Dual Chalcogen-Bonding Interaction for High-Performance Filterless Narrowband Organic Photodetectors.

A novel green-absorbing organic molecule featuring dual intramolecular chalcogen bonds is synthesized and characterized. This molecule incorporates two such bonds: one between a tellurium atom and the oxygen atom of a carbonyl moiety, and the other between the tellurium atom and the adjacent nitrogen atom within a pyridine moiety. The molecule, featuring dual intramolecular chalcogen bonds exhibits a narrow absorption spectrum and elevated absorption coefficients, closely aligned with a resonance parameter of approximately 0.5. This behavior is due to its cyanine-like characteristics and favorable electrical properties, which are a direct result of its rigid, planar molecular structure. Therefore, this organic molecule forming dual intramolecular chalcogen bonds achieves superior optoelectronic performance in green-selective photodetectors, boasting an external quantum efficiency of over 65% and a full-width at half maximum of less than 95 nm while maintaining the performance after 1000 h of heating aging at 85 °C. Such organic photodetectors are poised to enhance stacked organic photodetector-on-silicon hybrid image sensors, paving the way for the next-generation of high-resolution and high-sensitivity image sensors.

Bifurcation-enhanced ultrahigh sensitivity of a buckled cantilever.

Buckling, first introduced by Euler in 1744 [Euler L (1744) Opera Omnia I 24:231], a sudden mechanical sideways deflection of a structural member under compressive stress, represents a bifurcation in the solution to the equations of static equilibrium. Although it has been investigated in diverse research areas, such a common nonlinear phenomenon may be useful to devise a unique mechanical sensor that addresses the still-challenging features, such as the enhanced sensitivity and polarization-dependent detection capability. We demonstrate the bifurcation-enhanced sensitive measurement of mechanical vibrations using the nonlinear buckled cantilever tip in ambient conditions. The cantilever, initially buckled with its tip pinned, flips its buckling near the bifurcation point (BP), where the buckled tip becomes softened. The enhanced mechanical sensitivity results from the increasing fluctuations, unlike the typical linear sensors, which facilitate the noise-induced buckling-to-flipping transition of the softened cantilever. This allows the in situ continuous or repeated single-shot detection of the surface acoustic waves of different polarizations without any noticeable wear of the tip. We obtained the sensitivity above 106 V(m/s)-1, a 1,000-fold enhancement over the conventional seismometers. Our results lead to development of mechanical sensors of high sensitivity, reproducibility, and durability, which may be applied to detect, e.g., the directional surface waves on the laboratory as well as the geological scale.

Dynamic Responses of Electrically Driven Quartz Tuning Fork and qPlus Sensor: A Comprehensive Electromechanical Model for Quartz Tuning Fork.

A quartz tuning fork and its qPlus configuration show different characteristics in their dynamic features, including peak amplitude, resonance frequency, and quality factor. Here, we present an electromechanical model that comprehensively describes the dynamic responses of an electrically driven tuning fork and its qPlus configuration. Based on the model, we theoretically derive and experimentally validate how the peak amplitude, resonance frequency, quality factor, and normalized capacitance are changed when transforming a tuning fork to its qPlus configuration. Furthermore, we introduce two experimentally measurable parameters that are intrinsic for a given tuning fork and not changed by the qPlus configuration. The present model and analysis allow quantitative prediction of the dynamic characteristics in tuning fork and qPlus, and thus could be useful to optimize the sensors' performance.

A new multichannel method quantitating TUNEL in detached photoreceptor nuclei.

