Synthetic Potential of Fucosyltransferase III for the Synthesis of Fluorescent‐labeled Milk Oligosaccharides

Various fundamental biologic roles of milk oligosaccharides have been recognized; however, their structure‐affinity relationship is still not fully revealed. Herein, we describe the synthesis of the fluorescent‐labeled milk oligosaccharides 3‐(5‐dimethylaminonaphthalene‐1‐sulfonylamino)propyl β‐D‐galactopyranosyl‐(1→3)‐[α‐L‐fucopyranosyl‐(1→4)]‐2‐acetamido‐2‐deoxy‐β‐D‐glucopyranoside (1) and 3‐(5‐dimethylamino‐naphthalene‐1‐sulfonylamino)propyl β‐D‐galactopyranosyl‐(1→3)‐[α‐L‐fucopyranosyl‐(1→4)]‐β‐D-glucopyranoside (2) as useful tools for synthetic, analytic, and biologic applications. For the fucosylation of lactose and lacto‐N‐biose, the chemical and the enzymatic syntheses using fucosyltransferase III were compared.     

Traceability along the production chain of Italian tomato products on the basis of stable isotopes and mineral composition

The paper shows the variability of stable isotope ratios and mineral composition in tomato and derivatives along the production chain (juice, passata and paste) in order to evaluate the possibility of tracing their geographical origin. The ratios (13)C/(12)C, (15)N/(14)N, (18)O/(16)O, D/H, (34)S/(32)S and the content of Li, Be, B, Na, Mg, Al, P, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Mo, Ag, Cd, Sn, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Tm, Yb, Ir, Tl, Pb, U and of nitrates, chlorides, sulphates and phosphates were measured by Isotope Ratio Mass Spectrometry, Inductively Coupled Plasma Mass Spectrometry and Ion Chromatography, respectively. The tomato products were from three Italian regions - Piedmont, Emilia Romagna, and Apulia. By applying linear discriminant analysis on 17 of these parameters (Gd, La, Tl, Eu, Cs, Ni, Cr, Co, δ(34)S, δ(15)N, Cd, K, Mg, δ(13)C, Mo, Rb and U) excellent discrimination among products from the three regions was achieved. Irrespective of the processing technology, over 95% of the samples were correctly reclassified in cross-validation into the production site. The use of these parameters will allow the development of analytical control procedures that can be used to check the geographical provenance of Italian tomatoes and products derived from them.     

Distinctive Glycerophospholipid Profiles of Human Seminoma and Adjacent Normal Tissues by Desorption Electrospray Ionization Imaging Mass Spectrometry

Desorption electrospray ionization mass spectrometry (DESI-MS) has been successfully used to discriminate between normal and cancerous human tissue from different anatomical sites. On the basis of this, DESI-MS imaging was used to characterize human seminoma and adjacent normal tissue. Seminoma and adjacent normal paired human tissue sections (40 tissues) from 15 patients undergoing radical orchiectomy were flash frozen in liquid nitrogen and sectioned to 15 μm thickness and thaw mounted to glass slides. The entire sample was two-dimensionally analyzed by the charged solvent spray to form a molecular image of the biological tissue. DESI-MS images were compared with formalin-fixed, hematoxylin and eosin (H&E) stained slides of the same material. Increased signal intensity was detected for two seminolipids [seminolipid (16:0/16:0) and seminolipid (30:0)] in the normal tubule testis tissue; these compounds were undetectable in seminoma tissue, as well as from the surrounding fat, muscle, and blood vessels. A glycerophosphoinositol [PI(18:0/20:4)] was also found at increased intensity in the normal testes tubule tissue when compared with seminoma tissue. Ascorbic acid (i.e., vitamin C) was found at increased amounts in seminoma tissue when compared with normal tissue. DESI-MS analysis was successfully used to visualize the location of several types of molecules across human seminoma and normal tissues. Discrimination between seminoma and adjacent normal testes tubules was achieved on the basis of the spatial distributions and varying intensities of particular lipid species as well as ascorbic acid. The increased presence of ascorbic acid within seminoma compared with normal seminiferous tubules was previously unknown.     

