Showing papers by "Nagoya University published in 2022"

Synthesis of a Möbius carbon nanobelt

Abstract: Abstract Technologies for the creation of topological carbon nanostructures have greatly advanced synthetic organic chemistry and materials science. Although simple molecular nanocarbons with a belt topology have been constructed, analogous carbon nanobelts with a twist—more specifically, Möbius carbon nanobelts (MCNBs)—have not yet been synthesized owing to their high intrinsic strain. Here we report the synthesis, isolation and characterization of a MCNB. Calculations of strain energies suggest that large MCNBs are synthetically accessible. Designing a macrocyclic precursor with an odd number of repeat units led to a successful synthetic route via Z -selective Wittig reactions and nickel-mediated intramolecular homocoupling reactions, which yielded (25,25)MCNB over 14 steps. NMR spectroscopy and theoretical calculations reveal that the twist moiety of the Möbius band moves quickly around the MCNB molecule in solution. The topological chirality that originates from the Möbius structure was confirmed experimentally using chiral HPLC separation and circular dichroism spectroscopy.

Recent Observed Changes in Extreme High‐Temperature Events and Associated Meteorological Conditions over Africa

Abstract: More frequent and intensified high-temperature extremes are acceptable indicators of global warming, which pose serious socio-economic impacts. In the present research, the Climate Prediction Center daily minimum and maximum temperature are used to characterize high temperatures into intensity of hot days (TXx), hot nights (TNx), and frequency indices based on the 90th percentile of hot days (TX90p) and hot nights (TN90p) as defined by the Expert Team on Climate Change Detection and Indices from 1981 to 2020 over Africa. The regression approach based on iterative reweighted least squares and correlation analyses are used to estimate the trends in extreme high-temperature events and their relationship with various meteorological variables. Furthermore, the Pruned exact linear time algorithm is used to assess if the maximum temperature experienced an abrupt change. Results show that many parts of Africa experienced more frequent and intensified hot days and nights in the current period (1998–2020) compared to the recent past (1981–1997), suggesting a clear shift in climate. Thus, we used the climatological mean differences between meteorological parameters before and after the breakpoint to assess the relationship between atmospheric conditions and extreme high-temperature events. As a result, we found that the current period observed an increase in the geopotential height at 500 hPa and reduced total cloud cover, as well as an increase in upward longwave radiation resulting in an upsurge in the frequency of hot days over many African sub-regions. The present study's findings provide useful information for future planning and development of early warning systems to cope with risks associated with hot extremes.

Synthesis of octagon-containing molecular nanocarbons

Abstract: Nanocarbons, such as fullerenes, carbon nanotubes, and graphenes, have long inspired the scientific community. In order to synthesize nanocarbon molecules in an atomically precise fashion, many synthetic reactions have been developed. The ultimate challenge for synthetic chemists in nanocarbon science is the creation of periodic three-dimensional (3D) carbon crystals. In 1991, Mackay and Terrones proposed periodic 3D carbon crystals with negative Gaussian curvatures that consist of six- and eight-membered rings (the so-called Mackay-Terrones crystals). The existence of the eight-membered rings causes a warped nanocarbon structure. The Mackay-Terrones crystals are considered a "dream material", and have been predicted to exhibit extraordinary mechanical, magnetic, and optoelectronic properties (harder than diamond, for example). To turn the dream of having this wonder material into reality, the development of methods enabling the creation of octagon-embedding polycyclic structures (or nanographenes) is of fundamental and practical importance. This review describes the most vibrant synthetic achievements that the scientific community has performed to obtain curved polycyclic nanocarbons with eight-membered rings, building blocks that could potentially give access as templates to larger nanographenes, and eventually to Mackay-Terrones crystals, by structural expansion strategies.

