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Phosphasalen Indium Complexes Showing High Rates and Isoselectivities in rac-Lactide Polymerizations.

ABSTRACT: Polylactide (PLA) is the leading bioderived polymer produced commercially by the metal-catalyzed ring-opening polymerization of lactide. Control over tacticity to produce stereoblock PLA, from rac-lactide improves thermal properties but is an outstanding challenge. Here, phosphasalen indium catalysts feature high rates (30±3 m^-1 min^-1 , THF, 298 K), high control, low loadings (0.2 mol %), and isoselectivity (P_i =0.92, THF, 258 K). Furthermore, the phosphasalen indium catalysts do not require any chiral additives.

SUBMITTER: Myers D

PROVIDER: S-EPMC5434947 | biostudies-literature |

REPOSITORIES: biostudies-literature

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8-Quinolinolato gallium complexes: iso-selective initiators for rac-lactide polymerization.

Project description:The synthesis and characterization of a series of 8-quinolinolato gallium complexes is presented, and the complexes are analogous to a series of aluminum complexes previously reported. The complexes have been shown to be active initiators for the ring-opening polymerization of rac-lactide. High degrees of polymerization control are demonstrated, as exemplified by the linear evolution of molecular weight as the polymerization progresses, narrow polydispersity indices, and molecular weights corresponding to those predicted on the basis of initiator concentration. Some of the initiators show iso-selective polymerization of rac-lactide, with Pi = 0.70. The polymerization rates have been monitored, and the pseudo first-order rate constants are compared to those of analogous aluminum compounds. The 8-quinolinolato gallium initiators show rates approximately 3 times higher than those of the series of aluminum compounds, while maintaining equivalently high iso-selectivity (Pi = 0.70) and polymerization control.

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| S-EPMC4036730 | biostudies-literature

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| S-EPMC8048956 | biostudies-literature

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Lithium Complexes Derived of Benzylphosphines: Synthesis, Characterization and Evaluation in the ROP of rac-Lactide and ?-Caprolactone.

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| S-EPMC6017396 | biostudies-literature

Overcoming aggregation in indium salen catalysts for isoselective lactide polymerization.

Project description:A methodology for controlling aggregation in highly active and isoselective indium catalysts for the ring opening polymerization of racemic lactide is reported. A series of racemic and enantiopure dinuclear indium ethoxide complexes bearing salen ligands [(ONNOR)InOEt]2 (R = Br, Me, admantyl, cumyl, t-Bu) were synthesized and fully characterized. Mononuclear analogues (ONNOR)InOCH2Pyr (R = Br, t-Bu, SiPh3) were synthesized by controlling aggregation with the use of chelating 2-pyridinemethoxide functionality. The nuclearity of metal complexes was confirmed using PGSE NMR spectroscopy. Detailed kinetic studies show a clear initiation period for these dinuclear catalysts, which is lacking in their mononuclear analogues. The polymerization behavior of analogous dinuclear and mononuclear compounds is identical and consistent with a mononuclear propagating species. The isotacticity of the resulting polymers was investigated using direct integration and peak deconvolution methodologies and the two were compared.

| S-EPMC5669251 | biostudies-literature

Metal influence on the iso- and hetero-selectivity of complexes of bipyrrolidine derived salan ligands for the polymerisation of rac-lactide.

Project description:In this paper we have prepared a series of Ti(iv), Hf(iv) and Al(iii) complexes based on bipyrrolidine salan pro-ligands. The Hf(iv) complexes have all been characterised in the solid-state, the chiral ligands coordinate to Hf(iv) in an ?-cis manner whereas the meso ligand coordinates in a ?-cis geometry. The Hf(iv) complexes are all active for the ROP of rac-lactide in the melt, with the fluxional meso complex affording a strong isotactic bias Pm = 0.84. As expected Hf(3)(OiPr)2 polymerised l-LA faster than rac-LA (kapp = 5.9 × 10-3 min-1vs. 3.8 × 10-3 min-1). For Ti(iv) complexes atactic PLA was formed. The salan pro-ligands have also been complexed to Al(iii), and the novel Al-Me and Al-OiPr complexes were characterised in the solid and solution state. Al(1)(OiPr) was fluxional on the NMR timescale, whereas Al(3)(OiPr) was locked in solution with no exchange. Interestingly, the Al(iii) complexes of 3H2 produce PLA with a very strong heterotactic bias Pr upto 0.87, whereas atactic PLA is produced with 1H2. For Al(3)(OiPr) a linear relationship is observed with Mn and conversion. Experiments with the addition of an equivalent of rac-LA to the selective initiators have also been performed and are discussed.

| S-EPMC5664169 | biostudies-literature

Zinc-Catalyzed Highly Isoselective Ring Opening Polymerization of rac-Lactide.

Project description:A family of chiral zinc amido-oxazolinate complexes are shown to be highly active and isoselective initiators for the ring-opening polymerization (ROP) of rac-lactide, yielding isotactic stereoblock polylactides (PLA) with Pm up to 0.91. This represents the highest isoselectivity observed with zinc-based catalysts for ROP of rac-lactide.

| S-EPMC4105174 | biostudies-literature

Palladium complexes containing imino phenoxide ligands: synthesis, luminescence, and their use as catalysts for the ring-opening polymerization of rac-lactide.

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| S-EPMC5906497 | biostudies-literature

New Ruthenium-Cyclopentadienyl Complexes Affect Colorectal Cancer Hallmarks Showing High Therapeutic Potential.

Project description:Colorectal cancer (CRC) is among the most deadly cancers worldwide. Current therapeutic strategies have low success rates and several side effects. This relevant clinical problem requires the discovery of new and more effective therapeutic alternatives. Ruthenium drugs have arisen as one of the most promising metallodrugs, due to their high selectivity to cancer cells. In this work we studied, for the first time, the anticancer properties and mechanisms of action of four lead Ru-cyclopentadienyl compounds, namely PMC79, PMC78, LCR134 and LCR220, in two CRC-derived cell lines (SW480 and RKO). Biological assays were performed on these CRC cell lines to evaluate cellular distribution, colony formation, cell cycle, proliferation, apoptosis, and motility, as well as cytoskeleton and mitochondrial alterations. Our results show that all the compounds displayed high bioactivity and selectivity, as shown by low half-maximal inhibitory concentrations (IC50) against CRC cells. We observed that all the Ru compounds have different intracellular distributions. In addition, they inhibit to a high extent the proliferation of CRC cells by decreasing clonogenic ability and inducing cell cycle arrest. PMC79, LCR134, and LCR220 also induce apoptosis, increase the levels of reactive oxygen species, lead to mitochondrial dysfunction, induce actin cytoskeleton alterations, and inhibit cellular motility. A proteomic study revealed that these compounds cause modifications in several cellular proteins associated with the phenotypic alterations observed. Overall, we demonstrate that Ru compounds, especially PMC79 and LCR220, display promising anticancer activity in CRC cells with a high potential to be used as new metallodrugs for CRC therapy.

| S-EPMC10302444 | biostudies-literature

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