Search

Metal-organic frameworks (MOFs) exhibit high adsorption and catalytic activities for various gas species. Because gas adsorption can cause a temperature increase in the MOF, which decreases the capacity and adsorption rate, a strict evaluation of its effect on the thermal conductivity of MOFs is essential. In this study, the thermal conductivity measurement of the MOF under water vapor adsorption was performed using an oriented film of copper tetrakis(4-carboxyphenyl)porphyrin (Cu-TCPP) MOF. A recently developed bidirectional 3ω method enabled the anisotropic thermal conductivity measurement of layered Cu-TCPP while maintaining its ordered structure. The water adsorption was found to increase the thermal conductivity in both in-plane and cross-plane directions with different trends and magnitudes, owing to the structural anisotropy. Molecular dynamics simulations suggest that additional vibrational modes provided by the adsorbed water molecules were the reason for the thermal conductivity enhancement.

Catalytic photo-oxygenation of tau amyloid is a potential therapeutic approach to tauopathies, including Alzheimer disease (AD). However, tau is a complex target containing great molecular size and heterogeneous isoforms/proteoforms. Although catalytic photo-oxygenation has been confirmed when using catalyst 1 and recombinant tau pretreated with heparin, its effects on tau from human patients have not yet been clarified. In this study, focusing on the histidine residues being oxygenated, we have constructed two assay systems capable of quantitatively evaluating the catalytic activity when used on human patient tau: (1) fluorescence labeling at oxygenated histidine sites and (2) LC-MS/MS analysis of histidine-containing fragments. Using these assays, we identified 2 as a promising catalyst for oxygenation of human tau. In addition, our results suggest that aggregated tau induced by heparin is different from actual AD patient tau in developing effective photo-oxygenation catalysts.

Narrowband photodetectors (NPDs) with the capability of detecting light within a selective wavelength range are in high demand for numerous emerging applications such as imaging systems, machine vision, and optical communication. Halide perovskite materials have been developed for eliminating the current complex filtering systems in NPDs due to their beneficial properties, while currently NPDs using perovskite materials are limited by hardly fully eliminated short wavelength response, low charge collection efficiency (CCE), complex fabrication process, and so forth. Herein, a series of perovskite single-crystalline heterojunctions (PSCHs) with a structure of Bi-MAPbX 3 /MAPbY 3 are fabricated by liquid phase epitaxy for filter-free narrowband detection. By varying the halide component in the PSCH, the PSCH-based NPDs can realize continuously tunable spectral response range from blue to NIR regions and ultra-narrow full width at half-maximum (FWHM) of <20 nm. Specifically, the PSCH-based NPD with a high CCE under a large electric filed shows a high spectra rejection ratio of >1000, a fast response speed with rise/fall time of ∼160/∼225 μs, and long-term stability more than 3 months in ambient air. This work provides a simple strategy for designing low-cost and high-performance filter-free NPDs with a tunable spectral response.

Unsymmetric di(heteroaryl)ureas such as HetAr 1 -NHCONH-HetAr 2 are efficiently synthesized from two symmetric ureas, HetAr 1 -NHCONH-HetAr 1 and HetAr 2 -NHCONH-HetAr 2 , by rhodium-catalyzed exchange reactions. The equilibrium in some of the reactions can be shifted to the formation of unsymmetric ureas by the aggregation of the dimers formed by inter- and intramolecular hydrogen bonding.

High-performance In-Ga-Zn-O (IGZO) Schottky diodes (SDs) were fabricated using hydrogenated IGZO (IGZO:H) at a maximum process temperature of 150 °C. IGZO:H was prepared by Ar + O 2 + H 2 sputtering. IGZO:H SDs on a glass substrate exhibited superior electrical properties with a very high rectification ratio of 3.8 × 10 10 , an extremely large Schottky barrier height of 1.17 eV, and a low ideality factor of 1.07. It was confirmed that the hydrogen incorporated during IGZO:H deposition increased the band gap energy from 3.02 eV (IGZO) to 3.29 eV (IGZO:H). Thus, it was considered that the increase in band gap energy (decrease in electron affinity) of IGZO:H contributed to the increase in the Schottky barrier height of the SDs. Angle-resolved hard X-ray photoelectron spectroscopy analysis revealed that oxygen vacancies in IGZO:H were much fewer than those in IGZO, especially in the region near the film surface. Moreover, it was found that the density of near-conduction band minimum states in IGZO:H was lower than that in IGZO. Therefore, IGZO:H played a key role in improving the Schottky interface quality, namely, the increase of Schottky barrier height, decrease of oxygen vacancies, and reduction of near-conduction band minimum states. Finally, we fabricated a flexible IGZO:H SD on a poly(ethylene naphthalate) substrate, and it exhibited record electrical properties with a rectification ratio of 1.7 × 10 9 , Schottky barrier height of 1.12 eV, and ideality factor of 1.10. To the best of our knowledge, both the IGZO:H SDs formed on glass and poly(ethylene naphthalate) substrates achieved the best performance among the IGZO SDs reported to date. The proposed method successfully demonstrated great potential for future flexible electronic applications.

