Hydrophilic Chitosan Research Articles

Determining the Characteristics of Ultrathin Polymer Films: A Spectroscopic Ellipsometry Approach.

Ellipsometry is a powerful and convenient technique that is widely used to determine the thickness and optical characteristics of polymer thin films. The determination is accomplished by modeling the measured change in the polarization of an electromagnetic wave upon interacting with the thin film. However, due to the strong statistical correlations between the fit parameters in the model, simultaneous determination of the thickness and the refractive indices of optically anisotropic ultrathin films using ellipsometry remains a challenge. Here, we propose an approach that can be used to obtain reliable values of both the thickness and the optical anisotropy of ultrathin polymer films. The approach was developed by performing spectroscopic ellipsometry measurements on thin films of hydrophobic polystyrene and hydrophilic chitosan of thickness between a few tens to a few hundred nm and whose absolute value of the birefringence differed by approximately an order of magnitude. Careful consideration of the characteristics of the root mean squared error of the fits obtained by modeling the ellipsometry data and the statistical correlations between the fit parameters formed the basis of the proposed approach.

RP-HPLC METHOD DEVELOPMENT AND VALIDATION FOR SIMULTANEOUS ESTIMATION OF CURCUMIN AND RESVERATROL IN NANO-MICELLE: DUAL DRUG DUAL FORM SIMULTANEOUS ESTIMATION

Objective: To develop a reverse-phase high-performance liquid chromatography (RP-HPLC) method for simultaneous estimation of conjugated form of Curcumin (CCMN) and free form of Resveratrol (RSV) in nano-micelle. Methods: The conjugation of lipophilic CCMN and hydrophilic Chitosan (CHT) through succinyl linker produce amphipathic molecule that can self-assemble into RSV solution to form micelle. Here RSV exists in micelle core as free form and CCMN with micelle backbone as conjugated form. So it required to estimate conjugated drug and free drug simultaneously from nano-micelle. We developed a RP-HPLC method, utilized C18 column, follow flow rate of mobile phase 1.0 ml/min, which consist of acetonitrile with water (0.5% Ortho Phosphoric acid, pH 4.6) in the ratio of 1:1 for 20 min. Injection volume was 10μl and column temperature 25 ℃. Isosbestic detection of both drugs was at 254 nm. Results: The retention time of RSV and CCMN were at 8.15 min and 11.41 min respectively, completely distinguished sharp peak of CCMN and RSV developed with resolution 7.360±0.117, wide range of linearity with correlation coefficient value (R2) of CCMN and RSV were 0.99987 and 0.99992 respectively and recovery value of CCMN and RSV were 100.041±0.22 % and 100.041±0.21 % respectively. The RSD (relative standard deviation) for accuracy, precision and robustness of the method was found to be less than 2%. Conclusion: The develop method for simultaneous estimation of conjugated CCMN and free form of RSV in the nano-micelle formulation was consider to be accurate, precise, robust and sensitive.

Hydrophilic chitosan: modification pathways and biomedical applications

Chitosan, a natural and abundant polysaccharide, offers several advantageous properties, such as excellent biocompatibility, biodegradability, and antimicrobial activity, making it a highly versatile material. However, its extensive application is hindered by its insolubility in water and most organic solvents, due to numerous intramolecular/intermolecular hydrogen bonds. To overcome this limitation and optimize its benefits, chitosan is often chemically modified to enhance its utility in various industries. Biomedical materials, environmental management, biological papermaking, food preservation, and the daily chemical industry are a few examples. Modified chitosan retains the inherent properties of chitosan and acquires new physicochemical characteristics as a result of introduced functional groups. Hydrophilic modifications typically include carboxylation, phosphorylation, and quaternary ammonium modification reactions. The specific properties and applications of chitosan derivatives depend on the grafted groups. This review summarizes the reaction conditions, properties, and applications of hydrophilic chitosan derivatives in drug delivery and food preservation, serving as a reference for the development and use of chitosan-based biomaterials. <br>The bibliography includes 128 references.

