Tomographic reconstruction of oxygen orbitals in lithium-rich battery materials.

The electrification of heavy-duty transport and aviation will require new strategies to increase the energy density of electrode materials1,2. The use of anionic redox represents one possible approach to meeting this ambitious target. However, questions remain regarding the validity of the O2-/O- oxygen redox paradigm, and alternative explanations for the origin of the anionic capacity have been proposed3, because the electronic orbitals associated with redox reactions cannot be measured by standard experiments. Here, using high-energy X-ray Compton measurements together with first-principles modelling, we show how the electronic orbital that lies at the heart of the reversible and stable anionic redox activity can be imaged and visualized, and its character and symmetry determined. We find that differential changes in the Compton profile with lithium-ion concentration are sensitive to the phase of the electronic wave function, and carry signatures of electrostatic and covalent bonding effects4. Our study not only provides a picture of the workings of a lithium-rich battery at the atomic scale, but also suggests pathways to improving existing battery materials and designing new ones.

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.

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.

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.

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.

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.

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.

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.

Recent Advances in Hybrid Materials of Metal Nanoparticles and Polyoxometalates.

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.

Immediate effects of elastic tape application on the foot sole: a randomized controlled trial.

[Purpose] In this study, we investigated the effectiveness of elastic tape in increasing the dorsiflexion angle and plantar flexor strength in healthy individuals. [Participants and Methods] This randomized controlled trial included 24 healthy university students who were categorized into the following groups (12 participants in each group): the intervention group (elastic tape was applied to the dominant foot) and the control group (no intervention was performed). We performed intergroup comparison of the pre- and post-intervention dorsiflexion angles and plantar flexor strength. Additionally, we performed subgroup analyses based on a straight-leg raise angle of 70°. [Results] We observed no significant intergroup differences in the dorsiflexion angle or plantar flexor strength. However, the post-intervention dorsiflexion angle was significantly greater than the pre-intervention angle in the subgroup with a straight-leg raise angle of <70° among participants in the elastic tape group. [Conclusion] Elastic tape application may effectively increase the dorsiflexion angle in individuals without hamstring extensibility.

Enhanced phosphorylation of c-Jun by cisplatin treatment as a potential predictive biomarker for cisplatin response in combination with patient-derived tumor organoids.

Despite recent advances in sequencing technology and large-scale drug screenings employing hundreds of cell lines, the predictive accuracy of mutation-based biomarkers is still insufficient as a guide for cancer therapy. Therefore, novel types of diagnostic methods using alternative biomarkers would be highly desirable. We have hypothesized that sensitivity-specific changes in the phosphorylation of signaling molecules could be useful in this respect. Here, with the aim of developing a method for predicting the response of cancers to cisplatin using a combination of specific biomarker(s) and patient-derived tumor organoids (PDOs), we found that cisplatin-sensitive cell lines or PDOs showed enhanced phosphorylation of c-Jun (p-c-Jun) within 24 h after cisplatin treatment. We also compared the responses of 6 PDOs to cisplatin with the therapeutic effect of neoadjuvant chemotherapy (docetaxel/cisplatin/5-fluorouracil) in 6 matched patients. Mechanistically, the c-Jun induction was partly related to TNF signaling induced by cisplatin. Our data suggest that enhanced phosphorylation of c-Jun in response to cisplatin treatment could be a predictive biomarker for the efficacy of cisplatin in selected cancer patients.

Nanostructured Manganese Oxides within a Ring-Shaped Polyoxometalate Exhibiting Unusual Oxidation Catalysis.

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.

Ligand-Protecting Strategy for the Controlled Construction of Multinuclear Copper Cores within a Ring-Shaped Polyoxometalate.

