Development of Kraft Lignin Chemically Modified as a Novel Crosslinking Agent for the Synthesis of Active Hydrogels

In this research a chemical modification of kraft lignin was carried out using a basic nucleophilic substitution reaction (NSA) in order to functionalize it as a novel crosslinking agent for the synthesis of active hydrogels. The chemical modification success of the synthesized crosslinker was demonstrated by using several techniques such as volumetry probes, FTIR, 1H-NMR and DSC. Thus, the obtained materials were employed during the synthesis of acrylic acid-based hydrogels, due to its high-water absorption capacity to evaluate their retention potential of heavy metal ions. Characterization of the active hydrogels were performed by FTIR and SEM, showing the specific signals corresponding to the base monomers into the polymer skeleton and the efficiency of modified kraft lignin as a novel crosslinking agent. Additionally, to demonstrate the potential use of these hydrogels in wastewater treatment, metal ions adsorption experiments were conducted, showing adsorption percentages higher than 90% and 80% for Pb2+ and Cu2+, respectively

Colloidal Stability of Chitosan/DNA Polyelectrolyte Complexes in Presence of Biological Polyanions

International audienceNatural or synthetic polycations are used in nucleic acid‐based therapies as complexing agents which interact electrostatically with nucleic acids, condense them into nanoparticles, protect them and control their entry into cells. However, although the literature on the formation of nanoparticles known as complexes is well documented, fewer studies have focused on the physical chemistry behind their disassembly, especially under physicochemical conditions found in an intracellular environment. There are several theories of the disassembly of these complexes, one of them consisting in the exchange between the polycations of these particles with biological polyanions. This project is focused on the study of the complexation mechanism of chitosan and calf‐thymus DNA, as well as the stability of the obtained complexes in presence of biological polyanions, i.e., glycosaminoglycans (GAGs). In the presence of polyelectrolyte complexes, GAGs that are present in cells are expected to compete with nucleic acids and dissociate the complex if polycation–GAG association is thermodynamically favored. It is found that chitosan/DNA complexes colloidal stability depends on its [N+]/[P−] charge ratio (R). Furthermore, it is determined that the aggregation onset of the complexes, generated by the addition of different GAGs, depends on the structure and the charge density of the GAGs

Biopolymer‐Based Nanogels Synthesis, Characterization, and Stability for Doxorubicin Encapsulation and Delivery

International audienceNanogels are nanostructures with dimensions within the nanoscale, composed of crosslinked polymers through their functional groups. Nanogels can display sensitiveness to stimuli, such as pH or temperature. This characteristic has been used in the design of new platforms for the transport and release of active ingredients. Biopolymer‐based nanogels are of great interest due to their biodegradability, biocompatibility, nontoxicity, and among others. In this project, pH‐responsive nanogels are synthesized through a novel methodology, using two polysaccharides classified as safe, biocompatible, and easily accessible materials, i.e., chitosan (CS) and maltodextrin (MD). A reductive amination reaction between CS and partially oxidized MDs allows to synthesized MD/CS nanogels with sizes ranging from 90 ± 5 to 194 ± 40 nm and with a colloidal stability up to 7 weeks. It is found that the variation of nanogels size and charge depends on CS concentration, molecular weight, and pH, as well as on the % oxidation of the MD. As evidence of nanogels pH‐responsiveness, an increase of size and ζ‐potential is observed by decreasing the pH. This size increase is attributed to the swelling of the nanogels upon a change in pH. Finally, doxorubicin is encapsulated in MD/CS nanogels, with a loading capacity up to 57%

Effect of DNA's Molecular Weight on their Solution Viscosity, Critical Concentrations, and Liquid Crystals Formation

International audienceThe study of the dynamics of nucleic acids in solution, their flow properties, and viscoelasticity is of great importance for understanding their biological functions. Many important properties of nucleic acids, such as DNA, depend on polymer concentration, CDNA, molecular weight (MW), rigidity, and external salt content, the latter parameter affecting electrostatic interactions. Furthermore, DNA molecular chains can organize, in vitro, into liquid crystalline phases at high CDNA. In this work, three DNA samples with different MW were studied in solution in a broad concentration range (CDNA from 0.025 to 200 mg mL−1, depending on DNA MW). Firstly, the intrinsic viscosities and MW for all DNA samples were determined through capillary and rheological measurements. Then, the overlap concentrations, C*, were estimated from the relation C* ≈ [η]−1. DNA chain characteristics were then analyzed in terms of the influence of DNA MW on the solution viscosities and on the overlap parameter, CDNA[η]. Flow birefringence appearance was identified by screening a wide CDNA range through visual observations with crossed polarizers. Finally, crossed‐light polarized microscopy was used to identify the appearance of liquid crystals at rest, confirming that higher CDNA are needed to obtain liquid crystals for low MW DNA samples