A unidirectional water-transport antibacterial bilayer nanofibrous dressing based on chitosan for accelerating wound healing

Excessive accumulation of exudate from wounds often causes infection and hinders skin regeneration. To handle wound exudate quickly and prevent infection, we developed an antibacterial Janus nanofibrous dressing with a unidirectional water-transport function. The dressing consists of a hydrophilic chitosan aerogel (CS-A) as the outer layer and a hydrophobic laurylated chitosan (La-CS) nanofibrous membrane as the inner layer. These dressings achieved excellent liquid absorption performance (2987.8 ± 123.5 %), air and moisture permeability (997.8 ± 23.1 g/m2/day) and mechanical strength (5.1 ± 2.6 MPa). This performance was obtained by adjusting the density of CS-A and the thickness of the La-CS membrane. Moreover, the dressing did not induce significant toxicity to cells and can prevent bacterial aggregation and infection at the wound site. Animal experiments showed that the dressing can shorten the inflammatory phase, enhance blood vessel generation, and accelerate collagen deposition, thus promoting wound healing. Overall, these results suggest that this Janus dressing is a promising material for clinical wound care.

In-situ lignin regeneration facilitated corn straw-based photothermal evaporator with high cost-effectiveness

Solar evaporators are one of the most efficient and sustainable water purification strategies, but it requires the use of expensive photothermal materials. Herein, the surface of waste corn straw was modified with condensed lignin by means of in-situ lignin regeneration. The resulting material was composited with hydrophilic chitosan and then applied as a sustainable and cost-effective photothermal material to construct a solar evaporator. The non-radiative transport was conferred by π-π stacking between conjugated aromatic rings of lignin, allowing the composites to demonstrate promising photothermal conversion ability. The composites presented a max evaporation rate of ∼1.44 kg m−2 h−1 under 1 sun, plus they consistently produced clean water in aqueous organic dye solutions (100 ppm RhB dye and 100 ppm MB dye) and seawater. Due to the ultra-low cost of raw materials and uncomplicated manufacturing procedure, these composites displayed a cost-effectiveness of ∼475 g h−1 $−1. Thus, this work provides a green and sustainable method for converting agricultural waste into functional photothermal evaporators, which is meaningful for both materials and environmental science.

Chitosan-functionalized poly(3-hydroxybutyrate) bead as a novel biosupport for palladium in the Suzuki cross-coupling reaction

The utilization of environmentally friendly biopolymer poly(3-hydroxybutyrate) (PHB) as a support for metal catalysts is an unexplored area. Herein, exploring a stable and recyclable heterogeneous palladium (Pd) catalyst based on PHB for the Suzuki cross-coupling reaction is an attractive topic. In this study, a novel hydrophobic and hydrophilic core-shell bead supported Pd catalyst was developed by using PHB particle as a hydrophobic rigid framework and hydrophilic chitosan (CS) as the surface of the supporting matrix to fix Pd nanoparticles (NPs). The results of structural characterization showed that the Pd NPs with a small average size of 2.3±0.82 nm were uniformly distributed on the surface of the PHB-CS bead with a Pd content of 0.12 wt%. This demonstrated that the PHB-CS bead created a stable coordinated environment for Pd fixation, preventing Pd leaching. Furthermore, the Pd@PHB-CS catalyst exhibited high catalytic efficiency with 99% conversion in the Suzuki reaction under mild conditions, using a solvent mixture of EtOH and H2O (1:1) for 0.5 h. It is worth noting that the catalyst exhibits excellent stability, and reusability. It can be reused five times without a significant reduction in activity while maintaining its structural integrity. The successful construction of Pd@PHB-CS will further expand the application of PHB in the field of metal catalysts and may help establish a green and environmentally friendly multifunctional platform for the development of highly recyclable heterogeneous catalysts containing metal nanoparticles.

Self-Oxidated Hydrophilic Chitosan Fibrous Mats for Fatal Hemorrhage Control.

