Self-Assembled Hydrogel Membranes with Structurally Tunable Mechanical and Biological Properties.

Using supramolecular self-assembled nanocomposite materials made from protein and polysaccharide components is becoming more popular because of their unique properties, such as biodegradability, hierarchical structures, and tunable multifunctionality. However, the fabrication of these materials in a reproducible way remains a challenge. This study presents a new evaporation-induced self-assembly method producing layered hydrogel membranes (LHMs) using tropocollagen grafted by partially deacetylated chitin nanocrystals (CO-g-ChNCs). ChNCs help stabilize tropocollagen's helical conformation and fibrillar structure by forming a hierarchical microstructure through chemical and physical interactions. The LHMs show improved mechanical properties, cytocompatibility, and the ability to control drug release using octenidine dihydrochloride (OCT) as a drug model. Because of the high synergetic performance between CO and ChNCs, the modulus, strength, and toughness increased significantly compared to native CO. The biocompatibility of LHM was tested using the normal human dermal fibroblast (NHDF) and the human osteosarcoma cell line (Saos-2). Cytocompatibility and cell adhesion improved with the introduction of ChNCs. The extracted ChNCs are used as a reinforcing nanofiller to enhance the performance properties of tropocollagen hydrogel membranes and provide new insights into the design of novel LHMs that could be used for various medical applications, such as control of drug release in the skin and bone tissue regeneration.

An eco-friendly, highly efficient, and transparent coating derived from guar gum and citric acid for flame retardant treatment of cotton fabrics.

A highly efficient, bio-ecofriendly, and transparent flame retardant (FR) for cotton fabric was developed and deposited onto the cellulose skeletal structure of cotton fabric through a one-pot sol-gel process. The flame retardant functional coating is composed of ammonium polyphosphate (APP), guar gum (GG), citric acid (CA), and a negligible amount of catalyst. Cotton fabrics were impregnated with different concentrations of ammonium polyphosphate and guar gum, with citric acid as a crosslinking agent. The overall crosslinking and grafting process was proven by FTIR and XPS. Based on the results, the designed coating exhibits over 90 % transmittance in the visible region. A 15 g/m2 flame-retardant coating induces excellent flame retardant efficiency at ultra-low flame-retardant concentrations of less than 6.25 wt%. Only a 5.25 wt% flame retardant concentration demonstrated condensed phase action, which resulted in 58.5 % and 73.6 % reductions in the pHRR and THR, respectively. Moreover, the limiting oxygen index (LOI) value showed a 74 % increase. The mechanical performance of FR coated cotton fibers was slightly reduced.

Carboxymethyl starch as a reducing and capping agent in the hydrothermal synthesis of selenium nanostructures for use with three-dimensional-printed hydrogel carriers.

The hydrothermal method is a cost-effective and eco-friendly route for preparing various nanomaterials. It can use a capping agent, such as a polysaccharide, to govern and define the nanoparticle morphology. Elemental selenium nanostructures (spheres and rods) were synthesized and stabilized using a tailor-made carboxymethyl starch (CMS, degree of substitution = 0.3) under hydrothermal conditions. CMS is particularly convenient because it acts simultaneously as the capping and reducing agent, as verified by several analytical techniques, while the reaction relies entirely on green solvents. Furthermore, the effect of sodium selenite concentration, reaction time and temperature on the nanoparticle size, morphology, microstructure and chemical composition was investigated to identify the ideal synthesis conditions. A pilot experiment demonstrated the feasibility of implementing the synthesized nanoparticles into vat photopolymerization three-dimensional-printed hydrogel carriers based on 2-hydroxyethyl methacrylate (HEMA). When submersed into the water, the subsequent particle release was confirmed by dynamic light scattering (DLS), promising great potential for use in bio-three-dimensional printing and other biomedical applications.

Marine Biomaterials: Hyaluronan.

