Supported copper nanoparticles play a fundamental role in heterogeneous sustainable catalysis, particularly for the conversion of biomass-derived feedstocks (such as bioethanol) to platform chemicals. However, controlling their fine dispersion and, at the same time, their resistance to sintering remains a challenge, especially when using silica supports. We report a simple one-pot aerosol route to produce mesoporous Cu-SiO2 catalysts featuring small copper nanoparticles (2-4 nm) partially embedded in the silica matrix. To achieve this, we exploit the affinity between the copper and the thiol function of a mercapto-silane: (3-mercaptopropyl)-trimethoxysilane (MPTMS). As supported by characterization (in particular XRD, XPS, TEM, TPR, UV-VIS, and dispersion measurements) the addition of this molecule during synthesis markedly enhanced Cu dispersion in the calcined catalyst. This is shown to translate into enhanced time-on-stream stability during the ethanol non oxidative dehydrogenation to acetaldehyde. The catalyst obtained via thiol-assisted stabilization of copper demonstrates a sustained acetaldehyde productivity of 2.88 gaca gcat-1 h-1 during 23 h test time at 623 K.

Heteropolyacids such as H3PW12O40 (HPW) are Brønsted solid superacids making them an interesting prospect for acid catalysis in the solid state. However HPW faces several limitations, and modifications may be required to make it better match each reaction needs and increase its activity. In addition to its low specific surface area (below 10m²/g), bulk HPW is hydrophilic as it contains 6 tightly bonded water molecules constituting the crystalline structure HPW.6H2O. In the case of the methanolation of toluene, since methanol is a polar molecule it is easily activated by HPW, while toluene has a low affinity for the solvated HPW surface and therefore cannot be activated. In this work, we prepared PW heteropolyacids substituted with 0 to 3 ammonium cations and demonstrated that a partial substitution of protons with ammoniums drastically increases the heteropolyacid activity for the toluene methanolation. The ammonium substitution mechanism has been deeply understood via ATR-FTIR, XRD, N2-physisorption, TGA-MS, NH3-TPD, 31P ssNMR. It appeared that the substitution of 2.5 protons leads to the optimal combination of an increased specific surface area, a more hydrophobic surface arising from the presence of ammoniums, and the remaining of some strongly acidic protons able to activate methanol and alkylate toluene into xylenes.

Achieving CO₂ methanation via the Sabatier reaction represents a viable route for renewable energy storage and CO₂ valorization. While Ni-based catalysts are considered as the most cost-effective and efficient catalysts, they still require elevated activation temperatures and remain prone to sintering. Adding promoters or dopants to form bimetallic catalysts are possible strategies to counter these limitations. Metal-organic frameworks (MOFs) offer a structurally well-defined platform to confine and stabilize metal nanoparticles (NPs). However, bimetallic MOF-supported systems have not yet been reported for this reaction. Here, we present NiCo@MOF-545 as the first bimetallic NP@MOF catalyst for CO₂ methanation. The intimate NiCo alloying within the porous host is established by transmission electron microscopy coupled with ultramicrotomy and energy-dispersive X-ray mapping. Time-resolved in situ X-ray absorption spectroscopy reveals that cobalt incorporation into the Ni-based catalyst lowers the characteristic temperature of Ni²⁺→Ni⁰ reduction by 35°C relative to the cobalt-free counterpart. Under continuous-flow conditions, the bimetallic NiCo@MOF catalyst exhibits superior CO₂ conversion with 100% CH₄ selectivity across the 200–300°C range, with a reduced apparent activation energy (59.7 vs. 67.1 kJ·mol⁻¹). Operando XAS monitoring confirms the structural stability of the catalyst under reaction conditions, with no detectable change in oxidation state or local coordination environment. This work demonstrates that bimetallic NP@MOF design is an effective strategy for low-temperature CO₂ methanation.

