Phosphonate-Modified UiO-66 Brønsted Acid Catalyst and Its Use in Dehydra-Decyclization of 2-Methyltetrahydrofuran to Pentadienes

Phosphorus-modified all-silica zeolites exhibit activity and selectivity in certain Brønsted acid catalyzed reactions for biomass conversion. In an effort to achieve similar performance with catalysts having well-defined sites, we report the incorporation of Brønsted acidity to metal–organic frameworks with the UiO-66 topology, achieved by attaching phosphonic acid to the 1,4-benzenedicarboxylate ligand and using it to form UiO-66-PO₃H₂ by post-synthesis modification. Characterization reveals that UiO-66-PO₃H₂ retains stability similar to UiO-66, and exhibits weak Brønsted acidity, as demonstrated by titrations, alcohol dehydration, and dehydra-decyclization of 2-methyltetrahydrofuran (2-MTHF). For the later reaction, the reported catalyst exhibits site-time yields and selectivity approaching that of phosphoric acid on all-silica zeolites. Using solid-state NMR and deprotonation energy calculations, the chemical environments of P and the corresponding acidities are determined.     

Some quantitative versions of Ratner’s mixing estimates

We give explicit versions for some of Ratner’s estimates on the decay of matrix coefficients of SL(2,?)-representations.     

Impulsive non‐autonomous dynamical systems and impulsive cocycle attractors

In this work, we define the notions of ‘impulsive non‐autonomous dynamical systems’ and ‘impulsive cocycle attractors’. Such notions generalize (we will see that not in the most direct way) the notions of autonomous dynamical systems and impulsive global attractors in the current published literature. We also establish conditions to ensure the existence of an impulsive cocycle attractor for a given impulsive non‐autonomous dynamical system, which are analogous to the continuous case. Moreover, we prove the existence of such attractor for a non‐autonomous 2D Navier–Stokes equation with impulses, using energy estimates. Copyright © 2016 John Wiley & Sons, Ltd.     

Theoretical and infrared studies on the conformational isomerism of trans-2-bromo-alkoxycyclohexanes

The infrared spectra of trans-2-bromo-alkoxycyclohexanes (alcoxy = OMe, OEt, O(i)Pr and O(t)Bu) were obtained for the neat liquid, and the C-Br stretching mode was quantitatively analyzed to give insight about the conformational isomerism of these compounds. Frequency calculations supported the band assignments, and the relative band intensities suggest that the diaxial conformer is prevalent for the methoxy and tert-butoxy derivatives (51 and 56%, respectively), while the diequatorial form is preponderant for the ethoxy and isopropoxy derivatives (76 and 77%, respectively). Therefore, the size of the alkoxy group plays a determinant role in determining the conformational preferences of the title compounds.     

Structural and thermal properties of spray-dried methotrexate-loaded biodegradable microparticles

Drug–polymer interactions, structural properties, thermal behavior, and stability of biodegradable microparticles are fundamental aspects in the developing of new polymeric drug delivery systems. In this study, poly (d,l-lactide-co-glycolide) (PLGA) microparticles containing methotrexate (MTX) were successfully obtained by spray drying. Scanning electronic microscopy, differential scanning calorimetry (DSC), thermogravimetry (TG), X-ray diffraction (XRD), and drug-loading efficiency were used to investigate the effect of drug–polymer ratio and its interactions, in a new MTX-loaded PLGA spray-dried microparticles. High levels of encapsulation efficiency (about 90 %) and a prevalent spherical shape were identified for different drug–polymer ratios used (9, 18, and 27 % m/m). The thermal analyses (DSC and TG) and XRD indicate that MTX is homogeneously distributed in the polymeric matrix, with a prevalent amorphous state in a stable molecular dispersion. Therefore, a correlation between drug content and the structural-thermal properties of drug-loaded PLGA microparticles was established using the thermal analysis data. The biodegradable microparticle leads to an increment of thermal stability of MTX, confirming that spray drying is an efficient process for obtaining MTX-loaded PLGA microparticles.     

