Quaternized Carboxymethyl Chitosan Research Articles

A pH responsive tannic acid/quaternized carboxymethyl chitosan/oxidized sodium alginate hydrogels for accelerated diabetic wound healing and real-time monitoring

Treatment of diabetic wounds is a major clinical issue. Diabetic wound dressings have higher requirements for anti-oxidant, antibacterial and wound monitoring properties compared to conventional wound dressings. In this study, a novel tannic acid (TA)/quaternized carboxymethyl chitosan (QCMCS)/oxidized sodium alginate (OSA)@carbon quantum dots (CQD) (TA/QCMCS/OSA@CQD) hydrogels for promoting diabetic wound healing and real-time monitoring have been developed. The TA/QCMCS/OSA@CQD hydrogels exhibited excellent self-healing, antibacterial and antioxidant properties. Besides, these hydrogels possessed good biocompatibility and effective hemostasis in a mouse liver injury model and significantly facilitated the healing process in a diabetic wound model. In addition, these hydrogels can reliable and timely measure the diabetic wound pH information by collecting image signals of hydrogels to monitor the healing status. Therefore, the pH responsive TA/QCMCS/OSA@CQD hydrogels could be utilized as wound dressing for promoting diabetic wound healing and real-time monitoring.

Rapid self-healing carboxymethyl chitosan/hyaluronic acid hydrogels with injectable ability for drug delivery

In this study, the quaternized carboxymethyl chitosan (QCMCS), oxidized hyaluronic acid (OHA), 3,3′-dithiobis-(propionohydrazide) (DTP) were used as raw materials for the synthesis of hydrogels with excellent properties as carriers for drug release. The hydrogels were prepared by a simple “one-pot” method without external stimuli on the basis of interactions between formed dynamic covalent bonds (imine bonds, acylhydrazone bonds, disulfide bonds) and hydrogen bonds. The hydrogels had rapid self-healing properties, with a self-healing rate of 96 % after 30 min, as well as good pH responsiveness and excellent cytocompatibility (up to 98 % cell survival). The compressive stress of the hydrogels reached 423 kPa. Moreover, a representative drug (acetylsalicylic acid) demonstrated sustained release in the hydrogels (>72 h). The drug release behaviour was shown to be consistent with the Fick diffusion mechanism by kinetic modelling. Collectively, the findings demonstrate that the QCMCS + OHA + DTP injectable self-healing hydrogels are a potential material for the construction of pH-controlled drug delivery platforms.

Rapid hemostatic antibacterial self-gelling powder based on methacryloylsulfonyl betaine and quaternized carboxymethyl chitosan

Hemostatic powders can be used for deep wounds and wounds with irregular shapes that are frequently inaccessible to traditional hemostatic dressings like hemostatic gauze, sponges, and foams. In this study, sulfobetaine methacrylate (SBMA) and quaternized carboxymethyl chitosan (QCCS) were combined to create an antibacterial hemostatic hydrogel through photopolymerization under green LED irradiation, which was then changed into PSBMA/QCCS powder. PSBMA/QCCS powder could quickly form hydrogel with strong wet adhesion. The internal structure, water absorption capacity, and adhesion properties of the powder were evaluated. The coagulation ability, antimicrobial properties, and biocompatibility of the powder were also characterized. The PSBMA/QCCS powder could aggregate blood cells and platelets to enhance hemostasis. Meanwhile, PSBMA/QCCS powder also showed effective antibacterial ability against both gram-positive bacteria (Staphylococcus aureus) and gram-negative bacteria (Escherichia coli). In summary, PSBMA/QCCS powder is a promising hemostatic agent with the characteristics of quick hemostasis, tough wet adhesion, satisfactory biocompatibility, considerable antibacterial effect, and adaptability to any irregularly shaped wounds.

Dual-Cross-Linked Chitosan-Based Antibacterial Hydrogels with Tough and Adhesive Properties for Wound Dressing.

