Amino Cellulose Research Articles

Enhanced CO2 Capture and Utilization through Chemically and Physically Dual-Modified Amino Cellulose Aerogels Integrated with Microalgae-Immobilized Hydrogels

Enhanced CO₂ Capture and Utilization through Chemically and Physically Dual-Modified Amino Cellulose Aerogels Integrated with Microalgae-Immobilized Hydrogels

Preparation of amino cellulose aerogel and its formaldehyde adsorption properties

The aerogel prepared from cellulose has the advantages of low density, high porosity, large specific surface area, good gas diffusion and adsorption space, which is a good gas adsorption material. In this study, microcrystalline cellulose was used as raw material, and LiBr ionic liquid was used as a solvent system. In addition, cellulose aerogel was modified by polyethyleneimine, which retained three-dimensional network structure and had excellent formaldehyde adsorption capacity. The adsorption capacity of polyethyleneimine-modified cellulose aerogel (PCA) to formaldehyde can reach 12.3 mg/g at 25 ℃. It was found that the adsorption capacity of PCA aerogel for formaldehyde changed with the increase in nitrogen content. The adsorption of formaldehyde was mainly through the chemical adsorption of the Schiff base reaction between NH2 and formaldehyde molecules in polyethylenimine (PEI).

Synthesis of biomass hyperbranched polyamide resin from cellulose and citric acid for wood adhesive

Traditional wood adhesives have the problems of excessive dependence on fossil resources and environmental pollution. Cellulose, a renewable biomass resource with a low price and huge output, provides a basis for preparing biomass wood adhesives. In this study, a new type of polyamide resin was prepared by modifying microcrystalline cellulose and reacting with natural citric acid. Specifically, toluenesulfonyl cellulose (TS) was synthesized, and functional amino cellulose (AC) was prepared by a nucleophilic substitution reaction with hyperbranched polyamide (HP). Then cellulose-based hyperbranched polyamide resin (CHP) was prepared by polycondensation with citric acid. The structure of CHP resin was investigated by FTIR, XPS, 13C NMR and GPC, and plywood was prepared to study its mechanical properties. Due to the formation of hyperbranched cross-linked network structure inside the resin, the prepared plywood has excellent properties. The dry shear strength reaches 2.24 MPa, and the strength reaches 1.25 and 1.31 MPa after soaking in water at 63 °C and 93 °C for 3 h. The resin in this study has a simple preparation process and excellent performance, which provides a solid foundation for developing high-performance cellulose-based wood adhesives.

Multiple hydrogen bonds network enabled sustainable and reproducible cellulose/liquid metal composite elastomer for clean energy collection and conversion

Fabrication of sustainable, mechanically robustness and reproducible metal polymer composite elastomer is desirable but remains a challenge. Herein, a multiple hydrogen bonds crosslinked metal polymer composite elastomer derived from cellulose, plant oil, nature rubber and liquid metal was prepared, which exhibited excellent mechanical elasticity, reproducible and photothermal conversion performance. To fabricate the proposed composite elastomer, the liquid metal (LM) droplets were dispersed within a mixture of amino cellulose (AC), pimelic acid modified epoxy soybean oil (ESOPA) and nature rubber matrix through high-frequency ultrasonication. The active groups of the AC and ESOPA were able to not only construct a multiple hydrogen bonds network to endow the composite elastomer with excellent mechanical strength (1.51 MPa) and stretchability (515.3%), but also stabilize the LM particles. And the broken and reconstruction of the multiple hydrogen bonds network allowed the composite elastomer to be healed quickly at room temperature with high self-healing efficiency of 97.28%. In addition, the LM in the waste composite elastomers could be effectively recycled through dissolution and extraction as well as obtained a regenerative NR/ESOPA/AC elastomer, and the recycling efficiency of LM was up to 85%. Most importantly, the NR/ESOPA/AC/LM composite elastomer possessed stable photothermal conversion property, and has been successfully applied to convert light energy to thermal, electric and kinetic energy to drive the Stirling motor and electric fan, which paved a promising strategy for clean energy collection and conversion.

Bio-Based Polybenzoxazine-Cellulose Grafted Films: Material Fabrication and Properties.