First gadolinium loading to Super-Kamiokande

Abstract: In order to improve Super-Kamiokande’s neutron detection efficiency and to thereby increase its sensitivity to the diffuse supernova neutrino background flux, 13 tons of Gd2(SO4)3⋅8H2O (gadolinium sulfate octahydrate) was dissolved into the detector’s otherwise ultrapure water from July 14 to August 17, 2020, marking the start of the SK-Gd phase of operations. During the loading, water was continuously recirculated at a rate of 60 m3/h, extracting water from the top of the detector and mixing it with concentrated Gd2(SO4)3⋅8H2O solution to create a 0.02% solution of the Gd compound before injecting it into the bottom of the detector. A clear boundary between the Gd-loaded and pure water was maintained through the loading, enabling monitoring of the loading itself and the spatial uniformity of the Gd concentration over the 35 days it took to reach the top of the detector. During the subsequent commissioning the recirculation rate was increased to 120 m3/h, resulting in a constant and uniform distribution of Gd throughout the detector and water transparency equivalent to that of previous pure-water operation periods. Using an Am–Be neutron calibration source the mean neutron capture time was measured to be 115±1 μs, which corresponds to a Gd concentration of 111±2 ppm, as expected for this level of Gd loading. This paper describes changes made to the water circulation system for this detector upgrade, the Gd loading procedure, detector commissioning, and the first neutron calibration measurements in SK-Gd.

Non-invertible self-duality defects of Cardy-Rabinovici model and mixed gravitational anomaly

Abstract: A bstract We study properties of self-duality symmetry in the Cardy-Rabinovici model. The Cardy-Rabinovici model is the 4d U(1) gauge theory with electric and magnetic matters, and it enjoys the SL(2 , ℤ) self-duality at low-energies. SL(2 , ℤ) self-duality does not realize in a naive way, but we notice that the ST p duality transformation becomes the legitimate duality operation by performing the gauging of ℤ N 1-form symmetry with including the level- p discrete topological term. Due to such complications in its realization, the fusion rule of duality defects becomes a non-group-like structure, and thus the self-duality symmetry is realized as a non-invertible symmetry. Moreover, for some fixed points of the self-duality, the duality symmetry turns out to have a mixed gravitational anomaly detected on a K 3 surface, and we can rule out the trivially gapped phase as a consequence of anomaly matching. We also uncover how the conjectured phase diagram of the Cardy-Rabinovici model satisfies this new anomaly matching condition.

Hydrogen-Atom-Transfer-Mediated Acceptorless Dehydrogenative Cross-Coupling Enabled by Multiple Catalytic Functions of Zwitterionic Triazolium Amidate

Abstract: An unconventional cooperative catalysis for hydrogen-atom-transfer-mediated acceptorless dehydrogenative cross-coupling is described. The combined use of zwitterionic 1,2,3-triazolium amidate and an Ir-based photosensitizer as catalysts enables C–H/C–H cross-couplings between heteroatom-containing C–H donors and enamides or 1,1-diarylethenes under visible-light irradiation without the need for any oxidants, hydrogen evolution catalysts, or electrodes. A key to establishing this catalysis is the susceptibility of the conjugate acid of the triazolium amidate, amide triazolium, toward single-electron reduction to complete the catalytic cycle.

21 cm forest constraints on primordial black holes

Abstract: Primordial black holes (PBHs) as part of the Dark Matter (DM) would modify the evolution of large-scale structures and the thermal history of the universe. Future 21 cm forest observations, sensitive to small scales and the thermal state of the Inter Galactic Medium (IGM), could probe the existence of such PBHs. In this article, we show that the shot noise isocurvature mode on small scales induced by the presence of PBHs can enhance the amount of low mass halos, or minihalos, and thus, the number of 21 cm absorption lines. However, if the mass of PBHs is as large as $M_{\rm PBH}\gtrsim 10 \, M_\odot$, with an abundant enough fraction of PBHs as DM, $f_{\rm PBH}$, the IGM heating due to accretion onto the PBHs counteracts the enhancement due to the isocurvature mode, reducing the number of absorption lines instead. The concurrence of both effects imprints distinctive signatures in the number of absorbers, allowing to bound the abundance of PBHs. We compute the prospects for constraining PBHs with future 21 cm forest observations, finding achievable competitive upper limits on the abundance as low as $f_{\rm PBH} \sim 10^{-3}$ at $M_{\rm PBH}= 100 \, M_\odot$, or even lower at larger masses, in unexplored regions of the parameter space by current probes. The impact of astrophysical X-ray sources on the IGM temperature is also studied, which could potentially weaken the bounds.

