Synergistic Pathways in PLA Breakdown and PTMC Formation: A One-Pot Eutectic-Driven Recycling Mechanism.

This study introduces a novel one-pot strategy for the chemical valorization of poly(lactic acid) (PLA), coupling its base-catalyzed depolymerization with the ring-opening polymerization (ROP) of trimethylene carbonate (TMC). The process exploits an eutectic mixture of lactide (LA) and TMC, which lowers the thermal input required for PLA degradation. Using potassium aryloxide (KOAr) as a bifunctional catalyst, the PLA is first quickly hydrolyzed into oligomers or lactic acid, which subsequently initiate the slower polymerization of TMC.

3D-Printed Phenylboronic Acid-Bearing Hydrogels for Glucose-Triggered Drug Release.

Diabetes is a major health concern that the next-generation of on-demand insulin releasing implants may overcome via personalized therapy. Therein, 3D-printed phenylboronic acid-containing implants with on-demand glucose-triggered drug release abilities are produced using high resolution stereolithography technology. To that end, the methacrylation of phenylboronic acid is targeted following a two-step reaction.

RGD-tagging of star-shaped PLA-PEG micellar nanoassemblies enhances doxorubicin efficacy against osteosarcoma.

We developed cyclic RGD-tagged polymeric micellar nanoassemblies for sustained delivery of Doxorubicin (Dox) endowed with significant cytotoxic effect against MG63, SAOS-2, and U2-OS osteosarcoma cells without compromising the viability of healthy osteoblasts (hFOBs). Targeted polymeric micellar nanoassemblies (RGD-NanoStar@Dox) enabled Dox to reach the nucleus of MG63, SAOS-2, and U2-OS cells causing the same cytotoxic effect as free Dox, unlike untargeted micellar nanoassemblies (NanoStar@Dox) which failed to reach the nucleus and resulted ineffective, demonstrating the crucial role of cyclic RGD peptide in driving cellular uptake and accumulation mechanisms in osteosarcoma cells. Micellar nanoassemblies were obtained by nanoformulation of three-armed star PLA-PEG copolymers properly synthetized with and without decoration with the cyclic-RGDyK peptide (Arg-Gly-Asp-D-Tyr-Lys).

Stereocomplexed Functional and Statistical Poly(lactide-carbonate)s via a Simple Organocatalytic System.

The stereocomplexation of polylactide (PLA) has been widely relied upon to develop degradable, sustainable materials with increased strength and improved material properties in comparison to stereopure PLA. However, forming functionalized copolymers of PLA while retaining high crystallinity remains elusive. Herein, the controlled ring-opening copolymerization (ROCOP) of lactide (LA) and functionalized cyclic carbonate monomers is undertaken.

Quasi-alternating copolymerization of oxiranes driven by a benign acetate-based catalyst.

Alternating copolymers are distinctly unique in comparison with other copolymers. Herein, an in-depth investigation of the oxyanionic ring-opening copolymerization of propylene oxide (PO) and allyl glycidyl ether (AGE) from benzyl alcohol (BnOH) activated with potassium acetate (KOAc) complexed by 18-crown-6 ether (18C6) is described. We demonstrate that the 18C6/KOAc complex is an efficient and benign catalytic system to promote copolymerization of both oxirane monomers, leading to well-defined polyethers with varied comonomer content and low dispersity values (Ɖ < 1.

Reaching High Stereoselectivity and Activity in Organocatalyzed Ring-Opening Polymerization of Racemic Lactide by the Combined Use of a Chiral (Thio)Urea and a -Heterocyclic Carbene.

Stereochemical control during polymerization is a key strategy of polymer chemistry to achieve semicrystalline engineered plastics. The stereoselective ring-opening polymerization (ROP) of racemic lactide (-LA), which can lead to highly isotactic polylactide (PLA), is one of the emblematic examples in this area. Surprisingly, stereoselective ROP of -LA employing chiral organocatalysts has been under-leveraged.

Three-armed RGD-decorated starPLA-PEG nanoshuttle for docetaxel delivery.

A novel star-shaped amphiphilic copolymer based on three poly(lactide)-block-poly(ethylene glycol) (PLA-PEG) terminal arms extending from a glycerol multifunctional core was newly synthesized and decorated with the tumor-targeting ligand cyclic-RGDyK peptide (Arg-Gly-Asp-D-Tyr-Lys) to be eventually formulated in polymeric micelles incorporating a suitable anticancer drug (i.e., Docetaxel, DTX; drug loading 16 %, encapsulation efficiency 69 %).

Stereoretention in the Bulk ROP of l-Lactide Guided by a Thermally Stable Organocatalyst.

Polylactide (PLA) has emerged as one of the most promising bio-based alternatives to petroleum-based plastics, mainly because it can be produced from the fermentation of naturally occurring sugars and because it can be industrially compostable. In spite of these benefits, the industrial ring-opening polymerization (ROP) of l-lactide (L-LA) still requires the use of highly active and thermally stable metal-based catalysts, which have raised some environmental concerns. While the excellent balance between activity and functional group compatibility of organic acid catalysts makes them some of the most suitable catalysts for the metal-free ROP of L-LA, the majority of these acids are highly volatile and subject to decomposition at high temperature, which limits their use under industrially relevant conditions.

