The effect of avian eggshell membrane structure on microbial penetration: A simulation study.

Avian eggshells exhibit excellent antimicrobial properties. In this study, we conducted simulation experiments to explore the defense mechanisms of eggshell membranes with regards to their physical features. We developed a mathematical model for the movement of microorganisms and estimated their penetration ratio into eggshell membranes based on several factors, including membrane thickness, microbial size, directional drift, and attachment probability to membrane fibers. These results not only suggest that an eggshell membrane with multiple layers and low porosity indicates high antimicrobial performance, but also imply that the fibrous network structure of the membrane might contribute to effective defense. Our simulation results aligned with experimental findings, specifically in measuring the penetration time of Escherichia coli through the eggshell membrane. We briefly discuss the significance and limitations of this pilot study, as well as the potential for these results, to serve as a foundation for the development of antimicrobial materials.

Exploring the role of loop tunnels in enhancing termite food transport efficiency: A simulation approach.

Subterranean termites construct a network of tunnels beneath the ground, comprising a main tunnel and branch tunnels. While termites do not construct tunnels that turn back in a "U" shape, the intersection of main and branch tunnels often forms closed curved structures (a loop). The loop structure can have either a positive or negative effect on the transport efficiency of termites in food transportation. However, little research has been conducted on the impact of loop tunnels on transport efficiency (E) due to the technical difficulties associated with direct observation. In this study, we used an individual-based model to simulate termite behavior during food transportation within a tunnel composed of a main tunnel and a loop tunnel. The model incorporates four control variables: the number of introduced simulated termites (k1), the probability of a simulated termite using a loop tunnel when walking towards a food or nest site (k2 or k3), and the length of the loop tunnel (k4). The simulation results reveal that the E value is high for (k2, k3) = (high, high), (low, low), (high, low), and (low, high) when the length of the loop tunnel is relatively short. However, when the length of the loop tunnel is relatively long, E is high only for (k2, k3) = (high, low) and (low, high). We found that these results are primarily influenced by the frequency of traffic jams. Therefore, termites would benefit from adopting strategies that reduce the occurrence of traffic jams during food transportation. In the Discussion section, we briefly touch on the strategy from an ecological perspective.

SiSe2 for Superior Sulfide Solid Electrolytes and Li-Ion Batteries.

Among the various existing layered compounds, silicon diselenide (SiSe2) possesses diverse chemical and physical properties, owing to its large interlayer spacing and interesting atomic arrangements. Despite the unique properties of layered SiSe2, it has not yet been used in energy applications. Herein, we introduce the synthesis of layered SiSe2 through a facile solid-state synthetic route and demonstrate its versatility as a sulfide solid electrolyte (SE) additive for all-solid-state batteries (ASSBs) and as an anode material for Li-ion batteries (LIBs). Li-argyrodites with various compositions substituted with SiSe2 are synthesized and evaluated as sulfide SEs for ASSBs. SiSe2-substituted Li-argyrodites exhibit high ionic conductivities, low activation energies, and high air stabilities. In addition, when using a sulfide SE, the ASSB full cell exhibits a high discharge/charge capacity of 202/169 mAh g-1 with a high initial Coulombic efficiency (ICE) of 83.7% and stable capacity retention at 1C after 100 cycles. Furthermore, the Li-storage properties of SiSe2 as an anode material for LIBs are evaluated, and its Li-pathway mechanism is explored by using various cutting-edge ex situ analytical tools. Moreover, the SiSe2 nanocomposite anode exhibits a high Li- insertion/extraction capacity of 950/775 mAh g-1, a high ICE of 81.6%, a fast rate capability, and stable capacity retention after 300 cycles. Accordingly, layered SiSe2 and its versatile applications as a sulfide SE additive for ASSBs and an anode material for LIBs are promising candidates in energy storage applications as well as myriad other applications.

Exploring the effects of high curvature section distribution and density in termite tunnels on food transport efficiency: A simulation study.

