Effect of Methyl, Hydroxyl, and Chloro Substituents in Position 3 of 3',4',7-Trihydroxyflavylium: Stability, Kinetics, and Thermodynamics.

The effect of methyl, hydroxyl, and chloride substituents in position 3 of the 3',4',7-trihydroxyflavylium core structure was studied. The stability, relative energy of each of chemical species (thermodynamics), and their rates of interconversion (kinetics) are very dependent on these substituents. By comparing the mole fraction distribution at equilibrium of the three multistate systems with the parent 3',4',7-trihydroxyflavylium, introduction of a methyl substituent in position 3 increases the mole fraction of hemiketal at the expense of the trans-chalcone and increases the hydration rate very significantly; a hydroxyl substituent in position 3 gives rise to a degradation process, as observed in anthocyanidins. In the case of 3-chloro-3',4',7-trihydroxyflavylium, a dramatic increase of the flavylium cation acidity was observed and a photochromic system can be operated upon irradiation of the respective trans-chalcone in 1 m HCl. According to the photochromic response of 3,3',4',7-tetrahydroxyflavylium and 3',4',7-trihydroxyflavylium, some requirements for a good photochromic performance are discussed.

Novel bipyridinium ionic liquids as liquid electrochromic devices.

Novel mono and dialkylbipyridinium (viologens) cations combined with iodide, bromide, or bis(trifluoromethanesulfonyl)imide [NTf2] as anions were developed. Selective alkylation synthetic methodologies were optimized in order to obtain the desired salts in moderate to high yields and higher purities. All prepared mono- and dialkylbipyridinium salts were completely characterized by (1)H, (13)C, and (19)F NMR spectroscopy, Fourier-transform IR spectroscopy, and elemental analysis (in the case of NTf2 salts). Melting points, glass transition temperatures by differential scanning calorimetry (DSC) studies, and decomposition temperatures were also checked for different prepared organic salts. Viscosities at specific temperatures and activation energies were determined by rheological studies (including viscosity dependence with temperature in heating and cooling processes). Electrochemical studies based on cyclic voltammetry (CV), differential pulsed voltammetry (DPV), and square-wave voltammetry (SWV) were performed in order to determine the redox potential as well as evaluate reversibility behavior of the novel bipyridinium salts. As proof of concept, we developed a reversible liquid electrochromic device in the form of a U-tube system, the most promising dialkylbipyridinium-NTf2 ionic liquid being used as the electrochromic material and the room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)-imide [EMIM][NTf2], as a stable and efficient electrolyte.

Improving the Industrial Practice of Reactive Washing of Cork Stoppers Using a Fractional Factorial Design.

Reactive washing (RW) is a key process for disinfecting, purifying, and bleaching of cork stoppers to seal bottles with alcoholic beverages. Excessively severe treatment conditions deteriorate the surface properties of cork stoppers and must be strictly controlled. In this study, the conventional RW of natural cork stoppers was optimized employing a fractional factorial design. The RW variables (H2O2 and NaOH concentrations, oxidation time, and washing water volume) were correlated with the final ISO brightness of the stoppers. A three-level and four-factor fractional factorial design within the response surface methodology approach allowed a quadratic model to predict the process response, where the H2O2 concentration is the variable with the highest response (ISO brightness), followed by the NaOH concentration. The model obtained was validated, allowing the optimization of the process with savings of 37% in the concentration of H2O2 and 33% in the concentration of NaOH and volume of washing water, without deteriorating the final appearance of the stoppers. In addition, the less severe treatment of stoppers under optimized conditions led to less degradation of their surface, thus favoring the receptivity to functional coatings.

Structural Features of Cork Dioxane Lignin from Quercus suber L.

