Synthesis of a Gold-Silver Alloy Nanocluster within a Ring-Shaped Polyoxometalate and Its Photocatalytic Property.

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.

Bottom-up butterfly model with thorax-pitch control and wing-pitch flexibility.

The diversity in butterfly morphology has attracted many people around the world since ancient times. Despite morphological diversity, the wing and body kinematics of butterflies have several common features. In the present study, we constructed a bottom-up butterfly model, whose morphology and kinematics are simplified while preserving the important features of butterflies. The present bottom-up butterfly model is composed of two trapezoidal wings and a rod-shaped body with a thorax and abdomen. Its wings are flapped downward in the downstroke and backward in the upstroke by changing the geometric angle of attack (AOA). The geometric AOA is determined by the thorax-pitch and wing-pitch angles. The thorax-pitch angle is actively controlled by abdominal undulation, and the wing-pitch angle is passively determined because of a rotary spring representing the basalar and subalar muscles connecting the wings and thorax. We investigated the effectiveness of abdominal undulation for thorax-pitch control and how wing-pitch flexibility affects aerodynamic-force generation and thorax-pitch control, through numerical simulations using the immersed boundary-lattice Boltzmann method. As a result, the thorax-pitch angle perfectly follows the desired angle through abdominal undulation. In addition, there is an optimal wing-pitch flexibility that maximizes the flying speed in both the forward and upward directions, but the effect of wing-pitch flexibility on thorax-pitch control is not significant. Finally, we compared the flight behavior of the present bottom-up butterfly model with that of an actual butterfly. It was found that the present model does not reproduce reasonable body kinematics but can provide reasonable aerodynamics in butterfly flights.

Association between mental health social worker staffing in psychiatric emergency wards and readmission outcomes: A nationwide survey in Japan.

Aim: The mental healthcare system in Japan is transitioning from institution-based to community-based treatment. To prevent prolonged hospitalization and community integration of psychiatric patients, mental health social workers (MHSWs) are pivotal in coordinating post-discharge arrangements for psychiatric inpatients. This study aimed to propose a care model to improve clinical outcomes in psychiatric emergency wards in Japan. Methods: We conducted a mail-in questionnaire survey targeting medical facilities with psychiatric emergency wards. We collected data of the psychiatric care system, including facility profiles, staffing conditions and caseloads, and the provided psychiatric services and treatment options. Using multiple regression analyses, we explored associations between these data and clinical outcomes, focusing on the average number of days for hospitalization and the integration of patients into a community. Results: Data were collected from 82 facilities (response rate, 45.8%). The average number of days for hospitalization and community integration were 64.7 and 327.9 days, respectively. The caseloads for MHSWs were significantly associated with longer hospitalization (ß = 0.31, p = 0.009) and shorter duration of community living (ß = -0.28, p = 0.027). Conclusion: The clinical performance in psychiatric emergency wards surpassed the Japanese government's targets regarding these outcomes. We found that heavy caseloads on MHSWs were associated with worse clinical outcomes for patients in psychiatric emergency wards. These findings suggest that reducing MHSW caseloads (≤20 cases) may be a potential interventional strategy to prevent prolonged hospitalization and promote successful community integration of patients.

Self-assembled molecular hybrids comprising lacunary polyoxometalates and multidentate imidazole ligands.

Self-assembly via coordination bonding facilitates the creation of diverse inorganic-organic molecular hybrids with distinct structures and properties. Recent advances in this field have been driven by the versatility of organic ligands and inorganic units. Lacunary polyoxometalates are a class of well-defined metal-oxide clusters with a customizable number of reactive sites and bond directions, which make them promising inorganic units for self-assembled molecular hybrids. Herein, we report a novel synthesis method for self-assembled molecular hybrids utilizing the reversible coordination of multidentate imidazole ligands to the vacant sites of lacunary polyoxometalates. We synthesized self-assembled molecular hybrids including monomer, dimers, and tetramer, demonstrating the potential of our method for constructing intricate hybrids with tailored properties and functionalities.

Artificial Intelligence Imaging Diagnosis Using Super-Resolution and 3D Shape for Lymph Node Metastasis of Low Rectal Cancer: A Pilot Study From a Single Center.