Enhanced Enzyme Reuse through the Bioconjugation of L-Asparaginase and Silica-Based Supported Ionic Liquid-like Phase Materials

L-asparaginase (ASNase) is an amidohydrolase that can be used as a biopharmaceutical, as an agent for acrylamide reduction, and as an active molecule for L-asparagine detection. However, its free form displays some limitations, such as the enzyme’s single use and low stability. Hence, immobilization is one of the most effective tools for enzyme recovery and reuse. Silica is a promising material due to its low-cost, biological compatibility, and tunable physicochemical characteristics if properly functionalized. Ionic liquids (ILs) are designer compounds that allow the tailoring of their physicochemical properties for a given task. If properly designed, bioconjugates combine the features of the selected ILs with those of the support used, enabling the simple recovery and reuse of the enzyme. In this work, silica-based supported ionic liquid-like phase (SSILLP) materials with quaternary ammoniums and chloride as the counterion were studied as novel supports for ASNase immobilization since it has been reported that ammonium ILs have beneficial effects on enzyme stability. SSILLP materials were characterized by elemental analysis and zeta potential. The immobilization process was studied and the pH effect, enzyme/support ratio, and contact time were optimized regarding the ASNase enzymatic activity. ASNase–SSILLP bioconjugates were characterized by ATR-FTIR. The bioconjugates displayed promising potential since [Si][N₃₄₄₄]Cl, [Si][N₃₆₆₆]Cl, and [Si][N₃₈₈₈]Cl recovered more than 92% of the initial ASNase activity under the optimized immobilization conditions (pH 8, 6 × 10⁻³ mg of ASNase per mg of SSILLP material, and 60 min). The ASNase–SSILLP bioconjugates showed more enhanced enzyme reuse than reported for other materials and immobilization methods, allowing five cycles of reaction while keeping more than 75% of the initial immobilized ASNase activity. According to molecular docking studies, the main interactions established between ASNase and SSILLP materials correspond to hydrophobic interactions. Overall, it is here demonstrated that SSILLP materials are efficient supports for ASNase, paving the way for their use in the pharmaceutical and food industries.     

Spondias tuberosa (Anacardiaceae) leaves: profiling phenolic compounds by HPLC‐DAD and LC–MS/MS and in vivo anti‐inflammatory activity

Spondias tuberosa is a medicinal plant used by several local communities in northeast Brazil to treat infections, digestive disorders and inflammatory conditions. The study aimed to identify and quantify the major phenolic in hydroethanolic extract of leaves from S. tuberosa and to evaluate its anti‐inflammatory potential. The chemical profile of extract was analyzed by HPLC‐DAD and HPLC–MS. The in vivo anti‐inflammatory activity was investigated in carrageenan‐induced hind paw edema and peritonitis models in mice. Identified and quantified through HPLC‐DAD or HPLC‐MS analyses of S. tuberosa extract were the following compounds: chlorogenic acid, caffeic acid, rutin and isoquercitrin. The inflammatory response to carrageenan was significantly reduced in both models by S. tuberosa extract. In hind paw edema, the edematogenic response was reduced by up to 63.6% and the myeloperoxidase activity was completely inhibited. In the peritonitis model, the total cell migration into the peritoneal cavity was reduced by up to 65%. The results obtained give evidence of the anti‐inflammatory action of S. tuberosa and suggest the potential therapeutic benefit of this plant on inflammatory conditions. The chlorogenic acid, caffeic acid, rutin and isoquercitrin identified and quantified in S. tuberosa leaves enable us to suggest that these compounds could be used as chemical markers for quality control of derivative products from this species. Copyright © 2016 John Wiley & Sons, Ltd.     

Correlation of the thermal stability and the decomposition kinetics of six different vegetal fibers

The thermal degradation behavior of six different vegetal fibers was studied using thermogravimetry under nitrogen atmosphere at four different heating rates (5, 10, 20 and 40 °C min^?1). The degradation models Kissinger, Friedman and Flynn–Wall–Ozawa methods were used to determine the apparent activation energy and the frequency factor of these fibers. Furthermore, the solid state degradation mechanisms were determined using Criado’s method. Additionally, X-ray diffraction and Fourier transform infrared (FTIR) spectroscopy were analyzed to corroborate the obtained results. The results indicated that the apparent calculated activation energies can be more closely related to the exponential dependence of the rate of heterogeneous reactions than to the, necessary “energy”, which is commonly used. The Criado’s master curves indicated two different degradation mechanisms for the fibers: diffusion followed by random nucleation. The results also indicated that the crystallinity index as calculated by X-ray diffraction and determinated by FTIR does not necessarily represent higher thermal stability as noted by the thermogravimetric analysis curves. The thermal behavior and the degradation mechanism did not show to be influenced by the lignocellulosic components of the fibers, exception for buriti and sisal. This behavior was attributed to higher extractive content.