This study explores the food transport efficiency of termite using an individual-based model. Termites are believed to have evolved tunneling patterns that optimize food search and transport efficiency. However, few studies have investigated transport efficiency due to the difficulty of field observations. The model is characterized by four control variables: the number of simulated termites participating in transport (k1), the distribution of high curvature sections of the termite tunnel (k2), a quantity related to the density of the tunnel sections (k3), and the duration of traffic jams (k4). As k3 increases, the total length of the high curvature section decreases. Our simulation results show that the E(k1, k2) maps for k3 and k4 contain two modes: Mode A shows that E decreases with increasing k1 due to an increase in traffic jams, while Mode B shows E increasing with increasing k1 due to a decrease in the density of curved sections and an increase in jamming resolution time. The partial rank correlation coefficient analysis reveals that k1 and k2 have a negative effect on E, while k3 and k4 have a positive effect, with k1 having the greatest influence on E, followed by k3, k4, and k2. The ecological implications of the simulation results are briefly described, and the limitations of the model are discussed.

Effects of the surface irregularity of termite tunnels on food transport efficiency: a simulation study.

Termites are believed to have evolved in a way that optimizes their foraging efficiency, which involves both searching for food and transporting it efficiently. Although the search efficiency has been well-studied through tunnel pattern analysis, transport efficiency has received limited attention due to the challenges of directly observing behavior that is highly influenced by environmental conditions. In this study, we introduce an individual-based model to simulate transport behavior and examine transport efficiency (E) by considering the tunnel surface irregularities and curvature, which are critical environmental factors. The model is characterized by four control variables: tunnel curvature (k1), termite stopping time at irregularity sites (k2), irregularity distribution (k3), and irregularity density (k4). The simulation results indicate that as k1 increases, E decreases, while k3 has little impact on E. The impact of k4 on E is decisive; when k4 ≤ 6, an increase in k4 results in increased traffic jam frequency and a faster reduction in E. However, when k4 > 6, the jamming frequency is not significantly affected, reducing the decrease in E. k2 strongly contributes to reducing E without significantly affecting the frequency. In the discussion section, we explore potential mechanisms that termites use to maintain transport efficiency in heterogeneous soils, and discuss how to improve the model to better reflect real-termite systems.

Synthesis of dithioacetals via gold-catalysed hydrothiolation of vinyl sulfides.

The synthesis of unsymmetrical dithioacetals based on gold catalysis is described. Although many approaches to the preparation of symmetrical dithioacetals have been developed, the methods to access unsymmetrical ones remain limited. In this regard, we report a mild synthetic method with a broad substrate scope. Screening of various gold catalysts identified a catalyst, which allows the hydrothiolation of both activated and unactivated vinyl sulfides with high efficiency. Moreover, the reaction displays broad compatibility for both aryl and aliphatic thiols.

Catalyst-free electrosynthesis of benzothiophenes from 2-alkenylaryl disulfides.

The synthesis of benzothiophenes through electrosynthesis under oxidant- and metal-free conditions has been discovered. Electrolysis of symmetrical 2-alkenylaryl disulfides using an undivided cell leads to the formation of the corresponding benzothiophenes in good to moderate yields with good functional group tolerance. The usefulness of this methodology was further investigated with a scale-up experiment, which delivered a similar result to that of the small scale reaction. Several mechanistic investigations including DFT calculations were carried out to elucidate the reaction mechanism.

Li-Compound Anodes: A Classification for High-Performance Li-Ion Battery Anodes.

Four main anode types are generally considered as typical anodes for Li-ion batteries (LIBs): Li-metal, carbon-based, alloy-based, and oxide-based anodes. Although they exhibit satisfactory electrochemical performance as LIB anodes, they cannot simultaneously satisfy all key requirements for LIB anodes: high reversible capacity, high initial Coulombic efficiency (ICE), long cycle life, fast rate capability, structural stability, and no safety concerns. Here, we suggest Li-compound anodes as a promising class of high-performance LIB anodes. Three binary (LiSn, Li2Sb, and LiBi) and three ternary (Li2ZnSb, Li5GeP3, and Li5SnP3) Li compounds were introduced as Li-compound anodes. LiSn and Li5SnP3 were selected and further modified into their nanocomposites by solid-state synthetic routes using carbon sources for high-performance LIB anodes. The Li-compound nanocomposite anodes exhibited excellent performance and simultaneously fulfilled all the key requirements for high-performance LIB anodes. Therefore, Li-compound anodes are expected to be a promising and innovative category of high-performance LIB anodes.

