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An oxidative C–C bond cleavage of tert-cycloalkanols with tetramethylammonium hypochlorite (TMAOCl) has been developed. TMAOCl is easy to prepare from tetramethylammonium hydroxide, and the combination of TMAOCl and AcOH effectively promoted the C–C bond cleavage in a two-phase system without additional phase-transfer reagents. Unstrained tert-cycloalkanols were transformed into ω-chloroalkyl aryl ketones in moderate to excellent yields under metal-free and mild reaction conditions.

Next-generation sequencing technology may clarify microbiota that are as yet poorly understood in the soil, the rhizosphere, and the phyllosphere of vineyards. To provide new information on the interaction between grapevine and microorganisms, we focused on the endophytic microbiota in grapevine. We performed endophytic microbiome analysis of the shoot xylems of four cultivars, Vitis vinifera cvs. Chardonnay, Pinot Noir, Cabernet Sauvignon, and Vitis sp. cv. Koshu, grown in eleven vineyards in Japan. The number of endophytic fungal species was small in the grapevine shoot xylems and could not be analyzed further, whereas a total of 7,019,600 amplicon sequences (46,642–285,003 per shoot xylem) and 1305 bacterial operational taxonomic units were obtained by analysis of the V3–V4 region of the bacterial 16S rRNA gene. Gammaproteobacteria was predominant in the shoot xylems at the shoot elongation stage irrespective of the cultivar, whereas Alphaproteobacteria and Oxyphotobacteria were predominant at véraison. Actinobacteria, Bacteroidia, Bacilli, and Clostridia were also detected in the shoot xylems. The endophytic bacterial microbiota in Koshu and Pinot Noir shoot xylems were similar irrespective of the grapevine-growing region. In contrast, the endophytic bacterial microbiota in Chardonnay and Cabernet Sauvignon showed diversity and complexity among grapevine-growing regions. Alpha diversity analysis revealed that Koshu shoot xylems had a higher diversity of endophytic bacterial microbiota than Pinot Noir, Chardonnay, and Cabernet Sauvignon shoot xylems, and that grapevine shoot xylems at the shoot elongation stage had a higher diversity of endophytic bacterial microbiota than those at véraison. Principal coordinate analysis (PCoA) demonstrated that the profiles of the endophytic bacterial microbiota in grapevine shoot xylems at véraison were relatively uniform compared with those at the shoot elongation stage. Multidimensional scaling analysis showed that the plots of all cultivars were generally apart from each other at the shoot elongation stage and then became close to each other at véraison. The plots of all grapevine-growing regions cultivating Koshu were close to each other, whereas those of grapevine-growing regions cultivating Chardonnay and Cabernet Sauvignon were apart from each other. The findings of this study suggest that the endophytic bacterial microbiota in grapevine shoot xylems varied depending on the cultivar and the grapevine-growing region even for the same cultivars, and that the microbiota fluctuated depending on the shoot growth stage.

Rapid and frequent mapping of flood areas are essential for monitoring and mitigating flood disasters. The Advanced Land Observing Satellite-2 (ALOS-2) carries an L-band synthetic aperture radar (SAR) capable of rapid and frequent disaster observations. In this study, we developed a fully automatic, fast computation, and robust method for detecting flood areas using ALOS-2 and hydrodynamic flood simulation data. This study is the first attempt to combine flood simulation data from the Today’s Earth system (TE) with SAR-based disaster mapping. We used Bayesian inference to combine the amplitude/coherence data by ALOS-2 and the flood fraction data by TE. Our experimental results used 12 flood observation sets of data from Japan and had high accuracy and robustness for use under various ALOS-2 observation conditions. Flood simulation contributed to improving the accuracy of flood detection and reducing computation time. Based on these findings, we also assessed the operability of our method and found that the combination of ALOS-2 and TE data with our analysis method was capable of daily flood monitoring.

Floods can be devastating in densely populated regions along rivers, so attaining a longer forecast lead time with high accuracy is essential for protecting people and property. Although many techniques are used to forecast floods, sufficient validation of the use of a forecast system for operational alert purposes is lacking. In this study, we validated the flooding locations and times of dike breaking that had occurred during Typhoon Hagibis, which caused severe flooding in Japan in 2019. To achieve the goal of the study, we combined a hydrodynamic model with statistical analysis under forcing by a 39-h prediction of the Japan Meteorological Agency's Meso-scale model Grid Point Value (MSM-GPV) and obtained dike-break times for all flooded locations for validation. The results showed that this method was accurate in predicting floods at 130 locations, approximately 91.6% of the total of 142 flooded locations, with a lead time of approximately 32.75 h. In terms of precision, these successfully predicted locations accounted for 24.0% of the total of 542 locations under a flood warning, and on average, the predicted flood time was approximately 8.53 h earlier than a given dike-break time. More warnings were issued for major rivers with severe flooding, indicating that the system is sensitive to extreme flood events and can issue warnings for rivers subject to high risk of flooding.

The radical hydroarylation of alkenes is an efficient strategy for accessing linear alkylarenes with high regioselectivity. Herein, we report the electroreductive hydroarylation of electron-deficient alkenes and styrene derivatives using (hetero)aryl halides under mild reaction conditions. Notably, the present hydroarylation proceeded with high efficiency under transition-metal-catalyst-free conditions. The key to success is the use of 1,3-dicyanobenzene as a redox mediator and visible-light irradiation, which effectively suppresses the formation of simple reduction, i.e., hydrodehalogenation, products to afford the desired products in good to high yields. Mechanistic investigations proposed that a reductive radical-polar crossover pathway is likely to be involved in this transformation.