Despite the fact that amino cellulose (AC) is biodegradable, biocompatible, and has excellent film-forming properties, AC films have poor mechanical properties and are not thermally stable. An AC-based composite film prepared from AC and curcumin-stearylamine based benzoxazine (C-st) is reported in order to improve its performance and promote its application. As starting materials, C-st and AC were used to produce a C-st/AC composite film possessing a synergistic property through chemical cross-linking and hydrogen bonds. Two salient features with respect to the curing behavior were obtained. Firstly, the onset of curing was reduced to 163 °C when the benzoxazine monomer was synthesized from fully bio-based precursors (such as curcumin and stearylamine). Secondly, a synergistic effect in curing behavior was obtained by mixing C-st with AC. As a result of tensile tests and thermal analysis, the poly(C-st) benefited the composite films with pronounced mechanical and thermal properties, even at elevated temperatures. There was a 2.5-fold increase in tensile strength compared to the AC film, indicating that the composite films have the potential to be used for functional purposes. These poly(C-st)/AC films with improved mechanical and thermal properties have the ability to replace naturally occurring polymer films in film-related applications.

Preparation of amino cellulose nanofiber via ε-poly-L-lysine grafting with enhanced mechanical, anti-microbial and food preservation performance

A green and effective method was proposed for producing amino cellulose nanofibers (ε-PL-TOCNs) with a yield of > 60%, which was obtained via ε-poly-L-lysine-grafting of 2, 2, 6, 6-tetramethylpiperidine-N-oxyl (TEMPO)-oxidized cellulose (TOC). The different carboxyl group content of TOC, EDC/NHS molar ratio and their adding ways, ε-poly-L-lysine concentration on the yield, amino content and physicochemical properties of ε-PL-TOCNs were systematically investigated and optimized. The ε-PL-TOCNs with the characteristics of enhanced thermal stability, improved mechanical strength, and fluorescence properties was successfully produced. Moreover, the ε-PL-TOCNs was zwitterionic with both anionic and cationic charges due to the co-existence of carboxyl and amino groups, thus showed excellent dispersion stability in a wide pH range except for the isoelectric point around pH 9. Notably, the ε-PL-TOCNs possessed an excellent anti-microbial effect (>99%) against Escherichia coli and Saccharomyces cerevisiae at 200 μg/mL loading dosage because of the positive role of amino groups, which made it applicable to extend the freshness of fruits. This preparation approach of amino cellulose nanofibers was advantageous over traditional methods owing to green and efficient methods, which expanded the application of cellulose nanofibers in anti-microbial agent and food preservation.

A functional bimodal mesoporous silica nanoparticle with redox/cellulase dual-responsive gatekeepers for controlled release of fungicide

Integrating toxic fungicide into a functional stimuli-responsive nanosystem can effectively improve the fungus control specificity and reduce the effect on non-target organisms. We report here a redox and cellulase dual-responsive multifunctional nanoparticle based on bimodal mesoporous silica (BMMs) to deliver prochloraz (Pro) for the smart management of wilt disease (Pro-AC-SS-BMMs, known as P-ASB). The surface of the nanocarrier was modified with an aminosilane coupling agent, and Pro was encapsulated by physical adsorption using 2,2′-dithiodiacetic acid as a smart bridge and disulfide (SS) cross-linked aminocellulose (AC) as gatekeepers. P-ASB nanoparticles (NPs) had a spherical structure, and the size was 531.2 ± 4.9 nm. The loading rate of Pro was 28.5%, and the NPs possessed excellent redox/cellulase dual-responsive release characteristics in the presence of glutathione (GSH) and cellulase. The nanocarrier could effectively protect Pro against photodegradation and had better foliar wettability than the Pro technical. Fluorescence tracer results showed that the nanocarriers were taken up and activated by the mycelium. P-ASB NPs had better control efficacy against Rhizoctonia solani and had no significant toxicity to cells and bacteria. This study provides a new strategy for enhancing the environmental protection and promoting the development of green agriculture.

