High Molecular Weight Poly Research Articles

Synthetic Periodontal Guided Tissue Regeneration Membrane with Self-Assembling Biphasic Structure and Temperature-Sensitive Shape Maintenance.

Periodontal disease poses significant challenges to the long-term stability of oral health by destroying the supporting structures of teeth. Guided tissue regeneration techniques, particularly barrier membranes, enable local regeneration by providing an isolated, protected compartment for osseous wound healing while excluding epithelial tissue. Here, this study reports on a thermosensitive periodontal membrane (TSPM) technology designed to overcome the mechanical limitations of current membranes through a semi-interpenetrating network of high molecular weight poly(L-lactic acid) (PLLA) and in situ-polymerized mesh of poly(ε-caprolactone)diacrylate (PCL-DA), and poly lactide-co-glycolide diacrylate (PLGA-DA). An optimized composition allows facile reshaping at greater than 52 °C and rigid shape maintenance at physiological temperature. Its unique bilayer morphology is achieved through self-assembly and thermally-induced phase separation, resulting in distinct yet continuous smooth and nanofibrous compartments adequate for epithelial occlusion and regeneration. Incorporating PLGA-DA enhances the membrane's hydrophilicity and degradation properties, facilitating a more rapid and controlled degradation and therapeutic delivery. This study demonstrates its ability to promote local regeneration by serving as a barrier membrane and simultaneously as a scaffolding matrix in a rat orthotopic periodontal defect model. The TSPM outperformed a clinically available material (Epi-Guide) to facilitate robust alveolar bone and periodontal ligament regeneration at 4 and 8 weeks.

Poly(ethylene‐glycol)‐Dimethacrylate (PEGDMA) Composite for Stereolithographic Bioprinting

AbstractRecent progress in additive manufacturing has enabled the application of stereolithography (SLA) in bioprinting to produce 3D biomimetic structures. Bioinks for SLA often require synthetic polymers as supplements to ensure the structural integrity of the printed cell‐laden constructs. High molecular weight (MW) poly(ethylene‐glycol)‐diacrylate (PEGDA) (MW ≥ 3400 Da) is commonly used to enhance the mechanical property of crosslinked hydrogels. However, the production of bioink with high MW PEGDA requires in‐house polymer synthesis or the acquisition of costly reagents, which may not be readily available in all laboratory settings. As an alternative to high MW PEGDA, this research investigated the use of poly(ethylene‐glycol)‐dimethacrylate (PEGDMA) (MW = 1000 Da) as a supplement of a bioink to enhance the mechanical properties of the SLA‐printed constructs. The successful demonstration showcases 1) the fabrication of 3D constructs with overhang and complex architecture, and 2) the cytocompatibility, with high cell viability of 71–87% over 6 days of culture, of the GelMA‐PEGDMA bioink to enable cell‐laden bioprinting. This study suggests PEGDMA as a viable supplement in the formulation of SLA bioink. The accessibility to PEGDMA will facilitate the advance in 3D bioprinting to fabricate complex bioinspired structures and tissue surrogates for biomedical applications.

Calcium phosphate nanoclusters modify periodontium remodeling and minimize orthodontic relapse.

Orthodontic relapse is one of the most prevalent concerns of orthodontic therapy. Relapse results in patients' teeth reverting towards their pretreatment positions, which increases the susceptibility to functional problems, dental disease, and substantially increases the financial burden for retreatment. This phenomenon is thought to be induced by rapid remodeling of the periodontal ligament (PDL) in the early stages and poor bone quality in the later stages. Current therapies, including fixed or removable retainers and fiberotomies, have limitations with patient compliance and invasiveness. Approaches using biocompatible biomaterials, such as calcium phosphate polymer-induced liquid precursors (PILP), is an ideal translational approach for minimizing orthodontic relapse. Here, post-orthodontic relapse is reduced after a single injection of high concentration PILP (HC-PILP) nanoclusters by altering PDL remodeling in the early stage of relapse and improving trabecular bone quality in the later phase. HC-PILP nanoclusters are achieved by using high molecular weight poly aspartic acid (PASP, 14 kDa) and poly acrylic acid (PAA, 450 kDa), which resulted in a stable solution of high calcium and phosphate concentrations without premature precipitation. In vitro results show that HC-PILP nanoclusters prevented collagen type-I mineralization, which is essential for the tooth-periodontal ligament (PDL)-bone interphase. In vivo experiments show that the PILP nanoclusters minimize relapse and improve the trabecular bone quality in the late stages of relapse. Interestingly, PILP nanoclusters also altered the remodeling of the PDL collagen during the early stages of relapse. Further in vitro experiments showed that PILP nanoclusters alter the fibrillogenesis of collagen type-I by impacting the protein secondary structure. These findings propose a novel approach for treating orthodontic relapse and provide additional insight into the PILP nanocluster's structure and properties on collagenous structure repair.

