Tough Bioplastics from Babassu Oil-Based Acrylic Monomer, Hemicellulose Xylan, and Carnauba Wax.

We describe here the fabrication, characterization, and properties of tough bioplastics made of a babassu oil-based acrylic polymer (PBBM), hemicellulose xylan grafted with PBBM chains, and carnauba wax (CW). The plastic was primarily designed to obtain bioderived materials that can replace low-density polyethylene (LDPE) in certain food packaging applications. To obtain plastic, the radical polymerization of an original babassu oil-based acrylic monomer (BBM) in the presence of xylan macromolecules modified with maleic anhydride (X-MA) was conducted. The polymerization resulted in a material (PBBM-X) mostly consisting of highly branched PBBM/X-MA macromolecules. PBBM-X has a glass transition of 42 °C, a storage modulus of 130 MPa (at 25 °C, RT), and a Young's modulus of 30 MPa at RT. To increase the moduli, we blended PBBM-X with carnauba wax, a natural material with a high modulus and a melting temperature of ~80 °C. It was found that PBBM-X is compatible with the wax, as evidenced by the alternation of the material's thermal transitions and the co-crystallization of BBM side alkyl fragments with CW. As a result, the PBBM-X/CW blend containing 40% of the wax had a storage modulus of 475 MPa (RT) and a Young's modulus of 248 MPa (RT), which is close to that of LDPE. As polyethylene, the PBBM-X and PBBM-X/CW bioplastics have the typical stress-strain behavior demonstrated by ductile (tough) plastics. However, the bioplastic's yield strength and elongation-at-yield are considerably lower than those of LDPE. We evaluated the moisture barrier properties of the PBBM-X/(40%)CW material and found that the bioplastic's water vapor permeability (WVP) is quite close to that of LDPE. Our bioderived material demonstrates a WVP that is comparable to polyethylene terephthalate and lower than the WVP of nylon and polystyrene. Taking into account the obtained results, the fabricated materials can be considered as polyethylene alternatives to provide sustainability in plastics production in the packaging areas where LDPE currently dominates.

Nanoreactors based on DNAzyme-functionalized magnetic nanoparticles activated by magnetic field.

A new biomimetic nanoreactor design, MaBiDz, is presented based on a copolymer brush in combination with superparamagnetic nanoparticles. This cellular nanoreactor features two species of magnetic particles, each functionalized with two components of a binary deoxyribozyme system. In the presence of a target mRNA analyte and a magnetic field, the nanoreactor is assembled to form a biocompartment enclosed by the polymeric brush that enables catalytic function of the binary deoxyribozyme with enhanced kinetics. MaBiDz was demonstrated here as a cellular sensor for rapid detection and imaging of a target mRNA biomarker for metastatic breast cancer, and its function shows potential to be expanded as a biomimetic organelle that can downregulate the activity of a target mRNA biomarker.

Magnetic Field-Activated Sensing of mRNA in Living Cells.

Detection of specific mRNA in living cells has attracted significant attention in the past decade. Probes that can be easily delivered into cells and activated at the desired time can contribute to understanding translation, trafficking and degradation of mRNA. Here we report a new strategy termed magnetic field-activated binary deoxyribozyme (MaBiDZ) sensor that enables both efficient delivery and temporal control of mRNA sensing by magnetic field. MaBiDZ uses two species of magnetic beads conjugated with different components of a multicomponent deoxyribozyme (DZ) sensor. The DZ sensor is activated only in the presence of a specific target mRNA and when a magnetic field is applied. Here we demonstrate that MaBiDZ sensor can be internalized in live MCF-7 breast cancer cells and activated by a magnetic field to fluorescently report the presence of specific mRNA, which are cancer biomarkers.

Touch- and Brush-Spinning of Nanofibers.

Robust, simple, and scalable touch- and brush-spinning methods for the drawing of nanofibers, core-shell nanofibers, and their aligned 2D and 3D meshes using polymer solutions and melts are discussed.

Electrochemically controlled drug-mimicking protein release from iron-alginate thin-films associated with an electrode.