The marine-derived hyaluronic acid and other natural biopolymers offer exciting possibilities in the field of biomaterials, providing sustainable and biocompatible alternatives to synthetic materials. Their unique properties and abundance in marine sources make them valuable resources for various biomedical and industrial applications. Due to high biocompatible features and participation in biological processes related to tissue healing, hyaluronic acid has become widely used in tissue engineering applications, especially in the wound healing process. The present review enlightens marine hyaluronan biomaterial providing its sources, extraction process, structures, chemical modifications, biological properties, and biocidal applications, especially for wound healing/dressing purposes. Meanwhile, we point out the future development of wound healing/dressing based on hyaluronan and its composites and potential challenges.

The Effects of the Deacetylation of Chitin Nanowhiskers on the Performance of PCL/PLA Bio-Nanocomposites.

The multiple roles of organic nanofillers in biodegradable nanocomposites (NC) with a blend-based matrix is not yet fully understood. This work highlights combination of reinforcing and structure-directing effects of chitin nanowhiskers (CNW) with different degrees of deacetylation (DA), i.e., content of primary or secondary amines on their surface, in the nanocomposite with the PCL/PLA 1:1 matrix. Of importance is the fact that aminolysis with CNW leading to chain scission of both polyesters, especially of PLA, is practically independent of DA. DA also does not influence thermal stability. At the same time, the more marked chain scission/CNW grafting for PLA in comparison to PCL, causing changes in rheological parameters of components and related structural alterations, has crucial effects on mechanical properties in systems with a bicontinuous structure. Favourable combinations of multiple effects of CNW leads to enhanced mechanical performance at low 1% content only, whereas negative effects of structural changes, particularly of changed continuity, may eliminate the reinforcing effects of CNW at higher contents. The explanation of both synergistic and antagonistic effects of structures formed is based on the correspondence of experimental results with respective basic model calculations.

Effect of Polydopamine Coating of Cellulose Nanocrystals on Performance of PCL/PLA Bio-Nanocomposites.

In bio-nanocomposites with a poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) matrix with neat and polydopamine (PDA)-coated cellulose nanocrystals (CNCd), the use of different mixing protocols with masterbatches prepared by solution casting led to marked variation of localization, as well as reinforcing and structure-directing effects, of cellulose nanocrystals (CNC). The most balanced mechanical properties were found with an 80/20 PLA/PCL ratio, and complex PCL/CNC structures were formed. In the nanocomposites with a bicontinuous structure (60/40 and 40/60 PLA/PCL ratios), pre-blending the CNC and CNCd/PLA caused a marked increase in the continuity of mechanically stronger PLA and an improvement in related parameters of the system. On the other hand, improved continuity of the PCL phase when using a PCL masterbatch may lead to the reduction in or elimination of reinforcing effects. The PDA coating of CNC significantly changed its behavior. In particular, a higher affinity to PCL and ordering of PLA led to dissimilar structures and interface transformations, while also having antagonistic effects on mechanical properties. The negligible differences in bulk crystallinity indicate that alteration of mechanical properties may have originated from differences in crystallinity at the interface, also influenced by presence of CNC in this area. The complex effect of CNC on bio-nanocomposites, including the potential of PDA coating to increase thermal stability, is worthy of further study.

2-Methyl-6-(4-aminophenyl)-4,5-dihydro-3(2H)-pyridazinone Synthon for Some New Annelated 1,2,3-Selena/Thiadiazoles and 2H-Diazaphospholes with Anticipated Biological Activity and Quantum Chemical Calculations.

A convenient and efficient synthetic protocol for the new selenadiazole. Thiadiazole and diazaphosphole derivatives incorporating a pyridazine moiety originating from 4-(4-aminophenyl)-4-oxobutanoic acid (1) were described. All newly synthesized compounds were evaluated for their antimicrobial activity using the disk diffusion method, and their cytotoxicity was evaluated against brine shrimp lethality bioassay. Using density functional theory (DFT), the frontier molecular orbital (FMO) and molecular electrostatic potential (MEPS) were studied to estimate the chemical reactivity and kinetic stability of each structure. Therefore, global descriptor parameters like electronegativity (χ), chemical hardness (η), and global softness (σ) were calculated. Consequently, the attained results were compared with the experimental data of the biological activity of the studied structures.

Synergistic performance of collagen-g-chitosan-glucan fiber biohybrid scaffold with tunable properties.