Synthesis and characterization of biobased copolyesters based on pentanediol: (2) Poly(pentylene adipate‐co‐terephthalate)

AbstractTraditionally, most flexible food packaging is made of linear low‐density polyethylene (LLDPE) which cannot easily be recycled, nor will it degrade in a reasonable timescale. In this work, a biobased biodegradable polyester alternative was investigated as a possible replacement for LLDPE. High molecular weight poly (pentylene adipate‐co‐terephthalate) with a 40/60 adipic acid/terephthalic acid mole ratio was synthesized using direct esterification and polycondensation. Glycerol and hexane‐1,2,5,6‐tetrol were added as branching agents to better match the structure of the LLDPE which in turn might help the ability of these materials in film‐blowing. Thermal, mechanical, and rheological properties of the copolyesters were thoroughly investigated. All copolyesters had a weight‐average molecular weight of over 140,000 g/mol, which is necessary for proper rheology, and were thermally stable up to 350°C. The addition of branching agents led to a slight decrease in crystallinity, d‐spacing, melting temperature, enthalpy of melting, stress at break, and elongation at break. However, an increase in Young's modulus and complex viscosity at high frequency were observed compared to PPeAT60 without branching agent added. Although the improved crystallinity and mechanical properties of the copolyesters made them viable for film‐blowing, the slow crystallization rate creates a major challenge.Highlights Linear and branched poly(pentylene adipate‐co‐terephthalate) (PPeAT) synthesized. Properties compared to commercial poly(butylene adipate‐co‐terephthalate) (PBAT). Glass and melting temperatures comparable to commercial PBAT. Extensional and shear viscosity comparable to commercial PBAT. PPeAT stiffness is factor of 2 higher than PBAT; ultimate properties similar.

Unlocking the potential of supramolecular polymers with bimodal molecular weights for instant and strong underwater adhesion

Developing adhesives suitable for underwater environments remains a formidable challenge due to the barrier presented by water, hindering contact between the adhesive and adherend. In this work, supramolecular adhesives prepared by mixing low and high molecular weight poly(butyl acrylate)-based copolymers are manifested to function effectively for underwater adhesion regardless of substrates’ affinity to water. Optimization of adhesion performance is achieved by manipulating the copolymer composition, resulting in the remarkable adhesion strengths of 1290 N m-1 and 1047 N m-1 to hydrophobic PET and hydrophilic glass substrates, respectively. The observed high underwater adhesion is attributed to a synergistic effect: instant and efficient removal of the hydration layer facilitated by the low molecular weight polymer strands, and mechanical resilience conferred by the high molecular weight strands featured by chain entanglements. Adequate interfacial interactions are attained by the supramolecular interactions including cation-π and π-π bonding. Notably, owing to its inherent hydrophobicity, the adhesive can be stored underwater for over a week and still displays 842 N m-1 peel strength to glass substrate. This work unlocks the potential of supramolecular adhesives with bimodal molecular weight distribution for instant and strong underwater adhesion, providing a straightforward yet scalable strategy to produce high-performance underwater adhesives.