Benzocaine mesoporous silica nanoparticles/bio polysaccharides-based hydrogels loaded cotton bandage as a platform for topical anesthesia

A new topical delivery system based on bio polysaccharides-based hydrogels for the local anesthetics drug benzocaine, was primed to circumvent its limited efficacy and short duration of action. The new system based on encapsulating the drug within nano-mesoporous silica then incorporating into different types of natural bio polysaccharides-based hydrogels including pullulan, dextran, acacia, and amino cellulose. Polysaccharides based hydrogels were prepared by grafting of polyacrylic acid onto the nature polysaccharides and then confirmed. Mesoporous silica nanoparticles (MSNs) were prepared and the drug benzocaine was encapsulating within it. The size, and morphology of prepared nanoparticles and the loaded nanoparticles were visualized using TEM and SEM analysis. Drug loaded nanoparticles were then incorporated into the prepared bio polysaccharides-based hydrogels and these composites were used to treat cotton gauze to use it as anesthetics topical bandage. The resistance to microbial growth of the prepared hydrogels were investigated using culture count method and the mechanical properties of the treated cotton gauze was tested. Drug loaded silica rented in polysaccharide-based hydrogel were conducted in invitro-release and ex vivo drug permeation study through isolated rat skin. In comparison to free drug aqueous suspension the hydrogel patches revealed enhanced amplified skin permeation sustained all over 24 h.

Fabrication of cellulose/plant oil based flexible epoxy thermoset with excellent UV‐blocking performance

AbstractFlexible epoxy thermosets have promising applications in modern industry. However, the development of next‐generation flexible epoxy thermosets with high biomass content and multi‐functions remains challenging. In this work, a sustainable cellulose/plant oil based flexible epoxy thermoset with excellent mechanical property, reprocessing performance, and UV absorption property was prepared. First, the amino cellulose is synthesized and used as a reinforcement and curing agent, and then the flexible epoxy thermoset is prepared by curing reaction of amino cellulose, citric acid, and flexible epoxy resin using zinc acetylacetonate as the transesterification catalyst. The epoxy thermosets show excellent thermal stability, the temperature at maximum weight loss reached 425°C. Mechanical property tests indicate that these thermosets have high mechanical strength (19.6 MPa) and satisfactory stretchability (36.1%–118%). The dynamic transesterification ester groups endow the epoxy thermoset with reprocessing ability. In addition, these epoxy thermosets show outstanding and stable UV absorption properties even after long‐time UV‐light irradiation or heating treatment, which makes these flexible epoxy thermosets have promising applications in UV‐blocking coating.

Amino modified cellulose fibers loaded zinc oxide nanoparticles via paper-making wet-forming for antibacterial materials

Bacterial infection has become one of the major threats to human health all over the world, and the development and application of antibacterial materials has drawn great attention. Based on the Schiff-base structure, ZnONPs@ACFs are obtained by loading zinc oxide nanoparticles (ZnONPs) on amino cellulose fibers (ACFs) in-situ through the coordination of amino groups with metal ions. The results of FT-IR, XRD and UV-vis demonstrate that ZnONPs are successfully loaded and uniformly dispersed on ACF surface, and the ACFs maintain intact morphology observed by SEM. Furthermore, the zero-span tensile strength of ZnONPs@ACFs is 66.48 N/cm (ROL: 24.98 N/cm/s) under the optimum conditions, which indicates that ZnONPs@ACFs have a certain strength and can be used to make antibacterial sheet materials via paper-making wet-forming process. Accordingly, the ZnONPs@ACF composites show inhibition zones of 4.95 mm and 1.10 mm against E. coli and S. aureus, respectively. The new cellulose-based antibacterial materials demonstrate potential applications in the field of food packaging and biological medicine etc.

