Sustainable and environmental catalysis

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Pathogenetic and diagnostic significance of microRNA deregulation in peripheral T-cell lymphoma not otherwise specified

Peripheral T-cell lymphomas not otherwise specified (PTCLs/NOS) are rare and aggressive tumours whose molecular pathogenesis and diagnosis are still challenging. The microRNA (miRNA) profile of 23 PTCLs/NOS was generated and compared with that of normal T-lymphocytes (CD4+, CD8+, naive, activated). The differentially expressed miRNA signature was compared with the gene expression profile (GEP) of the same neoplasms. The obtained gene patterns were tested in an independent cohort of PTCLs/NOS. The miRNA profile of PTCLs/NOS then was compared with that of 10 angioimmunoblastic T-cell lymphomas (AITLs), 6 anaplastic large-cell lymphomas (ALCLs)/ALK+ and 6 ALCLs/ALK - . Differentially expressed miRNAs were validated in an independent set of 20 PTCLs/NOS, 20 AITLs, 19 ALCLs/ALK - and 15 ALCLs/ALK+. Two hundred and thirty-six miRNAs were found to differentiate PTCLs/NOS from activated T-lymphocytes. To assess which miRNAs impacted on GEP, a multistep analysis was performed, which identified all miRNAs inversely correlated to different potential target genes. One of the most discriminant miRNAs was selected and its expression was found to affect the global GEP of the tumours. Moreover, two sets of miRNAs were identified distinguishing PTCL/NOS from AITL and ALCL/ALK - , respectively. The diagnostic accuracy of this tool was very high (83.54%) and its prognostic value validated

Maximizing the antioxidant capacity of Padina pavonica by choosing the right drying and extraction methods

Marine algae are becoming an interesting source of biologically active compounds with a promising application as nutraceuticals, functional food ingredients, and therapeutic agents. The effect of drying (freeze-drying, oven-drying, and shade-drying) and extraction methods (shaking at room temperature, shaking in an incubator at 60 \ub0C, ultrasound-assisted extraction (UAE), and microwave-assisted extraction (MAE)) on the total phenolics content (TPC), total flavonoids content (TFC), and total tannins content (TTC), as well as antioxidant capacity of the water/ethanol extracts from Padina pavonica were investigated. The TPC, TFC, and TTC values of P. pavonica were in the range from 0.44 \ub1 0.03 to 4.32 \ub1 0.15 gallic acid equivalents in mg/g (mg GAE/g) dry algae, from 0.31 \ub1 0.01 to 2.87 \ub1 0.01 mg QE/g dry algae, and from 0.32 \ub1 0.02 to 10.41 \ub1 0.62 mg CE/g dry algae, respectively. The highest TPC was found in the freeze-dried sample in 50% ethanol, extracted by MAE (200 W, 60 \ub0C, and 5 min). In all cases, freeze-dried samples extracted with ethanol (both 50% and 70%) had the higher antioxidant activity, while MAE as a green option reduces the extraction time without the loss of antioxidant activity in P. pavonica

Development and validation of an adsorption process for phosphate removal and recovery from municipal wastewater based on hydrotalcite-related materials

In the current international context characterized by the tendency to stricter limits for P concentration in treated wastewater and a strong drive towards phosphate recovery, it is crucial to develop cost-effective technologies to remove and recover phosphate from municipal wastewater (MWW). In this study, an initial screening of the phosphate adsorption performances of 9 sorbents including several hydrotalcites led to the selection of calcined pyroaurite - an innovative material composed of mixed Mg/Fe oxides - as the best-performing one. The assessment of calcined pyroaurite by means of isotherms and continuous-flow adsorption/desorption tests conducted with actual MWW resulted in a high P sorption capacity (12 mgP g- 1 at the typical phosphate concentration in MWW), the capacity to treat 730 BVs at the 1 mgP L- 1 breakpoint imposed by the current EU legislation, and a 93 % phosphate recovery. Calcined pyroaurite resulted in satisfactory performances also in a test conducted with a saline MWW deriving from a hotspot of seawater intrusion, a rapidly increasing phenomenon as a result of climate change. Five consecutive adsorption/desorption cycles conducted in a 20-cm column at a 5-min empty bed contact time resulted stable in terms of P adsorption/recovery performances, specific surface area and chemical structure of calcined pyroaurite. In the perspective to apply phosphate recovery with calcined pyroaurite at full scale, the process scale-up to a 60-cm packed bed - close to the column heights of industrial applications- resulted in stable performances. Calcium phosphate, widely used to produce phosphate-based fertilizers, can be obtained from the desorbed product by precipitation with Ca(OH)2. 2 . These results point to calcined pyroaurite as a very promising material for phosphate removal and recovery from MWW and from other P-rich effluents in a circular economy perspective