Biocompatible chitosan-based hydrogels have attracted extensive attention in wound dressing due to their human skin-like tissue characteristics. However, it is a crucial challenge to fabricate chitosan-based hydrogels with versatile properties, including flexibility, stretchability, adhesivity, and antibacterial activity. In this work, a kind of chitosan-based hydrogels with integrated functionalities are facilely prepared by solution polymerization of acrylamide (AAm) and sodium p-styrene sulfonate (SS) in the presence of quaternized carboxymethyl chitosan (QCMCS). Due to the dual cross-linking between QCMCS and P(AAm-co-SS), the optimized QCMCS/P(AAm-co-SS) hydrogel exhibits tough mechanical properties (0.767MPa tensile stress and 1100% fracture strain) and moderate tissue adhesion (11.4kPa). Moreover, biological evaluation in vitro illustrated that as-prepared hydrogel possesses satisfactory biocompatibility, hemocompatibility, and excellent antibacterial ability (against S. aureus and E. coli are 98.8% and 97.3%, respectively). Then, the hydrogels are tested in a rat model for bacterial infection incision in vivo, and the results show that they can significantly accelerate epidermal regeneration and wound closure. This is due to their ability to reduce the inflammatory response, promote the formation of collagen deposition and granulation tissue. The proposed chitosan-based antibacterial hydrogels have the potential to be a highly effective wound dressing in clinical wound healing.

Retention of Intrafibrillar Minerals Improves Resin–Dentin Bond Durability

The concept of extrafibrillar demineralization involves selective removal of apatite crystallites from the extrafibrillar spaces of mineralized dentin without disturbing the intrafibrillar minerals within collagen. This helps avoiding activation of endogenous proteases and enables air-drying of partially demineralized dentin without causing collapse of completely demineralized collagen matrix that adversely affects resin infiltration. The objective of the present study was to evaluate the potential of quaternized carboxymethyl chitosan (QCMC)–based extrafibrillar demineralization in improving resin–dentin bond durability. Isothermal titration calorimetry indicated that QCMC synthesized by quaternization of O-carboxymethyl chitosan had moderate affinity for Ca2+ (binding constant: 8.9 × 104 M−1). Wet and dry bonding with the QCMC-based demineralization produced tensile bond strengths equivalent to the phosphoric acid (H3PO4)–based etch-and-rinse technique. Those bond strengths were maintained after thermocycling. Amide I and PO43− mappings of QCMC-conditioned dentin were performed with atomic force microscope–infrared spectroscopy (AFM-IR). Whereas H3PO4-etched dentin exhibited an extensive reduction in PO43− signals corresponding to apatite depletion, QCMC-conditioned dentin showed scattered dark areas and bright PO43− streak signals. The latter were consistent with areas identified as collagen fibrils in the amide I mapping and were suggestive of the presence of intrafibrillar minerals in QCMC-conditioned dentin. Young’s modulus mapping of QCMC-demineralized dentin obtained by AFM-based amplitude modulation–frequency modulation recorded moduli that were the same order of magnitude as those in mineralized dentin and at least 1 order higher than H3PO4-etched dentin. In situ zymography of the gelatinolytic activity within hybrid layers created with QCMC conditioning revealed extremely low signals before and after thermocycling, compared with H3PO4-etched dentin for both wet and dry bonding. Confocal laser scanning microscopy identified the antibacterial potential of QCMC against Streptococcus mutans and Enterococcus faecalis biofilms. Taken together, the QCMC-based demineralization retains intrafibrillar minerals, preserves the elastic modulus of collagen fibrils, reduces endogenous proteolytic activity, and inhibits bacteria biofilms to extend dentin bond durability.

