Crystallization and Properties of Poly(lactide)/Poly(δ-valerolactone) Alternating Supramolecular Copolymers Adjusted by Stereocomplexation.
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ABSTRACT:
SUBMITTER: Shi X
PROVIDER: S-EPMC6648093 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Lactide-valerolactone copolymers have potential application in the packaging sector. Different copolymers were synthesized, and the kinetics of the copolymerization reactions and the microstructure of the copolymers were analysed. Lactide showed higher reactivity than valerolactone which leads to composition drift through the reaction. Thermal, mechanical and barrier properties of the selected copolymers were studied. Overall, the incorporation of valerolactone results in copolymers with higher ductility than poly(lactide) with intermediate water and oxygen permeability which makes these materials appropriate candidates for use in the packaging sector.
| S-EPMC8747129 | biostudies-literature
Project description:The crystallization and morphology of PLA-mb-PBS copolymers and their corresponding stereocomplexes were studied. The effect of flexible blocks (i.e., polybutylene succinate, PBS) on the crystallization of the copolymers and stereocomplex formation were investigated using polarized light optical microscopy (PLOM), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), and carbon-13 nuclear magnetic resonance spectroscopy (13C-NMR). The PLA and PBS multiple blocks were miscible in the melt and in the glassy state. When the PLA-mb-PBS copolymers are cooled from the melt, the PLA component crystallizes first creating superstructures, such as spherulites or axialites, which constitute a template within which the PBS component has to crystallize when the sample is further cooled down. The Avrami theory was able to fit the overall crystallization kinetics of both semi-crystalline components, and the n values for both blocks in all the samples had a correspondence with the superstructural morphology observed by PLOM. Solution mixtures of PLLA-mb-PBS and PLDA-mb-PBS copolymers were prepared, as well as copolymer/homopolymer blends with the aim to study the stereocomplexation of PLLA and PDLA chain segments. A lower amount of stereocomplex formation was observed in copolymer mixtures as compared to neat L100/D100 stereocomplexes. The results show that PBS chain segments perturb the formation of stereocomplexes and this perturbation increases with the amount of PBS in the samples. However, when relatively low amounts of PBS in the copolymer blends are present, the rate of stereocomplex formation is enhanced. This effect dissappears when higher amounts of PBS are present. The stereocomplexation was confirmed by FTIR and solid state 13C-NMR analyses.
| S-EPMC6414904 | biostudies-literature
Project description:Advanced drug delivery strategies can be used to enhance the therapeutic effectiveness of locally delivered corticosteroids. Poly(δ-valerolactone-co-allyl-δ-valerolactone) microparticles (PVL-co-PAVL MPs) were evaluated for delivery of two corticosteroids, triamcinolone acetonide and triamcinolone hexacetonide. PVL-co-PAVL MPs were prepared using a modified oil-in-water emulsification method, followed by a UV-initiated cross-linking process. The resulting PVL-co-PAVL MPs were purified with an excess amount of water and then acetone to remove residual surfactant, cross-linker, and catalyst before lyophilization. Triamcinolone acetonide and triamcinolone hexacetonide were independently loaded into the resulting PVL-co-PAVL MPs via a post-loading swelling-equilibrium method. The drug-loaded MPs were characterized in terms of drug loading (determined by high-performance liquid chromatography, HPLC), thermal properties (determined by differential scanning calorimetry, DSC), and in vitro drug release kinetics (with quantification of drug using HPLC) to better understand the suitability of PVL-co-PAVL MPs for delivery of corticosteroids. These data demonstrate the potential of PVL-co-PAVL MPs as a promising drug delivery platform for the sustained release of corticosteroids. Raw data have been made available on Mendeley Data. Additional details on PVL-co-PAVL MPs were previously reported [1].
