Resolving Confusion Surrounding d-Ala-d-Ala Ligase Catalysis in Cyanobacterial Mycosporine-Like Amino Acid (MAA) Biosynthesis

Mycosporine-like amino acids (MAAs) are natural UV-absorbing sunscreens that evolved in cyanobacteria and algae to palliate harmful effects from obligatory exposure to solar radiation. Multiple lines of evidence prove that in cyanobacteria all MAAs are derived from mycosporine-glycine, which is typically modified by an ATP-dependent ligase encoded by the gene mysD. The function of the mysD ligase has been experimentally described but haphazardly named based solely upon sequence similarity to the d -alanine-d -alanine ligase of bacterial peptidoglycan biosynthesis. Combining phylogeny and alpha-fold tertiary protein structure prediction unambiguously distinguished mysD from d -alanine-d -alanine ligase. The renaming of mysD to mycosporine-glycine-amine ligase (MG-amine ligase) using recognised enzymology rules of nomenclature is, therefore, proposed, and considers relaxed specificity for several different amino acid substrates. The evolutionary and ecological context of MG-amine ligase catalysis merits wider appreciation especially when considering exploiting cyanobacteria for biotechnology, for example, producing mixtures of MAAs with enhanced optical or antioxidant properties.     

Development of stabilized zirconia–alkali salts dual membranes for carbon dioxide capture

Molten Na₂CO₃–K₂CO₃ (NKC, 56–44 mol%) eutectic compositions were vacuum-impregnated, at the eutectic temperature, into two porous ZrO₂:8.6 mol% MgO (magnesium-partially stabilized zirconia, MgPSZ) and ZrO₂:8 mol% Y₂O₂ (yttria-fully stabilized zirconia, 8YSZ) ceramics. Thermogravimetric analyses were performed in mixtures of that composition with MgPSZ and 8YSZ ceramic powders. Before impregnation, porosity was achieved in the two compounds by addition and thermal removal of 30 vol.% NKC. To ascertain the carbonates had filled up through the ceramic body, both sides of the parallel and fracture surfaces of the disk-shaped impregnated compositions were observed in a scanning electron microscope and analyzed by energy-dispersive X-ray spectroscopy. The electrical conductivity of the two ceramics, before and after impregnation, was evaluated by electrochemical impedance spectroscopy in the 5 Hz–13 MHz frequency range from approximately 530 to 740°C. The permeation of the carbonate ions through the membranes via the eutectic composition was assessed by the threshold temperatures of the onset of the carbonate ion percolation. The objectives were to prepare dual-phase membranes for the separation of carbon dioxide and for the development of carbon dioxide sensors.     

Efficacy and stability of ammoniation process as aflatoxin B1 decontamination technology in rice

Rice, a cereal widely used in Venezuela for human and animal nutrition, is susceptible to aflatoxin contamination in the field and during storage. Therefore, the goal of this research was the evaluation of the efficacy and permanence of the ammoniation process through high pressure/high temperature (HP/HT) and atmospheric pressure/moderate temperature (AP/MT) conditions applied to rice samples artificially contaminated with aflatoxin B1. For this purpose a 2k design was drawn up considering the temperature, the rice moisture and the process time as variables. Under both sets of conditions, aflatoxin B1 concentration was reduced in a range of 90% to 100%. After in vitro stomach digestion simulation, toxin reversion ranged from 0% to 19%. In conclusion, the process efficacy and permanence were achieved through the use of high temperature and long process time for both sets of conditions (HP/HT and AP/MT), respectively.     

Effect of water on the oxygen barrier properties of poly(ethylene terephthalate) and polylactide films

The aim of this work was to study the variations in the oxygen diffusion, solubility, and permeability coefficients of polylactide (PLA) films at different temperatures (5, 23, and 40°C) and water activities (0–0.9). The results were compared with the oxygen diffusion, solubility, and permeability coefficients obtained for poly(ethylene terephthalate) (PET) films under the same experimental conditions. The water sorption isotherm for PLA films was also determined. Diffusion coefficients were determined with the half‐sorption time method. Also, a consistency test for continuous‐flow permeability experimental data was run to obtain the diffusion coefficient with the lowest experimental error and to confirm that oxygen underwent Fickian diffusion in the PLA films. The permeability coefficients were obtained from steady‐state permeability experiments. The results indicated that the PLA films absorbed very low amounts of water, and no significant variation of the absorbed water with the temperature was found. The oxygen permeability coefficients obtained for PLA films (2–12 × 10^?18 kg m/m² s Pa) were higher than those obtained for PET films (1–6 × 10^?19 kg m/m² s Pa) at different temperatures and water activities. Moreover, the permeability coefficients for PLA and PET films did not change significantly with changes in the water activity at temperatures lower than 23°C. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1790–1803, 2004     