Peptidoglycan-inspired peptide-modified injectable hydrogels with enhanced elimination capability of bacterial biofilm for chronic wound healing

Majority of human infectious diseases is related to bacterial biofilm formation, especially the wound infection and delayed healing. Herein, recognizing peptide-modified polysaccharide based injectable hydrogel has been synthesized for effective anti-biofilm and infected wound healing. Inspiration from similar compatibility principle, the peptide (Alanine-glutamate-lysine-alanine), which is a part of the peptidoglycan, is grafted into the quaternized carboxymethyl chitosan （HTCC）for the first time. Afterwards, the quaternary ammonium salt groups in the synthetic injectable hydrogel cross-linked by the peptide modified quaternized carboxymethyl chitosan (HTCC-P) and oxidized dextran (OD), which can penetrate the bacterial cell wall and membrane under the recognition of peptide. Furthermore, the synergistic effect of quaternary ammonium salt groups and the peptide significantly enhance the anti-biofilm property of the hydrogels. In addition, the injectable hydrogel (HTCC-P/OD) cross-linked by Schiff base exhibits an excellent self-healing property and can completely cover the irregular wound shape. The cytotoxicity and in vivo wound healing also confirm the biocompatibility and capacity to accelerate tissue reconstruction of the hydrogels. Therefore, the hydrogels are expected to become competitive multifunctional dressings in biomedical field, including chronic wound infection and other bacterial biofilm related tissue repair.

Facile preparation of polysaccharides-based adhesive hydrogel with antibacterial and antioxidant properties for promoting wound healing

Infection, oxidative stress, and inflammation are the major obstacles to cutaneous wound healing. Designing adhesive wound dressings with inherent antibacterial and antioxidant properties are highly desirable. Herein, a series of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-doped multifunctional hydrogels were facilely prepared by combining quaternized carboxymethyl chitosan (QCMCS) and oxidized hyaluronate (HA-CHO). Schiff base crosslinking between amino groups in QCMCS and aldehyde groups in HA-CHO not only constructed hydrogel networks but also endowed hydrogels with good self-healing property. The hydrogel exhibited adjustable tissue adhesiveness, degradability, and rheological properties by changing the content of TEMPO groups. Moreover, the hydrogels presented excellent inherent antibacterial and antioxidant properties, along with the porous structures, swelling ability, good cytocompatibility and low hemolysis ratio, which are beneficial to promoting wound healing process. Overall, the TEMPO hydrogel showed excellent therapeutic effect in mice skin defect model, giving the hydrogel with fitness as wound dressings for treating skin wounds.

Application of Paclitaxel-loaded EGFR Peptide-conjugated Magnetic Polymeric Liposomes for Liver Cancer Therapy.

Developing the methodologies that allow for safe and effective delivery of therapeutic drugs to target sites is a very important research area in cancer therapy. In this study, polyethylene glycol (PEG)-coated magnetic polymeric liposome (MPL) nanoparticles (NPs) assembled from octadecyl quaternized carboxymethyl chitosan (OQC), PEGylated OQC, cholesterol, and magnetic NPs, and functionalized with epithelial growth factor receptor (EGFR) peptide, were successfully prepared for in-vivo liver targeting. The two-step liver targeting strategy, based on both magnetic force and EGFR peptide conjugation, was evaluated in a subcutaneous hepatocellular carcinoma model of nude mouse. The results showed that EGFR-conjugated MPLs not only accumulated in the liver by magnetic force, but could also diffuse into tumor cells as a result of EGFR targeting. In addition, paclitaxel (PTX) was incorporated into small EGFR-conjugated MPLs (102.0±0.7 nm), resulting in spherical particles with high drug encapsulation efficiency (>90%). The use of the magnetic targeting for enhancing the transport of PTX-loaded EGFR-conjugated MPLs to the tumor site was further confirmed by detecting PTX levels. In conclusion, PTX-loaded EGFR-conjugated MPLs could potentially be used as an effective drug delivery system for targeted liver cancer therapy.

Gold nanoparticles decorated graphene oxide/nanocellulose paper for NIR laser-induced photothermal ablation of pathogenic bacteria

A functionalized paper based on gold nanoparticles (Au NPs) conjugated graphene oxide (GO) was developed for near-infrared (NIR) laser triggered photothermal ablation against infectious bacterial pathogens. Firstly, quaternized carboxymethyl chitosan (QCMC) not only acted as reducing agent to synthesize Au NPs, but also functioned as coupling agent to link up Au NPs with GO. Au-QCMC-GO(+) was supposed to synergistically intensify the photothermal effect, which was then mixed with nanocellulose to form a functionalized paper via vacuum filtration. The photothermal efficiency, antibacterial treatment and mechanical property of Au-QCMC-GO(+)/nanocellulose paper were investigated. Excited by NIR laser irradiation, Au-QCMC-GO(+)/nanocellulose paper generated a temperature rise over 80 °C, sufficient for photothermal ablation upon both Gram-positive bacteria (Bacillus subtilis and Stapylococcus aureus) and Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). Additionally, Au-QCMC-GO(+)/nanocellulose paper showed a remarkable enhancement in tensile strength, bursting index and tear index compared to those of pure nanocellulose paper.

