Amino-functionalized Cellulose Research Articles

Tailoring amino-functionalized cellulose separators for improved lithium-ion battery performance

This study aims to enhance cellulose separators for energy storage, focusing on achieving high security and superior electrolyte wetting properties. Bacterial cellulose (BC) separators were initially prepared via vacuum filtration. Subsequently, carboxymethyl cellulose (CMC) underwent amino-functionalization by successfully cross-linking polyethyleneimine (PEI) using glutaraldehyde. The amino-functionalized CMC was then composited onto the BC separator. This composite separator demonstrated excellent thermal stability at 200 °C and favorable electrolyte wetting. The amino groups in PEI enhanced Li+ migration by forming hydrogen bonds with PF6− in the electrolyte. Additionally, molecular-level hydrogen bonding between amino groups on PEI and carboxyl/hydroxyl groups in CMC regulated the separator's porosity. The abundant carboxyl groups in CMC facilitated Li+ transfer, notably boosting the lithium-ion battery's electrochemical performance. After 90 charge and discharge cycles, the discharge capacity of the battery assembled with BC/CMC-PEI composite separator is 132.8 mAh/g, which is 25.1 % higher than the 106.1 mAh/g of the battery assembled with traditional PP separator. At a current density of 2C, the minimum discharge capacity of the battery assembled with the composite separator is 71.1 mAh/g, while the minimum discharge capacity of the battery assembled with the PP separator is 53.6 mAh/g. This approach using functional group modification provides a promising approach to improving the performance of lithium-ion batteries.

Synergistic cobalt‑copper metal-organic framework anchored amino-functionalized cellulose for antibiotic degradation: Interfacial engineering and mechanism insight.

Improving electron transfer rate of Co species and inhibiting aggregation of metal-organic frameworks (MOFs) particles are essential prerequisites for activating advanced oxidation process in wastewater treatment field. Here, we exploit Cu species with variable valence states to accelerate electron transfer of Co species and then to boost the unsatisfactory degradation efficiency for refractory pharmaceuticals via in-situ growth of copper and cobalt species on l-lysine functionalized carboxylated cellulose nanofibers. Utilizing the synergistic interplay of Co sites and deliberately exposed Cu0/Cu1+ atoms, the subtly designed catalyst exhibited a surprising degradation efficiency (~100 %) toward tetracycline hydrochloride within 10 min (corresponding to a catalytic capacity of 267.71 mg/g) without adjusting temperature and pH. Meanwhile, the catalyst displays good recyclability, well tolerance for coexisting ions and excellent antibacterial performance derived from the intrinsic antibacterial property of Cu-MOF. This research provided a novel strategy to construct MOFs-cellulose materials toward degrading various stubborn antibiotic pollutants.

Amino-functionalized cellulose composite for efficient simultaneous adsorption of tetracycline and copper ions: Performance, mechanism and DFT study

A novel cellulose composite (denoted as PEI@MMA-1) with porous interconnected structure was prepared by adsorbing methyl cellulose (MC) onto microcrystalline cellulose (MCC) and cross-linking polyethyleneimine (PEI) with MCC by the action of epichlorohydrin, which had the excellent adsorption property, wettability and elasticity. The performances of PEI@MMA-1 composite for removing tetracycline (TC), Cu2+ and coexistent pollutant (TC and Cu2+ mixture) were systematically explored. For single TC or Cu2+ contaminant, the maximum adsorption capacities were 75.53 and 562.23 mg/g at 30 °C, respectively, while in the dual contaminant system, they would form complexes and Cu2+ could play a “bridge” role to remarkably promote the adsorption of TC with the maximum adsorption capacities of 281.66 and 253.58 mg/g for TC and Cu2+. In addition, the adsorption kinetics, isotherms and adsorption mechanisms of single-pollutant and dual-pollutant systems have been thoroughly investigated. Theoretical calculations indicated that the amide group of TC molecule with the assistance of Cu2+ interacted with the hydroxyl group of PEI@MMA-1 composite to enhance the TC adsorption capacity. Cycle regeneration and fixed bed column experiments revealed that the PEI@MMA-1 possessed the excellent stability and utility. Current PEI@MMA-1 cellulose composite exhibited a promising application for remediation of heavy metals and antibiotics coexistence wastewater.

