Multiple Carbon Morphologies Derived from Polyion Complex-Based Double Hydrophilic Block Copolymers as Templates and Phenol as a Carbon Precursor.

This study demonstrates the multiple carbon morphology forming abilities of two dissimilar polyion complex (PIC)-based double hydrophilic block copolymers (DHBC) along with three different phenol concentrations when subjecting the blend in aqueous media via a hydrothermal-assisted carbonization strategy. The morphological transition from worm-like to spherical along with granular is found for the blend of oppositely charged poly(ethylene glycol) (PEG)-conjugated poly(amino acid) block copolymers, PEG-poly(l-lysine) (PEG-PLys) and PEG-poly(glutamic acid) (PEG-PGlu), along with three different concentrations of phenol. In contrast, after mixing the combination of PEG-PLys and PEG-poly(aspartic acid) (PEG-PAsp) separately with three different phenol contents, elliptical to irregular to spherical structural transition occurred. Fourier transform infrared and circular dichroism spectroscopic studies indicated that the formation of worm-like hybrid micellar structures is attributed to the presence of the ß-sheet structure, whereas spherical-shaped hybrid micellar structures are formed due to the existence of α-helix and random coil structures. We discuss the mechanism for the secondary structure-induced morphology formation based on the theory related to the packing parameter, which is commonly used for analyzing the shape of the micellar structures. Secondary structures of the PIC-based DHBC system are responsible for forming multiple carbon morphologies, whereas these structures are absent in the case of the amphiphilic block copolymer (ABC) system. Furthermore, ABC-based template methods require organic solvent, ultrasonication, and a prolonged solvent evaporation process to obtain multiple carbon morphologies. Scanning electron microscopy observations suggested there is no significant morphological change even after subjecting the hybrid micelles to carbonization at elevated temperatures. Raman scattering studies revealed that the degree of graphitization and the graphitic crystallite domain size of the carbonized sample depend on the phenol content. Carbon materials exhibited the highest specific surface area of 579 m2 g-1 along with a pore volume of 0.398 cc g-1, and this observation suggests that the prepared carbons are porous. Our findings illustrate the facile and effective strategy to fabricate the multiple carbon morphologies that can be used as potential candidates for energy storage applications.

Study of PLA pre-treatment, enzymatic and model-compost degradation, and valorization of degradation products to bacterial nanocellulose.

It is well acknowledged that microplastics are a major environmental problem and that the use of plastics, both petro- and bio- based, should be reduced. Nevertheless, it is also a necessity to reduce the amount of the already spread plastics. These cannot be easily degraded in the nature and accumulate in the food supply chain with major danger for animals and human life. It has been shown in the literature that advanced oxidation processes (AOPs) modify the surface of polylactic acid (PLA) materials in a way that bacteria more efficiently dock on their surface and eventually degrade them. In the present work we investigated the influence of different AOPs (ultrasounds, ultraviolet irradiation, and their combination) on the biodegradability of PLA films treated for different times between 1 and 6 h. The pre-treated samples have been degraded using a home model compost as well as a cocktail of commercial enzymes at mesophilic temperatures (37 °C and 42 °C, respectively). Degradation degree has been measured and degradation products have been identified. Excellent degradation of PLA films has been achieved with enzyme cocktail containing commercial alkaline proteases and lipases of up to 90% weight loss. For the first time, we also report valorization of PLA into bacterial nanocellulose after enzymatic hydrolysis of the samples.

Biodegradation of Poly (Butylene Succinate) (PBS)/Stearate Modified Magnesium-Aluminium Layered Double Hydroxide Composites under Marine Conditions Prepared via Melt Compounding.

In the present work, polybutylene succinate (PBS)/stearate modified magnesium-aluminium layered double hydroxide (St-Mg-Al LDH) composites were prepared via melt processing and the effect of different loadings of St-Mg-Al LDH on the degradation behaviour of PBS under marine conditions was investigated. The morphological, mechanical and thermal characteristics of the composites were studied using different characterisation techniques. Optical imaging and scanning electron microscopy revealed that the incorporation of St-Mg-Al LDH accelerates the degradation of PBS along with the activity of microorganisms adhered to the composite films. PBS/St-Mg-Al LDH composites are found to have lower thermal degradation temperatures than those of pure PBS. The decrease in thermal stability is correlated with the degradation of PBS due to the catalytic action Mg and Al present in LDH. Tensile and DMA analysis revealed that the addition of St-Mg-Al LDH did not have a significant impact on the mechanical properties of PBS.

Biodegradable Plastic Blends Create New Possibilities for End-of-Life Management of Plastics but They Are Not a Panacea for Plastic Pollution.

Plastic waste pollution is a global environmental problem which could be addressed by biodegradable plastics. The latter are blended together to achieve commercially functional properties, but the environmental fate of these blends is unknown. We have tested neat polymers, polylactic acid (PLA), polyhydroxybutyrate, polyhydroxyoctanoate, poly(butylene succinate), thermoplastic starch, polycaprolactone (PCL), and blends thereof for biodegradation across seven managed and unmanaged environments. PLA is one of the world's best-selling biodegradable plastics, but it is not home compostable. We show here that PLA when blended with PCL becomes home compostable. We also demonstrate that the majority of the tested bioplastics and their blends degrade by thermophilic anaerobic digestion with high biogas output, but degradation times are 3-6 times longer than the retention times in commercial plants. While some polymers and their blends showed good biodegradation in soil and water, the majority of polymers and their blends tested in this study failed to achieve ISO and ASTM biodegradation standards, and some failed to show any biodegradation. Thus, biodegradable plastic blends need careful postconsumer management, and further design to allow more rapid biodegradation in multiple environments is needed as their release into the environment can cause plastic pollution.