Structural Diversity and Defensive Properties of Norditerpenoid Alkaloids

We have tested the insect antifeedant and toxic activity of 43 norditerpenoid alkaloids on Spodoptera littoralis and Leptinotarsa decemlineata including eserine (physostigmine), anabasine, and atropine. Antifeedant effects of the test compounds were structure- and species-dependent. The most active antifeedants to L. decemlineata were 1,14-diacetylcardiopetaline (9) and 18-hydroxy- 14-O-methylgadesine (33), followed by 8-O-methylconsolarine (12), 14-O-acetyldelectinine (27), karakoline (7), cardiopetaline (8), 18-O-demethylpubescenine (13), 14-O-acetyldeltatsine (18), takaosamine (21), ajadine (24), and 8-O-methylcolumbianine (6) (EC50 < 1 microg/cm2). This insect showed a moderate response to atropine. S. littoralis had the strongest antifeedant response to 24, 18, 14-O-acetyldelcosine (19), and delphatine (29) (EC50 < 3 microg/cm2). None of the model substances affected the feeding behavior of this insect. The most toxic compound to L. decemlineata was aconitine (1), followed by cardiopetalidine (10) (% mortality > 60), 14-deacetylpubescenine (14), 18-O-benzoyl-18-O-demethyl-14-O-deacetylpubescenine (17), 14-O-acetyldelcosine (19), 14-deacetylajadine (25) and methyllycaconitine (30) (% mortality > 45). Orally injected S. littoralis larvae were negatively affected by 1, cardiopetaline (8), 10, 1,14-O-acetylcardiopetalidina (11), 12, 14, 1,18-O-diacetyl-19-oxo-gigactonine (41), olivimine (43), and eserine in varying degrees. Their antifeedant or insecticidal potencies did not parallel their reported nAChR binding activity, but did correlate with the agonist/antagonist insecticidal/antifeedant model proposed for nicotininc insecticides. A few compounds [14, tuguaconitine (38), 14-demethyldelboxine (40), 19, dehydrodelsoline (36), 18-O-demethylpubescenine (13), 41, 9, and delcosine (23)] had selective cytotoxic effects to ward insect-derived Sf9 cells. None were cytotoxic to mammalian CHO cells and none increased Trypanosoma cruzi mortality. The selective cytotoxic effects of some structures indicate that they can act on biological targets other than neuroreceptors.     

Tape casting of polysiloxane-derived ceramic with controlled porosity and surface properties

Tape casting has been applied to produce porous hybrid and SiOC ceramic tapes using ceramic precursors and commercially available polysiloxanes as polymeric binders. SiC particles of two different mean sizes (4.5 or 6.5?μm) were used as inert fillers to prevent shrinkage and increase mechanical stability. Macroporosity was adjusted by varying the azodicarbonamide (ADA) content from 0 to 30?wt.%. Decomposition of the polysiloxanes at 600?°C resulted in the generation of micropores with high specific surface area (187–267 m²?g^?1) and a predominant hydrophobic behavior. At 1000?°C mainly meso/macroporosity were observed (SSA: 32–162 m²?g^?1) accompanied by increased hydrophilicity. The influence of ADA content, SiC size, and pyrolysis temperature on open porosity (2.5–37%), average pore size (<0.01–1.76?μm), surface characteristics, and flexural strength (10.5–121?MPa) were investigated. The porous tapes with different surface characteristics and controlled structure are highly promising for applications involving membrane processes, particularly microfiltration systems (0.1–10?μm).     

Self‐aggregated nanoparticles of N‐dodecyl,N′‐glycidyl(chitosan) as pH‐responsive drug delivery systems for quercetin

In this study, pH‐responsive amphiphilic chitosan (CS) nanoparticles were used to encapsulate quercetin (QCT) for sustained release in cancer therapy. The novel CS derivatives were obtained by synthesis with 2,3‐epoxy‐1‐propanol, also known as glycidol, followed by acylation with dodecyl aldehyde. Characterization was performed by spectroscopic, viscosimetric, and size‐determination methods. Critical aggregation concentration, morphology, entrapment efficiency, drug release profile, cytotoxicity, and hemocompatibility studies were also carried out. The average size distribution of the self‐assembling nanoparticles measured by dynamic light scattering ranged from 140 to 300 nm. In vitro QCT release and Korsmeyer–Peppas model indicated that pH had a major role in drug release. Cytotoxicity assessments indicated that the nanoparticles were non‐cytotoxic. 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay further revealed that QCT‐loaded nanoparticles could inhibit MCF‐7 cell growth. In vitro erythrocyte‐induced hemolysis indicated the good hemocompatibility of the nanoparticles. These results suggest that the synthesized copolymers might be potential carriers for hydrophobic drugs in cancer therapy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45678.