Influence of preparation method on the catalytic properties of acid-activated tetramethylammonium-exchanged clays

Two montmorillonites STx-1 (Texas) and SWy-2 (Wyoming) were first activated with different amounts of 12 M HCl and then exchanged with a fixed amount of 1 M tetramethylammonium (TMA⁺) chloride solution (H/TMA samples) at room temperature. TMA⁺-exchanged samples and then acid activated (TMA/H samples) were also prepared to evaluate the resistance to displacement of TMA⁺ by protons. The surface area and the acidity were determined by BET and cyclohexylamine adsorption methods, respectively. The catalytic activity of these acid activated organoclays was directly measured using the isomerization of 1-butene at 300 °C to yield cis- and trans-2-butene. The total conversion for the isomerization of 1-butene was higher for the TMA/H-samples (70 and 47% for SWy-2 and STx-1, respectively) than for the H/TMA-samples (51 and 25% for SWy-2 and STx-1, respectively). TMA⁺ cations adsorbed on the clays were extremely resistant to exchange by protons, but protons were easily displaced by TMA⁺ cations.     

Characteristics of a NaOH-Activated Blast Furnace Slag Blended with a Fine Particle Silica Waste

Mortars of blast furnace slag blended with a geothermal silica waste at various replacement levels of 0%, 5%, 10%, 15%, and 20% were cured for up to 90 days. The binder was activated by 6 wt% Na₂O equivalent of sodium hydroxide. Lime was added as an activating agent and also to promote pozzolanic reaction with the silica. It was found that the presence of the silica waste increased the reactivity of the cementitious materials, as measured by means of nonevaporable water. The compressive strength was increased in the presence of the silica, except at the highest replacement level of 20%, the optimum silica replacement was that of 5%–10%. The microstructures of blended slag showed less porosity than those of neat slag mortars. The lime was completely consumed after 90 days of hydration.     

Adipose hormone-sensitive lipase preferentially releases polyunsaturated fatty acids from triglycerides

Rat adipose hormone-sensitive lipase-mediated release of fatty acids from triglycerides was studied in three model systems: i) cultured preadipocytes containing polyunsaturated fatty acid-enriched triglyceride; ii) perfused epididymal fat pads; and iii)in vitro incubations of crude preparations of hormone-sensitive lipase with synthetic triglyceride-analogues as substrates. We found that cultured preadipocytes challenged with 10μM norepinephrine tended to release more ω6 and ω3 polyunsaturated fatty acids than saturated fatty acids. Fat pads perfused with 10 μM norepinephrine preferentially released arachidonate and α-linolenate but tended to retain oleate and linoleate. Finally, crude preparations of hormonesensitive lipase released from the triglyceride-analogue substrates α-linolenate twice as fast as oleate. We conclude that rat adipose hormone-sensitive lipase preferentially releases polyunsaturated fatty acids from triglycerides. We suggest that this may be a mechanism by which these fatty acids are kept from being trapped in fat depots and maintained in the circulation.     

Different strategies to recover the activity of monomeric triosephosphate isomerase by directed evolution

A monomeric version of triosephosphate isomerase from Trypanosomabrucei, MonoTIM, has very low activity, and the same is truefor all of the additional monomeric variants so far constructed.Here, we subjected MonoTIM to directed evolution schemes toachieve an activity improvement. The construction of a suitablestrain for genetic selection provided an effective way to obtainactive catalysts from a diverse population of protein variants.We used this tool to identify active mutants from two differentstrategies of mutagenesis: random mutagenesis of the whole geneand randomization of loop 2. Both strategies converged in theisolation of mutations Ala43 to Pro and Thr44 to either Alaor Ser, when randomizing the entire gene or to Arg in the caseof randomization of loop 2. The kinetic characterization ofthe two more active mutants showed an increase of 11-fold ink_cat and a reduction of 4-fold in K_m for both of them, demonstratingthe sensitivity of the selection method. A small differencein growth rate is observed when both mutant genes are compared,which seems to be attributable to a difference in solubilityof the expressed proteins.     

