Buddlejasaponin IV induces apoptotic cell death by activating the mitochondrial­dependent apoptotic pathway and reducing α2ß1 integrin­mediated adhesion in HT­29 human colorectal cancer cells.

Colon cancer is one of the most frequent malignant neoplasms worldwide. Epidemiological studies suggested that the development of colon cancer can be prevented by plant­derived ingredients. In the present study, the chemopreventive activity of buddlejasaponin IV (BS­IV), isolated from the aerial part of Pleurospermum kamtschaticum, was investigated using cell viability, DNA fragmentation, caspase­3 activity, anoikis, cell adhesion, and flow cytometry assays and a murine lung metastasis model. Protein expression levels were detected by western blotting. Treatment with BS­IV significantly reduced cell viability and caused DNA fragmentation in HT­29 human colorectal cancer cells. BS­IV increased the ratio of Bax to Bcl­2 by significantly inhibiting Bcl­2 expression levels. BS­IV reduced expression levels of procaspase­9, procaspase­3, and full­length poly (ADP­ribose) polymerase (PARP) and increased cleaved PARP and nonsteroidal anti­inflammatory drug activated gene­1 expression levels and caspase­3 activity. In addition, BS­IV decreased the attachment of HT­29 cells to the extracellular matrix proteins collagen type I and IV and downregulated cell surface expression of α2ß1 integrin by inhibiting its glycosylation. BS­IV also reduced the expression and phosphorylation levels of focal adhesion kinase (FAK) and Akt, and the reduced FAK and Akt levels were rescued by treatment with a caspase­3 inhibitor Z­VAD­FMK. Furthermore, orally administered BS­IV inhibited the formation of tumor nodules in Balb/C mice intravenously injected with CT­26 murine colorectal cancer cells. Collectively, these findings indicated that BS­IV induces apoptosis via the mitochondrial­dependent pathway by increasing the ratio of Bax to Bcl­2 and activating caspases. BS­IV also induces anoikis by inhibiting α2ß1 integrin­mediated cell adhesion and signaling and inhibits the lung metastasis of colon cancer cells. Therefore, BS­IV may serve as a promising cancer chemopreventive agent.

Evaluation of mouse behavioral responses to nutritive versus nonnutritive sugar using a deep learning-based 3D real-time pose estimation system.

Animals are able to detect the nutritional content of sugar independently of taste. When given a choice between nutritive sugar and nonnutritive sugar, animals develop a preference for nutritive sugar over nonnutritive sugar during a period of food deprivation (Buchanan et al., 2022; Dus et al., 2011; 2015; Tan et al., 2020; Tellez et al., 2016). To quantify behavioral features during an episode of licking nutritive versus nonnutritive sugar, we implemented a multi-vision, deep learning-based 3D pose estimation system, termed the AI Vision Analysis for Three-dimensional Action in Real-Time (AVATAR)(Kim et al., 2022). Using this method, we found that mice exhibit significantly different approach behavioral responses toward nutritive sugar versus nonnutritive sugar even before licking a sugar solution. Notably, the behavioral sequences during the approach toward nutritive versus nonnutritive sugar became significantly different over time. These results suggest that the nutritional value of sugar not only promotes its consumption but also elicits distinct repertoires of feeding behavior in deprived mice.

Mass-Scalable Molecular Monolayer for Ni-Rich Cathode Powder: Solution for Microcrack Failure in Lithium-Ion Batteries.

Ni-rich layered oxide with high reversible capacity, low manufacturing cost, and high potential is recognized as the best practical cathode material for high energy density lithium-ion batteries for affordable electric vehicles. However, they suffer from a poor cycle life owing to internal microcracks, which have been perceived to be due to anisotropic volume changes. Herein, the failure mechanism as well as improved cycle life is demonstrated by a self-assembled molecular monolayer (SAM) on Ni-rich layered oxide powder with a gas-phase precursor of octyltrichlorosilane (OTS), enabling mass-scalable manufacturing. The SAM process with a low heating temperature of 130 °C compared to the commonly used coating is also suitable to the chemically fragile Ni-rich layered oxide. Also, a homogeneous angstrom-level OTS coating is beneficial for preserving the energy density of batteries. In particular, OTS, with electrolyte-phobic functionality, is very effective for mitigating the inherent microcrack failure of the particles by reducing the internal electrolyte decomposition by controlling electrolyte wetting into secondary particles. Systematic surface analyses of the cross section of Ni-rich electrode with the OTS coating found greatly improved particle stability after 100 cycles in comparison with pristine material.