Enriching erythrocytes and platelets in seconds and providing a fast seal in bleeding sites is vital to fatal hemorrhage control. Herein, hydrophilic chitosan fibrous mats (CECS-D mats) are fabricated by introducing hydrophilic carboxyethyl groups and subsequent catechol groups onto chitosan fibers. Due to strong hydrophilicity, CECS-D mats exhibit rapid liquid-absorption capacity, especially instantaneous absorptivity to the rabbit blood, which can achieve erythrocyte and platelet aggregations quickly by concentrating blood, thus promoting the formation of blood clots. Furthermore, the mats are self-oxidated to form quinone-amine adducts or quinone multimers by adjusting pH conditions, which not only provides tissue adhesion but also induces erythrocyte aggregation and platelet adhesion, further enhancing the seal and triggering quick closure to achieve fast hemostasis. Therefore, the mats reveal superior hemostatic performance in rabbit liver and spleen models over CECS mats and gauze. Especially in the fatal femoral artery injury model of rabbits, the mats reduce the blood loss by ∼75% and shortened the bleeding time by ∼50% compared with CECS mats, which have been reported to have the same hemostatic effect as commercialized Celox products in a swine femoral artery injury model. Besides, the mats are cytocompatible and degradable as well as antibacterial. This chitosan mat is a promising hemostatic material for fatal hemorrhage control.

Preparation of PDA-GO/CS composite scaffold and its effects on the biological properties of human dental pulp stem cells

Reduced graphene oxide (rGO) is an graphene oxide (GO) derivative of graphene, which has a large specific surface area and exhibited satisfactory physicochemical characteristics. In this experiment, GO was reduced by PDA to generate PDA-GO complex, and then PDA-GO was combined with Chitosan (CS) to synthesize PDA-GO/CS composite scaffold. PDA-GO was added to CS to improve the degradation rate of CS, and it was hoped that PDA-GO/CS composite scaffolds could be used in bone tissue engineering. Physicochemical and antimicrobial properties of the different composite scaffolds were examined to find the optimal mass fraction. Besides, we examined the scaffold’s biocompatibility by Phalloidin staining and Live and Dead fluorescent staining.Finally, we applied ALP staining, RT-qPCR, and Alizarin red S staining to detect the effect of PDA-GO/CS on the osteogenic differentiation of human dental pulp stem cells (hDPSCs). The results showed that PDA-GO composite was successfully prepared and PDA-GO/CS composite scaffold was synthesized by combining PDA-GO with CS. Among them, 0.3%PDA-GO/CS scaffolds improves the antibacterial activity and hydrophilicity of CS, while reducing the degradation rate. In vitro, PDA-GO/CS has superior biocompatibility and enhances the early proliferation, migration and osteogenic differentiation of hDPSCs. In conclusion, PDA-GO/CS is a new scaffold materialsuitable for cell culture and has promising application prospect as scaffold for bone tissue engineering.

Chitosan oligomer/silver nanoparticles/PCL composite electrospun membrane for severe burn wound healing

In the management of burn wounds, antimicrobial and wound healing properties are crucial. In this study, we prepared a three-layer electrospun poly(ε-caprolactone) (PCL) membrane for burn wound dressing. The hydrophobic electrospun PCL layer, embedded with silver nanoparticles (SNPs) (PCL-Ag), was coated with another layer of electrospun plasma-treated PCL-Ag to enhance the wettability of the membrane. This enhancement was to facilitate the absorption of the hydrophilic chitosan oligomer (COS) - the third layer of the dressing. The resultant membranes were characterised and tested for different properties to demonstrate their applicability as wound dressing materials. The combination of COS and SNPs of the fabricated membrane supports the healing process and reduces burn severity due to the healing capacity of COS and the antibacterial activity of SNPs, without compromising mechanical strength. We conducted several in vitro and in vivo experiments to evaluate its applicability for burn wound healing. The PCL-Ag/COS sample demonstrated outstanding in vitro biocompatibility and excellent antibacterial activity against Staphylococcus aureus strains. We used the membrane to treat burns on rabbits in the laboratory over 30 days, and consistently observed positive outcomes. This research offers insights into the development of bioactive dressings for wound healing and opens up opportunities for practical applications of COS-incorporated materials.

Application of electrospun chitosan-based nanofibers as immobilization matrix for biomolecules

