Anthocyanin profile of red fruits and black carrot juices,purees and concentrates by HPLC‐DAD‐ESI/MS‐QTOF

A fast and reliable method for anthocyanin extraction and identification by HPLC‐DAD‐ESI/MS‐QTOF was used to analyse the anthocyanin composition of commercial red fruit juices (blackberry, redcurrant and pomegranate), purees (strawberry, cherry and raspberry) and concentrates (elderberry, blueberry and red grape). The anthocyanin profile of black carrot juice is also reported. The extraction and analysis method allowed us to detect and quantify a wide range of individual anthocyanins in a simple and rapid way. Pelargonidin‐3‐glucoside was detected in redcurrant for the first time and petunidin‐3‐galactoside quantified for the first time in blueberries. Considering the health benefits that have been associated with anthocyanin consumption, all these fruit and vegetables processed products could appear as a good source of this group of phytochemical compounds for their direct consumption or their use as ingredients for the design of new food product or food supplements.     

In vitro digestibility of phenolic compounds from edible fruits: could it be explained by chemometrics?

The health benefits of phenolic compounds depend on the ingested amount, molecular diversity and gastrointestinal digestibility. The phenolic profile of eight fruits (blackberry, blueberry, strawberry, raspberry, mulberry, pomegranate, green and red globe grapes) was chemometrically associated with their in vitro digestibility (oral, gastric, intestinal). Extractable phenols, flavonoids and anthocyanins strongly correlated with each other (r ≥ 0.84), proanthocyanidins with anthocyanins (r = 0.62) and hydrolysable phenols with both extractable phenols (r = 0.45) and proanthocyanidins (r = ?0.54). Two principal components explained 93% of the variance [61% (free‐phenols), 32% (bounded‐phenols)], and four clusters were confirmed by hierarchical analysis, based in their phenolic richness (CLT 1‐4: low to high) and molecular diversity. In vitro digestibility of extractable phenols and flavonoids was blackberry (CLT‐4)> raspberry (CLT‐2)> red grape (CLT‐1) related to their phenolic richness (r ≥ 0.96; P < 0.001), but anthocyanins’ digestibility was pH‐dependent. Chemometrics is useful to predict the in vitro digestibility of phenolic compounds in the assayed fruits.     

Experimental evaluation of geosynthetics as reinforcement for shotcrete

One of the commonly used stabilization systems for rock tunnels is shotcrete. This fine aggregate mortar is usually reinforced for improving its tensile and shear strength. In deep tunnels, its capacity to absorb energy has been recently considered for design purposes, as large displacements of the wall are expected. Two of the most used materials of reinforcement are steel welded-wire mesh and fibers (steel or polypropylene) in the shotcrete mix. This study presents the results and discussion of an experimental test program conducted to obtain the load-deformation curves of reinforced shotcrete, according to ASTM C 1550, using geosynthetics grids and geotextiles as alternative reinforcement materials. In addition, plain shotcrete and steel welded-wire mesh reinforced shotcrete specimens are also considered in the experimental program as benchmark cases. The experimental results are analyzed in terms of maximum strength and toughness. Results show that the use of geosynthetics as a reinforcement material is a promising alternative to obtain shotcrete with energy absorption capacity comparable with the most common reinforcement materials used.     

Dynamic affinity-based classification of multi-class imbalanced data with one-versus-one decomposition: a fuzzy rough set approach

Although the relevance problem in recommender systems, which typically refers to the similarity between the preference of the user and the items the system recommends, has been well studied, the issue of making recommendations in right orders has barely been mentioned before. The order defines the way in which items should be better consumed in relation to each other. The analysis of real-world data sets demonstrates strong item consumption patterns in the degree of order. In this paper, we propose a novel method to tackle the right-order recommendation problem based on a graph structure that incorporates the item consumption orders. The proposed method can combine relevance and order effects in recommendations. We attempt to recommend the relevant items in the consecutive steps within a user session so that the user’s selected items in the consecutive steps can be stringed together in a right order. The experimental evaluation conducted on three real-world data sets shows that the recommendation accuracy is improved by considering item consumption orders compared with the baseline recommendation methods. In addition, the study on right-order recommendation contributes to the exploration on recommendation appropriateness besides relevance.     

Synthesis and characterization of poly (styrene‐b‐[(butadiene)1−x‐(ethylene‐co‐butylene)x] ‐b‐styrene) star‐like molecular polymers produced by partial hydrogenation of SBS

