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Alloying is an effective method for modulating metal nanoclusters to enrich their structural diversity and physicochemical properties. Recent investigations have demonstrated that polyoxometalates (POMs) can act as effective multidentate ligands for silver (Ag) nanoclusters to endow them with synergistic properties, reactivity, catalytic properties, and stability. However, the application of POMs as ligands has been confined predominantly to monometallic nanoclusters. Herein, we report a synthetic method for fabricating surface‐exposed gold (Au)−Ag alloy nanoclusters within a ring‐shaped POM ([P8W48O184]40−). Reacting an Ag nanocluster stabilized by the ring‐shaped POM with Au ions (Au+) was found to substitute several Ag atoms at the core of the nanocluster with Au atoms. The resultant {Au8Ag26} alloy nanocluster demonstrated superior photocatalytic activity and stability compared to the pristine Ag nanocluster in the aerobic oxidation of α‐terpinene under visible‐light irradiation. These findings provide fundamental insights into the formation and catalytic properties of POM‐stabilized alloy nanoclusters and advance exploration into the synthesis and applications of diverse metal nanoclusters. [ABSTRACT FROM AUTHOR]

Alloying is an effective method for modulating metal nanoclusters to enrich their structural diversity and physicochemical properties. Recent investigations have demonstrated that polyoxometalates (POMs) can act as effective multidentate ligands for silver (Ag) nanoclusters to endow them with synergistic properties, reactivity, catalytic properties, and stability. However, the application of POMs as ligands has been confined predominantly to monometallic nanoclusters. Herein, we report a synthetic method for fabricating surface‐exposed gold (Au)−Ag alloy nanoclusters within a ring‐shaped POM ([P8W48O184]40−). Reacting an Ag nanocluster stabilized by the ring‐shaped POM with Au ions (Au+) was found to substitute several Ag atoms at the core of the nanocluster with Au atoms. The resultant {Au8Ag26} alloy nanocluster demonstrated superior photocatalytic activity and stability compared to the pristine Ag nanocluster in the aerobic oxidation of α‐terpinene under visible‐light irradiation. These findings provide fundamental insights into the formation and catalytic properties of POM‐stabilized alloy nanoclusters and advance exploration into the synthesis and applications of diverse metal nanoclusters. [ABSTRACT FROM AUTHOR]

Objectives: The Cancer Control Act requires the maintenance of regional cooperation pathways (RCP) for cancer treatment. In 2008, we started RCP for early detection of new gastric cancer after endoscopic submucosal dissection (ESD). In gastric cancer treatment, RCP after surgical resection had been widely used, but little is known about RCP after ESD. This study aimed to evaluate the effectiveness of RCP after ESD. Methods: This study included 465 patients on whom our RCP was implemented from 2008 to 2018. A regional family physician performed surveillance endoscopy at 3 months and 1 year after ESD and annually thereafter. We retrospectively evaluated the cumulative incidence and treatment outcomes of new gastric cancer and compared them with previous reports. Results: During a median follow-up period of 70.5 months (3–120 months), 58 patients developed new gastric cancers, and metachronous gastric cancer was detected in 55 patients more than 1 year after ESD. The 5-year cumulative incidence rate was 9.8%. Three patients did not want treatment. Among the remaining 55 patients, the initial treatment was ESD in 51 and surgical resection in 4. Eventually, 50 patients (48 in the ESD group and 2 in the surgical resection group) fulfilled the pathologic criteria for curative ESD. There were no deaths due to gastric cancer. Conclusion: Our study was the first to reveal the incidence of new gastric cancer after ESD using RCP. Most lesions were cured with ESD, and no patients died of gastric cancer. Therefore, we consider RCPs to be an option for surveillance after ESD. [ABSTRACT FROM AUTHOR]

To respond to the increasing demands for practical applications, stabilization and property modulation of metal nanoparticles have emerged as a key research subject. Herein, we present a viable protocol for preparing small metal nanoparticles (<5 nm; Ag, Pd, Pt, and Ru) via multidentate polyoxometalate (POM, [SiW9O34]10−) modification. In addition to enhancing stability, the POMs can modulate the electronic states of metal nanoparticles. Moreover, immobilization of the POM-modified metal nanoparticles on solid supports enables further tuning of the electronic states via a cooperative effect between the POMs and the supports without altering the particle size. Notably, POM-modified Pd nanoparticles on carbon support exhibited superior catalytic activity and selectivity in hydrogenation reactions in comparison with the catalyst without the POM modification. [ABSTRACT FROM AUTHOR]