Fundamental limits of quantum error mitigation

Abstract: The inevitable accumulation of errors in near-future quantum devices represents a key obstacle in delivering practical quantum advantages, motivating the development of various quantum error-mitigation methods. Here, we derive fundamental bounds concerning how error-mitigation algorithms can reduce the computation error as a function of their sampling overhead. Our bounds place universal performance limits on a general error-mitigation protocol class. We use them to show (1) that the sampling overhead that ensures a certain computational accuracy for mitigating local depolarizing noise in layered circuits scales exponentially with the circuit depth for general error-mitigation protocols and (2) the optimality of probabilistic error cancellation among a wide class of strategies in mitigating the local dephasing noise on an arbitrary number of qubits. Our results provide a means to identify when a given quantum error-mitigation strategy is optimal and when there is potential room for improvement.

Efficient stabilization of soil, sand, and clay by a polymer network of biomass-derived chitosan and carboxymethyl cellulose

Abstract: Biomass-derived polymers are being increasingly utilized as eco-friendly functional materials in fields ranging from medicine and food to agriculture and environmental engineering. In this report, we developed a novel efficient method for improvement of soil materials based on in situ gelation of a polyion complex formed by biomass-derived carboxymethyl cellulose (CMC) and chitosan (CS). Self-organized network of polymer films and microfibers assembled via electrostatic interactions between oppositely-charged polyions interconnects particles of soil material and imparts the resulted composite with a considerable mechanical strength. Treatment of soil even with a high water content (ca. 30%) by a mixture of CMC and CS at m(CMC + CS)/m(soil) ratio of ca. 1% is sufficient to gain up to 150 kPa compression strength that further increases up to ca. 1 MPa after drying. Similar reinforcement effect by CMC-CS complex was observed for sand, and much higher yield strengths were measured for clay. Mechanical properties of soil materials strengthened by CMC-CS complex depended on structure and stability of CMC-CS polyion network and controlled by the polymerization degrees of macromolecules and the charge ratio between them. Being composed entirely of biomass-derived polymers, the proposed soil treatment system is particularly attractive due to environmental friendliness and sustainability and it can be utilized not only for the soil improvement but also for the construction of functional platforms for soil pollution control and remediation.

Experimental and numerical evaluation of effects of kidney-shape carbon fiber on transverse cracking of carbon fiber reinforced plastics

Abstract: This study aims to investigate the effects of fiber cross-sectional shape on the trans- verse crack extension of carbon fiber reinforced plastics (CFRP) both experimentally and numerically. Kidney-shape carbon fiber was compared with the laminates using conventional round-shape carbon fiber by monitoring the transverse crack accumu- lation behavior during static tensile tests. The experimental results showed that kidney-shape carbon fibers retard the initiation of transverse cracks and suppress their accumulation. Moreover, a micromechanical simulation based on finite ele- ment method was performed to consider the effects of fiber cross-sectional shape on crack propagation. In the case of the major damage process of the two kinds of CFRPs to be different in the simulations, the numerical results agreed well with the experimental ones. It was experimentally and numerically demonstrated that the kidney-shape carbon fiber suppresses the transverse crack accumulation and retards the crack initiation in CFRP laminates compared with round-shape carbon fiber.

