Whey Protein Isolate-Chitosan PolyElectrolyte Nanoparticles as a Drug Delivery System.

Whey protein isolate (WPI), employed as a carrier for a wide range of bioactive substances, suffers from a lack of colloidal stability in physiological conditions. Herein, we developed innovative stabilized PolyElectrolyte Nanoparticles (PENs) obtained by two techniques: polyelectrolyte complexation of negatively charged WPI and positively charged chitosan (CS), and ionic gelation in the presence of polyanion tripolyphosphate (TPP). Therefore, the WPI-based core was coated with a CS-based shell and then stabilized by TPP at pH 8. The nanostructures were characterized by physiochemical methods, and their encapsulation efficiency and in vitro release were evaluated. The spherical NPs with an average size of 248.57 ± 5.00 nm and surface charge of +10.80 ± 0.43 mV demonstrated high encapsulation efficiency (92.79 ± 0.69) and sustained release of a positively charged chemotherapeutic agent such as doxorubicin (DOX). Z-average size and size distribution also presented negligible increases in size and aggregates during the three weeks. The results obtained confirm the effectiveness of the simultaneous application of these methods to improve the colloidal stability of PEN.

A Self-Standing Binder-Free Biomimetic Cathode Based on LMO/CNT Enhanced with Graphene and PANI for Aqueous Rechargeable Batteries.

The electrochemical parameters of a novel binder-free self-standing biomimetic cathode based on lithium manganese oxide (LMO) and carbon nanotubes (CNT) for rechargeable Lithium-ion aqueous batteries (ReLIAB) are improved using polyaniline (PANI) core-shell in situ polymerization and graphene (Gr). The fabricated cathode material exhibits the so-called "tectonic plate island bridge" biomimetic structure. This constitution is created by combining three components as shown by a SEM and a TEM analysis: the Gr substrates support an entangled matrix of conductive CNT which connect island of non-conductive inorganic material composed of LMO. The typical spinel structure of the LMO remains unchanged after modifying the basic structure with Gr and PANI due to a simplified hydrothermal method used for synthesis. The Gr and PANI core-shell coating improves the electric conductivity from 0.0025 S/cm up to 1 S/cm. The electrochemical performances of the LMO/CNT-Gr/PANI composite electrode are optimized up to 136 mA h g-1 compared to 111 mA h g-1 of the LMO/CNT. Besides that, the new electrode shows good cycling stability after 200 galvanostatic charging/discharging cycles, making this structure a future candidate for cathode materials for ReLIAB.

Nanoparticle-Based Rifampicin Delivery System Development.

The alkaline milieu of chronic wounds severely impairs the therapeutic effect of antibiotics, such as rifampicin; as such, the development of new drugs, or the smart delivery of existing drugs, is required. Herein, two innovative polyelectrolyte nanoparticles (PENs), composed of an amphiphilic chitosan core and a polycationic shell, were synthesized at alkaline pH, and in vitro performances were assessed by 1H NMR, elemental analysis, FT-IR, XRD, DSC, DLS, SEM, TEM, UV/Vis spectrophotometry, and HPLC. According to the results, the nanostructures exhibited different morphologies but similar physicochemical properties and release profiles. It was also hypothesized that the simultaneous use of the nanosystem and an antioxidant could be therapeutically beneficial. Therefore, the simultaneous effects of ascorbic acid and PENs were evaluated on the release profile and degradation of rifampicin, in which the results confirmed their synergistic protective effect at pH 8.5, as opposed to pH 7.4. Overall, this study highlighted the benefits of nanoparticulate development in the presence of antioxidants, at alkaline pH, as an efficient approach for decreasing rifampicin degradation.

Biocompatibility and Biological Efficiency of Inorganic Calcium Filled Bacterial Cellulose Based Hydrogel Scaffolds for Bone Bioengineering.

