Synthesis of Multiblock Copolymer Composed of Biodegradable Poly(butylene succinate) and Poly(2-pyrrolidone): Impact of Each Block Length on the Mechanical Properties.

A series of multiblock copolymers comprising a systematic combination of biomass-originated and biodegradable poly(butylene succinate) (PBS) and poly(2-pyrrolidone) (PA4) units is synthesized with various mean degrees of polymerization (mDP) of each unit. Despite the inherent immiscibility of PBS and PA4, multiblock structure allows to mix the two components in the solution-cast films from solution. The mechanical properties of the cast films are highly dependent on the mDP of each unit, as demonstrated by tensile tests. The film of the copolymer with the lowest mDP of each unit (PBS: 17, PA4: 10) is transparent and exhibits extremely high elongation at break (> 400%) and high tensile stress (39.5 MPa) with strain hardening. The films with 50% or higher crystallinity are brittle and opaque, while a decrease in crystallinity can result in higher elongation, as revealed by wide-angle X-ray diffraction measurements.

Statistical Design of Biocarbon Reinforced Sustainable Composites from Blends of Polyphthalamide (PPA) and Polyamide 4,10 (PA410).

A full factorial design with four factors (the ratio of polyphthalamide (PPA) and polyamide 4,10 (PA410) in the polymer matrix, content percent of biocarbon (BioC), the temperature at which it was pyrolyzed and the presence of a chain extender (CE)), each factor with two levels (high and low), was carried out to optimize the mechanical properties of the resulting composites. After applying a linear model, changes in tensile strength, elongation at break and impact energy were not statistically significant within the considered material space, while the ones in the flexural modulus, the tensile modulus, density and heat deflection temperature (HDT) were. The two most influential factors were the content of BioC and its pyrolysis temperature, followed by the content of PPA. The affinity of PPA with a high-temperature biocarbon and the affinity of PA410 with a lower-temperature biocarbon, appear to explain the mechanical properties of the resulting composites. The study also revealed that the addition of CE hindered the mechanical properties. By maximizing the flexural modulus, tensile modulus and HDT, while minimizing the density, the optimal composite predicted is an 80 [PPA:PA410 (25:75)] wt% polymer composite, with 20 wt% of a BioC, pyrolyzed at a calculated 823 °C.

Crystallization and Performance of Polyamide Blends Comprising Polyamide 4, Polyamide 6, and Their Copolymers.

Polyamide 4 (PA4) is a biobased and biodegradable polyamide. The high hydrogen bond density of PA4 bestows it with a high melting point that is close to its thermal decomposition temperature, thereby limiting the melt processing of PA4. In this study, PA4 was blended with polyamide 6 (PA6) and further modified with copolyamide 4/6 (R46). The effects of composition on the crystallization behavior of the blends were studied. The results demonstrated that the binary PA4/PA6 (B46) and ternary PA4/PA6/R46 (B46/R46) blends formed two crystalline phases (PA4- and PA6-rich phases) through crystallization-induced phase separation. With increasing PA6 content, the thermal stability and crystallinity of the B46 blend increased and decreased, respectively, and the contribution of PA6 toward the crystallization of the PA4-rich phase diminished. Molecular dynamics simulations showed the molecular chain orientation of the B46 blends well. The melting points, crystallinities, and grain sizes of the B46/R46 blends were lower than those of the B46 blends. The crystallization of the PA4-rich phase was restrained by the dilution effect of molten-state PA6, and the nucleation and crystallization of the PA6-rich phase were promoted by the presence of crystallized PA4. The B46 blends with 30-40 wt% PA6 had the best mechanical properties.

Rapid determination of 4-aminobutyric acid and L-glutamic acid in biological decarboxylation process by capillary electrophoresis-mass spectrometry.

4-Aminobutylic acid (GABA) is a monomer of plastic polyamide 4. Bio-based polyamide 4 can be produced by using GABA obtained from biomass. The production of L-glutamic acid (Glu) from biomass has been established. GABA is produced by decarboxylation of Glu in biological process. High-performance liquid chromatography (HPLC) with derivatization is generally used to determine the concentration of GABA and Glu in reacted solution samples for the efficient production of GABA. In this study, we have investigated the rapid determination of GABA and Glu by capillary electrophoresis-mass spectrometry (CE-MS) without derivatization. The determination was achieved with the use of a shortened capillary, a new internal standard for GABA, and optimization of sheath liquid composition. Determined concentrations of GABA and Glu by CE-MS were compared with those by pre-column derivatization HPLC with phenylisothiocyanate. The determined values by CE-MS were close to those by HPLC with pre-column derivatization. These results suggest that the determination of GABA and Glu in reacted solution is rapid and simplified by the use of CE-MS.

Evaluating the Performance of a Semiaromatic/Aliphatic Polyamide Blend: The Case for Polyphthalamide (PPA) and Polyamide 4,10 (PA410).

This paper studies the structure-property-processing relationship of polyphthalamide (PPA) PPA/polyamide 4,10 (PA410) blends, via co-relating their thermal-mechanical properties with their morphology, crystallization, and viscoelastic properties. When compared to neat PPA, the blends show improved processability with a lower processing temperature (20 °C lower than neat PPA) along with a higher modulus/strength and heat deflection temperature (HDT). The maximum tensile modulus is that of the 25PPA/75PA410 blend, ~3 GPa, 25% higher than neat PPA (~2.4 GPa). 25PPA/75PA410 also exhibits the highest HDT (136 °C) among all the blends, being 11% more than PPA (122 °C). The increase in the thermo-mechanical properties of the blends is explained by the partial miscibility between the two polymers. The blends improve the processing performance of PPA and broaden its applicability.

Polyamide Microsized Particulate Polyplex Carriers for the 2'-OMethylRNA EFG1 Antisense Oligonucleotide.

Anti-EFG1 2'-OMethylRNA is an antisense oligonucleotide (ASO) that has the ability to recognize and block the EFG1 gene and to control Candida albicans filamentation. However, it is important to protect the anti-EFG1 2'-OMethylRNA ASO from the environmental human body conditions and to ensure that they will be delivered to their site of action, and polyplex microparticles (MPs) represent a class of vehicles to ASO cargo with these functionalities. Thus, the goal of this work was to develop polyplexes based on porous poly(γ-butyrolactam) (PA4) or poly(ε-caprolactam) (PA6) MPs for the anti-EFG1 2'-OMethylRNA ASO cargo and delivery. Two types of polyplexes were prepared with payloads of anti-EFG1 2'-OMethylRNA molecules, either entrapped or immobilized on prefabricated polyamide MPs. Our data confirm that PA4 and PA6 polyplex MPs can be feasible carriers for anti-EFG1 2'-OMethylRNA ASO molecules, using either the entrapment or immobilization strategies, whereby the released ASO maintains its activity against C. albicans cells.