A polymer supported palladium(II) \u3b2-ketoesterate complex as active and recyclable pre-catalyst for selective reduction of quinolines in water with sodium borohydride

A polymer supported palladium catalyst, obtained by copolymerization of Pd(AAEMA)2 [AAEMA- = deprotonated form of 2-(acetoacetoxy) ethyl methacrylate] with ethyl methacrylate (co-monomer) and ethylene glycol dimethacrylate (cross-linker), exhibited excellent activity and selectivity for the hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines in the presence of NaBH4 as hydrogen donor in water. Both the activity and selectivity could be maintained for at least seven reaction runs. No metal leaching into solution occurred during recycles. TEM analyzes carried out on the catalyst showed that the active species were supported palladium nanoparticles having a mean size of 3 nm, which did not aggregate with the recycles

COVID-19 atypical Parsonage-Turner syndrome: a case report

Background Neurological manifestations of Sars-CoV-2 infection have been described since March 2020 and include both central and peripheral nervous system manifestations. Neurological symptoms, such as headache or persistent loss of smell and taste, have also been documented in COVID-19 long-haulers. Moreover, long lasting fatigue, mild cognitive impairment and sleep disorders appear to be frequent long term neurological manifestations after hospitalization due to COVID-19. Less is known in relation to peripheral nerve injury related to Sars-CoV-2 infection. Case presentation We report the case of a 47-year-old female presenting with a unilateral chest pain radiating to the left arm lasting for more than two months after recovery from Sars-CoV-2 infection. After referral to our post-acute outpatient service for COVID-19 long haulers, she was diagnosed with a unilateral, atypical, pure sensory brachial plexus neuritis potentially related to COVID-19, which occurred during the acute phase of a mild Sars-CoV-2 infection and persisted for months after resolution of the infection. Conclusions We presented a case of atypical Parsonage-Turner syndrome potentially triggered by Sars-CoV-2 infection, with symptoms and repercussion lasting after viral clearance. A direct involvement of the virus remains uncertain, and the physiopathology is unclear. The treatment of COVID-19 and its long-term consequences represents a relatively new challenge for clinicians and health care providers. A multidisciplinary approach to following-up COVID-19 survivors is strongly advised

Tunable microwave-assisted aqueous conversion of seaweed-derived agarose for the selective production of 5-hydroxymethyl furfural/levulinic acid

A simple, highly efficient and tunable microwave-assisted conversion of seaweed-derived agarose into 5-hydroxymethyl furfural (5-HMF) or levulinic acid (LA), depending on the reaction conditions, is reported. The proposed system could be fine-tuned for the selective production of 5-HMF (ca. 51% yield) in the absence of any catalyst or alternatively to levulinic acid (64% yield) with the simple addition of 1% v/v sulfuric acid, both under optimized aqueous microwave irradiation conditions (10 min, 180 °C). Additionally, galactose could also be generated as the main product (45-77%) depending on the temperature and the addition of catalytic amounts of sulfuric acid. A plausible reaction mechanism is provided in which the formation of intermediates from the hydrolysis of agarose is critical to obtain 5-HMF and LA as final products

Polymer supported palladium nanocrystals as efficient and recyclable catalyst for the reduction of nitroarenes to anilines under mild conditions in water

Polymer supported palladium nanoparticles, generated in situ by Pd(II) reduction under reaction conditions, catalyzed the hydrogenation of nitroarenes to anilines with high efficiency in water at room temperature in the presence of NaBH4. The protocol proved to be highly selective and generally favored the formation of the desired aniline as single product in high yields with short reaction times. TEM analyses revealed that the size distribution of the formed Pd nanocrystals was regulated by the reductant agent. In details, when 1 atm H2 was used as the nitroarene reductant, the in situ generated polymer supported palladium nanoparticles were crystallites with diameters ranging from 6 to 10 nm. On the contrary, when the reaction was carried out in the presence of NaBH4 in water under N2 or air, the formation of Pd nanocrystallites was observed as well, but this time they were smaller (mean size diameter ca. 3 nm) and catalytically more active compared to the palladium nanoparticles formed under 1 atm H2 in the absence of NaBH4. The catalyst displayed excellent recyclability over twelve cycles and no leaching of metal into solution occurred, which made the overall system eco-friendly and economic

Phytosterols from Dunaliella tertiolecta reduce cell proliferation in sheep fed flaxseed during post partum

