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.

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.

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.

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.

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.

Structural color filters based on an all-dielectric metasurface exploiting silicon-rich silicon nitride nanodisks.

An all-dielectric metasurface is deemed to serve a potential platform to demonstrate spectral filters. Silicon-rich silicon nitride (SRN), which contains a relatively large portion of silicon, can exhibit higher refractive indices, when compared to silicon nitride. Meanwhile, the extinction coefficient of SRN is smaller than that of hydrogenated amorphous silicon, leading to reduced absorption loss in the shorter wavelength. SRN is therefore recommended as a scattering element from the perspective of realizing all-dielectric metasurfaces. In this work, we propose and embody a suite of highly efficient structural color filters, capitalizing on a dielectric metasurface that consists of a two-dimensional array of SRN nanodisks that are embedded in a polymeric layer. The SRN nanodisks may support the electric dipole (ED) and magnetic dipole (MD) resonances via Mie scattering, thereby leading to appropriate spectral filtering characteristics. The ED and MD are identified from field profile observation with the assistance of finite-difference time-domain simulations. The manufactured color filters are observed to produce various colors in both transmission and reflection modes throughout the visible band, giving rise to a high transmission of around 90% in the off-resonance region and a reflection ranging up to 60%. A variety of colors can be realized by tuning the resonance by adjusting the structural parameters such as the period, diameter, and height of the SRN nanodisks. The spectral position of resonances might be flexibly tuned by tailoring the polymer surrounding the SRN nanodisks. It is anticipated that the proposed coloring devices will be actively used for color displays, imaging devices, and photorealistic color printing.

Inhibiting Reductive Elimination as an Intramolecular Disulfide Dramatically Enhances the Thermal Stability of SAMs on Gold Derived from Bidentate Adsorbents.

The bidentate aromatic adsorbate, 5-(octadecyloxy)-1,3-benzenedimethanethiol (R1ArmDT), with a specific design of extended S-S distance and a geometric constraint to resist cyclic disulfide formation was synthesized. The film formation and thermal stability of self-assembled monolayers (SAMs) derived from R1ArmDT were investigated and compared to those of SAMs derived from an analogous bidentate dithiol 2-(4-(octadecyloxy)-phenyl)propane-1,3-dithiol (R1ArDT), in which the two sulfur atoms can readily form a cyclic disulfide upon reductive elimination from the surface. Although the SAMs derived from R1ArmDT were less densely packed than those derived from R1ArDT, as judged by the data obtained by X-ray photoelectron spectroscopy and polarization modulation infrared reflection absorption spectroscopy, the SAMs derived from R1ArmDT were markedly more thermally stable than those derived from R1ArDT. The greater thermal stability of the R1ArmDT SAMs can be rationalized on the basis of the structure of the bidentate R1ArmDT headgroup, in which the two pendant sulfur atoms cannot access each other intramolecularly to form a cyclic disulfide upon reductive elimination from the surface.

Angle-tolerant linear variable color filter based on a tapered etalon.

We propose and fabricate a linear variable color filter (LVCF) that possesses an enhanced angular tolerance in conjunction with a wide linear filtering range (LFR) by taking advantage of an Ag-TiO2-Ag configuration. The TiO2 cavity is tapered in thickness along the device so that the resonance wavelength can be continuously tuned according to the position. In addition, the metal-dielectric-metal structure is overlaid with a pre-designed graded anti-reflection coating in SiO2 to complete the etalon, thereby maximizing the transmission efficiency across the entire device. The tapered dielectric layers in the proposed filter were fabricated via glancing angle deposition without the help of any mask or moving parts. The center wavelength was scanned from 410 nm to 566 nm, resulting in an LFR of 156 nm, and the overall spectra exhibited an approximate peak transmission of 40% and spectral bandwidth of 68 nm. The angular tolerance was as large as 45°, incurring a fractional wavelength shift below 4.2%. The resonance wavelength was verified to be linearly dependent on the position, providing a linearity beyond 99%. The proposed LVCF will thus be actively utilized in a portable micro-spectrometer and spectral scanning device.

Structure, Wettability, and Thermal Stability of Organic Thin-Films on Gold Generated from the Molecular Self-Assembly of Unsymmetrical Oligo(ethylene glycol) Spiroalkanedithiols.

