Phosphoramide Hydrogels as Biodegradable Matrices for Inkjet Printing and Their Nano-Hydroxyapatite Composites.

Inkjet printing is a leading technology in the biofabrication of three-dimensional biomaterials, offering digital, noncontact deposition with micron-level precision. Among these materials, hydroxyapatite is widely recognized for its use in bone tissue engineering. However, most hydroxyapatite-laden inks are unsuitable for inkjet printing. To address this, we developed photocurable and biodegradable phosphoramide-based hydrogels containing thiol-functionalized polyethylene glycol via click chemistry. These hydrogels degrade into phosphates, the natural component of bone. The rheological properties of the inks are finely tuned through chemical design to meet the requirements of nanohydroxyapatite composite inks for piezoelectric inkjet printing. We demonstrated their printability using simple geometric patterns, showcasing a versatile and efficient solution for the precise inkjet printing of biomaterial composites.

Removal of different vat dyes by Aspergillus niger: A comparative study focusing on the molecular structure.

Vat dyes are the most commonly used dyes in the denim industry. Since the pollution of the textile industry is a worldwide problem, Aspergillus niger was used in this study, to treat vat dye wastewater by pre-culture and simultaneous-culture methods. A comparison between the two biosorption techniques used showed that pre-culture was about 30% more efficient than simultaneous culture. The adsorption capacity was determined using the Langmuir and Freundlich adsorption models, with Langmuir proving to be the most suitable model. The high saturation capacity of 121.35 mg/g for C.I. Vat Brown 1 calculated with the Langmuir adsorption model indicated that A.niger is a suitable sorbent for vat dye wastewater. To investigate the influence of dye structure on biosorption efficiency, eight vat dyes with different chemical characteristics were used. The results showed that the complete decolorization time was reduced by 200 and 150 min for planar and non-planar structures, respectively, due to the reduction of molecular mass, indicating that molecular mass is probably the dominant factor in vat dye removal. In addition, planar structures resulted in a 50-min reduction in biosorption time. The possible adsorption sites were analyzed by Fourier transfer infrared analysis. The results showed that the amino and carboxyl groups of the fungus could serve as sorption sites for vat dyes through hydrogen bonding."

Zwitterionic keratin coating on silk-Laponite fibrous membranes for guided bone regeneration.

Implant-related infection is one of the main challenges in periodontal diseases. According to the zwitterionic properties of keratin, we aim to develop guided bone regeneration (GBR) membrane with antibacterial and bioactivity properties using a keratin coating. In this study, electrospun silk fibroin (SF)-Laponite (LAP) fibrous membranes were developed as GBR membranes, and keratin extracted from sheep wool was electrosprayed on them. Here, the role of electrospraying time (2, 3, and 4h) on the properties of the GBR membranes was investigated. After physicochemical characterization of the keratin-modified membranes, in vitro bioactivity and degradation rate of the membranes were studied in simulated body fluid and phosphate buffer saline, respectively. Moreover, proliferation and differentiation of mesenchymal stem cells were evaluated in contact with the keratin-modified SF-LAP membrane. Finally, the antibacterial activity of membranes against gram-positive bacteria (Staphylococcus aureus) was investigated. Results demonstrated the successful formation of homogeneous wool keratin coating on SF-LAP fibrous membranes using a simple electrospray process. While wool keratin coating significantly enhanced the elongation and hydrophilicity of the SF-LAP membrane, the mechanical strength was not changed. In addition, keratin coating significantly improved the bioactivity and degradation rate of SF-LAP membranes, owing to the carboxyl groups of amino acids in keratin coating. In addition, the synergic role of LAP nanoparticles and keratin coating drastically improved osteoblast proliferation and differentiation. Finally, the zwitterionic property of wool keratin coating originating from their equal positive (NH3 + ) and negative (COO- ) charges considerably improved the antibacterial activity of the SF-LAP membrane. Overall, keratin-coated SF-LAP fibrous membranes with significant mechanical and biological properties could have the potential for GBR membranes.