BACKGROUND: Although accurate preoperative diagnosis of lymph node metastasis is essential for optimizing treatment strategies for low rectal cancer, the accuracy of present diagnostic modalities has room for improvement. OBJECTIVE: To establish a high-precision diagnostic method for lymph node metastasis of low rectal cancer using artificial intelligence. DESIGN: A retrospective observational study. SETTINGS: A single cancer center and a college of engineering in Japan. PATIENTS: Patients with low rectal adenocarcinoma who underwent proctectomy, bilateral lateral pelvic lymph node dissection, and contrast-enhanced multi-detector row computed tomography (slice ≤1 mm) between July 2015 and August 2021 were included in the present study. All pelvic lymph nodes from the aortic bifurcation to the upper edge of the anal canal were extracted, regardless of whether within or beyond the total mesenteric excision area, and pathological diagnoses were annotated for training and validation. MAIN OUTCOME MEASURES: Sensitivity, specificity, positive predictive value, negative predictive value, and accuracy. RESULTS: A total of 596 pathologically negative and 43 positive nodes from 52 patients were extracted and annotated. Four diagnostic methods, with and without using super-resolution images and without using 3D shape data, were performed and compared. The super-resolution + 3D shape data method had the best diagnostic ability for the combination of sensitivity, negative predictive value, and accuracy (0.964, 0.966, and 0.968, respectively), while the super-resolution only method had the best diagnostic ability for the combination of specificity and positive predictive value (0.994 and 0.993, respectively). LIMITATIONS: Small number of patients at a single center and the lack of external validation. CONCLUSIONS: Our results enlightened the potential of artificial intelligence for the method to become another game changer in the diagnosis and treatment of low rectal cancer. See Video Abstract.

Multidentate polyoxometalate modification of metal nanoparticles with tunable electronic states.

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.

A density functional study of the photocatalytic degradation of polycaprolactone by the decatungstate anion in acetonitrile solution.

A recent experimental study has reported that decatungstate [W10O32]4- can degrade various polyesters in the presence of light and molecular oxygen [Li et al., Nanoscale, 2023, 15, 15038]. We apply density functional theory to the photocatalyst-polycaprolactone model complex in acetonitrile solution and elucidate the degradation mechanisms and catalytic cycle. We consider hydrogen atom transfer (HAT) and single electron transfer (SET) mechanisms. The potential energy profiles show that the former proceeds exergonically in a single step but that the latter involves a subsequent proton transfer and finally yields HAT products as well. Oxygenated polymer species can regain the transferred hydrogen and regenerate the reduced photocatalyst. We propose a photocatalytic cycle that realizes both the photocatalyst regeneration and the polymer degradation.

Photocatalytic aerobic α-oxygenation of amides to imides using a highly durable decatungstate tetraphenylphosphonium salt.

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.

Small Copper Nanoclusters Synthesized through Solid-State Reduction inside a Ring-Shaped Polyoxometalate Nanoreactor.

Cu nanoclusters exhibit distinctive physicochemical properties and hold significant potential for multifaceted applications. Although Cu nanoclusters are synthesized by reacting Cu ions and reducing agents by covering their surfaces using organic protecting ligands or supporting them inside porous materials, the synthesis of surface-exposed Cu nanoclusters with a controlled number of Cu atoms remains challenging. This study presents a solid-state reduction method for the synthesis of Cu nanoclusters employing a ring-shaped polyoxometalate (POM) as a structurally defined and rigid molecular nanoreactor. Through the reduction of Cu2+ incorporated within the cavity of a ring-shaped POM using H2 at 140 °C, spectroscopic studies and single-crystal X-ray diffraction analysis revealed the formation of surface-exposed Cu nanoclusters with a defined number of Cu atoms within the cavities of POMs. Furthermore, the Cu nanoclusters underwent a reversible redox transformation within the cavity upon alternating the gas atmosphere (i.e., H2 or O2). These Cu nanoclusters produced active hydrogen species that can efficiently hydrogenate various functional groups such as alkenes, alkynes, carbonyls, and nitro groups using H2 as a reductant. We expect that this synthesis approach will facilitate the development of a wide variety of metal nanoclusters with high reactivity and unexplored properties.

