Synthesis of a New Co Metal-Organic Framework Assembled from 5,10,15,20-Tetrakis((pyridin-4-yl) phenyl)porphyrin "Co-MTPhPyP" and Its Application to the Removal of Heavy Metal Ions.

The synthesis of a Co metal-organic framework assembled from 5,10,15,20-tetrakis((pyridin-4-yl)phenyl)porphyrin; TPhPyP) "Co-MTPhPyP" is reported. The TPhPyP ligand was synthesized via aldehyde condensation in 28% yield and characterized by 1H nuclear magnetic resonance (1H NMR), Fourier-transform infrared (FTIR), high-resolution mass spectrometry (HRMS), and UV-visible spectroscopy (UV-vis). Co-MTPhPyP was prepared by the solvothermal method from TPhPyP and CoCl2·H2O in 55% yield and characterized by X-ray powder diffraction (XRD), FTIR, thermogravimetric analysis (TGA), field-emission scanning electron microscopy with energy-dispersive X-ray (FESEM-EDS), X-ray photoelectron spectroscopy (XPS), and dynamic light scattering (DLS), showing a particle size distribution of 418 ± 58 nm. The sorption properties of the Co-MTPhPyP for the effective removal of Pb(II) and Cu(II) were evaluated in an aqueous medium and Cthe results showed uptake capacities of 383.4 and 168 mg of the metal g-1 after 2 h, respectively. Kinetic studies of Pb(II) adsorption by Co-MTPhPyP were adjusted to the pseudo-second-order model with a maximum adsorption capacity of 458.8 mg g-1 at 30 min of exposition.

Microencapsulation of Red Sorghum Phenolic Compounds with Esterified Sorghum Starch as Encapsulant Materials by Spray Drying.

Phenolic compounds with antioxidant properties are highly sensitive molecules, which limits their application. In response, extruded esterified starch has been proposed as efficient encapsulating material. In this work, we aim to describe the encapsulation of red sorghum phenolic compounds by spray drying using extruded phosphorylated, acetylated and double esterified sorghum starch as wall material. Their respective encapsulation yields were 77.4, 67.4 and 56.8%, and encapsulation efficiency 91.4, 89.7 and 84.6%. Degree of substitution confirmed esterification of the sorghum starch and Fourier transform infrared spectroscopy showed the significant chemical and structural changes in the extruded esterified starch loaded with phenolic compounds. Microcapsules from phosphorylated sorghum starch showed the highest endothermic transition (173.89 °C) and provided a greater protection of the phenolic compounds during storage at 60 °C for 35 days than the other wall materials. Extruded esterified sorghum starch proved to be effective material for the protection of phenolic compounds due to its high encapsulation efficiency and stability during storage.

Co-based metal-organic frameworks for enhanced nickel adsorption and its impact on nitrifying microbial activity.

The release of nickel "Ni(II)" into aquatic environments is of great concern because of environmental and health issues. Metal-organic frameworks (MOFs) are one of the most promising technologies for removing heavy metals from water. In this work, an octahedral Co-based MOF (Co-MOF) was synthesized with a high Ni(II) removal capacity (qmax of 1534.09 ± 45.49 mg g-1) in aqueous media. For the first time, the effect of Co-MOF alone and in co-exposure with Ni(II) on nitrifying microbial consortium was assessed using dynamic microrespirometry. A single concentration of Co-MOF had no significant effects on nitrifying microbial consortium, while the concentration of Ni(II) exerted non-competitive inhibition on the nitrifying microbial consortium with an IC50 of 1.67 ± 0.03 mg L-1. In addition, the theoretical speciation analysis showed a decrease of 40% of IC50 when the free Ni(II) concentration was considered. Co-exposure of Co-MOF and Ni(II) during the nitrifying process allowed us to conclude that Co-MOF is an effective adsorbent for Ni(II) and can be used to mitigate the inhibitory effects of nickel on nitrifying microbial consortia, which is crucial for maintaining the good operation of wastewater treatment and balance of nitrogen cycle.

Complete and simultaneous removal of ammonium and m-cresol in a nitrifying sequencing batch reactor.