Electrochemical C(sp3)-H Functionalization of γ-Lactams Based on Hydrogen Atom Transfer.

We describe the electrochemical α-amidoalkylation of γ-lactams based on transition-metal-free cross-coupling via hydrogen atom transfer. The highly selective hydrogen atom transfer process allows for a broad substrate scope including both inter- and intramolecular reactions. Also, the construction of quaternary centers was realized by a double hydrogen atom transfer protocol to afford spirocycles. Detailed mechanistic studies including experimental and computational studies are provided to support the reaction pathway.

A chemical tool for blue light-inducible proximity photo-crosslinking in live cells.

We developed a proximity photo-crosslinking method (Spotlight) with a 4-azido-N-ethyl-1,8-naphthalimide (AzNP) moiety that can be converted to reactive aryl nitrene species using ambient blue light-emitting diode light. Using an AzNP-conjugated HaloTag ligand (VL1), blue light-induced photo-crosslinked products of various HaloTag-conjugated proteins of interest were detected in subcellular spaces in live cells. Chemical or heat stress-induced dynamic changes in the proteome were also detected, and photo-crosslinking in the mouse brain tissue was enabled. Using Spotlight, we further identified the host interactome of SARS-CoV-2 nucleocapsid (N) protein, which is essential for viral genome assembly. Mass analysis of the VL1-crosslinked product of N-HaloTag in HEK293T cells showed that RNA-binding proteins in stress granules were exclusively enriched in the cross-linked samples. These results tell that our method can reveal the interactome of protein of interest within a short distance in live cells.

Ortho-selective C-H arylation of phenols with N-carboxyindoles under Brønsted acid- or Cu(i)-catalysis.

Control over chemo- and regioselectivity is a critical issue in the heterobiaryl synthesis via C-H oxidative coupling. To address this challenge, a strategy to invert the normal polarity of indoles in the heterobiaryl coupling was developed. With N-carboxyindoles as umpoled indoles, an exclusively ortho-selective coupling with phenols has been realized, employing a Brønsted acid- or Cu(i)-catalyst (as low as 0.01 mol%). A range of phenols and N-carboxyindoles coupled with exceptional efficiency and selectivity at ambient temperature and the substrates bearing redox-active aryl halides (-Br and -I) smoothly coupled in an orthogonal manner. Notably, preliminary examples of atropselective heterobiaryl coupling have been demonstrated, based on a chiral disulfonimide or a Cu(i)/chiral bisphosphine catalytic system. The reaction was proposed to occur through SN2' substitution or a Cu(i)-Cu(iii) cycle, with Brønsted acid or Cu(i) catalysts, respectively.

Discovery of a dual-action small molecule that improves neuropathological features of Alzheimer's disease mice.

Alzheimer's disease (AD) is characterized by complex, multifactorial neuropathology, suggesting that small molecules targeting multiple neuropathological factors are likely required to successfully impact clinical progression. Acid sphingomyelinase (ASM) activation has been recognized as an important contributor to these neuropathological features in AD, leading to the concept of using ASM inhibitors for the treatment of this disorder. Here we report the identification of KARI 201, a direct ASM inhibitor evaluated for AD treatment. KARI 201 exhibits highly selective inhibition effects on ASM, with excellent pharmacokinetic properties, especially with regard to brain distribution. Unexpectedly, we found another role of KARI 201 as a ghrelin receptor agonist, which also has therapeutic potential for AD treatment. This dual role of KARI 201 in neurons efficiently rescued neuropathological features in AD mice, including amyloid beta deposition, autophagy dysfunction, neuroinflammation, synaptic loss, and decreased hippocampal neurogenesis and synaptic plasticity, leading to an improvement in memory function. Our data highlight the possibility of potential clinical application of KARI 201 as an innovative and multifaceted drug for AD treatment.