Unconventional Approaches to Light-Promoted Dynamic Surface Morphing on Polymer Films

Abstract: Recent progress in research of light-promoted surface morphing on polymer materials is reviewed. Photoinduced mass transport motions in azobenzene polymers leading to surface relief gratings (widely called SRGs) formation are well-known and extensively discussed. Among many efforts, this article focuses on unconventional approaches, most of which are seemingly less highlighted. The first part introduces investigations using azobenzene polymers; introducing supramolecular approaches with tunable and removable azobenzene units, self-structuring of surface morphology upon single laser beam irradiation, photo-triggered migration via Marangoni flow, SRG formation and other functions of polymer brushes etc. The second part overviews the mass transport motions driven by other photoreaction classes such as photopolymerization, photocrosslinking, and photoisomerization of non-azobenzene components. The final part describes new dynamic surface morphing processes observed in fingerprint texture of liquid crystals and liquid crystal polymer networks, which can be applied to reversible friction control and self-cleaning. These uncommon attempts at photo-assisted dynamic morphing extend the possibilities of microfabrication on polymer films and are expected to find new opportunities to create new surface functions in soft materials. Recent progress in the research of light-promoted surface morphing on polymer materials is reviewed. This article focuses to unconventional approaches, most of which are seemingly less highlighted so far. Such uncommon attempts on photo-assisted dynamic morphing are expected to extend the possibilities of microfabrication on polymer films and find new opportunities to create new surface functions in soft materials.

Central sympathetic network for thermoregulatory responses to psychological stress

Abstract: In mammals, many types of psychological stressors elicit a variety of sympathoexcitatory responses paralleling the classic fight-or-flight response to a threat to survival, including increased body temperature via brown adipose tissue thermogenesis and cutaneous vasoconstriction, and increased skeletal muscle blood flow via tachycardia and visceral vasoconstriction. Although these responses are usually supportive for stress coping, aberrant sympathetic responses to stress can lead to clinical issues in psychosomatic medicine. Sympathetic stress responses are mediated mostly by sympathetic premotor drives from the rostral medullary raphe region (rMR) and partly by those from the rostral ventrolateral medulla (RVLM). Hypothalamomedullary descending pathways from the dorsomedial hypothalamus (DMH) to the rMR and RVLM mediate important, stress-driven sympathoexcitatory transmission to the premotor neurons to drive the thermal and cardiovascular responses. The DMH also likely sends an excitatory input to the paraventricular hypothalamic nucleus to stimulate stress hormone release. Neurons in the DMH receive a stress-related excitation from the dorsal peduncular cortex and dorsal tenia tecta (DP/DTT) in the ventromedial prefrontal cortex. By connecting the corticolimbic emotion circuit to the central sympathetic and somatic motor systems, the DP/DTT → DMH pathway plays as the primary mediator of the psychosomatic signaling that drives a variety of sympathetic and behavioral stress responses. These brain regions together with other stress-related regions constitute a central neural network for physiological stress responses. This network model is relevant to understanding the central mechanisms by which stress and emotions affect autonomic regulations of homeostasis and to developing new therapeutic strategies for various stress-related disorders.

Structure and dynamics of Odinarchaeota tubulin and the implications for eukaryotic microtubule evolution

Abstract: Tubulins are critical for the internal organization of eukaryotic cells, and understanding their emergence is an important question in eukaryogenesis. Asgard archaea are the closest known prokaryotic relatives to eukaryotes. Here, we elucidated the apo and nucleotide-bound x-ray structures of an Asgard tubulin from hydrothermal living Odinarchaeota (OdinTubulin). The guanosine 5′-triphosphate (GTP)–bound structure resembles a microtubule protofilament, with GTP bound between subunits, coordinating the “+” end subunit through a network of water molecules and unexpectedly by two cations. A water molecule is located suitable for GTP hydrolysis. Time course crystallography and electron microscopy revealed conformational changes on GTP hydrolysis. OdinTubulin forms tubules at high temperatures, with short curved protofilaments coiling around the tubule circumference, more similar to FtsZ, rather than running parallel to its length, as in microtubules. Thus, OdinTubulin represents an evolutionary stage intermediate between prokaryotic FtsZ and eukaryotic microtubule-forming tubulins.

