Aggregation and Gelation Behavior of Stereocomplexed Four-Arm PLA-PEG Copolymers Containing Neutral or Cationic Linkers.

Poly(lactide) (PLA) and poly(ethylene glycol) (PEG)-based hydrogels were prepared by mixing phosphate buffer saline (PBS, pH 7.4) solutions of four-arm (PEG-PLA)2-R-(PLA-PEG)2 enantiomerically pure copolymers having the opposite chirality of the poly(lactide) blocks. Dynamic Light Scattering, rheology measurements, and fluorescence spectroscopy suggested that, depending on the nature of the linker R, the gelation process followed rather different mechanisms. In all cases, mixing of equimolar amounts of the enantiomeric copolymers led to micellar aggregates with a stereocomplexed PLA core and a hydrophilic PEG corona. Yet, when R was an aliphatic heptamethylene unit, temperature-dependent reversible gelation was mainly induced by entanglements of PEG chains at concentrations higher than 5 wt.%. When R was a linker containing cationic amine groups, thermo-irreversible hydrogels were promptly generated at concentrations higher than 20 wt.%. In the latter case, stereocomplexation of the PLA blocks randomly distributed in micellar aggregates is proposed as the major determinant of the gelation process.

Thermal, Mechanical, and Rheological Properties of Biocomposites Made of Poly(lactic acid) and Potato Pulp Powder.

The thermal, mechanical, and rheological properties of biocomposites of poly(lactic acid) (PLA) with potato pulp powder were investigated in order to (1) quantify how the addition of this filler modifies the structure of the polymeric material and (2) to obtain information on the possible miscibility and compatibility between PLA and the potato pulp. The potato pulp powder utilized is a residue of the processing for the production and extraction of starch. The study was conducted by analyzing the effect of the potato pulp concentration on the thermal, mechanical, and rheological properties of the biocomposites. The results showed that the potato pulp powder does not act as reinforcement but as filler for the PLA polymeric matrix. A progressive decrease in elastic modulus, tensile strength, and elongation at break was observed with increasing the potato pulp percentage. This moderate loss of mechanical properties, however, still meets the technical requirements indicated for the production of rigid packaging items. The incorporation of potato pulp powder to PLA offers the possibility to reduce the cost of the final products and promotes a circular economy approach for the valorization of agro-food waste biomass.

Interactive impacts of microplastics and arsenic on agricultural soil and plant traits.

The ability of microplastics (MPs) to interact with environmental pollutants is currently of great concern due to the increasing use of plastic. Agricultural soils are sinks for multipollutants and the safety of biodegradable MPs in field conditions is questioned. However, still few studies have investigated the interactive effects between MPs and metals on the soil-plant system with agricultural soil and testing crops for human consumption. In this work, we tested the effect on soil and plant parameters of two common MPs, non-degradable plastic low-density polyethylene and biodegradable polymer polylactic acid at two different sizes (<250 µm and 250-300 µm) in association with arsenic (As). Lettuce (Lactuca sativa L.) was used as a model plant in a small-scale experiment lasting 60 days. Microplastics and As explained 12 % and 47 % of total variance, respectively, while their interaction explained 21 %, suggesting a higher toxic impact of As than MPs. Plant growth was promoted by MPs alone, especially when biodegradable MPs were added (+22 %). However, MPs did not affect nutrient concentrations in roots and leaves. The effect of MPs on enzyme activities was variable depending on the time of exposure (with larger effects immediately after exposure), the type and size of the MPs. On the contrary, the co-application of MP and As, although it did not change the amount of bioavailable As in soil in the short and medium term, it resulted in a significant decrease in lettuce biomass (-19 %) and root nutrient concentrations, especially when polylactic acid was applied. Generally, MPs in association with As determined the plant-soil toxicity. This work provides insights into the risk of copollution of MPs and As in agricultural soil and its phytotoxic effect for agricultural crops. However, the mechanisms of the joint effect of MP and As on plant toxicity need further investigation, especially under field conditions and in long-term experiments.

Towards the design of highly selective recognition sites into molecular imprinting polymers: a computational approach.

A computational approach to simulate the formation of possible imprinted polymers in acetonitrile solution for theophylline (THO) is proposed, using combined molecular dynamics (MD), molecular mechanics (MM), docking and site mapping computational techniques. Methacrylic acid (MAA) and methylmethacrylate (MMA) monomers are used to simulate possible homo and copolymer structures. The model is able predict binding affinity and selectivity when considering THO analogues, such as caffeine, theobromine, xanthine and 3-methylxanthine. Comparison with available experimental data is proposed.