Synthesis and NMR characterization of 3,4′-dibutoxy-2,2′-bithiophene

3,4′-Dibromo-2,2′-bithiophene was converted, in high yield, into the corresponding dibutoxy derivative. The ¹H ¹³C and nmr data are discussed in comparison with those of 3,3′- and 4,4′-dibutoxy-2,2′-bithiophene in relation to regiochemistry.     

Unravelling the Phytochemical Composition and the Pharmacological Properties of an Optimized Extract from the Fruit from Prunus mahaleb L.: From Traditional Liqueur Market to the Pharmacy Shelf

Prunus mahaleb L. fruit has long been used in the production of traditional liqueurs. The fruit also displayed scavenging and reducing activity, in vitro. The present study focused on unravelling peripheral and central protective effects, antimicrobial but also anti-COVID-19 properties exerted by the water extract of P. mahaleb. Anti-inflammatory effects were studied in isolated mouse colons exposed to lipopolysaccharide. Neuroprotection, measured as a blunting effect on hydrogen-peroxide-induced dopamine turnover, was investigated in hypothalamic HypoE22 cells. Antimicrobial effects were tested against different Gram+ and Gram- bacterial strains. Whereas anti-COVID-19 activity was studied in lung adenocarcinoma H1299 cells, where the gene expression of ACE2 and TMPRSS2 was measured after extract treatment. The bacteriostatic effects induced on Gram+ and Gram- strains, together with the inhibition of COX-2, TNFα, HIF1α, and VEGFA in the colon, suggest the potential of P. mahaleb water extract in contrasting the clinical symptoms related to ulcerative colitis. The inhibition of the hydrogen peroxide-induced DOPAC/DA ratio indicates promising neuroprotective effects. Finally, the downregulation of the gene expression of ACE2 and TMPRSS2 in H1299 cells, suggests the potential to inhibit SARS-CoV-2 virus entry in the human host. Overall, the results support the valorization of the local cultivation of P. mahaleb.     

Neuroprotective Effects of Curcumin in Methamphetamine-Induced Toxicity

Curcumin (CUR), a natural polyphenol extracted from rhizome of the Curcuma longa L, has received great attention for its multiple potential health benefits as well as disease prevention. For instance, CUR protects against toxic agents acting on the human body, including the nervous system. In detail, CUR possesses, among others, strong effects as an autophagy activator. The present study indicates that CUR counteracts methamphetamine (METH) toxicity. Such a drug of abuse is toxic by disturbing the autophagy machinery. We profited from an unbiased, low variable cell context by using rat pheochromocytoma PC12 cell line. In such a system, a strong protection was exerted by CUR against METH toxicity. This was associated with increased autophagy flux, merging of autophagosomes with lysosomes and replenishment of autophagy vacuoles with LC3, which instead is moved out from the vacuoles by METH. This is expected to enable the autophagy machinery. In fact, while in METH-treated cells the autophagy substrates α-synuclein accumulates in the cytosol, CUR speeds up α-synuclein clearance. Under the effects of CUR LC3 penetrate in autophagy vacuoles to commit them to cell clearance and promotes the autophagy flux. The present data provide evidence that CUR counteracts the neurotoxic effects induced by METH by promoting autophagy.     

Volatiles and Antifungal-Antibacterial-Antiviral Activity of South African Salvia spp. Essential Oils Cultivated in Uniform Conditions

Spontaneous emissions of S. dentata Aiton and S. scabra Thunb., as well as the essential oil (EO) composition of the cited species, together with S. aurea L., were investigated. The chemical profile of the first two species is reported here for the first time. Moreover, in vitro tests were performed to evaluate the antifungal activity of these EOs on Trichophyton mentagrophytes, Microsporum canis, Aspergillus flavus, Aspergillus niger, and Fusarium solani. Secondly, the EO antibacterial activity against Escherichia coli, Staphylococcus aureus, and Staphylococcus pseudointermedius was examined, and their antiviral efficacy against the H1N1 influenza virus was assessed. Leaf volatile organic compounds (VOCs), as well as the EOs obtained from the arial part of Salvia scabra, were characterized by a high percentage of sesquiterpene hydrocarbons (97.8% and 76.6%, respectively), mostly represented by an equal amount of germacrene D (32.8% and 32.7%, respectively). Both leaf and flower spontaneous emissions of S. dentata, as well as the EO composition, showed a prevalence of monoterpenes divided into a more or less equal amount of hydrocarbon and oxygenated compounds. Interestingly, its EO had a non-negligible percentage of oxygenated sesquiterpenes (29.5%). S. aurea EO, on the contrary, was rich in sesquiterpenes, both hydrocarbons and oxygenated compounds (41.5% and 33.5%, respectively). S. dentata EO showed good efficacy (Minimal Inhibitory Concentration (MIC): 0.5%) against M. canis. The tested EOs were not active against E. coli and S. aureus, whereas a low inhibition of S. dentata EO was observed on S. pseudointermedius (MIC = 10%). Once again, S. dentata EO showed a very good H1N1 inhibition; contrariwise, S. aurea EO was completely inactive against this virus. The low quantity of S. scabra EO made it impossible to test its biological activity. S. dentata EO exhibited interesting new perspectives for medicinal and industrial uses.     