The kinetic behavior, oxidizing ability and tolerance to m-cresol of a nitrifying sludge exposed to different initial concentrations of m-cresol (0-150 mg C L(-1)) were evaluated in a sequencing batch reactor fed with 50 mg NH4 (+)-N L(-1) and operated during 4 months. Complete removal of ammonium and m-cresol was achieved independently of the initial concentration of aromatic compound in all the assays. Up to 25 mg m-cresol-C L(-1) (C/N ratio of 0.5), the nitrifying yield (Y-NO3 (-)) was 0.86 ± 0.05, indicating that the nitrate was the main product of the process; no biomass growth was detected. From 50 to 150 mg m-cresol-C L(-1) (1.0 ≤ C/N ≤ 3.0), simultaneous microbial growth and partial ammonium-to-nitrate conversion were obtained, reaching a maximum microbial total protein concentration of 0.763 g L(-1) (247 % of its initial value) and the lowest Y-NO3 (-) 0.53 ± 0.01 at 150 mg m-cresol-C L(-1). m-Cresol induced a significant decrease in the values of both specific rates of ammonium and nitrite oxidation, being the ammonium oxidation pathway the mainly inhibited. The nitrifying sludge was able to completely oxidize up to 150 mg m-cresol-C L(-1) by SBR cycle, reaching a maximum specific removal rate of 6.45 g m-cresol g(-1) microbial protein-N h(-1). The number of SBR cycles allowed a metabolic adaptation of the nitrifying consortium since nitrification inhibition decreased and faster oxidation of m-cresol took place throughout the cycles.

Induction of cytotoxic effects and changes in DNA methylation-related gene expression in a human fibroblast cell line by the metal-organic framework [H2NMe2]3 [Tb(III)(2,6 pyridinedicarboxylate)3] (Tb-MOF).

Lanthanide metal-organic frameworks (lanthanide MOFs) may be utilized for a variety of environmental and human health applications due to their luminescent properties and high thermal and water stability. However, the cytotoxic and epigenetic effects produced in human cells are not known. Therefore, we evaluated the cytotoxic effects, internalization, and changes in the mRNA abundance of DNA methylation and demethylation enzymes by exposing human fibroblast cells to a metal-organic framework [H2NMe2]3 [Tb(III)(2,6 pyridinedicarboxylate)3] (Tb-MOF). For this purpose, the cells were exposed to six concentrations (0.05 to 1.6 mg/mL) of Tb-MOF for 48 h. Field emission electron microscopy coupled to linear energy dispersive spectroscopy (FESEM‒EDS) and confocal microscopy analysis were performed. The cytotoxicity was determined with crystal violet and MTT assays. The results demonstrated the internalization of Tb-MOF at concentrations as low as 0.05 mg/mL, as well as concentration-dependent toxicity. Additionally, we detected significant changes in the gene expression levels of DNA methyltransferases and demethylases due to the presence of Tb-MOF, suggesting that Tb-MOF could generate epigenetic changes even at low concentrations. The results of our study may establish a foundation for future research attempting to develop and apply secure nanomaterials (e.g., MOFs) to minimize damage to the environment and human health.

(25R)-16ß-Acet-oxy-3ß-bromo-23',26-ep-oxy-23',25-dimethyl-5α-cholest-23,23'-en-6-one dichloro-methane monosolvate.

The crystal structure of the title compound, C31H45BrO5·CH2Cl2, prepared in six steps from diosgenin, confirmed that the configurations of the stereogenic centers, positions 20S and 25R, remain unchanged during the reaction. The six-membered A, B and C rings have chair conformations. The five-membered ring D has an envelope conformation (with the methyl-substituted C atom fused to ring C as the flap) and the six-membered dihydro-pyran ring E adopts a twist-boat conformation. In the crystal, mol-ecules are linked via C-H⋯O and C-H⋯Cl hydrogen bonds, the latter involving the dichloro-methane solvent mol-ecule, forming a three-dimensional supra-molecular network.

Effect of amylose/amylopectin content and succinylation on properties of corn starch nanoparticles as encapsulants of anthocyanins.

