Effects of processing on five selected metals in the durum wheat food chain

The concentration levels of five metals, namely Cd, Cr, Fe, Ni and Pb, were investigated along the durum wheat processing chain, from grain to the final product. Cadmium and Pb are well-known toxic elements and their levels in wheat grain are regulated by the European legislation. Chromium, Fe and Ni were included in the study as markers of metal release from equipment during processing. Durum wheat grain, semolina and pasta were sampled at an industrial plant for milling and pasta making. Samples were taken at different stages along processing in order to elucidate the influence of each stage on the element content. Samples of the water used for grain tempering and dough preparation were also collected. The whole analytical procedure, from sampling to final analytical determinations, was carried out according to a pre-established quality assurance protocol. Analyses were performed by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES).Milling was the key process influencing the concentrations of the studied elements and reduced the metal levels according to a definite element-specific pattern. Purity of the water used as ingredient, element deposition from plant air and metal release from equipment were identified as critical issues in contamination control during processing. In the conditions of this study, it was found that a simple relationship can be established between the original concentrations in durum wheat grain and those in pasta for Cd and Fe, while for Pb, Cr and Ni, a greater uncertainty in the estimation of the levels in the final product is expected.     

Substituted 1-amino-cyclopentenes from 2,3-diamino-1,3-butadienes and nitroalkenes

2,3-Diamino-1,3-butadienes (1) reacted with β-nitrostyiene or nitroethene to afford a mixture ofisomeric 1,5-diaminoo-5-methyl-4-nitro-cyclopentenes (3 and 4). The configuration of the main isomers (3) was established by X-ray diffraction analysis which also revealed the great steric crowding of this molecule. The conformation of the cyclopentene ring in 3 in the solid state is also discussed. The enamines (3 and 4) were hydrolyzed to the corresponding aminoketones (5 and 6) which, on reduction, gave the same diaminoketone (7).     

Structural effects on the acidity of E-α-phenyl-β-arylacrylic acids

The dissociation equilibrium constants of some is-α-phenyl-β-arylacrylic acids (Ar = 2-pyridyl, 3-pyridyl, 4-pyridyl, 1-naphthyl, 2-naphthyl, anthracen-9-yl) have been measured in 80% aqueous 2-methoxyethanol at 25°. The pKa values of these acids, together with those of p-substituted phenyl, 2-furyl, 2-thienyl and selenophen-2-yl derivatives, have been rationalized by an equation involving separate contributions of polar, conjugative and steric effects of heterocycles. The pKa values of some E-α-phenyl-β-alkylacrylic acids (alk = methyl; ethyl; n-propyl; i-propyl; n-butyl; i-butyl) are also reported.     

Non–existence of theta–shaped self–similarly shrinking networks moving by curvature

We prove that there are no networks homeomorphic to the Greek “Theta” letter (a double cell) embedded in the plane with two triple junctions with angles of 120 degrees, such that under the motion by curvature they are self–similarly shrinking.

This fact completes the classification of the self–similarly shrinking networks in the plane with at most two triple junctions, see [5 Chen, X., Guo, J.-S. (2007). Self-similar solutions of a 2-D multiple-phase curvature flow. Phys. D. 229(1):22–34.[Crossref], [Web of Science ®] , [Google Scholar], 10 Hättenschweiler, J. (2007). Mean curvature flow of networks with triple junctions in the plane. Master’s thesis. ETH Zürich. [Google Scholar], 25 Schnürer, O. C., Azouani, A., Georgi, M., Hell, J., Nihar, J., Koeller, A., Marxen, T., Ritthaler, S., Sáez, M., Schulze, F., Smith, B. (2011). Evolution of convex lens–shaped networks under the curve shortening flow. Trans. Am. Math. Soc. 363(5):2265–2294.[Crossref], [Web of Science ®] , [Google Scholar], 2 Baldi, P., Haus, E., Mantegazza, C. (2016). Networks self-similarly moving by curvature with two triple junctions. Networks self-similarly moving by curvature with two triple junctions. 28(2017):323–338. [Google Scholar]].     

HPLC‐ESI‐MS analysis of oral human fluids reveals that gingival crevicular fluid is the main source of oral thymosins β4 and β10

Thymosin β₄ (Tβ₄), its sulfoxide, and thymosin β₁₀ (Tβ₁₀) were detected in human saliva and identified by different strategies based on RP HPLC coupled to electrospray multidimensional IT MS. Tβ₄ was almost always detected in whole saliva, its sulfoxide sporadically, Tβ₁₀ rarely. Tβ₄ was undetectable in parotid saliva and less concentrated in submandibular/sublingual saliva than in whole saliva. Analysis of gingival crevicular fluid revealed high relative amounts of Tβ₄, Tβ₄ sulfoxide, and Tβ₁₀ in all the samples. Tβ₄ mean concentration was 200 times higher in crevicular fluid (20 μmol/L, N = 9) than in whole saliva (0.1 μmol/L, N = 9). Crevicular fluid concentration of Tβ₄ (ca. 5% represented by its sulfoxide) and β₁₀ significantly correlated (r = 0.856; N = 9), and their ratio was about 5. A significant correlation was also observed between Tβ₄ concentrations in whole saliva and gingival crevicular fluid (r = 0.738; N = 9). Immunohistochemical analysis of the major salivary glands showed that immunoreactivity for Tβ₄ is restricted to ductal cells, with minor degree of focal positivity in some acinar cells. On the whole, results indicate that gingival sulcus is a main, although not the sole, source for oral Tβ₄ and Tβ₁₀.     