There is no optimal reconstruction after radical distal esophagectomy for cancers of the esophagogastric junction. We designed a novel reconstruction technique using pedicled ileocolic interposition with intrathoracic anastomosis between the esophagus and the elevated ileum. Two patients underwent the surgery. Case 1 was a 70‐year‐old man with esophagogastric junction adenocarcinoma with 3 cm of esophageal invasion. Case 2 was a 70‐year‐old man with squamous cell carcinoma of the esophagogastric junction; the epicenter of which was located just at the junction. These two patients underwent radical distal esophagectomy and pedicled ileocolic interposition with intrathoracic anastomosis. They were discharged on postoperative days 17 and 14, respectively, with no major complication. Pedicled ileocolic interposition is characterized by sufficient elevation and perfusion of the ileum, which is fed by the ileocolic artery and vein. As a result, we can generally adapt this reconstruction method to most curable esophagogastric junction cancers. [ABSTRACT FROM AUTHOR]

Background and Aim: Changes in the number of surgeries for gastric cancer during the coronavirus disease 2019 (COVID‐19) pandemic have been reported, but data are insufficient to understand the impact at the national level. This study aimed to determine the impact of the COVID‐19 pandemic on gastric surgery in Japan. Methods: Insurance claims data registered from January 2015 to January 2021 were used. Changes in the number of endoscopic resections and gastrectomies for gastric cancer were estimated using an interrupted time‐series analysis. Results: The number of endoscopic resections significantly decreased in July 2020 (−1565; 95% confidence interval [CI]: −2022, −1108) and January 2021 (−539; 95% CI: −970, −109), and the number of laparoscopic surgeries significantly decreased in July 2020 (−795; 95% CI: −1097, −492), October 2020 (−313; 95% CI: −606, −19), and January 2021 (−507; 95% CI: −935, −78). Meanwhile, the number of open gastrectomies remained unchanged, and the number of robot‐assisted gastrectomies steadily increased since their coverage by public health insurance in April 2018. Conclusions: The decreased number of endoscopic resections and laparoscopic surgeries in Japan suggests a decline in early‐stage gastric cancer diagnosis, likely due to the suspension of gastric cancer screening and diagnostic testing during the pandemic. Meanwhile, the number of open and robot‐assisted gastrectomies remained unchanged and increased, respectively, indicating that these applications were not affected by the pandemic‐related medical crisis. These findings highlight that procedures for cancer diagnosis, including screening, should still be provided during pandemics. [ABSTRACT FROM AUTHOR]

Decatungstate is a potent photocatalyst for hydrogen atom transfer (HAT) but faces degradation issues when using a typical tetra-n-butylammonium salt. Herein, we employed tetraphenylphosphonium as a countercation to yield a highly durable and efficient HAT photocatalyst, enabling α-oxygenation of amides to their corresponding imides using O2 as an oxidant. [ABSTRACT FROM AUTHOR]

Owing to their remarkable properties, gold nanoparticles are applied in diverse fields, including catalysis, electronics, energy conversion and sensors. However, for catalytic applications of colloidal gold nanoparticles, the trade-off between their reactivity and stability is a significant concern. Here we report a universal approach for preparing stable and reactive colloidal small (~3 nm) gold nanoparticles by using multi-dentate polyoxometalates as protecting agents in non-polar solvents. These nanoparticles exhibit exceptional stability even under conditions of high concentration, long-term storage, heating and addition of bases. Moreover, they display excellent catalytic performance in various oxidation reactions of organic substrates using molecular oxygen as the sole oxidant. Our findings highlight the ability of inorganic multi-dentate ligands with structural stability and robust steric and electronic effects to confer stability and reactivity upon gold nanoparticles. This approach can be extended to prepare metal nanoparticles other than gold, enabling the design of novel nanomaterials with promising applications. For catalytic nanoparticles there is often a trade-off between stability and activity. Here the authors report a route to ultra-stable and catalytically active colloidal small (~3 nm) gold nanoparticles using multi-dentate polyoxometalates as protecting agents in nonpolar solvents. [ABSTRACT FROM AUTHOR]

