Oxidized Palladium Supported on Ceria Nanorods for Catalytic Aerobic Oxidation of Benzyl Alcohol to Benzaldehyde in Protic Solvents

In the present study, the catalytic activity of palladium oxide (PdOx) supported on ceria nanorods (CeO2-NR) for aerobic selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (PhCHO) was evaluated. The CeO2-NR was synthesized hydrothermally and the Pd(NO3)2 was deposited by a wet impregnation method, followed by calcination to acquire PdOx/CeO2-NR. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), transmission electron microscopy (TEM), Brunauer–Emmet–Teller (BET) surface area analysis, and X-ray photoelectron spectroscopy (XPS). In addition, the TPR-reduced PdOx/CeO2-NR (PdOx/CeO2-NR-Red) was studied by XRD, BET, and XPS. Characterizations showed the formation of CeO2-NR with (111) exposed plane and relatively high BET surface area. PdOx (x > 1) was detected to be the major oxide species on the PdOx/CeO2-NR. The activities of the catalysts in BnOH oxidation were evaluated using air, as an environmentally friendly oxidant, and various solvents. Effects of temperature and palladium oxidation state were investigated. The PdOx/CeO2-NR showed remarkable activity when protic solvents were utilized. The best result was achieved using PdOx/CeO2-NR and boiling ethanol as solvent, leading to 93% BnOH conversion and 96% selectivity toward PhCHO. A mechanistic hypothesis for BnOH oxidation with PdOx/CeO2-NR in ethanol is presente

Magnetic resonance imaging to assess cartilage invasion in recurrent laryngeal carcinoma after transoral laser microsurgery

Objective: To evaluate the diagnostic performance of magnetic resonance (MR) with surface coils in assessing cartilage invasion in recurrent laryngeal carcinoma after carbon dioxide transoral laser microsurgery (CO2 TOLMS). Methods: Two expert head and neck radiologists assessed cartilage invasion (infiltrated or non-infiltrated) in submucosal recurrences of laryngeal carcinoma after CO2 TOLMS: results were compared with histopathological report after salvage laryngectomy. Results: Thirty patients met the inclusion criteria and 90 cartilages were assessed. Overall sensitivity, specificity, and positive and negative predictive values for cartilage infiltration were 76, 93, 72 and 94%, respectively; for thyroid cartilage, the values were 82, 79, 69 and 88% respectively; for cricoid cartilage, all values were 100%; and for arytenoids, the values were 33, 96, 56 and 93% respectively. Conclusions: MR with surface coils was able to detect most thyroid and cricoid infiltration in the complex setting of post-CO2 TOLMS laryngeal carcinoma recurrence. In particular, the optimal performance in assessing cricoid invasion can be valuable in choosing the most appropriate treatment among total laryngectomy, open partial horizontal laryngectomies and non-surgical strategies

Metavariables resuming host immune features and nodal involvement are associated with oncological outcomes in oral cavity squamous cell carcinoma

Oral cavity squamous cell carcinoma (OSCC) is a common head and neck cancer characterized by a poor prognosis associated with locoregional or distant failure. Among the predictors of prognosis, a dense infiltration of adaptive immune cells is protective and associated with improved clinical outcomes. However, few tools are available to integrate immune contexture variables into clinical settings. By using digital microscopy analysis of a large retrospective OSCC cohort (n = 182), we explored the clinical significance of tumor-infiltrating CD

Carcinoma adenosquamoso del distretto testa-collo: studio retrospettivo monocentrico

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Prognostic Nomograms in Oral Squamous Cell Carcinoma: The Negative Impact of Low Neutrophil to Lymphocyte Ratio

Objectives: To investigate the prognostic significance of preoperative neutrophil to lymphocyte ratio (NLR) and the impact of different clinical-pathologic factors in a series of primary oral squamous cell carcinomas (OSCC).Materials and Methods: All naive OSCCs treated with upfront surgery between 2000 and 2014 were retrospectively reviewed. Patients with distant metastasis, synchronous head and neck cancer, immunological disorders, or who had received previous chemotherapy and/or radiation of the head and neck area were excluded. The main outcomes were overall (OS), disease-specific (DSS), loco-regional free (LRFS), and distant metastasis free (DMFS) survivals. Univariate (Kaplan-Meier) and multivariate (Cox regression model) analysis were performed, and nomograms developed for each outcome. NLR was analyzed as a continuous variable using restricted cubic spline multivariable Cox regression models.Results: One-hundred-eighty-two patients were included. Five-year estimates for LRFS, DMFS, DSS, and OS were 67, 83.7, 69.5, and 61.2%, respectively. NLR had a complex influence on survival and risk of recurrence: negative for very low and high values, while positive in case of intermediate ratios. At univariate analysis, T classification, 7th AJCC stage, nodal metastasis, perineural spread, and lymphovascular invasion were statistically significant. At multivariate analysis, extranodal extension (ENE) and perineural spread were the most powerful independent prognostic factors. NLR was an independent prognosticator for the risk of recurrence. In nomograms, NLR and ENE had the strongest prognostic effect.Conclusions: In OSCC, very low preoperative NLR values have a negative prognostic impact on survival and recurrence, similarly to high ratios. ENE and perineural spread are the most important clinical-pathologic prognosticators