Ultrasound-Assisted Microencapsulation of Soybean Oil and Vitamin D Using Bare Glycogen Nanoparticles

Ultrasonically synthesized core-shell microcapsules can be made of synthetic polymers or natural biopolymers, such as proteins and polysaccharides, and have found applications in food, drug delivery and cosmetics. This study reports on the ultrasonic synthesis of microcapsules using unmodified (natural) and biodegradable glycogen nanoparticles derived from various sources, such as rabbit and bovine liver, oyster and sweet corn, for the encapsulation of soybean oil and vitamin D. Depending on their source, glycogen nanoparticles exhibited differences in size and ‘bound’ proteins. We optimized various synthetic parameters, such as ultrasonic power, time and concentration of glycogens and the oil phase to obtain stable core-shell microcapsules. Particularly, under ultrasound-induced emulsification conditions (sonication time 45 s and sonication power 160 W), native glycogens formed microcapsules with diameter between 0.3 μm and 8 μm. It was found that the size of glycogen as well as the protein component play an important role in stabilizing the Pickering emulsion and the microcapsules shell. This study highlights that native glycogen nanoparticles without any further tedious chemical modification steps can be successfully used for the encapsulation of nutrients.     

Atropisomerism in 1,5-bridged calix[8]arenes

[structure: see text] The first example of two discrete calix[8]arene conformational isomers, 2 and 2a, has been obtained by exhaustive benzylation of 1,5-tetramethylene-bridged calix[8]arene 1. It is demonstrated, with the aid of X-ray crystallography, that these atropisomers have two 3/4-cone halves oriented syn or anti with respect to the bridge/bridgeheads moiety. VT NMR studies indicate that the tert-butyl-through-the-annulus inversion is inhibited in 1, while groups larger than n-hexyl or benzyl are required for curtailing the O-through-the-annulus route.     

Evaluation of the degree of cross-linking of cellulose-based superabsorbent hydrogels: a comparison between different techniques

Three different techniques have been applied to the evaluation of the degree of cross-linking of superabsorbent cellulose-based hydrogels obtained from water solutions of carboxymethylcellulose sodium salt (CMCNa) and hydroxyethylcellulose (HEC), chemically cross-linked with divinyl sulfone. These polyelectrolyte hydrogels are biodegradable and have the same sorption capacity as acrylate-based superabsorbents on the market. A ¹³C solid state NMR analysis was carried out on dry samples of hydrogel to obtain the degree of cross-linking, an important parameter that affects the swelling and mechanical properties of a hydrogel. Dynamic mechanical analysis was performed during the hydrogel cross-linking using a parallel plate rheometer under oscillatory deformations in order to monitor the evolution of the hydrogel viscoelastic properties during the synthesis. The value of |G*| and the slope of the stress-deformation ratio plots from uniaxial compression tests were used to evaluate the elastically effective degree of cross-linking according to classical rubber elasticity theory. Moreover, a dynamic mechanical analysis was carried out on cross-linked hydrogels at different degrees of swelling in order to investigate the influence of the swelling on the mechanical properties and the application of rubber elasticity theory to swollen hydrogels.     

Characterization of foxing stains in early twentieth century photographic and paper materials

Abstract

The subject of this present work is a group of nine historical pictures shot in Palermo by the Sicilian photographer E. Interguglielmi in 1912. They are nine matte-collodion prints mounted on the original cardboard supports and all of them show foxing stains affecting the paper surface. In order to characterise the chemical composition of the supports and investigate foxing spots, non-destructive and micro-destructive analysis were carried out. X-rays fluorescence (XRF) analysis was used to characterise the elemental composition of all the mounting boards, allowing a comparison between the foxing spots and non-affected areas. Laser-Induced Breakdown Spectroscopy was used to investigate the presence of lower atomic number elements, not detectable by XRF, while SEM imaging allowed the investigation of surface appearance and nature of original paper samples from the cardboards.     

Application of microemulsions for the removal of synthetic resins from paintings on canvas

Abstract

Traditional cleaning methods with organic solvents often are not suitable for removal of aged resin so researchers have to find new formulations. In this work, a case study is reported in which new microemulsions were applied on the surface of a painting covered by some aged resin layers used during a previous restoration. Based on the quality of the intervention and the analysis of a sample of the varnish carried out with both MALDI-TOF and ATR-IR spectrometers, it was conjectured that this undesired material could be an acrylic polymer. So it was chosen to use xylene, ethyl acetate and propylene carbonate (XYL and EAPC) microemulsions (O/W oil in water). The first is able to solubilise only acrylic polymers, the second may solve both acrylic and vinyl resins. The first has had the greatest effect allowing complete varnish removal and original artwork restoration.     

Surface and volume non-invasive methods for the structural monitoring of the bass-relief ‘Madonna con Bambino’ (Gorizia,Northern Italy)

Abstract

Structural analysis of marble statues, carried out by non-invasive and in situ methods, is crucial to define the state of conservation of the artworks and to identify the deterioration phenomena that can affect them. In this work, we combined in situ non-destructive techniques, ultrasonic tomography (US), ultraviolet-induced visible fluorescence (UV-IF) and X-ray fluorescence (XRF) to study the bass-relief ‘Madonna con Bambino’ (Gorizia, Italy). The US revealed the presence of some metallic pivots, associated with areas of high sound velocity; moreover, a more degraded area has been identified in the lower part of the bass-relief. The acquired UV-IF image confirmed the presence of surface degradation, allowing a preliminary evaluation of the extension of a fracture, from surface to bulk. In addition, the different materials (both original and/or integrations) that compose the studied surface have been identified. The XRF has contributed to define the nature of the inorganic materials applied during undocumented previous restoration works on the surface as filler for lacunae.