New Laccase-Mediated System Utilized for Bio-Discoloration of Indigo-Dyed Denim Fabrics.

In this study, indigo-dyed denim fabric was decolorized via separate and simultaneous applying of laccase, sodium hydrosulfite, and cellulase. In this regard, the surface reflectance and color coordinates of the discolored fabrics were evaluated and scanning electron microscopy (SEM) images of the cellulase treated fabric were prepared to analyze their surfaces. Finally, the characterization of the treated samples was investigated, including moisture content, crease recovery angle, air permeability, and abrasion resistance. The color experiments showed that simultaneous applying of laccase, sodium hydrosulfite, and cellulose had a 55.79% improvement in the samples' lightness (L*). Furthermore, the color coordinate test of specimens revealed that the hue of the treated samples was changed to blue and green, and the purity of color (C*) was modified. The increment in the moisture content and air permeability of the treated specimens indicated that the comfort of the jeans clothing had been enhanced. As a result, sodium hydrosulfite demonstrates a high-efficiency denim discoloration in the laccase-mediated system.

Fabrication of Cellulase Catalysts Immobilized on a Nanoscale Hybrid Polyaniline/Cationic Hydrogel Support for the Highly Efficient Catalytic Conversion of Cellulose.

A novel conductive nanohydrogel hybrid support was prepared by in situ polymerization of polyaniline nanorods on an electrospun cationic hydrogel of poly(ε-caprolactone) and a cationic phosphine oxide macromolecule. Subsequently, the cellulase enzyme was immobilized on the hybrid support. Field-emission scanning electron microscopy and Brunauer-Emmett-Teller analyses confirmed a mesoporous, rod-like structure with a slit-like pore geometry for the immobilized support and exhibiting a high immobilization capacity and reduced diffusion resistance of the substrate. For comparison, the catalytic activity, storage stability, and reusability of the immobilized and free enzymes were evaluated. The results showed that the immobilized enzymes have higher thermal stability without changes in the optimal pH (5.5) and temperature (55 °C) for enzyme activity. A high immobilization efficiency (96%) was observed for the immobilized cellulose catalysts after optimization of parameters such as the pH, temperature, incubation time, and protein concentration. The immobilized enzyme retained almost 90% of its original activity after 4 weeks of storage and 73% of its original activity after the ninth reuse cycle. These results strongly suggest that the prepared hybrid support has the potential to be used as a support for protein immobilization.

Investigation and comparison of new galactosylation methods on PCL/chitosan scaffolds for enhanced liver tissue engineering.

In liver tissue engineering, improving the ability of the scaffold to increase the tendency of cells to grow and proliferate is very important. In this study, new methods for modifying the surface of Polycaprolactone (PCL)/Chitosan (Cs) nanofiber for use in liver tissue engineering have been proposed. Galactosylation of chitosan was performed in three ways. According to the FE-SEM, FTIR, NMR and DSC analysis, presence of galactose in uniform nanofibers confirmed and led to a decrease in crystallinity. The hydrophobicity of the scaffolds by contact angle showed that the scaffold with galactosylated after electrospinning, had the highest contact angle of 82.22 ± 2° compared to raw scaffold with 98.52 ± 4°. According to the results of degradation in PBS, the highest rate of degradation was observed in scaffolds that were galactosylated after electrospinning. By culturing HepG2 cells on and based on the results of SEM and MTT analysis, found that the presence of galactose in the scaffolds significantly increased cell growth and proliferation without any toxicity. The immersion method shows a greater ability to improve the growth of liver cells. Also, using in-situ way due to the roughness created in this method may lead to better results especially for in-vivo tests.

Improving physical and biological properties of nylon monofilament as suture by Chitosan/Hyaluronic acid.

