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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.

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.

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.

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.

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.

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.

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.

Determining the distribution and dynamics of water on land at any given moment poses a significant challenge due to the constraints of observation. Consequently, as advancements in land surface models (LSMs) have been made, numerical simulation has emerged as an increasingly accurate and effective method for hydrological research. Nonetheless, systems that represent multiple land surface parameters in a near‐real‐time manner are scarce. In this study, we present an innovative land surface and river simulation system, termed Today's Earth (TE), which generates state and flux values for the near‐surface environment with multiple outputs in near‐real‐time. There are currently three versions of TE, distinguished by the forcing data utilized: JRA‐55 version, employing the Japanese 55‐year Reanalysis (JRA‐55, from 1958 to the present); GSMaP version, utilizing, the Global Satellite Mapping of Precipitation (GSMaP, from 2001 to the present), and MODIS version, utilizing the Moderate Resolution Imaging Spectroradiometer (MODIS, from 2003 to the present). These long‐term forcing data set allow for outputs of the JRA‐55 version from 1958, the GSMaP version from 2001, and the MODIS version from 2003. Aiming to provide water and energy values on a global scale in real‐time, the TE system utilizes the LSM Minimal Advanced Treatments of Surface Interaction and Runoff (MATSIRO) (Takata et al., 2003, https://doi.org/10.1016/s0921‐8181(03)00030‐4; Yamazaki et al., 2011, https://doi.org/10.1029/2010wr009726) at a horizontal resolution of 0.5°, along with the river routing model CaMa‐Flood (Yamazaki et al., 2011, https://doi.org/10.1029/2010wr009726) at a horizontal resolution of 0.25°. Both land surface and river products are available in 3‐hourly, daily, and monthly intervals across all three versions. A notable feature of TE is its ability to release both state and flux parameters in near‐real‐time, offering convenience for various aspects of hydrological research. In addition to presenting the general features of TE‐Global, this study examines the performance of snow depth, soil moisture, and river discharge data in daily intervals from 2003 to 2021, with validation spanning 2003 to 2016. When comparing snow depth results, the correlation coefficient ranged between 0.644 and 0.658, while for soil moisture it ranged between 0.471 and 0.494. These findings suggest that the LSM yields comparable results when utilizing JRA‐55, MODIS, or GSMaP. Interestingly, river output from the three products exhibited distinct characteristics varying from GSMaP to JRA‐55 and MODIS. For river discharge, the correlation coefficient ranged from 0.494 to 0.519, the root mean square error ranged from 3,730 m3/s to 6,330 m3/s, and the mean absolute error ranged from 3,000 m3/s to 5,160 m3/s among the different forcing versions. The overall bias in river discharge from GSMaP was 1,570 m3/s, in contrast to −589 m3/s for JRA‐55 and −200 m3/s for MODIS. These metrics demonstrate that the TE system is capable of generating practical land surface and river products, highlighting differences arising from the use of various types of forcing data. This comprehensive system would be valuable for monitoring water‐related movements, predicting disasters, and contributing to sophisticated water resource management. Regarding its application, the TE system has been included in the World Meteorological Organization as a Global Hydrological Modelling System. All TE‐Global products can be freely accessed through File Transfer Protocol. Plain Language Summary Understanding the distribution and movement of water on land in real‐time is difficult due to observation limitations. However, recent advancements in land surface models (LSMs) have allowed numerical simulations to become more accurate and effective for hydrological research. This study introduces a new system named Today's Earth (TE), which provides near‐real‐time data on the state of the Earth's surface and water movement. The TE system uses three different versions, using JRA55, GSMaP, and MODIS to generate outputs from the past to the present. It combines two models, LSM Minimal Advanced Treatments of Surface Interaction and Runoff, and CaMa‐Flood, for land surface and river simulation, respectively. The TE system offers state and flux values at different time intervals and has been tested for its performance in estimating snow depth, soil moisture, and river discharge data. The results show that the TE system produces comparable outcomes across different data sources. The river discharge, however, varied among the different versions. Overall, the TE system is valuable for monitoring water‐related movements, predicting disasters, and managing water resources effectively. It is recognized by the World Meteorological Organization as a Global Hydrological Modelling System, and the TE‐Global products are freely accessible through FTP. Key Points We present an innovative land surface and river simulation system, Today's Earth (TE) TE releases state and flux parameters in near‐real‐time, offering convenience for various aspects of hydrological research The TE system can generate practical land surface and river products, highlighting differences arising from various types of forcing data