In this study, succinylated nanoparticles from normal (NPS-N), high-amylose (NPS-H), and high-amylopectin corn starch (NPS-W) were synthesized, characterized, and studied for the nanoencapsulation of the Ardisia compressa anthocyanins. The nanoparticle‒anthocyanin interaction was also investigated. The succinylated starch nanoparticles (S-SNPs) had hydrodynamic sizes of 65-390 nm, degrees of substitution (DS) of 0.014-0.032, ζ-potential values of up to -34 mV and a nanocolloid behavior. NPS-N and NPS-W showed the highest (p < 0.05) encapsulation efficiencies (EE) (52 and 49 %, respectively) compared than NPS-H (45 %). Thereby, the lowest DS obtained, and the branched amylopectin structure favored the EE. The nanoparticle-anthocyanin interaction occurred through hydrophobic and electrostatic interactions and influenced significantly (p < 0.05) the hydrodynamic size and surface properties of the resulting nanocapsules. The relative crystallinity (RC) decreased significantly (p < 0.05) in the S-SNPs, but the nanocapsules mostly experimented a structural recrystallization and showed melting temperatures>150 °C.

Synthesis and succinylation of starch nanoparticles by means of a single step using sonochemical energy.

In the present research work, esterified nanoparticles with 2-octen-1-ylsuccinic anhydride were synthesized from waxy corn starch, to our knowledge for the first time, in a single step of ultrasonic treatment. First, the ultrasound time to produce non-esterified nanoparticles was studied. The results showed that non-esterified nanoparticles had sizes ranging from 63 to 48 nm, as well as polydispersity indexes (PDI) ranging from 0.458 to 0.224 and ζ-potential values ranging from -16 to -24 mV in ultrasonication times ranging from 20 to 100 min. Succinylated nanoparticles were obtained at 80 min with two degrees of substitution i.e., 0.003 and 0.01, hydrodynamic sizes of 57 and 83 nm, PDI of 0.479 and 0.91, and ζ-potential values of -6.27 and -14.03 mV, respectively. The succinylation of nanoparticles was confirmed by FTIR spectroscopy, and it was possible to elucidate the conversion of amylopectin molecules into amylose blocks. The nanoparticles showed stability during storage in aqueous suspension at 4 °C. By means of the ultrasonic technology, destructuring of the waxy corn starch and, at the same time, the succinylation of the nanoparticles in a total time of 120 min was effectively achieved.

Solvent-free synthesis of 6ß-phenylamino-cholestan-3ß,5α-diol and (25R)-6ß-phenylaminospirostan-3ß,5α-diol as potential antiproliferative agents.

In this paper is described a synthetic route to 6ß-phenylamino-cholestan-3ß,5α-diol and (25R)-6ß-phenylaminospirostan-3ß,5α-diol, starting from cholesterol and diosgenin, respectively. The products were obtained in two steps by epoxidation followed by aminolysis, through an environmentally friendly and solvent-free method mediated by SZ (sulfated zirconia) as catalyst. The use of SZ allows chemo- and regioselective ring opening of the 5,6α-epoxide during the aminolysis reaction eliminating the required separation of the epoxide mixture. The products obtained were spectroscopically characterized by 1H, PENDANT 13C NMR and HETCOR experiments, and complemented with FTIR-ATR and HRMS. The antiproliferative effect of the ß-aminoalcohols was evaluated on MCF-7 cells after 48h of incubation, by MTT and CVS assays. These methodologies showed that both compounds have antiproliferative activity, being more active the cholesterol analogue. Additionally, the cell images obtained by Harris' Hematoxylin and Eosin (H&E) staining protocol, evidenced formation of apoptotic bodies due to the presence of the obtained ß-aminoalcohols in a dose-dependent manner.

Regioselective cleavage of rings E and F in sarsasapogenin.

Sapogenins from the 25R and 25S series show a marked difference on the E/F regioselectivity of the spiroketal cleavage with BF(3)/Ac(2)O. In contrast to the high yield of single E-ring cleavage products from diosgenin (3) and hecogenin (5), sapogenins of the 25R series (equatorial C-27 methyl), sarsasapogenin (1, 25S series, axial C-27 methyl) yields the corresponding acetyldihydropyran, (25S)-23-acetyl-22,26-epoxy-5beta-cholest-22-ene-3beta,16beta-diyl diacetate (8), two isomeric furostenes: (E)- and (Z)-(25S)-23-acetyl-5beta-furost-22-ene-3beta,26-diyl diacetate (9 and 10) and a third one bearing an additional acetyl group: (E)-(20S,25S)-20,23-diacetyl-5beta-furost-22-ene-3beta, 26-diyl diacetate (11). The structures of the compounds were unambiguously established using two dimensional NMR techniques. The lower E/F selectivity in the cleavage of 1 is attributed to steric hindrance resulting from the axial methyl in F ring on a beta elimination forming the dihydropyran double bond in the major product 8.