One way to give some properties such as antibacterial and good frictional properties to sutures is the application of natural antibacterial and hydrophilic components on their surfaces through layer by layer assembly (LBL) technique. In this regard, Chitosan as an antibacterial polycationic natural polymer along with Hyaluronic acid (HA) as a polyanionic polysaccharide could be used to form a polyelectrolyte complex. In this study, HA was extracted from rooster comb using different solvents. Characterization of the extracted HA by FTIR and GPC analysis showed extracted HA with Mw = 2.53 × 105 Da had no cytotoxicity. Then, a nylon monofilament (NMy) was coated by the extracted HA and chitosan with different concentrations using bilayer coating technique. Two dyes also were loaded to coating layer to investigate the release behavior of these two drug models. The morphology of coated layer showed that coating NMy by chitosan (4% w/v) following by HA (8% w/v) with roughness of 164 ± 129 nm and friction coefficient of 0.26 had suitable interaction between two layers to prevent from exfoliation of coating layers. The antibacterial activity and controlled release of coated NMy indicated how a NMy coated by Chitosan and HA is a promising material for using as a suture.

Structurally Tunable pH-responsive Phosphine Oxide Based Gels by Facile Synthesis Strategy.

Design and synthesis of nanostructured responsive gels have attracted increasing attention, particularly in the biomedical domain. Polymer chain configurations and nanodomain sizes within the network can be used to steer their functions as drug carriers. Here, a catalyst-free facile one-step synthesis strategy is reported for the design of pH-responsive gels and controlled structures in nanoscale. Transparent and impurity free gels were directly synthesized from trivinylphosphine oxide (TVPO) and cyclic secondary diamine monomers via Michael addition polymerization under mild conditions. NMR analysis confirmed the consumption of all TVPO and the absence of side products, thereby eliminating post purification steps. The small-angle X-ray scattering (SAXS) elucidates the nanoscale structural features in gels, that is, it demonstrates the presence of collapsed nanodomains within gel networks and it was possible to tune the size of these domains by varying the amine monomers and the nature of the solvent. The fabricated gels demonstrate structure tunability via solvent-polymer interactions and pH specific drug release behavior. Three different anionic dyes (acid blue 80, acid blue 90, and fluorescein) of varying size and chemistry were incorporated into the hydrogel as model drugs and their release behavior was studied. Compared to acidic pH, a higher and faster release of acid blue 80 and fluorescein was observed at pH 10, possibly because of their increased solubility in alkaline pH. In addition, their release in phosphate buffered saline (PBS) and simulated body fluid (SBF) matrix was positively influenced by the ionic interaction with positively charged metal ions. In the case of hydrogel containing acid blue 90 a very low drug release (<1%) was observed, which is due to the reaction of its accessible free amino group with the vinyl groups of the TVPO. In vitro evaluation of the prepared hydrogel using human dermal fibroblasts indicates no cytotoxic effects, warranting further research for biomedical applications. Our strategy of such gel synthesis lays the basis for the design of other gel-based functional materials.

Effects of different drying methods on the physicochemical properties and antioxidant activities of isolated acorn polysaccharides.

Our earlier studies showed that the Acorn Polysaccharides (AP), as a forest byproduct, have a good prebiotic properties and antioxidant activity, hence can be used as an ingredient to produce functional foods. Three drying methods (freeze, hot air and vacuum drying) in different temperatures were comparatively studied on the physicochemical properties (solubility, water and oil-holding capacity [OHC/WHC]), bioactivity (resistance to acidic and enzymatic digestions, effect on a probiotic strain growth) and antioxidant activity of AP along with the structural changes. Results suggest that the drying methods in combinations of temperatures and time of drying process affect physicochemical properties, antioxidant activity and bioactivities of AP. Freeze dried AP exhibited the highest solubility, WHC, OHC and antioxidant activity, digestibility with simulated gastrointestinal juices and fermentable by a Lactobacillus plantarum. Whereas, hot air dried (80 °C) exhibited second highest antioxidant and functional activities like solubility, WHC, OHC and fermentation. FTIR analysis showed that the changes caused by varying drying methods of AP starch are related to its amorphous or crystallinity structure and differences in functional group. Overall, these results suggest that freeze drying and hot air drying at 80 °C can be appropriately use to obtain a functional polysaccharide from acorn, as a prebiotic (resistant starch).

Investigating the performance of drug delivery system of fluconazole made of nano-micro fibers coated on cotton/polyester fabric.