The ring-shaped polyoxometalate (POM) [P8W48O184]40- contains a large cavity and is an attractive inorganic multidentate ligand for accumulating metal cations. Until now, several multinuclear metal cores are constructed within the {P8W48} framework in aqueous solvents. However, it is still challenging to control the number and arrangement of introduced metal cations because of the numerous coordination sites inside the {P8W48} framework. In this study, we developed a novel approach for the selective synthesis of several multinuclear copper-containing ring-shaped POMs in organic solvents using methoxy groups as organic protecting ligands for the reactive coordination sites. Reacting a tetra-n-butylammonium (TBA) salt of [P8W48O184]40- (P8W48) with 4 and 8 equiv of copper(II) acetate in the presence of methanol (MeOH), tetra- and octacopper cores were incorporated into the cavity to form TBA11H13[Cu4(H2O)4P8W48O176(OCH3)8]·28H2O·3CH3NO2 (Cu4) and TBA14H2[Cu8(H2O)12P8W48O176(OCH3)8]·24H2O·CH3CN (Cu8), respectively. For both structures, methoxy groups served as protecting ligands and temporarily inactivated vacant coordination sites. Without MeOH, dodeca- and hexadecacopper cores were constructed inside the cavity to form TBA14H2[Cu12(H2O)16P8W48O184]·4H2O (Cu12) and TBA16H8[Cu16(OH)16(H2O)4P8W48O184]·12H2O·C3H6O (Cu16), respectively. The arrangement of copper ions on the same {P2W12} units could be controlled by the input number of copper ions. Moreover, all four POMs could be synthesized from P8W48 by the stepwise addition of 4 equiv of copper(II) acetate, clarifying the introduction process.

Coordination of Palladium(II) and Platinum(II) Complexes to One Vacant Site in an α-Keggin-Type Polyoxotungstate.

A palladium-platinum bimetal complex containing a mono-lacunary α-Keggin-type polyoxotungstate is demonstrated. The bimetallic complex Cs2.5{PdII(bpy)}0.25[α-PW11O39{PdII(bpy)}{cis-PtII(NH3)2}]·12H2O·2CH3CN (bpy = 2,2'-bipyridine) (PdPt) was synthesized by the reaction of Cs4.9K0.1[α-PW11O39{cis-PtII(NH3)2}]·10H2O (Pt1) with PdII(bpy)Cl2 in aqueous solution. The compound PdPt was characterized via elemental analysis, thermogravimetric/differential thermal analysis, and Fourier transform infrared, ultraviolet-visible, cold-spray ionization mass, and solution (1H, 13C, and 31P) nuclear magnetic resonance spectroscopies. The coordination of {cis-PtII(NH3)2} and {PdII(bpy)} moieties to the mono-vacant site of [PW11O39]7- resulted in an asymmetric, monomeric compound. A unique exchange reaction between the counter cation [PdII(bpy)]2+ and {cis-PtII(NH3)2} moiety in [α-PW11O39{PdII(bpy)}{cis-PtII(NH3)2}]3- in a dimethylsulfoxide solution was also observed.

Success rate of acquiring informed consent and barriers to participation in a randomized controlled trial of laparoscopic versus open surgery for non-curative stage IV colon cancer in Japan (JCOG1107).

BACKGROUND: Successful achievement of randomized controlled trials (RCTs) is dependent on the acquisition of informed consent (IC) from patients. The aim of this study was to prospectively calculate the proportion of participation in a surgical RCT and to identify the reasons for failed acquisition of IC. METHODS: A 50-insitution RCT was conducted to evaluate oncological outcomes of open and laparoscopic surgery for stage IV colon cancer (JCOG1107: UMIN-CTR 000000105). The success rate of obtaining IC was evaluated in eight periods between January 2013 and January 2021. In addition, reasons for failed acquisition of IC were identified from questionnaires. RESULTS: In total, 391 patients were informed of their eligibility for the trial, and 168 (42%) were randomly assigned to either the laparoscopic surgery group (n = 84) or open surgery group (n = 84). The success rate of IC acquisition ranged from 33 to 58% in three periods. The most common reasons for failed IC acquisition were the patients' preference for one approach of surgery based on recommendations from referring doctors and family members, and anxiety/unhappiness about randomization. CONCLUSIONS: The success rate of acquiring IC from patients for an RCT of laparoscopic versus open surgery for stage IV colon cancer was lower than the expected rate planned in the protocol. To obtain the planned rate, investigators should make efforts to inform patients and their families about the medical contributions a surgical RCT can make and recognize that the period in equipoise may be limited.

Serum lipopolysaccharide-binding protein levels and the incidence of metabolic syndrome in a general Japanese population: the Hisayama Study.