Characteristics of Heat Waves From a Disaster Perspective.

In September 2018, heat waves were declared to be a type of natural disaster by the Framework Act on the Management of Disasters and Safety. The present study examined the characteristics of heat waves from the perspectives of meteorological phenomena and health damage. The government's efforts to minimize the damages incurred by heat waves are summarized chronologically. Furthermore, various issues pertaining to heat waves that are being raised in our society despite the government's efforts are summarized by analyzing big data derived from reported news and academic articles.

Rapid, biphasic CRF neuronal responses encode positive and negative valence.

Corticotropin-releasing factor (CRF) that is released from the paraventricular nucleus (PVN) of the hypothalamus is essential for mediating stress response by activating the hypothalamic-pituitary-adrenal axis. CRF-releasing PVN neurons receive inputs from multiple brain regions that convey stressful events, but their neuronal dynamics on the timescale of behavior remain unknown. Here, our recordings of PVN CRF neuronal activity in freely behaving mice revealed that CRF neurons are activated immediately by a range of aversive stimuli. By contrast, CRF neuronal activity starts to drop within a second of exposure to appetitive stimuli. Optogenetic activation or inhibition of PVN CRF neurons was sufficient to induce a conditioned place aversion or preference, respectively. Furthermore, conditioned place aversion or preference induced by natural stimuli was significantly decreased by manipulating PVN CRF neuronal activity. Together, these findings suggest that the rapid, biphasic responses of PVN CRF neurons encode the positive and negative valences of stimuli.

Selective bright and dark mode excitation in coupled nanoantennas.

Coupled nanoantennas as metamaterial unit elements possess peculiar spectral and radiational behaviors. We show that nanoantennas made of two identical plasmonic slot resonators can greatly enhance the quality factors of resonance spectra and control radiation patterns through the selective excitation of bright and dark coupled modes. We confirm experimentally the enhanced quality factor of a bright mode in coupled nanoantennas. Adding phase modulators to the coupled microwave antennas, we demonstrate the "dark mode only" excitation of coupled microwave antennas with an incident plane wave. We also show that the bright-to-dark mode conversion and the related changes in radiation patterns can be controlled by the polarization of incident waves. In particular, we achieve leftward or rightward uni-directional radiation upon the injection of left or right circularly polarized waves.

Crystal structure of N,N'-dibenzyl-3,3'-di-meth-oxy-benzidine.

The title compound, (systematic name: N,N'-dibenzyl-3,3'-dimeth-oxy-1,1'-biphenyl-4,4'-di-amine), C28H28N2O2, was synthesized by the reduction of a Schiff base prepared via a condensation reaction between o-dianisidine and benzaldehyde under acidic conditions. The mol-ecule lies on a crystallographic inversion centre so that the asymmetric unit contains one half-mol-ecule. The biphenyl moiety compound is essentially planar. Two intra-molecular N-H⋯O hydrogen bonds occur. The dihedral angle between the terminal phenyl and phenyl-ene rings of a benzidine unit is 48.68 (6)°. The methyl-ene C atom of the benzyl group is disordered over two sets of sites, with occupancy ratio 0.779 (18):0.221 (18). In the crystal, mol-ecules are connected by hydrogen bonding between o-dianisidine O atoms and H atoms of the terminal benzyl groups, forming a one-dimensional ladder-like structure. In the data from DFT calculations, the central biphenyl showed a twisted conformation.

Crystal structure of flucetosulfuron.

The title compound, {systematic name: 1-[3-({[(4,6-di-meth-oxy-pyrimidin-2-yl)carbamo-yl]amino}-sulfon-yl)pyridin-2-yl]-2-fluoro-propyl 2-meth-oxy-acetate}, C18H22FN5O8S, is used as a herbicide (pyrimidinyl-sulfonyl-urea herbicide). The dihedral angle between the mean planes of the pyridine and pyrimidine rings is 86.90 (7)°. In the crystal, N/C-H⋯O hydrogen bonds, C-H⋯F and C-H⋯π inter-actions link adjacent mol-ecules, forming a chain along [020]. A further two C-H⋯O hydrogen bonds together with weak π-π inter-actions [ring centroid separation = 3.7584 (12) Å] further aggregate the structure into a three-dimensional architecture.

