Selective Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran or 2-Formyl-5-furancarboxylic Acid in Water by using MgO⋅CeO2 Mixed Oxides as Catalysts

Mixed oxides based on MgO⋅CeO2 were used as efficient catalysts in the aerobic oxidation of 5-hydroxymethylfurfural (5-HMF) to afford, with very high selectivity, either 2,5-diformylfuran (DFF, 99 %) or 2-formyl-5-furancarboxylic acid (FFCA, 90 %), depending on the reaction conditions. 5-Hydroxymethyl-2-furancarboxylic acid (HMFCA, 57–90 %) was formed only at low concentration of 5-HMF (<0.03 m) or in presence of external bases. The conversion of 5-HMF ranged from a few percent to 99 %, according to the reaction conditions. The oxidation was performed in water, with O2 as oxidant, without any additives. The surface characterization of the catalysts gave important information about their acid–base properties, which drive the selectivity of the reaction towards DFF. FFCA was formed from DFF at longer reaction times. Catalysts were studied by XPS and XRD before and after catalytic runs to identify the reason why they undergo reversible deactivation. XRD showed that MgO is hydrated to Mg(OH)2, which, even if not leached out, changes the basic properties of the catalyst that becomes less active after some time. Calcination of the recovered catalyst allows recovery of its initial activity. The catalyst is thus recoverable (>99 %) and reusable. The use of mixed oxides allows tuning of the basicity of the catalysts, avoiding the need for external bases for efficient and selective conversion of 5-HMF and waste formation, resulting in an environmentally friendly, sustainable process

Impact of the laminar flame speed correlation on the results of a quasi-dimensional combustion model for Spark-Ignition engine

Abstract In the present study, the impact of the laminar flame speed correlation on the prediction of the combustion process and performance of a gasoline engine is investigated using a 1D numerical approach. The model predictions are compared with experimental data available for full- and part-load operations of a small-size naturally aspirated Spark-Ignition (SI) engine, equipped with an external EGR circuit. A 1D model of the whole engine is developed in the GT-Power™ environment and is integrated with refined sub-models of the in-cylinder processes. In particular, the combustion is modelled using the fractal approach, where the burning rate is directly related to the laminar flame speed. In this work, three laminar flame speed correlations are assessed, including both experimentally- and numerically-derived formulations, the latter resulting from the fitting of laminar flame speeds computed by a chemical kinetic solver. Each correlation is implemented within the combustion sub-model, which is properly tuned to reproduce the experimental performance of the engine at full load. Then, the reliability of the considered flame speed formulations is proved at part-loads, even under external EGR operations

Fluid dynamic-based Engineering design of a Full-Scale Device for the improvement of Extra Virgin Olive Oil Yield and Quality by means of Combined Acoustic Cavitation and Thermal Conditioning

After some hesitations, the scientific community is jointly converging on the benefits due to the ultrasound treatment by means of mechanical effects generated by acoustic cavitation phenomena occurring into the olive oil paste proposed initially by Amirante and Clodoveo. In recent works, many authors have now confirmed that this promising emerging technology produces relevant beneficial effects if applied to the extraction process under well-controlled conditions. In the last years, the industrial applications of ultrasound (US) in the Extra-Virgin Olive Oil (EVOO) extraction process are changing the paradigm of the knowledge in this field of interest due to a great effort of the research activity. In the present work, the design of the device by means a Three-Dimensional (3D) Multiphase Computational Fluid Dynamic (CFD) analysis was performed, which describes the ultrasound effects in the olive paste, necessary to control the US waves propagation. Thus, fluid dynamic analysis allowed to predict the flow path in the ultrasound devices, to evaluate the flow parameters of the olive paste inside the SHE and the cavitation phenomenon, with the aim to find an optimal design, capable to ensure the best ultrasounds and mixing effects. Moreover, experimental results demonstrated that the machine can guarantee an actual simultaneous improvement of the olive oil extraction yield, as well as of the product quality. Finally, the results from sensory evaluations are summarized confirming the goodness of EVOO obtained by means of US