Organic thin-films on gold were prepared from a set of new, custom-designed bidentate alkanethiols possessing a mixture of normal alkane and methoxy-terminated tri(ethylene glycol) chains. The new unsymmetrical spiroalkanedithiol adsorbates were of the form [CH3O(CH2CH2O)3(CH2)5]-[CH3(CH2)n+1]C[CH2SH]2 where n = 3 and 14; designated EG3C7-C7 and EG3C7-C18, respectively. Their corresponding self-assembled monolayers (SAMs) on gold were characterized and compared with monothiol SAMs derived from an analogous normal alkanethiol (C18SH) and an alkanethiol terminated with an oligo(ethylene glycol) (OEG) moiety (i.e., EG3C7SH). Ellipsometric data revealed reduced film thicknesses for the double-chained dithiolate SAMs, which perhaps arose from the phase-incompatible merger of a hydrocarbon chain with an OEG moiety, contributing to disorder in the films and/or an increase in chain tilt. The comparable wettabilities of the SAMs derived from EG3C7SH and EG3C7-C7, using water as the contacting liquid, are consistent with exposure of the OEG moieties at both interfaces, whereas the lower wettability of the SAM derived from EG3C7-C18 is consistent with exposure of hydrocarbon chains at the interface. The data collected by X-ray photoelectron spectroscopy confirmed the formation of the new OEG-terminated dithiolate SAMs, and also revealed them as less densely packed monolayers due in part to the large molecular cross section of the OEG moieties and to their double-chained structure with dual surface bonds. Mixed SAMs formed from pairs of monothiols having chain compositions analogous to those of the chains of the new dithiols showed that an EG3C7SH/heptanethiol-mixed SAM and the EG3C7-C7 SAM produced almost identical characterization data, revealing the favorable film formation dynamics for adsorbate structures where the alkyl chains can assemble beneath the phase-incompatible OEG termini. For the mixed SAM formed from EG3C7SH/C18SH, the data indicate that the EG3C7SH component failed to incorporate in the film, demonstrating that the blending of phase-incompatible chains is sometimes best accomplished when both chains exist on a single adsorbate structure. Furthermore, the results of solution-phase thermal desorption tests revealed that the OEG-terminated films generated from the bidentate EG3C7-C7 and EG3C7-C18 adsorbates exhibit enhanced thermal stability when compared to the film generated from monodentate EG3C7SH. In a brief study of protein adsorption, the multicomponent SAMs showed a greater ability to resist the adsorption of fibrinogen on their surfaces when compared to the SAM derived from C18SH, but not better than the monolayer derived from EG3C7SH.

Bidentate Aromatic Thiols on Gold: New Insight Regarding the Influence of Branching on the Structure, Packing, Wetting, and Stability of Self-Assembled Monolayers on Gold Surfaces.

A series of 2-phenylpropane-1,3-dithiol derivatives with single (R1ArDT), double (R2ArDT), and triple (R3ArDT) octadecyloxy chains substituted at the 4-, 3,5-, and, 3,4,5-positions, respectively, on the aromatic ring were synthesized and used to form self-assembled monolayers (SAMs) on gold. Insight into the relationship between the surface chain and headgroup packing densities was investigated by varying the number of surface chains for the bidentate adsorbates in these monolayers. Characterization of the resulting SAMs using ellipsometry, X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, and contact angle goniometry revealed that the tailgroups become more comformationally ordered and more densely packed as the number of alkyl chains per adsorbate was increased. Conversely, the molecular packing density (i.e., number of molecules per unit area) decreased as the number of alkyl chains per adsorbate was increased. Of particular interest, the desorption profiles obtained in isooctane at 80 °C suggested that the bidentate adsorbate with the most densely packed alkyl chains, R3ArDT, was significantly more stable than the other SAMs, producing the following relative order for thermal stability for the dithiolate SAMs: R3ArDT > R2ArDT > R1ArDT.

Robust Maleimide-Functionalized Gold Surfaces and Nanoparticles Generated Using Custom-Designed Bidentate Adsorbates.

A series of custom-designed alkanethioacetate ligands were synthesized to provide a facile method of attaching maleimide-terminated adsorbates to gold nanostructures via thiolate bonds. Monolayers on flat gold substrates derived from both mono- and dithioacetates, with and without oligo(ethylene glycol) (OEG) moieties in their alkyl spacers, were characterized using X-ray photoelectron spectroscopy, polarization modulation infrared reflection-absorption spectroscopy, ellipsometry, and contact angle goniometry. For all adsorbates, the resulting monolayers revealed that a higher packing density and more homogeneous surface were generated when the film was formed in EtOH, but a higher percentage of bound thiolate was obtained in THF. A series of gold nanoparticles (AuNPs) capped with each adsorbate were prepared to explore how adsorbate structure influences aqueous colloidal stability under extreme conditions, as examined visually and spectroscopically. The AuNPs coated with adsorbates that include OEG moieties exhibited enhanced stability under high salt concentration, and AuNPs capped with dithioacetate adsorbates exhibited improved stability against ligand exchange in competition with dithiothreitol (DTT). Overall, the best results were obtained with a chelating dithioacetate adsorbate that included OEG moieties in its alkyl spacer, imparting improved stability via enhanced solubility in water and superior adsorbate attachment owing to the chelate effect.

Semifluorinated Alkylphosphonic Acids Form High-Quality Self-Assembled Monolayers on Ag-Coated Yttrium Barium Copper Oxide Tapes and Enable Filamentization of the Tapes by Microcontact Printing.