Purpose: This study aimed to reveal the impact of coronavirus disease 2019 on the number of practices commonly used for cancer diagnosis in Japan. Methods: The sampling dataset of the National Database of Japan from January 2015 to January 2021 was used to generate 25-point time-series data for the number of practices (21 points before and 4 points during the pandemic outbreak). The decreased number was estimated by interrupted time-series analysis using a seasonal autoregressive integrated moving average model. Using the pre-pandemic data, expected counterfactual numbers during the pandemic were predicted, and decreased rate was calculated. Results: In most practices, the number dramatically decreased in the early stage of the pandemic and recovered rapidly thereafter. As of April 2020, gastric endoscopy decreased at the top of the practices (− 42.1%, with 95% confidence intervals of − 50.5% and − 33.7%), followed by gastric biopsy (− 38.6%, with 95% confidence intervals of − 46.7% and − 30.6%). The period of declined practices for lung cancer was relatively prolonged. The number of sentinel lymph node biopsies for breast cancer and colposcopies and biopsies for cervical cancer did not decrease in April 2020, but significantly decreased later in July 2020, which is assumed to be the time lapse after the primary testing before surgical treatment or intense scrutiny. Conclusion: In general, the number of practices for cancer diagnosis in Japan showed only a temporary decline, which was concordant with reports from several other countries. [ABSTRACT FROM AUTHOR]

Introduction: Laparoscopic retro‐muscular Rives‐Stoppa (RS) ventral hernia repair using the enhanced‐view totally extraperitoneal (eTEP) technique (eTEP‐RS) is becoming common. Although self‐fixating mesh is useful with good fixation, some surgeons think the fixating surface must be oriented towards the rectus abdominis muscle for safety reasons in eTEP‐RS. Attaching the self‐fixating mesh to the rectus abdominis, the ceiling of the operative field, is challenging and time‐consuming. Material and Surgical Technique: First, the self‐fixating mesh is folded in half with the fixation surface facing outwards. Second, we create a partition sheet and insert the sheet between the two arms of the folded mesh. The folded mesh is then inserted intracorporeally. We can unfold the mesh easily from one‐quarter width to half width on the rectus abdominis muscle because of the insertion of the partition sheet. Finally, the mesh is unfolded to full width, and the mesh placement is completed. Discussion: The eTEP‐RS is still a new procedure and has not yet been standardized. However, our technique will increase the use of self‐fixating mesh and improve the outcomes of eTEP‐RS. [ABSTRACT FROM AUTHOR]

Various countries have reported a decrease in breast cancer surgeries during the coronavirus disease 2019 (COVID-19) pandemic; however, inconsistent results have been reported in Japan. This study revealed changes in the number of surgeries during the pandemic using the National Database of Health Insurance Claims and Specific Health Checkups of Japan (NDB) from January 2015 to January 2021, where insurance claims data from Japan as a whole are comprehensively accumulated. The number of breast-conserving surgeries (BCS) without axillary lymph node dissection (ALND) significantly decreased in July (− 846; 95% confidence interval (CI) − 1190 to − 502) and October 2020 (− 540; 95% CI − 861 to − 218). No decrease was observed for other types of surgery, BCS with ALND, and mastectomy with or without ALND. In the age-specific subgroup analysis, significant and transient reduction in BCS without ALND was observed in all age groups (0–49, 50–69, and ≥ 70 years). The number of BCS without ALND significantly decreased for a relatively short period in the early pandemic stages, suggesting reduced surgery for patients with a relatively low stage of cancer. Some patients with breast cancer might have been left untreated during the pandemic, and an unfavorable prognosis would be a concern. [ABSTRACT FROM AUTHOR]

