Biopolymers for Enhanced Health Benefits.

The definition of the term biopolymer is often controversial, and there is no clear distinction between "biopolymers", "bioplastics", and "bio-based polymers" [...].

Amphiphilic Polypeptides Obtained by the Post-Polymerization Modification of Poly(Glutamic Acid) and Their Evaluation as Delivery Systems for Hydrophobic Drugs.

Synthetic poly(amino acids) are a unique class of macromolecules imitating natural polypeptides and are widely considered as carriers for drug and gene delivery. In this work, we synthesized, characterized and studied the properties of amphiphilic copolymers obtained by the post-polymerization modification of poly(α,L-glutamic acid) with various hydrophobic and basic L-amino acids and D-glucosamine. The resulting glycopolypeptides were capable of forming nanoparticles that exhibited reduced macrophage uptake and were non-toxic to human lung epithelial cells (BEAS-2B). Moreover, the developed nanoparticles were suitable for loading hydrophobic cargo. In particular, paclitaxel nanoformulations had a size of 170-330 nm and demonstrated a high cytostatic efficacy against human lung adenocarcinoma (A549). In general, the obtained nanoparticles were comparable in terms of their characteristics and properties to those based on amphiphilic (glyco)polypeptides obtained by copolymerization methods.

Advancing PHBV Biomedical Potential with the Incorporation of Bacterial Biopigment Prodigiosin.

The quest for sustainable biomaterials with excellent biocompatibility and tailorable properties has put polyhydroxyalkanoates (PHAs) into the research spotlight. However, high production costs and the lack of bioactivity limit their market penetration. To address this, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was combined with a bacterial pigment with strong anticancer activity, prodigiosin (PG), to obtain functionally enhanced PHBV-based biomaterials. The samples were produced in the form of films 115.6-118.8 µm in thickness using the solvent casting method. The effects of PG incorporation on the physical properties (morphology, biopolymer crystallinity and thermal stability) and functionality of the obtained biomaterials were investigated. PG has acted as a nucleating agent, in turn affecting the degree of crystallinity, thermal stability and morphology of the films. All samples with PG had a more organized internal structure and higher melting and degradation temperatures. The calculated degree of crystallinity of the PHBV copolymer was 53%, while the PG1, PG3 and PG3 films had values of 64.0%, 63.9% and 69.2%, respectively. Cytotoxicity studies have shown the excellent anticancer activity of films against HCT116 (colon cancer) cells, thus advancing PHBV biomedical application potential.

An Accessible Method to Improve the Stability and Reusability of Porcine Pancreatic α-Amylase via Immobilization in Gellan-Based Hydrogel Particles Obtained by Ionic Cross-Linking with Mg2+ Ions.

Amylase is an enzyme used to hydrolyze starch in order to obtain different products that are mainly used in the food industry. The results reported in this article refer to the immobilization of α-amylase in gellan hydrogel particles ionically cross-linked with Mg2+ ions. The obtained hydrogel particles were characterized physicochemically and morphologically. Their enzymatic activity was tested using starch as a substrate in several hydrolytic cycles. The results showed that the properties of the particles are influenced by the degree of cross-linking and the amount of immobilized α-amylase enzyme. The temperature and pH at which the immobilized enzyme activity is maximum were T = 60 °C and pH = 5.6. The enzymatic activity and affinity of the enzyme to the substrate depend on the particle type, and this decreases for particles with a higher cross-linking degree owing to the slow diffusion of the enzyme molecules inside the polymer's network. By immobilization, α-amylase is protected from environmental factors, and the obtained particles can be quickly recovered from the hydrolysis medium, thus being able to be reused in repeated hydrolytic cycles (at least 11 cycles) without a substantial decrease in enzymatic activity. Moreover, α-amylase immobilized in gellan particles can be reactivated via treatment with a more acidic medium.

Drug-Loaded Polymeric Micelles Based on Smart Biocompatible Graft Copolymers with Potential Applications for the Treatment of Glaucoma.

