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Academia and industry are interested in using autotrophic microorganisms as a sustainable/green production platform to produce biochemical products and commercially relevant commodities, including biopolymers. Unlike heterotrophs that require carbohydrates and amino acids for growth, autotrophs have evolved to fix carbon dioxide and drive metabolic processes utilizing either light (photoautotrophs) or chemical compounds (chemolithotrophs) as energy sources. Here, we review the current state-of-the-art in the construction of autotrophic microbial cell factories for efficient biopolymer production and recent breakthroughs in natural autotrophs focusing on biopolymer production.
Reverse osmosis (RO) membranes composed of polyamides and cellulose acetates are used as separation layers in pure-water production. However, improving the separation performance and antifouling properties of RO membranes is necessary. This focus review described the composite reverse osmosis membranes with optimal amounts of polyhedral oligomeric silsesquioxanes (POSS), which are cage-shaped, subnanosized molecules exhibiting organic–inorganic hybrid structures, showed improved water flux, NaCl rejection, antichlorine and antifouling properties, and mechanical strength.
Optically active polymers and supramolecules that form well-defined architectures are important materials with a wide range of applications. Amino acids and sugars are great candidates for the preparation of optically active functional materials because of their versatile structures and functional groups. In these chiral units, intra- and intermolecular noncovalent interactions play significant roles in the generation of smart functions. In this focus review, the author reviews his recent studies related to the fabrication and functions of chiral conjugated polymers and chiral supramolecules based on these natural chiral compounds.
Postfunctionalization of aromatic C – H bonds at the main chains of π-conjugated polymers (CPs) is ideal for tuning various functionalities of precursor CPs. In this study, we investigated the electrochemical C – H phosphonylation of the main chain of poly(3-hexylthiophene) (P3HT). Anodic phosphonylation of P3HT was successfully achieved using trialkyl phosphite as an electrically neutral nucleophile in the presence of nonnucleophilic dopants. The chemical structures and the optoelectronic properties of phosphonylated P3HT were characterized. The introduction of phosphonate moieties into the main chain of CPs is potentially useful for improving their processibilities and imparting sensing abilities to them.
The crystalline phase and phase transition behavior of an optically transparent film of star-shaped (heptaisobutyl-T8-silsesquioxy)propyl-substituted octadimethylsiloxy-Q8-silsesquioxane (star-POSS) were studied by DSC and WAXS measurements. This star-POSS exhibited a crystalline phase with a hexagonal system at room temperature and underwent melting above the melting temperature (Tm). The specimens underwent recrystallization even at temperature above Tm, resulting in the same hexagonal system with slightly larger a- and c-axis lengths. The amorphous state of the surrounding isobutyl substituents on the T8-cage framework provides an optically transparent film.
Tetrazine based one-dimensional organic polymers have been investigated as sensing materials for room-temperature sensing of NO2 gas. The well-defined N-heteroatom functionalization within the polymer’s backbone promotes strong hydrogen-bonding interactions with the analyte and detects various concentrations of NO2 (25–150 ppm). The sensing was also highly selective towards NO2 over other tested analytes such as NH3, EtOH, MeOH, Acetone, 2-nitro toluene, and humidity.
Cationic block copolymers consisting of quaternized pyridinium salt and hydrophobic acrylate segments were synthesized and their basic properties as ink dispersants were evaluated. Among all polymers, the copolymer of 4-vinylpyridine and butyl acrylate shows the best properties in rheology and dispersion stability. However, further optimization of molecular design is necessary to achieve suitable redispersion properties as ink dispersants. Through this study, we demonstrated the potential of cationic block copolymers as ink dispersants and the issues that need to be improved for better ink performance.
Supramolecular nylon-based materials exhibited changes in their Young’s moduli and underwent bending upon irradiation with UV light as a result of isomerization in 1:2 complexes of γ-cyclodextrin and azobenzene. The photoisomerization of azobenzenes led to photoresponsive actuation of the supramolecular materials. The movable cross-links contributed to the mechanical toughness and photoresponsive actuation of these materials. Shape restoration of the nylon-based materials resulted in an extraordinarily high work efficiency.
The results of comprehensive research on the thermal behavior, molecular and crystalline structures of poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB-HV) films of different thicknesses, their molecular weights (Mw) and 3-hydroxyvalerate (3-HV) contents are reported. The film thickness affects the PHB film crystalline structure and crystallinity. A decrease in Mw leads to a smaller number of piezoactive domains in PHB films. The addition of HV significantly reduces the crystallinity and piezoresponse of PHB films. A decrease in Mw results in the increased crystallinity of PHB-HV films.
The addition of rGO affected the molecular and crystalline structures of electrospun PLLA scaffolds, leading to the enhanced piezoresponse. An increase of rGO content up to 1 wt% resulted in the increased number of polar C=O functional groups at the surface of fibers and degree of crystallinity of scaffolds. The maximum increase of the effective local lateral piezoresponse (13.9 pm/V) was achieved for 0.2 wt% rGO doping, which is explained by the presence of the shear piezoelectric α-phase (P212121) in uniaxially oriented PLLA fibers and C=O bond rotation in the polymer chains.
