Characterization of cocoa liquors by GC-MS and LC-MS/MS: focus on alkylpyrazines and flavanols

Flavor is one of the most important characteristics of chocolate products and is due to a complex volatile fraction, depending both on the cocoa bean genotype and the several processes occurring during chocolate production (fermentation, drying, roasting and conching). Alkylpyrazines are among the most studied volatiles, being one of the main classes of odorant compounds in cocoa products. In this work, a mass spectrometric approach was used for the comparison of cocoa liquors from different countries. A headspace solid-phase microextraction gas chromatography-mass spectrometry method was developed for the qualitative study of the volatile fraction; the standard addition method was then used for the quantitative determination of five pyrazines (2-methylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine and tetramethylpyrazine). Satisfactory figures of merit were obtained: Limits of quantitation were in the range 0.1-2.7?ng/g; repeatability and reproducibility varied between 3% and 7% and between 8% and 14%, respectively. The total content of the pyrazines was remarkably different in the considered samples, ranging from 99 to 708?ng/g. Tetramethylpyrazine showed the highest concentration in all samples, with a maximum value of 585?ng/g. A preliminary study was also performed on the nonvolatile fraction using LC-MS/MS, identifying some flavanols such as catechin, epicatechin and procyanidins. Copyright ? 2012 John Wiley & Sons, Ltd.     

High-throughput tools for the study of protein-nanostructured surface interaction

The aim of this review is to describe and to analyze the ingredients that are necessary in order to develop a robust and effective experimental approach for the high-throughput characterization of protein-nanostructured surface interaction. In the first part of this paper we review the nanostructured surface synthesis methods that are potentially able to create nanostructured inorganic surface libraries. In the second part, we address another fundamental aspect consisting in the availability of high-throughput proteins detection methods. We describe in details new emerging analytical tools compatible with nanostructured surfaces, analyzing different possible strategies, depending on the objective of the experiment and on the library format.     

Drug–Polymer Interactions in Hydrogel‐based Drug‐Delivery Systems: An Experimental and Theoretical Study

In drug‐delivery systems, drug transport is a key step, but the interpretation of the transport mechanism is still controversial. Here, we investigated a promising hydrogel library loaded with the anticonvulsant drug ethosuximide (ESM). The self‐diffusion coefficient of ESM was measured using two methods: a direct and advanced measurement with a pulsed field gradient spin‐echo (PFGSE) method, using an NMR spectrometer equipped with high‐resolution magic angle spinning (HR‐MAS) probe, and an indirect one based on fitting in vitro drug‐delivery data. Starting from the experimental data a mathematical model without fitted parameters was developed and all the phenomena involved, that is, adsorption and diffusion, were considered. At low drug concentrations, adsorption prevails and consequently the diffusivity in the gels is lower than that in water. At high drug concentrations, where all adsorption sites are saturated, the diffusion in the gels is similar to that in a water solution. This study may pave the way for better device design.     

Harnessing the Liquid‐Phase Exfoliation of Graphene Using Aliphatic Compounds: A Supramolecular Approach

The technological exploitation of the extraordinary properties of graphene relies on the ability to achieve full control over the production of a high‐quality material and its processing by up‐scalable approaches in order to fabricate large‐area films with single‐layer or a few atomic‐layer thickness, which might be integrated in working devices. A simple method is reported for producing homogenous dispersions of unfunctionalized and non‐oxidized graphene nanosheets in N‐methyl‐2‐pyrrolidone (NMP) by using simple molecular modules, which act as dispersion‐stabilizing compounds during the liquid‐phase exfoliation (LPE) process, leading to an increase in the concentration of graphene in dispersions. The LPE‐processed graphene dispersion was shown to be a conductive ink. This approach opens up new avenues for the technological applications of this graphene ink as low‐cost electrodes and conducting nanocomposite for electronics.     