Glaucoma is the second leading cause of blindness in the world. Despite the fact that many treatments are currently available for eye diseases, the key issue that arises is the administration of drugs for long periods of time and the increased risk of inflammation, but also the high cost of eye surgery. Consequently, numerous daily administrations are required, which reduce patient compliance, and even in these conditions, the treatment of eye disease is too ineffective. Micellar polymers are core-shell nanoparticles formed by the self-assembly of block or graft copolymers in selective solvents. In the present study, polymeric micelles (PMs) were obtained by dialysis from smart biocompatible poly(ε-caprolactone)-poly(N-vinylcaprolactam-co-N-vinylpyrrolidone) [PCL-g-P(NVCL-co-NVP)] graft copolymers. Two copolymers with different molar masses were studied, and a good correlation was noted between the micellar sizes and the total degree of polymerisation (DPn) of the copolymers. The micelles formed by Cop A [PCL120-g-P(NVCL507-co-NVP128)], with the lowest total DPn, have a Z-average value of 39 nm, whereas the micellar sizes for Cop B [PCL120-g-P(NVCL1253-co-NVP139)] are around 47 nm. These PMs were further used for the encapsulation of two drugs with applications for the treatment of eye diseases. After the encapsulation of Dorzolamide, a slight increase in micellar sizes was noted, whereas the encapsulation of Indomethacin led to a decrease in these sizes. Using dynamic light scattering, it was proved that both free and drug-loaded PMs are stable for 30 days of storage at 4 °C. Moreover, in vitro biological tests demonstrated that the obtained PMs are both haemo- and cytocompatible and thus can be used for further in vivo tests. The designed micellar system proved its ability to release the encapsulated drugs in vitro, and the results obtained were validated by in vivo tests carried out on experimental animals, which proved its high effectiveness in reducing intraocular pressure.

Polysaccharides-Based Complex Particles' Protective Role on the Stability and Bioactivity of Immobilized Curcumin.

The curcumin degradation represents a significant limitation for its applications. The stability of free curcumin (FC) and immobilized curcumin in complex particles (ComPs) based on different polysaccharides was studied under the action of several factors. Ultraviolet-visible (UV-VIS) and Fourier-transform infrared (FTIR) spectroscopy proved the FC photodegradation and its role as a metal chelator: 82% of FC and between 26% and 39.79% of curcumin within the ComPs degraded after exposure for 28 days to natural light. The degradation half-life (t1/2) decreases for FC when the pH increases, from 6.8 h at pH = 3 to 2.1 h at pH = 9. For curcumin extracted from ComPs, t1/2 was constant (between 10 and 13 h) and depended on the sample's composition. The total phenol (TPC) and total flavonoids (TFC) content values increased by 16% and 13%, respectively, for FC exposed to ultraviolet light at λ = 365 nm (UVA), whereas no significant change was observed for immobilized curcumin. Antioxidant activity expressed by IC50 (µmoles/mL) for FC exposed to UVA decreased by 29%, but curcumin within ComPs was not affected by the UVA. The bovine serum albumin (BSA) adsorption efficiency on the ComPs surface depends on the pH value and the cross-linking degree. ComPs have a protective role for the immobilized curcumin.

Polysaccharide-Based Drug Delivery Systems for the Treatment of Periodontitis.

Periodontal diseases are worldwide health problems that negatively affect the lifestyle of many people. The long-term effect of the classical treatments, including the mechanical removal of bacterial plaque, is not effective enough, causing the scientific world to find other alternatives. Polymer-drug systems, which have different forms of presentation, chosen depending on the nature of the disease, the mode of administration, the type of polymer used, etc., have become very promising. Hydrogels, for example (in the form of films, micro-/nanoparticles, implants, inserts, etc.), contain the drug included, encapsulated, or adsorbed on the surface. Biologically active compounds can also be associated directly with the polymer chains by covalent or ionic binding (polymer-drug conjugates). Not just any polymer can be used as a support for drug combination due to the constraints imposed by the fact that the system works inside the body. Biopolymers, especially polysaccharides and their derivatives and to a lesser extent proteins, are preferred for this purpose. This paper aims to review in detail the biopolymer-drug systems that have emerged in the last decade as alternatives to the classical treatment of periodontal disease.

Efficient removal of Indigo Carmine dye by a separation process.