Nuclear co-localization labels are critical to ocular research. Among these, the TUNEL assay has been established as a gold standard of cell death and apoptosis. While several validated computer-based methods exist to quantitate these markers, including ImageJ Retina Analysis (RA) Toolkit and ImagePro, none verify the count with the nuclear counter stain to confirm nuclear co-localization. We established a new ImageJ-based automated multichannel thresholding (MCT) method to quantitate nuclear co-localized labeling. The MCT method was validated by comparing it with the two published TUNEL analysis in TUNEL-positive photoreceptors in an experimental retinal detachment (RD) model. RDs were induced in murine eyes and cross-sectional images of TUNEL and DAPI counter stain were obtained. Images were classified as "typical" or high density "hotspot" TUNEL regions (n = 10/group). Images were analyzed and compared between the MCT method and the published techniques including both "standard" and "high" settings of the RA Toolkit for detecting lower or higher TUNEL densities, respectively. Additional testing of the MCT method with built-in ImageJ thresholding algorithms was performed to produce fully automated measurements. All images were compared with Bland-Altman mean difference plots to assess the difference in counts and linear regression plots to assess correlation. Comparison between the MCT method and the ImagePro method were found to be well correlated (typical: R2 = 0.8972, hotspot: R2 = 0.9000) with minor to non-significant differences. The RA Toolkit settings were found to be mostly well correlated as well (standard/typical: R2 = 0.8036, standard/hotspot: R2 = 0.4309, high/typical: R2 = 0.7895, high/hotspot: R2 = 0.8738) but were often found to have significantly higher counts than the MCT. In conclusion, the MCT method compared favorably with validated computer-based methods of nuclear marker immunofluorescence quantitation and avoids staining artifacts through the incorporation of the nuclear counter stain to confirm positive cells.

Probing nonlinear rheology layer-by-layer in interfacial hydration water.

Viscoelastic fluids exhibit rheological nonlinearity at a high shear rate. Although typical nonlinear effects, shear thinning and shear thickening, have been usually understood by variation of intrinsic quantities such as viscosity, one still requires a better understanding of the microscopic origins, currently under debate, especially on the shear-thickening mechanism. We present accurate measurements of shear stress in the bound hydration water layer using noncontact dynamic force microscopy. We find shear thickening occurs above ∼ 10(6) s(-1) shear rate beyond 0.3-nm layer thickness, which is attributed to the nonviscous, elasticity-associated fluidic instability via fluctuation correlation. Such a nonlinear fluidic transition is observed due to the long relaxation time (∼ 10(-6) s) of water available in the nanoconfined hydration layer, which indicates the onset of elastic turbulence at nanoscale, elucidating the interplay between relaxation and shear motion, which also indicates the onset of elastic turbulence at nanoscale above a universal shear velocity of ∼ 1 mm/s. This extensive layer-by-layer control paves the way for fundamental studies of nonlinear nanorheology and nanoscale hydrodynamics, as well as provides novel insights on viscoelastic dynamics of interfacial water.

Buckling-Based Non-Linear Mechanical Sensor.

Mechanical sensors provide core keys for high-end research in quantitative understanding of fundamental phenomena and practical applications such as the force or pressure sensor, accelerometer and gyroscope. In particular, in situ sensitive and reliable detection is essential for measurements of the mechanical vibration and displacement forces in inertial sensors or seismometers. However, enhancing sensitivity, reducing response time and equipping sensors with a measurement capability of bidirectional mechanical perturbations remains challenging. Here, we demonstrate the buckling cantilever-based non-linear dynamic mechanical sensor which addresses intrinsic limitations associated with high sensitivity, reliability and durability. The cantilever is attached on to a high-Q tuning fork and initially buckled by being pressed against a solid surface while a flexural stress is applied. Then, buckling instability occurs near the bifurcation region due to lateral movement, which allows high-sensitive detection of the lateral and perpendicular surface acoustic waves with bandwidth-limited temporal response of less than 1 ms.

Pin1-mediated Modification Prolongs the Nuclear Retention of ß-Catenin in Wnt3a-induced Osteoblast Differentiation.

The canonical Wnt signaling pathway, in which ß-catenin nuclear localization is a crucial step, plays an important role in osteoblast differentiation. Pin1, a prolyl isomerase, is also known as a key enzyme in osteogenesis. However, the role of Pin1 in canonical Wnt signal-induced osteoblast differentiation is poorly understood. We found that Pin1 deficiency caused osteopenia and reduction of ß-catenin in bone lining cells. Similarly, Pin1 knockdown or treatment with Pin1 inhibitors strongly decreased the nuclear ß-catenin level, TOP flash activity, and expression of bone marker genes induced by canonical Wnt activation and vice versa in Pin1 overexpression. Pin1 interacts directly with and isomerizes ß-catenin in the nucleus. The isomerized ß-catenin could not bind to nuclear adenomatous polyposis coli, which drives ß-catenin out of the nucleus for proteasomal degradation, which consequently increases the retention of ß-catenin in the nucleus and might explain the decrease of ß-catenin ubiquitination. These results indicate that Pin1 could be a critical target to modulate ß-catenin-mediated osteogenesis.

