Structural Determinants of the Selectivity of 3‐Benzyluracil‐1‐acetic Acids toward Human Enzymes Aldose Reductase and AKR1B10

The human enzymes aldose reductase (AR) and AKR1B10 have been thoroughly explored in terms of their roles in diabetes, inflammatory disorders, and cancer. In this study we identified two new lead compounds, 2‐(3‐(4‐chloro‐3‐nitrobenzyl)‐2,4‐dioxo‐3,4‐dihydropyrimidin‐1(2H)‐yl)acetic acid (JF0048, 3 ) and 2‐(2,4‐dioxo‐3‐(2,3,4,5‐tetrabromo‐6‐methoxybenzyl)‐3,4‐dihydropyrimidin‐1(2H)‐yl)acetic acid (JF0049, 4 ), which selectively target these enzymes. Although 3 and 4 share the 3‐benzyluracil‐1‐acetic acid scaffold, they have different substituents in their aryl moieties. Inhibition studies along with thermodynamic and structural characterizations of both enzymes revealed that the chloronitrobenzyl moiety of compound 3 can open the AR specificity pocket but not that of the AKR1B10 cognate. In contrast, the larger atoms at the ortho and/or meta positions of compound 4 prevent the AR specificity pocket from opening due to steric hindrance and provide a tighter fit to the AKR1B10 inhibitor binding pocket, probably enhanced by the displacement of a disordered water molecule trapped in a hydrophobic subpocket, creating an enthalpic signature. Furthermore, this selectivity also occurs in the cell, which enables the development of a more efficient drug design strategy: compound 3 prevents sorbitol accumulation in human retinal ARPE‐19 cells, whereas 4 stops proliferation in human lung cancer NCI‐H460 cells.     

N‐Oligo(3‐hydroxybutyrate)‐functionalized polypyrroles: towards bio‐erodible conducting copolymers

New copolymer materials have been prepared by chemical grafting of oligomeric 3‐hydroxybutyric acid (OHB) onto polypyrrole (PPy) derivatives. The influence of grafting density and molecular weight of OHB brushes on the physicochemical properties of prepared copolymers was investigated. PPy substrates were prepared by FeCl₃‐driven oxidative homopolymerization of N‐(2‐carboxyethyl)pyrrole or its copolymerization with pyrrole. The grafting method employed involved controlled anionic polymerization of β‐butyrolactone on pyrrole‐tethered potassium carboxylate active sites. Obtained PPy‐g‐OHB copolymers of varying grafting density and pendant polyester chain length were characterized and the observed structure–property relationships discussed. The impact of real time exposure to phosphate‐buffered saline environment was investigated and the residue products were characterized. Cross‐correlation of spectroscopic, thermal, electrical and elemental analysis data afforded comprehensive evaluation of the structure of prepared materials and their behaviour in hydrolytic medium. Erosion and degradation pathways have been identified, indicating ways to consciously tailor the physicochemical properties of these new biomimetic materials. © 2016 Society of Chemical Industry     

Influence of Alkaline Additives and Buffers on Mineral Trapping of CO2 under Mild Conditions

Carbon dioxide (CO₂) gas is the main contributor to climate change. CO₂ storage in underground brines and oil‐field brines by mineral trapping has been considered as a promising alternative in order to reduce CO₂ emissions. However, permanent storage of CO₂ in stable carbonate minerals is greatly dependent on brine pH, being favored over an alkaline pH. The effect of alkaline additives (NaOH, KOH, CaO) and buffer solutions (NaHCO₃/NaOH, Na₂HPO₄/NaOH, NH₄Cl/NH₄OH) on the mineral trapping of CO₂ under mild conditions using a synthetic brine is investigated. The results indicate that both NaOH+NH₄Cl/NH₄OH and KOH+NH₄Cl/NH₄OH mixtures promote precipitation mainly of calcium carbonate (CaCO₃).     