This study is aimed at developing an innovative approach for Indigo Carmine dye removal from synthetic solutions by electrodialysis, carried out using ion exchange membranes. The batch electrodialysis system was operated at various current intensities: 0.05, 0.1 and 0.15 A. The pH and conductivity of solutions were measured before and after using electrodialysis process. The colour removal efficiency (CR %) was determined by spectrographic analysis and the energy consumption (EC) was calculated. The obtained results show that the pH of treated solution increases due to the increase in solution conductivity. Moreover, the values of CR % and EC increase when increasing current intensity. The optimal value was obtained at 0.15 A (CR > 97%). The membranes were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy.

Effect of poly(vinyl alcohol-co-vinyl acetate) copolymer blockiness on the dynamic interfacial tension and dilational viscoelasticity of polymer-anionic surfactant complex at the water-1-chlorobutane interface.

Poly(vinyl alcohol-co-vinyl acetate) (PVA) copolymers obtained by partial hydrolysis of poly(vinyl acetate) (PVAc) are of practical importance for many applications, including emulsion and suspension polymerization processes. Their molecular characteristics have a major influence on the colloidal and interfacial properties. The most significant characteristics are represented by the average degree of hydrolysis D̅H̅, average degree of polymerization D̅P̅w̅ but also by the average acetate sequence length n(VAc)(0) which designates the so-called blockiness. Colloidal aggregates were observed in the aqueous PVA solutions having a D̅H̅ value of 73 mol%. The volume fraction of these aggregates at a given D̅H̅ value is directly correlated to the blockiness. Three PVA samples with identical D̅H̅ and D̅P̅w̅ but different blockiness were examined. By pendant drop and oscillating pendant drop techniques it was shown that the PVA sample having the lowest blockiness and thus the lowest volume fraction of colloidal aggregates has lower interfacial tension and elastic modulus E' values. On the contrary, the corresponding values are highest for PVA sample of higher blockiness. In the presence of sodium dodecyl sulfate (SDS), the colloidal aggregates are disaggregated by complex formation due to the hydrophobic-hydrophobic interactions. The PVA-SDS complex acts as a partial polyelectrolyte that induces the stretching of the chains and thus a reduction of the interface thickness. In this case, the interfacial tension and the elastic modulus both increase with increasing SDS concentration for all three PVA samples and the most significant effect was noticed for the most "blocky" copolymer sample.

Degradable Polymeric Bio(nano)materials and Their Biomedical Applications: A Comprehensive Overview and Recent Updates.

Degradable polymers (both biomacromolecules and several synthetic polymers) for biomedical applications have been promising very much in the recent past due to their low cost, biocompatibility, flexibility, and minimal side effects. Here, we present an overview with updated information on natural and synthetic degradable polymers where a brief account on different polysaccharides, proteins, and synthetic polymers viz. polyesters/polyamino acids/polyanhydrides/polyphosphazenes/polyurethanes relevant to biomedical applications has been provided. The various approaches for the transformation of these polymers by physical/chemical means viz. cross-linking, as polyblends, nanocomposites/hybrid composites, interpenetrating complexes, interpolymer/polyion complexes, functionalization, polymer conjugates, and block and graft copolymers, are described. The degradation mechanism, drug loading profiles, and toxicological aspects of polymeric nanoparticles formed are also defined. Biomedical applications of these degradable polymer-based biomaterials in and as wound dressing/healing, biosensors, drug delivery systems, tissue engineering, and regenerative medicine, etc., are highlighted. In addition, the use of such nano systems to solve current drug delivery problems is briefly reviewed.

Peptide-functionalized chitosan-based microcapsules for dual active targeted treatment of lung infections.