In this study, the synthesis of N -alkyl-2-halophenazin-1-ones has been established. Six N -alkyl-2-halophenazin-1-ones, including WS-9659 B and marinocyanins A and B, were synthesized by the direct oxidative condensation of 4-halo-1,2,3-benzenetriol with the corresponding N -alkylbenzene-1,2-diamines. One of the most significant features of the present method is that it can be successfully applied to the synthesis of N -alkyl-2-chlorophenazin-1-ones. The traditional chlorination of N -alkyl-phenazin-1-ones with N -chlorosuccinimide selectively occurs at the 4-position to afford the undesired N -alkyl-4-chlorophenazin-1-ones. Our synthetic route successfully circumvents this problem, culminating in the first chemical synthesis of WS-9659 B. The cytotoxicity of six N -alkyl-2-halophenazin-1-ones and three N -alkylphenazin-1-ones against human promyelocytic leukemia HL-60, human lung cancer A549, and normal MRC-5 cells was evaluated. Among the compounds tested in this study, 2-chloropyocyanin possesses significant selectivity toward A549 cells. The cytotoxic evaluation provides structural insights into the potency and selectivity of these compounds for cancer cells., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

The new binary chromium sulfide CrS 3 has been synthesized by reaction of Cr 3 S 4 and sulfur mixtures at 800 °C and 13 GPa. CrS 3 crystallizes in an orthorhombic unit cell with a = 4.6742(7) Å, b = 5.7315(8) Å, c = 10.603(2) Å, and V = 284.873(4) Å 3 . It has a novel structure composed of Cr 2 S 10 edge-shared octahedral dimers, which share all of their corners to form a three-dimensional structure. All of the sulfur atoms form S 2 2- disulfide ions with a S-S distance of 2.063(5) or 2.068(8) Å. The structure of CrS 3 is a derivative of the crystal structure of marcasite FeS 2 , in which one in three metal sites of the marcasite structure is vacant in the CrS 3 structure.

The quantities of (5 S )- and (5 R )-5,6-dihydrothymidine (total DHdThd) in frozen beef liver samples were compared between those irradiated by an electron beam (EB) and those subjected to γ-irradiation. DNA extracted from the samples was enzymatically digested to nucleosides and analyzed by liquid chromatography-tandem mass spectrometry for total DHdThd and 2'-deoxythymidine (dThd). Total DHdThd was formed radiospecifically and dose-dependently and the dose-response curves of the ratio of total DHdThd to dThd (total DHdThd/dThd) were similar for both the EB- and γ-irradiated samples. The total DHdThd/dThd was stable after long-term storage (4 months) at -20 °C and the followed heat treatment in a microwave oven. The total DHdThd/dThd could be a robust marker and is equally effective at quantitating both EB- and γ-ray irradiation history. The irradiation doses of raw beef liver samples were estimated using the dose-response curves of the total DHdThd/dThd of other irradiated samples. The ratio of the estimated dose to the actual dose was 0.74-1.30 in the irradiation range of 4.67-7.62 kGy., Competing Interests: The authors declare no competing financial interest.

The drug efflux transporter P-glycoprotein, which is encoded by MDR1 ( ABCB1 ), plays important roles in drug absorption, distribution, and elimination. We previously reported that dietary polyphenols such as quercetin, curcumin, honokiol, magnolol, caffeic acid phenetyl ester (CAPE), xanthohumol, and anacardic acid inhibit P-glycoprotein-mediated drug transport. In the present study, we investigated the effects of polyphenols on the expression of P-glycoprotein using human intestinal epithelial LS174T cells and a reporter plasmid expressing 10.2 kbp of the upstream regulatory region of MDR1 . Honokiol, magnolol, CAPE, xanthohumol, and anacardic acid activated the MDR1 promoter in LS174T cells, and the cellular uptake of rhodamine 123 and calcein-AM, fluorescent substrates of P-glycoprotein, decreased in polyphenol-treated LS174T cells. These results suggest that dietary natural polyphenols can induce the drug efflux transporter P-glycoprotein and have the potential to promote food-drug interactions., Competing Interests: The authors declare no competing financial interest.