The principal focus of this work is the in-depth analysis of the biological efficiency of inorganic calcium-filled bacterial cellulose (BC) based hydrogel scaffolds for their future use in bone tissue engineering/bioengineering. Inorganic calcium was filled in the form of calcium phosphate (ß-tri calcium phosphate (ß-TCP) and hydroxyapatite (HA)) and calcium carbonate (CaCO3). The additional calcium, CaCO3 was incorporated following in vitro bio-mineralization. Cell viability study was performed with the extracts of BC based hydrogel scaffolds: BC-PVP, BC-CMC; BC-PVP-ß-TCP/HA, BC-CMC-ß-TCP/HA and BC-PVP-ß-TCP/HA-CaCO3, BC-CMC-ß-TCP/HA-CaCO3; respectively. The biocompatibility study was performed with two different cell lines, i.e., human fibroblasts, Lep-3 and mouse bone explant cells. Each hydrogel scaffold has facilitated notable growth and proliferation in presence of these two cell types. Nevertheless, the percentage of DNA strand breaks was higher when cells were treated with BC-CMC based scaffolds i.e., BC-CMC-ß-TCP/HA and BC-CMC-ß-TCP/HA-CaCO3. On the other hand, the apoptosis of human fibroblasts, Lep-3 was insignificant in BC-PVP-ß-TCP/HA. The scanning electron microscopy confirmed the efficient adhesion and growth of Lep-3 cells throughout the surface of BC-PVP and BC-PVP-ß-TCP/HA. Hence, among all inorganic calcium filled hydrogel scaffolds, 'BC-PVP-ß-TCP/HA' was recommended as an efficient tissue engineering scaffold which could facilitate the musculoskeletal (i.e., bone tissue) engineering/bioengineering.

A New Route of Fucoidan Immobilization on Low Density Polyethylene and Its Blood Compatibility and Anticoagulation Activity.

Beside biomaterials' bulk properties, their surface properties are equally important to control interfacial biocompatibility. However, due to the inadequate interaction with tissue, they may cause foreign body reaction. Moreover, surface induced thrombosis can occur when biomaterials are used for blood containing applications. Surface modification of the biomaterials can bring enhanced surface properties in biomedical applications. Sulfated polysaccharide coatings can be used to avoid surface induced thrombosis which may cause vascular occlusion (blocking the blood flow by blood clot), which results in serious health problems. Naturally occurring heparin is one of the sulfated polysaccharides most commonly used as an anticoagulant, but its long term usage causes hemorrhage. Marine sourced sulfated polysaccharide fucoidan is an alternative anticoagulant without the hemorrhage drawback. Heparin and fucoidan immobilization onto a low density polyethylene surface after functionalization by plasma has been studied. Surface energy was demonstrated by water contact angle test and chemical characterizations were carried out by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Surface morphology was monitored by scanning electron microscope and atomic force microscope. Finally, their anticoagulation activity was examined for prothrombin time (PT), activated partial thromboplastin time (aPTT), and thrombin time (TT).

In vitro study of partially hydrolyzed poly(2-ethyl-2-oxazolines) as materials for biomedical applications.

Polymers based on 2-oxazoline, such as poly(2-ethyl-2-oxazolines) (PETOx), are considered to be a type of 'pseudopeptide' with the ability to form novel biomaterials. The hydrolysis of PETOx was carried out to evaluate its use in biomedical applications. In the present work, PETOx samples with a range of molar masses were prepared by living cationic polymerization. Hydrolysis was carried out at time intervals ranging from 15 to 180 min to prepare copolymers with different amounts of ethylene imine units. (1)H NMR spectroscopy was used to identify the structure of the hydrolyzed polymers. The dependence of in vitro cell viability on the degree of hydrolysis was determined using three different model cell lines, namely, mouse embryonic 3T3 fibroblasts, pancreatic ßTC3 cells, and mouse lymphoid macrophages P388.D1. It was demonstrated that increasing the degree of hydrolysis decreased cell viability for all cell types. Fibroblast cells displayed the highest tolerance; additionally, the effect of polymer size showed no observable significance. Macrophage cells, immune system representatives, displayed the highest sensitivity to contact with hydrolyzed PETOx. The effect of polymer hydrolysis, polymer concentration and the incubation time on cell viability was experimentally observed. Confocal laser-scanning microscopy provided evidence of cellular uptake of pyrene-labeled (co)polymers.

Hybrid nanostructured Ag/ZnO decorated powder cellulose fillers for medical plastics with enhanced surface antibacterial activity.