Self-Healing Graphene-Templated Platinum-Nickel Oxide Heterostructures for Overall Water Splitting.

Electrocatalysts with dramatically enhanced water splitting efficiency, derived from controlled structures, phase transitions, functional activation, etc., have been developed recently. Herein, we report an in situ observation of graphene-based self-healing, in which this functional activation is induced by a redox reaction. Specifically, graphene on stainless steel (SUS) switches between graphene (C-C) and graphene oxide (C-O) coordination via an electrical redox reaction to activate water splitting. A heterostructure comprising Pt-NiO thin films on single-layer graphene directly grown on a SUS substrate (Pt-NiO/Gr-SUS) was also synthesized by electrodeposition. Pt-NiO/Gr-SUS exhibited water splitting activity with low Pt loading (<1 wt %). The findings provide valuable insight for designing robust electrodes based on reversible redox-induced self-healable graphene to develop more efficient catalysts.

Novel Features for Binary Time Series Based on Branch Length Similarity Entropy.

Branch length similarity (BLS) entropy is defined in a network consisting of a single node and branches. In this study, we mapped the binary time-series signal to the circumference of the time circle so that the BLS entropy can be calculated for the binary time-series. We obtained the BLS entropy values for "1" signals on the time circle. The set of values are the BLS entropy profile. We selected the local maximum (minimum) point, slope, and inflection point of the entropy profile as the characteristic features of the binary time-series and investigated and explored their significance. The local maximum (minimum) point indicates the time at which the rate of change in the signal density becomes zero. The slope and inflection points correspond to the degree of change in the signal density and the time at which the signal density changes occur, respectively. Moreover, we show that the characteristic features can be widely used in binary time-series analysis by characterizing the movement trajectory of Caenorhabditis elegans. We also mention the problems that need to be explored mathematically in relation to the features and propose candidates for additional features based on the BLS entropy profile.

Pd Nanocluster/Monolayer MoS2 Heterojunctions for Light-Induced Room-Temperature Hydrogen Sensing.

Developing sensing approaches that can exploit visible light for the detection of low-concentration hydrogen at room temperatures has become increasingly important for the safe use of hydrogen in many applications. In this study, heterostructures composed of monolayer MoS2 and Pd nanoclusters (Pd/MoS2) acting as photo- and hydrogen-sensitizers are successfully fabricated in a facile and scalable manner. The uniform deposition of morphologically isotropic Pd nanoclusters (11.5 ± 2.2 nm) on monolayer MoS2 produces a plethora of active heterojunctions, effectively suppressing charge carrier recombination under light illumination. The dual photo- and hydrogen-sensitizing functionality of Pd/MoS2 can enable its use as an active sensing layer in optoelectronic hydrogen sensors. Gas-sensing examinations reveal that the sensing performance of Pd/MoS2 is enhanced three-fold under visible light illumination (17% for 140 ppm of H2) in comparison with dark light (5% for 140 ppm of H2). Photoactivation is also found to enable excellent sensing reversibility and reproducibility in the obtained sensor. As a proof-of-concept, the integration of Pd nanoclusters and monolayer MoS2 can open a new avenue for light-induced hydrogen gas sensing at room temperature.

Programmable site-selective labeling of oligonucleotides based on carbene catalysis.

Site-selective modification of oligonucleotides serves as an indispensable tool in many fields of research including research of fundamental biological processes, biotechnology, and nanotechnology. Here we report chemo- and regioselective modification of oligonucleotides based on rhodium(I)-carbene catalysis in a programmable fashion. Extensive screening identifies a rhodium(I)-catalyst that displays robust chemoselectivity toward base-unpaired guanosines in single and double-strand oligonucleotides with structurally complex secondary structures. Moreover, high regioselectivity among multiple guanosines in a substrate is achieved by introducing guanosine-bulge loops in a duplex. This approach allows the introduction of multiple unique functional handles in an iterative fashion, the utility of which is exemplified in DNA-protein cross-linking in cell lysates.