Crystal structure of fipronil.

The title compound, C12H4Cl2F6N4OS {systematic name: 5-amino-1-[2,6-di-chloro-4-(tri-fluoro-meth-yl)phen-yl]-4-[(tri-fluoro-methane)sulfinyl]-1H-pyrazole-3-carbo-nitrile}, is a member of the phenyl-pyrazole group of acaricides, and one of the phenyl-pyrazole group of insecticides. The dihedral angle between the planes of the pyrazole and benzene rings is 89.03 (9)°. The fluorine atoms of the tri-fluoro-methyl substituent on the benzene ring are disordered over two sets of sites, with occupancy ratios 0.620 (15):0.380 (15). In the crystal, C-N⋯π inter-actions [N⋯ring centroid = 3.607 (4) Å] together with N-H⋯N and C-H⋯F hydrogen bonds form a looped chain structure along [10[Formula: see text]]. Finally, N-H⋯O hydrogen bonds and C-Cl⋯π inter-actions [Cl⋯ring centroid = 3.5159 (16) Å] generate a three-dimensional structure. Additionally, there are a short inter-molecular F⋯ F contacts present.

A two-dimensional copper(I) coordination polymer based on 1-[2-(cyclo-hexyl-sulfan-yl)eth-yl]pyridin-2(1H)-one.

The reaction of copper(I) iodide with 1-[2-(cyclo-hexyl-sulfan-yl)eth-yl]pyridin-2(1H)-one (L, C13H19NOS) in aceto-nitrile/di-chloro-methane results in a crystalline coordination polymer, namely poly[bis-{µ2-1-[2-(cyclo-hexyl-sulfan-yl)eth-yl]pyridin-2(1H)-one}tetra-µ3-iodido-tetra-copper(I)], [Cu4I4L2] n . The asymmetric unit comprises two ligand mol-ecules, four copper(I) ions and four iodide ions. Inter-estingly, the O atoms are bound to the soft copper(I) ions. The stair-step clusters of Cu and I atoms in the asymmetric unit are linked repeatedly, giving rise to infinite chains along [100]. Neighbouring infinite chains are linked through the L mol-ecules, forming a two-dimensional brick-wall structure. These two-dimensional networks are stacked alternately along [001]. Additionally, there are inter-molecular C-H⋯I hydrogen bonds and C-H⋯π inter-actions between the ligands.

Metasurface electrode light emitting diodes with planar light control.

The ability of metasurfaces to manipulate light at the subwavelength scale offers unprecedented functionalities for passive and active lasing devices. However, applications of metasurfaces to optical devices are rare due to fabrication difficulties. Here, we present quantum dot light emitting diodes (QDLEDs) with a metasurface-integrated metal electrode and demonstrate microscopically controlled LED emission. By incorporating slot-groove antennas into the metal electrode, we show that LED emission from randomly polarized QD sources can be polarized and directed at will. Utilizing the relation between polarization and emission direction, we also demonstrate microscopic LED beam splitting through the selective choice of polarization.

Crystal structure of penoxsulam.

The title compound, C16H14F5N5O5S [systematic name: 2-(2,2-di-fluoro-eth-oxy)-N-(5,8-dimeth-oxy-1,2,4-triazolo[1,5-c]pyrimidin-2-yl)-6-(tri-fluoro-meth-yl)benzene-sulfonamide], is used as a herbicide. The asymmetric unit of this structure comprises two independent mol-ecules, A and B. The dihedral angles between the ring planes of the triazolo-pyrimidine ring systems and the benzene rings are 68.84 (7)° for A and 68.05 (6)° for B. In the crystal, weak inter-molecular π-π inter-actions, with centroid-centroid separations of 3.4456 (17) and 3.5289 (15) Šand C-F⋯π [3.5335 (17) Šand 107.92 (13)°] contacts link adjacent mol-ecules into chains along [001]. C-H⋯O and C-H⋯F hydrogen bonds link type B mol-ecules into chains parallel to (100). Additional C-H⋯F hydrogen bonds together with short F⋯F contacts further aggregate the structure into a three-dimensional network.