Lung infections, such as: pneumonia, chronic obstructive cystic fibrosis, tuberculosis are generally caused by viruses, bacteria and fungi. As these infections are very difficult to treat, new therapeutic approaches are investigated in order to maximize the efficiency of the treatment and to reduce the major complications that can occur. The main objective of this study was focused on the preparation of drug-loaded peptides-functionalized microcapsules, obtained by a double emulsion, based on carboxylated chitosan (CMCS), poly(vinyl alcohol) (PVA) and an activator [4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride] (DMT-MM), for the dual active targeting and treatment of pulmonary infections. The microcapsules were functionalized on the surface with both CGSPGWVRC and indolicidin (IN) peptides, as effective ligands for the active targeting of both alveolar capillary endothelial cells and bacterial cells. FTIR spectroscopy confirmed the formation of ester and amide bonds into the structure of prepared microcapsules. Microcapsules diameter varied between 893 and 965 nm. The swelling degree in PBS, at pH 7.4, ranged between 1760 %- 2100 %. All the analyzed samples showed hemolysis degrees lower than 2 %, which demonstrated their non-hemolytic character. Evaluation of the impact of microcapsules on WI-38 normal human lung cells and RAW 264.7 mouse macrophages revealed a non-toxic or slightly cytotoxic effect. Internalization assay proved that microcapsules were localized at intracellular level.

Effect of Filler Content on the Morphology and Physical Properties of Poly(Lactic Acid)-Hydroxyapatite Composites.

The effect of hydroxyapatite (HAp) synthesized by the chemical precipitation process on the morphology and properties of composites based on poly(lactic acid) (PLA) was investigated at various filler content ratios, i.e., 5, 10 and 15 wt%. Both neat PLA and PLA-based composites were first prepared using the solvent casting method, followed by melt compounding in an internal mixer, whereas tensile specimens were obtained by thermo-compression. The study revealed that the addition of 5 wt% of HAp into the PLA led to a slight improvement in both the thermal stability and tensile properties of the composite material in comparison with neat PLA and other composite samples. Indeed, the values of the tensile strength and modulus increased from approximately 61 MPa and 2.9 GPa for the neat PLA to almost 64 MPa and 3.057 GPa for the composite sample, respectively. Moreover, the degradation temperature at a 5 wt% mass loss also increased by almost 5 °C compared to other samples, due probably to a finer dispersion of the HAp particles in the PLA, as observed under a scanning electron microscope. Furthermore, the FT-IR spectra displayed some changes in the chemical structure of the PLA/HAp (5 wt%), indicating the occurrence of filler-matrix interactions. At a higher filler content ratio, a decrease in the properties of the PLA/HAp composites was observed, being more pronounced at 15 wt%. The PLA composite containing 5 wt% HAp presents the best compromise among the investigated properties. The study highlighted the possibility of using HAp without any prior surface treatment as a reinforcement in PLA composite materials.

Self-Assembly of Block Copolymers in Thin Films Swollen-Rich in Solvent Vapors.

In this study we have employed a polymer processing method based on solvent vapor annealing in order to condense relatively large amounts of solvent vapors onto thin films of block copolymers and thus to promote their self-assembly into ordered nanostructures. As revealed by the atomic force microscopy, a periodic lamellar morphology of poly(2-vinylpyridine)-b-polybutadiene and an ordered morphology comprised of hexagonally-packed structures made of poly(2-vinylpyridine)-b-poly(cyclohexyl methacrylate) were both successfully generated on solid substrates for the first time.

Electrohydrodynamic Techniques for the Manufacture and/or Immobilization of Vesicles.

The development of accurate drug delivery systems is one of the main challenges in the biomedical field. A huge variety of structures, such as vesicles, nanoparticles, and nanofibers, have been proposed as carriers for bioactive agents, aiming for precision in administration and dosage, safety, and bioavailability. This review covers the use of electrohydrodynamic techniques both for the immobilization and for the synthesis of vesicles in a non-conventional way. The state of the art discusses the most recent advances in this field as well as the advantages and limitations of electrospun and electrosprayed amphiphilic structures as precursor templates for the in situ vesicle self-assembly. Finally, the perspectives and challenges of combined strategies for the development of advanced structures for the delivery of bioactive agents are analyzed.

How Retting Could Affect the Mechanical Behavior of Flax/Epoxy Biocomposite Materials?