We explore two approaches for preparing supported catalysts based on volcanic ash (VA) as support for effective Fenton heterogeneous catalysis. Firstly, the plasma deposition of FeOOH (goethite) on VA activated chemically by HCl (AM-FeOOH-30/0C) was performed. Secondly, the plasma-activation of VA and -deposition of FeOOH (VA-FeOOH-30/0) were carried out simultaneously, taking advantage of the gliding-arc-plasma acidic and oxidizing properties. Prepared materials were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), N2 physisorption, and scanning electron microscopy coupled energy-dispersive X-ray spectroscopy (SEM/EDX). Performing chemical activation of VA using HCl induces a better microstructure's modification (specific surface area and porosity) and allows a better plasma-deposition of FeOOH (AM-FeOOH-30/0C) compared to performing both processes simultaneously by plasma (VA-FeOOH-30/0) which did not change its microstructure but slightly improved the texture. Otherwise, aging (plasma post-discharge treatment) of AM-FeOOH-30/0C material induces crystallite's nucleation, thus an increase of the specific surface area (AM-FeOOH-30/4C). Fenton catalytic degradation of Rhodamine-6G (25 mg/L) for 20 min revealed elimination degrees of 22%, 87%, 78%, and 82%, respectively, for VA-FeOOH-30/0, AM-2C, AM-FeOOH-30/0C, and AM-FeOOH-30/4C materials. The recyclability tests confirmed the higher catalytic stability of AM-FeOOH-30/0C compared to VA-FeOOH-30/0 material after 4 cycles, thus highlighting the necessity to perform the activation and deposition separately.

Gaining insight into the role of metal promoters in CO2 methanation is essential for designing more effective methanation catalysts. In this study, Ru-based catalysts supported on V2O5-TiO2 were prepared via sequential wet impregnation to unravel the origin of the promotional effect of vanadia on Ru/TiO2 catalysts. Tuning the relative composition of TiO2 and V2O5 allows the synergistic interactions between the support components and Ru nanoparticles to be optimized. At 200 degrees C, Ru/12%V2O5-TiO2 catalyst achieves CH4 formation rate of 1.22 mu molg(cat)(-1)s(-1), outperforming both Ru/TiO2 and Ru/V2O5 catalysts. Its superior activity is attributed to the combined effects of TiO2, which helps maintaining relatively high Ru dispersion, and V2O5, which is reduced by hydrogen spillover from Ru, generating surface oxygen vacancies and hydroxyl groups. The latter species are shown to promote the formation of formate intermediates, while higher Ru dispersion facilitates their decomposition to adsorbed CO prior to hydrogenation to CH4.

Glaucoma is a neurodegenerative condition involving optic nerve damage and retinal ganglion cells death. Animal studies suggested that the pathway linking these events can be mediated by mobile zinc secreted into the intraretinal space and exerting cytotoxic effects. Whether this mechanism is relevant for human glaucoma and what are the targets of extracellular zinc is unknown. We report that increased zinc content in the aqueous humor and retina is indeed a characteristic of glaucomatous neuropathy, and excess extracellular zinc may be recognized by the key retinal neurotrophic factor PEDF. Biophysical and X-ray crystallographic studies show that PEDF coordinates zinc ions in five types of intermolecular high-affinity sites, leading to a decrease in negative surface charge and reversible oligomerization of the protein, thereby masking the target recognition sites responsible for its neurotrophic and antiangiogenic activities and collagen binding. Notably, PEDF secretion is enhanced in both glaucoma and retinal cell models in response to zinc stress; however, zinc binding negatively affects axogenic, differentiative and prosurvival functions of PEDF by suppressing its ability to activate receptor PEDF-R/PNPLA2. We suggest that glaucomatous neurodegeneration is associated with direct inhibition of PEDF signaling by extracellular zinc, making their complex a promising target for neuroprotective therapy.

The reductive catalytic fractionation (RCF) is an attractive method for the conversion of lignin toward valuable low-molecular weight aromatics during the pretreatment of lignocellulosic biomass. A prominent limitation to the upscaling of such technology is represented by the use of pressurized hydrogen gas. In this contribution, the role of hydrogen gas within the RCF of wheat straw biomass is investigated. The use of H2 was shown to enhance lignin depolymerization, by virtue of an improved hydrogenolysis and hydrogenation of lignin fragments, with a yield of phenolic monomers that increased from ~12 wt% of acid-insoluble lignin in the initial biomass under inert atmosphere, up to ~25 wt% under H2, for a reaction in methanol, at 250 °C, with Ru/C. The adoption of methanol, ethanol and isopropanol as hydrogen-donor solvents was also investigated in the absence of H2, and the use of ethanol was found to give the highest yield of monophenolics (up to ~20 wt%) owing to a better balance between solvolysis, hydrogenolysis, and hydrogenation of lignin. Nevertheless, a substantial loss of the carbohydrate fraction was observed for reactions performed at 250 °C, irrespective of hydrogen pressure and of the solvent employed. The use of a lower temperature of 200 °C in combination with H3PO4 resulted in an improved recovery of cellulose in the pulp and in the solubilization of hemicellulose and lignin, with the formation of monosaccharides (~14 wt% of polysaccharides in the initial biomass) and phenolic monomers (up to 18 wt%, in the absence of H2). Overall, the obtained results show that a tradeoff exists between the removal of H2 from the process and the production of low-MW phenolics during RCF, which can be improved by accurately tuning the process conditions.