| S-EPMC10025086 | biostudies-literature
Project description:The importance of noncovalent interactions in the realm of biological materials continues to inspire efforts to create artificial supramolecular polymeric architectures. These types of self-assembled materials hold great promise as environmentally stimuli-responsive materials because they are capable of adjusting their various structural parameters, such as chain length, architecture, conformation, and dynamics, to new surrounding environments upon exposure to appropriate external stimuli. Nevertheless, in spite of considerable advances in the area of responsive materials, it has proved challenging to create synthetic self-assembled materials that respond to highly disparate analytes and whose environmentally induced changes in structure can be followed directly through both various spectroscopic and X-ray diffraction analyses. Herein, we report a new set of artificial self-assembled materials obtained by simply mixing two appropriately chosen, heterocomplementary macrocyclic receptors, namely a tetrathiafulvalene-functionalized calix[4]pyrrole and a bis(dinitrophenyl)-meso-substituted calix[4]pyrrole. The resulting polymeric materials, stabilized by combination of donor-acceptor and hydrogen bonding interactions, undergo dynamic, reversible dual guest-dependent structural transformations upon exposure to two very different types of external chemical inputs, namely chloride anion and trinitrobenzene. The structure and dynamics of the copolymers and their analyte-dependent responsive behavior was established via single crystal X-ray crystallography, SEM, heterocomplementary isodesmic analysis, 1- and 2D NMR, and dynamic light scattering spectroscopies. Our results demonstrate the benefit of using designed heterocomplementary interactions of two functional macrocyclic receptors to create synthetic, self-assembled materials for the development of "smart" sensory materials that mimic the key biological attributes of multianalyte recognition and substrate-dependent multisignaling.
| S-EPMC3248540 | biostudies-literature
Project description:Supramolecular copolymers are an emerging class of materials, which bring together different properties and functionalities of multiple components via noncovalent interactions. While it is widely acknowledged that the repeating unit sequence plays an essential role on the performance of these materials, mastering and tuning the supramolecular copolymer sequence is still an open challenge. To date, only statistical supramolecular copolymers have been reported using cyclic peptide-polymer conjugates as building blocks. To enrich the diversity of tubular supramolecular copolymers, we report here a strategy of controlling their sequences by introducing an extra complementary noncovalent interaction. Hence, two conjugates bearing one electron donor and one electron acceptor, respectively, are designed. The two conjugates can individually assemble into tubular supramolecular homopolymers driven by the multiple hydrogen bonding interactions between cyclic peptides. However, the complementary charge transfer interaction between the electron donor and acceptor makes each conjugate more favorable for complexing with its counterpart, resulting in an alternating sequence of the supramolecular copolymer. Following the same principle, more functional supramolecular alternating copolymers are expected to be designed and constructed via other complementary noncovalent interactions (electrostatic interactions, metal coordination interactions, and host-guest interactions, etc.).
| S-EPMC8261775 | biostudies-literature
Project description:The self-assembly of block copolymers into 1D, 2D and 3D nano- and microstructures is of great interest for a wide range of applications. A key challenge in this field is obtaining independent control over molecular structure and hierarchical structure in all dimensions using scalable one-pot chemistry. Here we report on the ring opening polymerization-induced crystallization-driven self-assembly (ROPI-CDSA) of poly-L-lactide-block-polyethylene glycol block copolymers into 1D, 2D and 3D nanostructures. A key feature of ROPI-CDSA is that the polymerization time is much shorter than the self-assembly relaxation time, resulting in a non-equilibrium self-assembly process. The self-assembly mechanism is analyzed by cryo-transmission electron microscopy, wide-angle x-ray scattering, Fourier transform infrared spectroscopy, and turbidity studies. The analysis revealed that the self-assembly mechanism is dependent on both the polymer molecular structure and concentration. Knowledge of the self-assembly mechanism enabled the kinetic trapping of multiple hierarchical structures from a single block copolymer.
