Trunk Injection of Citrus Trees with a Polymeric Nanobactericide Reduces Huanglongbing Severity Caused by Candidatus Liberibacter asiaticus.

Huanglongbing (HLB) is a disease caused by the phloem- limited Candidatus Liberibacter asiaticus (CLas) that affects the citrus industry worldwide. To date, only indirect strategies have been implemented to eradicate HLB. Included among these is the population control of the psyllid vector (Diaphorina citri), which usually provides inconsistent results. Even though strategies for direct CLas suppression seem a priori more promising, only a handful of reports have been focused on a confrontation of the pathogen. Recent developments in polymer chemistry have allowed the design of polycationic self-assembled block copolymers with outstanding antibacterial capabilities. Here, we report the use of polymeric nano-sized bactericide particles (PNB) to control CLas directly in the phloem vasculature. The field experiments were performed in Rioverde, San Luis Potosí, and is one of the most important citrusproducing regions in Mexico. An average 52% reduction in the bacterial population was produced when PNB was injected directly into the trunk of 20 infected trees, although, in some cases, reduction levels reached 97%. These results position PNB as a novel and promising nanotechnological tool for citrus crop protection against CLas and other related pathogens.

All-Aqueous, Surfactant-Free, and pH-Driven Nanoformulation Methods of Dual-Responsive Polymer Nanoparticles and their Potential use as Nanocarriers of pH-Sensitive Drugs.

All-aqueous, surfactant-free, and pH-driven nanoformulation methods to generate pH- and temperature-responsive polymer nanoparticles (NPs) are described. Copolymers comprising a poly(methyl methacrylate) (PMMA) backbone with a few units of 2-(dimethylamino)ethyl methacrylate (DMAEMA) are solubilized in acidic buffer (pH 2.0) to produce pH-sensitive NPs. Copolymers of different molar mass (2.3-11.5 kg mol-1 ) and DMAEMA composition (7.3-14.2 mol%) are evaluated using a "conventional" pH-driven nanoformulation method (i.e., adding an aqueous polymer solution (acidic buffer) into an aqueous non-solvent (basic buffer)) and a robotized method for pH adjustment of polymer dispersions. Dynamic light scattering, zeta-potential (ζ), and sedimentation-diffusion analyses suggest the formation of dual-responsive NPs of tunable size (from 20 to 110 nm) being stable for at least 28 days in the pH and temperature intervals from 2.0 to 6.0 and 25 to 50 °C, respectively. Ultraviolet-visible spectroscopic experiments show that these NPs can act as nanocarriers for the pH-sensitive dipyridamole drug, expanding its bioavailability and potential controlled release as a function of pH and temperature. These approaches offer alternative strategies to prepare stimuli-responsive NPs, avoiding the use of harmful solvents and complex purification steps, and improving the availability of biocompatible polymer nanoformulations for specific controlled release of pH-sensitive cargos.

Development of Photocurable Polyacrylate-Based PolyHIPEs and the Study of the Kinetics of Photopolymerization, and of Their Thermal, Mechanical and Hydrocarbon Absorption Properties.

This article describes a comprehensive study to obtain polymeric porous materials via a photopolymerization technique, using acrylate-based high internal phase emulsions (HIPEs), as a template. The aim of obtaining these polymers was to use them as hydrocarbon absorbing materials. Kinetics of photopolymerization of the acrylate monomers and of the HIPEs were conducted to optimize the process. The obtained monoliths were characterized by thermal analysis such as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The morphology and surface area were analyzed by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) analysis. The compression properties of the materials were determined, as well as their absorption properties of hydrocarbons such as hexane, diesel, toluene and chloroform. The findings show that the acrylate-HIPEs displayed high reactivity photopolymerizing in 20 min. The glass transition temperature of the materials were in the range of 2 to 83 °C, depending on the ratio of acrylates in the photocurable formulation, displaying the characteristic morphology with voids and interconnecting windows. The polyHIPEs exhibited superior properties of absorption of the studied hydrocarbons. The order of capability of absorption was chloroform > toluene > hexane > diesel. The optimum absorbing material was that with trimethylolpropane triacrylate, ethylhexyl acrylate and isobornyl acrylate in a 1:0.9:2.1 ratio, which absorbed 778% of chloroform, 378% of toluene, 306 % of hexane and 236% of diesel.