Sequential extraction of fucoidan, laminarin, mannitol, alginate and protein from brown macroalgae Ascophyllum nodosum and Fucus vesiculosus.

The study involves development of a green biorefinery process for obtaining fucoidan, laminarin, mannitol, alginate and protein from dry and fresh Fucus vesiculosus and Ascophyllum nodosum using hydrochloric acid and a green extraction solvent. After the extraction of fucoidan which was the targeted biomolecule, an extract and by-product (residual biomass) were obtained. The extract was passed through an ultrafiltration membrane, where fucoidan was obtained in the ultrafiltration retentate while ultrafiltration permeate was analysed for laminarin and mannitol. The residual biomass was used for obtaining alginate using ultrasound (20 kHz, 64 % amplitude and 32 min, optimum parameters for alginate extraction based on our previous study). All the samples, showed good results for alginate, laminarin and mannitol, indicating that the by-products can be utilised using this green extraction process. The comparison of both dry and fresh seaweed is relevant from an industry perspective, as fresh seaweed can directly be used for extraction, avoiding drying which adds significantly to the cost of the process. Life cycle impact assessment of the complete seaweed value chain has been carried out to identify the energy demand and key environmental hotspots. This biorefinery process can be used by industry to improve their processes and utilise the by-products generated efficiently.

Fabrication and Evaluation of Filtration Membranes from Industrial Polymer Waste.

Polyvinylidene fluoride (PVDF) polymers are known for their diverse range of industrial applications and are considered important raw materials for membrane manufacturing. In view of circularity and resource efficiency, the present work mainly deals with the reusability of waste polymer 'gels' produced during the manufacturing of PVDF membranes. Herein, solidified PVDF gels were first prepared from polymer solutions as model waste gels, which were then subsequently used to prepare membranes via the phase inversion process. The structural analysis of fabricated membranes confirmed the retention of molecular integrity even after reprocessing, whereas the morphological analysis showed a symmetric bi-continuous porous structure. The filtration performance of membranes fabricated from waste gels was studied in a crossflow assembly. The results demonstrate the feasibility of gel-derived membranes as potential microfiltration membranes exhibiting a pure water flux of 478 LMH with a mean pore size of ~0.2 µm. To further evaluate industrial applicability, the performance of the membranes was tested in the clarification of industrial wastewater, and the membranes showed good recyclability with about 52% flux recovery. The performance of gel-derived membranes thus demonstrates the recycling of waste polymer gels for improving the sustainability of membrane fabrication processes.

Comparison Study of an Optimized Ultrasound-Based Method versus an Optimized Conventional Method for Agar Extraction, and Protein Co-Extraction, from Gelidium sesquipedale.

Agar is a hydrocolloid found in red seaweeds, which has been of industrial interest over the last century due to its multiple applications in the food, cosmetic, and medical fields. This polysaccharide, extracted by boiling for several hours, is released from the cell wall of red seaweeds. However, the environmental impact coming from the long processing time and the energy required to reach the targeted processing temperature needs to be reduced. In this study, a response surface methodology was employed to optimize both conventional extraction and ultrasound-assisted extractions. Two different models were successfully obtained (R2 = 0.8773 and R2 = 0.7436, respectively). Additionally, a further re-extraction confirmed that more agar could be extracted. Protein was also successfully co-extracted in the seaweed residues. Optimized conditions were obtained for both the extractions and the re-extraction of the two methods (CE: 6 h, 100 °C; and UAE: 1 h, 100% power). Finally, FT-IR characterization demonstrated that the extracts had a similar spectrum to the commercial agar. Compared to commercial samples, the low gel strength of the agar extracts shows that these extracts might have novel and different potential applications.

Improved Surface Functional and Photocatalytic Properties of Hybrid ZnO-MoS2-Deposited Membrane for Photocatalysis-Assisted Dye Filtration.

The synergistic mechanism of photocatalytic-assisted dye degradation has been demonstrated using a hybrid ZnO-MoS2-deposited photocatalytic membrane (PCM). Few layers of MoS2 sheets were produced using the facile and efficient surfactant-assisted liquid-phase exfoliation method. In this process, hydrophilic moieties of an anionic surfactant were adsorbed on the surface of MoS2, which aided exfoliation and promoted a stable dispersion due to the higher negative zeta potential of the exfoliated MoS2 sheets. Further, the decoration of ZnO on the exfoliated MoS2 sheets offered a bandgap energy reduction to about 2.77 eV, thus achieving an 87.12% degradation of methylene blue (MB) dye within 15 min of near UV-A irradiation (365 nm), as compared with pristine ZnO achieving only 56.89%. The photocatalysis-enhanced membrane filtration studies on the ZnO-MoS2 PCM showed a complete removal of MB dye (~99.95%). The UV-assisted dye degradation on the ZnO-MoS2 PCM offered a reduced membrane resistance, with the permeate flux gradually improving with the increase in the UV-irradiation time. The regeneration of the active ZnO-MoS2 layer also proved to be quite efficient with no compromise in the dye removal efficiency.