Reversible Crystal Transformations and Luminescence Vapochromism by Fast Guest Exchange in Cu(I) Coordination Polymers.

Six Cu(I) coordination polymers (CPs)-[Cu2I2L2]n (1), {[Cu2I2L2]·2MeCN}n (2), [Cu4I4L2]n (3), {[Cu4I4L2]·CH2Cl2}n (4), {[Cu4I4L2]·CHCl3}n (5), and {[Cu4I4L2]·C6H6}n (6)-were synthesized by self-assembly reactions of CuI and the flexible mixed N/S donor ligand 4-(2-(cyclohexylthio)ethoxy)pyridine (L). Single-crystal X-ray diffraction analyses reveal that these 1D CPs form sets of supramolecular isomers; 1 and 2 are based on Cu2I2 rhomboids, while 3-6 are based on cubane Cu4I4 clusters. Crystal-to-crystal transformations of CPs 1-6 were reversible under heat or in an appropriate solvent (acetonitrile, dichloromethane, chloroform, or benzene). In addition, crystal transformations between CPs 1 and 3 occurred through addition of L or CuI. Moreover, CPs 3-6 exhibited reversible guest exchange and crystal transformations on exposure to the vapor of volatile organic compounds and heat. Remarkably, a guest molecule was exchanged by other guest molecules in the vapor phase within very short times and without the use of acetonitrile as a solvent, which normally plays a key role in trapped solvent exchange experiments.

Crystal structure of catena-poly[[bis-(N-acethyl-thio-morpholine-κS)copper(I)]-µ-iodido].

The reaction of copper(I) iodide with N-acetyl-thio-morpholine (L, C6H11NOS) in aceto-nitrile results in a coordination polymer with composition [CuI(L)2] n . The CuI atom is coordinated by two S atoms and two I atoms, adopting a distorted tetra-hedral environment. The µ2-bridging mode of the I atoms gives rise to chains extending parallel to [010]. C-H⋯O hydrogen-bonding inter-actions between the chains lead to a three-dimensional network.

Non-Phase-Transition Luminescence Mechanochromism of a Copper(I) Coordination Polymer.

A copper(I) coordination polymer, [Cu2I2L2]n (CP 1), shows luminescence mechanochromism with a color change from greenish-blue to yellow upon the application of pressure. Powder X-ray diffraction and Raman studies reveal that the changes in the bond lengths in crystalline CP 1 are the main cause of luminescence mechanochromism. The luminescence mechanochromic process of CP 1 preserves its crystallinity with a small lattice distortion, despite very high pressure, and it is a non-phase-transition process. After the addition of several drops of acetonitrile to the ground and compressed samples, the original greenish-blue emissive and crystalline states are restored. Therefore, the luminescence color conversion processes are fully reversible.

Crystal structure of catena-poly[[(N,N-diethyl-3-mesitylsulfonyl-1H-1,2,4-triazole-1-carboxamide-κN1)silver(I)]-µ-nitrato-κ3O,O':O].

The reaction of silver nitrate and cafenstrole (N,N-diethyl-3-mesitylsulfonyl-1H-1,2,4-triazole-1-carboxamide), a triazole herbicide, leads to the title coordination polymer, [Ag(NO3)(C16H22N4O3S)] n , whose asymmetric unit comprises one cafenstrole ligand mol-ecule, one AgI atom and one nitrate ion. The AgI atom, with a distorted trigonal-pyramidal environment, is coordinated by one nitro-gen atom of a triazole ring, two oxygen atoms of a nitrate ion and one oxygen atom of a neighboring nitrate ion. The coordination bonds between silver and oxygen atoms give rise to a one-dimensional (1D) coordination polymer structure along [001]. The dihedral angle between the planes of the triazole and benzene rings is 87.13 (11)°. In the crystal, the coordination polymer is stabilized by C-H⋯O hydrogen bonds and C-H⋯π inter-actions, resulting in a three-dimensional architecture.

A second triclinic polymorph of azimsulfuron.