Effects of MgCl2 Crystallographic Structure on Active Centre Formation in Immobilized Single‐Centre and Ziegler–Natta Catalysts for Ethylene Polymerization

The ability of a MgCl₂ support to activate a transition metal catalyst has been found to depend both on the crystallographic structure of the support and on the nature of the catalyst. A high degree of crystallographic disorder can be very effective for the immobilization and activation of titanium and vanadium complexes, but is not necessarily effective for zirconocene activation. A highly disordered support prepared by the reaction of MgBu₂ with HCl gave high activity with TiCl₄ but low activity with (n‐PrCp)₂ZrCl₂. High polymerization activities with the zirconocene were only obtained with supports of type MgCl₂/AlR_n(OEt)_3−n prepared from the reaction of AlR₃ with MgCl₂ · 1.1EtOH. These supports are characterized by additional peaks in the X‐ray diffraction pattern, indicating the presence of a crystalline structure which is absent in the other supports and contains highly Lewis acidic sites able to generate the active metallocenium species.

     

Enhanced imaging of magnetic structures in micropatterned arrays of Co dots and antidots

A specific technique of numerical treatment of atomic force microscopy (AFM) and magnetic force microscopy (MFM) signal has been developed to enhance the quality of raw images, in order both to improve their contrast and to gain better insight on the sample topography and on the local arrangement of the magnetisation vector. Basically, the technique consists in computing the optimum conformal transformation that allows one to superimpose two AFM images of the same area, acquired performing subsequent scans whose fast scan axis were mutually perpendicular, and applying the inverse transform to the second image. After MFM image superposition, the two datasets were either summed or subtracted, in order to improve the magnetic contrast. Computations have been done in a Matlab^® workspace with the help of Image Processing Toolbox 4.2. Improved MFM images obtained on both dots and antidots thin evaporated Co arrays in the demagnetised state (after performing alternate field demagnetisation parallel and perpendicular to the array plane) have been interpreted. Samples consisting of large-size patterns (1×1 mm) of circular dots/antidots with square/hexagonal lattices and minimum diameters of 1 μm were prepared by optical lithography. The magnetic film thickness was chosen depending on resist thickness, and varied between 25 and 150 nm, with a fixed ratio 1:4 between metal/resist film thickness. MFM was exploited to obtain images of either intra-dot or inter-antidot magnetic structures.     

Surface‐enhanced Raman spectroscopy (SERS) on silver colloids for the identification of ancient textile dyes: Tyrian purple and madder

Surface‐enhanced Raman spectroscopy (SERS) was used for the identification of natural organic dyes belonging to indigoid and anthraquinone classes in archeological samples, and good agreement with the corresponding reference commercial materials was found. Special attention was paid to the well‐known problem of anomalous bands that arise sometimes in the SERS spectra on colloids: as suggested in the literature, this problem could be reduced by the use of poly‐L ‐lysine and ascorbic acid as aggregating agents, but we observed that also the addition first of the analyte and subsequently of suitable electrolytes to the colloid in an inverted order compared to the most widely used method can be of help in limiting the intensity of such spurious bands. This procedure allowed us to obtain, for the first time, the SERS spectra of both modern and ancient Tyrian purple and to solve a specific problem observed in the analysis of archeological wool samples dyed with madder lake, i.e. the competition in the SERS response between the dye and other compounds possibly deriving from the degradation of the peptide chain during the hydrolysis treatment during the extraction of the dye from the wool fiber. Copyright © 2009 John Wiley & Sons, Ltd.     

The Use of UV-Visible Diffuse Reflectance Spectrophotometry for a Fast,Preliminary Authentication of Gemstones

The identification of gemstones is an important topic in the field of cultural heritage, given their enormous value. Particularly, the most important precious stones, namely diamond, emerald, ruby and sapphire, are frequently subjected to counterfeit by substitution with objects of lesser value with similar appearance, colour or shape. While a gemmologist is able to recognise a counterfeit in most instances, more generally, it is not easy to do this without resorting to instrumental methods. In this work, the use of UV-visible diffuse reflectance spectrophotometry with optic fibres (FORS) is proposed as a fast and easy method for the preliminary identification of gemstones, alternative to the classical methods used by gemmologists or to Raman spectroscopy, which is by far the instrumental method with the best diagnostic potential, but it cannot be used in situations of problematic geometric hindrance. The possibilities and the limitations given by the FORS technique are critically discussed together with the spectral features of the most important gemstones. Finally, the application of chemometric pattern recognition methods is described for the treatment of large sets of spectral data deriving from gemstones identification.     