A rapid and reliable method for determining irradiation histories of ground beef and prawns was developed on the basis of a method for determining the irradiation history of beef liver by liquid chromatography-tandem mass spectrometry (LC-MS/MS) of 5,6-dihydrothymidine (DHdThd). Improvements in the method included the following: (1) 50% ethanol precipitation in the DNA extraction step was conducted before the RNase step, (2) snake venom phosphodiesterase I was used for DNA digestion to boost liberation of DHdThd, and (3) a matrix-matched calibration curve was used for determining DHdThd by LC-MS/MS analysis. This method successfully determined irradiation histories of ground beef and prawns. Furthermore, a close correlation between the formation of DHdThd and 2-alkylcyclobutanones, which are an established index of irradiation histories, was observed in ground beef. DHdThd in DNA could be a promising candidate for a new index of irradiation histories of various foods.

The effect of drain bias (V(DS)) on the negative gate bias and illumination stress (NBIS) stability of amorphous InGaZnO (a-IGZO) thin-film transistors was investigated using a double-sweeping gate voltage (V(GS)) mode. The variation in the transfer characteristics was explored using current-voltage and capacitance-voltage characteristics. In the initial stage (<1000 s) of NBIS with grounded V(DS) (V(GS) = -40 V and V(DS) = 0 V), the transfer characteristics shifted negatively with an insignificant change in the subthreshold swing (SS) because of hole trapping at an IGZO/gate insulator interface. On the other hand, on-current degradation was observed and was accelerated in the forward measurement as the NBIS duration increased. The results indicated that NBIS induced donor-like defects near the conduction band; however, the transfer curves in the reverse measurement shifted positively without on-current and SS degradations. It was found that the degradations were enhanced by applying a positive V(DS) bias (V(GS) = -40 V and V(DS) = 40 V); in contrast, they could be reduced by applying a small negative V(DS) of V(DS) > V(GS) (V(GS) = -40 V and V(DS) = -20 V). Furthermore, it was confirmed that the NBIS degradations could be suppressed by applying a large negative V(DS) bias of V(DS) < V(GS) (V(GS) = -40 V and V(DS) = -60 V) during NBIS.

Zein, a predominant corn protein, is an alcohol-soluble protein extracted from corn and is characterized by unique film-forming properties. The characteristic brittleness of zein diminishes its usefulness as a structural material. The objective of this work was to study the effect of gamma-irradiation on improving the performance of zein films in packaging applications. This goal has been achieved by irradiating zein film-forming solutions with various doses of gamma-rays, namely, 10, 20, 30, and 40 kGy at dose rate of 10.5 kGy/h, using a Co(60) gamma-radiation source. The impact of radiation process on the structural properties has been explored through far-UV CD spectral analysis and scanning electron microscopy. Additionally, viscosity changes that reflect the effect of radiation treatment on degradation and/or cross-linking of protein chains have been measured. However, improvements in the performance of zein films as packaging materials that can be accomplished by radiation treatment have been investigated via monitoring of the color, surface density, roughness, mechanical properties (tensile strength and elongation percentage), water uptake, and water barrier properties. The results indicated that gamma-irradiation treatment of the film-forming solution can be used to improve the water barrier properties, as well as color and appearance of the zein films. Moreover, a sterilization effect is considered to be an additional advantage for applying gamma- irradiation.

The inactivation of Cryptosporidium parvum was investigated by the use of three different sonicators utilizing the squeeze-film effect, which may occur when ultrasound is irradiated into an extremely thin space and generate intensified pressure in the sample suspension. To expand from the small-scale horn-type sonicator to large-scale cylindrical or cleaning bath sonicators, the inactivation effectwas improved. In the case of the cylindrical sonicator (26.6 kHz, 30 W), 97% of the initial concentration of 2260 oocysts mL(-1) was inactivated at33 mL min(-1) (residence time of approximately 5.2 min). Hundreds of cubic meters of water can be treated per day at several kW using this sonicator. In addition, the simultaneous use of sonication and chlorination showed a beneficial effect on inactivation for C. parvum based on the evaluation of infectivity testing and morphological observation.