Hybrid biocomposite scaffolds (HBS) that serve as a carrier for cell proliferation and differentiation are increasingly used for tissue regeneration. 3D hybrid scaffold based on collagen-grafted-chitosan-glucan fiber (CO-g-CGF-HBS) was prepared by freeze-drying technique. The swelling percentage, hydrolytic stability, and modulus of elasticity of HBS were enhanced after the chemical modification of CO with CGF. Pore size and porosity of HBS were decreased with an increased CGF ratio. HBS exhibits a higher reduction rate against different types of bacteria compared with a control sample. Thus, chemical modification of CO with different ratios of CGF significantly improved the physicochemical, antibacterial properties of HBS.

Synthesis of Some Mono- and Disaccharide-Grafting Phthalazine Derivatives and Some New Se-Nucleoside Analogues: Antibacterial Properties, Quantum Chemical Calculations, and Cytotoxicity.

A highly efficient and versatile synthetic approach for the synthesis of 4-(pyren-1-ylmethyl)-1-(d-glycosyloxy) phthalazine nucleosides 11a,b, 13, ß-S-nucleosides 16, 18, 20, and acyclo C-nucleosides 23a,b, 24, 25 and 27a-f was described and fully characterized. Furthermore, a series of desired new nucleoside analogues containing Se of 4-(pyren-1-ylmethyl) phthalazine-1(2H)-selenone 28-33 were synthesized. The structures of all reported compounds were confirmed by IR, 1H-NMR, 13C-NMR, MS and elemental analysis. All compounds have been screened for their antibacterial and antifungal activities. Maximum activity was shown by 20 and 33a comparable to the standard drugs with lower toxicity. The cytotoxicity of the selected compound was measured and evaluated. The energy gap between the highest occupied molecular orbital and lowest unoccupied molecular orbital was calculated using theoretical computations to reflect the chemical reactivity and kinetic stability of the synthesized compounds. Using density functional theory (DFT), electronic parameters such as the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) and the molecular electrostatic potential (MEPS) were calculated. On the basis of different studied structures, these properties were computed in order to elucidate the chemical reactivity and the kinetic stability. Obviously, the band gap energy (Eg) of structures studied reveals that the lowest band gap obtained for the structure 16-a indicates that it has the highest chemical reactivity and lowest kinetic stability.

Chitosan-glucan complex hollow fibers reinforced collagen wound dressing embedded with aloe vera. II. Multifunctional properties to promote cutaneous wound healing.

This study presents an innovative multifunctional system in fabricating new functional wound dressing (FWD) products that could be used for skin regeneration, especially in cases of infected chronic wounds and ulcers. The innovation is based on the extraction, characterization, and application of collagen (CO)/chitosan-glucan complex hollow fibers (CSGC)/aloe vera (AV) as a novel FWS. For the first time, specific hollow fibers were extracted with controlled inner (500-900 nm)/outer (2-3 µm) diameters from mycelium of Schizophyllum commune. Further on, research and evaluation of morphology, hydrolytic stability, and swelling characteristics of CO/CSGC@AV were carried out. The obtained FWS showed high hydrolytic stability with enhanced swelling characteristics compared to native collagen. The hemostatic effect of FWS increased significantly in the presence of CSGC, compared to native CO and displayed excellent biocompatibility which was tested by using normal human dermal fibroblast (NHDF). The FWS showed high antibacterial activity against different types of bacteria (positive/negative grams). From in vivo measurements, the novel FWS increased the percentage of wound closure after one week of treatment. All these results imply that the new CO/CSGC@AV-FWD has the potential for clinical skin regeneration and applying for controlled drug release.

Hyaluronan biofilms reinforced with partially deacetylated chitin nanowhiskers: Extraction, fabrication, in-vitro and antibacterial properties of advanced nanocomposites.