MPEG grafted quaternized carboxymethyl chitosan for demulsification of crude oil emulsions

ABSTRACTFour novel environmentally friendly and highly branched crude oil demulsifiers were prepared by using different molecular weight (Mn = 350, 750, 1000, 1900 g/mol) of methoxy poly(ethylene glycol) to modify quaternized N,O‐carboxymethyl chitosan. Fourier transform infrared and 1H‐nuclear magnetic resonance were employed to confirm the structure of the demulsifiers. The surface tension of demulsifies was determined and hydrophile–lipophile balance value was calculated at the critical micelle concentration. The demulsification performance was evaluated by the bottle test method against water‐in‐oil emulsions simulated in the laboratory and it was found that the dehydration rate of four demulsifiers can come to 74.2%–80.4%, which have better demulsification performance than the commercial demulsifier JL‐1. Demulsification mechanism was discussed, and it was encouraging to find that the tiny water droplets in the emulsion coalesced to form the water phase and separated with the water from the polarization microscope. Results show that methoxy poly(ethylene glycol) grafted quaternized carboxymethyl chitosan has a promising application as a demulsifiers for dealing with W/O crude oil emulsions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45867.

Quaternized carboxymethyl chitosan/organic montmorillonite nanocomposite as a novel cosmetic ingredient against skin aging

It is of technical and economic importance to develop an effective cosmetic ingredient against skin aging through low-cost and facile production. This study developed a polymer/layered silicate nanocomposite as cosmetic ingredient against skin aging. Firstly, quaternized carboxymethyl chitosan (QCMC)/organic montmorillonite (OMMT) nanocomposite (QCOM) was fabricated via solution-induced intercalation. QCOM with different mass ratios of QCMC to OMMT were studied by various characterizations as well as moisture-adsorption and retention activities and UV-protection capacity. QCOM was then added into a cosmetic formulation to prepare a cosmetic cream. And the evaluation of its efficacy about skin care was conducted. The results showed that the optimal QCOM had better moisture-adsorption and retention behaviors than hyaluronic acid, and QCOM solution displayed good UV-protection ability. Furthermore, the QCOM-containing cosmetic cream meets the hygienic standard for cosmetics; it has negligible dermal irritation and a prominent moisture-retention efficacy on human stratum corneum.

Quaternized Carboxymethyl Chitosan-Based Silver Nanoparticles Hybrid: Microwave-Assisted Synthesis, Characterization and Antibacterial Activity.

A facile, efficient, and eco-friendly approach for the preparation of uniform silver nanoparticles (Ag NPs) was developed. The synthesis was conducted in an aqueous medium exposed to microwave irradiation for 8 min, using laboratory-prepared, water-soluble quaternized carboxymethyl chitosan (QCMC) as a chemical reducer and stabilizer and silver nitrate as the silver source. The structure of the prepared QCMC was characterized using Fourier transform infrared (FT-IR) and 1H nuclear magnetic resonance (NMR). The formation, size distribution, and dispersion of the Ag NPs in the QCMC matrix were determined using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible (UV-Vis), transmission electron microscopy (TEM), and field emission scanning electron microscope (FESEM) analysis, and the thermal stability and antibacterial properties of the synthesized QCMC-based Ag NPs composite (QCMC-Ag) were also explored. The results revealed that (1) QCMC was successfully prepared by grafting quaternary ammonium groups onto carboxymethyl chitosan (CMC) chains under microwave irradiation in water for 90 min and this substitution appeared to have occurred at -NH2 sites on C2 position of the pyranoid ring; (2) uniform and stable spherical Ag NPs could be synthesized when QCMC was used as the reducing and stabilizing agent; (3) Ag NPs were well dispersed in the QCMC matrix with a narrow size distribiution in the range of 17–31 nm without aggregation; and (4) due to the presence of Ag NPs, the thermal stability and antibacterial activity of QCMC-Ag were dramatically improved relative to QCMC.