This study focuses on the retting effect on the mechanical properties of flax biobased materials. For the technical fiber, a direct link was established between the biochemical alteration of technical flax and their mechanical properties. In function of the retting level, technical fibers appeared smoother and more individualized; nevertheless, a decrease in the ultimate modulus and maximum stress was recorded. A biochemical alteration was observed as the retting increased (a decrease in the soluble fraction from 10.4 ± 0.2 to 4.5 ± 1.2% and an increase in the holocellulose fractions). Regarding the mechanical behavior of biocomposites manufactured by thermocompression, a non-elastic behavior was observed for the tested samples. Young moduli (E1 and E2) gradually increased with retting. The retting effect was more pronounced when a normalization was performed (according to the fiber volume and porosity). A 40% increase in elastic modulus could be observed between under-retting (-) and over-retting (+). Moreover, the porosity content (Vp) increased overall with fiber content. Setup 3, with optimized processing parameters, was the most desirable processing protocol because it allowed the highest fiber fraction (Vf) for the lowest Vp.

Design and characterization of dexamethasone phosphate -loaded microcapsules obtained by a double-emulsion method.

Polymeric microcapsules are extensively investigated as drug delivery systems for a broad range of applications. In the present study, Dexamethasone-loaded carboxylated chitosan (CCS)/poly (vinyl alcohol) (PVA)-based microcapsules were prepared in view of their potential administration by inhalation for the treatment of lung diseases. The crosslinking between PVA and CCS was activated by [4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride] (DMT-MM) and the FTIR results proved the formation of ester bonds between the two polymers. The sizes of the obtained microcapsules are influenced by the ratio between the polymers but also by the concentration of the DMT-MM activator. Moreover, the amount of PVA in the system has an important influence on swelling degree, encapsulation efficiency, drug release degree, biodegradation and protein adsorption. The sample with the highest amount of PVA has the highest crosslinking density and thus the lowest swelling degree and encapsulation efficiency. However, an encapsulation degree of 61.3% was obtained for the sample MCP-6 with the lowest PVA content. The same sample showed the lowest BSA adsorption. A controlled and sustained Dexamethasone release of around 90% was observed in PBS at pH 7.4 and 37 °C during 24 h. All the obtained samples were hemocompatibles and thus can be used as efficient drug delivery systems.

Stimuli-Responsive Triblock Terpolymer Conversion into Multi-Stimuli-Responsive Micelles with Dynamic Covalent Bonds for Drug Delivery through a Quick and Controllable Post-Polymerization Reaction.

Stimuli-responsive copolymers are of great interest for targeted drug delivery. This study reports on a controllable post-polymerization quaternization with 2-bromomethyl-4-fluorophenylboronic acid of the poly(4-vinyl pyridine) (P4VP) block of a common poly(styrene)-b-poly(4-vinyl pyridine)-b-poly(ethylene oxide) (SVE) triblock terpolymer in order to achieve a selective responsivity to various diols. For this purpose, a reproducible method was established for P4VP block quaternization at a defined ratio, confirming the reaction yield by 11B, 1H NMR. Then, a reproducible self-assembly protocol is designed for preparing stable micelles from functionalized stimuli-responsive triblock terpolymers, which are characterized by light scattering and by cryogenic transmission electron microscopy. In addition, UV-Vis spectroscopy is used to monitor the boron-ester bonding and hydrolysis with alizarin as a model drug and to study encapsulation and release of this drug, induced by sensing with three geminal diols: fructose, galactose and ascorbic acid. The obtained results show that only the latter, with the vicinal diol group on sp2-hybridized carbons, was efficient for alizarin release. Therefore, the post-polymerization method for triblock terpolymer functionalization presented in this study allows for preparation of specific stimuli-responsive systems with a high potential for targeted drug delivery, especially for cancer treatment.

Influence of ZnO Nanoparticles on the Properties of Ibuprofen-Loaded Alginate-Based Biocomposite Hydrogels with Potential Antimicrobial and Anti-Inflammatory Effects.