Polymer-based drug delivery systems are suitable to optimize the therapeutic properties of drugs and to render them safer, more effective and reliable. Long-term or repeated use of oral administration of fluconazole for treating chronic candidiasis in the patient and partially abandoned treatment lead to the resistant strains of the fungus Candida albicans and severity of the disease. In this study, the use of nanofibers and microfibers containing fluconazole for local drug delivery to increase the efficiencies and reduce the side effects caused by taking the drug was studied. Morphology, microstructure and chemical composition of PVA nanofibers containing fluconazole were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). As well as, the DSC test was indicated presence of fluconazole in PVA fibrous mats. The rate of drug release was investigated by UV-Vis spectrophotometery and swelling technique. SEM images showed that the nanofibers with uniform structure without beads were produced. The mechanical properties of the pristine PVA nanofiber and fibrous mat containing drug were evaluated. The release of fluconazole from PVA nanofibers in pH of 7.4 and at 37 °C was investigated. The results presented that the drug release rate is dependent on the morphology and structure of PVA nanofibers and could be adjusted in desired dosage. The presented products are applicable in the high production form for medical textile industry.

Protein-based nanoformulations for α-tocopherol encapsulation.

Nanoparticles of BSA and silk fibroin (SF) with entrapped α-tocopherol were produced via ultrasonic emulsification. Populations with particle size of 200-300 nm and highly negatively charged were obtained for all the tested formulations. Entrapment efficiencies of around 99% revealed the effective encapsulation of α-tocopherol into the produced nanoformulations. Generally, these nanodevices did not induce significant cytotoxicity to human skin keratinocytes for all the concentrations tested. The developed formulations showed free radical scavenging of ABTS.+ ability resulting from the synergistic effect between the proteins in formulation and the entrapped tocopherol. Overall, the results contribute for the establishment of BSA:VO and BSA:SF:VO as biodegradable and non-toxic nanoformulations for the functionalization of textile devices and controlled delivery of tocopherol into the skin.

Mutation of bacterium Vibrio gazogenes for selective preparation of colorants.

A novel marine bacterium strain effectively produced prodiginine type pigments. These colorants could dye wool, silk and synthetic fabrics such as polyester and polyacrylic and also show antibacterial properties against Escherichia coli and Staphylococcus aureus bacteria on the dyed products. Methyl nitrosoguanidine was used as a mutation agent to increase the genetic diversity and the production yield of the bacteria of the family of Vibrio gazogenes. The analysis of the mutated samples showed that two new main colorants as well as three previously found ones were produced. Liquid chromatography electro spray ionization mass spectrometry (LC-ESI-MS) and nuclear magnetic resonance (NMR) spectroscopic techniques were used to elucidate the structures of the newly produced colorants. Mass measurements revealed that the colorants C1, C2, C3, C4 have molecular masses of 321, 323, 351, and 295 Da. One unstable colorant C5 with molecular mass of 309 Da was detected as well. The mutated bacteria strains increased the yield of pigment production by about 81% and produced prodigiosin in 97% purity. The antibiotic activities of pure colorants are discussed as well. Based on their bio-activity and excellent dyeing capabilities, these colorants could be employed in cosmetic and textile industries.

Antibacterial colorants: characterization of prodiginines and their applications on textile materials.

A strain of Vibrio sp. isolated from marine sediments produced large quantities of bright red pigments that could be used to dye many fibers including wool, nylon, acrylics, and silk. Characterization of the pigments by electrospray ionization mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR) revealed three prodiginine-like structures with nonpolar characteristics and low molecular mass. UV-visible spectra of the major constituent in methanol solution showed absorbance at lambda max 530 nm wavelength. The accurate mass result showed that the main isolated product has a molecular mass of m/z 323.1997. Further analysis using mass fragmentation (MS/MS), 1H NMR, COSY, HMQC NMR and DEPT confirmed the detailed structure of the pigment with an elementary composition of C20H25N3O. Fabrics dyed with the microbial prodiginines demonstrated antibacterial activity.