Adding Value in Production of Multifunctional Polylactide (PLA)–ZnO Nanocomposite Films through Alternative Manufacturing Methods

Due to the added value conferred by zinc oxide (ZnO) nanofiller, e.g., UV protection, antibacterial action, gas-barrier properties, poly(lactic acid) (PLA)–ZnO nanocomposites show increased interest for utilization as films, textile fibers, and injection molding items. The study highlights the beneficial effects of premixing ZnO in PLA under given conditions and its use as masterbatch (MB), a very promising alternative manufacturing technique. This approach allows reducing the residence time at high processing temperature of the thermo-sensitive PLA matrix in contact of ZnO nanoparticles known for their aptitude to promote degradation effects onto the polyester chains. Various PLA–ZnO MBs containing high contents of silane-treated ZnO nanoparticles (up to 40 wt.% nanofiller specifically treated with triethoxycaprylylsilane) were produced by melt-compounding using twin-screw extruders. Subsequently, the selected MBs were melt blended with pristine PLA to produce nanocomposite films containing 1–3 wt.% ZnO. By comparison to the more traditional multi-step process, the MB approach allowed the production of nanocomposites (films) having improved processing and enhanced properties: PLA chains displaying higher molecular weights, improved thermal stability, fine nanofiller distribution, and thermo-mechanical characteristic features, while the UV protection was confirmed by UV-vis spectroscopy measurements. The MB alternative is viewed as a promising flexible technique able to open new perspectives to produce more competitive multifunctional PLA–ZnO nanocomposites.     

A Mild and Highly Efficient Method for the Preparation of Silyl Ethers using Fe(HSO4)3/Et3N by Chlorosilanes

A very efficient and mild procedure for preparation of silyl ethers from benzylic, allylic, propargilic alcohols, phenols, naphtoles and some of phenolic drugs with trimethylsilylchloride (TMSCl), triethylsilylchloride (TESCl) and t‐buthyldimethylsilyl chloride (TDSCl) ethers in the presence of Fe(HSO₄)₃/Et₃N in room temperature in excellent yields is reported. This procedure also allows the excellent selectivity for silylation of alcohols and phenols.     

Gel-assisted synthesis of anatase TiO2 nanoparticles and application for electrochemical determination of L-tryptophan

Anatase titanium dioxide nanoparticles (TiO₂-NPs) were synthesized with and without gelatin via the sol-gel method. The TiO₂-NPs were characterized by a number of techniques, such as thermogravimetric analysis (TGA), X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FT-IR) and ultraviolet visible spectroscopy (UV-Vis). The particle sizes of the TiO₂-NPs prepared with and without gelatin were ～13 and ～17 nm, respectively. The main advantage of using gelatin as a stabilizing agent is that it provides long-term stability for nanoparticles by preventing particles agglomeration. The results indicated that gelatin was a reliable green stabilizer, which can be used as a polymerization agent in the sol-gel method for synthesis of tiny size TiO₂-NPs. Moreover, the composite film was prepared by synthesized TiO₂-NPs nanoparticles and multi wall carbon nanotube (MWNT) on glassy carbon electrode (TiO₂-MWNT/GCE). The TiO₂-MWNT/GCE responded linearly to L-tryptophan (L-Trp) in the concentration of 1.0 × 10^?6 to 1.5 × 10^?4 M with detection limit of 5.2 × 10^?7 M at 3 using amperometry. The studied sensor exhibited good reproducibility and long-term stability.     

Cationation of dimethylallyl alcohols by B(C6F5)3 as models of the (Re)initiation reaction in the bio‐inspired cationic polymerization of isoprene