Synthesis of long-chain aliphatic poly(β-thioester)s via thiol-Michael polyaddition and their applications in noble metal recovery and information encryption

Long-chain aliphatic polyesters are recognized as the most promising polyethylene mimics in that these materials show comparative physicochemical properties to polyolefins and own the unique merits of degradability and/or recyclability. Nevertheless, the application scenarios of these polymers are rather limited owing to the lack of functional groups. Herein, sulfur atoms are incorporated into the microstructures of long-chain aliphatic polyesters to decipher the variations of physicochemical properties upon replacing specific methylene units by thioether moieties and simultaneously impart polyethylene-like materials with functionalities. First of all, high molecular weight polyesters P1-P4 and poly(β-thioester)s P5-P8 were obtained via condensation polymerization and thiol-Michael polyaddition, respectively. As for phase transition behaviors, poly(β-thioester)s show inferior crystallization/melting temperatures and the corresponding enthalpy changes than their polyester counterparts, and a loosely packed crystalline structure should be responsible for such thermal property degradation. It is reasonable that replacing specific methylene units of long-chain aliphatic polyesters by sulfur atoms, the much bulkier functional entities, will definitely cause great disturbance to the regular arrangement of polymer chains. The rapid hydrolytic degradation of poly(β-thioester)s in acidic and alkaline media can be ascribed to the easy penetration of water molecules into their incompact amorphous/crystalline regions. In the meantime, these poly(β-thioester)s exhibit great prospects in noble metal recovery and information encryption (optical anticounterfeiting). For instance, poly(β-thioester) P5 is an excellent adsorbent to abstract gold ions from water due to its outstanding metal coordination capability. Moreover, poly(β-thioester) P5 emits bright blue photoluminescence in concentrated solution and solid state upon UV irradiation as a result of the clustering-triggered through space electron delocalization and rigidified polymer chain conformation.

Aluminum oxyhydroxide-Poly(I:C) combination adjuvant with balanced immunostimulatory potentials for prophylactic vaccines

The development of high-purity antigens promotes the urgent need of novel adjuvant with the capability to trigger high levels of immune response. Polyinosinic-polycytidylic (Poly(I:C)) is a synthetic double-stranded RNA (dsRNA) that can engage Toll-like receptor 3 (TLR3) to initiate immune responses. However, the Poly(I:C)-induced toxicity and inefficient delivery prevent its applications. In our study, combination adjuvants are formulated by aluminum oxyhydroxide nanorods (AlOOH NRs) and Poly(I:C), named Al-Poly(I:C), and the covalent interaction between the two components is further demonstrated. Al-Poly(I:C) mediates enhanced humoral and cellular immune responses in three antigen models, i.e., HBsAg virus-like particles (VLPs), human papilloma virus (HPV) VLPs and varicella-zoster virus (VZV) glycoprotein E (gE). Further mechanistic studies demonstrate that the dose and molecular weight (MW) of Poly(I:C) determine the physicochemical properties and adjuvanticity of the Al-Poly(I:C) combination adjuvants. Al-Poly(I:C) with higher Poly(I:C) dose promotes antigen-bearing dendritic cells (DCs) recruitment and B cells proliferation in lymph nodes. Al-Poly(I:C) formulated with higher MW Poly(I:C) induces higher activation of helper T cells, B cells, and CTLs. This study demonstrates that Al-Poly(I:C) potentiates the humoral and cellular responses in vaccine formulations. It offers insights for adjuvant design to meet the formulation requirements in both prophylactic and therapeutic vaccines.

ZnGA/DMC catalysts for the synthesis of high molecular weight poly(propylene carbonate): The crucial role of water treatment

Zinc glutarate (ZnGA) is a prominent catalyst for the production of CO2-based poly(propylene carbonate). The original catalysts, ZnO-GA (Cat 1) and ZnAc2-GA (Cat 3), were prepared using ZnO and ZnAc2 as Zn sources, respectively. ZnO-GA-H2O (Cat 2) and ZnAc2-GA-H2O (Cat 4) were prepared by water treatment of Cat 1 and Cat 3, respectively. After water treatment, both Cat 2 and Cat 4 showed enhanced performance for copolymerization of CO2 and propylene oxide. The characterizations demonstrated that H2O is a critical component that not only improves the crystallinity and external surface area of ZnGA, but also increases the number of surface Zn-OH groups. By adding a portion of cyanide, further modification on Cat 4 resulted in a group of ZnAc2-GA-H2O/DMC catalysts (m-Cat 4). The polymerization reached a high yield of 1729 g poly/g Cat and a selectivity of 98.7 % at molar ratio of DMC/ZnGA = 1: 10 (t = 24 h; T = 70 °C; P = 4 MPa). The modified ZnGA/DMC catalyst exhibited remarkable yield and selectivity for the copolymerization of CO2 and propylene oxide to produce high molecular weight alternating copolymers (2.3 × 105 g/mol).