Codelivery of paclitaxel and small interfering RNA by octadecyl quaternized carboxymethyl chitosan-modified cationic liposome for combined cancer therapy.

Conventional therapeutic approaches for cancer are limited by cancer cell resistance, which has impeded their clinical applications. The main goal of this work was to investigate the combined antitumor effect of paclitaxel with small interfering RNA modified by cationic liposome formed from modified octadecyl quaternized carboxymethyl chitosan. The cationic liposome was composed of 3β-[N-(N', N'-dimethylaminoethane)-carbamoyl]-cholesterol, dioleoylphosphatidylethanolamine, and octadecyl quaternized carboxymethyl chitosan. The cationic liposome properties were characterized by Fourier transform infrared spectroscopy, dynamic light scattering and zeta potential measurements, transmission electron microscopy, atomic force microscopy, and gel retardation assay. The cationic liposome exhibited good properties, such as a small particle size, a narrow particle size distribution, a good spherical shape, a smooth surface, and a good binding ability with small interfering RNA. Most importantly, when combined with paclitaxel and small interfering RNA, the composite cationic liposome induced a great enhancement in the antitumor activity, which showed a significantly higher in vitro cytotoxicity in Bcap-37 cells than liposomal paclitaxel or small interfering RNA alone. In conclusion, the results indicate that cationic liposome could be further developed as a codelivery system for chemotherapy drugs and therapeutic small interfering RNAs.

Synthesis and preservative application of quaternized carboxymethyl chitosan containing guanidine groups

A chitosan derivative, quaternized carboxymethyl chitosan containing guanidine groups (QGCMC), was synthesized and structurally characterized using FT-IR, 1H NMR spectroscopy. The elemental composition of QGCMC was also investigated. Increase in the molar ratio of materials used for QGCMC synthesis and an increase in the reaction time of QGCMC synthesis led to an increased degree of substitution. QGCMC demonstrated a strong antimicrobial activity at acidic, neutral, and basic pH conditions and could significantly lengthen the shelf life of strawberries.

Layer-by-layer immobilization of quaternized carboxymethyl chitosan/organic rectorite and alginate onto nanofibrous mats and their antibacterial application.

Quaternized carboxymethyl chitosan (QCM-chitosan) and organic rectorite (OREC) immobilized nanofibrous mats are fabricated via layer-by-layer (LBL) technique in a self-assembly manner. The negatively charged cellulose nanofibrous mats hydrolyzed from electrospun cellulose acetate (CEL) mats are alternately modified with the positively charged QCM-chitosan and OREC intercalated composites and the negatively charged sodium alginate (ALG) via LBL technique. The morphology and antibacterial activity of the resultant mats are studied by changing the number of deposition bilayers, the compositions of dipping solutions and outermost layer. X-ray photoelectron spectroscopy results imply that QCM-chitosan and OREC are coated on cellulose mats. Besides, wide angle X-ray diffraction and small angle X-ray diffraction are applied to investigate the crystalline of the composite mats and the interlayer distance of OREC, respectively. The antibacterial activity of the mats increases with the incorporation of OREC into LBL films.