MnO2 nanostructures were successfully synthesized via the reduction of KMnO4 solutions using the gliding arc plasma (Plasma Glidarc) approach. Here, we highlight the effect of different plasmagenic gases, such as moist air (atmospheric air), dry air, nitrogen (N2) or oxygen (O2). The obtained materials were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), nitrogen physisorption and scanning electron microscopy (SEM). The crystalline structures of obtained MnO2 polymorphs are mainly γ-MnO2 and α-MnO2, regardless of the feeding gas. The main reactive species, in addition to nitrogenous species like NO· radical generated with moist air, dry air or N2 gas, other oxygenated species such as H2O2 (E°(O2/H2O2) = 0.69 V) are produced with O2 able to reduce KMnO4 solution (E°(KMnO4/MnO2) = 1.70 V). Helium gas did not allow for the plasma reduction of the KMnO4 solution, even after 60 min of exposure. Furthermore, gas humidification did not significantly affect the precipitation time or the properties of plasma-synthesized MnO2. Atmospheric humidified air appears to be the best plasmagenic gas, as it allows for a shorter synthesis time and leads to a large specific surface area. All plasma-synthesized MnO2 showed good activity during the catalytic oxidation of benzene. The use of different MnO2 polymorphs (α-, δ- and γ-MnO2) showed that, in addition to the specific surface area, the crystalline structure significantly affects the catalytic oxidation of benzene. K+ species inserted within the MnO2 structure allow for their stability during the catalytic process. This work highlights the possibility to use different plasmagenic gases to prepare MnO2 nanostructures through plasma glidarc for the catalytic oxidation of benzene.

BACKGROUND:STIM1 is a key regulator of calcium homeostasis in the endoplasmic reticulum (ER), activated upon ER calcium depletion through calcium dissociation from its EF-hand domain. While much is known about its domain organization and activation-induced structural rearrangements, certain regulatory mechanisms remain unclear. A short conserved region upstream of the EF-hand has been previously implicated in redox modulation of STIM1, but its exact function was unknown. METHODS:We used a combination of biochemical assays, mutagenesis, and imaging approaches to investigate the structural and functional role of this conserved region. Zinc binding was assessed by spectroscopy, and STIM1 clustering was monitored by fluorescence microscopy. Statistical analyses were applied where appropriate to evaluate significance. RESULTS:We demonstrate that this conserved segment coordinates zinc ions and is essential for STIM1 activation. Zinc binding to this region enhances STIM1 clustering, a prerequisite for Orai-mediated calcium influx. Mutations disrupting zinc coordination impaired clustering and downstream calcium signaling. CONCLUSIONS:Our results identify a zinc-binding module upstream of the EF-hand as a critical determinant of STIM1 activation. These findings provide new insights into the molecular interplay between zinc and calcium signaling and suggest a regulatory mechanism by which cellular zinc levels may influence ER calcium homeostasis.

