Biobased Waterborne Polyurethane-Ureas Modified with POSS-OH for Fluorine-Free Hydrophobic Textile Coatings.

Waterborne polyurethane-urea dispersions (WPUD), which are based on fully biobased amorphous polyester polyol and isophorone diisocyanate (IPDI), have been successfully synthesized obtaining a finishing agent that provides textiles with an enhanced hydrophobicity and water column. Grafting of trans-cyclohexanediol isobutyl POSS (POSS-OH) to the biobased polymer backbone has also been investigated for the first time and its properties compared to a standard chain extender, 1,3-propanediol (PDO). The chemical structure of WPUD has been characterized by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The thermal properties have been evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Mechanical properties have been studied by tensile stress-strain analysis. Moreover, the particle size, particle size distribution (PSD), and stability of developed waterborne dispersions have been assessed by dynamic light scattering (DLS), Z-potential, storage aging tests, and accelerated aging tests by analytical centrifuge (LUM). Subsequently, selected fabrics have been face-coated by the WPUD using the knife coating method and their properties have been assessed by measuring the water contact angle (WCA), oil contact angle (OCA), water column, fabric stiffness, air permeability, and water vapor resistance (breathability). Finally, the surface morphology and elemental composition of uncoated and coated fabrics have been studied by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), respectively. All of the synthesized polyurethane-ureas provided the coated substrates with a remarkable hydrophobicity and water column, resulting in a more sustainable alternative to waterproof coatings based on fluoropolymers, such as PTFE. Grafting POSS-OH to the polymeric backbone has led to textile coatings with enhanced hydrophobicity, maintaining thermal, mechanical, and water column properties, giving rise to multifunctional coatings that are highly demanded in protective workwear and technical textiles.

A Biodegradable Copolyester, Poly(butylene succinate-co-ε-caprolactone), as a High Efficiency Matrix Former for Controlled Release of Drugs.

A biodegradable copolyester, poly(butylene succinate-co-ε-caprolactone) (PBS_CL), was used for first time as an excipient for pharmaceutical dosage forms using direct compression and hot processing techniques (ultrasound-assisted compression (USAC) and hot melt extrusion (HME)). Robust binary systems were achieved with hot processing techniques, allowing a controlled release of the drug. With only 12% v/v of PBS_CL, controlled release forms were obtained using USAC whereas in HME over 34% v/v of excipient is necessary. Amounts over 23% v/v allowed a long-extended release for more than 72 h following diffusional kinetic. Thanks to the high melting point of theophylline and the physicochemical properties of PBS_CL selected and synthesized, the structure of the excipient inside the USAC tablets and HME filaments corresponds to a continuum medium. A percolation threshold around 23% v/v was estimated, which agrees with a continuum percolation model. The polymer shows a high excipient efficiency value using HME and USAC. A nanostructured matrix with wall thicknesses lower than 0.1 µm was obtained. This leads to a very effective coating of the drug particles by the excipient, providing a slow and reproducible release. The present study therefore supports the use of PBS_CL, for the preparation of controlled release dosage forms using hot processing techniques.

Synthesis, Structure, Crystallization and Mechanical Properties of Isodimorphic PBS-ran-PCL Copolyesters.

Isodimorphic behavior is determined by partial inclusion of comonomer segments within the crystalline structure and arises from the comparatively similar repeating chain units of the parental homopolymers. Isodimorphic random copolymers are able to crystallize irrespective of their composition and exhibit a pseudo-eutectic behavior when their melting point values are plotted as a function of comonomer content. At the pseudo-eutectic point or region, two crystalline phases can coexist. On the right-hand and the left-hand side of the pseudo-eutectic point or region, only one single crystalline phase can form which is very similar to the crystalline structures of the parent homopolymers. This article aims to study the synthesis method, structure, crystallization behavior and mechanical properties of isodimorphic random PBS-ran-PCL copolyesters. Moreover, this study provides a comprehensive analysis of our main recent results on PBS-ran-PCL random copolyesters with three different molecular weights. The results show that the comonomer composition and crystallization conditions are the major factors responsible for the crystalline morphology, crystallization kinetics and mechanical performance of isodimorphic random copolyesters. Our studies demonstrate that in the pseudo-eutectic region, where both crystalline phases can coexist, the crystallization conditions determine the crystalline phase or phases of the copolymer. The relationships between the comonomer composition and mechanical properties are also addressed in this work.