Superwetting of TiO2 by light-induced water-layer growth via delocalized surface electrons.

Titania, which exhibits superwetting under light illumination, has been widely used as an ideal material for environmental solution such as self-cleaning, water-air purification, and antifogging. There have been various studies to understand such superhydrophilic conversion. The origin of superwetting has not been clarified in a unified mechanism yet, which requires direct experimental investigation of the dynamic processes of water-layer growth. We report in situ measurements of the growth rate and height of the photo-adsorbed water layers by tip-based dynamic force microscopy. For nanocrystalline anatase and rutile TiO2 we observe light-induced enhancement of the rate and height, which decrease after O2 annealing. The results lead us to confirm that the long-range attraction between water molecules and TiO2, which is mediated by delocalized electrons in the shallow traps associated with O2 vacancies, produces photo-adsorption of water on the surface. In addition, molecular dynamics simulations clearly show that such photo-adsorbed water is critical to the zero contact angle of a water droplet spreading on it. Therefore, we conclude that this "water wets water" mechanism acting on the photo-adsorbed water layers is responsible for the light-induced superwetting of TiO2. Similar mechanism may be applied for better understanding of the hydrophilic conversion of doped TiO2 or other photo-catalytic oxides.

A Polar Titanium-Organic Chain with a Very Large Second-Harmonic-Generation Response.

A noncentrosymmetric (NCS) titanium-organic compound, [H2N(CH3)2]TiO{[NC5H3(CO2)2][NC5H4(CO2)]} (CAUMOF-18), has been synthesized by a solvothermal reaction. The aligned unidimensional polar chain structure of CAUMOF-18 consisting of corner-shared distorted TiO5N2 pentagonal bipyramids is attributed to strong hydrogen-bonding and π-π interactions. CAUMOF-18 reveals a very strong second-harmonic-generation efficiency of 400 times that of α-SiO2 and is phase-matchable (type I). Water-molecule-driven reversible centricity conversion and topotactic transformation to TiO2 microrods for CAUMOF-18 are also presented.

Viscometry of single nanoliter-volume droplets using dynamic force spectroscopy.

The viscometry of minute amounts of liquid has been in high demand as a novel tool for medical diagnosis and biological assays. Various microrheological techniques have shown the capability to handle small volumes. However, as the liquid volume decreases down to nanoliter scale, increasingly dominant surface effects complicate the measurement and analysis, which remain a challenge in microrheology. Here, we demonstrate an atomic force microscope-based platform that determines the viscosity of single sessile drops of 1 nanoliter Newtonian fluids. We circumvent interfacial effects by measuring the negative-valued shear elasticity, originating from the retarded fluidic response inside the drop. Our measurement is independent of the liquid-boundary effects, and thus is valid without a priori knowledge of surface tension or contact angle, and consistently holds at a 1 milliliter-scale volume. Importantly, while previous methods typically need a much larger 'unrecoverable' volume above 1 microliter, our simple platform uses only ∼1 nanoliter. Our results offer a quantitative and unambiguous methodology for viscosity measurements of extremely minute volumes of Newtonian liquids on the nanoliter scale.

The Fumigation Toxicity of Three Benzoate Compounds against Phosphine-Susceptible and Phosphine-Resistant Strains of Rhyzopertha dominica and Sitophilus oryzae.

Phosphine (PH3) has been widely used as a fumigant in food storage, but increasing PH3 resistance in major pests makes finding alternative fumigants urgent. Methyl benzoate (MBe), a volatile organic compound regarded to be a food-safe natural product, has recently demonstrated significant toxicity against a variety of insect pests. This study is the first evaluation of the fumigation toxicity of three benzoate compounds, MBe, vinyl benzoate, and ethyl benzoate, against PH3-susceptible and PH3-resistant strains of Rhyzopertha dominica and Sitophilus oryzae. All strains were exposed to the compounds at concentrations up to 20 µL/1.5 L air for 24 h. Compared to vinyl benzoate and ethyl benzoate, MBe induced higher mortality rates in all strains at all concentrations. When food was made available, the lethal median concentration for MBe was 10-17-fold higher than when tested without food. Moreover, no significant differences were observed between the responses of the PH3-susceptible and PH3-resistant strains to the compounds. Notably, S. oryzae was more susceptible to MBe. In laboratory settings, MBe successfully controlled PH3-resistant strains of R. dominica and S. oryzae, making it a viable option for PH3-resistance management. Thus, MBe might be suitable for food security programs as an environmentally benign alternative fumigant.