Designing hydrolysis-resistant Ti/Zn bimetallic catalyst based on the coordination activation mechanism to synthesize high molecular weight poly (1,5-pentene terephthalate) (PPeT)

The high molecular weight poly (1,5-pentene terephthalate) synthesis and its molecular weight distribution control are still challenging, and one of the critical problems is the lack of efficient catalysts. Based on the coordination activation mechanism, a heavy metal free, hydrolysis-resistant and 1,5-Pentanediol soluble Ti/Zn bimetallic catalyst has been synthesized and characterized. The Ti/Zn bimetallic active center increases electron-absorption effect in catalyst to promote the esterification process, and the diol-metal alkoxide structure increases the production of oligomer ligands, which can effectively improve transesterification efficiency. The optimal polycondensation reaction temperature for PPeT synthesized with Ti/Zn bimetallic catalyst can be reduced to 230 °C, with an average reaction rate of 90.33 g mol−1·min−1. The number average molecular weight of PPeT can be increased to 3.02 × 104 g mol−1, and the polymer dispersive index can be as low as 1.90. As the number average molecular weight increases, poly (1,5-pentene terephthalate) has a tensile strength of 29.80 MPa and an elongation at break of 16.39%. More importantly, Ti/Zn bimetallic catalyst retains excellent catalytic activity after treatment with boiling water and has significantly improved hydrolysis resistance and storage stability. Ti/Zn bimetallic catalyst can significantly increase the molecular weight and melt viscosity of poly (1,5-pentene terephthalate), giving it the potential for a wider range of applications in plastics and fiber fields.

Sustainable aerogels based on biobased poly (itaconic acid) for adsorption of cationic dyes

This work reports the synthesis of poly (itaconic acid) by thermal polymerization mediated by 2,2′-Azobis(2-methylpropionamidine) dihydrochloride. Furthermore, physical hydrogels were prepared by using high molecular weight poly (itaconic acid) characterized by low dispersity and laponite RD. The hydrogels presented porous 3D network structures, with a high-water penetration of almost 2000 g/g of swelling ratio, which can allow the adsorption sites of both poly (itaconic acid) and laponite RD to be easily exposed and facilitate the adsorption of dyes. The water adsorption followed Schott's pseudo-second-order model. The mechanism of the adsorption process was investigated using 1H and 31P NMR. The hydrogel is able to fast adsorb by a combination of electrostatic interactions and hydrogen bonding by the synergic effect of the clay and poly (itaconic acid). Moreover, the prepared aerogels exhibited a fast removal of Basic Fuchsin, with an adsorption capacity of 67.56 mg/g and a high removal efficiency (~99 %). The adsorption followed the pseudo-second-order kinetic model and Langmuir isotherm model. Furthermore, the thermodynamic parameters showed that the BF process of adsorption was spontaneous and feasible, endothermic, and followed physisorption. These results indicated that the PIA/laponite-based aerogel can be considered a promising adsorbent material in textile wastewater treatment.

Solvent-cast 3D printing with molecular weight polymer blends to decouple effects of scaffold architecture and mechanical properties on mesenchymal stromal cell fate.

The biochemical and physical properties of a scaffold can be tailored to elicit specific cellular responses. However, it is challenging to decouple their individual effects on cell-material interactions. Here, we solvent-cast 3D printed different ratios of high and low molecular weight (MW) poly(caprolactone) (PCL) to fabricate scaffolds with significantly different stiffnesses without affecting other properties. Ink viscosity was used to match processing conditions between inks and generate scaffolds with the same surface chemistry, crystallinity, filament diameter, and architecture. Increasing the ratio of low MW PCL resulted in a significant decrease in modulus. Scaffold modulus did not affect human mesenchymal stromal cell (hMSC) differentiation under osteogenic conditions. However, hMSC response was significantly affected by scaffold stiffness in chondrogenic media. Low stiffness promoted more stable chondrogenesis whereas high stiffness drove hMSC progression toward hypertrophy. These data illustrate how this versatile platform can be used to independently modify biochemical and physical cues in a single scaffold to synergistically enhance desired cellular response.