Exogenous Application of Polycationic Nanobactericide on Tomato Plants Reduces the Candidatus Liberibacter Solanacearum Infection.

Candidatus Liberibacter solanacearum (CaLso) is associated with diseases in tomato crops and transmitted by the tomato psyllid Bactericera cockerelli. A polymeric water-dispersible nanobactericide (PNB) was evaluated against CaLso as a different alternative. PNB is a well-defined polycationic diblock copolymer designed to permeate into the vascular system of plants. Its assessment under greenhouse conditions was carried out with tomato plants previously infected with CaLso. Using a concentration as low as 1.0 mg L-1, a small but significant reduction in the bacterial load was observed by real-time qPCR. Thus, to achieve an ecologically friendly dosage and set an optimum treatment protocol, we performed experiments to determine the effective concentration of PNB to reduce ~65% of the initial bacterial load. In a first bioassay, a 40- or 70-fold increase was used to reach that objective. At this concentration level, other bioassays were explored to determine the effect as a function of time. Surprisingly, a real reduction in the symptoms was observed after three weeks, and there was a significant decrease in the bacterial load level (~98%) compared to the untreated control plants. During this period, flowering and formation of tomato fruits were observed in plants treated with PNB.

Improving Recycled Poly(lactic Acid) Biopolymer Properties by Chain Extension Using Block Copolymers Synthesized by Nitroxide-Mediated Polymerization (NMP).

The aim of this contribution is to assess the use poly(styrene-co-glycidyl methacrylate-b-styrene) copolymers synthesized by nitroxide mediated polymerization (NMP) as chain extenders in the recycling of poly(lactic acid) biopolyester. Concisely, the addition of such block copolymers during the melt processing of recycled poly(lactic acid) (rPLA) leads to important increases in the viscosity average molecular weight of modified polymeric materials. Molar masses increase from 31,000 g/mol for rPLA to 48,000 g mol-1 for the resulting rPLA/copolymer blends (bPLA). Fortuitously, this last value is nearly the same as the one for pristine PLA, which constitutes a first piece of evidence of the molar mass increase of the recycled biopolymer. Thermograms of chain extended rPLA show significant decreases in cold crystallization temperature and higher crystallinity degrees due to the chain extension process using NMP-synthesized copolymers. It was found that increasing epoxide content in the NMP-synthesized copolymers leads to increased degrees of crystallinity and lower cold crystallization temperatures. The rheological appraisal has shown that the addition of NMP synthesized copolymers markedly increases complex viscosity and elastic modulus of rPLA. Our results indicate that P(S-co-GMA)-b-S) copolymers act as efficient chain extenders of rPLA, likely due to the reaction between the epoxy groups present in P(S-co-GMA)-b-PS and the carboxyl acid groups present in rPLA. This reaction positively affects viscometric molar mass of PLA and its performance.

Combinations of Antimicrobial Polymers with Nanomaterials and Bioactives to Improve Biocidal Therapies.

The rise of antibiotic-resistant microorganisms has become a critical issue in recent years and has promoted substantial research efforts directed to the development of more effective antimicrobial therapies utilizing different bactericidal mechanisms to neutralize infectious diseases. Modern approaches employ at least two mixed bioactive agents to enhance bactericidal effects. However, the combinations of drugs may not always show a synergistic effect, and further, could also produce adverse effects or stimulate negative outcomes. Therefore, investigations providing insights into the effective utilization of combinations of biocidal agents are of great interest. Sometimes, combination therapy is needed to avoid resistance development in difficult-to-treat infections or biofilm-associated infections treated with common biocides. Thus, this contribution reviews the literature reports discussing the usage of antimicrobial polymers along with nanomaterials or other inhibitors for the development of more potent biocidal therapies.