How to discriminate between leucine and isoleucine by low energy ESI-TRAP MS<Superscript>n</Superscript>

In peptide sequencing experiments involving a single step tandem mass acquisition, leucine and isoleucine are indistinguishable because both are characterized by a 113 Da mass difference from the other peptide fragments in the MS2 spectrum. In this work, we propose a new method to distinguish between these two amino acids in consecutive MSn experiments, exploiting a gas-phase fragmentation of isoleucine that leads to a diagnostic 69 Da ion. We used this method to assess the Leu/Ile residues of several synthetic peptides. The procedure was then tested on a tryptic digest of myoglobin, assigning the correct amino acid in the majority of the peptides. This work was performed with an old and low-resolution instrument, thus demonstrating that our method is suitable for a wide number of ion trap mass spectrometers, not necessarily expensive or up-to-date.     

The Second Life of Citrus Fruit Waste: A Valuable Source of Bioactive Compounds

Citrus fruits (CF) are among the most widely cultivated fruit crops throughout the world and their production is constantly increasing along with consumers’ demand. Therefore, huge amounts of waste are annually generated through CF processing, causing high costs for their disposal, as well as environmental and human health damage, if inappropriately performed. According to the most recent indications of an economic, environmental and pharmaceutical nature, CF processing residues must be transformed from a waste to be disposed to a valuable resource to be reused. Based on a circular economy model, CF residues (i.e., seeds, exhausted peel, pressed pulp, secondary juice and leaves) have increasingly been re-evaluated to also obtain, but not limited to, valuable compounds to be employed in the food, packaging, cosmetic and pharmaceutical industries. However, the use of CF by-products is still limited because of their underestimated nutritional and economic value, hence more awareness and knowledge are needed to overcome traditional approaches for their disposal. This review summarizes recent evidence on the pharmacological potential of CF waste to support the switch towards a more environmentally sustainable society.     

Properties of networks based on poly(alkylene glycol) diacrylates

Three series of poly(alkylene glycol) diacrylates, namely poly(ethylene glycol), poly(propylene glycol) and poly(tetramethylene glycol) α,ω-diacrylates have been prepared by acryloylation of the corresponding bis-OH-terminated oligomers. Their MW was in the range 200–1000 and their acrylic functionality was close to two. They were subjected to UV curing as thin films obtaining, by FTIR analysis, complete terminal double bond conversion in all cases with the exception of the lowest MW oligomers. Thermal and mechanical properties of the networks were investigated by means of DSC, TMA and DMTA analyses. Concerning the PPGDA oligomers, products totally amorphous and rubbery were obtained; PEGDA and PTMGDA oligomers gave similar amorphous structures with the exception of the highest MWs which showed partial crystallinity. By means of thermal and DMTA measurements, T_g values and E' moduli were obtained and correlated to the MW of the oligomers used. In particular, T_g values, as function of the crosslinking density, agreed with those calculated by the Nielsen equation for the three series investigated. The equilibrium swelling in water was determined for various networks as a function of the MW of the oligomers. The values obtained were compared and discussed in terms of the solubility parameters and the crosslinking density of various structures.     

Synthesis of New Carnosine Derivatives of β‐Cyclodextrin and Their Hydroxyl Radical Scavenger Ability

Several in vitro and in vivo studies have suggested that carnosine can act as a scavenger of reactive oxygen species and intracellular proton buffer. On the other hand, carnosinase is a specific peptidase able to destroy the biological active dipeptide. To overcome this constraint, β‐cyclodextrin (β‐CD) was functionalized with carnosine to give the following new compounds: 6^A‐[(3‐{[(1S)‐1‐carboxy‐2‐(1H‐imidazol‐4‐yl)ethyl]amino}‐3‐oxopropyl)amino]‐6^A‐deoxy‐β‐cyclodextrin ( 1 ), 6^A‐[(β‐alanyl‐L ‐histidyl)amino]‐β‐cyclodextrin ( 2 ), and (2^AS,3^AR)‐3^A‐[(3‐{[(1S)‐1‐carboxy‐2‐(1H‐imidazol‐4‐yl)ethyl]amino}‐3‐oxopropyl)amino]‐3^A‐deoxy‐β‐cyclodextrin ( 3 ). Pulse‐radiolysis investigation showed that the β‐CD derivatives 1 – 3 are excellent scavengers of OH^. radicals. Their activity is not only due to the formation of the stable imidazole‐centered radical, but also to the scavenger ability of the glucose moieties of the macrocycle (Scheme). This effect is independent of the disposition of the imidazole ring. In fact, the quenching constant values are similar for the three compounds.     