Signaling of the cytokine interleukin-6 (IL-6) via its soluble IL-6 receptor (sIL-6R) is responsible for the proinflammatory properties of IL-6 and constitutes an attractive therapeutic target, but how the sIL-6R is generated in vivo remains largely unclear. Here, we use liquid chromatography-mass spectrometry to identify an sIL-6R form in human serum that originates from proteolytic cleavage, map its cleavage site between Pro-355 and Val-356, and determine the occupancy of all O- and N-glycosylation sites of the human sIL-6R. The metalloprotease a disintegrin and metalloproteinase 17 (ADAM17) uses this cleavage site in vitro, and mutation of Val-356 is sufficient to completely abrogate IL-6R proteolysis. N- and O-glycosylation were dispensable for signaling of the IL-6R, but proteolysis was orchestrated by an N- and O-glycosylated sequon near the cleavage site and an N-glycan exosite in domain D1. Proteolysis of an IL-6R completely devoid of glycans is significantly impaired. Thus, glycosylation is an important regulator for sIL-6R generation.

Glycerol is the main side product in the biodiesel manufacturing process, and the development of glycerol valorization methods would indirectly contribute the sustainable biodiesel production and decarbonization. Transformation of glycerol to optically active C3 units would be one of the attractive routes for glycerol valorization. We herein present the asymmetric sulfonylative desymmetrization of glycerol by using a CuCN/(R,R)-PhBOX catalyst system to provide an optically active monosulfonylated glycerol in high efficiency. A high degree of enantioselectivity was achieved with a commercially available chiral ligand and an inexpensive carbonate base. The optically active monosulfonylated glycerol was successfully transformed into a C3 unit attached with differentially protected three hydroxy moieties. In addition, the synthetic utility of the present reaction was also demonstrated by the transformation of the monosulfonylated glycerol into an optically active synthetic ceramide, sphingolipid E.

We ordinarily speak fluently, even though our perceptions of our own voices are disrupted by various environmental acoustic properties. The underlying mechanism of speech is supposed to monitor the temporal relationship between speech production and the perception of auditory feedback, as suggested by a reduction in speech fluency when the speaker is exposed to delayed auditory feedback (DAF). While many studies have reported that DAF influences speech motor processing, its relationship to the temporal tuning effect on multimodal integration, or temporal recalibration, remains unclear. We investigated whether the temporal aspects of both speech perception and production change due to adaptation to the delay between the motor sensation and the auditory feedback. This is a well-used method of inducing temporal recalibration. Participants continually read texts with specific DAF times in order to adapt to the delay. Then, they judged the simultaneity between the motor sensation and the vocal feedback. We measured the rates of speech with which participants read the texts in both the exposure and re-exposure phases. We found that exposure to DAF changed both the rate of speech and the simultaneity judgment, that is, participants’ speech gained fluency. Although we also found that a delay of 200 ms appeared to be most effective in decreasing the rates of speech and shifting the distribution on the simultaneity judgment, there was no correlation between these measurements. These findings suggest that both speech motor production and multimodal perception are adaptive to temporal lag but are processed in distinct ways.

Electrochemical pinacol coupling of carbonyl compounds in an undivided cell with a sacrificial anode would be a promising approach toward synthetically valuable vic -1,2-diol scaffolds without using low-valent metal reductants. However, sacrificial anodes produce an equimolar amount of metal waste, which may be a major issue in terms of sustainable chemistry. Herein, we report a sacrificial anode-free electrochemical protocol for the synthesis of pinacol-type vic -1,2-diols from sec -alcohols, namely benzyl alcohol derivatives and ethyl lactate. The corresponding vic -1,2-diols are obtained in moderate to good yields, and good to high levels of stereoselectivity are observed for sec -benzyl alcohol derivatives. The present transformations smoothly proceed in a simple undivided cell under constant current conditions without the use of external chemical oxidants/reductants, and transition-metal catalysts.

Introduction Yam cultivation in West Africa, the largest yam production area, has expanded to the northern Guinea savanna, which receives an annual rainfall of 800–1000 mm. However, variations in rainfall are problematic for the stable productivity of yams. Integrated soil fertility management is urgently needed to improve and stabilise yam productivity. Plants have complex interactions with bacterial communities, influencing their health and environmental adaptability. Although the growth of water yams (Dioscorea alata L.) at various rainfall levels might be related to their interaction with the bacterial community, their structure under water limitation is yet to be elucidated. Here, we evaluated the bacterial community structure in the rhizosphere (Rh) and roots of ‘A‐19’ under water limitation conditions. Materials and Methods Plants were grown under normal conditions, and watering was reduced to less than 70% for 1 month. Rh and root samples were collected for DNA extraction, and downstream amplicon sequencing analyses were performed. Results The dry weight of the shoots, particularly the leaves, decreased under water limitation. Bacterial diversity in the rhizocompartments was significantly reduced. However, bacterial community composition was not affected by water limitation. Despite water‐limited conditions, bacterial community structure was robust in the Burkholderia‐Caballeronia‐Paraburkholderia and Streptomyces clades. These taxa accounted for approximately 60% of the relative abundance in the roots under water limitation. Conclusion identifying bacterial community composition of ‘A‐19’ under water‐limited conditions provides fundamental information for developing integrated soil fertility management strategies across rainfall gradients in West Africa. Our study indicates that ‘A‐19’ has a robust bacterial community structure for beneficial interactions with bacteria despite soil water conditions.