The title compound, C13H16N10O5S (systematic name: 1-(4,6-di-meth-oxypyrimidin-2-yl)-3-{[1-methyl-4-(2-methyl-2H-tetra-zol-5-yl)pyrazol-5-yl]sulfonyl}urea), is a second triclinic polymorph of this crystal [for the other, see: Jeon et al., (2015 ▸). Acta Cryst. E71, o470-o471]. There are two mol-ecules, A and B, in the asymmetric unit; the dihedral angles between the pyrazole ring and the tetra-zole and di-meth-oxy-pyrimidine ring planes are 72.84 (10) and 37.24 (14)°, respectively (mol-ecule A) and 84.38 (9) and 26.09 (15)°, respectively (mol-ecule B). Each mol-ecule features an intra-molecular N-H⋯N hydrogen bond. In the crystal, aromatic π-π stacking inter-actions [centroid-centroid separations = 3.9871 (16), 3.4487 (14) and 3.5455 (16) Å] link the mol-ecules into [001] chains. In addition, N-H⋯N, N-H⋯O, C-H⋯O and C-H⋯N hydrogen bonds occur, forming a three-dimensional architecture. We propose that the dimorphism results from differences in conformations and packing owing to different inter-molecular inter-actions, especially aromatic π-π stacking.

Gene-gene interactions in gastrointestinal cancer susceptibility.

Cancer arises from complex, multi-layer interactions between diverse genetic and environmental factors. Genetic studies have identified multiple loci associated with tumor susceptibility. However, little is known about how germline polymorphisms interact with one another and with somatic mutations within a tumor to mediate acquisition of cancer traits. Here, we survey recent studies showing gene-gene interactions, also known as epistases, affecting genetic susceptibility in colorectal, gastric and esophageal cancers. We also catalog epistasis types and cancer hallmarks with respect to the interacting genes. A total of 22 gene variation pairs displayed all levels of statistical epistasis, including synergistic, redundant, suppressive and co-suppressive interactions. Five genes primarily involved in base excision repair formed a linear topology in the interaction network, MUTYH-OGG1-XRCC1-PARP1-MMP2, and three genes in mTOR cell-proliferation pathway formed another linear network, PRKAG2-RPS6KB1-PIK3CA. Discrete pairwise epistasis was also found in nucleotide excision repair, detoxification, proliferation, TP53, TGF-ß and other pathways. We propose that three modes of biological interaction underlie the molecular mechanisms for statistical epistasis. The direct binding, linear pathway and convergence modes can exhibit any level of statistical epistasis in susceptibility to gastrointestinal cancers, and this is likely true for other complex diseases as well. This review highlights the link between cancer hallmarks and susceptibility genes.

Large Work Function Modulation of Monolayer MoS2 by Ambient Gases.

Although two-dimensional monolayer transition-metal dichalcogenides reveal numerous unique features that are inaccessible in bulk materials, their intrinsic properties are often obscured by environmental effects. Among them, work function, which is the energy required to extract an electron from a material to vacuum, is one critical parameter in electronic/optoelectronic devices. Here, we report a large work function modulation in MoS2 via ambient gases. The work function was measured by an in situ Kelvin probe technique and further confirmed by ultraviolet photoemission spectroscopy and theoretical calculations. A measured work function of 4.04 eV in vacuum was converted to 4.47 eV with O2 exposure, which is comparable with a large variation in graphene. The homojunction diode by partially passivating a transistor reveals an ideal junction with an ideality factor of almost one and perfect electrical reversibility. The estimated depletion width obtained from photocurrent mapping was ∼200 nm, which is much narrower than bulk semiconductors.

Crystal structure of fenclorim.

In the title compound, C10H6Cl2N2 (systematic name: 4,6-di-chloro-2-phenyl-pyrimidine), which is used commercially as the herbicide safener, fenclorim, the dihedral angle between the di-chloro-pyrimidyl and phenyl rings is 9.45 (10)°. In the crystal, C-H⋯N hydrogen bonds link adjacent mol-ecules, forming chains along the c-axis direction. In addition, weak inter-molecular C-Cl⋯π [3.6185 (10) Å] and π-π [3.8796 (11) Å] inter-actions are present, forming a three-dimensional network.