The Stellar Mass versus Stellar Metallicity Relation of Star-forming Galaxies at 1.6 ≤ z ≤ 3.0 and Implications for the Evolution of the α-enhancement

Abstract: We measure the relationship between stellar mass and stellar metallicity, the stellar mass--metallicity relation (MZR), for 1336 star-forming galaxies at $1.6\le z\le3.0$ (=2.2) using rest-frame far-ultraviolet spectra from the zCOSMOS-deep survey. High signal-to-noise composite spectra containing stellar absorption features are fit with population synthesis model spectra of a range of metallicity. We find stellar metallicities, which mostly reflect iron abundances, scaling as $(Z_{Fe,\ast}/Z_{Fe,\odot})=-(0.81\pm0.01)+(0.32+0.03)\log(M_\ast/10^{10}M_\odot)$ across the mass range of $10^9\lesssim M_\ast/M_\odot\lesssim10^{11}$, being $\approx6\times$ lower than seen locally at the same masses. The instantaneous oxygen-to-iron ratio ($\alpha$-enhancement) inferred using the gas-phase oxygen MZRs, is on average found to be [O/Fe]$\approx0.47$, being higher than the local [O/Fe]$\approx0$. The observed changes in [O/Fe] and [Fe/H] are reproduced in simple flow-through gas-regulator models with steady star-formation histories (SFHs) that follow the evolving main sequence. Our models show that the [O/Fe] is determined almost entirely by the instantaneous specific star formation rate alone while being independent of the SFHs, mass, and the gas-regulation characteristics of the systems. We find that the locations of $\sim10^{10}M_\odot$ galaxies at z~2 in the [O/Fe]--metallicity planes are in remarkable agreement with the sequence of low-metallicity thick-disk stars in our Galaxy. This manifests a beautiful concordance between the results of Galactic archaeology and observations of high-redshift Milky Way progenitors. However, there remains a question of how and when the old metal-rich, low-$\alpha$/Fe stars seen in the bulge had formed by z~2 because such a stellar population is not seen in our data and difficult to explain in the context of our models.

Central sympathetic network for thermoregulatory responses to psychological stress

Abstract: In mammals, many types of psychological stressors elicit a variety of sympathoexcitatory responses paralleling the classic fight-or-flight response to a threat to survival, including increased body temperature via brown adipose tissue thermogenesis and cutaneous vasoconstriction, and increased skeletal muscle blood flow via tachycardia and visceral vasoconstriction. Although these responses are usually supportive for stress coping, aberrant sympathetic responses to stress can lead to clinical issues in psychosomatic medicine. Sympathetic stress responses are mediated mostly by sympathetic premotor drives from the rostral medullary raphe region (rMR) and partly by those from the rostral ventrolateral medulla (RVLM). Hypothalamomedullary descending pathways from the dorsomedial hypothalamus (DMH) to the rMR and RVLM mediate important, stress-driven sympathoexcitatory transmission to the premotor neurons to drive the thermal and cardiovascular responses. The DMH also likely sends an excitatory input to the paraventricular hypothalamic nucleus to stimulate stress hormone release. Neurons in the DMH receive a stress-related excitation from the dorsal peduncular cortex and dorsal tenia tecta (DP/DTT) in the ventromedial prefrontal cortex. By connecting the corticolimbic emotion circuit to the central sympathetic and somatic motor systems, the DP/DTT → DMH pathway plays as the primary mediator of the psychosomatic signaling that drives a variety of sympathetic and behavioral stress responses. These brain regions together with other stress-related regions constitute a central neural network for physiological stress responses. This network model is relevant to understanding the central mechanisms by which stress and emotions affect autonomic regulations of homeostasis and to developing new therapeutic strategies for various stress-related disorders.