Structural Behavior of Amphiphilic Triblock Copolymer P104/Water System

International audienceA detailed study of the different structural transitions of the triblock copolymer PEO27-PPO61-PEO27 (P104) in water, in the dilute and semi-dilute regions, is addressed here as a function of temperature and P104 concentration (C-P104) by mean of complimentary methods: viscosimetry, densimetry, dynamic light scattering, turbidimetry, polarized microscopy, and rheometry. The hydration profile was calculated through density and sound velocity measurements. It was possible to identify the regions where monomers exist, spherical micelle formation, elongated cylindrical micelles formation, clouding points, and liquid crystalline behavior. We report a partial phase diagram including information for P104 concentrations from 1 x 10(-4) to 90 wt.% and temperatures from 20 to 75 degrees C that will be helpful for further interaction studies with hydrophobic molecules or active principles for drug delivery

Optimization of the Obtaining of Cellulose Nanocrystals from <i>Agave tequilana</i> Weber Var. Azul Bagasse by Acid Hydrolysis

A multilevel factorial design of 23 with 12 experiments was developed for the preparation of cellulose nanocrystals (CNC) from Agave tequilana Weber var. Azul bagasse, an agro-industrial waste from tequila production. The studied parameters were acid type (H2SO4 and HCl), acid concentration (60 and 65 wt% for H2SO4, 2 and 8N for HCl) temperature (40 and 60 °C for H2SO4, 50 and 90 °C for HCl), and hydrolysis time (40, 55 and 70 min for H2SO4; and 30, 115 and 200 min for HCl). The obtained CNC were physical and chemically characterized using dynamic light scattering (DLS), atomic force microscopy (AFM), Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XDR) techniques. The maximum CNC yield was 90 and 96% for HCL and H2SO4, respectively, and the crystallinity values ranged from 88–91%. The size and morphology of A. tequilana CNC strongly depends on the acid type and hydrolysis time. The shortest CNC obtained with H2SO4 (65 wt%, 40 °C, and 70 min) had a length of 137 ± 68 nm, width 33 ± 7 nm, and height 9.1 nm, whereas the shortest CNC obtained with HCl (2 N, 50 °C and 30 min) had a length of 216 ± 73 nm, width 69 ± 17 nm, and height 8.9 nm. In general, the obtained CNC had an ellipsoidal shape, whereas CNC prepared from H2SO4 were shorter and thinner than those obtained with HCl. The total sulfate group content of CNC obtained with H2SO4 increased with time, temperature, and acid concentration, exhibiting an exponential behavior of CSG=aebt

THE USE OF POLYSACCHARIDES EXTRACTED FROM SEED OF Persea americana var. Hass ON THE SYNTHESIS OF ACRYLIC HYDROGELS

This paper reports the use of polysaccharides extracted from seed of Persea americana var. Hass in the synthesis of acrylic hydrogels. The effects of the chemical composition (acrylamide/acrylic acid), the concentration of crosslinking agent (glycerol diacrylate) and the type of initiation (redox, photoinitiation) of the hydrogels were evaluated with and without polysaccharides. Xerogels were characterized by FTIR spectroscopy, differential scanning calorimetry (DSC) and scanning electron microscopy (SEM), while for the swollen hydrogels the swelling kinetic and mechanical properties were evaluated. The kinetic parameters were obtained using the second order equation proposed by Schott, where it is reported that by increasing the concentration of the crosslinking agent, the degree of swelling is reduced because of the greater structural level. The increase of the amount of acrylamide and the amount of polysaccharides causes also a decrease in the swelling degree. The type of initiation also affected the hydrogels swelling kinetic, the photoinitiated hydrogels were the ones that captured less water. Moreover, the increasing of the glass transition temperature and the compression modulus with the crosslinking agent concentration and molar ratio AAm/AAc are observed for hydrogels with and without polysaccharides. The results demonstrate a successful incorporation of polysaccharides into the polymeric network

THE USE OF POLYSACCHARIDES EXTRACTED FROM SEED OF Persea americana var. Hass ON THE SYNTHESIS OF ACRYLIC HYDROGELS

<div><p>This paper reports the use of polysaccharides extracted from seed of Persea americana var. Hass in the synthesis of acrylic hydrogels. The effects of the chemical composition (acrylamide/acrylic acid), the concentration of crosslinking agent (glycerol diacrylate) and the type of initiation (redox, photoinitiation) of the hydrogels were evaluated with and without polysaccharides. Xerogels were characterized by FTIR spectroscopy, differential scanning calorimetry (DSC) and scanning electron microscopy (SEM), while for the swollen hydrogels the swelling kinetic and mechanical properties were evaluated. The kinetic parameters were obtained using the second order equation proposed by Schott, where it is reported that by increasing the concentration of the crosslinking agent, the degree of swelling is reduced because of the greater structural level. The increase of the amount of acrylamide and the amount of polysaccharides causes also a decrease in the swelling degree. The type of initiation also affected the hydrogels swelling kinetic, the photoinitiated hydrogels were the ones that captured less water. Moreover, the increasing of the glass transition temperature and the compression modulus with the crosslinking agent concentration and molar ratio AAm/AAc are observed for hydrogels with and without polysaccharides. The results demonstrate a successful incorporation of polysaccharides into the polymeric network.</p></div