Hybrid inorganic-organic fillers based on nanostructured silver/zinc oxide decorations on micro-cellulose carrier particles were prepared by stepwise microwave assisted hydrothermal synthesis using soluble salts as precursors of silver and zinc oxide. Hexamethylenetetramine was used as precipitating agent for zinc oxide and reducing agent for silver. The inorganics covered all available surfaces of the cellulose particles with a morphology resembling a coral reef. Prepared particulate fillers were compounded to medical grade poly(vinyl chloride) matrix. Scanning electron microscopy and powder X-ray diffractometry were used to investigate the morphology and crystalline phase structure of fillers. The scanning electron microscopy was used for morphological study of composites. With respect to prospective application, the composites were tested on electrical and antibacterial properties. A small effect of water absorption in polymer composites on their dielectric properties was observed but no adverse effect of water exposure on prepared materials was manifested. Electrical conductivity of fillers and composites was measured and no influence of water soaking of composites was found at all. The surface antibacterial activity of prepared composites was evaluated according to the standard ISO 22196. Excellent performance against Escherichia coli and very high against Staphylococcus aureus was achieved.

Antibacterial performance of alginic acid coating on polyethylene film.

Alginic acid coated polyethylene films were examined in terms of surface properties and bacteriostatic performance against two most representative bacterial strains, that is, Escherichia coli and Staphylococcus aureus. Microwave plasma treatment followed by brush formation in vapor state from three distinguished precursors (allylalcohol, allylamine, hydroxyethyl methacrylate) was carried out to deposit alginic acid on the substrate. Surface analyses via various techniques established that alginic acid was immobilized onto the surface where grafting (brush) chemistry influenced the amount of alginic acid coated. Moreover, alginic acid was found to be capable of bacterial growth inhibition which itself was significantly affected by the brush type. The polyanionic character of alginic acid as a carbohydrate polymer was assumed to play the pivotal role in antibacterial activity. The cell wall composition of two bacterial strains along with the substrates physicochemical properties accounted for different levels of bacteriostatic performance.

Carboxymethylated and Sulfated Furcellaran from Furcellaria lumbricalis and Its Immobilization on PLA Scaffolds.

This study involved the creation of highly porous PLA scaffolds through the porogen/leaching method, utilizing polyethylene glycol as a porogen with a 75% mass ratio. The outcome achieved a highly interconnected porous structure with a thickness of 25 µm. To activate the scaffold's surface and improve its hydrophilicity, radiofrequency (RF) air plasma treatment was employed. Subsequently, furcellaran subjected to sulfation or carboxymethylation was deposited onto the RF plasma treated surfaces with the intention of improving bioactivity. Surface roughness and water wettability experienced enhancement following the surface modification. The incorporation of sulfate/carboxymethyl group (DS = 0.8; 0.3, respectively) is confirmed by elemental analysis and FT-IR. Successful functionalization of PLA scaffolds was validated by SEM and XPS analysis, showing changes in topography and increases in characteristic elements (N, S, Na) for sulfated (SF) and carboxymethylated (CMF). Cytocompatibility was evaluated by using mouse embryonic fibroblast cells (NIH/3T3).

Effect of Gentamicin Sulfate and Polymeric Polyethylene Glycol Coating on the Degradation and Cytotoxicity of Iron-Based Biomaterials.

The work is focused on the degradation, cytotoxicity, and antibacterial properties, of iron-based biomaterials with a bioactive coating layer. The foam and the compact iron samples were coated with a polyethylene glycol (PEG) polymer layer without and with gentamicin sulfate (PEG + Ge). The corrosion properties of coated and uncoated samples were studied using the degradation testing in Hanks' solution at 37 °C. The electrochemical and static immersion corrosion tests revealed that the PEG-coated samples corroded faster than samples with the bioactive PEG + Ge coating and uncoated samples. The foam samples corroded faster compared with the compact samples. To determine the cytotoxicity, cell viability was monitored in the presence of porous foam and compact iron samples. The antibacterial activity of the samples with PEG and PEG + Ge against Escherichia coli CCM 3954 and Staphylococcus aureus CCM 4223 strains was also tested. Tested PEG + Ge samples showed significant antibacterial activity against both bacterial strains. Therefore, the biodegradable iron-based materials with a bioactive coating could be a suitable successor to the metal materials studied thus far as well as the materials used in the field of medicine.