Ni/CeO2-Al2O3 catalysts for the dry reforming of methane: the effect of CeAlO3 content and nickel crystallite size on catalytic activity and coke resistance

-The catalytic performances of Ni/CeO2–Al2O3 catalysts for the dry reforming of CH4 (DRM) were investigated. Catalysts with different Ni dispersion and different amount of CeAlO3 species were prepared by different methods and characterized by BET, XRD, XPS, Raman, TPR and TPO techniques. Catalytic activity was studied during time on streamin the range 873–1073K with amixture of CH4:CO2:Ar = 40:40:20 vol.% and GHSV 90,000 cm3 g−1 h−1. The intrinsic catalytic activity increased with the increasing of Ni crystallite size. Carbon was deposited as nano-fibres and graphite when catalysts worked atlower temperature, and the largest amount was found on the catalyst with the largest Ni crystallite size. The formation of graphitic deposits is limited by the presence of CeAlO3 species formed during catalyst activation. CA preparation method results particularly attractive because it allows to obtain catalysts with small Ni crystallite size and high content of CeAlO3 species, which both have a role in suppressing the carbon deposition and therefore in obtaining stable catalytic performances

Solvent-Free Oxidation of Benzyl Alcohol Derivatives by In Situ Generated Redox Couple Pd(0)/PdO_x Supported on Ceria Nanorods

Benzyl alcohol (BnOH) oxidation to benzaldehyde (PhCHO) is a pivotal industrial reaction. The aerobic oxidation of BnOH in solvent-free conditions is highly compatible with the necessity of low environmental impact. In this research work, palladium oxide (PdOx) supported on ceria nanorods (CeO2-NR), was synthesized, and utilized for aerobic solvent-free oxidation of BnOH derivatives to the corresponding aldehydes. The catalyst, PdOx/CeO2-NR, was characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy/energy-dispersive spectroscopy (FE-SEM/EDS), N2 adsorption-desorption analysis, temperature-programmed reduction with hydrogen (H2-TPR), and X-ray Photoelectron Spectroscopy (XPS), proving that the PdOx (x > 1) particles were highly dispersed on CeO2-NR and have a strong interaction with the support. The PdOx/CeO2-NR catalyst permitted the aerobic oxidation of various benzyl alcohol derivatives with good conversion, and high selectivity towards the corresponding aldehydes. The presence of electron donating groups (EDG) on the benzylic ring enhanced the reactivity as opposed to the electron withdrawing groups (EWG) which were detrimental for the catalytic activity. During the reaction a partial reduction of the metal produced a Pd(0)/PdOx/CeO2-NR redox couple stable in the reaction condition, more reactive and recyclable. Some mechanistic hypotheses are presented

Primary parotid carcinoma: analysis of risk factors and validation of a prognostic index

Primary cancer of the parotid gland (PG) is a rare disease characterized by a wide variety of histologies and subtypes. The aim of the study was to identify factors influencing survival and validate the prognostic scores (PS1 and PS2) by Vander Poorten et al. STUDY DESIGN: Retrospective cohort study

Ni supported on YSZ: XAS and XPS characterization and catalytic activity for CO2 methanation

Ni supported on yttrium-stabilized zirconium oxide catalysts have been prepared by electroless plating method. Structure, electronic and chemical state of Ni as a function of Ni content (1, 7 and 12 wt%) have been characterized combining X-ray diffraction, X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction (H2-TPR) and BET. The catalytic activity for the CO2 methanation was studied in the 250–500 °C temperature range, finding the highest CO2 conversion and CH4 selectivity for the catalyst with the largest Ni loading. A dependence of activity and CH4 selectivity on Ni crystallites size was highlighted