Attempted Oxidative Deamination of N-Deacetylcolchicinoids with 3,5-Di(tert-butyl)-1,2-benzoquinone: Synthesis of 2H-1,4-Benzoxazine-Type Adducts

In an attempt to use 3,5-di(tert-butyl)-1,2-benzoquinone for the oxidative deamination of N-deacetylcolchicine ( 4 ) and N-deacetylthiocolchicine (=N-deacetyl-10-demethoxy-10-(methylthio)colchicine; 5 ) to give the corresponding ketones 2 and 3 , the 2H-1,4-benzoxazine-type adducts 8 / 9 and 11 / 12 , respectively, were formed instead, showing a new and unexpected behavior of Corey's reagent. The adducts were separated and spectroscopically characterized, and a plausible scheme of formation is reported.     

Dimethyl carbonate as a novel methylating reagent for fatty acids in analytical pyrolysis

Dimethyl carbonate (DMC) was investigated as a mild, harmless and odorless reagent for pyrolytic methylation of fatty acids. Soybean oil was selected as test material for its high content of (poly)unsaturated fatty acids. Pyrolyses were performed at 500, 700 and 900 degrees C by means of a heated platinum filament pyrolyser on-line and off-line to the GC-MS apparatus. Methyl esters of palmitic, linoleic, oleic and stearic acid were formed as prominent products from off-line pyrolysis of soybean oil in the presence of DMC and zeolite 13X. Fatty acid methyl esters (FAMEs) were not observed at important levels in the absence of zeolite, while on-line Py-GC-MS experiments resulted principally in the formation of free fatty acids and hydrocarbons. The FAME profiles obtained from the DMC/zeolite off-line pyrolysis were compared to those resulting from tetramethylammonium hydroxide (TMAH) thermochemolysis and BF3-methanol procedure. The observed differences between pyrolysis and methanolysis methods were principally attributed to the thermal degradation of unsaturated fatty acids. The effectiveness of the DMC/zeolite pyrolytic methylation was further demonstrated by the analysis of tripalmitine and soybean seeds.     

Quantum dots-based reverse phase protein microarray

CdSe nanocrystals, also called quantum dots (Qdots) are a novel class of fluorophores, which have a diameter of a few nanometers and possess high quantum yield, tunable emission wavelength and photostability. They are an attractive alternative to conventional fluorescent dyes. Quantum dots can be silanized to be soluble in aqueous solution under biological conditions, and thus be used in bio-detection. In this study, we established a novel Qdot-based technology platform that can perform accurate and reproducible quantification of protein concentration in a crude cell lysate background. Protein lysates have been spiked with a target protein, and a dilution series of the cell lysate with a dynamic range of three orders of magnitude has been used for this proof-of-concept study. The dilution series has been spotted in microarray format, and protein detection has been achieved with a sensitivity that is at least comparable to standard commercial assays, which are based on horseradish peroxidase (HRP)-catalyzed diaminobenzidine (DAB) chromogenesis. The data obtained through the Qdot method has shown a close linear correlation between relative fluorescence unit and relative protein concentration. The Qdot results are in almost complete agreement with data we obtained with the well-established HRP-DAB colorimetric array (R² = 0.986). This suggests that Qdots can be used for protein quantification in microarray format, using the platform presented here.     

Acid-base equilibria in organic solvents : Part 2. Cyclic voltammetry in the study of hydrogen-bond formation

The cyclic voltammetric technique is used to study hydrogen-bond formation in some polar organic solvents (S) of electroanalytical interest (1,2-dimethoxy, tetrahydrofuran, dimethylformamide, dimethyl sulphoxide and pyridine). The cathodic shift of the proton reduction caused by stepwise addition of the solvent investigated to a solution of anhydrous perchloric acid in acetonitrile is utilized. The theoretical treatment applied produced evidence that HS⁺ and HS⁺₂ are the only acidic species involved, so that the relevant formation constants can be evaluated. The data obtained mostly compare well with those available in the literature. The features that condition the tendency to hydrogen-bonding and the effect of hydrogen bonding on solvent basicity are discussed.     