| S-EPMC7499262 | biostudies-literature
Project description:Well-defined six-arm star-branched bio-degradable block copolymers of l-lactide and ε-caprolactone were prepared using controlled ring-opening polymerization and a sequential monomer addition method using dipentaerythritol as the initiator core and organocatalysts at low temperatures in solution. Sequence of enchainment was changed by reversing the order of monomer addition giving, either, a crystalline PLA block or an amorphous PCL block as the outer segment. Well-defined six-arm poly(ε-caprolactone-b-l-lactide, 6s-PCL-b-PLA) block copolymers were obtained with a range of segment molecular weights. However, in the case of six-arm poly(l-lactide-b-ε-caprolactone, 6s-PLA-b-PCL), disruption of the block structure was observed on account of competing transesterification reactions accompanying a chain-growth reaction. Such sequence-controlled block copolymers showed interesting phase morphologies, as evidenced by differential scanning calorimetry (DSC) studies. 6s-PCL-b-PLA showed two glass-transition temperatures and two melting temperatures characteristic of the amorphous and crystalline blocks. 6s-PCL-b-PLA and 6s-PLA-b-PCL with different segment chain lengths were solution blended (10 wt %) with a commercially sourced PLA. All the blends were highly transparent. The structure and properties of the blend were examined by DSC, measurement of mechanical properties, and scanning electron microscopy. The results show that a phase-separated 6s-PCL-b-PLA copolymer results in two- to three-fold improvement in tensile toughness without the loss of modulus. A possible hypothesis for the mechanism of tensile toughness in the blend has been proposed.
| S-EPMC8945082 | biostudies-literature
Project description:A tri(ethylene glycol)-containing lactide analogue was synthesized via thiol-ene chemistry between a bi-functional triethylene glycol and allyl lactide. Subsequent tin-octoate-catalyzed ring-opening polymerization yielded well-defined poly(lactide)-graft-poly(ethylene glycol) copolymers with molecular weights of 6000 g/mol and polydispersity indices of 1.6. The tri(ethylene glycol) chains along the copolymers contain azide termini that are capable of 'click'-type postpolymerization functionalization. The utility of this strategy was demonstrated via successful Staudinger ligation to install the Gly-Arg-Gly-Asp-Ser (GRGDS) peptide.
| S-EPMC3713803 | biostudies-literature
Project description:In the present work, crystallization of a soluble nucleator N, N', N″-tricyclohexyl-1,3,5-benzenetricarboxylamide (TMC-328) in a poly(l-lactic acid) (PLLA) matrix has been studied at different temperatures. Based on the change in solubility with temperature, different levels of supersaturation of TMC-328 in a PLLA matrix can be obtained. This nucleator presents a fibrous structure produced via self-assembling and develops into an interconnected network when the temperature is lowered. The TMC-328 crystal nuclei density is quantified via optical microscopy, using the average distance of the adjacent fibrillar structure, which shows a steady decrease with the decrease in temperature. The crystallization rates of TMC-328 were assessed through rheological measurements of network formation. Both fibrils' density and crystallization kinetics display a power law dependence on supersaturation. For the first time, the solid-melt interfacial energy, the size of the critical nucleus, and the number of molecules making up the critical nucleus of the nucleator TMC-328 in the PLLA matrix have been determined by adopting the classical nucleation theory. The subsequent crystallization of PLLA induced by this nucleator was investigated as a function of the fibrils' spatial density. The crystallization rate of PLLA is enhanced with the increase in the TMC-328 fibrils' density because of the availability of a larger nucleating surface. The self-assembled fibril of TMC-328 can serve as shish to form a hybrid shish-kebab structure after the crystallization of PLLA, regardless of the number of nucleation sites.
| S-EPMC8499044 | biostudies-literature
Project description:The influence of macromolecular architecture on shear-induced crystallization of poly(L-lactide) (PLLA) was studied. To this aim, three star PLLAs, 6-arm with Mw of 120 and 245 kg/mol, 4-arm with Mw of 123 kg/mol, and three linear PLLAs with Mw of 121, 240 and 339 kg/mol, were synthesized and examined. The PLLAs were sheared at 170 and 150 °C, at 5/s, 10/s and 20/s for 20 s, 10 s and 5 s, respectively, and then cooled at 10 or 30 °C/min. Shear-induced crystallization during cooling was followed by a light depolarization method, whereas the crystallized specimens were examined by DSC, 2D-WAXS, 2D-SAXS and SEM. The effect of shear depended on the shearing conditions, cooling rate and polymer molar mass but it was also affected by the macromolecular architecture. The shear-induced crystallization of linear PLLA with Mw of 240 kg/mol was more intense than that of the 6-arm polymer with similar Mw, most possibly due to its higher Mz. However, the influence of shear on the crystallization of the star polymers with Mw close to 120 kg/mol was stronger than on that of their linear analog. This was reflected in higher crystallization temperature, as well as crystallinity achieved during cooling.
| S-EPMC8588257 | biostudies-literature