We have reported several precisely designed metal‐oxo clusters on lacunary polyoxometalate (POM) tetra‐n‐butylammonium (TBA) salts in organic solvents. However, owing to their low thermostability and/or low effective surface area, POM TBA salts are not amenable to heterogeneous catalysts for gas‐phase reactions at high temperature. To avoid this problem, we developed a new preparation method that obtains highly dispersed supported‐POM Cs salts (Cs−POM/support) via cation exchange from the corresponding TBA salts on supports. In this study, a model Keggin‐type POM called TBA4PVMo11O40 (TBA−PVMo11) is supported on oxides (TBA−PVMo11/support) using an incipient wetness method in acetonitrile. This TBA−PVMo11/support was cation‐exchanged with cesium trifluoromethanesulfonate in ethanol to obtain supported‐POM Cs salts (Cs−PVMo11/support). Various characterizations revealed that the TBA−PVMo11/support maintained the original Keggin structure during cation exchange and that Cs−PVMo11 was highly dispersed on the supports. Furthermore, Cs−PVMo11/support maintained the Keggin structure even after calcination at 573 K under an aerobic condition. [ABSTRACT FROM AUTHOR]

Polyoxometalates (POMs), anionic metal‐oxygen nanoclusters that possess various composition‐dependent properties, are widely used to modify the existing properties of metal nanoparticles and to endow them with new ones. Herein, we present an overview of recent advances in hybrid materials that consist of metal nanoparticles and POMs. Following a brief introduction on the inception of this area and its development, representative properties and applications of these materials in various fields such as electrochemistry, photochemistry, and catalysis are introduced. We discuss how the combination of two classic inorganic materials facilitates cooperative and synergistic behavior, and we also give personal perspectives on the future development of this field. [ABSTRACT FROM AUTHOR]

Polyoxometalates (POMs), anionic metal‐oxygen nanoclusters that possess various composition‐dependent properties, are widely used to modify the existing properties of metal nanoparticles and to endow them with new ones. Herein, we present an overview of recent advances in hybrid materials that consist of metal nanoparticles and POMs. Following a brief introduction on the inception of this area and its development, representative properties and applications of these materials in various fields such as electrochemistry, photochemistry, and catalysis are introduced. We discuss how the combination of two classic inorganic materials facilitates cooperative and synergistic behavior, and we also give personal perspectives on the future development of this field. [ABSTRACT FROM AUTHOR]

Regioselective transformations of tertiary amines, which are ubiquitously present in natural products and drugs, are important for the development of novel medicines. In particular, the oxidative α-C–H functionalisation of tertiary amines with nucleophiles via iminium cations is a promising approach because, theoretically, there is almost no limit to the type of amine and functionalisation. However, most of the reports on oxidative α-C–H functionalisations are limited to α-methyl-selective or non-selective reactions, despite the frequent appearance of α-methylene-substituted amines in pharmaceutical fields. Herein, we develop an unusual oxidative regiospecific α-methylene functionalisation of structurally diverse tertiary amines with alkynes to synthesise various propargylic amines using a catalyst comprising Zn salts and hydroxyapatite-supported Au nanoparticles. Thorough experimental investigations suggest that the unusual α-methylene regiospecificity is probably due to a concerted one-proton/two-electron transfer from amines to O2 on the Au nanoparticle catalyst, which paves the way to other α-methylene-specific functionalisations.The selective α-methylene functionalization of tertiary amines is challenging. Here, the authors report the gold nanoparticles-catalyzed α-methylene alkynylation of tertiary amines via concerted one-proton/two-electron transfer to O2. [ABSTRACT FROM AUTHOR]

Although supported anionic gold nanoparticle catalysts have been theoretically investigated for their efficacy in activating O2 in aerobic oxidation reactions, limited studies have been reported due to the difficulty of designing these catalysts. Herein, we developed a feasible method for preparing supported anionic gold nanoparticle catalysts using multivacant lacunary polyoxometalates with high negative charges. We confirmed the strong and robust electronic interaction between gold nanoparticles and multivacant lacunary polyoxometalates, and the electronic states of the supported gold nanoparticle catalysts can be sequentially modulated. Particularly, the catalyst prepared using [SiW9O34]10− acted as an efficient reusable heterogeneous catalyst, showing superior catalytic performance for the oxidative dehydrogenation of piperidone derivatives to the corresponding enaminones and remarkably higher stability than supported gold nanoparticle catalysts without this modification. [ABSTRACT FROM AUTHOR]