A new analytical procedure has been developed to analyze 2-alkylcyclobutanones to detect gamma-ray-irradiated fat-containing foodstuffs. Samples were extracted with an accelerated solvent extraction system via hot and pressurized ethyl acetate in cells. A large amount of fat in the extract was precipitated and removed with filtration by standing at -20 degrees C after the addition of acetonitrile. The extract was further cleaned with a 1 g silica gel mini column, and the radiolytic compounds of 2-docecylcyclobutanone (2-DCB) and 2-tetradecylcyclobutanone (2-TCB) were determined with gas chromatography with mass spectrometry (GC/MS). Sample preparation time before GC/MS was 7-8 h. At first, the procedure was evaluated with a recovery test in eight samples spiked with 2-DCB and 2-TCB at 20 ng/g, resulting in 70-105% recoveries with mostly less than 10% relative standard deviations. The procedure was further evaluated with beef, pork, chicken, and salmon samples irradiated with gamma-rays from 0.7 to 7.0 kGy at -19 degrees C. Both 2-DCB and 2-TCB in most samples were detected with good dose-response relations at all doses, while salmon was detected more than 2 kGy irradiation. The amounts of 2-alkylcyclobutanones produced reflected precursor fatty acids levels in samples, especially for the combination of 2-TCB and stearic acid. The results indicated that the production rate of 2-TCB to stearic acid was more obvious than that of 2-DCB to palmitic acid in frozen samples with gamma-ray irradiation.

We have developed new procedures to identify proteins after they are detected by Western blotting or other interactions such as lectin blotting on membranes. Our method is based on the combination of on-membrane MALDI-TOF mass spectrometry with piezoelectric chemical inkjet technology. Using this method the GroEL, FtsZ, DnaK, and GroES proteins were successfully identified from Escherichia coli after separation on two-dimensional gels, immunostaining, and on-membrane digestion. A glycoprotein detected by lectin blotting with concanavalin A was also identified using this technique.

We constructed a system for the microscale identification of membrane-blotted proteins by proteolytic digestion using an instrument developed with piezoelectric chemical inkjet technology and MS/MS analyses of the resulting peptides with a matrix-assisted laser desorption/ionization-quadrupole ion trap-time-of-flight tandem mass spectrometer (MALDI-QIT-TOF MS). Using this system, bovine serum albumin was clearly identified at levels less than 100 fmol, and proteins from an Escherichia coli extract were also identified by an MS/MS ion search.

A number of compounds used for cancer chemotherapy exert their effects by inhibiting DNA replication. New inhibitors of DNA polymerases, therefore, could be potential candidates for new anti-cancer drugs. This study tested the effects of two phenalenone-skeleton-based compounds, which were isolated from a marine-derived fungus Penicillium sp., sculezonone-B (SCUL-B) and sculezonone-A (SCUL-A), upon DNA polymerase activity. Both compounds inhibited bovine DNA polymerases alpha and gamma, moderately affected the activity of DNA polymerase epsilon, and had almost no effect on HIV-reverse transcriptase and an E. coli DNA polymerase I Klenow fragment. Most notably, whereas SCUL-A inhibited pol beta (IC(50) = 17 microM), SCUL-B has only a weak influence upon this polymerase (IC(50) = 90 microM). Kinetic studies showed that inhibition of both DNA polymerases alpha and beta by either SCUL-A or SCUL-B was competitive with respect to dTTP substrate and noncompetitive with the template-primer. Whereas pol alpha inhibition by SCUL-B is competitive with respect to dATP, the inhibition by SCUL-A was found to be a mixed type with dATP substrate. The K(i) values of SCUL-B were calculated to be 1.8 and 6.8 microM for DNA polymerases alpha and gamma, respectively. The K(i) of DNA polymerase beta for SCUL-A was 12 microM and that for DNA polymerase alpha, 16 microM. Therefore, deletion of the OH-group at C12 enhanced inhibition of DNA polymerase beta. Since computational analyses of these two inhibitors revealed a remarkable difference in the distribution of negative electrostatic charge on the surface of molecules, we infer that different electrostatic charges might elicit different inhibition spectra from these two compounds.