Facile Synthesis of High Molecular Weight Poly(ethylene glycol)-b-poly(amino acid)s by Relay Polymerization.

Poly(amino acid)s (PAAs) are one kind of favorable biopolymer that can be used as a drug or gene carrier. However, conventional ring-opening polymerization of PAAs is slow and needs a strict anhydrous environment with an anhydrous reagent as well as the product without enough high molecular weight (Mn), which limits the expanding of PAAs' application. Herein, we took BLG-NCA as the monomer to quickly synthesize one kind of high Mn amphiphilic copolymer, poly(ethylene glycol)-b-poly(γ-benzyl-l-glutamic acid) (PEG-PBLG), by relay polymerization with a simple one-pot method within 3 h in mild conditions (open air, moisture insensitive). In the polymerization process, ring-opening polymerization-induced self-assembly in sodium bicarbonate aqueous solution first occurred to obtain low Mn PEG-PBLG seeds without purification. Then γ-benzyl-l-glutamate N-carboxyanhydride (BLG-NCA) dichloromethane solution was added into PEG-PBLG seeds directly and stirred vigorously to form am emulsion; during this process, the amphiphilic PEG-PBLG seeds will anchor on the interface of DCM and water to ensure the concentration of α-helix rigid PBLG in DCM to maintain the following relay polymerization. Then, high Mn PEG-PBLG was obtained in mild conditions in one pot. We found that the α-helix rigid structure was essential for relay polymerization by studying the synthetic speed of amphiphilic copolymer with different secondary structures. MOE simulation results showed that PBLG and BLG-NCA tended to form a double hydrogen bond, which was beneficial to relay polymerization because of higher local concentrations that can produce more double hydrogen bonds. Our strategy can quickly obtain high Mn PEG-PBLG (224.9 KDa) within 3 h from PEG-NH2 and BLG-NCA in one pot and did not need an extra initiator. After deprotection, the poly(ethylene glycol)-b-poly(l-glutamate acid) (PEG-PGA) with high Mn as a second product can be used as an excellent antitumor drug carrier. The high Mn PEG-PGA can achieve an encapsulation rate of 86.7% and a drug loading rate of 47.3%, which is twice that of the low Mn PEG-PGA. As a result, the synthesis of PEG-PBLG by relay polymerization simplified the process of PEG-PAA polymerization and increased the Mn. In addition, this method opened a way to obtain other kinds of high Mn PEG-PBLG values in the future.

Synthesis of high molecular weight poly(ricinoleic acid) via a direct solution polycondensation in hydrophobic ionic liquids

Ricinoleic acid, a natural hydroxy fatty acid, is a good candidate for preparing biodegradable polymer elastomers. Herein, high molecular weight poly(ricinoleic acid) (PRA) with a weight average molecular weight up...

Supramolecular nanoarchitectonics of propionylated polyrotaxanes with bulky nitrobenzyl stoppers for light-triggered drug release.

Cyclodextrin (CD)-based polyrotaxanes (PRXs) are supramolecular polymers comprising multiple CDs mechanically interlocked onto a linear polymer chain by capping the polymer ends with bulky stoppers. Among various PRX derivatives, propionylated PRXs (Pr-PRXs) composed of propionylated α-CD and high molecular-weight poly(ethylene glycol) (PEG) form self-assembled nanoparticles in aqueous solution through hydrophobic interactions. Although Pr-PRX nanoparticles can encapsulate hydrophobic drugs in their hydrophobic domains, their release rate is limited. To improve the efficiency of drug release from Pr-PRX nanoparticles, ultraviolet (UV) light-dissociable Pr-PRXs were designed using 4,5-dimethoxy 2-nitrobenzyl groups as UV-cleavable bulky stopper molecules to facilitate UV-induced drug release. Photodegradable Pr-PRX (Pr-PD-PRX) was synthesized, and its UV-induced dissociation was examined. Pr-PD-PRX was completely dissociated via UV irradiation (365 nm) for 30 min. Additionally, Pr-PD-PRX nanoparticles encapsulating hydrophobic drugs collapsed upon UV irradiation, which promoted the release of the encapsulated drugs compared to non-degradable Pr-PRX nanoparticles. UV irradiation of drug-loaded Pr-PD-PRX nanoparticles resulted in higher cytotoxicity than non-irradiated Pr-PD-PRX and non-degradable Pr-PRX. Consequently, designing photodegradable PRX-based nanoparticles provides new insights into developing photoresponsive drug carriers and smart biomedical materials.