Cortical thinning and clinical heterogeneity in amyotrophic lateral sclerosis

Amyotrophic lateral sclerosis (ALS) has heterogeneous clinical features that could be translated into specific patterns of brain atrophy. In the current study we have evaluated the relationship between different clinical expressions of classical ALS and measurements of brain cortical thickness. Cortical thickness analysis was conducted from 3D-MRI using FreeSurfer software in 29 ALS patients and 20 healthy controls. We explored three clinical traits of the disease, subdividing the patients into two groups for each of them: the bulbar or spinal onset, the higher or lower upper motor neuron burden, the faster or slower disease progression. We used both a whole brain vertex-wise analysis and a ROI analysis on primary motor areas. ALS patients showed cortical thinning in bilateral precentral gyrus, bilateral middle frontal gyrus, right superior temporal gyrus and right occipital cortex. ALS patients with higher upper motor neuron burden showed a significant cortical thinning in the right precentral gyrus and in other frontal extra-motor areas, compared to healthy controls. ALS patients with spinal onset showed a significant cortical thinning in the right precentral gyrus and paracentral lobule, compared to healthy controls. ALS patients with faster progressive disease showed a significant cortical thinning in widespread bilateral frontal and temporal areas, including the bilateral precentral gyrus, compared to healthy controls. Focusing on the primary motor areas, the ROI analysis revealed that the mean cortical thickness values were significantly reduced in ALS patients with higher upper motor neuron burden, spinal onset and faster disease progression related to healthy controls. In conclusion, the thickness of primary motor cortex could be a useful surrogate marker of upper motor neuron involvement in ALS; also our results suggest that cortical thinning in motor and non motor areas seem to reflect the clinical heterogeneity of the disease. © 2013 Mezzapesa et al

Qualitative analysis of the capacity to consent to treatment in patients with a chronic neurodegenerative disease. Alzheimer's Disease.

Objective: Informed consent is an essential element in doctor–patient relationship. In particular, obtaining valid informed consent from patients with neurocognitive diseases is a critical issue at present. For this reason, we decided to conduct research on elderly patients with Alzheimer’s disease (Diagnostic and Statistical Manual of Mental Disorders, 5th Edition (DSM-5) to assess their capacity to make treatment decisions. Methods: The experimental group comprised 70 Alzheimer patients who were admitted to the Neurodegenerative Disease Unit of the University of Bari. The control group consisted of 83 elderly patients without neurocognitive disorders who were hospitalized in the Geriatric Unit at the same university. After providing written consent to participate in the research, each subject underwent the following assessments: (a) assessment of comprehension sheet, (b) Neuropsychiatric Inventory (NPI) and Global Functioning Evaluation (GFE), (c) neurological evaluation, (d) neuropsychological assessment with a full battery of tests, (d) The MacArthur Treatment Competence Study (MacArthur Competence Assessment Tool for Treatment (MacCAT-T); understanding, appreciating, reasoning and expressing a choice) and (e) a semi-structured interview administered by the patient’s caregiver. Results/conclusion: The present survey was designed to analyze possible qualitative and quantitative correlations between cognitive functioning and capacity to consent in relation to different degrees of severity of the neurodegenerative disorder. A large portion of the patients in our experimental sample did not appear to have the capacity to provide a valid consent. The authors present initial results of this study and discuss their possible implications

Use of social networks as a CSR communication tool

The aim of this paper is to analyse the use of online social networks as a tool for Corporate Social Responsibility (CSR) communication and management. To this end, an analysis was performed of the messages posted by the 20 Spanish companies with the highest market capitalisation and the responses that they received on two of the most popular online social networks, Facebook and Twitter. The results of the analysis of these data show that the tendency has been to use social networks for the one-way communication of aspects of CSR related with the organisation. Therefore, it is necessary to change the way companies communicate their CSR issues by shifting to a two-way communication approach, as has been the case in other kinds of enterprise relations with their stakeholders.The authors received no direct funding for this research

Catalysis over zinc-incorporated berlinite (ZnAlPO4) of the methoxycarbonylation of 1,6-hexanediamine with dimethyl carbonate to form dimethylhexane-1,6-dicarbamate