Ethyl Formate Fumigation against Pineapple Mealybug, Dysmicoccus brevipes, a Quarantine Insect Pest of Pineapples.

Pineapple mealybug, Dysmicoccus brevipes (Hemiptera: Pseudococcidae), is a significant pest in pineapple production and a key trade barrier. We explored the potential use of ethyl formate (EF) as a methyl bromide alternative for the postharvest fumigation of D. brevipes in imported pineapples. When treated at 8 °C for 4 h, EF fumigation was effective against D. brevipes with LCt99, the lethal concentration × time product of EF necessary to achieve 99% mortality of D. brevipes nymphs and adults at 64.2 and 134.8 g h/m3, respectively. Sorption trials conducted with 70 g/m3 EF for 4 h at 8 °C using 7.5, 15 and 30% pineapple loading ratios (w/v) indicated that loading ratio lower than 30% is necessary to achieve the LCt99 values required to control D. brevipes. In a scaled up trial using 1 m3 chamber, EF fumigation with 70 g/m3 for 4 h at 8 °C with 20% pineapple loading ratio (w/v) resulted in a complete control of D. brevipes treated. There were no significant differences in hue values, sugar contents, firmness, and weight loss between EF-treated and untreated pineapples. Our results suggest that EF is a promising alternative to methyl bromide fumigation for the postharvest phytosanitary disinfection of D. brevipes in pineapples.

Unified stress tensor of the hydration water layer.

We present the general stress tensor of the ubiquitous hydration water layer (HWL), based on the empirical hydration force, by combining the elasticity and hydrodynamics theories. The tapping and shear component of the tensor describe the elastic and damping properties of the HWL, respectively, in good agreement with experiments. In particular, a unified understanding of HWL dynamics provides the otherwise unavailable intrinsic parameters of the HWL, which offer additional but unexplored aspects to the supercooled liquidity of the confined HWL. Our results may allow deeper insight on systems where the HWL is critical.

Development of a Concurrent Treatment Technique of Ethyl Formate and Mixtures (Nitrogen, Phosphine) to Control Citrus Mealybug (Planococcus citri).

Currently, the fumigant ethyl formate (EF) is stored as a liquified gas in metal cylinders mixed with carbon dioxide (CO2), but this product type is expensive to manufacture, transport, and maintain in cylinders. To address these problems, we developed a new EF fumigation technique with a nitrogen (N2) carrier. In this report, the susceptibility of citrus mealybugs, one of the most resistant mealybugs to fumigants, to EF was assessed; the phytotoxicity of an EF + N2 concurrent treatment applied to banana fruit was examined to evaluate the efficacy compared to the current EF + CO2 product; and the increased efficacy with a phosphine (PH3) addition to EF + N2 was also assessed. Concurrent treatment of EF and N2 was performed at an LC50 concentration of EF. N2 was applied in seven doses from concentrations of 79% to 95%. The phytotoxicity of EF to bananas was assessed by applying EF at 35 mg/L with N2 at 79%, and the color, sugar content, and weight loss of bananas were measured for 14 days after treatment. The EF with N2 treatment resulted in more than 50% mortality at all growth stages of the mealybug, and there was no significant difference between the untreated and treated banana fruits. EF mixed with PH3 showed a higher efficacy than treatment with EF alone, but only a slight increase in efficacy was observed when the PH3 concentration increased. These results indicate that concurrent treatment with EF and N2 can be used to control mealybugs on banana fruits, and combined treatment with EF and PH3 can also enhance the efficacy against mealybugs.

Giant fluidic impedance of nanometer-sized water bridges: Shear capillary force at the nanoscale.

We analytically show that the interfacial fluid's molecular dynamics of capillary bridges induces both elastic and dissipative forces to the shearing plane. Surprisingly, the nanometer-sized, liquid-solid contact line of the bridges exerts a giant "shear" force on the solid surface, which is 10^{5} higher than the usual viscous interaction and comparable to that of solid-solid direct-contact friction. These results are consistent with previously reported experimental data and may provide clues to longstanding questions on the apparent viscosity of the nanoconfined fluids.

Synergistic Effect of Cold Treatment Combined with Ethyl Formate Fumigation against Drosophila suzukii (Diptera: Drosophilidae).