Although supported anionic gold nanoparticle catalysts have been theoretically investigated for their efficacy in activating O2 in aerobic oxidation reactions, limited studies have been reported due to the difficulty of designing these catalysts. Herein, we developed a feasible method for preparing supported anionic gold nanoparticle catalysts using multivacant lacunary polyoxometalates with high negative charges. We confirmed the strong and robust electronic interaction between gold nanoparticles and multivacant lacunary polyoxometalates, and the electronic states of the supported gold nanoparticle catalysts can be sequentially modulated. Particularly, the catalyst prepared using [SiW9O34]10− acted as an efficient reusable heterogeneous catalyst, showing superior catalytic performance for the oxidative dehydrogenation of piperidone derivatives to the corresponding enaminones and remarkably higher stability than supported gold nanoparticle catalysts without this modification. [ABSTRACT FROM AUTHOR]

A catalyst prepared by modifying the surface of Au nanoparticles (NPs) on Al2O3 with [Nb6O19]8− clusters had specific base and reduction abilities, and the reduction of p-nitrophenol to p-aminophenol using H2 as a reductant proceeded efficiently with the dual functional catalyst. At the interface between Au NPs and basic [Nb6O19]8−, heterolytically cleaved hydrogen species are generated, which can efficiently react with nitrophenolate ions generated by base catalysis. Moreover, this surface modification strategy was applicable to the reduction of other nitro compounds. [ABSTRACT FROM AUTHOR]

Background: Anastomotic stenosis can occur after esophagectomy and gastric tube reconstruction. The effective surgical treatment for refractory anastomotic stenosis, which seems difficult to resolve with endoscopic treatment, has not been established. We report a case of refractory stenosis due to esophageal torsion in which reconstructive surgery was possible using a left thoracoscopic approach in the supine position. Case presentation: A 72-year-old man who underwent thoracoscopic subtotal esophagectomy and retrosternal gastric tube reconstruction for esophageal cancer 6 months previously presented to us. Postoperative endoscopy revealed that the residual esophagus was twisted approximately 360°, just above the anastomotic site. Conservative endoscopic treatment failed to improve the condition due to severe passage obstruction, and reconstructive surgery was repeated. Surgery was performed in the supine position using a left thoracoscopic approach. The entire circumferences of the gastric tube and residual esophagus were dissected from the inferior mediastinum to the top of the sternum, with focus on preserving the right gastroepiploic vein and gastric-tube wall. Subsequently, laparoscopic surgery was performed to remove the gastric tube from the thoracoabdominal junction. After separating the esophagus on the oral side of the torsion from the left cervical wound, the abdomen was opened, the gastric tube was pulled out through the abdominal wound, and adhesions in the abdominal cavity were peeled off to raise the gastric tube cranially via the retrosternal route. An end-to-side anastomosis was performed using a circular stapler, and the esophageal torsion and previous anastomosis were resected. Oral intake was resumed on the 7th postoperative day, and the patient was discharged on the 38th day. Conclusions: After subtotal esophagectomy and retrosternal gastric tube reconstruction, the left thoracoscopic approach is one of the most minimally invasive approaches and is especially useful for preserving the right gastroepiploic artery and veins and for mobilizing the gastric tube wall. [ABSTRACT FROM AUTHOR]

One of the ideal green esterification reactions is aerobic oxidative esterification using only a stoichiometric amount of different alcohols via intermolecular selective alcohol oxidation followed by hemiacetal formation by the addition of the other alcohol and hemiacetal oxidation to esters. However, oxalic acid diester synthesis via oxidative esterification has not been reported to date, possibly owing to the difficulty of selectivity control of intermolecular alcohol oxidation and the chelating effects of ethylene glycol-derived alcohols/hemiacetals on inhibiting oxidation catalysts. Herein, using a CuCl/tetramethylethylenediamine/1,5-dimethyl-9-azanoradamantane N-oxyl catalyst, we describe a highly efficient aerobic oxidative esterification reaction of ethylene glycol to various oxalic acid diesters via selective oxidation of ethylene glycol-derived alcohols/hemiacetals even in the presence of other aliphatic primary alcohols. Notably, the green reaction works well using an ideal stoichiometric ratio of ethylene glycol and primary/secondary alcohols. Thorough experimental investigation and theoretical calculations revealed that highly selective oxidative esterification is enabled by the preferential bidentate coordination of ethylene glycol-derived alcohols/hemiacetals to the Cu(II) species, followed by efficient two-electron/one-proton transfer. [ABSTRACT FROM AUTHOR]