Preparation and characterization of β‐cyclodextrin‐linked chitosan microparticles

Hydrophobically modified chitosan containing β‐cyclodextrin (CD) units was synthesized by using tosylated β‐CD. The final product was characterized by Fourier transform infrared (FTIR) spectroscopy, elemental analysis and TGA, and rheometry. The polymer bearing β‐CD moieties was used to obtain crosslinked microparticles by spray‐drying which could then be used in a controlled release system for drugs. FTIR confirmed the formation of an amide linkage between cyclodextrin and chitosan. As fluorescence spectroscopy demonstrated, hydrophobic microenvironments were formed by chitosan bearing cyclodextrin in solution at lower concentrations than for chitosan. Rheometry and FTIR showed the crosslinking of the new polymer using genipin, a molecule of natural origin. Microspheres (MS) obtained by spray‐drying showed narrow size distribution when β‐CD was grafted onto chitosan and ξ‐potential of MS was slightly lower although it remained positive. In conclusion, β‐CD linked chitosan polymer can be considered as a very promising controlled drug delivery system for drugs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The Effect of Spray-Freeze Drying of Montmorillonite on the Morphology,Dispersion, and Crystallization in Polypropylene Nanocomposites

The spray-freeze drying (SFD) technique was applied to sonicated aqueous suspensions of spray-dried montmorillonite clay (MMT) to produce highly porous agglomerates (SFD-MMT). Both MMT (used as a reference) and SFD-MMT were subsequently incorporated in polypropylene (PP) via melt compounding to produce 2 wt % nanocomposites with and without maleic anhydride grafted polypropylene (PP-g-MA). Polypropylene nanocomposites containing SFD-MMT exhibited thinner silicate flake layers compared to large agglomerates in PP/MMT nanocomposites. SFD-MMT particles became even more finer in the presence of PP-g-MA (i.e., in PP/PP-g-MA /SFD-MMT) where it hindered PP crystallization instead of serving as nucleation sites for the PP crystallization during rapid cooling. SFD-MMT improved the thermal stability of PP/PP-g-MA by 30°C compared to only 5–8°C for MMT/nanocomposites. MMT acts as a heterogeneous nucleating agent in the nucleation-controlled PP nanocomposites, but the hindrance effect was observed for the PP/PP-g-MA with SFD-MMT. PP/PP-g-MA/SFD-MMT exhibited twice the edge surface energy as compared to PP/PP-g-MA/MMT. The incorporation of both types of MMT raised the tensile moduli of PP and PP/PP-g-MA, with no improvement in their tensile strength and a decrease in the elongation at break. The PP/PP-g-MA/SFD-MMT showed brittle failure. POLYM. ENG. SCI., 60:168–179, 2020. © 2019 Society of Plastics Engineers     

Synthesis and characterization of a titanium phosphate-tellurite glass for Faraday rotators

This work is focused on investigation of thermal, structural, optical, magnetic, and magneto-optical properties of novel titanium phosphate-tellurite glass applied as Faraday rotators. The glass belonging to the system 35Li₂O–10Al₂O₃–5TiO₂–45P₂O₅–5TeO₂ was prepared by a nonconventional wet route of raw materials processing, followed by melting-quenching-annealing steps. Some important physical properties of the investigated glass have been measured and calculated, providing knowledge related to glass compactness, electronic structure, glass forming capability, etc. XRD analysis evidenced an amorphous network structure of the investigated glass. The optical absorption in the Vis domain is mainly due to Ti³⁺ ions and Te₂ clusters formed during the glass melting process. A relatively low optical absorption is noticed over 600 nm that activates a significant Faraday magneto-optical effect. Photoluminescence bands in the blue, red, and infrared domains are observed, caused by Te₂ clusters formed during the glass melting process. The magnetization in dependency on applied magnetic field reveals a complex behavior of the glass, depending on temperature. Thus, it is found a ferromagnetic behavior up to 2000 Oe, a paramagnetic component up to 40 000 Oe, followed by a diamagnetic one over 40 000 Oe. Faraday rotation angle and Verdet constant values in the visible domain are correlated with the reduced TeO₂ content of the glass.     

Pharmacokinetic Parameters of HIV-1 Protease Inhibitors

Since the beginning of the HIV epidemic, research has been carried out to control the virus. Understanding the mechanisms of replication has given access to the various classes of drugs that over time have transformed AIDS into a manageable chronic disease. The class of protease inhibitors (PIs) gained notice in anti-retroviral therapy, once it was found that peptidomimetic molecules act by blocking the active catalytic center of the aspartic protease, which is directly related to HIV maturation. However, mutations in enzymatic internal residues are the biggest issue for these drugs, because a small change in biochemical interaction can generate resistance. Low plasma concentrations of PIs favor viral natural selection; high concentrations can inhibit even partially resistant enzymes. Food-drug/drug-drug interactions can decrease the bioavailability of PIs and are related to many side effects. Therefore, this review summarizes the pharmacokinetic properties of current PIs, the changes when pharmacological boosters are used and also lists the major mutations to help understanding of how long the continuous treatment can ensure a low viral load in patients.