Essential Oil from Eucalyptus globulus (Labill.) Activates Complement Receptor-Mediated Phagocytosis and Stimulates Podosome Formation in Human Monocyte-Derived Macrophages

Eucalyptus essential oil and its major constituent eucalyptol are extensively employed in the cosmetic, food, and pharmaceutical industries and their clinical use has recently expanded worldwide as an adjuvant in the treatment of infective and inflammatory diseases. We previously demonstrated that essential oil from Eucalyptus globulus (Labill.) (EO) stimulates in vitro the phagocytic activity of human monocyte-derived macrophages and counteracts the myelotoxicity induced by the chemotherapeutic 5-fluorouracil in immunocompetent rats. Here we characterize some mechanistic aspects underlying the immunostimulatory ability exerted by EO on macrophages. The internalization of fluorescent beads, fluorescent zymosan BioParticles, or apoptotic cancer cells was evaluated by confocal microscopy. Pro-inflammatory cytokine and chemokine release was determined by flow cytometry using the BD cytometric bead array. Receptor involvement in EO-stimulated phagocytosis was assessed using complement- or IgG-opsonized zymosan particles. The localization and expression of podosome components was analyzed by confocal microscopy and western blot. The main results demonstrated that: EO-induced activation of a macrophage is ascribable to its major component eucalyptol, as recently demonstrated for other cells of innate immunity; EO implements pathogen internalization and clearance by stimulating the complement receptor-mediated phagocytosis; EO stimulates podosome formation and increases the expression of podosome components. These results confirm that EO extract is a potent activator of innate cell-mediated immunity and thereby increase the scientific evidence supporting an additional property of this plant extract besides the known antiseptic and anti-inflammatory properties.     

Potential Use of Tea Tree Oil as a Disinfectant Agent against Coronaviruses: A Combined Experimental and Simulation Study

The COVID-19 pandemic has highlighted the relevance of proper disinfection procedures and renewed interest in developing novel disinfectant materials as a preventive strategy to limit SARS-CoV-2 contamination. Given its widely known antibacterial, antifungal, and antiviral properties, Melaleuca alternifolia essential oil, also named Tea tree oil (TTO), is recognized as a potential effective and safe natural disinfectant agent. In particular, the proposed antiviral activity of TTO involves the inhibition of viral entry and fusion, interfering with the structural dynamics of the membrane and with the protein envelope components. In this study, for the first time, we demonstrated the virucidal effects of TTO against the feline coronavirus (FCoVII) and the human coronavirus OC43 (HCoV-OC43), both used as surrogate models for SARS-CoV-2. Then, to atomistically uncover the possible effects exerted by TTO compounds on the outer surface of the SARS-CoV-2 virion, we performed Gaussian accelerated Molecular Dynamics simulations of a SARS-CoV-2 envelope portion, including a complete model of the Spike glycoprotein in the absence or presence of the three main TTO compounds (terpinen-4-ol, γ-terpinene, and 1,8-cineole). The obtained results allowed us to hypothesize the mechanism of action of TTO and its possible use as an anti-coronavirus disinfectant agent.     

Orange Peel Biomass-derived Carbon Supported Cu Electrocatalysts Active in the CO2-Reduction to Formic Acid

We report a green, wet chemistry approach towards the production of C-supported Cu electrocatalysts active in the CO₂ reduction to formic acid. We use citrus peels as a C support precursor and as a source of reducing agents for the Cu cations. We show that orange peel is a suitable starting material compared to lemon peel for the one-pot hydrothermal synthesis of Cu nanostructures affording better Cu dispersion as well as productivity and selectivity towards formic acid. We rationalize this finding in terms of the beneficial chemical composition of the orange peel, which favors both the reduction of the Cu precursor as well as the carbon matrix. This work demonstrates new viable opportunities for the reuse of citrus waste on a rational basis.