Many cancers cannot be detected early due to lack of effective disease biomarkers, leading to poor prognosis. We applied an existing biophysical technology nanoDSF in a novel way to answer this unmet biomedical need. We developed a breakthrough digital biomarker method for cancer detection based on AI-classification of plasma denaturation profiles (PDPs) obtained by nanoDSF technology. PDPs from 300 plasma samples from patients with melanoma, brain, digestive or lung cancers were automatically distinguished from healthy profiles with an accuracy of 94%. Moreover, our method was able to distinguish different types of cancers from each other with an accuracy of 80%, making it an effective way to help cancer diagnosis and monitoring. Our technology thus paves the way for a long-sought multi-cancer early detection (MCED) test that is blood-based, cost-effective and easy-to-implement in any clinical setting. ### Competing Interest Statement The authors have declared no competing interest. ### Funding Statement This study was partly funded by Canceropole PACA, Institut National du Cancer and Region Sud, MIC grant from ITMO Cancer of Aviesan, Patient association ARTC Sud and by INCa-DGOS-Inserm_12560 grant (SiRIC CURAMUS). ### Author Declarations I confirm all relevant ethical guidelines have been followed, and any necessary IRB and/or ethics committee approvals have been obtained. Yes The details of the IRB/oversight body that provided approval or exemption for the research described are given below: Ethic committee of Assistance Publique des Hopitaux de Marseille AP-HM (CRB BB-0033-00097) gave ethical approval for this work. I confirm that all necessary patient/participant consent has been obtained and the appropriate institutional forms have been archived, and that any patient/participant/sample identifiers included were not known to anyone (e.g., hospital staff, patients or participants themselves) outside the research group so cannot be used to identify individuals. Yes I understand that all clinical trials and any other prospective interventional studies must be registered with an ICMJE-approved registry, such as ClinicalTrials.gov. I confirm that any such study reported in the manuscript has been registered and the trial registration ID is provided (note: if posting a prospective study registered retrospectively, please provide a statement in the trial ID field explaining why the study was not registered in advance). Yes I have followed all appropriate research reporting guidelines, such as any relevant EQUATOR Network research reporting checklist(s) and other pertinent material, if applicable. Yes All data produced in the present study are available upon reasonable request to the authors

BACKGROUND:Breast cancer (BC) is a major problem of public health in western countries. The long-term survival improved thanks to therapeutic progresses and mass screening. Mass screening is based on mammography but displays limitations. Efforts are ongoing to develop accurate and minimally invasive tools for early BC detection. Analysis of liquid biopsies is a promising option, among which the ones based on thermal denaturation profiling provide a "thermodynamic signature" of disease through analysis of plasma protein denaturation profiles. We recently developed a major technical breakthrough of differential scanning calorimetry by switching to nanoDSF (Differential Scanning Fluorimetry), more easily transferrable in clinical routine. Here, we applied it for the first time to samples form BC patients. METHODS:We retrospectively applied nanoDSF to plasma samples from 176 patients collected in two prospective clinical trials and 61 healthy controls (HC). The profiles were analyzed using four artificial intelligence (AI) algorithms. Our primary objective was to test the potential of this approach to distinguish BC versus HC samples. We also assessed its ability to distinguish early versus advanced BC, and major molecular subtypes of disease. RESULTS:The four algorithms provided predictive models displaying very good performances for distinguishing patients from HC. For example, the random forest-based model displayed 96.6% accuracy in properly classifying subjects, 99.4% sensitivity, and 88.5% specificity. These performances were not dependent on the clinicopathological characteristics of BC, and compared favorably to those of mammography-based screening. For comparison, the performances of predictive models centered on the secondary objectives (early versus metastatic stage, hormone receptor (HR)-positive versus HR-negative status, and HER2-positive versus HER2-negative status) were good, but inferior, likely because of the stronger unbalance in the number of patients in each group and of more subtle differences in thermograms between patients' groups than between patients and HC. CONCLUSIONS:We reveal the potential of nanoDSF and AI applied to plasma samples to discriminate between BC patients and HC. If these results are confirmed, such approach could represent a minimally-invasive, low risk, quick and low-cost technique, which could help to improve the screening of BC.

This work explored the possibility of doping MnO2 structure simultaneously by cationic (Na+, Mg2+ or K+) and nitrogen species during its synthesis through gliding arc plasma route. Therefore, NaMnO4, Mg(MnO4)2 or KMnO4 precursor has been precipitated via plasmachemical reduction thanks to NO⋅ and NO2− respectively being short and long-lived species generated in plasma plume (gas phase) and plasma post-discharge (liquid phase). Physicochemical characterizations revealed nanostructured NaN–MnO2, MgN–MnO2 and KN–MnO2 respectively with specific surface areas of 36, 110 and 116 m2/g, nitrogen atomic loading at surface of 0.6, 1.0 and 1.5