Methyl Methacrylate Production Processes: A Comparative Analysis of Alternatives Using the Life Cycle Assessment Methodology

Green chemistry is part of the chemical industry’s response to calls for improved environmental responsibility. It is also one of the industry’s several paths to redemption from its erstwhile infamous reputation as one of the most polluting sectors. We studied the impacts of implementing some of these principles on the production of methyl methacrylate (MMA), the monomer of PMMA popularly known as acrylic glass. This study used life cycle assessment (LCA) methodology to compare the potential environmental impacts of three different approaches to the production of MMA. Two of these are established industrial pathways: the acetocyanohydrin process (ACH-MMA) and the Alpha Lucite process (AL-MMA), which represent the conventional and a fastrising industrial route, respectively, while the third, the in situ formaldehyde process (inFAL-MMA) is a lab-based process. The scenarios were evaluated using cumulative energy demand (CED) and the ReCiPe 2016 impact assessment methods. The results obtained highlighted some hotspots that can benefit from process improvements and careful material and energy source selection. It also underscored that AL-MMA can record significant improvements in environmental performance by reducing the overall resource intensity of the process. inFAL-MMA synthesis was adjudged to be the most evolved of the three alternatives with respect to green chemistry principles; hence, the study sought to investigate possible environmental gains attributable to this. Some limitations of the methodology uncovered during the study necessitated the use of an additional tool for further assessment of the potential risk. Thus, the GREEN MOTION was adopted to examine this relationship. Overall, the study established hotspots and areas for process improvements in the scenarios examined. It also confirmed the importance of different factors like data quality, degree of process optimization, energy source, and others on the results that can be obtained in a LCA

Levulinic acid biorefinery in a life cycle perspective

Nowadays there is a strong urge to replace the fossil-based chemicals and fuels with biobased ones. In this context, the 7th principle of the green chemistry, the Sustainable Development Goals (SDGs) and the recent Safe and Sustainable by Design (SSbD) approach are the main references. Among the various biorefineries, lignocellulosic biomasses represent the most abundant resource to explore. Considering the vast plethora of useful molecules produced from lignocellulosic biomasses, levulinic acid embodies a potential starting material for the preparation of high value-added chemicals. This review explores the preparation of levulinic acid form lignocellulosic biomasses and its further valorization to high-value added compounds (gamma-valerolactone, ketals and methyl/ethyl levulinate), considering the current state of the art of the available synthetic strategies, in a life cycle perspective considering the adoption of the life cycle assessment (LCA) methodology

An innovative catalytic pathway for the synthesis of acyl furans: the cross-ketonization of methyl 2-furoate with carboxylic acids

The usefulness of ketonization reactions for the valorization of a wide plethora of biomass-derived carboxylic acids is widely recognized; however, the full potential of this reaction has yet to be suitably exploited for the production of high added-value aromatic and/or aliphatic asymmetric ketones. For this reason, herein we report for the first time in the literature the continuous-flow, gas-phase synthesis of 2-acetyl furan (AF) by means of the catalytic cross-ketonization of bio-based 2-methyl furoate (2-MF) and acetic acid (AA) over a simple and cheap ZrO2 catalyst. Interestingly, AF is considered a valuable food additive and a pharmaceutical intermediate for the synthesis of antibiotics. The optimization of the molar ratio between reactants at 350 °C allowed us to achieve 87% AF selectivity at 90% 2-MF conversion, with a space-time yield of 0.152 h−1, a value that is similar to the ones obtained by following the traditional Friedel-Crafts acylation and Wacker oxidation routes. On the other hand, the E-factor of the herein-proposed process is several times lower compared to the aforementioned traditional routes performed in the liquid phase and under batch conditions. Finally, the versatility of the cross-ketonization synthetic approach was successfully demonstrated and applied for the selective synthesis of other valuable acyl furans (i.e., propionyl furan and butyryl furan)

Peripheral t‐cell lymphoma, not otherwise specified : Clinical manifestations, diagnosis, and future treatment