Micro-Mesoporous Carbons from Cyclodextrin Nanosponges Enabling High-Capacity Silicon Anodes and Sulfur Cathodes for Lithiated Si-S Batteries

Manufactured globally on industrial scale, cyclodextrins (CD) are cyclic oligosaccharides produced by enzymatic conversion of starch. Their typical structure of truncated cone can host a wide variety of guest molecules to create inclusion complexes; indeed, we daily use CD as unseen components of food, cosmetics, textiles and pharmaceutical excipients. The synthesis of active material composites from CD resources can enable or enlarge the effective utilization of these products in the battery industry with some economical as well as environmental benefits. New and simple strategies are here presented for the synthesis of nanostructured silicon and sulfur composite materials with carbonized hyper cross-linked CD (nanosponges) that show satisfactory performance as high-capacity electrodes. For the sulfur cathode, the mesoporous carbon host limits polysulfide dissolution and shuttle effects and guarantees stable cycling performance. The embedding of silicon nanoparticles into the carbonized nanosponge allows to achieve high capacity and excellent cycling performance. Moreover, due to the high surface area of the silicon composite, the characteristics at the electrode/electrolyte interface dominate the overall electrochemical reversibility, opening a detailed analysis on the behavior of the material in different electrolytes. We show that the use of commercial LP30 electrolyte causes a larger capacity fade, and this is associated with different solid electrolyte interface layer formation and it is also demonstrated that fluoroethylene carbonate addition can significantly increase the capacity retention and the overall performance of our nanostructured Si/C composite in both ether-based and LP30 electrolytes. As a result, an integration of the Si/C and S/C composites is proposed to achieve a complete lithiated Si−S cell.     

Selective Detection of Mg2+ for Sensing Applications in Drinking Water

A new series of ligands containing the 2-(2-hydroxy-3- naphthyl)-4-methylbenzoxazole (HNBO) fluorophore showed selectivity for Mg²⁺ ions, without the interference of Ca²⁺. The most promising representative L3 resulted the best performing sensor for Mg²⁺ both in solution and embedded in an all-solid-state optode, especially towards real samples of drinkable water.     

Glycidol syntheses and valorizations: Boosting the glycerol biorefinery

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Ozone-based electrochemical advanced oxidation processes

Novel processes have recently been developed that provide for the enhancement of ozonation through combination with electrochemical treatments. These are processes that can be included among those defined as advanced oxidation processes as they proceed via electrogeneration of highly oxidizing radical species.These processes are generally carried out by sparging ozone in both divided and undivided electrochemical cells in order to promote its decomposition through different mechanisms, depending on the electrode materials adopted, and in some cases still debated.This mini review presents the most recent advances in the field of electrochemically assisted ozonation.In particular, the first section is focused on the process known as electroperoxone (EP) where the ozone decomposition is enhanced by the adoption of carbon-based cathodes, due to the electrogeneration of hydrogen peroxide, while the second section is focused on the process that implies ozonation in a cell adopting metal-based cathodes.     

Organic‐acid mediated bulk polymerization of ε‐caprolactam and its copolymerization with ε‐caprolactone

Polyamides (PA) constitute one of the most important classes of polymeric materials and have gained strong position in different areas, such as textiles, fibers, and construction materials. Whereas most PA are synthesized by step‐growth polycondensation, PA 6 is synthesized by ring opening polymerization (ROP) of ε‐caprolactam (ε‐CLa). The most popular ROP methods involve the use of alkaline metal catalyst difficult to handle at large scale. In this article, we propose the use of organic acids for the ROP of ε‐CLa in bulk at 180 °C (below the polymer's melting point). Among evaluated organic acids, sulfonic acids were found to be the most effective for the polymerization of ε‐CLa , being the Brønsted acid ionic liquid: 1‐(4‐sulfobutyl)?3‐methylimidazolium hydrogen sulfate the most suitable due to its higher thermal stability. End‐group analysis by ¹H nuclear magnetic resonance and model reactions provided mechanistic insights and suggested that the catalytic activity of sulfonic acids was a function of not only the acid strength, but of the nucleophilic character of conjugate base as well. Finally, the ability of sulfonic acid to promote the copolymerization of ε‐CLa and ε‐caprolactone is demonstrated. As a result, poly(ε‐caprolactam‐co‐ε‐caprolactone) copolymers with considerably randomness are obtained. This benign route allows the synthesis of poly(ester amide)s with different thermal and mechanical properties. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2394–2402     

Effect of limonene on the frontal ring opening metathesis polymerization of dicyclopentadiene

The frontal ring opening metathesis polymerization (FROMP) of dicyclopentadiene (DCPD) in the presence of limonene, using second generation Grubbs’ catalysts, is reported. The effect of limonene on the amount of catalyst and the typical frontal polymerization parameters, as maximum temperature (T_max) and velocity of the front (V_f), is studied. In addition, the influence of limonene on the mechanical properties of the polymeric samples is reported. Finally, a deep study on the swelling properties of polymers is done. It has been demonstrated that limonene acts as both inhibitor and solvent of the catalyst. The T_max, V_f, T_g, and Young modulus values decrease as the amount of limonene increases, and the polymer samples swell in THF depending on the amount of limonene. All results indicate that the limonene addition on FROMP of results in advantages on the polymerization reaction and its parameters and on the final polymer properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 63–68