Comparison of postoperative clinical outcome in medial-pivotal and gradually reducing radius design cruciate-retaining total knee arthroplasty-A multicenter analysis of propensity-matched cohorts.

Purpose: To clarify differences in surgery duration, postoperative knee range of motion (ROM), anterior and posterior (AP) laxity, and Forgotten Joint Score (FJS) in patients undergoing medial-pivot (MP) and GRADIUS cruciate-retaining (CR) total knee arthroplasty (TKA) surgeries. Methods: We examined patients who underwent either MP or CR TKA at six different Japanese centres. Patients were propensity score matched for age, sex, and preoperative hip-knee angle (HKA). We compared the groups' average surgery duration, postoperative knee ROM, AP laxity, and FJS 1 year after surgery. Results: There were 86 study patients: 43 MP and 43 CR TKA matched for age, sex, and preoperative HKA. The MP group enjoyed a significantly shorter surgery duration (89.1 ± 10.9 mins vs. 95.7 ± 12.0 mins, p = 0.0091) and significantly better postoperative knee flexion than the CR group (123.7 ± 9.1° vs. 115.3 ± 12.4°, p < 0.001). The MP had significantly smaller postoperative AP laxity with 30° of knee flexion than the CR group (3.4 ± 1.3 vs. 5.6 ± 2.2 mm, p < 0.001). Conversely, postoperative AP laxity with 90° of knee flexion was significantly larger for the MP group (3.6 ± 1.3 vs. 2.7 ± 1.9 mm, p = 0.0098). There were no between-group differences in postoperative FJS. Conclusions: The MP group showed better postoperative knee flexion, midrange AP knee stability, and shorter surgery duration. Level of Evidence: Level III, retrospective comparative study.

Multi-stimuli-responsive polymer degradation by polyoxometalate photocatalysis and chloride ions.

Photocatalytic polymer degradation based on harnessing the abundant light energy present in the environment is one of the promising approaches to address the issue of plastic waste. In this study, we developed a multi-stimuli-responsive photocatalytic polymer degradation system facilitated by the photocatalysis of a polyoxometalate [γ-PV2W10O40]5- in conjunction with chloride ions (Cl-) as harmless and abundant stimuli. The degradation of various polymers was significantly accelerated in the presence of Cl-, which was attributed to the oxidation of Cl- by the polyoxometalate photocatalysis into a highly reactive chlorine radical that can efficiently generate a carbon-centered radical for subsequent polymer degradation. Although organic and organometallic photocatalysts decomposed under the conditions for photocatalytic polymer degradation in the presence of Cl-, [γ-PV2W10O40]5- retained its structure even under these highly oxidative conditions.

Self-controlled Case Series Study for Acute Kidney Injury after Starting Proton Pump Inhibitors or Potassium-Competitive Acid Blocker in Patients with Cancer Using a Large Claims Database.

To investigate the risk of acute kidney injury (AKI) in patients with cancer following the initiation of proton pump inhibitors (PPIs) and potassium-competitive acid blocker (PCAB), considering sex and anti-cancer drug use. We conducted a self-controlled case-series study using the Japan Medical Data Center claims data from 12422 patients with cancer who were prescribed PPIs or PCAB between January 2017 and December 2019. Considering the timing of PPI or PCAB, control period (days -120 to -1), risk period 1 (days 0 to +30), and risk period 2 (days +31 to +365) were defined. To assess the incidence rate ratio (IRR) and 95% confidence interval (CI) as the risk ratio, we adjusted for anti-cancer drugs to assess the risk of AKI. Additionally, we also examined sex differences to identify the risk of AKI. AKI was observed in risk period 1 [2.05 (1.12-3.72), p = 0.0192], but a slight reduction was noted in risk period 2 [0.60 (0.36-1.00), p = 0.0481]. A sex-specific increase in the risk of AKI was observed only in males during risk period 1 [2.18 (1.10-4.32), p = 0.0260], with a reduction in risk period 2 [0.48 (0.26-0.89), p = 0.0200]. We identified an increased risk of AKI in patients with cancer starting PPIs or PCAB particularly in males within 30 d after PPI or PCAB initiation, emphasizing the need for vigilant monitoring and management of AKI in this patient population.