Reactivity of rimsulfuron in newly formed inclusion combinations by using cyclodextrin and zeolite

Extending our investigations on environment protection by agrochemicals diffusion and accumulation, newly formed inclusion combinations of rimsulfuron into zeolite-NaY (Z-NaY) and β-cyclodextrin (β-CD) were studied and compared. The reactivity of the included herbicide under UV-irradiation and in the dark was assessed. Many guest/host ratios were tested: the best results were found using 3?g (6.953?mmol) of rimsulfuron per kilogram of zeolite, with 80% inclusion success (5.562?mmol?kg^?1), and a 1:?2 molar ratio, 190?g of rimsulfuron per kilogram of β-CD with 58% inclusion success. The herbicide Z-NaY-combined underwent rapid and effective (halflive 2–7?h) degradation either catalytically or photochemically, giving rise to different identified by-products. On the contrary, β-CD was able to protect rimsulfuron totally both in the dark and under 24-h direct UV irradiation. On the basis of the obtained results, a different utilization of the two inclusion materials has been suggested.     

Nitrogen‐doped Carbon–CoOx Nanohybrids: A Precious Metal Free Cathode that Exceeds 1.0 W cm−2 Peak Power and 100 h Life in Anion‐Exchange Membrane Fuel Cells

Efficient and durable nonprecious metal electrocatalysts for the oxygen reduction (ORR) are highly desirable for several electrochemical devices, including anion exchange membrane fuel cells (AEMFCs). Here, a 2D planar electrocatalyst with CoO_x embedded in nitrogen‐doped graphitic carbon (N‐C‐CoO_x) was created through the direct pyrolysis of a metal–organic complex with a NaCl template. The N‐C‐CoO_x catalyst showed high ORR activity, indicated by excellent half‐wave (0.84 V vs. RHE) and onset (1.01 V vs. RHE) potentials. This high intrinsic activity was also observed in operating AEMFCs where the kinetic current was 100 mA cm^?2 at 0.85 V. When paired with a radiation‐grafted ETFE powder ionomer, the N‐C‐CoO_x AEMFC cathode was able to achieve extremely high peak power density (1.05 W cm^?2) and mass transport limited current (3 A cm^?2) for a precious metal free electrode. The N‐C‐CoO_x cathode also showed good stability over 100 hours of operation with a voltage decay of only 15 % at 600 mA cm^?2 under H₂/air (CO₂‐free) reacting gas feeds. The N‐C‐CoO_x cathode catalyst was also paired with a very low loading PtRu/C anode catalyst, to create AEMFCs with a total PGM loading of only 0.10 mg_Pt‐Ru cm^?2 capable of achieving 7.4 W mg^?1_PGM as well as supporting a current of 0.7 A cm^?2 at 0.6 V with H₂/air (CO₂ free)—creating a cell that was able to meet the 2019 U.S. Department of Energy initial performance target of 0.6 V at 0.6 A cm^?2 under H₂/air with a PGM loading <0.125 mg cm^?2 with AEMFCs for the first time.     

Artificial Molecular Ratchets: Tools Enabling Endergonic Processes

Non-equilibrium chemical systems underpin multiple domains of contemporary interest, including supramolecular chemistry, molecular machines, systems chemistry, prebiotic chemistry, and energy transduction. Experimental chemists are now pioneering the realization of artificial systems that can harvest energy away from equilibrium. In this tutorial Review, we provide an overview of artificial molecular ratchets: the chemical mechanisms enabling energy absorption from the environment. By focusing on the mechanism type—rather than the application domain or energy source—we offer a unifying picture of seemingly disparate phenomena, which we hope will foster progress in this fascinating domain of science.     

Deformation and failure kinetics of iPP polymorphs

In this study, the mechanical performance of the different polymorphs of isotactic polypropylene, typically present in iPP crystallized under industrial processing conditions, is assessed. Different preparation strategies were used to obtain samples consisting of almost solely α, β, or γ crystals. X‐Ray measurements were used to validate that the desired phase was obtained. The intrinsic true stress ‐ true strain response of all individual phases was measured in uniaxial compression at several strain rates (deformation kinetics). Moreover, measurements were performed over a wide temperature range, covering the window in between the glass transition and the melting temperature. The relation between obtained yield stress and the strain rate is described with a modification of the Ree‐Eyring model. Differences and similarities in the deformation kinetics of the different phases are presented and discussed. Furthermore, the presence of three deformation processes, acting in parallel, is revealed. The Ree‐Eyring equation enables lifetime prediction for given thermal and mechanical conditions. These predictions were experimentally validated using constant load tests in uniaxial compression. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 729–747