Polyphenolic extracts of edible flowers incorporated onto atelocollagen matrices and their effect on cell viability.

The phenolic extract of chives flowers (Allium schoenoprasum, Liliaceae), introduced Sage (Salvia pratensis, Lamiaceae), European elderberry (Sambucus nigra, Caprifoliaceae) and common dandelion (Taraxacum officinale, Asteraceae) were characterised by High Performance Liquid Chromatography and incorporated in different concentrations onto atelocollagen thin films. In order to assess the biological impact of these phenolic compounds on cell viability, human immortalised non-tumorigenic keratinocyte cell line was seeded on the thin films and cell proliferation was determined by using an MTT assay. In addition, their antimicrobial activity was estimated by using an agar diffusion test. Data indicated the concomitance between cell viability and concentration of polyphenols. These findings suggest that these phenolic-endowed atelocollagen films might be suitable for tissue engineering applications, on account of the combined activity of polyphenols and collagen.

Carbonized Leather Waste: A Review and Conductivity Outlook.

The carbonization of collagen-based leather waste to nitrogen-containing carbon is reviewed with respect to the preparation, characterization of carbonized products, and applications proposed in the literature. The resulting nitrogen-containing carbons with fibrous morphology have been used as adsorbents in water pollution treatment, in electrocatalysis, and especially in electrodes of energy-storage devices, such as supercapacitors and batteries. Although electrical conductivity has been implicitly exploited in many cases, the quantitative determination of this parameter has been addressed in the literature only marginally. In this report, attention has been newly paid to the determination of conductivity and its dependence on carbonization temperature. The resulting powders cannot be compressed into pellets for routine conductivity determination. A new method has been used to follow the resistivity of powders as a function of pressure up to 10 MPa. The conductivity at this pressure increased from 9.4 × 10-8 S cm-1 for carbonization at 500 °C to 5.3 S cm-1 at 1000 °C. The conductivity of the last sample was comparable with conducting polymers such as polypyrrole. The carbonized leather thus has the potential to be used in applications requiring electrical conduction.

Fucoidan- and Ciprofloxacin-Doped Plasma-Activated Polymer Coatings on Biodegradable Zinc: Hemocompatibility and Drug Release.

Blood-contacting medical devices such as biodegradable metallic bone implant materials are expected to show excellent hemocompatibility both in vitro and in vivo. Different approaches are being studied and used to modify biomaterial surfaces for enhanced biocompatibility and hemocompatibility. However, the composition of degradable biomaterial must address several drawbacks at once. Iron-reinforced zinc material was used as a metallic substrate with improved mechanical properties when compared with those of pure zinc. Poly(lactic) acid (PLA) or polyethylenimine (PEI) was selected as a polymeric matrix for further doping with antibiotic ciprofloxacin (CPR) and marine-sourced polysaccharide fucoidan (FU), which are known for their antibacterial and potential anticoagulant properties, respectively. Radiofrequency air plasma was employed to induce metallic/polymer-coated surface activation before further modification with FU/CPR. Sample surface morphology and composition were studied and evaluated (contact angle measurements, AFM, SEM, and FT-IR) along with the hemolysis ratio and platelet adhesion test. Successful doping of the polymer layer by FU/CRP was confirmed. While PEI induced severe hemolysis over 12%, the PLA-coated samples exhibited even lower hemolysis (∼2%) than uncoated samples while the uncoated samples showed the lowest platelet adhesion. Moreover, gradual antibiotic release from PLA determined by the electrochemical methods using screen-printed carbon electrodes was observed after 24, 48, and 72 h, making the PLA-coated zinc-based material an attractive candidate for biodegradable material design.

Engineering of inhalable nano-in-microparticles for co-delivery of small molecules and miRNAs.