The dioxane lignin was isolated from extractives- and suberin-free cork (Quercus suber L.) by a modified acidolytic procedure and submitted to structural analysis by permanganate oxidation, analytical pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC-MS), liquid- and solid-state nuclear magnetic resonance (NMR) spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. The molecular weight (Mw = 2500 Da) was assessed by size exclusion chromatography (SEC). The results obtained show that the cork lignin is of syringyl (S)/guaiacyl (G) type with a small proportion of p-hydroxyphenyl (H) units (S:G:H molar ratio of 23:72:5). Among a dozen detected lignin structures, those linked by ether bonds, such as ß-O-4' (38 mol %) and 4-O-5' (5 mol %), were the most abundant. The frequency of occurrence of ß-5', ß-ß', 5-5', tetrahydrofuran type, and structures arising from the condensation with concomitant procyanidins was assessed. Ferulates were the only cinnamic structure detected in the cork dioxane lignin.

A Novel Acylated Anthocyanin with a Linear Trisaccharide from Flowers of Convolvulus althaeoides.

An acylated anthocyanin trioside was isolated from pink flowers of Convolvulus althaeoides using a combination of chromatographic techniques. On the basis of MS (MALDI-TOF) and NMR (1H NMR, 1H-1H COSY, 1D TOCSY, HSQC, HMBC, 13C CAPT) its structure was determined as cyanidin 3-O-[6-O-(4-O- (6-O-(E-caffeoyl)-ß-D-glucopyranosyl)-ß-L-rhamnopyranosyl)-ß-D-glucopyranoside]-5-O-ß-D-glucopyranoside. The absolute configuration of the aldose enantiomer moieties was determined from the separation of the corresponding thiazolidine diastereoisomer derivatives by HPLC-DAD. This is a novel trisaccharide within the flavonoids, and the first complete characterization of a linear glucosyl-rhamnosyl-glucoside (4'-glucosylrutinoside) within the anthocyanins. Whilst acylation of rhamnose moieties in position 4 is quite common, the occurrence in anthocyanins of a glycosylated rhamnose is a unique trait. Although many complex anthocyanins have been found amongst the Convolvulaceae, the genus Convolvulus had not yet been surveyed for anthocyanins and thus this account could be of significance within the current chemotaxonomy of this family.

Mimicking Positive and Negative Copigmentation Effects in Anthocyanin Analogues by Host-Guest Interaction with Cucurbit[7]uril and ß-Cyclodextrins.

Copigmentation and the anti-copigmentation effects can be mimicked by the interaction of anthocyanin's model compounds respectively with cucurbit[7]uril (CB7) and ß-cyclodextrin (ß-CD). The complex network of chemical reactions displayed by this family of compounds includes the colored flavylium cation, AH(+), and quinoidal base, A, along with the colorless hemiketal, B, cis-chalcone, Cc, and trans-chalcone, Ct. Whereas AH(+) is stable only at very acidic pH values, the remaining species are formed at slightly acidic and neutral conditions. However, under these conditions, for most of the natural and synthetic flavylium salts, the colorless species predominate (B, Cc, and Ct) at the expense of A. The host CB7 was found to improve the color of solutions in two different ways: first, it stabilizes AH(+) at higher pH values by decreasing its acidity and, second, it enhances the mole fraction of A due to selective complexation of this species in the pH range where the flavylium cation is no longer stable. In contrast, ß-CD increases the acidity of AH(+), favoring the formation of Ct at the expense of all the other multistate species (Basílio et al. New J. Chem. 2013, 37, 3166-3173; Petrov et al. J. Phys. Chem. A 2013, 117, 10692-10701; Gago et al. Dyes Pigments 2014, 110, 106-112; and Lopes-Costa et al. Photochem. Photobiol. Sci. 2014, 13, 1420-1426). Although both hosts have a large effect on the hydration rate and pH domain of the flavylium cation, the effect on the degradation kinetics of anthocyanidins is modest. CB7 decreases the hydration rate and decreases the acid-base (AH(+)/A) equilibrium constant (Ka), leading respectively to a slowing and a speeding of the anthocyanin degradation rate. On the other hand, ß-CD increases the hydration rate but increases Ka, both effects acting in opposite directions.

Synthesis and characterization of luminescent room temperature ionic liquids based on Ru(bpy)(CN)(4)(2-).

Novel ammonium and phosphonium room temperature ionic liquids based on Ru(bpy)(CN)4 as a luminescent complex anion have been developed and characterized by comparative absorption, emission, NMR and electrochemical studies as well as the evaluation of their polarity behaviour.