Biobased Waterborne Polyurethane-Urea/SWCNT Nanocomposites for Hydrophobic and Electrically Conductive Textile Coatings.

Waterborne polyurethane-urea dispersions (WPUD), which are based on 100% bio-based semi-crystalline polyester polyol and isophorone diisocyanate, have been successfully synthesized and doped with single-walled carbon nanotubes (SWCNT) to obtain a finishing agent that provides textiles with multifunctional properties. The chemical structure of WPUD has been characterized by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The thermal properties have been evaluated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). Mechanical properties have been studied by tensile stress-strain analysis. Moreover, the particle size, particle size distribution (PSD), and stability of developed waterborne dispersions have been assessed by dynamic light scattering (DLS), Z-potential, and accelerated aging tests (analytical centrifugation). Subsequently, selected fabrics have been face-coated by the WPUD using knife coating method and their properties have been assessed by measuring water contact angle (WCA), water column, fabric stiffness, and air permeability. The electrical conductivity of textiles coated with SWCNT-doped WPUD has been evaluated by EN 1149 standard. Finally, the surface morphologies of uncoated and coated fabrics have been studied by scanning electron microscopy (SEM). All of the synthesized polyurethane-ureas provide the coated substrates with remarkable water-repellency and water column, being therefore a more sustainable alternative to waterproof coatings based on fluoropolymers, such as PTFE. The additivation of the polymeric matrices with SWCNT has led to textile coatings with excellent electrical conductivity, maintaining water column properties, giving rise to multifunctional coatings that are highly demanded in protective workwear and technical textiles.

Isohexide and Sorbitol-Derived, Enzymatically Synthesized Renewable Polyesters with Enhanced Tg.

Sugar-based polyesters derived from sorbitol and isohexides were obtained via solvent-free enzymatic catalysis. Pendant hydroxyl groups, coming from the sorbitol units, were present along the polyester backbone, whereas the two isohexides, namely, isomannide and isoidide dimethyl ester monomers, were selected to introduce rigidity into the polyester chains. The feasibility of incorporating isomannide as a diol compared to the isoidide dimethyl ester as acyl-donor via lipase-catalyzed polycondensation was investigated. The presence of bicyclic units resulted in enhanced Tg with respect to the parent sorbitol-containing polyester lacking isohexides. The different capability of the two isohexides to boost the thermal properties confirmed the more flexible character provided by the isoidide diester derivative. Solvent-borne coatings were prepared by cross-linking the sugar-based polyester polyols with polyisocyanates. The increased rigidity of the obtained sugar-based polyester polyols led to an enhancement in hardness of the resulting coatings.

Modification of Microbial Polymalic Acid With Hydrophobic Amino Acids for Drug-Releasing Nanoparticles.

Microbial poly(ß, l-malic acid) was modified with either l-leucine ethyl ester (L) or l-phenylalanine methyl ester (F) to produce amphiphylic copolymers. The degradation of these copolymers in aqueous buffer took place under physiological conditions in a few weeks by hydrolysis of the side chain ester group followed by cleavage of the main chain. Spherical nanoparticles with diameters ranging between 70 and 230 nm were prepared from these copolymers by the dialysis-precipitation method. No alteration of the cell viability was observed after incubation of these nanoparticles in different cell lines. Anticancer drugs temozolomide and doxorubicin were encapsulated in the nanoparticles. Temozolomide was released within several hours whereas doxorubicin took several weeks to be completely liberated.