A New Measure to Characterize the Degree of Self-Similarity of a Shape and Its Applicability.

We propose a new measure (Γ) to quantify the degree of self-similarity of a shape using branch length similarity (BLS) entropy which is defined on a simple network consisting of a single node and its branches. To investigate the properties of this measure, we computed the Γ values for 70 object groups (20 shapes in each group) in the MPEG-7 shape database and performed grouping on the values. With relatively high Γ values, identical groups had visually similar shapes. On the other hand, the identical groups with low Γ values had visually different shapes. However, the aspect of topological similarity of the shapes also warrants consideration. The shapes of statistically different groups exhibited significant visual difference from each other. Also, in order to show that the Γ can have a wide variety of applicability when properly used with other variables, we showed that the finger gestures in the (Γ, Z) space are successfully classified. Here, the Z means a correlation coefficient value between entropy profiles for gesture shapes. As shown in the applications, Γ has a strong advantage over conventional geometric measures in that it captures the geometrical and topological properties of a shape together. If we could define the BLS entropy for color, Γ could be used to characterize images expressed in RGB. We briefly discussed the problems to be solved before the applicability of Γ can be expanded to various fields.

Metal-Free Synthesis of Indolopyrans and 2,3-Dihydrofurans Based on Tandem Oxidative Cycloaddition.

The synthesis of versatile scaffold indolopyrans based on C-C radical-radical cross-coupling under metal-free conditions is described. The reaction involving single electron transfer between coupling partners followed by cage collapse allows highly selective cross-coupling while employing only equimolar amounts of coupling partners. Moreover, the mechanistic manifold was expanded for the functionalization of enamines to give the stereoselective synthesis of 2,3-dihydrofurans. This iodine-mediated oxidative coupling features mild conditions and fast reaction kinetics.

N-AS-triggered SPMs are direct regulators of microglia in a model of Alzheimer's disease.

Sphingosine kinase1 (SphK1) is an acetyl-CoA dependent acetyltransferase which acts on cyclooxygenase2 (COX2) in neurons in a model of Alzheimer's disease (AD). However, the mechanism underlying this activity was unexplored. Here we show that N-acetyl sphingosine (N-AS) is first generated by acetyl-CoA and sphingosine through SphK1. N-AS then acetylates serine 565 (S565) of COX2, and the N-AS-acetylated COX2 induces the production of specialized pro-resolving mediators (SPMs). In a mouse model of AD, microglia show a reduction in N-AS generation, leading to decreased acetyl-S565 COX2 and SPM production. Treatment with N-AS increases acetylated COX2 and N-AS-triggered SPMs in microglia of AD mice, leading to resolution of neuroinflammation, an increase in microglial phagocytosis, and improved memory. Taken together, these results identify a role of N-AS in the dysfunction of microglia in AD.

Alkyne-Alkene [2 + 2] cycloaddition based on visible light photocatalysis.

UV-activated alkyne-alkene [2 + 2] cycloaddition has served as an important tool to access cyclobutenes. Although broadly adopted, the limitations with UV light as an energy source prompted us to explore an alternative method. Here we report alkyne-alkene [2 + 2] cycloaddition based on visible light photocatalysis allowing the synthesis of diverse cyclobutenes and 1,3-dienes via inter- and intramolecular reactions. Extensive mechanistic studies suggest that the localized spin densities at sp2 carbons of alkenes account for the productive sensitization of alkenes despite their similar triplet levels of alkenes and alkynes. Moreover, the efficient formation of 1,3-dienes via tandem triplet activation of the resulting cyclobutenes is observed when intramolecular enyne cycloaddition is performed, which may serve as a complementary means to the Ru(II)-catalyzed enyne metathesis. In addition, the utility of the [2 + 2] cycloaddition has been demonstrated by several synthetic transformations including synthesis of various extended π-systems.