Fabrication of nanocomposite biofilms with enhanced mechanical and antibacterial properties was successfully achieved from hyaluronan (HA) and partially deacetylated chitin nanowhiskers (ChNWs) by a casting-evaporation method. The hydrolysis process of chitin showed an important role in the dimensions, stability, and the crystallinity of extracted ChNWs in a time-dependent manner. The volume fraction of ChNWs nanofiller varying from (0.001 to 0.5) exhibited a great influence on the mechanical properties of the biofilms (young modulus, strength) was enhanced by the high load-bearing capacity of NWs compared with net HA film. The antibacterial activity of the nanocomposite biofilms exhibited significant bactericidal activity against different types of bacteria (-/+ gram). HA/ChNWs Nanocomposite biofilms did not show any toxicity against normal human dermal fibroblasts (NHDF) and human primary osteogenic sarcoma (Saos-2) cell lines. The new biofilms with unique properties like edibleness, environmental friendliness, high mechanical properties, antibacterial performance, and non-cytotoxicity that could be used in skin tissue regenerations, and drug delivery applications.

Comparative study of chitosan and silk fibroin staple microfibers on removal of chromium (VI): Fabrication, kinetics and thermodynamic studies.

Short staple microfibers (SSM) based on chitosan (CS) or silk fibroin (SF) were fabricated via the wet-rotate-spinning technique and employed to adsorb hexavalent chromium from aqueous solution. Adsorption efficiencies, physicochemical and morphological properties of CS and SF-SSM were systematically investigated and evaluated before and after adsorption of Cr(VI) using different techniques like ATR-FTIR, TGA, XRD, XPS, and SEM. CS and SF-SSM showed removal efficiency (>90 %) toward Cr(VI) ions. Pseudo-second order kinetic and Langmuir isotherm models could describe the Cr(VI) ions uptake process. Considering the inexpensive, sustainability and higher adsorption capacity of CS and SF-SSM hold great promising applications as natural adsorbent materials for removing different hazardous metals from aqueous medium.

Chitosan-glucan complex hollow fibers reinforced collagen wound dressing embedded with aloe vera. Part I: Preparation and characterization.

Collagen (CO)/chitosan-glucan complex (CSGC) hollow fibers encapsulated aloe vera (AV) dressing scaffold (CO/CSGC@AV) were fabricated for the first time by the freeze-dried process. Extraction process, morphology, mechanical properties, pore size, porosity, swelling ability, and degradation behavior of composites scaffold were investigated. CSGC hollow fibers were extracted from mycelium of Schizophyllum commune CSGC hollow fiber exhibited inner diameter of (600 ±â€¯250 nm) and outer fiber diameter of (2.5 ±â€¯0.5 µm). The results of swelling and hydrolytic degradation studies demonstrated that the physicochemical of CO/CSGC@AV was significantly enhanced by CSGC in a concentration-dependent manner. The mechanical property of the CO/CSGC@AV was improved after encapsulated AV into CSGC hollow fibers compared with native CO. The pore size and porosity of the CO/CSGC@AV were slightly decreased in the presence of AV. All these results suggested that the new dressing scaffold has a potential for clinical skin regeneration, particularly for infected chronic wounds and ulcers.

Electrospinning of hyaluronan/polyvinyl alcohol in presence of in-situ silver nanoparticles: Preparation and characterization.

Novel nanofibers mats were fabricated by electrospinning of polyvinyl alcohol/hyaluronan (PVA/HA) solutions in the presence of silver nanoparticles (AgNPs). The AgNPs were synthesized by in-situ chemical reduction of silver ions (Ag+) using HA as a reducing and stabilizing agent. Narrow size distribution and spherical shape of AgNPs were achieved by optimizing the initial silver nitrate concentration (0.01 to 1 M) and reaction time (10-60 min). HA-AgNPs nanocomposite and PVA/HA-AgNPs nanofibrous mats were fabricated by electrospinning technique from aqueous solution containing a different mass ratio of PVA and HA-AgNPs and characterized by UV/Vis spectroscopy, SEM, TEM, DLS, XRD, TGA, and ATR-FTIR. Mechanical and rheological properties were also investigated and discussed. The novel nanofibrous mats show great potential in skin regeneration and drug carrier applications.

A novel in situ silver/hyaluronan bio-nanocomposite fabrics for wound and chronic ulcer dressing: In vitro and in vivo evaluations.

