Valorization of Hermetia illucens breeding rejects by chitins and chitosans production. Influence of processes and life cycle on their physicochemical characteristics.

Breeding of the black soldier fly is carried out to produce proteins. It is accompanied by releases during the life cycle of this insect. This work is a study of the valorization of these rejects through the production of chitins and chitosans with controlled characteristics. An extraction process is developed with an order of treatments and reaction conditions that provide chitins with high contents. These contents increase as the stages of the life cycle progress and drop for the adult. However, the exuviae chitins present organic impurities which will be eliminated at the N-deacetylation reaction for pupe and after a purification treatment for chitosan from larval stages. All these chitins have an α structure although certain physicochemical characteristics of the larval exuviae chitins are close to those presented by γ chitin. The observed shifts are linked to the effect of impurities rather than to a difference in structure. N-deacetylation of chitins makes possible the valorization of all rejects by the production of pure chitosans with high yields which retain a porous structure for the exuviae and fibrous for the adult which allow complementary applications. These chitosans are highly to completely deacetylated and their molar masses can vary depending on the process and life stage.

Amphiphilic derivatives of chitosan using microwave irradiation. Toward an eco-friendly process to chitosan derivatives.

Conventional heating and microwave irradiation have been compared for the synthesis of chitosans grafted with alkyl chains. Reaction time (1-60 min), temperature (25 and 40 °C) and chitosan molar mass have been studied onto the yield of alkylation. The irradiation mode has been scrupulously controlled to highlight the effect of the use of microwaves. The chemical structure of modified polymers (degree of alkylation) is determined from NMR. In relation to the rheological behavior and surface tension measurements, the evolution of hydrophobic interactions is studied as a function of the yield of alkylation. A maximum of intrinsic viscosity and hydrodynamic diameter was observed for a degree of alkylation of around 10%. All the results tend to prove that microwave assisted synthesis is a powerful method to obtain modified chitosan under extremely low reaction time without any degradation and/or property modifications.

Phases in the temporal multiscale evolution of the drug release mechanism in IPN-type chitosan based hydrogels.

The study proposes modeling calcein release kinetics (considered as a hydrophilic drug model) from an interpenetrating network matrix of hydrogels, based on the combination of two polymers, of which chitosan is the most commonly used polymer. The release process is analyzed for different increasing time intervals, based on the evolution of the release kinetics. For each time interval, a dominant release mechanism was identified and quantitative analyses were performed, to probe the existence of four distinct stages during its evolution with each stage governed by a different kinetics model. An interesting and original aspect, which is analyzed through a novel approach, is that of drug release at longer time scales, which is often overlooked. It revealed that the system behaves as a complex one and its evolution can be described through a nonlinear theoretical model, which offers us new insights into its order-disorder evolution.

Saponins: a renewable and biodegradable surfactant from its microwave-assisted extraction to the synthesis of monodisperse lattices.

Synthetic surfactants are widely used in emulsion polymerization, but it is increasingly desirable to replace them with naturally derived molecules with a reduced environmental burden. This study demonstrates the use of saponins as biodegradable and renewable surfactants for emulsion polymerization. This chemical has been extracted from soapnuts by microwave assisted extraction and characterized in terms of surfactant properties prior to emulsion polymerization. The results in terms of particle size distribution and morphology control have been compared to those obtained with classical nonionic (NP40) or anionic (SDS) industrial surfactants. Microwave-extracted saponins were able to lead to latexes as stable as standard PS latex, as shown by the CMC and CCC measurements. The saponin-stabilized PS particles have been characterized in terms of particle size and distribution by Dynamic Light Scattering and Asymmetrical Flow Field Flow Fractionation. Monomodal and monodispersed particles ranging from 250 to 480 nm in terms of diameter with a particle size distribution below 1.03 have been synthesized.

Theoretical and experimental study of low band gap polymers for organic solar cells.

A combined theoretical and experimental investigation of the electronic structure and optical properties of poly(3-hexylthiophene) (P3HT), poly[3-(4-octylphenyl)thiophene] (POPT) and poly[3-(4-octylphenoxy)thiophene] (POPOT) is reported. In comparison with P3HT, POPT and POPOT exhibit better stabilities and the presence of an oxygen atom and/or a phenyl ring in the side chains enhances conjugation. Quantum chemical calculations have been performed on oligomers of increasing chain length to establish the changes in the electronic and optical properties when going from P3HT to the new derivative POPOT. The knowledge of the structure of these polymers is of utmost importance in understanding their optical properties in different phases (solution and condensed phase). The calculations indicate that, in opposition to P3HT and POPT polymers where the introduction of alkyl chains and the pendant phenyl disturbs the planarity of the backbone of the conjugated segment, POPOT has a better degree of organization in both states: the conjugated chain remains planar even in the presence of the phenoxy groups. Finally, the exciton binding energy is evaluated for these polymers and allows us to conclude that the POPOT is a promising polymer for photovoltaic applications when compared to P3HT and POPT.