Cognitive Impairment and Early-onset Cerebral Amyloid Angiopathy in a Middle-aged Man with a History of Childhood Traumatic Brain Injury.

We herein report the a 42-year-old man with early-onset cerebral amyloid angiopathy (CAA) and a history of traumatic brain injury and neurosurgery in childhood. Computed tomography revealed cognitive impairment and recurrent lobar intracerebral hemorrhaging. Magnetic resonance imaging indicated cerebral microbleeds, and Pittsburgh compound B positron emission tomography detected brain amyloid deposition, mainly in the region of trauma and occipital lobes. Interestingly, the patient had no genetic predispositions or relevant family history. This case suggests that a single traumatic brain injury or neurosurgery in childhood can cause early-onset CAA.

Ultra-stable and highly reactive colloidal gold nanoparticle catalysts protected using multi-dentate metal oxide nanoclusters.

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.

Characterization of residual cancer by comparison of a pair of organoids established from a patient with esophageal squamous cell carcinoma before and after neoadjuvant chemotherapy.

Neoadjuvant chemotherapy (NAC) followed by surgery is a standard approach for management of locally advanced esophageal squamous cell carcinoma (ESCC). Patients who do not respond well to NAC have a poor prognosis. Despite extensive research, the mechanisms of chemoresistance in ESCC remain largely unknown. Here, we established paired tumor organoids-designated as PreNAC-O and PostNAC-O-from one ESCC patient before and after NAC, respectively. Although the two organoids did not exhibit significant differences in proliferation, morphology or drug sensitivity in vitro, the tumorigenicity of PostNAC-O in vivo was significantly higher than that of PreNAC-O. Xenografts from PreNAC-O tended to exhibit keratinization, while those from PostNAC-O displayed conspicuous necrotic areas. The tumorigenicity of PostNAC-O xenografts during the chemotherapy was comparable to that of PreNAC-O without treatment. Furthermore, the gene expression profiles of the xenografts suggested that expression of genes involved in the EMT and/or hypoxia response might be related to the tumorigenicity of PostNAC-O. Our data suggested that the tumorigenicity of residual cancer had been enhanced, outweighing the effects of chemotherapy, rather than being attributable to intrinsic chemoresistance. Further studies are required to clarify the extent to which residual cancers share a common mechanism similar to that revealed here.

Porphyrin-Polyoxotungstate Molecular Hybrid as a Highly Efficient, Durable, Visible-Light-Responsive Photocatalyst for Aerobic Oxidation Reactions.

Organic-polyoxometalate (POM) hybrids have recently attracted considerable interest because of their distinctive properties and wide-ranging applications. For the construction of organic-POM hybrids, porphyrins are promising building units owing to their optical properties and reactivity, including strong visible-light absorption and subsequent singlet-oxygen (1O2*) generation. However, the practical utilization of porphyrins as photocatalysts and photosensitizers is often hindered by their own degradation by 1O2*. Therefore, there is a substantial demand for the development of porphyrin-derived photocatalysts with both high efficiency and durability. Herein, we present a porphyrin-polyoxotungstate molecular hybrid featuring a face-to-face stacked porphyrin dimer (I) fastened by four lacunary polyoxotungstates. Hybrid I exhibited remarkable efficiency and durability in photocatalytic aerobic oxidation reactions, and the selective oxidation of various dienes, alkenes, sulfides, and amines proceeded using just 0.003 mol % of the catalyst. Mechanistic investigations suggested that the high activity of I stems from the efficient generation of 1O2*, resulting from the heavy-atom effect of POMs. Furthermore, despite its high efficiency in 1O2* generation compared to free porphyrins, I exhibited superior durability against 1O2*-induced degradation under photoirradiation.

[Questionnaire Survey on IVR Dose Management in Tokai Region].