Catalyst-free synthesis of high-molecular weight poly(alkylene oxalate)s

In this work, a catalyst-free protocol, “volatility-assisted competitive transesterification polymerization”, was proposed to synthesize poly(alkylene oxalate)s with short reaction times.

Hydroxide Conducting Naphthalene-Containing Polymers and Membranes Via Polyhydroxyalkylations

Anion exchange membranes (AEMs) are critical components of alkaline membrane water electrolyzers and fuel cells that are under development today [1,2]. Consequently, there is a strong demand for highly conductive and alkali-stable AEMs. In this context, polyhydroxyalkylation has emerged as one of the most efficient synthetic pathways to chemically resistant polymer backbones for AEMs. In these Friedel-Crafts type polycondensations, an electron-rich aromatic compound reacts with an activated ketone or aldehyde to produce an aryl-ether-free polymer. The desired quaternary ammonium cations are then usually introduced through a Menshutkin reaction [3,4].In the current work, we have employed naphthalene-based compounds as monomers in polyhydroxyalkylations to prepare a series of high-molecular weight poly(naphthalene alkylene)s with various naphthalene contents. These polymers were then quaternized and cast into AEMs. Here, we will discuss the influence of the naphthalene monomer type and content on AEM properties such as solubility, water uptake, ion conductivity, ionic clustering, thermal and alkaline stability, and also the prospects of using these AEMs in electrochemical systems.

Innate immune response to double-stranded RNA in American heritage chicken breeds

Backyard poultry flocks that employ heritage breeds of chicken play a crucial role in the maintenance of poultry pathogens of economic and zoonotic importance. This study examined innate immunity to viral pathogens in heritage chicken breeds using a model of viral double-stranded RNA (dsRNA). Following intraperitoneal injection of high molecular weight (HMW) -poly(I:C)/Lyovec into 4-wk-old chicks, we evaluated gene expression in peripheral blood mononuclear cells (PBMCs) and splenocytes. There was a significant difference across breeds in the expression of IL-4, IL-12p40, IFNγ, and B-cell activating factor (BAFF) in the spleen. In PBMCs, a significant difference in IFN-α expression was seen across breeds. Approximately 57% of IFN-α transcripts in PBMCs was explained by levels of expression of MDA5 transcripts. Using flow cytometry, we showed that only monocytes/macrophages (KUL01+ cells) expressed the scavenger receptor CD163. Regression analysis showed that 42% of fold change in CD163 expression on PBMCs was explained by breed (P < 0.0004). In general, breeds that responded to HMW-poly(I:C) by showing higher upregulation of IFNγ, IL-1β, and IL-12p40 transcripts in the spleen, and higher IFNα transcripts in peripheral blood, expressed less CD163 on blood monocytes. These findings suggest a genetic basis for the response of chickens to double-stranded RNA. Surface expression of the scavenger receptor CD163 in PBMCs following injection of high molecular weight poly(I:C) may be a rapid method to select chickens for breeding based on innate immune response to viral dsRNA.

Combining isosorbide and lignin-related benzoic acids for high-Tg polymethacrylates