Microparticles based on natural and synthetic polymers for ophthalmic applications.

Sodium salt of carboxymethylcellulose/poly(vinyl alcohol) particles suitable for application in ocular drug administration were prepared by crosslinking with epichlorohydrin in an alkaline medium, in reverse emulsion. The influence of parameters related with the particles elaboration process (ratio between polymer mixture and crosslinking agent, concentration of polymer solution, duration of crosslinking reaction, stirring intensity, etc.) based on their composition, size, and swelling ability was studied. Obtained microparticles fulfill the requirements for biomaterials-they are formed from biocompatible polymers; the acute toxicity value (LD(50)) is high enough to consider these materials as weakly toxic (hence able to introduce within the organism); they are able to include and release drugs in a controlled way. The in vivo adrenalin ocular delivery from the microparticles was tested on voluntary human patient. The particles showed good adhesion properties without irritation to the patient and proved the capability to treat the ocular congestion.

Magnetic microparticles based on natural polymers.

Magnetic micro- and nanoparticles based on ferrofluid (maghemite) were elaborated by inverse emulsion crosslinking of sodium salt of carboxymethylcellulose (CMCNa) and gelatin. Crosslinking was carried out with glutaric aldehyde within aqueous droplets dispersed into toluene in presence of surfactants. The influence of parameters such as the ratio of polymers and maghemite in the initial mixture on the composition, size, size dispersity, particle swelling and their ability for drug inclusion was studied. The ability to take-up drugs is directly correlated with the degree of swelling and gelatin content within the particles. Particle size is between tens of nanometers and a few microns. The magnetic properties of particles are demonstrated from saturation magnetization (between 43 and 44 emu g(-1)) when their superparamagnetic character was shown by the absence of hysteresis on the magnetization curve. Polymer-drug systems elaborated under particles keep their bactericide activity for at least 48 h. The absence of toxicity, associated with the bactericide activity, make these systems potential drug carriers.

Chitosan-graft-polyaniline-based hydrogels: elaboration and properties.

Intrinsically conducting polymers are of great interest for a large number of applications. But among the major drawbacks are their low solubility in common solvents and their poor mechanical properties. Elaboration of composites associating a matrix, bringing its mechanical properties, and polyaniline, as the conducting polymer, is a way of overcoming these disadvantages. Chitosan-graft-polyaniline copolymers were synthesized by simple oxidative method. The grafting reaction was quite complete, and it was found that the copolymers cross-linked to yield a composite hydrogel in which the polyaniline was homogeneously embedded. The conductivity of precursor (block copolymer) and gels was found to be larger than 10(-2) S x cm(-1). The composite gels were characterized in terms of swelling and rheological properties. They can be classified as "superabsorbent" hydrogels, and the swelling is reversible. The composite gels were then successfully used as actuators.

Viscosity of semiflexible chitosan solutions: influence of concentration, temperature, and role of intermolecular interactions.

The influence of polymer concentration and temperature on the rheological behavior of chitosan solution was studied. The threshold concentrations for the different viscometric regimes were determined and the different power laws exponents were calculated and compared with those predicted from models. Different observations and the high values of these exponents within the high concentration region lead to consideration of the presence of intermolecular interactions as soon as the polymer concentration is larger than the overlap concentration. The activation energy was determined as a function of the polymer concentration, and its evolution was compared with theoretical predictions. A gel-sol transition was demonstrated at high concentrations.

Two types of hydrophobic aggregates in aqueous solutions of chitosan and its hydrophobic derivative.

The aggregation phenomena in aqueous solutions of hydrophobically modified (HM) chitosan, containing 4 mol % of n-dodecyl side chains, were studied by viscometry and fluorescence spectroscopy with pyrene as a probe. The results are compared with those for unmodified chitosan. Surprisingly, fluorescence data reveal the appearance of intermolecular hydrophobic aggregates both in chitosan and in HM chitosan. Nevertheless, these polymers exhibit quite different rheological properties: upon the formation of aggregates the viscosity of HM chitosan sharply increases, while that of unmodified chitosan raises only slightly. The aggregation models for both chitosan and its hydrophobic derivative were proposed. It was shown that in solutions of HM chitosan two types of hydrophobic domains exist: hydrophobic domains typical for different associating polymers with hydrophobic side chains and hydrophobic domains inherent to chitosan itself.

Solid state NMR for determination of degree of acetylation of chitin and chitosan.