A custom-designed semifluorinated phosphonic acid, (9,9,10,10,11,11,12,12,13,13,14,14,15,15,16,16,16-heptadecafluorohexadecyl)phosphonic acid (F8H8PA), and a normal hexadecylphosphonic acid (H16PA) were synthesized and used to generate self-assembled monolayers (SAMs) on commercially available yttrium barium copper oxide (YBCO) tapes. In this study, we wished to evaluate the effectiveness of these monolayer films as coatings for selectively etching YBCO. Initial films formed by solution deposition and manual stamping using a non-patterned polydimethylsiloxane stamp allowed for a comparison of the film-formation characteristics. The resulting monolayers were characterized by X-ray photoelectron spectroscopy (XPS), contact angle goniometry, and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). To prepare line-patterned (filamentized) YBCO tapes, standard microcontact printing (µ-CP) procedures were used. The stamped patterns on the YBCO tapes were characterized by scanning electron microscopy (SEM) before and after etching to confirm the effectiveness of the patterning process on the YBCO surface and energy-dispersive X-ray spectroscopy (EDX) to obtain the atomic composition of the exposed interface.

Unveiling of novel regio-selective fatty acid double bond hydratases from Lactobacillus acidophilus involved in the selective oxyfunctionalization of mono- and di-hydroxy fatty acids.

The aim of this study is the first time demonstration of cis-12 regio-selective linoleate double-bond hydratase. Hydroxylation of fatty acids, abundant feedstock in nature, is an emerging alternative route for many petroleum replaceable products thorough hydroxy fatty acids, carboxylic acids, and lactones. However, chemical route for selective hydroxylation is still quite challenging owing to low selectivity and many environmental concerns. Hydroxylation of fatty acids by hydroxy fatty acid forming enzymes is an important route for selective biocatalytic oxyfunctionalization of fatty acids. Therefore, novel fatty acid hydroxylation enzymes should be discovered. The two hydratase genes of Lactobacillus acidophilus were identified by genomic analysis, and the expressed two recombinant hydratases were identified as cis-9 and cis-12 double-bond selective linoleate hydratases by in vitro functional validation, including the identification of products and the determination of regio-selectivity, substrate specificity, and kinetic parameters. The two different linoleate hydratases were the involved enzymes in the 10,13-dihydroxyoctadecanoic acid biosynthesis. Linoleate 13-hydratase (LHT-13) selectively converted 10 mM linoleic acid to 13S-hydroxy-9(Z)-octadecenoic acid with high titer (8.1 mM) and yield (81%). Our study will expand knowledge for microbial fatty acid-hydroxylation enzymes and facilitate the designed production of the regio-selective hydroxy fatty acids for useful chemicals from polyunsaturated fatty acid feedstocks.

Enhancement of color saturation and color gamut enabled by a dual-band color filter exhibiting an adjustable spectral response.

The enhancement of color saturation and color gamut has been demonstrated, by taking advantage of a dual-band color filter based on a subwavelength rectangular metal-dielectric resonant grating, which exhibits an adjustable spectral response with respect to its relative transmittances at the two bands of green and red, thereby producing any color in between green and red, through the adjustment of incoming light polarization. Also, the prominent features of the spectral response of the filter, namely the bandwidth and resonant wavelength, can be readily adjusted by varying the dielectric layer thickness and the grating pitch, respectively. The dependence of chromaticity coordinates of the filter in the CIE (International Commission on Illumination) 1931 chromaticity diagram upon the parameters of the spectral response, including the center wavelength, spectral bandwidth and sideband level, has been rigorously examined, and their influence on the color gamut and the excitation purity, which is a colorimetric measure of saturation, has been analytically explored at the same time, in order to optimize the color performance of the filters. In particular, a device with wider spectral bandwidth was observed to efficiently extend the color gamut and enhance the color saturation, i.e. the excitation purity for a given sideband level. Two dual-band green-red filters, exhibiting different bandwidths of about 17 and 36 nm, were specifically designed and fabricated. As compared with the case with narrower bandwidth, the device with wider bandwidth was observed to provide both higher excitation purity leading to better color saturation and greater separation of the chromaticity coordinates for the filter output for different incident polarizations, which provides extended color gamut. The proposed device structure may permit the color tuning span to encompass all primary color bands, by adjusting the grating pitch.

Electrically tunable color filter based on a polarization-tailored nano-photonic dichroic resonator featuring an asymmetric subwavelength grating.

We have demonstrated a highly efficient electrically tunable color filter, which provides precise control of color output, taking advantage of a nano-photonic polarization-tailored dichroic resonator combined with a liquid-crystal based polarization rotator. The visible dichroic resonator based on the guided mode resonance, which incorporates a planar dielectric waveguide in Si3N4 integrated with an asymmetric two-dimensional subwavelength Al grating with unequal pitches along its principal axes, exhibited polarization specific transmission featuring high efficiency up to 75%. The proposed tunable color filters were constructed by combining three types of dichroic resonators, each of which deals with a mixture of two primary colors (i.e. blue/green, blue/red, and green/red) with a polarization rotator exploiting a twisted nematic liquid crystal cell. The output colors could be dynamically and seamlessly customized across the blend of the two corresponding primary colors, by altering the polarization via the voltage applied to the polarization rotator. For the blue/red filter, the center wavelength was particularly adjusted from 460 to 610 nm with an applied voltage variation of 2 V, leading to a tuning range of up to 150 nm. And the spectral tuning was readily confirmed via color mapping. The proposed devices may permit the tuning span to be readily extended by tailoring the grating pitches.

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.

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.

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.

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.