Poly(methyl malate) nanoparticles: formation, degradation, and encapsulation of anticancer drugs.

PMLA nanoparticles with diameters of 150-250 nm are prepared, and their hydrolytic degradation is studied under physiological conditions. Degradation occurs by hydrolysis of the side chain methyl ester followed by cleavage of the main-chain ester group with methanol and L-malic acid as the final degradation products. No alteration of the cell viability is found after 1 h of incubation, but toxicity increases significantly after 3 d, probably due to the noxious effect of the released methanol. Anticancer drugs temozolomide and doxorubicin are encapsulated in the NPs with 20-40% efficiency, and their release is monitored using in vitro essays. Temozolomide is fully liberated within several hours, whereas doxorubicin is steadily released from the particles over a period of 1 month.

Nanoparticles made of microbial poly(gamma-glutamate)s for encapsulation and delivery of drugs and proteins.

This study focused on the preparation and evaluation of nanoparticles made of alkyl esters of microbial poly(gamma-glutamic acid) (PGGA) to be used as drugs and proteins carrier and delivery systems. Racemic PGGA of bacterial origin was fully methylated or partially esterified to render non-water-soluble polymers. A set of co-polymers containing poly(glutamic acid) and ethyl, hexyl, dodecyl and octadecyl glutamate units with alkyl contents of 50 and 75% was prepared. Spherical nanoparticles with a diameter of 200-250 nm and a narrow distribution were generated from the alkylated polymers by the precipitation-dialysis method. These nanoparticles readily degraded hydrolytically upon incubation in simulated physiological medium at a rate dependent on the alkylation degree and the length of the alkyl group. All these nanoparticles were able to encapsulate efficiently erythromycin. Those made of carboxyl containing polyglutamates were also effective to load alpha-chymotrypsin. The release of such compounds from nanoparticles upon incubation proceeded essentially following the same profile that is followed in the hydrolysis of the corresponding substrate polymers. The loss of enzyme activity of the incubated protein diminished significantly upon encapsulation in these systems.

Synthesis, degradability, and drug releasing properties of methyl esters of fungal poly(beta,L-malic acid).

Methyl esters of microbial poly(beta,L-malic acid) for conversion degrees of 25, 50, 75, and 100% were prepared by treatment of the polyacid with diazomethane. Esterification proceeded with retention of the molecular weight of the parent polyacid and the copolymers displayed a blocky microstructure consisting of short segments of malic and methyl malate sequences. The thermal stability of the copolyesters was lower than those of the parent homopolymers and all of them were fairly crystalline with melting temperatures within the range of 170-175 degrees C. They were degraded rapidly by water, the hydrolysis rate being highly dependent on the methylation degree. Microspheres with mean-average diameters in the range of 1-20 microm were prepared from the 100% methylated product by the emulsion-evaporation solvent method. Encapsulation of erythromycin was efficiently performed in these microparticles and its releasing upon incubation in simulated physiological medium was evaluated for different drug loads. Drug delivery was observed to occur by a releasing mechanism largely determined by the hydrodegradation of the host polymer and independent of the amount of loaded drug.

Ionic complexes of biosynthetic poly(malic acid) and poly(glutamic acid) as prospective drug-delivery systems.

The hydrolytic degradability and erythromycin release from stoichiometric ionic complexes of biotechnological poly(beta,L-malic acid)s and poly(gamma,D-glutamic acid)s with alkyltrimethylammonium surfactants were investigated. The influence of pH, temperature and antibiotic load on hydrolysis rate was examined. It was found that poly(malic acid) complexes degraded by a surface erosion mechanism at a higher rate than poly(glutamic acid) complexes, which eroded in bulk. Erythromycin was lodged in the paraffinic subphase of the complexes and upon aging it was delivered according to a sigmoidal profile that appeared to be independent on the antibiotic load.