Development of poly(butylene oxalate-co-furanoate) copolymers with enhanced sustainability and hydrolytic degradability.

Polyoxalate, a novel intrinsically hydrolysable polyester, garners significant interest for its high cost-effectiveness and versatility. However, concerns persist regarding its durability in practical applications. This study integrates bio-based poly(butylene furanoate) (PBF), which possesses remarkable barrier performance, into the poly(butylene oxalate) (PBOx) framework to synthesize poly(butylene oxalate­co­furanoate) (PBOF) with tunable degradation rates. The influence of incorporating BF units on thermal, crystalline, mechanical, and barrier properties was systematically analyzed. Results demonstrated the addition of BF units dramatically improved the balance between degradation and physical properties. Laboratory degradation experiments indicated that PBOF possessed significant degradation effects. Among them, PBOF-41 (with 41 % molar furanoate) decreased in weight by 20 % in freshwater, 70 % in an enzyme solution, and 8 % in artificial seawater within 30 days. After 28 days of degradation in soil, the residual weight was reduced to 80 % of its initial weight. Theoretical calculations and experiments have clarified the enhancement of the Gibbs free energy and energy barrier of the hydrolysis reaction by the BF unit. In summary, PBOF copolyesters have excellent gas barrier performance, adjustable thermal properties, well-balanced mechanical properties, and degradability, making them highly promising for sustainable plastic products.

Poly(butylene oxalate-co-terephthalate): A PBAT-like but rapid hydrolytic degradation plastic.

Concerns over worldwide plastic pollution have led to the development of biodegradable polyester materials with excellent physical and chemical properties through the copolymerization of poly(butylene oxalate) (PBOx). As a result, poly(butylene oxalate-co-terephthalate)s (PBOTs) with varying compositions, were prepared by incorporating aromatic units. Studies have indicated that PBOT-47 (with a 47% molar terephthalate), exhibits exceptional mechanical properties. With an elongation at break of 1160% and a tensile strength that remains above 30 MPa, similar to or even better than those of the commercial biodegradable plastic poly(butylene adipate-co-terephthalate) PBAT-47 (47% molar terephthalate). Moreover, the permeability coefficients of PBAT-47 for H2O, CO2 and O2 were 5.8, 50.6 and 5.6 times higher than that of PBOT-47, revealing the superior barrier properties of PBOT. Through experimental research and theoretical simulation, the mechanism of the copolymer hydrolysis was elucidated. The readily hydrolytic nature of the oxalate unit endows it with the capacity for rapid degradation, possessing the potential to be a short-term degradable material with physical properties similar to PBAT.

Synthesis of renewable furan-based phosphate and the superior flame retardancy in biodegradable polylactide.

Currently, it has long been considered a challenge to provide sustainable additives for polylactide (PLA) in green way to endow it excellent comprehensive properties. Given the flammability and unsatisfactory crystallization performance of PLA, a furan-based phosphate furfurylamine trimethylphosphate (FATMP) was synthesized from 2-furfurylamine and amino trimethylphosphonic acid by a simple hydration reaction, and the PLA/FATMP composites were prepared by melting blending process. The tensile performance, crystallization behaviors, flame retardancy, and flame-retardant mechanism received special attention. Results showed that the incorporation of only 3 wt% FATMP could indeed increase the LOI value of PLA from 19.8 to 27.3 %, and simultaneously acquired V-0 rating in the vertical burning test owing to the favorable synergistic effect between the vapor phase and the condensed phase. Additionally, the half-crystallization time of PLA was decreased from 12.4 to 5.1 mins with the addition of FATMP, which acted as a nucleating agent. More appealingly, the tensile performance of PLA/FATMP composites was also well maintained. In general, the PLA/FATMP composites we proposed could be promising candidates in application fields where favorable flame retardancy and crystallization ability are required.

Differential development and electrophysiological activity in cultured cortical neurons from the mouse and cynomolgus monkey.