Novel biocompatible hybrid-material composed of iron-ion-cross-linked alginate with embedded protein molecules has been designed for the signal-triggered drug release. Electrochemically controlled oxidation of Fe(2+) ions in the presence of soluble natural alginate polymer and drug-mimicking protein (bovine serum albumin, BSA) results in the formation of an alginate-based thin-film cross-linked by Fe(3+) ions at the electrode interface with the entrapped protein. The electrochemically generated composite thin-film was characterized by electrochemistry and atomic force microscopy (AFM). Preliminary experiments demonstrated that the electrochemically controlled deposition of the protein-containing thin-film can be performed at microscale using scanning electrochemical microscopy (SECM) as the deposition tool producing polymer-patterned spots potentially containing various entrapped drugs. Application of reductive potentials on the modified electrode produced Fe(2+) cations which do not keep complexation with alginate, thus resulting in the electrochemically triggered thin-film dissolution and the protein release. Different experimental parameters, such as the film-deposition time, concentrations of compounds and applied potentials, were varied in order to demonstrate that the electrodepositon and electrodissolution of the alginate composite film can be tuned to the optimum performance. A statistical modeling technique was applied to find optimal conditions for the formation of the composite thin-film for the maximal encapsulation and release of the drug-mimicking protein at the lowest possible potential.

Fluorescent nanoparticles stabilized by poly(ethylene glycol) containing shell for pH-triggered tunable aggregation in aqueous environment.

Fluorescent silica nanoparticles decorated with a responsive shell, a mixed polymer brush, were synthesized. Specifically, a poly(2-vinylpyridine), P2VP, and poly(ethylene glycol), PEG, binary polymer brush was synthesized on silica nanoparticles via the "grafting to" technique. The selection of the components (PEG and P2VP) for the responsive brush shell was motivated by potential biomedical applications. Poly(glycidyl methacrylate), PGMA, labeled with Rhodamine B, RhB, was used to form a reactive and fluorescent shell on the nanoparticle surface. The interaction between the particles themselves and the particles and their environment can be precisely tuned by a change in pH. At lower pH, aqueous dispersions of the particles are stable, since PEG and P2VP are water-soluble, extended and contribute to the steric and electrostatic mechanisms of colloidal stability. An increase of pH to 6 causes a slow aggregation as a consequence of the hydrophobic attraction between the collapsed and almost nonprotonated P2VP macromolecules. The aggregation was well controlled and occurred within 90-120 min of the pH change. The aggregation was fully reversible after the decrease in pH. The pH variation did not quench the fluorescence of the colloidal suspensions. The pH-tunable aggregation of the fluorescent nanoparticles could find diverse applications for labeling and contrasting of cells and tissues when the size of the label and the intensity of the optical signals can be tuned by and related to the pH of the host environment.

Stimuli-responsive properties of peptide-based copolymers studied via directional growth of self-assembled patterns on solid substrate.

We studied the self-assembly of peptide-based ABA and CBC triblock-copolymers (obtained by bacterial expression) containing random coiled hydrophilic central B blocks flanked with helical A or C blocks. The A and C blocks were of different compositions with respect to the fraction of lysine residues which provided a higher pH sensitivity of the copolymer solutions. The interchain interactions of the copolymers driven by external stimuli (pH and temperature) were explored in the process of macromolecular self-assembling in the thin films of the copolymer solutions deposited on the solid substrate. The interactions involved in the macromolecular association affected the morphology of the developed patterns. The polypeptide of the B block was not involved in the formation of the secondary structures, while the A and C blocks demonstrated helical folding responsible for the intermolecular association. The mechanism of the responsive behavior of the copolymers is based on the reversible assembling of the helices into coiled-coil structures upon the change of pH or temperature. It was found that at low pH values, when electrostatic repulsion was strong and the A/C blocks unfolded, assembling yielded fractal dendrites. Increasing the pH resulted in the recovery of the helical conformation of the A/C blocks and caused a transition from the fractal to compact structures. An elevation of temperature resulted in the disruption of the dendritic structures. The reported here approach to the evaluation of the intermolecular interactions, based on the analysis of the dendritic patterns, provides a rapid and simple method for the characterization of complex processes of self-assembling biomacromolecules.