SC List-Flip Decoding of Polar Codes by Shifted Pruning: A General Approach

In the successive cancellation (SC) list decoding, the tree pruning operation retains the L best paths with respect to a metric at every decoding step. However, the correct path might be among the L worst paths due to the imposed penalties. In this case, the correct path is pruned and the decoding process fails. shifted pruning (SP) scheme can recover the correct path by additional decoding attempts when decoding fails, in which the pruning window is shifted by κ≤L paths over certain bit positions. A special case of the shifted pruning scheme where κ=L is known as SCL-flip decoding, which was independently proposed in 2019. In this work, a new metric that performs better in particular for medium and long codes is proposed, and nested shift-pruning schemes are suggested for improving the average complexity.     

Characterization and Authentication of “Ricotta” Whey Cheeses through GC-FID Analysis of Fatty Acid Profile and Chemometrics

The fatty acid (FA) profiles of 240 samples of ricotta whey cheese made from sheep, goat, cow, or water buffalo milk were analyzed by gas-chromatography (GC). Then, sequential preprocessing through orthogonalization (SPORT) was used in order to classify samples according to the nature of the milk they were made from. This strategy achieved excellent results, correctly classifying 77 (out of 80) validation samples. Eventually, since 36 (over 114) sheep ricotta whey cheeses were PDO products, a second classification problem, finalizing the discrimination of PDO and Non-PDO dairies, was faced. In this case, two classifiers were used, SPORT and soft independent modelling by class analogy (SIMCA). Both approaches provided more than satisfying results; in fact, SPORT properly assigned 63 (of 65) test samples, whereas the SIMCA model accepted 14 PDO individuals over 15 (93.3% sensitivity) and correctly rejected all the other samples (100.0% specificity). In conclusion, all the tested approaches resulted as suitable for the two fixed purposes. Eventually, variable importance in projection (VIP) analysis was used to understand which FAs characterize the different categories of ricotta. Among the 22 analyzed compounds, about 10 are considered the most relevant for the solution of the investigated problems.     

Proton solvation in protic and aprotic solvents

Protonation pattern strongly affects the properties of molecular systems. To determine protonation equilibria, proton solvation free energy, which is a central quantity in solution chemistry, needs to be known. In this study, proton affinities (PAs), electrostatic energies of solvation, and pK_A values were computed in protic and aprotic solvents. The proton solvation energy in acetonitrile (MeCN), methanol (MeOH), water, and dimethyl sulfoxide (DMSO) was determined from computed and measured pK_A values for a specially selected set of organic compounds. pK_A values were computed with high accuracy using a combination of quantum chemical and electrostatic approaches. Quantum chemical density functional theory computations were performed evaluating PA in the gas‐phase. The electrostatic contributions of solvation were computed solving the Poisson equation. The computations yield proton solvation free energies with high accuracy, which are in MeCN, MeOH, water, and DMSO ?255.1, ?265.9, ?266.3, and ?266.4 kcal/mol, respectively, where the value for water is close to the consensus value of ?265.9 kcal/mol. The pK_A values of MeCN, MeOH, and DMSO in water correlates well with the corresponding proton solvation energies in these liquids, indicating that the solvated proton was attached to a single solvent molecule. © 2016 Wiley Periodicals, Inc.     

Recent Advances in Photoinduced Modification of Amino Acids,Peptides, and Proteins

The chemical modification of biopolymers like peptides and proteins is a key technology to access vaccines and pharmaceuticals. Similarly, the tunable derivatization of individual amino acids is important as they are key building blocks of biomolecules, bioactive natural products, synthetic polymers, and innovative materials. The high diversity of functional groups present in amino acid-based molecules represents a significant challenge for their selective derivatization Recently, visible light-mediated transformations have emerged as a powerful strategy for achieving chemoselective biomolecule modification. This technique offers numerous advantages over other methods, including a higher selectivity, mild reaction conditions and high functional-group tolerance. This review provides an overview of the most recent methods covering the photoinduced modification for single amino acids and site-selective functionalization in peptides and proteins under mild and even biocompatible conditions. Future challenges and perspectives are discussed beyond the diverse types of photocatalytic transformations that are currently available.