The degree of acetylation (DA) of various samples has been evaluated by 1H liquid-state NMR and 13C and 15N CP-MAS solid-state NMR over the whole range of DA. A good agreement has been found for all the experiments. The 13C and 15N CP-MAS experiments have permitted the evaluation of the chitin DA and content in the structural polysaccharides in a fungus named Aspergillus niger. The fungus structural carbohydrates mainly consist in pure chitin associated with glucans. Comparison of the 13C CP-MAS spectra with standard (1-->3)-beta-D-glucans strongly suggests that chitin and glucans are linked via covalent bonds.

Physico-chemical characterization of Ca-alginate microparticles produced with different methods.

In the present paper the physico-chemical characterization of Ca-alginate microparticles produced with different methods is presented. Ca-alginate microparticles were obtained either by emulsification method or by dripping an aqueous alginate solution into a solution of calcium salt. Inverse Size Exclusion Chromatography (ISEC) was used for the determination of dimensions of the pores and porous volume of microparticles having a mean diameter of 220 microm when obtained by emulsification method. The same technique was used to study the variation of the pore size and porous volume with pH. The results were related with the content of calcium and sodium in the microparticles, before and after their treatment with different HCl solutions. For the particles with a mean diameter of 1.2 mm (obtained by dripping method) we adopted an other approach based on the steric exclusion of solute at equilibrium. For a convenient interpretation of the obtained data, determination of water regain, swelling degree, and scanning electron microscopy (SEM) were performed. Finally, a comparison of the characteristics of microparticles produced by ionic and epichlorohydrin crosslinkings was made. The maximum dimensions of the pores of the microparticles obtained by emulsification were found smaller than those obtained by other technics. The variation of the dimensions of the pores and porous volume with pH is not significant. The structure of the chemically crosslinked beads with epichlorohydrin is more elastic and the swelling is reversible; after drying and reswelling process, the dimensions of the pores and porous volume of these microparticles remain unchanged. On the opposite, for the microparticles obtained by emulsification or dripping method in the presence of calcium ions, these characteristics are changed after a first drying process.

Hydrophobic derivatives of chitosan: characterization and rheological behaviour.

Chitosans which are substituted with alkyl chains having a minimum of six carbon atoms demonstrate hydrophobic interactions in solution. The chemical structure of synthetized polymers is determined from NMR spectroscopy and microanalysis and the distribution between the different types of substituted units is obtained. In relation to the rheological behaviour different parameters are studied such as the nature of the hydrophobic chain and the substitution degree, the polymer concentration, the temperature and the ionic content of the polymeric solution. All the observations tend to prove the hydrophobic nature of the interaction mechanism.

Characterisation of sorbed water molecules on neutral and ionic polysaccharides.

Ionic and neutral polysaccharides with well-defined structures were chosen to investigate the mechanism of water sorption at different relative humidities. From an experimental point of view, the freezing water was determined by DSC when the total sorbed water was obtained from thermogravimetry. The isotherms of sorption and enthalpies of interaction were determined using the combination of a microbalance and a microcalorimeter. It is shown that freezing water appears for P/P(zero) > 0.85 especially with the neutral polymers. The differential molar enthalpy of interaction is higher for P/P(zero) < 0.85 corresponding to the fixation of two water molecules forming double H-bonds; this result is confirmed by molecular modelling; saturation is obtained experimentally for 4 water molecules interacting per glucose unit. On ionic polymers, the water retention increases especially over P/P(zero) approximately 0.8 and the enthalpy of interaction is higher for the first water molecules sorbed. For P/P(zero) approximately equal to 0.8, the numbers of bound water molecules found are 2 per glucopyranosyl unit for neutral polysaccharides, 5 for glucuronan and 9-10 for carboxymethylcellulose (CMC) of DS = 2 and hyaluronan (HA).

Hydration of alpha-maltose and amylose: molecular modelling and thermodynamics study.

Hydration of alpha-maltose and amylose were investigated using molecular modelling and thermodynamics methods. The structure and energy of hydration of three low-energy conformers of alpha-maltose were determined by the MM3 molecular mechanics method. The hydration structure was found to be sensitive to the conformation of alpha-maltose and hydration numbers 10 or 11 were estimated for the different conformers. Differential scanning calorimetry and thermogravimetric analysis were used to determine the number of water molecules specifically bonded (non-freezing water) to amylose and different samples of alpha-maltose. Due to high crystallinity of alpha-maltose samples, the observed non-freezing water content was lower than predicted by molecular modelling. In contrast, the experimental number of non-freezing molecules of water per D-glucopyranose residue for amorphous amylose (nh = 3.8) is in good accordance with the value of 3.8 extracted from our calculations.