Nanofiber meshes from electrospun chitosan, highly modified with biotin and arylazides, are well-suited for application as enzyme immobilization matrices. To test this, catalytically active biomolecules were immobilized onto photocrosslinked nanofibrous nonwovens consisting mainly of biotinylated fungal chitosan and a small amount (10 w%) of poly ethylene oxide. In this study, we show that over 10 μg eugenol oxidase per milligram dry polymer matrix can be loaded on UV-crosslinked chitosan nanofibers. We further demonstrate that bound enzyme activity can be fully retained for over 7 days of storage at ambient conditions in aqueous buffer. Samples loaded at maximum enzyme carrying capacity were tested in a custom-made plug-flow reactor system with online UV-VIS spectroscopy for activity determination. High wettability and durability of the hydrophilic chitosan support matrix enabled continuous oxidation of model substrate vanillyl alcohol into vanillin with constant turnover at flow rates of up to 0.24 L/h for over 6 h. This proves the above hypothesis and enables further application of the fibers as stacked microfluidic membranes, biosensors, or structural starting points for affinity crosslinked enzyme gels.Key points•Biotinylated chitosan-based nanofibers retain enzymes via mild affinity interactions•Immobilized eugenol oxidase shows high activity and resists continuous washing•Nanofiber matrix material tolerated high flow rates in a continuous-flow setupGraphical

Chitosan-Based High-Intensity Modification of the Biodegradable Substitutes for Cancellous Bone.

An innovative approach to treating bone defects is using synthetic bone substitutes made of biomaterials. The proposed method to obtain polylactide scaffolds using the phase inversion technique with a freeze extraction variant enables the production of substitutes with morphology similar to cancellous bone (pore size 100-400 µm, open porosity 94%). The high absorbability of the implants will enable their use as platelet-rich plasma (PRP) carriers in future medical devices. Surface modification by dipping enabled the deposition of the hydrophilic chitosan (CS) layer, maintaining good bone tissue properties and high absorbability (850% dry weight). Introducing CS increases surface roughness and causes local changes in surface free energy, promoting bone cell adhesion. Through this research, we have developed a new and original method of low-temperature modification of PLA substitutes with chitosan. This method uses non-toxic reagents that do not cause changes in the structure of the PLA matrix. The obtained bone substitutes are characterised by exceptionally high hydrophilicity and morphology similar to spongy bone. In vitro studies were performed to analyse the effect of morphology and chitosan on cellular viability. Substitutes with properties similar to those of cancellous bone and which promote bone cell growth were obtained.

Co-delivery of curcumin and quercetin in the bilayer structure based on complex coacervation

The formation of Zein-chitosan complex coacervates (ZCSC) with a co-encapsulated bilayer structure were successfully fabricated from Zein (Z) and chitosan (CS) for co-encapsulating the curcumin (Cur) and quercetin (Que). A combination of electrostatic attraction, hydrophobic effects and hydrogen bonding was demonstrated to be responsible for the formation of bilayer structure with chitosan covering on the surfaces of the Zein nanoparticles co-loading with curcumin and quercetin. The impacts of pH, type of polyphenols, protein-polyphenol ratio and curcumin-quercetin ratio on formation mechanism of bilayer structure was studied using the size, PDI, ζ-potential, size distribution and phase diagram measurement. The chemical structure and microstructure were further explored by Fourier transformed infrared spectroscopy (FTIR), UV–visible spectroscopy and Scanning electron microscope (SEM). Interestingly, the phase diagram and SEM images revealed that larger coacervates were favorably formed far away from the polyphenol-polyphenol ratio of 1:1 and near neutral pH. The bilayer-structured complexes showed high encapsulation efficiency (EE) for curcumin and quercetin, as well as a slow-release effect for both compounds. Additionally, these complexes were physically stable throughout a 3-week storage period. In conclusion, the nano-scale complexes and micron-level coacervates with a co-encapsulated bilayer structure based on hydrophobic Zein core and hydrophilic chitosan shell are an effective co-delivery system for two bioactive agents with different molecular characteristics.

Synthesis of a New Poly(ε-caprolactone)-g-Chitosan Amphiphilic Graft Copolymer with a "Reverse" Structure.

Hydrophilic chitosan (CHT) and hydrophobic polyε-caprolactone (PCL) are well-known biocompatible and biodegradable polymers that have many applications in the biomedical and pharmaceutical fields. But the mixtures of these two compounds are considered incompatible, which makes them not very interesting. To avoid this problem and to further extend the properties of these homopolymers, the synthesis of a new graft copolymer, the fully biodegradable amphiphilic poly(ε-caprolactone-g-chitosan) (PCL-g-CHT) is described, with an unusual "reverse" structure formed by a PCL backbone with CHT grafts, unlike the "classic" CHT-g-PCL structure with a CHT main chain and PCL grafts. This copolymer is prepared via a copper-catalyzed 1,3-dipolar Huisgen cycloaddition between propargylated PCL (PCL-yne) and a new azido-chitosan (CHT-N3 ). In order to obtain an amphiphilic copolymer regardless of the pH, chitosan oligomers, soluble at any pH, are prepared and used. The amphiphilic PCL-g-CHT copolymer spontaneously self-assembles in water into nanomicelles that may incorporate hydrophobic drugs to give novel drug delivery systems.