The polymerization of isoprene initiated by dimethylallyl alcohols (DMAOH) in the presence of Lewis acids (LAs) as coinitiators has been selected as a potential model of the proposed cationic mechanisms involved in natural rubber (NR) biosynthesis. In view to investigate the activation/ionization mechanism of the allyl alcohol chain terminus (PIAllOH), which was shown to exist in NR, different isomers of DMAOH were used as simple models of polyisoprene chain‐end structures in the presence of tris(pentafluorophenyl)borane (BLA) as a LA. It is shown that cationation of 3,3‐DMAOH by BLA proceeds by direct OH abstraction. However, this process is strongly retarded in the presence of 2,6‐di‐tert‐butylpyridine (d^tBP), due to the formation of different BLA complexes, one with 3,3‐DMAOH, active for cationation, and a dormant one involving its ionized form 3,3‐DMAO^?. The monomer generated in situ by ionization/proton elimination steps subsequently adds on the primary allylic carbocation form, then resulting in the formation of oligoisoprenes, whereas the tertiary carbocation form of the allylic carbocation yields exclusively to proton elimination and isoprene formation, a possible mechanism of chain‐end termination. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Recent strategies in the synthesis of thiophene derivatives: highlights from the 2012–2020 literature

Molecular Diversity - Thiophene-based analogs have been fascinated by a growing number of scientists as a potential class of biologically active compounds. Furthermore, they play a vital role for...     

Multiplicity of positive solutions for a critical quasilinear elliptic system with concave and convex nonlinearities

In this paper, by using the Lusternik–Schnirelmann category, we obtain a multiplicity result for a quasilinear elliptic system with both concave and convex nonlinearities and critical growth terms in bounded domains.     

Multicomponent reactions for the synthesis of new cyclopentadienephosphonate derivatives in water

A series of polysubstituted cyclopentadienephosphonate derivatives were synthesized via one-pot multicomponent reactions of primary amines and phosphites with activated acetylenic compounds in water as the solvent at room temperature.

Particularly valuable features of this method include high yields of products, broad substrate scope, short reaction time and a straightforward procedure.     

A new hybrid method for solving global optimization problem

In this paper we present a new hybrid method, called the SASP method. The purpose of this method is the hybridization of the simulated annealing (SA) with the descent method, where we estimate the gradient using simultaneous perturbation. Firstly, the new hybrid method finds a local minimum using the descent method, then SA is executed in order to escape from the currently discovered local minimum to a better one, from which the descent method restarts a new local search, and so on until convergence.The new hybrid method can be widely applied to a class of global optimization problems for continuous functions with constraints. Experiments on 30 benchmark functions, including high dimensional functions, show that the new method is able to find near optimal solutions efficiently. In addition, its performance as a viable optimization method is demonstrated by comparing it with other existing algorithms. Numerical results improve the robustness and efficiency of the method presented.     

Transition-Metal-Mediated Glycosylation with Thioglycosides

Thioglycosides are among the most common glycosyl donors that find broad application in the synthesis of glycans and glycoconjugates. However, the requirement for toxic and/or large access of activators needed for common glycosylations with thioglycosides remains a notable drawback. Due to the increased awareness of the chemical waste impact on the environment, synthetic studies have been driven by the goal of finding non-toxic reagents. The main focus of this review is to highlight recent methods for thioglycoside activation that rely on transition metal catalysis.     

Structure–retardation factor relationship of natural amino acids in two different mobile phases of RP-TLC

Abstract

Separation of amino acids (AAs) and their simple and inexpensive determination/identification is an interesting topic in biological and protein science, different food industries, and drug factories. Also, the presentation of the chromatographic behavior of compounds in a predictive model can be effective to estimate the structural/chemical properties of analyte and mobile phases. In this work for the first time, retardation factor (R_F) of 42 AAs in reversed-phase thin layer chromatography (RP-TLC) was modeled. Acetonitrile-sodium azide solution and 1,2 dioxane-sodium azide solution were two mobile phases which have been studied in this work. Results showed that the values of R_F are correlated with the structural properties of AAs and these properties had some similarities and differences in two noted mobile phases. For the TLC data in two mobile phases, five parametric linear models were suggested (R²_train = 0.93 and 0.97; R²_test = 0.93 and 0.99). The models were also evaluated with different statistical approaches. It was shown that increasing the sum of geometrical distances between N and O in AAs causes decreasing their R_F in RP-TLC using both mobile phases. Other structural effects of AAs on their separation in the desired RP-TLC system were also discussed.