Purkinje fibers were connected to each other, forming multiple layers. Some Purkinje fibers were directly connected within the false tendon between the papillary muscles or between the trabeculations. Some free-running Purkinje fibers were directly connected to the papillary muscle from the left bundle. CONCLUSION: Using widefield OCM, we were able to observe the left bundle and its branching patterns in ovine left ventricle without tissue destruction. This might be applied to future cardiac ablation procedures.