N.M.R. Spectra of the Fuchs0Nes: Structure of Naphthofuchsone

Following the initial synthesis of the fuchsones¹I, (α, η -diphenyl-1,4-benzoquinone methides), numerous substituted members of this series have been described by workers interested in triphenylmethane dyes. The fuchsones have been synthesized by the sulfuric acid condensation of benzilic acid and appropriate phenol¹, by dehydration of 4-hydroxytriphenylcarbinol², by oxidation 4-hydroxytri-phenylmethane and by photochemically induced reactions benzophenones with 2,6-dialkylphenols⁴.     

Mild Bioconjugation Through the Oxidative Coupling of ortho‐Aminophenols and Anilines with Ferricyanide

Using a small‐molecule‐based screen, ferricyanide was identified as a mild and efficient oxidant for the coupling of anilines and o‐aminophenols on protein substrates. This reaction is compatible with thiols and 1,2‐diols, allowing its use in the creation of complex bioconjugates for use in biotechnology and materials applications.     

Recent developments in the synthesis and functionalization of conducting poly(thiophenes)

The mechanism of the electropolymerization of thiophene derivatives has been investigated by varying the electrosynthesis conditions and the monomer structure. The results of these analyses led to the definition of optimized electrosynthesis conditions allowing the control of the electrical and electrochemical properties of poly(thiophenes). On the basis of these results, the properties of these polymers have been modified by means of a new one-step electrosynthesis of conducting composite materials and by the direct electropolymerization of tailor-made functionalized monomers. For this purpose, the steric conditions associated to the various possibilities of covalent derivatization have been analyzed, leading to the definition of a “functionalization space”, compatible with the preservation of high conductivity and electrochemical reversibility in the resulting polymers. This concept has been applied to the synthesis of highly conducting chiral poly(thiophenes) on which an effect of enantioselective molecular recognition has been demonstrated for the first time.     

The Varietal Influence of Flavour Precursors from Grape Marc on Monoterpene and C13-Norisoprenoid Profiles in Wine as Determined by Membrane-Assisted Solvent Extraction (MASE) GC-MS

The winemaking by-product grape marc (syn. pomace) contains significant quantities of latent flavour in the form of flavour precursors which can be extracted and used to modulate the volatile composition of wine via chemical hydrolysis. Varietal differences in grapes are widely known with respect to their monoterpene content, and this work aimed to extend this knowledge into differences due to cultivar in volatiles derived from marc precursors following wine-like storage conditions. Marc extracts were produced from floral and non-floral grape lots on a laboratory-scale and from Muscat Gordo Blanco marc on a winery -scale, added to a base white wine for storage over five to six months, before being assessed using a newly developed membrane-assisted solvent extraction gas chromatography-mass spectrometry (GC-MS) method. The geraniol glucoside content of the marc extracts was higher than that of juices produced from each grape lot. In all wines with added marc extract from a floral variety, geraniol glucoside concentration increased by around 150–200%, with increases also observed for non-floral varieties. The relative volatile profile from extracts of the floral varieties was similar but had varied absolute concentrations. In summary, while varietally pure extracts would provide the greatest control over flavour outcomes when used in winemaking, aggregated marc parcels from floral cultivars may provide a mechanism to simplify the production logistics of latent flavour extracts for use in the wine sector.     

Astringency Sensitivity to Tannic Acid: Effect of Ageing and Saliva

Astringency is an important sensory characteristic of food and beverages containing polyphenols. However, astringency perception in elderly people has not been previously documented. The aim of the present work was to evaluate sensitivity to astringency as a function of age, salivary flow and protein amount. Fifty-four panellists, including 30 elderly people (age = 75 ± 4.2 years) and 24 young people (age = 29.4 ± 3.8 years), participated in this study. Astringency sensitivity was evaluated by the 2-alternative forced choice (2-AFC) procedure using tannic acid solutions. Whole saliva was collected for 5 min before and after the sensory tests. The results showed that the astringency threshold was significantly higher in the elderly group than the young group. No correlation was observed between the salivary protein amount and threshold value. However, a negative correlation between salivary flow and threshold was observed in the young group only. These results showed a difference in oral astringency perception as a function of age. This difference can be linked to salivary properties that differ as a function of age.     

A high-throughput search for direct methanol fuel cell anode electrocatalysts of type PtxBiyPbz

We used a high-throughput method to screen for direct methanol fuel cell anode electrocatalysts in the Pt-Bi-Pb system. Previous studies showed that PtBi and PtPb (both NiAs structure type) were active electrocatalysts for the oxidation of formic acid, but only PtPb was active in oxidizing methanol. We synthesized thin films with continuous composition spreads of the three elements by magnetron sputtering at deposition temperatures from ambient to 510 °C. A fluorescence method was then used to identify compositions that were active toward methanol oxidation. Only films deposited between temperatures of 160 and 400 °C showed electrocatalytic activity. The areas that were active for methanol oxidation showed predominantly the NiAs structure type according to XRD, with optimal activity for compositions near PtBi_0.01Pb_0.53.     