In-situ formed hyaluronan/silver (HA/Ag) nanoparticles (NPs) were used to prepare composite fibers/fabrics for the first time. Different concentrations of silver nitrate (1, 2mg/100ml) were added at ambient temperature to sodium hyaluronate solution (40mg/ml), then the pH was increased to 8 by adding sodium hydroxide. The in-situ formed HA/Ag-NPs were used to prepare fibers/nonwoven fabrics by wet-dry-spinning technique (WDST). UV/vis spectroscopy, SEM, TEM, DLS, XPS, XRD and TGA were employed to characterize the structure and composition of the nanocomposite, surface morphology of fiber/fabrics, particle size of Ag-NPs, chemical interactions of Ag0 and HA functional groups, crystallinity and thermal stability of the wound dressing, respectively. The resultant HA/Ag-NPs1 and HA/Ag-NPs2 composite showed uniformly dispersed throughout HA fiber/fabrics (SEM), an excellent distribution of Ag-NPs with 25±2, nm size (TEM, DLS) and acceptable mechanical properties. The XRD analysis showed that the in-situ preparation of Ag-NPs increased the crystallinity of the resultant fabrics as well as the thermal stability. The antibacterial performance of medical HA/Ag-NPs fabrics was evaluated against gram negative bacteria E. coli K12, exhibiting significant bactericidal activity. The fibers did not show any cytotoxicity against human keratinocyte cell line (HaCaT). In-vivo animal tests indicated that the prepared wound dressing has strong healing efficacy (non-diabetics/diabetics rat model) compared to the plain HA fabrics and greatly accelerated the healing process. Based on our results, the new HA/Ag-NPs-2mg nonwoven wound dressing fabrics can be used in treating wounds and chronic ulcers as well as cell carrier in different biological research and tissue engineering.

Preparation and characterization of alginate/silver/nicotinamide nanocomposites for treating diabetic wounds.

Silver/Alginate/Nicotinamide nanoparticles composite (Ag/ALG/Nic) was prepared and used for the first time to fabricate wound dressing material. Sodium alginate (ALG) was used as reducing and stabilizing agents for preparation of silver nanoparticles (Ag-NPs). Effect of concentrations of alginate (ALG) on the particle size of silver were studied and confirmed by different techniques like UV/vis spectroscopy, transmission electron microscope (TEM) and dynamic light scattering (DLS). Nonwoven viscous fabrics were used as a carrier for silver/alginate/nanoparticles composite by impregnated the nonwoven fabrics as per the padding-curing technique. Nicotinamide (Nic) as anti-inflammatory drug was entrapped into Ag-NPS/ALG/nonwoven fabrics. Scanning electron microscope and energy dispersive x-ray (SEM-EDX) were used to evaluate the presence of Ag/ALG/Nic nanoparticles composite anchored the nonwoven fabrics. The antibacterial activity of the Ag/ALG/Nic wound dressing material was evaluated against Escherichia coli (E. coli) and Staphylococcus Aureus (St. Aureus). The wound healing and histological studied were evaluated by using burn diabetic rat animals.

Novel chitin/chitosan-glucan wound dressing: Isolation, characterization, antibacterial activity and wound healing properties.

Chitin/chitosan-glucan complex (ChCsGC) was isolated from Schizophyllum commune (S. commune) and dissolved for the first time in precooled (-15°C) 8wt.% urea/6wt.% NaOH aqueous solution. Novel nonwoven microfiber mats were fabricated by wet-dry-spinning technique and evaluated the mechanical of fabrics mats and surface morphology. Isolated and nonwoven mat were characterized employing FTIR-ATR, Optical microscope, TGA, DSC, H/C NMR, SEM and XRD techniques. According to the physical/chemical characterization measurements we can assumed that, the net and the novel dressing mats have the same chemical structure with slightly changes in the thermal stability for the dressing mats.The biological activity of the nonwoven ChCsGC fabric was tested against different types of bacteria exhibiting excellent antibacterial activity. Cell viability of the plain complex and nonwovens mats were evaluated utilizing mouse fibroblast cell line varying concentrations and treatment time. ChCsGC did not show any cytotoxicity against mouse fibroblast cells and the cell-fabrics interaction was also investigated using fluorescence microscope. The novel ChCsGC nonwovens exhibited excellent surgical wound healing ability when tested using rat models.