STIM1 is pivotal in the tightly regulated mechanism controlling calcium homeostasis in the ER. It is activated by calcium dissociation from its EF-hand domain when ER calcium levels decrease, leading to its interaction with the ORAI channel to initiate calcium influx. Despite advancements in understanding the complex STIM1 machinery, including its domain organization and structural rearrangements upon activation, many aspects of this process remain poorly understood. In this study, we focused on a small conserved region situated upstream to the EF-hand, which has been previously shown to be involved in the modulation of STIM1 by ROS. Our findings reveal that this region binds zinc and plays a pivotal role in STIM1 activation by promoting its clustering, a process essential for the activation of calcium influx. These results revealed the functional importance of this domain and added a crucial piece to the puzzle of how calcium and zinc signaling are interconnected. ![Figure][1] Graphical abstract ### Competing Interest Statement The authors have declared no competing interest. * SOCE : store-operated calcium entry ORAI : calcium release-activated calcium channel protein CRAC : calcium release-activated channels STIM : stromal interaction molecule ITC : isothermal titration calorimetry DLS : dynamic light scattering DSF : differential scanning fluorimetry EF-STIM1 : 27-212 a.a. fragment of STIM1 luminal domain Association francaise contre les myopathies, Mothard [1]: pending:yes

The preparation of powdery heterogeneous catalysts often involves the use of solvents, costly precursors, and thermal treatments in multi‐step processes. Herein, we demonstrate the preparation of Ru nanoparticles on TiO 2 via spark ablation coupled with powder aerosolization, offering a clean and simple route with minimal waste generation and reduced pre‐ and post‐synthesis processing. The as‐prepared Ru/TiO 2 catalyst is readily active in CO 2 methanation reaction, achieving CH 4 formation rate of 0.21 mmolg Ru −1 s −1 and TOF of 0.11 s −1 at 200 °C, outperforming the corresponding formulation prepared by wetness impregnation followed by calcination. The enhanced performance is attributed to a higher fraction of surface metallic Ru, as spark ablation under inert atmosphere typically yields metallic Ru nanoparticles. Additionally, Ru nanoparticles in the spark‐made catalyst are well‐distributed over both anatase and rutile TiO 2 , driven by Brownian motion and van der Waals adhesion. By contrast, Ru/TiO 2 ‐WI exhibits preferential Ru layer around rutile TiO 2 due to pre‐existing RuO 2 ‐rutile TiO 2 epitaxial interactions formed during calcination. This work highlights a sustainable approach for designing highly active low‐temperature CO 2 methanation catalysts, with potential versatility for broader catalytic applications.

Microtubule targeting agents (MTAs) constitute a vital category of tubulin-binding compounds deployed across anticancer therapies. Despite the array of MTA drugs developed by pharmaceutical entities, the quest for novel efficacious molecules continues unabated. We unveil an innovative in vitro MTA screening methodology employing nano-differential scanning fluorimetry (nanoDSF), presenting distinct advantages over known assays. This novel approach not only assesses compound-tubulin binding but also quantitatively analyzes its impact on tubulin polymerization, facilitating structure-activity relationship discovery. The proposed nanoDSF assay was rigorously validated using the Prestwick Chemical Library, which encompasses 1520 approved compounds, successfully identifying all previously known MTAs. This screening has unearthed potential antitubulin agents among drugs currently utilized for unrelated medical conditions, offering insights into their mechanisms of action in inhibiting cancer cell proliferation and/or inducing cytotoxicity. Finally, we have identified a previously unrecognized structure-activity relationship within the carbendazim and phenothiazine drug clusters, providing valuable insights for the rational optimization of compounds from these families. These discoveries open new opportunities for drug repositioning of the newly identified MTAs and significantly streamline the screening process of large chemical libraries for MTAs with novel chemical scaffolds.