Background: This study aimed to prevent missing gastric cancer and point out low-quality images by developing a double-check support system (DCSS) for esophagogastroduodenoscopy (EGD) still images using artificial intelligence. Methods: We extracted 12,977 still EGD images from 855 cases with cancer [821 with early gastric carcinoma (EGC) and 34 malignant lymphoma (ML)] and developed a lesion detection system using 10,994 images. The remaining images were used as a test dataset. Additional validation was performed using a new dataset containing 50 EGC and 1,200 non-GC images by comparing the interpretation of ten endoscopists (five trainees and five experts). Furthermore, we developed another system to detect low-quality images, which are not suitable for diagnosis, using 2198 images. Results: In the validation of 1983 images from the 124 cancer cases, the DCSS diagnosed cancer with a sensitivity of 89.2%, positive predictive value (PPV) of 93.3%, and an accuracy of 83.3%. EGC was detected in 93.2% and ML in 92.5% of cases. Comparing with the endoscopists, sensitivity was significantly higher in the DCSS, and the average diagnostic time was significantly shorter using the DCSS than that by the trainees. The sensitivity, specificity, PPV, and accuracy in detecting low-quality images were 65.8%, 93.1%, 79.6%, and 85.2% for "Blur" and 57.8%, 91.7%, 82.2%, and 78.1% for "Mucus adhesion," respectively. Conclusions: The DCSS showed excellent capability in detecting lesions and pointing out low-quality images. [ABSTRACT FROM AUTHOR]

Nanosized manganese oxides have recently received considerable attention for their synthesis, structures, and potential applications. Although various synthetic methods have been developed, precise synthesis of novel nanostructured manganese oxides are still challenging. In this study, using a structurally defined nanosized cavity inside a ring‐shaped polyoxometalate, we succeeded in synthesizing two types of discrete 18 and 20 nuclear nanostructured manganese oxides, Mn18 and Mn20, respectively. In particular, Mn18 showed much higher catalytic activity than other manganese oxides for the oxygenation of alkylarenes including electron‐deficient ones, and the reaction proceeded through a unique reaction mechanism due to its unusual manganese oxide structure. [ABSTRACT FROM AUTHOR]

Vanadium-containing phosphomolybdates have outstanding catalytic and electrochemical properties. However, their traditional one-pot synthesis in aqueous media generates a mixture of randomly distributed isomers and undesirable impurities, which has hampered the in-depth study of the catalysis and reaction mechanism of these compounds. Here, the selective synthesis of a tetranuclear vanadium-containing phosphomolybdate, [PV3Mo9O40(VO)]3−, was achieved for the first time by using a pyridine-protected [A-α-PMo9O31(py)3]3− (py = pyridine) as the template. [ABSTRACT FROM AUTHOR]

Atomically precise silver (Ag) nanoclusters are promising materials as catalysts, photocatalysts, and sensors because of their unique structures and mixed‐valence states (Ag+/Ag0). However, their low stability hinders the in‐depth study of their intrinsic reactivity and catalytic property accompanying their redox processes. Herein, we demonstrate that a molecular hybrid of an atomically precise {Ag27}17+ nanocluster and polyoxometalates (POMs) can efficiently cleave H2 into protons and electrons. The Ag nanocluster accommodates electrons through the redox reaction from {Ag27}17+ to {Ag27}13+, and the POM ligands play the following important roles: (i) a significant stabilization of the typically unstable Ag nanocluster to preserve its structure during the redox reaction with H2, (ii) formation of a unique interface between the Ag nanocluster and metal oxides for efficient H2 cleavage, and (iii) storage of the generated protons on the negatively charged basic surface. [ABSTRACT FROM AUTHOR]