Controlled Oxyanionic Polymerization of Propylene Oxide: Unlocking the Molecular-Weight Limitation by a Soft Nucleophilic Catalysis.

The oxyanionic ring-opening polymerization of propylene oxide (PO) from an exogenous alcohol activated with benign (complexed) metal-alkali carboxylates is described. The equimolar mixture of potassium acetate (KOAc) and 18-crown-6 ether (18C6) is demonstrated to be the complex of choice for preparing poly(propylene oxide) (PPO) in a controlled manner. In the presence of 18C6/KOAc, hydrogen-bonded alcohols act as soft nucleophiles promoting the PO S 2 process at room temperature and in solvent-free conditions while drastically limiting the occurrence of parasitic hydrogen abstraction generally observed during the anionic ROP of PO.

On the Conformation of Anionic Peptoids in the Gas Phase.

Although -()-phenylethyl peptoids are known to adopt helical structures in solutions, the corresponding positively charged ions lose their helical structure during the transfer from the solution to the gas phase due to the so-called charge solvation effect. We, here, considered negatively charged peptoids to investigate by ion mobility spectrometry-mass spectrometry whether the structural changes described in the positive ionization mode can be circumvented in the negative mode by a fine-tuning of the peptoid sequence, that is, by positioning the negative charge at the positive side of the helical peptoid macrodipole. -()-(1-carboxy-2-phenylethyl) (scp) and -()-phenylethyl (spe) were selected as the negative charge carrier and as the helix inductor, respectively.

Helical Peptoid Ions in the Gas Phase: Thwarting the Charge Solvation Effect by H-Bond Compensation.

Folding and unfolding processes are key aspects that should be mastered for the design of foldamer molecules for targeted applications. In contrast to the solution phase, in vacuo conditions represent a well-defined environment to analyze the intramolecular interactions that largely control the folding/unfolding dynamics. Ion mobility mass spectrometry coupled to theoretical modeling represents an efficient method to decipher the spatial structures of gaseous ions, including foldamers.

Accelerating the crystallization kinetics of linear polylactides by adding cyclic poly (L-lactide): Nucleation, plasticization and topological effects.

Polylactide is one of the most versatile biopolymers, but its slow crystallization limits its temperature usage range. Hence finding ways to enhance it is crucial to widen its applications. Linear and cyclic poly (L-lactide) (l-PLLA and c-PLLA) of similarly low molecular weights (MW) were synthesized by ring-opening polymerization of L-lactide, and ring-expansion methodology, respectively.

A chiral thiourea and a phosphazene for fast and stereoselective organocatalytic ring-opening-polymerization of racemic lactide.

Control of stereoregularity is inherent to precision polymerization chemistry for the development of functional materials. A prototypal example of this strategy is the ring-opening polymerization (ROP) of racemic lactide (rac-LA), a bio-sourced monomer. Despite significant advances in organocatalysis, stereoselective ROP of rac-LA employing chiral organocatalysts remains unexplored.

Assessing the Structural Heterogeneity of Isomeric Homo and Copolymers: an Approach Combining Ion Mobility Mass Spectrometry and Molecular Dynamics Simulations.

Synthetic polymers occupy a unique place in the field of ion mobility mass spectrometry (IMS-MS). Indeed, due to their intrinsic dispersity, they have the asset to offer a broad range of homologous ions with different lengths that can be detected in several charge states. In addition, the gas-phase structure of polymer ions mostly depends on their ability to screen the adducted charges.

Tough and Three-Dimensional-Printable Poly(2-methoxyethyl acrylate)-Silica Composite Elastomer with Antiplatelet Adhesion Property.

Poly(2-methoxyethyl acrylate) (PMEA) has attracted attention as a biocompatible polymer that is used as an antithrombotic coating agent for medical devices, such as during artificial heart and lung fabrication. However, PMEA is a viscous liquid polymer with low , and its physical strength is poor even if a cross-linker is used, so it is difficult to make tough and freestanding objects from it. Here, we design and fabricate a biocompatible elastomer made of tough, self-supporting PMEA-silica composites.

Design of naturally inspired jellyfish-shaped cyclopolylactides to manage osteosarcoma cancer stem cells fate.

We report the synthesis, characterization and biological profile of new bis-triazoled cyclopolylactides (c-PLA, c-PLA-FA, c-PLA-Rhod) obtained by an optimized combination of ROP and click chemistry reactions. Cyclo-PLA having a number average molecular weight of 6000 g mol and a polydispersity index of 1.52 was synthetized by click ring-closure of well-defined α,ω-heterodifunctional linear precursors, followed by quaternarization of N-triazole nodes, and subsequent CuAAC with azido-folate and azido-rhodamine yielding jellyfish-shaped c-PLA-FA and c-PLA-Rhod.

Organocatalytic Synthesis of Alkyne-Functional Aliphatic Polycarbonates via Ring-Opening Polymerization of an Eight-Membered-N-Cyclic Carbonate.

