Methanol Conversion to Hydrocarbons (MTH) Over H-ITQ-13 (ITH) Zeolite

Product flexibility is key to meeting fluctuating chemicals demands in the future. In this contribution, the methanol to hydrocarbons (MTH) reaction was investigated over two Ge-containing H-ITQ-13 samples, one with needle-like (H-ITQ-13(N), with (Si+Ge)/Al) = 42) and another with plate-like (H-ITQ-13(P), with (Si+Ge)/Al > 100) morphology. The samples were characterised using XRD, BET, SEM/EDS and FTIR spectroscopy, and their MTH performance was compared with the performance of H-ZSM-5 and H-ZSM-22. Similar specific surface areas (413 and 455 m² g^?1 for H-ITQ-13(N) and (P), respectively) and similar acid strength (Δν ~ ?327(?310) cm^?1) was observed for the two H-ITQ-13 samples. Testing of H-ITQ-13(N) at weight hourly space velocity (WHSV) = 2–8 h^?1 at 350–450 °C revealed that C₅₊ alkenes were the main products (35–45 % selectivity at 400 °C), followed by propene and butene. A low but significant selectivity for aromatic products was observed (6–8 % selectivity at 400 °C). Product selectivity was found to be independent of deactivation. The methanol conversion capacity of H-ITQ-13(N) was 120–150 g methanol g^?1 catalyst at 400 °C. Testing H-ITQ-13 at high (30 atm) and ambient pressure, respectively, at 350 °C showed that a high pressure led to enhanced C₅₊ selectivity, but close to a tenfold decrease in methanol conversion capacity. H-ITQ-13(P) was tested at 400 °C and 2 h^?1. It gave lower conversion than H-ITQ-13(N). Furthermore, when compared at the same conversion level, H-ITQ-13(P) gave higher C₅₊ alkene selectivity, lower aromatics selectivity, and a higher propene to ethene ratio than H-ITQ-13(N). The H-ITQ-13 samples yielded a product spectrum intermediate of H-ZSM-22 and H-ZSM-5. The effluent product cut-off of H-ITQ-13 was similar to that of H-ZSM-5 with tetramethylbenzene as the largest significant product, while H-ZSM-22 produced mainly linear and branched alkenes. The lifetime of H-ITQ-13(N) was clearly enhanced compared to H-ZSM-22, but inferior to H-ZSM-5.     

Evaluation of 4-(4-Fluorobenzyl)piperazin-1-yl]-Based Compounds as Competitive Tyrosinase Inhibitors Endowed with Antimelanogenic Effects

There is a considerable attention for the development of inhibitors of tyrosinase (TYR) as therapeutic strategy for the treatment of hyperpigmentation disorders in humans. Continuing in our efforts to identify TYR inhibitors, we describe the design, synthesis and pharmacophore exploration of new small molecules structurally characterized by the presence of the 4-fluorobenzylpiperazine moiety as key pharmacophoric feature for the inhibition of TYR from Agaricus bisporus (AbTYR). Our investigations resulted in the discovery of the competitive inhibitor [4-(4-fluorobenzyl)piperazin-1-yl]-(3-chloro-2-nitro-phenyl)methanone 26 (IC₅₀=0.18 μM) that proved to be ∼100-fold more active than reference compound kojic acid (IC₅₀=17.76 μM). Notably, compound 26 exerted antimelanogenic effect on B16F10 cells in absence of cytotoxicity. Docking analysis suggested its binding mode into AbTYR and into modelled human TYR.     

Functionalised hybrid Poly(ether ether ketone) containing MnO2: Investigation of operative conditions for hydrogen sorption

A composite material synthesis, based on Manganese oxide (MnO₂) anchored to a functionalized polymeric matrix, was optimized. For this investigation two different MnO₂ loadings were selected (16 and 80 wt%) in order to understand the relation between the oxide content, chemical-physical characteristic and the H₂ sorption properties. SEM, XRD were carried out and the obtained results were correlated to the H₂ sorption/desorption characterizations by Sievert apparatus.From these measurements at 50 °C/40 bar, the sample containing 16 wt% of metal oxide content has revealed a low H₂ sorption capability (0,04 wt%), while the 80 wt% sample showed a very high H₂ storage value (3 wt%). A short sorption/desorption cycles were carried out and a good reversibility was revealed.A modelling study, ab-initio Density Functional Theory (DFT) calculations, was carried out. The starting unit cell was MnO₂ while Mn₂₄O₄₈ was considered as a supercell. The number of H atoms was gradually increased and desorption energy was calculated. Desorption energy starts from 366 kJ/mol and decreases by increasing the number of H atoms. For the experimental H₂ sorption value (1,7 wt%) it was calculated the number of the respective H atoms (36) and the corresponding desorption energy (150 kJ/mol).     