On the Surface Nature of Bimetallic PdZn Particles Supported on a ZnO–CeO<Subscript>2</Subscript> Nanocomposite for the Methanol Steam Reforming Reaction

CO adsorption—as a molecular probe—was studied by transmission IR spectroscopy on pre-reduced Pd and bimetallic PdZn nanoparticles. Palladium was supported (2 wt% Pd) on pure CeO₂, ZnO and a ZnO–CeO₂ composite (atomic ratio Zn:Ce?=?1:2). The Pd 3d_5/2 binding energy shift, together with the formation of metallic zinc were consistent with the development of a PdZn alloy over the zinc-containing supports at increasing reduction temperature, as revealed by XPS. Following H₂ reduction at 623 K the bimetallic particles showed only linear CO adsorption (CO_L) at initial contact time (10 Torr CO, 298 K), giving rise to a convoluted IR band ascribed to different Pd sites, where it was assumed that the Pd–Pd distances were larger than for pure Pd crystallites, indicating the presence of a PdZn alloyed surface. However, for longer exposure time to CO and/or higher superimposed pressure, the appearance of bridge and hollow coordinated CO (CO_B and CO_H, respectively) on the Pd sites suggested the degradation of the PdZn surface alloy, most likely due to the segregation of Pd surface patches. The temperature-programmed, dynamic isobaric adsorption of CO (TPA-CO), under flowing CO(1%)/He on the catalysts pre-reduced at 623 K (that is, for similar conditions to those found in the methanol steam reforming—MSR-process) showed faster desorption of CO_L as compared to CO_B?+?CO_H species for supported Pd/CeO₂, as expected. However, the TPA-CO results on Pd/ZnO–CeO₂ were atypical: even under the superimposed, low CO partial pressure, and for a temperature range similar to those found at high methanol conversion in the MSR reaction, the PdZn bimetallic surface nature was recovered, which could be an explanation of the good selectivity to CO₂ of Pd/ZnO-based catalysts and—in particular—of the catalytically stable Pd/ZnO–CeO₂ materials.

Graphical Abstract

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Color stability of denture shade tabs is affected by exposure to daylight and decontamination protocols

The purpose of this study was to investigate the effect of light exposure and decontamination protocols on the color stability of denture shade guide tabs. Fifty tabs for shades 62, 66, and 69 (Biotone IPN, Dentsply Sirona) were submitted to baseline L*a*b* measurements (EasyShade, Vita), separated into 5 experimental groups (n = 10), and subjected to one of the following conditions: G1–distilled water (DW‐H₂O)–control; G2 ?70% alcohol; G3–sodium hypochlorite 1% (NaClO); G4–no light exposure; G5–natural light exposure for 6 months. The experimental conditions were designed to simulate 6 months of clinical use. After the test period, final color measurements were recorded. The mean tristimulus coordinate difference (ΔL*,Δa*,Δb*) and total color difference values () were analyzed using 2‐way ANOVA and the Tukey test, α = .05. G2 (alcohol) produced less (P < .05) color change in shade 69 than G3 (NaClO). G5 (light exposure) affected the color stability for all shades, producing a statistical difference (P < .05) from G4 (no light exposure). It was concluded that natural light changes the color stability of the shade guides and that decontamination with 70% alcohol had the least impact on the color stability of the shade guide tabs.     

Spectroscopic evaluation of the colour play effect of thermochromic liquid crystal printing inks

Colour changes of a thermochromic liquid crystal (TLC) ink printed on a black substrate are clearly observed by the naked eye, and therefore it is reasonable to expect that every approach recommended for colour measurements of samples with solid colour would be appropriate. In addition, the published spectroscopic analyses of TLC inks do not provide any guidance or limitations for the measurement geometry. On the other hand, our study demonstrates that spectroscopic measurements of such samples are not so straightforward. When using the most simple and commonly used measurement equipment with a directional illumination and viewing approach, the temperature-dependent spectral features resolve in a narrow spectral region that gives only a small part of the colour play effect. Detection of the entire effect requires the use of integrating spheres, which spatially integrate the radiant flux reflected on a sample in any direction; better results are obtained by spheres of larger diameter. The comparision of spectroscopic and colorimetric results obtained when different measurement geometries are applied on the same sample may demonstrate certain properties of the liquid crystal material inside microcapsules and help in understanding some details of the optical properties of the ink layer.     