The insertion of rigid aliphatic or aromatic building blocks in polymer structures is an efficient synthetic strategy towards high-Tg polymer materials. In the present work, we have functionalized isosorbide 5-methacrylate with various aromatic lignin-inspired esters to yield a series of isosorbide-2-aryl carboxylate-5-methacrylate monomers (ArIMAs) as single regioisomers. The selection of phenyl carboxylate side groups included benzoate, p-cyanobenzoate, meta/para-methoxybenzoates, and different vanillic acid esters. This afforded a range of seven bio-based monomers with different size, polarity, and substitutions. Polymerizations were carried out by conventional free radical initiation to obtain the corresponding high molecular-weight poly(aryl carboxylate isosorbide methacrylate)s (PArIMAs). The polymerizations were evaluated in different solvents, including toluene, EtOAc, γ-valerolactone, 2-MeTHF, and DMSO to identify the most suitable conditions. The polymers exhibited high glass transition temperatures in a broad range, from 80 to 168 °C, and were thermally stable up to 268 °C. Furthermore, dynamic rheology experiments indicated that the polymers were sufficiently stable for melt processing. The availability of the building blocks combined with the high stability of the polymers make these materials attractive for use as high-performance plastics and coatings.

Temperature-responsive PCL-PLLA nanofibrous tissue engineering scaffolds with memorized porous microstructure recovery.

Biomaterial scaffolds in tissue engineering facilitate tissue regeneration and integration with the host. Poor healing outcomes arise from lack of cell and tissue infiltration, and ill-fitting interfaces between matrices or grafts, resulting in fibrous tissue formation, inflammation, and resorption. Existing tissue engineering scaffolds struggle to recover from deformation to fit irregularly shaped defects encountered in clinical settings without compromising their mechanical properties and favorable internal architecture. This study introduces a synthetic biomaterial scaffold composed of high molecular weight poly (L-lactic acid) (PLLA) and an interpenetrating network of poly (ε-caprolactone) (PCL), in a composition aiming to address the need for conformal fitting synthetic matrices which retain and recover their advantageous morphologies. The scaffold, known as thermosensitive memorized microstructure (TS-MMS), forms nanofibrous materials with memorized microstructures capable of recovery after deformation, including macropores and nanofibers. TS-MMS nanofibers, with 50-500 nm diameters, are formed via thermally induced phase separation (TIPS) of PLLA after in situ polymerization of PCL-diacrylate. A critical partial-melting temperature of TS-MMS at 52°C enables bulk deformation above this temperature, while retaining the nanofibrous and macroporous structures upon cooling to 37°C. Incorporation of drug-loaded poly (lactide-co-glycolide) (PLGA) nanoparticles directly into TS-MMS nanofibers during fabrication allows sustained release of a model drug for up to 40 days. Subcutaneous implantation in vivo using LysM-Cre;td-Tomato; Col1eGFP mice demonstrates successful cellularization and integration of deformed/recovered TS-MMS materials, surpassing the limitations of deformed PLLA scaffolds, to facilitate cell and vasculature infiltration requisite for successful bone regeneration. Additionally we demonstrated a method for embedding controlled release vehicles directly into the scaffold nanofibers; controlled release of simvastatin enhances vascularization and tissue maturation. TS-MMS scaffolds offer promising improvements in clinical handling and performance compared to existing biomaterial scaffolds.

Tetrabutylammonium Halides as Selectively Bifunctional Catalysts Enabling the Syntheses of Recyclable High Molecular Weight Salicylic Acid‐Based Copolyesters

AbstractTo synthesize high molecular weight poly(phenolic ester) via a living ring‐opening polymerization (ROP) of cyclic phenolic ester monomers remains a critical challenge due to serious transesterification and back‐biting reactions. Both phenolic ester bonds in monomer and polymer chains are highly active, and it is difficult so far to distinguish them. In this work, an unprecedented selectively bifunctional catalytic system of tetra‐n‐butylammonium chloride (TBACl) was discovered to mediate the syntheses of high molecular weight salicylic acid‐based copolyesters via a living ROP of salicylate cyclic esters (for poly(salicylic methyl glycolide) (PSMG), Mn=361.8 kg/mol, Ð&lt;1.30). Compared to previous catalysis systems, the side reactions were suppressed remarkably in this catalysis system because phenolic ester bond in monomer can be selectively cleaved over that in polymer chains during ROP progress. Mechanistic studies reveal that the halide anion and alkyl‐quaternaryammonium cation work synergistically, where the alkyl‐quaternaryammonium cation moiety interacts with the carbonyl group of substrates via non‐classical hydrogen bonding. Moreover, these salicylic acid‐based copolyesters can be recycled to dimeric monomer under solution condition, and can be recycled to original monomeric monomers without catalyst under sublimation condition.