The synthesis of well-defined propargyl-functional aliphatic polycarbonates is achieved via the organocatalytic ring-opening polymerization of prop-2-yn-1-yl 2-oxo-1,3,6-dioxazocane-6-carboxylate (P-8NC) using a wide variety of commercially available or readily made, shelf-stable organocatalysts. The resulting homopolymers show low dispersities and end-group fidelity, with the versatility of the system being demonstrated by the synthesis of telechelic copolymers and block copolymers with molar mass up to 40 kDa.

Synthesis of Poly(Dimethylmalic Acid) Homo- and Copolymers to Produce Biodegradable Nanoparticles for Drug Delivery: Cell Uptake and Biocompatibility Evaluation in Human Heparg Hepatoma Cells.

Hydrophobic and amphiphilic derivatives of the biocompatible and biodegradable poly(dimethylmalic acid) (PdiMeMLA), varying by the nature of the lateral chains and the length of each block, respectively, have been synthesized by anionic ring-opening polymerization (aROP) of the corresponding monomers using an initiator/base system, which allowed for very good control over the (co)polymers' characteristics (molar masses, dispersity, nature of end-chains). Hydrophobic and core-shell nanoparticles (NPs) were then prepared by nanoprecipitation of hydrophobic homopolymers and amphiphilic block copolymers, respectively. Negatively charged NPs, showing hydrodynamic diameters (Dh) between 50 and 130 nm and narrow size distributions (0.

Development of Inherently Flame-Retardant Phosphorylated PLA by Combination of Ring-Opening Polymerization and Reactive Extrusion.

In this study, a highly efficient flame-retardant bioplastic poly(lactide) was developed by covalently incorporating flame-retardant DOPO, that is, 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide. To that end, a three-step strategy that combines the catalyzed ring-opening polymerization (ROP) of L,L-lactide (L,L-LA) in bulk from a pre-synthesized DOPO-diamine initiator, followed by bulk chain-coupling reaction by reactive extrusion of the so-obtained phosphorylated polylactide (PLA) oligomers (DOPO-PLA) with hexamethylene diisocyanate (HDI), is described. The flame retardancy of the phosphorylated PLA (DOPO-PLA-PU) was investigated by mass loss cone calorimetry and UL-94 tests.

Reactive Extrusion and Magnesium (II) -Heterocyclic Carbene Catalyst in Continuous PLA Production.

Reactive extrusion and magnesium (II) -heterocyclic carbene catalyst are successfully employed in continuous polylactide synthesis. The possibility of using six-membered -heterocyclic carbene adducts to act as efficient catalysts towards the sustainable synthesis of poly(l-lactide) through ring-opening polymerization of l-lactide (LA) is first investigated in bulk batch reactions. Under optimized solvent-free conditions, polylactide (PLA) of moderate to high molecular weights and excellent optical activities are successfully achieved.

Preparation of a mimetic and degradable poly(ethylene glycol) by a non-eutectic mixture of organocatalysts (NEMO) a one-pot two-step process.

A one-pot, two-step method for the preparation of degradable PEG is here presented. The full process addresses the requirements imposed by green chemistry and involves the use of a single and nontoxic non-eutectic mixture of organocatalysts. The strategy relies on the polycondensation of PEG800 after its functionalization by bio-derived 5-membered γ-butyrolactone.

Update and Challenges in Carbon Dioxide-Based Polycarbonate Synthesis.

The utilization of carbon dioxide as a comonomer to produce polycarbonates has attracted a great deal of attention from both industrial and academic communities because it promises to replace petroleum-derived plastics and supports a sustainable environment. Significant progress in the copolymerization of cyclic ethers (e.g.

Limitations of ion mobility spectrometry-mass spectrometry for the relative quantification of architectural isomeric polymers: A case study.

Unlabelled: Since their discovery, cyclic polymers have attracted great interest because of their unique properties. Today, the preparation of these macrocyclic structures still remains a challenge for polymer chemists, and most of the preparation pathways lead to an inescapable contamination by linear by-products. As the properties of the polymers are closely related to their structure, it is of prime importance to be able to assess the architectural purity of a sample.

Photoactive Boron-Nitrogen-Carbon Hybrids: From Azo-borazines to Polymeric Materials.

In this paper, we describe synthetic routes for preparing a novel switchable BNC-based chromophore, composed of a borazine core peripherally functionalized with azobenzene moieties. Capitalizing on the Pd-catalyzed Suzuki cross-coupling reaction between a tris-triflate borazine and an organoboron azobenzene derivative, a photoswtichable azo-borazine derivative was successfully prepared. The molecule showed reversible / photoisomerization upon irradiation at the maximum of the intense π-π* absorption feature (360 nm).

One Step Further in the Characterization of Synthetic Polymers by Ion Mobility Mass Spectrometry: Evaluating the Contribution of End-groups.

Several families of polymers possessing various end-groups are characterized by ion mobility mass spectrometry (IMMS). A significant contribution of the end-groups to the ion collision cross section (CCS) is observed, although their role is neglected in current fitting models described in literature. Comparing polymers prepared from different synthetic procedures might thus, be misleading with the current theoretical treatments.