Valeric acid (VA), readily obtainable in the biorefinery from sugary biomass streams, can be upgraded to 5-nonanone, a versatile chemical building block with numerous applications. This study investigates the performance of nine metal oxide catalysts (SnO2, SiO2, Y2O3, CeO2, ZrO2, TiO2, La2O3, Cr2O3, and Al2O3) in the gas-phase ketonization of VA to 5-nonanone in the 350-450 degrees C range. The screening reveals a correlation between the metal oxides lattice energy and their catalytic activity for valeric acid ketonization. ZrO2, TiO2, and La2O3, characterized by high lattice energy, demonstrate the highest catalytic activity, whereas Y2O3, SnO2, and SiO2, showing low lattice energy, are barely active. However, exceptions to this trend were observed: Cr2O3 and Al2O3 displayed poor catalytic performance despite their elevated lattice energy. The comprehensive characterization of the catalysts, encompassing XRD, N2-physisorption, NH3-TPD, and CO2-TPD analyses, has unveiled the crucial role of important parameters including acid-base properties in addition to lattice energy. Only oxides showing amphoteric properties can catalyze the reaction effectively. Interestingly, low-lattice energy and amphoteric oxides such as SnO2 (showing poor performance) become significantly active at higher temperature (500 degrees C). Analysis of by-products by online GCMS and spent catalyst characterization indicated that in this case the ketonization mechanism changed from the so-called surface mechanism to the so-called bulk mechanism.

Mn or Co supported CeO2 fiber catalysts were synthesized following a biotemplating route and evaluated in soot combustion and benzene total oxidation. The catalysts were characterized by SEM, EDX, N2 physisorption, FTIR-ATR, XRD, RAMAN and XPS. SEM results confirmed that the “twisted ribbon” morphology of the biotemplate was mostly maintained. XRD and Raman showed that Mn and Co cations partially insert into ceria lattice and also segregate at the surface of the fibers. XPS allowed to determine that both set of catalysts exhibit Ce3+ and Ce4+ species, in addition to adsorbed and lattice oxygen. Also, the average oxidation state (AOS) of surface Mn could be calculated. Compared to bare Fib Ce, the performances for both reactions were improved for the supported catalysts, except from the catalyst with lowest Mn content for soot combustion. The catalytic activity was discussed in terms of the physicochemical features of the supported catalysts.

Growing evidence has unveiled the pathological significance of Tau in many cancers, including the most aggressive and lethal brain tumor glioblastoma multiform (GBM). In this regard, we have recently examined the structure–activity relationship of a new series of seventeen 2-aminothiazole-fused to flavonoid hybrid compounds (TZF) on Tau-overexpressing GBM cells. Here, we evaluated the anticancer activities of the two lead compounds 2 and 9 using multi-cellular spheroids (MCSs) which represent an easy 3D human cell model to mimic GBM organization, physical constraints and drug penetration. The two compounds reduced cell evasion from spheroids up to three times, especially for Tau-expressing cells. As a first step towards a therapeutic approach, we quantified the effects of these compounds on MCS growth using two complementary protocols: single and repeated treatments. A single injection with compound 9 slowed down the growth of MCSs formed with U87 shCTRL cells by 40% at 10 µM. More interestingly, multiple treatment with compound 9 slowed the growth of U87 shCTRL spheroids by 40% at a concentration of 5 µM, supporting the increased bioavailability of compound 9 within MCSs. In conclusion, compound 9 deserves particular attention as promising candidate for specifically targeting Tau-expressing cancers such as GBM.

Ultrasound-assisted co-precipitation method was used to synthesize Ni-LDH based catalysts for CO2 methanation. The influence of ultrasonic irradiation power density (90, 180, 270, and 360 WL-1) on the physico-chemical properties of the catalysts as well as on their catalytic behavior was studied as compared to catalysts prepared by conventional co-precipitation. Based on the XRD results, ultrasound decreases the crystallite size of LDH structure whatever the power density used as compared to the conventional method, and by increasing the ultrasound power density, the crystallite size increases. This effect on dried samples leads to an increase in the size of nickel particles on the catalysts. 90 WL-1 improves Ni particle distribution, catalyst basicity, and reducibility. Finally, Ni Us 90, the most performant catalyst in the studied series, shows a CO2 conversion of 80 % and a CH4 selectivity of 99.9 % at 350 degree celsius with no deactivation for 100 hours under reaction conditions.

By varying the precursor ratios, cobalt doped manganese oxide nanocluster catalysts with different cobalt contents were prepared using the colloidal method. Catalysts were applied to a gas phase benzene oxidation reaction. Among them, the catalyst with a Mn:Co ratio of 90:10 showed the highest conversion. The addition of cobalt changing the valence of manganese was observed by XANES analysis, and that is thought to be the reason for the high activity.