Wound healing of different molecular weight of hyaluronan; in-vivo study.

Recruitment of cells and mediators is altered during impaired wound healing, thereby delaying this process. To overcome this problem, the correlation of wound healing in older rats, and the impact of different molecular weight of hyaluronan without silver nanoparticles; (low-HA1), (High-HA2), (Medium- HA3) and with silver nanoparticles (High-HA4) is investigated. The superior HA were selected to be further investigated onto diabetic wounds. Our results pointed to a marked deficiency in wounds granulation in older rats, which was accompanied with impairment of healing process. In older rats group treated with HA2 or HA4, granulation and dermal construction were improved. Furthermore, the number of pathogenic bacteria on wounds was declined throughout the first 24h by HA2 and HA4. The wound size in HA4-treated older rats was significantly smaller than that in other HA1, HA2 or HA3-treated older ones. Also, diabetes impaired the level of inflammatory cytokine, in diabetic model. On contrary, HA4 was found to normalize the level of inflammatory cytokine, in the diabetic model. Furthermore, HA4 was found to recover all oxidative and toxicity markers in diabetic models. This data confirms the critical role of HA4 to improve granulation and inflammatory mediators in impaired older and diabetic rat wound healing.

Accurate micro-computed tomography imaging of pore spaces in collagen-based scaffold.

In this work we have used X-ray micro-computed tomography (µCT) as a method to observe the morphology of 3D porous pure collagen and collagen-composite scaffolds useful in tissue engineering. Two aspects of visualizations were taken into consideration: improvement of the scan and investigation of its sensitivity to the scan parameters. Due to the low material density some parts of collagen scaffolds are invisible in a µCT scan. Therefore, here we present different contrast agents, which increase the contrast of the scanned biopolymeric sample for µCT visualization. The increase of contrast of collagenous scaffolds was performed with ceramic hydroxyapatite microparticles (HAp), silver ions (Ag(+)) and silver nanoparticles (Ag-NPs). Since a relatively small change in imaging parameters (e.g. in 3D volume rendering, threshold value and µCT acquisition conditions) leads to a completely different visualized pattern, we have optimized these parameters to obtain the most realistic picture for visual and qualitative evaluation of the biopolymeric scaffold. Moreover, scaffold images were stereoscopically visualized in order to better see the 3D biopolymer composite scaffold morphology. However, the optimized visualization has some discontinuities in zoomed view, which can be problematic for further analysis of interconnected pores by commonly used numerical methods. Therefore, we applied the locally adaptive method to solve discontinuities issue. The combination of contrast agent and imaging techniques presented in this paper help us to better understand the structure and morphology of the biopolymeric scaffold that is crucial in the design of new biomaterials useful in tissue engineering.

Wound dressing based on chitosan/hyaluronan/nonwoven fabrics: Preparation, characterization and medical applications.

Thin layers of chitosan (positively charged)/sodium hyaluronate (negatively charged)/nonwoven fabrics were constructed by polyelectrolyte multilayer pad-dry-cure technique. Pure chitosan (CS) was isolated from shrimp shell and immobilized onto nonwoven fabrics (NWFs) using citric acid (CTA) as cross linker and solvent agents through a pad-dry-cure method. The prepared thin layer of chitosan citrate/nonwoven fabrics (CSCTA/NWFs) were consequently impregnated with hyaluronan (CSCTA/HA/NWFs) in the second path through a pad-dry-cure method. Chitosan/hyaluronan/nonwoven fabrics wound dressing was characterized by different techniques such as FTIR-ATR, TGA and SEM. The antibacterial activity and the cytotoxicity of the dressing sheets were evaluated against Escherichia coli (E. coli) and Streptococcus aureus (S. aureus), mouse fibroblast (NIH-3T3) and keratinocytes (HaCaT) cell lines, respectively. The cell-fabrics interaction was also investigated using fluorescence microscope, based on live/dead staining assay of 3T3 cells. The healing properties of the new wound dressing were evaluated and compared with the control sample.