The post partum period is characterized by immunosuppression and increased disease susceptibility. Both phytosterols from microalga Dunaniella tertiolecta and dietary supplementation with n-3 polyunsaturated fatty acids (PUFA) influence cell proliferation and cytokine release during inflammation. The objective of this paper was the evaluation of the effects of physterols, extracted and purified from D. tertiolecta, on the in vitro immune responses of ewes supplemented with flaxseed during post partum. Twenty Comisana parturient ewes were divided in two balanced groups, and supplemented with flaxseed (FS, 250 g/day) or fed with a conventional diet (CON). Blood samples (15 mL) were collected for five weeks, starting from lambing, in order to isolate peripheral blood mononuclear cells (PBMC). Stimulated PBMC were treated with a total sterols fraction from D. tertiolecta (TS), a mix of ergosterol and 7-dehydroporiferasterol (purified extract, PE), and a mix of acetylated ergosterol and 7-dehydroporiferasterol (acetylated purified extract, AcPE), extracted and purified from D. tertiolecta at two concentrations (0.4 and 0.8 mg/mL). Results of the experiment demonstrated that n-3 PUFA from flaxseed induced an anti-inflammatory cytokine profile, with an increase of both IL-10, IL-6 and a decrease of IL-1β. TS, PE, and AcPE purified from D. tertiolecta showed an anti-proliferative effect on sheep PBMC regardless their chemical composition and concentration

Reproductive biology characteristics of red mullet (

The main important reproductive aspects of Mullus barbatus, one of the most important target species for the fishery in the Mediterranean basin, have been studied on the basis of MEDITS trawl survey and sampling of commercial landing. The total length (TL) of females has been demonstrated to be positively correlated with egg sizes and plasmatic concentration of vitellogenin. The possible implications of these aspects on the management of red mullet resources are discussed in this work. Moreover, the relationship between TL and fecundity follows an exponential pattern with a temporal trend during the spawning season. These results represent an important input for more effective management measures, such as the seasonal closure of fishery in summertime. The frequency distribution of the oocytes’ diameters showed an asynchronous ovarian organization with batch spawning pattern. Monthly variations in the gonadosomatic index and maturity stages percentage showed that males spawn during almost the entire year showed an increasing trend from November to June and a decreasing trend from July to October, while females in spawning phase are recorded from April to July, with peaks in May and June. The length at 50% maturity (L50) estimated respectively for females and males are 12.1 cm (±0.083) and 10.1 cm (±0.073)

A holistic approach to the age validation of Mullus barbatus L., 1758 in the Southern Adriatic Sea (Central Mediterranean)

Abstract The growth of Mullus barbatus has been widely studied using different methods, but no previous study has focused on age validation. The uncertainty in estimating the age of the red mullet by otolith reading is linked to the number of false-growth increments laid down before the annulus. The capture of red mullets in the early life stage allowed us to estimate their size at the metamorphosis from the pelagic to the demersal phase. The comparison between the metamorphosis size and the back-calculated length of the first growth increment clarified the position of the false growth increment on the otolith. Moreover, the analyses of the otolith marginal increments in adult and juvenile specimens allowed us to define the deposition patterns of their annuli. The modal components of the length–frequency distribution analysis (LFDA) were identified in the winter survey (ELEFAN and Bhattacharya methods), and they did not show significant differences from the length back-calculation of the annuli. Moreover, no significant differences were found between the growth curves calculated by otolith reading (back-calculation and direct otolith reading) and the LFDA. The agreement between the length–frequency results and the otolith age estimation either corroborated or indirectly validated the growth pattern estimated in the otoliths of the red mullet, mainly when the direct validation methods (e.g. mark-recapture, captivity, radiochemical) were difficult to implement, like the case of this species. The comparison of the results of the present work to previous Mediterranean studies showed agreement with the slow growth pattern

CAFs and TGF-β Signaling Activation by Mast Cells Contribute to Resistance to Gemcitabine/Nabpaclitaxel in Pancreatic Cancer

Tumor–stroma interactions are of key importance for pancreatic ductal adenocarcinoma (PDAC) progression. Our aim was to investigate whether cancer associated fibroblasts (CAFs) and mast cells (MC) affected the sensitivity of PDAC cells to gemcitabine/nabpaclitaxel (GEM/NAB). For this purpose, the combination cytotoxicity and the effect on tumor invasion and angiogenesis were evaluated with or without a conditioned medium from the mast cell line HMC-1 (human mast cell line-1 cells) and CAFs. Beside the clinical outcome of a homogenous population of PDAC patients, receiving GEM/NAB, was correlated to the circulating levels of mast cell tryptase and to a panel of inflammatory and immunosuppressive cytokines. CAFs neither affected drugs’ cytotoxicity nor the inhibition of angiogenesis, but promoted tumor cell invasion. The MC instead, caused resistance to drugs by reducing apoptosis, by activating the TGF-β signalling and by promoting tumor invasion. Indeed, the inhibition of TβRI serine/threonine kinase activity by galunisertib restored drugs cytotoxicity. Moreover, MC induced the release of TGF-β1, and increased expression of PAR-2, ERK1/2 and Akt activation. Accordingly, TGF-β1, tryptase and other pro-inflammatory and immunosuppressive cytokines increased in the unresponsive patients. In conclusion, MC play a pivotal role in the resistance to GEM/NAB. A correlation between high level of circulating pro-inflammatory/ immunosuppressive cytokines and unresponsiveness was found in PDAC patients