Atomically precise silver (Ag) nanoclusters are promising materials as catalysts, photocatalysts, and sensors because of their unique structures and mixed‐valence states (Ag+/Ag0). However, their low stability hinders the in‐depth study of their intrinsic reactivity and catalytic property accompanying their redox processes. Herein, we demonstrate that a molecular hybrid of an atomically precise {Ag27}17+ nanocluster and polyoxometalates (POMs) can efficiently cleave H2 into protons and electrons. The Ag nanocluster accommodates electrons through the redox reaction from {Ag27}17+ to {Ag27}13+, and the POM ligands play the following important roles: (i) a significant stabilization of the typically unstable Ag nanocluster to preserve its structure during the redox reaction with H2, (ii) formation of a unique interface between the Ag nanocluster and metal oxides for efficient H2 cleavage, and (iii) storage of the generated protons on the negatively charged basic surface. [ABSTRACT FROM AUTHOR]

By utilizing hydrazine (N2H4) as the nitrogen source in the presence of a hydroxyapatite-supported Pd nanoparticle catalyst (Pd/HAP), various primary anilines can be selectively synthesized from cyclohexanones via acceptorless dehydrogenative aromatization. The strong nucleophilicity of N2H4 and the stability of the hydrazone intermediates can effectively suppress the formation of the undesired secondary aniline byproducts. [ABSTRACT FROM AUTHOR]

Objective: We determined the anastomotic site during gastric tube reconstruction in esophagectomy according to the "90-to 60-s rule" using indocyanine green (ICG) fluorescence angiography. We evaluated its safety and efficacy in a prospective multicenter setting. Methods: We enrolled 129 patients who underwent subtotal esophagectomy for esophageal cancer. ICG fluorescence angiography was performed after making a wide gastric tube, and the time from the initial enhancement of the right gastroepiploic artery to the tip of the gastric tube was used as a parameter. Esophago-gastro anastomosis was made at the area that was enhanced within 90 s (preferably within 60 s). The enhancement time and the incidence of anastomotic leakage were compared. Results: In all cases, anastomosis was made at the site enhanced within 90 s. Anastomotic leakage was found in only 4 (3.1%) of 129 cases; specifically, it was detected in 3 (2.4%) of 126 cases whose anastomotic site was enhanced within 60 s and in 1 (33.3%) of 3 cases where the enhancement time exceeded 60 s (p = 0.09). Conclusions: Determining the anastomotic site using the 90-to 60-s rule with ICG imaging in gastric tube reconstruction helps reduce the rate of anastomotic leakage. [ABSTRACT FROM AUTHOR]

This study rationally designed a heterogeneously catalyzed system (i.e., using Ni–Pd alloy nanoparticles supported on hydroxyapatite (Ni–Pd/HAP) under an H2 atmosphere) achieving an efficient base-free formal C–S bond metathesis of various thiols via suppression of the Ni catalysis deactivation. [ABSTRACT FROM AUTHOR]

Introduction: A vertical penetration of the thread through the abdominal wall for the hernia defect closure in laparoscopic ventral/incisional hernia repair (LVIHR) is difficult especially in the large defect cases when applying the existing techniques. Materials: Sixteen LVIHRs were performed using the suture technique for defect closure we newly developed. Surgical technique: With the subcutaneous switching, our technique only requires the suture‐passer and easily enables the vertical penetration of the thread through the abdominal muscular wall even in the large defect cases. Discussion: The defect closure in LVIHR tends to be complicated in the large defect cases. Thus, we devised this technique for the easy, reliable, and firm closure even in the large defect cases. Although the sample size was currently very small, we consider that the favorable outcomes have been obtained through our technique because any noticeable complications, such as mesh bulging or recurrence, have not been observed currently. [ABSTRACT FROM AUTHOR]