In this study, novel Trojan particles were engineered for direct delivery of doxorubicin (DOX) and miR-34a as model drugs to the lungs to raise local drug concentration, decrease pulmonary clearance, increase lung drug deposition, reduce systemic side effects, and overcome multi-drug resistance. For this purpose, targeted polyelectrolyte nanoparticles (tPENs) developed with layer-by-layer polymers (i.e., chitosan, dextran sulfate, and mannose-g-polyethyleneimine) were spray dried into a multiple-excipient (i.e., chitosan, leucine, and mannitol). The resulting nanoparticles were first characterized in terms of size, morphology, in vitro DOX release, cellular internalization, and in vitro cytotoxicity. tPENs showed comparable cellular uptake levels to PENs in A549 cells and no significant cytotoxicity on their metabolic activity. Co-loaded DOX/miR-34a showed a greater cytotoxicity effect than DOX-loaded tPENs and free drugs, which was confirmed by Actin staining. Thereafter, nano-in-microparticles were studied through size, morphology, aerosolization efficiency, residual moisture content, and in vitro DOX release. It was demonstrated that tPENs were successfully incorporated into microspheres with adequate emitted dose and fine particle fraction but low mass median aerodynamic diameter for deposition into the deep lung. The dry powder formulations also demonstrated a sustained DOX release at both pH values of 6.8 and 7.4.

Insight into the Li-Storage Property of Surface-Modified Ti2Nb10O29 Anode Material for High-Rate Application.

Ti-based anode materials are considered to be an alternative to graphite anodes to accomplish high-rate application requirements. Ti2Nb10O29 (TNO15) has attracted much attention due to its high lithium storage capacity through the utilization of multiple redox couples and a suitable operating voltage window of 1.0 to 2.0 V vs Li/Li+. However, poor intrinsic electronic conductivity has limited the futuristic applicability of this material to the battery anode. In this work, we report the modification of TNO15 by introducing oxygen vacancies and using few-layered carbon and copper coatings on the surface to improve its Li+ storage property. With the support of the galvanostatic intermittent titration technique (GITT), we found that the diffusion coefficient of carbon/copper coated TNO15 is 2 orders of magnitude higher than that of the uncoated sample. Here, highly conductive copper metal on the surface of the carbon-coated oxygen-vacancy-incorporated TNO15 increases the overall electronic and ionic conductivity. The prepared TNO15-800-C-Cu-700 half-cell shows a significant rate capability of 92% when there is a 10-fold increase in the current density. In addition, the interconnected TNO15 nanoparticles create a porous microsphere structure, which enables better Li-ion transportation during charge/discharge process, and experiences an enhancement after the carbon and copper coating on the surface of the primary TNO15 nanocrystallites.

Composite Scaffolds Based on Bacterial Cellulose for Wound Dressing Application.

Wound dressing materials fabricated using biocompatible polymers have become quite relevant in medical applications, and one such material is bacterial cellulose (BC) with exceptional properties in terms of biocompatibility, high purity, crystallinity (∼88%), and high water holding capacity. However, the lack of antibacterial activity slightly restricts its application as a wound dressing material. In this work, polycaprolactone (PCL) was first impregnated into the BC matrix to fabricate flexible bacterial cellulose-based PCL membranes (BCP), which was further functionalized with antibiotics gentamicin (GEN) and streptomycin (SM) separately, to form wound dressing composite scaffolds to aid infectious wound healing. Fourier transform infrared spectroscopy (FT-IR) results confirmed the presence of characteristic PCL and cellulose peaks in the composite scaffolds at 1720 cm-1, 3400 cm-1, and 2895 cm-1, respectively, explaining the successful interaction of PCL with the BC matrix, which is further corroborated by scanning electron microscopy (SEM) images. X-ray diffraction (XRD) studies revealed the formation of highly crystalline BCP films (∼86%). In vitro studies of the BC and BCP scaffolds against baby hamster kidney (BHK-21) cells revealed their cytocompatible nature; also the wettability studies indicated the hydrophilicity of the developed scaffolds, qualifying the main criterion in wound dressing applications. Energy dispersive X-ray analysis (EDX) of the drug loaded scaffolds showed the presence of sulfur in the composites. The prepared scaffolds also exhibited excellent antimicrobial activity against Escherichia coli and Staphylococcus aureus. The release profiles initially indicated a burst release (6 h) followed by controlled release of GEN (∼42%) and SM (∼58%) from the prepared scaffolds within 48 h. Hence, these results interpret that the prepared drug-functionalized cellulosic scaffolds have great potential as a wound dressing material in biomedical applications.