Drug-independent NADPH-consuming micelles collaborate with ROS-generator for cascade ferroptosis amplification by impairing redox homeostasis.

Ferroptosis as promising antitumor therapy strategy could be comprised by intracellular antioxidants, especially GSH and thioredoxin (Trx). They are both cofactors of Gpx4, the enzyme catalyzing the production of lipid peroxides to relieve oxidative stress, which drives the acquired ferroptosis resistance in tumors. Herein, the NADPH-consuming micelles are specially designed, which could collaborate with the ROS generating photodynamics therapy (PDT) by depleting intracellular GSH and Trx under hypoxia condition, resulting in ruined redox homeostasis and the final cascade amplified ferroptosis. The tailored micelle was briefly prepared by conjugating hypoxia-sensitive segment p-nitrobenzyl chloroformate (PNZ-Cl) to the hydrophilic chitosan (CS), the resulting micelle was further modified with photosensitizer Ce6 via PEG linkage. When receiving laser irradiation, the photosensitizer would generate ROS and consume oxygen in the meanwhile. The resulting anabatic hypoxia in turns promote the NTR-catalyzed electron-accepting response of micelles, with evidently enhanced NADPH consumption and ultimately ruined redox homeostasis, contributing to cascade amplified ferroptosis with robust ROS. Most importantly, the accompanied immunogenic cell death (ICD) and releasing danger-associated molecular patterns (DAMPs) could boost dendritic cells (DCs) maturation and the subsequent T-cell-mediated profound immune response. Collectively, the work excavates the other biochemical reaction during the hypoxia-sensitive process of C-N-Ce6 by diminishing intracellular GSH and Trx, providing a candidate of ferroptosis inducers against solid tumors.

High strength, controlled release of curcumin-loaded ZIF-8/chitosan/zein film with excellence gas barrier and antibacterial activity for litchi preservation

Polysaccharide films containing protein additives have good application prospects in agriculture and food field. However, interfacial incompatibility between hydrophobic proteins and hydrophilic polymers remains a major technical challenge. In this work, the interfacial compatibility between hydrophobic zein and hydrophilic chitosan (CS) is improved by the chemical crosslinking between zinc ions of curcumin-loaded zeolitic imidazolate framework-8 (Cur-ZIF-8) with CS and zein. With the improvement of interface compatibility, the results show that the elongation at break and O2 barrier property of synthesized Cur-ZIF-8/CS/Zein are 9.2 and 1.5 times higher than CS/Zein, respectively. And the Cur-ZIF-8/CS/Zein exhibits superior antibacterial and antioxidant properties as well. Importantly, Cur-ZIF-8/CS/Zein can also be used as an intelligent-responsive release platform for curcumin. As a result, Cur-ZIF-8/CS/Zein can keep the freshness and appearance of litchi at least 8 days longer than that of CS/Zein. Therefore, this study provides a novel method to improve the interfacial compatibility between hydrophobic proteins and hydrophilic polymers, and is expected to expand the application of protein/polymer composites in agriculture and food field.

Thermal-assisted synthesis of ferulic acid-chitosan complex in water and its application as safe antioxidant

Safe antioxidants are highly demanded in food preservation, yet existing preparation methods of typical bio-based antioxidants all suffer from either toxic catalysts or poor water solubility of the products. Herein, a water-soluble safe antioxidant, ferulic acid-chitosan complex, was facilely prepared in water with the assistance of mild-temperature heating. The chemical structure of ferulic acid-chitosan complex was determined by spectroscopy, and its thermal stability and rheological properties were studied in detail. Different from its precursors, the ferulic acid-chitosan complex exhibits much improved water solubility, thanks to its ionic structure. The as-prepared chitosan-ferulic acid complex displays higher antioxidative property than free ferulic acid, which was illustrated by the good preservation of freshly prepared apple juice. Such thermal-assisted synthesis strategy is demonstrated as an effective approach to prepare hydrophilic chitosan complex bearing hydrophobic organic acid, which enables great feasibility to the development of chitosan-based functional biomaterials.