Polyoxometalates (POMs) have received increasing attention over the last decades for extending their application and properties that originate from novel structures. For the synthesis of a variety of POM structures, multivacant lacunary POMs are key precursors, which are typically synthesized by empirically controlling the complex equilibrium in aqueous solvents. Unfortunately, despite the excellent catalytic and electrochemical properties of "polyoxomolybdates", only one multivacant lacunary species, i.e. [A‐α‐PMo9O34]9−, has been identified and isolated because multivacant lacunary polyoxomolybdates are typically unstable. Here we report a ligand‐directed approach for the selective formation of an unprecedented lacunary polyoxomolybdate in organic solvents. By structure transformation of a pyridine‐coordinated [A‐α‐PMo9O34]9−, a new γ‐Keggin‐type divacant lacunary polyoxomolybdate [γ‐PMo10O36]7− was obtained, which can be further used as a precursor for synthesizing a POM–organic hybrid. [ABSTRACT FROM AUTHOR]

Polyoxometalates (POMs) have received increasing attention over the last decades for extending their application and properties that originate from novel structures. For the synthesis of a variety of POM structures, multivacant lacunary POMs are key precursors, which are typically synthesized by empirically controlling the complex equilibrium in aqueous solvents. Unfortunately, despite the excellent catalytic and electrochemical properties of "polyoxomolybdates", only one multivacant lacunary species, i.e. [A‐α‐PMo9O34]9−, has been identified and isolated because multivacant lacunary polyoxomolybdates are typically unstable. Here we report a ligand‐directed approach for the selective formation of an unprecedented lacunary polyoxomolybdate in organic solvents. By structure transformation of a pyridine‐coordinated [A‐α‐PMo9O34]9−, a new γ‐Keggin‐type divacant lacunary polyoxomolybdate [γ‐PMo10O36]7− was obtained, which can be further used as a precursor for synthesizing a POM–organic hybrid. [ABSTRACT FROM AUTHOR]

Intrathoracic omental herniation is an esophageal hiatal hernia that does not involve the stomach and has been previously misdiagnosed as a lipomatous tumor. We report the case of a 72-year-old man who was referred to our hospital for investigation of a chest abnormal shadow. The large mediastinal mass with fat density was not recognized 5 years ago. Although it mimicked a mediastinal lipomatous tumor, we could preoperatively diagnose it as intrathoracic omental herniation. Contrast-enhanced computed tomography was effective in making an accurate diagnosis, showing the mass and vessels passing through the esophageal hiatus from the abdominal cavity. Laparoscopic surgery was performed, and the hiatus was repaired. To diagnose the mediastinal lipidic mass as intrathoracic omental herniation preoperatively can provide less invasive procedure. [ABSTRACT FROM AUTHOR]

Supersilyl, –Si(SiMe3)3, serves as an effective ligand to afford a series of four-coordinate manganese(II) complexes. A dinuclear complex, [(THF)Mn{Si(SiMe3)3}(μ-Br)]2 (2), was readily synthesized by the reaction of MnBr2 with KSi(SiMe3)3. A subsequent ligand exchange of Br in 2 to –OtBu, methyl, or hydride afforded the corresponding manganese(II) complexes. [ABSTRACT FROM AUTHOR]

Background: Currently, there is no consensus for an optimal minimally invasive esophagectomy (MIE) approach. This study aimed to compare hybrid MIE (hMIE) with neck-abdominal first approach to standard open esophagectomy (OE). Methods: Data from a cohort of 301 patients were retrospectively analyzed. All participants received either hMIE or OE for the treatment of esophageal squamous cell carcinoma at Tokyo Medical and Dental University between January 2003 and December 2013. Analyses included propensity score matching and the Kaplan–Meier statistical method to determine overall survival (OS) and disease-free survival (DFS) of the cohort. Results: After one-to-one propensity score matching, there were 68 patient pairs. The hMIE group had significantly lower incidence of severe postoperative complications (20.1% vs. 7.4%; p = 0.026) and severe respiratory complications (7.4% vs. 0%; p = 0.058) than the OE group. The 5-year oncological outcomes of the two groups were almost equivalent (OS: OE, 55.0%; hMIE, 69.0%; p = 0.063 and DFS: OE, 54.0%; hMIE, 62.0%; p = 0.28). Conclusions: This study compared hMIE with neck-abdominal first approach to standard OE. The results showed significantly less severe postoperative complications for hMIE with neck-abdominal first approach in comparison with OE, without a compromise in long-term oncological outcomes. [ABSTRACT FROM AUTHOR]