Antimicrobial Preservative Coating Prepared with Quaternized Carboxymethyl Chitosan

Antimicrobial Preservative Coating Prepared with Quaternized Carboxymethyl Chitosan

Effect of rectorite on the synthesis of Ag NP and its catalytic activity

Silver nanoparticles (Ag NPs) were synthesized greenly into the lamellar space of rectorite (REC) with quaternized carboxymethyl chitosan (QCMC), meanwhile quaternized carboxymethyl chitosan/rectorite/silver bionanocomposite was obtained. Results showed that QCMC and rectorite acted as reducing agent and solid support for Ag NPs, respectively. Exfoliated rectorite (REC) and organic rectorite (OREC) were obtained, simultaneously Ag NPs were formed on their interlayer and external surface. With the confinement effect of rectorite, the average diameters of Ag NPs changed from 45 nm to 22 nm, along with the change in size distributions from 30–65 nm to 18–28 nm, and their shapes changed from sphere to oval. The obtained quaternized carboxymethyl chitosan/rectorite/silver bionanocomposites were made into beads (∼1 mm) to catalyze the reduction of 4-nitrophenol (4-NP), the catalytic rate followed the order: the beads with OREC > those with REC > those without rectorite. The beads with quaternized carboxymethyl chitosan/rectorite/silver bionanocomposites without any treatments still performed well for four consecutive catalytic experiments. Using rectorite to stabilize Ag NPs and get smaller Ag NPs with narrower size distribution may extend the synthesis strategy of other nanoparticles.

Flocculation of algal cells by amphoteric chitosan-based flocculant

A kind of amphoteric chitosan-based flocculant (quaternized carboxymethyl chitosan, denoted as QCMC) has been prepared. QCMC presented significant improvement of water solubility in the whole pH range. The effects of pH, dosage, temperature and original turbidity of algal water on the flocculation performance were investigated. The optimal dosages of QCMC at pH 5, 9 and 12 with original turbidity of 20NTU at 20°C were 0.1, 0.6 and 2.0mg/L, respectively, which were much less than that of chitosan, PAM, Al2(SO4)3 and FeCl3. The floc properties during grow, breakage and regrow period were also evaluated at different pH values in terms of floc size, strength and density. It was demonstrated that QCMC produced larger, stronger and denser flocs than Al2(SO4)3. There is every indication that QCMC is more suitable for algal harvesting than other traditional coagulants or flocculants.

Preparation and biological activity of quaternized carboxymethyl chitosan conjugated with collagen peptide

Tissue repair is a spontaneous process which initiated on wounding. If this complex mechanism is disturbed or impaired, the use of biomaterials might increase the chance of successful healing. In this view, a water-soluble chitosan derivative, quaternized carboxymethyl chitosan (QCMC) was prepared and collagen peptides (COPs) were grafted to the backbone by carbodiimide method. The reaction conditions affecting the degree of substitution (DS) were studied including the mass ratio of collagen peptide to QCMC, reaction temperature and reaction time. The hydrogen peroxide-scavenging activity could be different by changing the DS, concentration and molecular weight. MTT assay was used to investigate the cell viability of the derivative. The results indicated that the introduction of collagen peptide into the QCMC improved its hydrogen peroxide-scavenging activity and cell viability with the DS and concentration increased. Therefore, QCMC conjugated with collagen peptides may prove beneficial to the process of the wound-healing.

Novel antibacterial paper based on quaternized carboxymethyl chitosan/organic montmorillonite/Ag NP nanocomposites

An environmentally friendly antibacterial agent, namely, Ag NP-loaded quaternized carboxymethyl chitosan/organic montmorillonite (QAOM) nanocomposite, was prepared. The novel QAOM nanocomposite was obtained through an environmentally friendly process by using quaternized carboxymethyl chitosan (QCMC) and organic montmorillonite (OMMT) as reducing and stabilizing agent for Ag NP synthesis. Finished papers with QAOM nanocomposites were prepared by performing surface coating and internal additive methods. Physical properties and antimicrobial activity of the finished paper were investigated. The results revealed that Ag NP remained spherical in dry QAOM nanocomposites with uniform size and good dispersion, and the exfoliated montmorillonite layers were evenly distributed in the QCMC matrix. The presence of QAOM nanocomposites positively affected the tensile, tear, and bursting strengths of the finished paper. The paper prepared by using surface coating performed better than that produced by using the internal additive method. Moreover, the finished paper with QAOM nanocomposites showed an excellent antimicrobial capacity, and the antibacterial capacity of paper produced by using surface coating was stronger than that produced by using internal additive method. Therefore, this study provides basic data for an efficient and safe antibacterial agent that can be applied in the paper industry.