This article reports the synthesis and characterization of four arm star‐shaped poly(styrene‐b‐[(butadiene)_1?x‐(ethylene‐co‐butylene)_x]‐b‐styrene) (SBEBS) copolymers. A series of SBEBS copolymers with different compositions of the elastomeric block were produced by hydrogenating a given poly(styrene‐b‐butadiene‐b‐styrene) (SBS) copolymer using a catalyst prepared from bis(η⁵‐cyclopentadienyl)titanium(IV) dichloride and n‐butyllithium. The characterization was accomplished by proton nuclear magnetic resonance spectroscopy (¹H NMR), infrared spectroscopy (FTIR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). The results indicate that there is a selective saturation of the polybutadiene block over the polystyrene block; this selectivity was determined by the Ti/Li molar ratio and the concentration of Ti. It was observed that the saturation rate of the 1,2‐vinyl was higher than that of the 1,4‐trans and 1,4‐cis poly(butadiene)‐b isomers. The DSC and DMA results indicate that the degree of hydrogenation had a profound effect on the polymer's relaxation behavior. All samples exhibited a biphasic system behavior with two distinct transitions corresponding to the elastomeric and polystyrene blocks. SBEBS copolymers with higher saturation levels (>33%) exhibited a crystalline character. The TGA results indicated a characteristic weight loss temperature in all samples, with slightly higher thermal degradation stabilities in the materials with higher degrees of saturation. POLYM. ENG. SCI., 54:2332–2344, 2014. © 2013 Society of Plastics Engineers     

Novel Tacrine‐Grafted Ugi Adducts as Multipotent Anti‐Alzheimer Drugs: A Synthetic Renewal in Tacrine–Ferulic Acid Hybrids

Herein we describe the design, multicomponent synthesis, and biological, molecular modeling and ADMET studies, as well as in vitro PAMPA‐blood–brain barrier (BBB) analysis of new tacrine–ferulic acid hybrids (TFAHs). We identified (E)‐3‐(hydroxy‐3‐methoxyphenyl)‐N‐{8[(7‐methoxy‐1,2,3,4‐tetrahydroacridin‐9‐yl)amino]octyl}‐N‐[2‐(naphthalen‐2‐ylamino)2‐oxoethyl]acrylamide (TFAH 10 n ) as a particularly interesting multipotent compound that shows moderate and completely selective inhibition of human butyrylcholinesterase (IC₅₀=68.2 nM ), strong antioxidant activity (4.29 equiv trolox in an oxygen radical absorbance capacity (ORAC) assay), and good β‐amyloid (Aβ) anti‐aggregation properties (65.6 % at 1:1 ratio); moreover, it is able to permeate central nervous system (CNS) tissues, as determined by PAMPA‐BBB assay. Notably, even when tested at very high concentrations, TFAH 10 n easily surpasses the other TFAHs in hepatotoxicity profiling (59.4 % cell viability at 1000 μM ), affording good neuroprotection against toxic insults such as Aβ_1–40, Aβ_1–42, H₂O₂, and oligomycin A/rotenone on SH‐SY5Y cells, at 1 μM . The results reported herein support the development of new multipotent TFAH derivatives as potential drugs for the treatment of Alzheimer′s disease.     

A New View of Relationships of the N–N Bond Dissociation Energies of Cyclic Nitramines. Part II. Relationships with Impact Sensitivity

The values of bond dissociation energies, BDE, of the weakest N–N bonds and total energies, E_total, of molecules have been calculated for 14 cyclic nitramines by means of the UB3LYP/6-31G? and UB3LYP/6-31 + G? // PM3 methods. The relationships found between the BDE values and logarithms of impact sensitivity of these nitramines, expressed as drop energy, E_dr, are not unambiguous. Replacement of these BDE values by the BDE/E_total ratio has not resulted in any simplification of the said relationships, but their quality improved, particularly with application of the UB3LYP/6-31 + G? // PM3 (UHF) method. The reason of ambiguity of the relationships found mainly lies in real conformation of the respective molecules and intermolecular force effects in real molecular crystals, which are included in neither of the two calculation methods.     

Correlation of film structure and molecular oxygen reduction at nitrogen doped amorphous carbon thin film electrochemical electrodes

Nitrogen doped amorphous carbon (a-C:N) thin film electrodes with a range of film structures have been deposited using a filtered cathodic vacuum arc system. The correlation between film structure and electro-reduction of molecular oxygen in aqueous media at the electrodes has been explored. In aqueous 0.1 M NaOH, dioxygen reduction is inhibited at all the a-C:N electrodes compared with that at glassy carbon electrodes. The potential of the dioxygen reduction current peak shifts negatively at a-C:N electrodes as the sp³ C fraction in the a-C:N materials increases, while the current peak height decreases simultaneously. The a-C:N electrodes possess high sensitivity for investigating the mechanism of dioxygen reduction. It was found that the catalytic H₂O₂ reduction to H₂O on carbon materials is attributed to oxygen species at sp² C sites.     

Vinylene-linked pyridine-pyrrole donor–acceptor conjugated polymers

Vinylene-linked donor–acceptor–donor semiconducting polymers have been prepared by electropolymerization of the new monomers 2,6-bis[(E)-2-(1-methylpyrrol-2-yl)vinyl]pyridine and 2,5-bis[(E)-2-(1-methylpyrrol-2-yl)vinyl]pyridine. The monomers, consisting of two pyrrole donor units and a central pyridine acceptor ring spaced by vinylene links, differ by the substitution pattern around the central pyridine core (2,6 vs. 2,5-substitution). The electropolymerization process is more efficient on the 2,5-derivative. The new polymers show reversible electrochemistry dominated by a strong charge trapping effect. Poly(2,5-bis[(E)-2-(1-methylpyrrol-2-yl)vinyl]pyridine) energy levels closely match those of design rules for optimized polymers in combination with fullerene derivatives in bulk heterojunction solar cells.