Gellan gum/bacterial cellulose hydrogel crosslinked with citric acid as an eco-friendly green adsorbent for safranin and crystal violet dye removal.

In this study, ex-situ crosslinked gellan gum (GG)/bacterial cellulose (BC) hydrogels have been investigated as good absorbents for the removal of safranin and crystal violet dye pollutants. The preparation involves a cost-effective and easy-to-perform crosslinking procedure, using citric acid (CA) as a green crosslinker. The physicochemical and mechanical properties of the crosslinked hydrogels were examined by FTIR, TGA, SEM, XRD, and unconfined compression analyses. The swelling capacity of the hydrogels as a function of pH was investigated. CA depicted to improve structural stability as a crosslinker. The dye removal capacity of the hydrogels as good adsorbents was explored and showed higher efficiency in the removal of safranin dye as compared to crystal violet with optimum adsorption capacities obtained as 17.57 and 13.49 mg/g, respectively. Adsorption kinetics and isotherm models as well as thermodynamics examined. Results showed the adsorption process well fitted the pseudo 2nd-order kinetic and Langmuir-Freundlich models while temperature dependence study depicted to be exothermic. Furthermore, no significant loss of removal efficiency of the hydrogel adsorbent was observed even after five adsorption-desorption cycles. Based on the revealed results, the prepared hydrogel may serve as an effective adsorbent for the removal of dyes from the aqueous phase.

Chitosan Modified by Kombucha-Derived Bacterial Cellulose: Rheological Behavior and Properties of Convened Biopolymer Films.

This work investigates the rheological behavior and characteristics of solutions and convened biopolymer films from Chitosan (Chi) modified by kombucha-derived bacterial cellulose (KBC). The Arrhenius equation and the Ostwald de Waele model (power-law) revealed that the Chi/KBC solutions exhibited non-Newtonian behavior. Both temperature and KBC concentration strongly affected their solution viscosity. With the selection of a proper solvent for chitosan solubilization, it may be possible to improve the performances of chitosan films for specific applications. The elasticity of the prepared films containing KBC 10% w/w was preferable when compared to the controls. FTIR analysis has confirmed the presence of bacterial cellulose, chitosan acetate, and chitosan lactate as the corresponding components in the produced biopolymer films. The thermal behaviors of the Chi (lactic acid)/KBC samples showed slightly higher stability than Chi (acetic acid)/KBC. Generally, these results will be helpful in the preparation processes of the solutions and biopolymer films of Chi dissolved in acetic or lactic acid modified by KBC powder to fabricate food packaging, scaffolds, and bioprinting inks, or products related to injection or direct extrusion through a needle.

Electrochemical performance of composite electrodes based on rGO, Mn/Cu metal-organic frameworks, and PANI.

Benzendicarboxylic acid (BDC)-based metal-organic frameworks (MOFs) have been widely utilized in various applications, including supercapacitor electrode materials. Manganese and copper have solid diamond frames formed with BDC linkers among transition metals chosen for MOF formation. They have shown the possibility to enlarge capacitance at different combinations of MOFs and polyaniline (PANI). Herein, reduced graphene oxide (rGO) was used as the matrix to fabricate electrochemical double-layer SCs. PANI and Mn/Cu-MOF's effect on the properties of electrode materials was investigated through electrochemical analysis. As a result, the highest specific capacitance of about 276 F/g at a current density of 0.5 A/g was obtained for rGO/Cu-MOF@PANI composite.

Phenolic compounds from Allium schoenoprasum, Tragopogon pratensis and Rumex acetosa and their antiproliferative effects.

Experimental studies have shown that phenolic compounds have antiproliferative and tumour arresting effects. The aim of this original study was to investigate the content of phenolic compounds (PhC) in flowers of Allium schoenoprasum (chive), Tragopogon pratensis (meadow salsify) and Rumex acetosa (common sorrel) and their effect on proliferation of HaCaT cells. Antiproliferative effects were evaluated in vitro using the following concentrations of phenolic compounds in cultivation medium: 100, 75, 50 and 25 µg/mL. Phenolic composition was also determined by HPLC. The results indicate that even low concentrations of these flowers' phenolic compounds inhibited cell proliferation significantly and the possible use of the studied herb's flowers as sources of active phenolic compounds for human nutrition.