BACKGROUND: The association between chronic lipopolysaccharide exposure and the development of metabolic syndrome (MetS) is unclear. In this study we examined the association between serum lipopolysaccharide-binding protein (LBP) levels, an indicator of lipopolysaccharide exposure, and the development of MetS in a general Japanese population. METHODS: 1,869 community-dwelling Japanese individuals aged ≥40 years without MetS at baseline examination in 2002-2003 were followed up by repeated examination in 2007-2008. MetS was defined according to the Japanese criteria. Serum LBP levels were classified into quartiles (quartiles 1-4: 2.20-9.56, 9.57-10.78, 10.79-12.18, and 12.19-24.34 µg/mL, respectively). Odds ratios (ORs) for developing MetS were calculated using a logistic regression model. RESULTS: At the follow-up survey, 159 participants had developed MetS. Higher serum LBP levels were associated with greater risk of developing MetS after multivariable adjustment for age, sex, smoking, drinking, and exercise habits (OR [95% confidence interval] for quartiles 1-4: 1.00 [reference], 2.92 [1.59-5.37], 3.48 [1.91-6.35], and 3.86 [2.12-7.03], respectively; P for trend <0.001). After additional adjustment for homeostasis model assessment of insulin resistance, this association was attenuated but remained significant (P for trend=0.007). On the other hand, no significant association was observed after additional adjustment for serum high-sensitivity C-reactive protein (P for trend=0.07). CONCLUSIONS: In the general Japanese population, our findings suggest that higher serum LBP levels are associated with elevated risk of developing MetS. Low-grade endotoxemia could play a role in the development of MetS through systemic chronic inflammation and insulin resistance.

Arthroscopic handlebar technique for the treatment of posterior malleolar fractures.

Treating posterior malleolar fractures of the ankle remains a challenge. The arthroscopic handlebar technique is our novel surgical method used for reduction and fixation of posterior malleolar fractures and involves the restoration of posterior malleolar fractures under anterior arthroscopic guidance and the use of Kirschner wires that penetrates the fractured posterior malleolus. Arthroscopy enables visualization of the intra-articular fracture of the posterior malleolus, and a handlebar reduction bar is used to control the fractured posterior malleolus. The arthroscopic handlebar technique is a promising procedure for reduction and internal fixation of the posterior malleolar fractures.

Endoscopic imaging modalities for diagnosing the invasion depth of superficial esophageal squamous cell carcinoma: a systematic review.

Endoscopic diagnosis of the invasion depth of superficial esophageal squamous cell carcinoma (ESCC) is an important determinant of the treatment strategy. The three endoscopic imaging modalities commonly used to predict the invasion depth of superficial ESCC in Japan are non-magnifying endoscopy (non-ME), magnifying endoscopy (ME), and endoscopic ultrasonography (EUS). However, which of these three modalities is most effective remains unclear. We performed a systematic review of the literature to compare the diagnostic accuracy of the three modalities for prediction of the invasion depth of superficial ESCC. We used Medical Subject Heading terms and free keywords to search the PubMed, Cochrane Central, and Ichushi databases to identify direct comparison studies published from January 2000 to August 2020. The results of direct comparison studies were used to compare the diagnostic accuracy of each modality. The primary outcome was defined as the proportion of overdiagnosis of pT1b-SM2/3 cancers, and the main secondary outcome was the proportion of underdiagnosis of pT1b-SM2/3 cancers. Other secondary outcomes were the sensitivity and specificity values of the modalities. Four articles were finally selected for qualitative evaluation. Although ME showed no significant advantages over non-ME in terms of sensitivity and specificity, it had a slightly lower proportion of overdiagnosis. EUS had sensitivity and specificity similar to those of non-ME and ME, but EUS had a higher proportion of overdiagnosis. Non-ME and ME are useful for the diagnosis of cancer invasion depth. EUS may increase overdiagnosis, and caution is required in determining its indications.

Supported Anionic Gold Nanoparticle Catalysts Modified Using Highly Negatively Charged Multivacant Polyoxometalates.

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 [SiW9 O34 ]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.

{Mo126 W30 }: Polyoxometalate Cages Shaped by π-π Interactions.

Here we report the formation of giant {Mo126 W30 } polyoxometalate cages templated by π-conjugated planar ligands. Their inorganic shells incorporate arrays of 18 stacked aromatic carboxylates, such as 1,3,5-benzenetricarboxylate or 5-nitroisophthalate, and the assembly is stabilized by multiple π-π interactions. NMR data confirmed that the cages are stable in solution and the inner aromatic templates can be postsynthetically replaced by selected aliphatic dicarboxylates, paving the way for endo-functionalization and exploration of the reactivities within the cage cavities.