Sargassum@magnetite Composite EDTA-Functionalized for the Potential Removal of Mercury.

Sargassum spp. affects the Caribbean shores; thus, its remotion or valorization is a priority. This work aimed to synthesize a low-cost magnetically retrievable Hg+2 adsorbent functionalized with ethylenediaminetetraacetic acid (EDTA) based on Sargassum. The Sargassum was solubilized to synthesize by co-precipitation a magnetic composite. A central composite design was assessed to maximize the adsorption of Hg+2. The solids yield magnetically attracted mass, and the saturation magnetizations of the functionalized composite were 60.1 ± 17.2%, 75.9 ± 6.6%, and 1.4 emu g-1. The functionalized magnetic composite yielded 29.8 ± 0.75 mg Hg+2 g-1 of chemisorption after 12 h, pH 5, and 25 °C achieving 75% Hg+2 adsorption after four reuse cycles. Crosslinking and functionalization with Fe3O4 and EDTA created differences in surface roughness as well as the thermal events of the composites. The Fe3O4@Sargassum@EDTA composite was a magnetically recovered biosorbent of Hg2+.

Sustainable xanthophylls-containing poly(ε-caprolactone)s: synthesis, characterization, and use in green lubricants.

Three xanthophylls [(3R,3'R,6'R)-lutein (1), (3R,3'S)-zeaxanthin (2), and (3R,3'S)-astaxanthin (3)] were used for the first time as initiators in the ring-opening polymerization (ROP) of ε-caprolactone (CL) catalyzed by tin(ii) 2-ethylhexanoate [Sn(Oct)2] for the synthesis of novel sustainable xanthophyll-containing poly(ε-caprolactone)s (xanthophylls-PCL). The obtained polyesters were characterized by 1H and 13C NMR, FT-IR, DSC, SEC, and MALDI-TOF MS, and their use as additives in green lubricants was evaluated using a sliding friction test under boundary conditions. Xanthophylls-PCL were obtained with good conversions and with molecular weights determined by SEC to be between 2500 and 10 500 Da. The thermal properties of xanthophyll-polyesters showed a crystalline domain, detected by DSC. Lastly, the green lubricant activity of these polymers was evaluated and the results showed that xanthophylls-PCL could be employed as additives for biodegradable lubricant applications since they have better tribological behavior than current additives, which demonstrates their potential as future commercial materials with interesting eco-friendly properties for diverse applications.

Effect of Salicylic Acid in the Yield of Ricinine in Ricinus communis under Greenhouse Condition.

Castor bean (Ricinus communis) seeds contain ricinine, an alkaloid with insecticidal and insectistatic activities. Elicitation with salicylic acid (SA) has proven to stress R. communis and might modify the ricinine concentration. The aim of this study was to evaluate the concentration of ricinine in the bagasse of seeds from R. communis elicited with exogenous SA under greenhouse conditions. Plants were grown and divided into five groups, which were sprayed with SA and drench with 50 mL 60 days after sowing with concentrations of SA (0, 100, 300, 600 and 900 µM). Clusters were mixed and separated according to the treatment, and dried. The seeds were ground, the oil was extracted by Soxhlet with hexane, and then the bagasse was extracted with methanol. Ricinine was determined by HPLC. Elicitation did not change the plant height or diameter; the control group had 9.17 µg mL-1 of ricinine; and the concentrations followed a hormesis curve with the peak at 300 µM of SA that had a ricinine concentration of 18.25 µg mL-1. Elicitation with SA might be a cost-effective technique to increase ricinine from R. communis bagasse.

On the Tribological and Oxidation Study of Xanthophylls as Natural Additives in Castor Oil for Green Lubrication.

The present study focuses on an introductory analysis of the use of three xanthophylls as additives for green lubricant applications. For this purpose, the additives were characterized by FTIR and 1H-NMR techniques, and the bio-lubricants were described by their physical properties. The effect of the natural compounds on the friction and wear properties of bio-lubricants were evaluated by sliding friction tests under boundary conditions, as confirmed by an analysis of the lubricating film thickness. The antioxidant capacity was analyzed by FTIR spectroscopy. It was observed better wear protection in castor oil with xanthophylls than without these additives. The wear rate was reduced up to 50% compared with neat oil. Lesser beneficial effects were appreciated in friction coefficient since it was increased 25%. The best contribution was observed with astaxanthin as an additive. In addition, a significant improvement in the oxidation of castor oil, complemented with this additive, was exhibited by FTIR analysis. It was found that xanthophylls could be employed as additives for totally biodegradable lubricant applications since they have better tribological and antioxidant behavior than current additives.

Selective synthesis of trisubstituted pyrroles through the reactions of alkynyl Fischer carbene complexes with oxazolones.

An efficient and simple synthesis of novel trisubstituted 1H-pyrroles 4a-qvia 1,3-dipolar cycloaddition of Δ3-trifluoromethyloxazolones 2a-d with both chromium and tungsten alkynyl Fischer carbene complexes (1a-h) is described. An unexpected and unreported -CF3 group elimination process was observed in the pyrrole structure. Our experimental and theoretical data suggested that the metal fragment may be responsible for this phenomenon. The dipolar cycloaddition proceeded efficiently to produce a single regioisomer, which was unambiguously established through NMR and single-crystal X-ray diffraction studies. Nevertheless, the reaction of alkynyl carbenes bearing an α,ß,γ,δ-unsaturated moiety with excess oxazolone 2a produced a polycyclic compound 6 speculatively formed through a cascade reaction involving 1,6-, 1,4- and 1,2-nucleophilic addition steps.

A Simple and Efficient Method for the Partial Synthesis of Pure (3R,3'S)-Astaxanthin from (3R,3'R,6'R)-Lutein and Lutein Esters via (3R,3'S)-Zeaxanthin and Theoretical Study of Their Formation Mechanisms.

Carotenoids are natural compounds that have important roles in promoting and maintaining human health. Synthetic astaxanthin is a highly requested product by the aquaculture industry, but natural astaxanthin is not. Various strategies have been developed to synthesize this carotenoid. Nonetheless, these approaches have not only provided limited global yields, but its main commercial source also carries several health risks for humans. In this contribution, the one-pot base-catalyzed reaction of (3R,3'R,6'R)-lutein (1) esters has resulted in a successful isomerization process to easily obtain up to 95% meso-zeaxanthin (2), which in turn is oxidized to (3R,3'S)-astaxanthin (3) with a global yield of 68%. The same oxidation performed with UV irradiation (365 nm) for 5 min provided the highest global yield (76%). These chemical transformations have also been achieved with a significant reduction of the health risks associated with its potential human consumption. Furthermore, this is the first time only one of the configurational isomers has been obtained semisynthetically. The poorly understood formation mechanisms of these two compounds were also investigated using Density-Functional Theory (DFT) calculations. These theoretical studies revealed that the isomerization involves a base-catalyzed deprotonation at C-6', followed by C-4' protonation, while the oxidation occurs via free radical mechanisms.