<p>Abstract</p> <p>Background</p> <p>The alkoxycarbonylation of diamines with dialkyl carbonates presents promising route for the synthesis of dicarbamates, one that is potentially 'greener' owing to the lack of a reliance on phosgene. While a few homogeneous catalysts have been reported, no heterogeneous catalyst could be found in the literature for use in the synthesis of dicarbamates from diamines and dialkyl carbonates. Because heterogeneous catalysts are more manageable than homogeneous catalysts as regards separation and recycling, in our study, we hydrothermally synthesized and used pure berlinite (AlPO₄) and zinc-incorporated berlinite (ZnAlPO₄) as heterogeneous catalysts in the production of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine (HDA) and dimethyl carbonate (DMC). The catalysts were characterized by means of XRD, FT-IR and XPS. Various influencing factors, such as the HDA/DMC molar ratio, reaction temperature, reaction time, and ZnAlPO₄/HDA ratio, were investigated systematically.</p> <p>Results</p> <p>The XRD characterization identified a berlinite structure associated with both the AlPO₄and ZnAlPO₄catalysts. The FT-IR result confirmed the incorporation of zinc into the berlinite framework for ZnAlPO₄. The XPS measurement revealed that the zinc ions in the ZnAlPO₄structure possessed a higher binding energy than those in ZnO, and as a result, a greater electron-attracting ability. It was found that ZnAlPO₄catalyzed the formation of dimethylhexane-1,6-dicarbamate from the methoxycarbonylation of HDA with DMC, while no activity was detected on using AlPO₄. Under optimum reaction conditions (i.e. a DMC/HDA molar ratio of 8:1, reaction temperature of 349 K, reaction time of 8 h, and ZnAlPO₄/HDA ratio of 5 (mg/mmol)), a yield of up to 92.5% of dimethylhexane-1,6-dicarbamate (with almost 100% conversion of HDA) was obtained. Based on these results, a possible mechanism for the methoxycarbonylation over ZnAlPO₄was also proposed.</p> <p>Conclusion</p> <p>As a heterogeneous catalyst ZnAlPO₄berlinite is highly active and selective for the methoxycarbonylation of HDA with DMC. We propose that dimethylhexane-1,6-dicarbamate is formed <it>via </it>a catalytic cycle, which involves activation of the DMC by a key active intermediate species, formed from the coordination of the carbonyl oxygen with Zn(II), as well as a reaction intermediate formed from the nucleophilic attack of the amino group on the carbonyl carbon.</p

The Italian fund for Alzheimer's and other dementias: strategies and objectives to face the dementia challenge

The Italian Fund for Alzheimer's and other dementias was approved and signed in December 2021. The Fund is financed with 15 million euros in three years. The main goal is to provide new strategies in the field of dementia with a Public Health perspective. The Fund includes eight main activities that will be monitored and supervised by the Italian National Institute of Health: 1) development of a guideline for the assessment, management and support for people with dementia and their families/carers; 2) updating of the Dementia National Plan (DNP); 3) implementation of the documents of the DNP; 4) conducting surveys dedicated to the Italian Dementia Services; 5) promotion of dementia prevention strategies; 6) training strategies for healthcare professionals, families and caregivers; 7) creation of a National Electronic Record for Dementia; 8) evaluation and monitoring of activities promoted by Regions and Autonomous Provinces in the field of dementia, together with the dementia National Permanent Table. These activities are outlined in detail in the present paper

Phospholipase C Isozymes Are Deregulated in Colorectal Cancer – Insights Gained from Gene Set Enrichment Analysis of the Transcriptome

Colorectal cancer (CRC) is one of the most common cancer types in developed countries. To identify molecular networks and biological processes that are deregulated in CRC compared to normal colonic mucosa, we applied Gene Set Enrichment Analysis to two independent transcriptome datasets, including a total of 137 CRC and ten normal colonic mucosa samples. Eighty-two gene sets as described by the Kyoto Encyclopedia of Genes and Genomes database had significantly altered gene expression in both datasets. These included networks associated with cell division, DNA maintenance, and metabolism. Among signaling pathways with known changes in key genes, the “Phosphatidylinositol signaling network”, comprising part of the PI3K pathway, was found deregulated. The downregulated genes in this pathway included several members of the Phospholipase C protein family, and the reduced expression of two of these, PLCD1 and PLCE1, were successfully validated in CRC biopsies (n = 70) and cell lines (n = 19) by quantitative analyses. The repression of both genes was found associated with KRAS mutations (P = 0.005 and 0.006, respectively), and we observed that microsatellite stable carcinomas with reduced PLCD1 expression more frequently had TP53 mutations (P = 0.002). Promoter methylation analyses of PLCD1 and PLCE1 performed in cell lines and tumor biopsies revealed that methylation of PLCD1 can contribute to reduced expression in 40% of the microsatellite instable carcinomas. In conclusion, we have identified significantly deregulated pathways in CRC, and validated repression of PLCD1 and PLCE1 expression. This illustrates that the GSEA approach may guide discovery of novel biomarkers in cancer