Drosophila suzukii is a quarantine pest that is rapidly spreading in berries. This study evaluated the synergistic effect of combination treatment with ethyl formate (EF) and cold temperature for D. suzukii control on imported grapes. A higher insecticidal effect was observed at 1 °C than at 5 °C at all developmental stages, and the pupal stage showed the strongest tolerance to cold temperature. After EF fumigation alone, eggs showed the highest tolerance at 216.67 mg·h/L (LCT99 value), and adults showed the highest susceptibility at <27.24 mg·h/L. Among the combination treatment methods, cold temperature after fumigation resulted in the best synergistic effect. The effect of this combination was significant, with 23.3% higher mortality for eggs, 22.4% for larvae, and 23.4% for pupae than observed with EF fumigation alone. Furthermore, the period of complete D. suzukii control in the 12 L desiccator was shorter in the combination treatment group at the LCT80 value than at the LCT50 value of the egg stage. EF showed a very high sorption rate (24%) after 4 h of exposure at a grape loading ratio of 15% in a 0.65 m3 fumigation chamber. As the grape loading ratio for combination treatment decreased, D. suzukii mortality increased, but when EF was administered at the LCT80 value, there was little difference in the mortalities of the eggs and larvae but not the pupae. All D. suzukii developmental stages were completely controlled within 7 days after combination treatment, and phytotoxicity was not observed in grapes. These results suggest that the combination of cold-temperature treatment and EF fumigation could be used for D. suzukii control.

Efficacy and Phytotoxicity Assessment of Successive Application of Methyl Bromide and Cold Treatment on Export Strawberry Fruits.

Recently, spotted wing Drosophila, Drosophila suzukii, is globally prevalent and causes agricultural losses to many fruits. To export Korean strawberry, methyl bromide fumigation is required to remove D. suzukii infestations, but Korean strawberry farmers are worried about fruit damage because methyl bromide can cause phytotoxicity on fresh commodities. In this report, we assessed the efficacy and phytotoxicity of single and successive application of methyl bromide and cold treatment on an export variety of strawberry to reduce fruit damage. The currently recommended dosage of methyl bromide, 40 g/m3 for 3 h at 18 °C, was enough to control all stages of D. suzukii without phytotoxicity. A dosage of 20 g/m3 of methyl bromide treatment for 3 h, followed by 1 d of cold (0 °C) treatment, showed 100% mortality in all growth stages of D. suzukii without fruit damage. Successive application of methyl bromide and cold treatment shows potential as a method of decreasing phytotoxicity and reducing the use of methyl bromide for environmental considerations.

Bacillus anthracis capsule activates caspase-1 and induces interleukin-1beta release from differentiated THP-1 and human monocyte-derived dendritic cells.

The poly-gamma-d-glutamic acid (PGA) capsule is one of the major virulence factors of Bacillus anthracis, which causes a highly lethal infection. The antiphagocytic PGA capsule disguises the bacilli from immune surveillance and allows unimpeded growth of bacilli in the host. Recently, efforts have been made to include PGA as a component of anthrax vaccine; however, the innate immune response of PGA itself has been poorly investigated. In this study, we characterized the innate immune response elicited by PGA in the human monocytic cell line THP-1, which was differentiated into macrophages with phorbol 12-myristate 13-acetate (PMA) and human monocyte-derived dendritic cells (hMoDCs). PGA capsules were isolated from the culture supernatant of either the pXO1-cured strain of B. anthracis H9401 or B. licheniformis ATCC 9945a. PGA treatment of differentiated THP-1 cells and hMoDCs led to the specific extracellular release of interleukin-1beta (IL-1beta) in a dose-dependent manner. Evaluation of IL-1beta processing by Western blotting revealed that cleaved IL-1beta increased in THP-1 cells and hMoDCs after PGA treatment. Enhanced processing of IL-1beta directly correlated with increased activation of its upstream regulator, caspase-1, also known as IL-1beta-converting enzyme (ICE). The extracellular release of IL-1beta in response to PGA was ICE dependent, since the administration of an ICE inhibitor prior to PGA treatment blocked induction of IL-1beta. These results demonstrate that B. anthracis PGA elicits IL-1beta production through activation of ICE in PMA-differentiated THP-1 cells and hMoDCs, suggesting the potential for PGA as a therapeutic target for anthrax.