N-(Anilinoethyl)amide Melatonergic Ligands with Improved Water Solubility and Metabolic Stability

The MT₂-selective melatonin receptor ligand UCM765 (N-(2-((3-methoxyphenyl)(phenyl)amino)ethyl)acetamide), showed interesting sleep inducing, analgesic and anxiolytic properties in rodents, but suffers from low water solubility and modest metabolic stability. To overcome these limitations, different strategies were investigated, including modification of metabolically liable sites, introduction of hydrophilic substituents and design of more basic derivatives. Thermodynamic solubility, microsomal stability and lipophilicity of new compounds were experimentally evaluated, together with their MT₁ and MT₂ binding affinities. Introduction of a m-hydroxymethyl substituent on the phenyl ring of UCM765 and replacement of the replacement of the N,N-diphenyl-amino scaffold with a N-methyl-N-phenyl-amino one led to highly soluble compounds with good microsomal stability and receptor binding affinity. Docking studies into the receptor crystal structure provided a rationale for their binding affinity. Pharmacokinetic characterization in rats highlighted higher plasma concentrations for the N-methyl-N-phenyl-amino derivative, consistent with its improved microsomal stability and makes this compound worthy of consideration for further pharmacological investigation.     

Optical properties of hybrid T3Pyr/SiO2/3C-SiC nanowires

A new class of nanostructured hybrid materials is developed by direct grafting of a model thiophene-based organic dye on the surface of 3C-SiC/SiO₂ core/shell nanowires. TEM-EDX analysis reveals that the carbon distribution is more spread than it would be, considering only the SiC core size, suggesting a main contribution from C of the oligothiophene framework. Further, the sulfur signal found along the treated wires is not detected in the as-grown samples. In addition, the fluorescent spectra are similar for the functionalized nanostructures and T3Pyr in solution, confirming homogeneous molecule grafting on the nanowire surface. Chemical and luminescence characterizations confirm a homogeneous functionalization of the nanowires. In particular, the fluorophore retains its optical properties after functionalization.     

Zinc supplementation of Friesian cows: Effect on chemical-nutritional composition and aromatic profile of dairy products

Zinc represents an essential microelement for several biochemical mechanisms. The body's inability to store zinc necessarily requires a constant dietary supply to avoid alteration of physiological functions. The aim of the present study was to investigate the effect of dietary enrichment with zinc on chemical-nutritional and aromatic properties of milk and cheese. Thirty commercial dairy cows, balanced for parity, milk production, and days in milk, were randomly assigned to 2 groups. The control group was fed with a conventional complete diet (22 kg of dry matter/animal per day), whereas the experimental group received a daily zinc supplementation of 60 mg per kg of dry complete feed. During the experimental period, the milk yield was monitored and samples of milk and caciotta cheese were collected to obtain information about the chemical-nutritional composition and aromatic profile. Dietary zinc integration did not influence milk yield and composition, but induced a marked reduction of somatic cell count and improved the oxidative stability of ripened caciotta cheese. In both milk and cheese, the experimental group samples were characterized by a lower concentration of saturated fatty acids and an increase in oleic acid, vaccenic acid, and rumenic acid. The aromatic profile of dairy products was also positively affected by dietary zinc intake, with an increase in concentration of carboxylic acids, aldehydes, and esters. The present results suggest a positive role of zinc in improving animal health and nutraceutical properties of milk and corresponding cheese. Taking into account the analysis of volatile compounds, zinc dietary supplementation of dairy cows should contribute to the production of cheeses with interesting organoleptic properties, although more studies are necessary to confirm the consumer acceptability of these changes.     

Double Mutant Cycles as a Tool to Address Folding,Binding, and Allostery

Quantitative measurement of intramolecular and intermolecular interactions in protein structure is an elusive task, not easy to address experimentally. The phenomenon denoted ‘energetic coupling’ describes short- and long-range interactions between two residues in a protein system. A powerful method to identify and quantitatively characterize long-range interactions and allosteric networks in proteins or protein–ligand complexes is called double-mutant cycles analysis. In this review we describe the thermodynamic principles and basic equations that underlie the double mutant cycle methodology, its fields of application and latest employments, and caveats and pitfalls that the experimentalists must consider. In particular, we show how double mutant cycles can be a powerful tool to investigate allosteric mechanisms in protein binding reactions as well as elusive states in protein folding pathways.