Highly antibacterial hydrogels prepared from amino cellulose, dialdehyde xylan, and Ag nanoparticles by a green reduction method

Highly antibacterial hydrogels prepared from amino cellulose, dialdehyde xylan, and Ag nanoparticles by a green reduction method

A systematic study to unravel the potential of using polysaccharides based organic-nanoparticles versus hybrid-nanoparticles for pesticide delivery

To daze conventional pesticide release limitations, nanotechnology-mediated pesticide delivery using natural polymers has been actively investigated. However, the lack of information on what are the beneficial/non-beneficial aspects of using hybrid- and organic-nanoparticles (NP) and among the polysaccharides which are better suited concerning pesticide loading efficiency (PLE wt%), entrapment efficiency, and sustained pesticide release (SPR %) has prompted us to investigate this study. In this report, we systematically investigated a series of polysaccharides such as starch (S), cellulose (C), aminocellulose (AC), and sodium carboxymethylcellulose (NaCMC) coated on magnetite NP (MNP, Fe3O4) and complete organic nanocarrier systems (starch and cellulose) that have no MNP part were compared for the PLE wt% and SPR % efficiencies for chlorpyrifos (ChP) insecticide. Overall, all nanocarriers (NCs) have shown good to excellent PLE wt% due to the smaller-sized NP obtained through optimal conditions. However, among the hybrid polysaccharides studied, starch MNP has shown a maximum PLE of 111 wt% in comparison with other polysaccharides (80–94 wt%) coated hybrid-NCs as well as with organic-NCs (81–87 wt%). The use of inorganic support does improve the PLE wt% markedly for starch but not for cellulose derivatives. Similarly, the SPR results of S-NP showed a remarkably better sustained release profile for ChP of 88% in 14 d. In contrast, other unfunctionalized and functionalized celluloses exhibited poor release profiles of 60%–20% for the same period. This study may help the researchers choose the right system for designing and achieving enhanced pesticide efficiency.

Aminocellulose-Grafted Polymeric Nanoparticles for Selective Targeting of CHEK2-Deficient Colorectal Cancer.

We report the formulation of aminocellulose-grafted polymeric nanoparticles containing LCS-1 for synthetic lethal targeting of checkpoint kinase 2 (CHEK2)-deficient HCT116 colon cancer (CRC) cells to surpass the limitations associated with the solubility of LCS-1 (a superoxide dismutase inhibitor). Aminocellulose (AC), a highly biocompatible and biodegradable hydrophilic polymer, was grafted over polycaprolactone (PCL), and a nanoprecipitation method was employed for formulating nanoparticles containing LCS-1. In this study, we exploited the synthetic lethal interaction between SOD1 and CHEK2 for the specific inhibition of CHEK2-deficient HCT116 CRC cells using LCS-1-loaded PCL-AC NPs. Furthermore, the effects of formation of protein corona on PCL-AC nanoparticles were also assessed in terms of size, cellular uptake, and cell viability. LCS-1-loaded NPs were evaluated for their size, zeta potential, and polydispersity index using a zetasizer, and their morphological characteristics were assessed by transmission electron microscopy, scanning electron microscopy, and atomic force microscopy analyses. Cellular internalization using confocal microscopy exhibited that nanoparticles were uptaken by HCT116 cells. Also, nanoparticles were cytocompatible as they did not induce cytotoxicity in hTERT and HEK-293 cells. The LCS-1-loaded PCL-AC NPs were quite hemocompatible and were 240 times more selective in killing CHEK2-deficient cells as compared to CHEK2-proficient CRC cells. Moreover, PCL-AC NPs exhibited that the protein corona-coated nanoparticles were incubated in the human and fetal bovine sera as visualized by SDS-PAGE. A slight increment in hydrodynamic diameter was observed for corona-coated PCL-AC nanoparticles, and size increment was further confirmed by TEM. Corona-coated PCL-AC NPs also exhibited cellular uptake as demonstrated by flow cytometric analysis and did not cause cytotoxic effects on hTERT cells. The nanoformulation was developed to enhance therapeutic potential of the drug LCS-1 for enhanced lethality of colorectal cancer cells with CHEK2 deficiency.