Fruits and vegetables intake and characteristics associated among adolescents from Southern Brazil

Background

Pseudomonas aeruginosa adhesion to animal/human cells for infection establishment involves adhesive proteins, including its galactose- and fucose-binding lectins PA-IL (LecA) and PA-IIL (LecB). The lectin binding to the target-cell receptors may be blocked by compatible glycans that compete with those of the receptors, functioning as anti-adhesion glycodecoys. The anti-adhesion treatment is of the utmost importance for abrogating devastating antibiotic-resistant P. aeruginosa infections in immunodeficient and cystic fibrosis (CF) patients. This strategy functions in nature in protecting embryos and neonates. We have shown that PA-IL, PA-IIL, and also CV-IIL (a PA-IIL homolog produced in the related pathogen Chromobacterium violaceum) are highly useful for revealing natural glycodecoys that surround embryos in diverse avian eggs and are supplied to neonates in milks and royal jelly. In the present study, these lectins were used as probes to search for seed embryo-protecting glycodecoys.

Methods

The lectin-blocking glycodecoy activities were shown by the hemagglutination-inhibition test. Lectin-binding glycoproteins were detected by Western blotting with peroxidase-labeled lectins.

Results

The present work reports the finding - by using PA-IL, PA-IIL, and CV-IIL - of rich glycodecoy activities of low (< 10 KDa) and high MW (> 10 kDa) compounds (including glycoproteins) in extracts of cashew, cocoa, coffee, pumpkin, and tomato seeds, resembling those of avian egg whites, mammal milks, and royal jelly.

Conclusions

Edible seed extracts possess lectin-blocking glycodecoys that might protect their embryos from infections and also might be useful for hampering human and animal infections.     

Application of new oligomeric plasticizers based on waste poly(ethylene terephthalate) for poly(vinyl chloride) compositions

In this study, chemical recycling products of waste poly(ethylene terephthalate) with oligoesters were used as new plasticizers for poly(vinyl chloride) (PVC). The preparation conditions of the dry blend mixtures of the suspension PVC containing synthesised plasticizers were similar to the conditions of the preparing mixtures with commercial plasticizers. The plasticization efficiency of PVC plasticizers was then examined by analysis of the mechanical, physical and chemical properties, as well as the thermal resistance and migration of plasticizer molecules from polymer matrix. Test results proved that compositions with synthesised oligomeric plasticizers possessed similar or better properties than those containing commercial oligomeric plasticizers and much better properties than those having monomeric plasticizers. Thermal stabilities of the proposed plasticizers were higher than those of the commercial plasticizers either monomeric (bis(2-ethylhexyl)phthalate) or oligomeric, despite the fact that the synthesised oligoesters did not contain any antioxidant. The best properties, especially low volatility, very good mechanical properties, low migration were resulted of the transesterification of the waste PET with oligoesters based on adipic acid, triethylene glycol and 2-ethylhexanol which were selected as plasticizers synthesised on the technical scale. The tested plasticized PVC compositions possessed very good tear resistance, tensile strength, decrease of weight loss after 168 h at 80 °C and low migration. Processing properties of PVC compositions containing these synthesised plasticizers confirmed their effectiveness in these compositions for extrusion process.     

Unmasking Sensory Defects of Olive Oils Flavored with Basil and Oregano Using an Electronic Tongue-Chemometric Tool

Olive oil price and consumers’ preference depend on the commercial grade classification that can decrease if any sensory defect is perceived leading to an economic loss. Enriched oils, obtained by incorporating dried aromatic herbs, spices, or essential oils, which is a common practice in the Mediterranean region, are commercially available. This practice may conceal the fraudulent purpose of masking the perception of sensory defects. The detection of this type of fraud is a difficult task, requiring sensory analysis. Thus, in this study, extra-virgin and lampante olive oils, the latter classification being due to the perception of an intense winey-vinegary defect, were deliberately enriched with different amounts of basil-dried herbs and oregano-dried herbs. Sensory analysis showed that, depending on the aromatic herb and on the added amount (0.011–0.110 g herb per kg oil), the defect intensity could be masked leading to an erroneous classification of flavored lampante oils as flavored virgin oils. In contrast, the electronic tongue-chemometric approach could unmask the defect in flavored oils (predictive sensitivities: 70–78%) and semiquantitatively discriminate flavored oils according to the added levels of basil or oregano (predictive sensitivities: 93–100%). The electronic tongue approach showed satisfactory unmasking performance when compared with the sensory panel, and so, its future application as a quality control taste-sensor device for disclosing olive oil sensory defects masked by the incorporation of flavoring agents may be forseen.