PURPOSE: National diagnostic reference levels in Japan 2020 (DRLs 2020) have been published. In the field of angiography, in addition to the fluoroscopic dose rate, incident air kerma at the patient entrance reference point displayed on the equipment (Ka,r: mGy) and air kerma-area product displayed on the equipment (PKA: Gycm2) were set. A questionnaire survey was conducted at each facility in the Tokai region to confirm the status of medical radiation dose control in the region. METHOD: A questionnaire survey was conducted at each facility in the Tokai region. The items were fluoroscopic dose rate in each area (head and neck, cardiac, chest and abdomen, and limbs), DA and DSA dose rates, and dose area product meter (Ka,r, PKA) for the main procedures in each area. RESULT: The median values in this study were lower than those in the DRLs 2020, indicating that appropriate dose control is being implemented in the Tokai region. The trends of fluoroscopic and radiographic dose rates were different in each area, and there was some variation among the facilities. CONCLUSION: We believe that the incorporation of fluoroscopic and radiographic dose rates by area into the DRLs will facilitate more appropriate dose control at each facility in the future.

Highly efficient degradation of polyesters and polyethers by decatungstate photocatalysis.

Photocatalytic polymer degradation has been recognized as a promising solution to the global disposal of waste plastics. In this work, we revealed that various polyesters and polyethers were efficiently degraded in the presence of a polyoxometalate photocatalyst, specifically, decatungstate ([W10O32]4-, W10). A catalytic amount of W10 initiated the degradation of various polyesters and polyethers under photo-irradiation with a xenon lamp (λ > 350 nm) using O2 (1 atm) as the oxidant in acetonitrile or water. Moreover, this system can promote polymer degradation even under sunlight. The degradation efficiency, assessed from the degradation rate (Mw0 - Mw)/Mw0 (%) (where Mw0 is the Mw before the reaction), of W10 was notably higher than those of previously reported photocatalysts such as titanium oxide, other polyoxometalates, organometallic compounds, and organic dyes.

Association of immune-related expression profile with sensitivity to chemotherapy in esophageal squamous cell carcinoma.

Neoadjuvant chemotherapy (NAC) followed by surgery is one of the standard therapeutic approaches in Japan for patients with locally advanced esophageal carcinoma. Recently, the JCOG1109 study revealed that NAC with docetaxel, cisplatin and 5-fluorouracil (5-FU) (DCF-NAC) is superior to NAC with cisplatin and 5-FU, and has now become the standard preoperative chemotherapy. Using a microarray system, we have previously investigated the expression profiles of endoscopic biopsy samples from patients with esophageal squamous cell carcinoma (ESCC) before DCF-NAC (preNAC) and identified 17 molecules as biomarkers predictive of a pathologically complete response to DCF-NAC. Here, we re-grouped our previous dataset based on the histopathological response grade with the addition of several microarray profiles and conducted a re-analysis using bioinformatic web tools including DAVID, GSEA, UALCAN, and CIBERSORTx. We identified 204 genes that were differentially expressed between the highly resistant and sensitive groups. Some of these differentially expressed genes (DEGs) were related to the immune response and showed higher expression in the sensitive group. UALCAN showed that high expression of 28 of the top 50 DEGs was associated with a favorable prognosis (p < 0.25), and that this reached a significant (p < 0.05) level for 18 of them, suggesting that patients with high expression of these genes might have benefited from chemotherapy and thus had a better outcome. In preNAC biopsy tissues from a DCF-sensitive case, we demonstrated the presence of cells expressing mRNA for CXCL9, one of the prognosis-related DEGs. Our results highlight the association of immune-related expression profile in preNAC ESCC with the DCF-NAC efficacy.

Molecular hybrids of trivacant lacunary polyoxomolybdate and multidentate organic ligands.

Functional molecular inorganic-organic hybrids of lacunary polyoxometalates and organic ligands attract much attention for advanced material applications. However, the inherent instability of lacunary polyoxomolybdates hinders the synthesis of hybrids and their utilization. Herein, we present a viable approach for the synthesis of molecular hybrids of trivacant lacunary Keggin-type polyoxomolybdates and multidentate organic ligands including carboxylates and phosphonates, which is based on the use of a lacunary structure stabilized by removable pyridyl ligands as a starting material.