Solvent triggered shape morphism of 4D printed hydrogels

4D printing of smart materials is a viable field of research for fabricating dynamic structures for various biomedical applications. 4D printing of hydrogel structures is challenging due to poor printability of hydrogels and poor shape fidelity of printed patterns when direct-ink writing-based 3D printers are used. In this study, chitosan (CS) hydrogel ink cross-linked with citric acid (CA) was made printable, exhibiting a shape-morphing behaviour when exposed to solvent as an external trigger. As one side of a printed structure is exposed to solvent, the solvent diffuses in and a concentration gradient is developed across the section. This concentration gradient results in displacement field, which finally leads to out-of-plane bending of the structure. This actuation is irreversible in nature since the concentration gradient is maintained between hydrophilic chitosan and hydrophobic silane layers. The reversibility of the morphed structures was achieved by dipping them in ethanol, which takes up solvent over time and thus diminishes the concentration gradient.The optimized CS/CA ink exhibited excellent rheological properties, with good extrudability and shape fidelity of printed structures. The chitosan ink was printed into various complex 3D architectures and was modified by hydrophobic coating of trimethyl silane (TMS). These hydrophobic patterns were coated on printed structures with varied interspacing, angles, and hinges to generate programmable designs. A printed soft gripper was demonstrated as an application that could lift an object seven times its weight. The shape morphing CS/CA hydrogel with excellent printability exhibits potential for 4D printing that has wide applications in soft robots, actuators, grippers, and sensors.

Electrospun chitosan nanofiber constructing superhigh-water-flux forward osmosis membrane

Forward osmosis (FO) technology exhibits great potential in seawater desalination and wastewater treatment due to its negligible energy consumption and high antifouling, however, the weak desalination capability, especially low water flux, remains challenging. Herein, a cost-effective and high-desalination-performance chitosan (CS)-based FO membrane is developed via coupling the electrospinning CS nanofibers and interfacial-polymerized polyamide (PA). The electrospun nanofibers construct the porous and hydrophilic CS layer with the large pore-diameter of ~274 nm and low thickness of ~10 μm, enabling the effective transport of water molecules, specifically, a superhigh water flux of 107.53 LMH at a low salt-water ratio of 0.24 g·L−1. In addition, such superior desalination performance of the as-prepared FO membrane is universal for the various salt species and concentrations. Our CS nanofiber-based membrane with the high separation capability of water-salt, desirable antibacterial activity, as well as the low cost, offers a roadmap toward the sustainable membrane materials.

Frontispiece: Hydrophilic Chitosan Derivatives: Synthesis and Applications

Frontispiece: Hydrophilic Chitosan Derivatives: Synthesis and Applications

Fe-MOF induced biopolymer-based sustainable self-cleaning membranes for effective selective separation and wastewater treatment

Recently, there is an outgrowing attention for biopolymer based thin film composite (TFC) membranes attributed to its sustainable factors. However, biopolymers show high fouling propensity thus, membrane fouling and the limited recyclability have always been the most severe problem during long-term use confining the industrial applications. Thus, the objectives of the study is to develop an anti-fouling membrane for increased shelf life with self-cleaning ability for successful regeneration of a membrane surface by the assistance of multifunctional nanocomposites. In this strategy, an iron-based metal organic framework (Fe-MOF) incorporated crosslinked chitosan-based loose nanofiltration membrane for selective filtration of solute and various wastewater treatment were developed. The structural functionality and stability of the thin-film composite (TFC) membranes was examined using ATR-IR and FE-SEM characterization and further surface charges were determined by zeta potential measurements. When the membrane's performance was examined for various feed streams under varied testing settings, it was discovered that the optimized membrane had a dye rejection rate of >85% (both cationic and anionic), and < 11.0% rejection for MgSO4 with flux rate of 40.0–50.0 L.m−2.h−1. In summary, the hydrophilic chitosan based TFC membranes was demonstrated as prominent candidate for wastewater treatment which can potentially substitute commercially successful commercial polyamide membranes attributed to high performance and anti-fouling capability along with self-cleaning ability.