Preparation of 6-amino-6-deoxy cellulose and its derivatives used as chiral separation materials

In order to find a facile and practical method to synthesize amino cellulose in bulk with high regional selectivity and high degree of substitution, the reaction conditions to brominate cellulose and to reduce azido group were carefully studied and some interesting phenomena were observed. With the optimized method, 6-amino-6-deoxy cellulose could be easily prepared with very simple separation techniques. The degree of substitution of the amino group amounted to 0.97 which was determined by 1H NMR spectrum of 6-benzamido-6-deoxy cellulose. Moreover, the amino group was evidenced to be at the C6 of glucose unit by 1H-1H COSY NMR and 1H-13C HSQC NMR spectra. In addition, three cellulose 6-acetamido-6-deoxy-2,3-bis(phenylcarbamate)s were prepared from the 6-amino-6-deoxy cellulose prepared with the techniques optimized in the present study. The developed cellulose derivatives were used as chiral selectors with which chiral stationary phases (CSPs) were prepared. The CSPs exhibited enantioseparation power to some chiral compounds.

Development of sustainable and antimicrobial film based on polybenzoxazine and cellulose

A new class of bio based polymer blends have been prepared from a modified chitosan based benzoxazine precursor (E-ch) and amino cellulose (AC). AC was derived from cellulose with excellent film-forming, biocompatibility and biodegradability property. E-ch was synthesized from eugenol, modified chitosan and paraformaldehyde. The chemical structure was confirmed by FT-IR and 1H NMR analyses. Bio films were prepared by mixing E-ch and AC with diluted acetic acid, in different ratios. These films were further cross-linked by applying heat, via ring-opening polymerization of benzoxazine without any curing agent. FT-IR and DSC were used to study the effects of AC on E-ch to form cross-linked network polymer films [poly(E-ch)/AC]. Hydrogen bonding interactions were found to exist between poly(E-ch) and AC. These kinds of interactions considerably improve the mechanical and thermal properties and char yield of the polymer films. Additionally, these biofilms; poly(E-ch) and poly(E-ch)/AC have been examined for bio-activity with S. aureus. It is confirmed that these bio-films are effective in inhibiting bio-film related infection. In a similar way, both the bio-films act against C. albicans and thus avoid the formation of mycological infection. These results expose that poly(E-ch) and AC bio-films are capable to act as anti-microbial and anti-fungal agents.

Protein repellent anti-coagulative mixed-charged cellulose derivative coatings

This study describes the formation of cellulose based polyelectrolyte charge complexes on the surface of biodegradable polycaprolactone (PCL) thin films. Anionic sulphated cellulose (CS) and protonated cationic amino cellulose (AC) were used to form these complexes with a layer-by-layer coating technique. Both polyelectrolytes were analyzed by charge titration methods to elucidate their pH-value dependent protonation behavior. A quartz crystal microbalance with dissipation (QCM-D) in combination with X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were used to follow the growth, stability and water content of up to three AC/CS bi-layers in aqueous environment. This was combined with coagulation studies on one, two and three bilayers of AC/CS, measuring the thrombin formation rate and the total coagulation time of citrated blood plasma with QCM-D. Stable mixed charged bilayers could be prepared on PCL and significantly higher masses of AC than of CS were present in these complexes. Strong hydration due to the presence of ammonium and sulphate substituents on the backbone of cellulose led to a significant BSA repellent character of three bilayers of AC/CS coatings. The total plasma coagulation time was increased in comparison to neat PCL, indicating an anticoagulative nature of the coatings. Surprisingly, a coating solely composed of an AC layer significantly prolonged the total coagulation time on the surfaces although it did not prevent fibrinogen deposition. It is suggested that these cellulose derivative-based coatings can therefore be used to prevent unwanted BSA deposition and fibrin clot formation on PCL to foster its biomedical application.

A novel amino cellulose derivative using ATRP method: Preparation, characterization, and investigation of its antibacterial activity

In this study, we prepared a novel amino cellulose derivative (benzyl cellulose-g-poly [2-(N,N-Dimethylamino)ethyl methacrylate]) via a homogeneous ATRP method. The successful synthesis of the novel amino cellulose was confirmed by FT-IR and 1H NMR. This study addressed the different characteristics of the prepared polymer including the thermal stability, solubility, and X-ray diffraction pattern. The antibacterial activity of the synthesized cellulose derivative was investigated using the diffusion disk method against both gram-negative (Escherichia coli, Salmonella enterica) and gram-positive (Staphylococcus aureus, Bacillus subtilis) bacteria. Based on the inhibition zone, it was confirmed that the prepared benzyl cellulose-g-PDMAEMA possesses acceptable antibacterial activity against Escherichia coli, Salmonella enterica, and Staphylococcus aureus while Bacillus subtilis is resistant to the prepared polymer. Also according to the inhibition zone, it was shown that benzyl cellulose-g-PDMAEMA has more impact on E. coli and Salmonella enterica than Staphylococcus aureus. Molecular dynamics simulation was also used to study the interaction of the synthesized cellulose derivative with a model membrane which presented atomistic details of the polymer-lipid interactions. According to the results obtained from the molecular dynamics simulation, the polymer was able to destabilize the structure of the membrane and clearly express its signs of degradation.