Peripheral T‐cell lymphoma, not otherwise specified (PTCL_NOS) corresponds to about one fourth of mature T‐cell tumors, which overall represent 10–12% of all lymphoid malignancies. This category comprises all T‐cell neoplasms, which do not correspond to any of the distinct entities listed in the WHO (World Health Organization) Classification of Tumours of Haematopoietic and Lymphoid Tissues. In spite of the extreme variability of morphologic features and phenotypic profiles, gene expression profiling (GEP) studies have shown a signature that is distinct from that of all remaining PTCLs. GEP has also allowed the identification of subtypes provided with prognostic relevance. Conversely to GEP, next‐generation sequencing (NGS) has so far been applied to a limited number of cases, providing some hints to better understand the pathobiology of PTCL_NOS. Although several pieces of information have emerged from pathological studies, PTCL_NOS still remains a tumor with a dismal prognosis. The usage of CHOEP (cyclophosphamide, doxorubicin, vincristine, prednisone, etoposide) followed by autologous stem cell transplantation may represent the best option, by curing about 50% of the patients whom such an approach can be applied to. Many new drugs have been proposed without achieving the expected results. Thus, the optimal treatment of PTCL_NOS remains unidentified

Kumulativni traumatski poremećaji gornjih udova u radnika na poljoprivrednom dobru

The work associated with repetitive efforts and inadequate resting periods, strong physical exertion, awkward postures or static positioning exposes workers to the risk of cumulative trauma disorders of the upper limbs. These risk factors are present in many agricultural activities. A study was carried out among workers on an agricultural farm. The workers\u27 histories were taken and they were given periodical medical check-ups. The presence of upper limb disorders was shown in a group of workers. A sample of 42 people was selected for the study by means of specific tests: electromyography, ultrasonography and laser-doppler ftowmetry. The tests showed a high incidence of carpal tunnel syndrome and microcirculation disorders. The study confirmed that electromyography, ultrasonography and/or laser-doppler flowmetry are highly useful tools for identifying cumulative trauma disorders.Pokreti koji se ponavljaju, neprimjereni odmori, teška fizička opterećenja te nefiziološki položaji tijela dovode do povećanog rizika razvoja bolesti kumulativne traume gornjih udova. Ovi čimbenici rizika prisutni su u mnogim poljoprivrednim djelatnostima. Od 74 radnika na poljoprivrednom dobru podvrgnuta periodskim pregledima, u 42 je primijenjena elektromiografija, ultrasonografija i mjerenje krvnog protoka laser-doppler metodom. Testovima je utvrđena visoka učestalost sindroma karpalnog tunela i poremećaja mikrocirkulacije. Ispitivanje je potvrdilo da su eiektromiografija, ultrasonografija i/ili laser-doppler mjerenje krvnog protoka veoma korisne metode u dijagnostici bolesti kumulativne traume

Acetonitrile from Bioethanol Ammoxidation : Process Design from the Grass-Roots and Life Cycle Analysis

The growing interest for new routes to obtain acetonitrile led to the development of catalysts active toward the ammoxidation of various substrates. Among these, a C2 molecule such as ethanol represents a good choice in terms of atom economy and, being renewable, sets the basis for a long-term sustainable process. This paper describes a fully integrated, newly designed process for the production of acetonitrile from bioethanol, currently not present in the literature. The target is the production and purification of 10 kg/h of acetonitrile, unit of production used for calculations, obtained from ethanol, ammonia, and air as raw materials. All the byproducts, mainly ammonium bicarbonate and sodium cyanide, are considered marketable chemicals and represent an added value, instead of a disposal issue. Their optimized recovery is included in this flowsheet as a basis for the future economic assessment of the system. The process consumes CO2 without its direct emission. In principle, all the carbon atoms and 90% of the nitrogen atoms are turned into reaction products, and the main loss is gaseous N2. The process design has been performed by means of the Aspen PLUS process simulator, on the basis of literature data and other experimental results. In addition, for an evaluation of the potential benefits of the innovative biobased route, a life cycle analysis was carried out including all the stages involved in the bioacetonitrile production (from raw materials extraction up to the gate plant). The results were then compared with those achieved for the traditional fossil route (SOHIO process), showing a sensible decrease of the environmental burdens in terms of nonrenewable resources and damage to ecosystems (e.g., toxicity, climate change, etc.). Finally, a simplified sensitivity analysis was carried out by substituting the starting raw material for the production of bioethanol (corn) with other materials conventionally used worldwide, such as sugar cane and wood. The latter option seems to make the system more competitive in terms of carbon neutrality, thanks to the usage of the residual lignocellulosic fraction available on the market