Search Results (5)

This paper presents an alternative for enhancing the durability of poly (L-lactide) (PLLA) by racemic nucleation following stereo-complexation with a selected poly (D-lactide) (PLDA). The compounds are obtained by melt blending of a PLLA grade, previously designed for 3D printing but with a low heat deflection temperature and impact resistance, with grades of PLDA differing in their molecular weight (Mw), D-lactide content (DS) and concentration. Our method considered how to reveal the racemic nucleation caused by stereo-complexation and its influence on functional properties. The FTIR study we performed showed that, depending on Mw, DS and concentration of the stereo-complexer (PDLA) used, bigger or smaller spectral changes can occur. The stereo-complexation was confirmed by the DSC analysis and, for the selected compound, by the POM, SEM, AFM microscopies, functional property and shapeability as 3D printing filaments. All the obtained results sustain the idea that, if a PLLA with M_w of 4.5 × 10⁴ g·mol⁻¹ is modified with PDLA with a medium M_w of 11.6 × 10⁴ g·mol⁻¹, medium DS of 4% and 1% concentration, a racemic nucleation is possible. It produces a racemic polylactic acid (PDLLA) with improved durability and good shapeability as 3D printing filaments. These results are explicable if the dependence of the intermolecular interactions appears between the PLLA and stereo-complexer PDLA. To enlarge the durable applicability of racemic polylactic acid (PDLLA), future research should identify other parameters controling the PLA stereo-complexing as the intensifying the mobility of the macromolecules, the finding of the optimal recemic cristalization window. Full article

The resolution of 2-hydroxy-5,5-dimethyl-4-phenyl-1,3,2-dioxaphosphorinan 2-oxide (phencyphos) was achieved by dissolution of anhydrous racemic phencyphos, a racemic compound, accompanied by simultaneous secondary nucleation of the dissolved racemate on to enantiopure seeds of phencyphos hydrate, a conglomerate. The seeds were placed in separate compartments and the pure enantiomers could be conveniently collected from these compartments after the dissolution of the anhydrous racemate. Full article

The intrinsic drawback of slow crystallization rate of poly(l-lactide) (PLLA) inevitably deteriorates its final properties of the molded articles. In this work, we proposed a new strategy towards poly(l-lactide) with enhanced crystallization rate by ring opening polymerization (ROP) of l-lactide (l-LA) catalyzed by biocompatible zinc salts of amino acids. For the first time we developed a one-pot facile method of zinc salts of amino acids acting dual roles of catalysis of l-LA polymerization and in situ nucleation of the as-prepared PLLA. Nine zinc salts of different amino acids, including three kinds of amino acids ligands (alanine, phenylalanine, and proline) with l/d-enantiomers and their equimolar racemic mixtures, were first prepared and tested as catalysts of l-LA polymerization. A partial racemization was observed for zinc salts of amino acids whereas no racemization was detected for the reference stannous octoate. The polymerization mechanism study showed that the interaction of zinc salts of amino acids and benzyl alcohol forms the actual initiator for l-LA polymerization. Isothermal crystallization kinetics analysis showed that the residual zinc salts of amino acids exhibited a significant nucleation effect on PLLA, evidenced by the promotion of the crystallization rate, depending on the amino acid ligand and its configuration. Meanwhile, the residual zinc salts of amino acids did not compromise the thermal stability of the pristine PLLA. Full article

Chromatographic interaction between infiltrating solutions of racemic mixtures of enantiomers and enantiomorphic minerals with chiral excess has been proposed as a scenario for the emergence of biomolecular homochirality. Enantiomer separation is supposed to be produced by different partition coefficients of both enantiomers with regard to crystal faces or walls of capillary tubes in the enantiomorphic mineral. Besides quartz, nepheline is the only common magmatic mineral with enantiomorphic symmetry. It crystallizes from SiO₂-undersaturated melts with low viscosity and is a promising candidate for chiral enrichment by autocatalytic secondary nucleation. Under liquidus conditions, the dynamic viscosity of silicate melts is mainly a function of polymerization. Melts with low concentrations of SiO₂ (<55 wt%) and rather high concentrations of Na₂O (>7 wt%) are only slightly polymerized and hence are characterized by low viscosities. Such melts can ascend, intrude or extrude by turbulent flow. Fourteen volcanic and subvolcanic samples from alkaline provinces in Africa and Sweden were chemically analyzed. Polished thin sections containing fresh nepheline phenocrysts were etched with 1% hydrofluoric acid at 20 °C for 15 to 25 min. Nepheline crystals suitable for a statistical evaluation of their etch figures were found in four samples. Crystals with chiral etch figures are mainly not twinned. Their chiral proportions in grain percentages of single crystals are close to parity in three samples. Only one sample shows a slight chiral excess (41.67% L-type vs. 58.33% D-type) but at a low level of significance (15 vs. 21 crystals, respectively). Full article

The separation of enantiomers is of great importance due to their possible differences in therapeutic properties. Preferential crystallization in various configurations of coupled batch crystallizers is used as an attractive means to separate the conglomerate-forming enantiomers from racemic mixtures. However, the productivity of such batch processes can be limited by the nucleation of the counter enantiomer and consumption of the supersaturation. In this work, a recently proposed process configuration, which uses coupled mixed suspension mixed product removal (MSMPR) with liquid phase exchange, is investigated by simulation studies. A detailed study on the effect of process parameters (e.g., feed flow rate, seed mass, and liquid phase exchange) on the productivity and yield of the coupled MSMPR has been presented. Moreover, a comparison of various coupled crystallizer configurations is carried out. It is shown through simulation studies that the productivity of the enantiomeric separation can be significantly improved compared to the previously proposed batch modes when the continuous configuration is used. The effect of nucleation kinetic parameters on the performances of various crystallizer configurations is studied as well. A set of coupled population balance equations (PBEs) was used to describe the evolution of the crystal phase of the both enantiomers in each vessel. These equations were solved numerically using the quadrature method of moments. The insights obtained in this study will be useful in the process design of coupled crystallizer systems. Full article