In vitro cultures of primary cortical neurons are widely used to investigate neuronal function. However, it has yet to be fully investigated whether there are significant differences in development and function between cultured rodent and primate cortical neurons, and whether these differences influence the utilization of cultured cortical neurons to model pathological conditions. Using in vitro culture techniques combined with immunofluorescence and electrophysiological methods, our study found that the development and maturation of primary cerebral cortical neurons from cynomolgus monkeys were slower than those from mice. We used a microelectrode array technique to compare the electrophysiological differences in cortical neurons, and found that primary cortical neurons from the mouse brain began to show electrical activity earlier than those from the cynomolgus monkey. Although cultured monkey cortical neurons developed slowly in vitro, they exhibited typical pathological features-revealed by immunofluorescent staining-when infected with adeno-associated viral vectors expressing mutant huntingtin (HTT), the Huntington's disease protein. A quantitative analysis of the cultured monkey cortical neurons also confirmed that mutant HTT significantly reduced the length of neurites. Therefore, compared with the primary cortical neurons of mice, cultured monkey cortical neurons have longer developmental and survival times and greater sustained physiological activity, such as electrophysiological activity. Our findings also suggest that primary cynomolgus monkey neurons cultured in vitro can simulate a cell model of human neurodegenerative disease, and may be useful for investigating time-dependent neuronal death as well as treatment via neuronal regeneration. All mouse experiments and protocols were approved by the Animal Care and Use Committee of Jinan University of China (IACUC Approval No. 20200512-04) on May 12, 2020. All monkey experiments were approved by the IACUC protocol (IACUC Approval No. LDACU 20190820-01) on August 23, 2019 for animal management and use.

End-Chain Fluorescent Highly Branched Poly(l-lactide)s: Synthesis, Architecture-Dependence, and Fluorescent Visible Paclitaxel-Loaded Microspheres.

A facile method in combination of "grafting from" and "end-functionalization" was developed for the synthesis of fluorescent highly branched poly(l-lactide)s (PLLA-COU) via ring opening polymerization (ROP) and esterification end-capping. These resulting PLLA-COU with four kinds of architectures, including linear, star, linear-comb, and star-comb structures, were subjected to characterization and application as fluorescent visible paclitaxel-loaded microspheres. The mutual effects of architecture and end-groups on thermal and fluorescence properties, enzymatic degradation, and drug release behaviors were focused. Contrast to linear and star PLLA-COU, two comb-shaped analogues demonstrated higher fluorescence quantum yield, faster drug release, and lower enzymatic degradation rate. All the fluorescent microspheres could maintain fluorescence traceability. The fluorescent PLLA-COU displayed negligible toxicity and good biocompatibility. This work highlights that the fluorescent highly branched poly(l-lactide)s are properties-tailored and used as fluorescent visible drug delivery systems (DDS) for potential theranostic applications.

Development of biodegradable polyesters based on a hydroxylated coumarin initiator towards fluorescent visible paclitaxel-loaded microspheres.

In this work, we developed a facile end-functionalization method using hydroxylated coumarin to initiate the ring-opening polymerization of cyclic esters to synthesize a series of fluorescent biodegradable aliphatic polyesters with tailorable properties. The resulting fluorescent functionalized poly(l-lactide) (PLLA-COU), poly(ε-caprolactone) (PCL-COU) poly(δ-valerolactone) (PVL-COU) and poly(trimethylene carbonate) (PTMC-COU) were investigated to evaluate the dependence of fluorescence on the chemical structure and molecular weight of the materials. The differences in the electron withdrawing ability and the density of ester groups are responsible for the changes in the fluorescence quantum yield. Then, two representative biodegradable materials, namely, PLLA-COU and PCL-COU, were used to prepare fluorescent paclitaxel-loaded microspheres. During in vitro drug release, the release rate of the PCL-COU microspheres is dramatically faster than that of the PLLA-COU microspheres due to the difference in the material nature and their surface morphologies, possibly achieving a tunable degradation and release rate for the drug carriers. Fluorescent functionalized polyester microspheres can retain their fluorescence properties and emit bright blue light for fluorescence tracing during the degradation process. Biological evaluations showed that both fluorescent polyesters are devoid of any significant toxicity and have good biocompatibility. The results demonstrated that the obtained fluorescent polyesters are promising for use in traceable and controlled drug delivery with tunable drug release.