Modeling of MIG/MAG welding with experimental validation using an active contour algorithm applied on high speed movies

This paper investigates some issues in physical modeling of metal inert gas/metal active gas (MIG/MAG) welding process in the short arc mode. In this mode, a metal supply is molten in the arc state and then transferred to the weld pool during the short-circuit state. A hybrid model having two distinct continuous states whose switchings are controlled by two guard conditions is proposed. Due to the complexity of the physical phenomena involved in the welding process, simplifications are used to obtain a model accounting for the main physical contributions but simple enough to yield an efficient, fast and numerically tractable simulator which can be used intensively for evaluating different control strategies. In an attempt to validate the proposed model, different measurements have been made including supply voltage and current sampled synchronously with high speed digital video. In order to extract some relevant quantities representative of the metal transfer from image sequences, an active contour algorithm is developed and tested. The effectiveness of the proposed model in the prediction of major tendencies of a welding process, especially in the arc state, is shown using experimental data. Some limitations of the model during the metal transfer are also stressed and possible remedies are then proposed.     

The use of Raman microscopy and laser desorption ionization mass spectrometry in the examination of synthetic organic pigments in modern works of art

Synthetic organic pigments are widely used in modern and contemporary works of art. They have been examined by a variety of techniques including spectroscopic methods such as Fourier transform infrared spectroscopy, Raman, and X‐ray powder diffraction as well as chromatographic or mass spectrometric techniques such as pyrolysis‐gas chromatography/mass spectrometry and laser desorption ionization mass spectrometry (LDI–MS). Often, a combination of techniques has been used to examine these pigments. This paper describes use of Raman spectroscopy to create a database of colorants including two pigments not previously reported, PO1 and PO2. Then, using Raman spectroscopy in combination with LDI–MS, samples from modern works of art by artists including Mark Rothko, Barnett Newman, and José de Rivera were examined in order to identify the pigments present. One finding was that Rothko used a variety of red pigments over the course of his career including PR11 which has not been previously reported in artwork, and PO2 found with its positional isomer PR1. Knowledge of the colorants serves to inform conservators about display and treatment decisions. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.     

Accuracy and variability of acoustic measures of voicing onset

Five commonly used methods for determining the onset of voicing of syllable-initial stop consonants were compared. The speech and glottal activity of 16 native speakers of Cantonese with normal voice quality were investigated during the production of consonant vowel (CV) syllables in Cantonese. Syllables consisted of the initial consonants /ph/, /th/, /kh/, /p/, /t/, and /k/ followed by the vowel /a/. All syllables had a high level tone, and were all real words in Cantonese. Measurements of voicing onset were made based on the onset of periodicity in the acoustic waveform, and on spectrographic measures of the onset of a voicing bar (f0), the onset of the first formant (F1), second formant (F2), and third formant (F3). These measurements were then compared against the onset of glottal opening as determined by electroglottography. Both accuracy and variability of each measure were calculated. Results suggest that the presence of aspiration in a syllable decreased the accuracy and increased the variability of spectrogram-based measurements, but did not strongly affect measurements made from the acoustic waveform. Overall, the acoustic waveform provided the most accurate estimate of voicing onset; measurements made from the amplitude waveform were also the least variable of the five measures. These results can be explained as a consequence of differences in spectral tilt of the voicing source in breathy versus modal phonation.     

Ionic liquid enhanced magnesium-based polymer electrolytes for electrical double-layer capacitors

This paper describes the preparation and characterization of poly(vinyl alcohol) (PVA)-added ionic liquid-based ion conductors. The polymer electrolyte is incorporated with magnesium triflate [Mg(CF₃SO₃)₂ or MgTf] as salt and 1-butyl-3-methylimidazolium bromide (BmImBr) as ionic liquid. Differential scanning calorimetry (DSC) is carried out to investigate the glass transition temperature which is used to study the plasticizing effect of the ionic liquid. The highest conducting ionic liquid-based polymer electrolyte is used to fabricate electrical double-layer capacitors (EDLC). The electrochemical potential window is evaluated using linear sweep voltammetry (LSV). The electrochemical capacitance of the EDLC is evaluated through cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD). The electrochemical potential window of ionic liquid-added polymer electrolyte is extended from 1.35 to 2.6 V. Cyclic voltammetry (CV) proves the improvement in specific capacitance of the electrical double-layer capacitors (EDLCs) containing ionic liquid-added polymer electrolyte.