Layer‐By‐Layer Coating of Aminocellulose and Quorum Quenching Acylase on Silver Nanoparticles Synergistically Eradicate Bacteria and Their Biofilms

AbstractThe emergence of antibiotic‐resistant bacteria and the failure of the existing antibacterial therapeutics call for development of novel treatment strategies. Furthermore, the formation of bacterial biofilms restricts drug penetration and efficiency, causing life‐threatening infections. Bacterial attachment and biofilm formation are regulated by the cell‐to‐cell communication phenomenon called quorum sensing (QS). In this work, antimicrobial silver nanoparticles (AgNPs) are decorated in a layer‐by‐layer fashion with the oppositely charged aminocellulose (AM) and acylase to generate hybrid nanoentities with enhanced antibacterial and antibiofilm activities as well as reduced cytotoxicity. Acylase, a quorum‐quenching enzyme that degrades the QS signals in the extracellular environment of bacteria, disrupts the bacterial QS process and together with the bactericidal AM synergistically lowers fourfold the minimum inhibitory concentration of the AgNPs templates toward Gram‐negative Pseudomonas aeruginosa (P. aeruginosa). The hybrid nanoparticles in eightfold‐lower concentration than the AgNPs inhibit 45% of the QS‐regulated virulence factors produced by the reporter Chromobacterium violaceum bacterial strain and reduce by 100% the P. aeruginosa biofilm formation. Moreover, the sequential deposition of antibacterial/antibiofilm active and biocompatible biopolymers onto the AgNPs allows the engineering of safe nanomaterials that do not affect the viability of human cells.

A green method for preparation of amino acids functionalized 2,3-dialdehyde cellulose

This study depicts the preparation of a new amino cellulose derivative of cellulose extracted from bagasse. 2,3-dialdehyde cellulose (DAC) with 60% degree of oxidation was prepared from cellulose by periodate oxidation. The obtained DAC was functionalized by Schiff base reaction with several amino acids up to 2.55% nitrogen content. Aliphatic/Aromatic, Mono/Dibasic, and Mono carboxylic/Dicarboxylic amino acids were investigated for the Schiff base reaction. FTIR spectra confirmed the successful introduction of the amino acids functional groups (carboxyl and amino groups). The successful interaction of amino acids with DAC composites were characterized and confirmed by elemental analysis, EDAX, TEM, SEM, XRD and TGA. A green method for preparation of amino acids functionalized 2,3-dialdehyde cellulose could be obtained in an efficient manner by controlling the amino acid type and degree of substitution while producing the DAC composites.

Synthesis and characterization of novel water-soluble 6-deoxy-6-(2-amino-2-(hydroxymethyl)propane-1,3-diol)cellulose derivatives

Amino celluloses are semisynthetic polysaccharide derivatives that are functionalized with amino groups. This class of bio-based polymers has a number of interesting properties for advanced applications such as potential antimicrobial activity and pronounced surface affinity towards various materials. Herein, the synthesis of a novel type of 6-deoxy-6-amino cellulose derivatives with a polar and highly branched substituent (2-amino-2-(hydroxymethyl)propane-1,3-diol/TRIS) is described for the first time. Fundamental principles for the synthesis by nucleophilic displacement of tosylated intermediates are highlighted, thus, providing access to materials with well-defined molecular structures. TRIS-functionalized cellulose derivatives with degrees of substitution (DS) of up to 0.5 were obtained. The solubility and rheological properties of the products showed a strong dependence on the pH value. Due to the unique structural features of the substituent, TRIS amino cellulose derivatives possess a high application potential.