Hydrogels are a favorable alternative to accelerate the burn wound healing process and skin regeneration owing to their capability of absorbing contaminated exudates. The bacterial infections that occur in burn wounds might be treated using different topically applied materials, but bacterial resistance to antibiotics has become a major problem worldwide. Therefore, the use of non-antibiotic treatments represents a major interest in current research. In this study, new antibiocomposite hydrogels with anti-inflammatory and antimicrobial properties based on hyaluronic acid (HA) and sodium alginate (AG) were obtained using 4-(4,6-dimethoxy-1,3,5-triazinyl-2)-4-methylmorpholinium chloride as an activator. The combination of Ibuprofen, a non-steroidal anti-inflammatory drug commonly used to reduce inflammation, fever and pain in the body, with zinc oxide nanoparticles (ZnO NPs) was used in this study aimed at creating a complex hydrogel with anti-inflammatory and antimicrobial action and capable of improving the healing process of wounds caused by burns. FTIR spectra confirmed the cross-linking of AG with HA as well as the successful incorporation of ZnO NPs. Using electronic microscopy, it was noticed that the morphology of hydrogels is influenced by the incorporation of ZnO nanoparticles. Moreover, the incorporation of ZnO nanoparticles into hydrogels also has an influence on the swelling behavior at both pH 7.4 and 5.4. In fact, the swelling rate is lower when the amounts of the activator, HA and ZnO NPs are high. A drug release rate of almost 100% was observed for hydrogels without ZnO NPs, whereas the addition of nanoparticles to hydrogels led to a decrease in the release rate to 68% during 24 h. Cellular viability tests demonstrated the non-cytotoxic behavior of the hydrogels without the ZnO NPs, whereas a weak to moderate cytotoxic effect was noticed for hydrogels with ZnO NPs. The hydrogels containing 4% and 5% ZnO NPs, respectively, showed good antimicrobial activity against the S. aureus strain. These preliminary data prove that these types of hydrogels can be of interest as biomaterials for the treatment of burn wounds.

Molecular Dynamics Simulations of Docetaxel Adsorption on Graphene Quantum Dots Surface Modified by PEG-b-PLA Copolymers.

Cancer is associated with a high level of morbidity and mortality, and has a significant economic burden on health care systems around the world in almost all countries due to poor living and nutritional conditions. In recent years, with the development of nanomaterials, research into the drug delivery system has become a new field of cancer treatment. With increasing interest, much research has been obtained on carbon-based nanomaterials (CBNs); however, their use has been limited, due to their impact on human health and the environment. The scientific community has turned its research efforts towards developing new methods of producing CBN. In this work, by utilizing theoretical methods, including molecular dynamics simulation, graphene quantum dots (GQD) oxide was selected as a carbon-based nanocarriers, and the efficiency and loading of the anticancer drug docetaxel (DTX) onto GQD oxide surfaces in the presence and in the absence of a PEG-b-PLA copolymer, as a surface modifier, were investigated. According to the results and analyzes performed (total energy, potential energy, and RMSD), it can be seen that the two systems have good stability. In addition, it was determined that the presence of the copolymer at the interface of GQD oxide delays the adsorption of the drug at first; but then, in time, both the DTX adsorption and solubility are increased.

Palladium-Doped Single-Walled Carbon Nanotubes as a New Adsorbent for Detecting and Trapping Volatile Organic Compounds: A First Principle Study.

Volatile organic compounds (VOCs) are in the vapor state in the atmosphere and are considered pollutants. Density functional theory (DFT) calculations with the wb97xd exchange correlation functional and the 6-311+G(d,p) basis set are carried out to explore the potential possibility of palladium-doped single-walled carbon nanotubes (Pd/SWCNT-V), serving as the resource for detecting and/or adsorbing acetonitrile (ACN), styrene (STY), and perchloroethylene (PCE) molecules as VOCs. The suggested adsorbent in this study is discussed with structural parameters, frontier molecular orbital theory, molecular electrical potential surfaces (MEPSs), natural bond orbital (NBO) analyses, and the density of states. Furthermore, following the Bader theory of atoms in molecules (AIM), the topological properties of the electron density contributions for intermolecular interactions are analyzed. The obtained results show efficient VOC loading via a strong chemisorption process with a mean adsorption energy of -0.94, -1.27, and -0.54 eV for ACN, STY, and PCE, respectively. Our results show that the Pd/SWCNT-V can be considered a good candidate for VOC removal from the environment.