Dimethyl ether as circular hydrogen carrier: Catalytic aspects of hydrogenation/dehydrogenation steps

The intermittent nature of renewable resources requires for most applications the development of efficient and cost-effective technologies for steady supply of ...     

Limit analysis of masonry vaults by means of curved shell finite elements and homogenization

The study of masonry vaults should take into account the essentials of the material “masonry” – i.e. heterogeneity, almost no resistance to tension combined with a good compressive strength and a high friction coefficient, as well as the overall importance of the geometry for achieving the equilibrium.In this paper, a new six-noded triangular curved element, specifically developed for the kinematic limit analysis of masonry shells, is presented. Plastic dissipation is allowed only at the interfaces (generalized cylindrical hinges) between adjoining elements for combined membrane actions, bending moment, torsion and out-of-plane shear, as it is required for the analysis of thick (Reissner–Mindlin) shells. An upper bound of the collapse load is so obtained, since, looking at the dual formulation, the admissibility of the stress state is imposed only at the element boundaries. Masonry strength domain at each interface between contiguous triangular elements is evaluated resorting to a suitable upper bound FE homogenization procedure. The model is assessed through several numerical simulations on a number of masonry shells experimentally tested until collapse. In particular, the dependence of the collapse multiplier on the mesh and on the material parameters (sensitivity analysis) is thoroughly discussed.     

Solid–Gas Hydrogenation of Hex-3-yne and 1,4-Cyclohexadiene in the Presence of Ru3(CO)9(μ-H)(μ-PPh2), Ru3(CO)10(μ-H)(μ-PPh2), Ru3(CO)7(μ-PPh2)2(C6H4), and Ru4(CO)11(μ4-PPh)(C6H4) Deposited on Pyrex Glass, Silica, and Alumina

The title complexes were tested in the hydrogenation of hex-3-yne and of 1,3- and 1,4-cyclohexadiene (CHD) under solid–gas conditions. The clusters were deposited on three “standard” supports, that is, pyrex glass, alumina, and silica. All the clusters, particularly (μ-H)Ru₃(CO)₁₀(PPh₂), show hydrogenation activity. However, they are not particularly selective toward the formation of monoenes; “disproportionation” of 1,3- and 1,4-CHD to hydrogenated products and benzene also occurs. The hydrogenation activity of the clusters is dependent on their nature, the type of substrate, and the characteristics of the supporting material; silica and pyrex glass are usually more active than alumina. Attempts at detecting the formation of organometallic intermediates or by-products (through IR spectroscopy) were made. HRTEM was used to check for eventual decomposition on some supports.     

Non adiabatic vibrational resonances in molecules containing low barrier moieties: a classical dynamics study

 We discuss the classical dynamics of a CH-stretching and an OH-stretching vibration coupled to a hindered rotation around a CC (OC) bond of a CH₃ group or an OH group. Our model is based on a two-dimensional system, in which zero angular momentum is assumed. The model is further simplified by considering only kinetic coupling between the CH (OH) stretching and the hindered rotation. Through numerical calculations, a new set of states is found, which originates from n:1 resonances between the internal rotation frequency and the stretching frequency, n being associated to the order of symmetry (n = 3 and 6 for the cases investigated). We also present a perturbative approach based on the Lie series method, which provides insight into these nonadiabatic states. Received: 28 April 1999 / Accepted: 21 September 1999 / Published online: 15 December 1999     

Non-Hydrolytic Routes for the Synthesis of NASICON

The study of non-hydrolytic reactions for the synthesis of NASICON is reported. Different procedures have been considered, changing the precursors and their addition order, and varying the reaction solvent; dichloromethane, acetonitrile and tetrahydrofuran (THF). The most promising results in terms of homogeneous reactivity were obtained using PO(On-C₄H₉)₃, Zr(Ot-C₄H₉)₄, SiCl₄ and Na(Ot-C₄H₉) in acetonitrile. The reactions were followed using heteronuclear Nuclear Magnetic Resonance (NMR) spectroscopy (¹³C, ³¹P). NASICON powders were prepared by the thermal decomposition of the gels between 900 and 1200°C. The powders were analyzed by XRD to check the formation of the NASICON phase.