Bentonite/amino-functionalized cellulose composite as effective adsorbent for removal of lead: Kinetic and isotherm studies

In this study, bentonite/amino-functionalized cellulose composite (BAC) adsorbent was synthesized by intercalating the hexadecyl trimethyl ammonium bromide surfactant (HDTMA) into bentonite followed by exfoliating the HDTMA-modified bentonite (MB) into amino-functionalized cellulose (AC). The physicochemical properties of BAC were evaluated by FTIR, XRD, FE-SEM, EDX, TGA, and Zeta potential measurement. A series of batch mode adsorption experiments were carried out to identify the optimal adsorption conditions as a function of experimental variables such as pH of solution, uptake time, initial Pb2+ concentrations, BAC dosage, and assess both percent removal (%) and Pb2+ uptake (mg g−1). The result demonstrated that the synergetic advantage of combining HDTMA-modified bentonite (MB) and amino-functionalized cellulose (AC) in Pb2+ uptake (69 mg g−1) surpassed that of HDTMA-modified bentonite (12.14 mg g−1) and amino-functionalized cellulose (31.33 mg g−1) alone. Further, Pb2+ uptake onto BAC was higher than the HDTMA-modified bentonite/cellulose composite (BC) (42.12 mg g−1) due to the introduction of the amino group to cellulose through grafting with ethylenediamine (EDA). The adsorption of Pb2+ from aqueous solution by BAC fit well with pseudo - 2nd-order kinetic (R2 = 0.998) and Langmuir isotherm (R2 = 0.999) models. The kinetic study indicated that the active sites in the BAC exhibit heterogeneity and possess different activation energies for chemisorption. The monolayer attachment of Pb2+ onto the BAC surface was realized from the isotherm study, and the maximum predicted adsorption capacity was found to be 71.869 mg g−1. Regeneration studies showed that BAC maintained its good Pb2+ uptake capacity for up to four cycles.

Amino-functionalized cellulose fibers recovered from newspaper waste for efficient adsorption of crystal violet: Optimization using central composite design

In this work, the adsorption of crystal violet (CV) dye by amino-functionalized cellulose fibers recovered from newspaper waste (NH2-RCF) was studied for the first time. Characterization of the prepared adsorbent was performed by FE-SEM, EDS, FTIR, and BET techniques. Adsorption tests were carried out considering the desired range of influencing factors in adsorption, including dye concentration, pH, adsorbent dose and contact time at room temperature. The response surface methodology (RSM) was selected to study the effect of interaction independent input variables and a dependent output response variable (crystal violet removal efficiency). The results including p-value (2.2 × 10−16), high F-value (560.633), multi. R2 (0.9929), adj. R2 (0.9882) and absence of significance of the model's lack-of fit (0.147) showed that the diminished second order- model is very significant for the elimination of crystal violet dye by the adsorbent. The most removal efficiency of crystal violet dye was found to be 95.1 %, under optimal operational parameters including: adsorbent cycle rate of 0.125 g L−1, pH equal to 9, contact time 92.5 min, and CV concentration of 14 mg L−1. In addition, the results indicated that the pseudo second order kinetic model is the most suitable model for dye adsorption on cellulose adsorbent, and the adsorption behavior of crystal violet dye on NH2-RCF follows the Freundlich model (R2 =0.9955). The negative values of ΔG° at all temperatures exhibited that the spontaneously adsorbed process of crystal violet onto NH2-RCF. In addition, the capacity adsorption and the gradually decreasing in negative values of ΔG° with increasing temperature, implied that the adsorption of crystal violet onto NH2-RCF made more favorable at higher temperature. Collectively, the results showed that the adsorbent created from waste newspaper is an efficient and cheap method to remove crystal violet from aqueous solutions.

Amino-Functionalized Cellulose Nanofiber/Lignosulfonate New Aerogel Adsorbent for the Removal of Dyes and Heavy Metals from Wastewater.

Due to the increasingly widespread water pollutants and the high cost of treatment methods, there is a demand for new, inexpensive, renewable, and biodegradable adsorbent materials for the purification of wastewater contaminants. In this study, a new biocomposite aerogel (Amf-CNF/LS) was prepared using a chemically cross-linking method between the amino-functionalized cellulose nanofibers (Amf-CNF) and lignosulfonates (LS). The physical and chemical properties of the prepared aerogel were investigated using several techniques including elemental analysis, scanning electron microscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), and N2 adsorption-desorption analysis. The Amf-CNF/LS aerogel was then applied for the removal of methylene blue (MB), rhodamine B dye (RhB), and the heavy metal cadmium ion (Cd2+) from synthetic wastewater solutions. The adsorption parameters controlling the adsorption process including the pH, contact time, adsorbent dosage, and adsorbate concen-tration were optimized. High adsorption kinetics and isotherms were observed, with the adsorption isotherms of the Amf-CNF/LS aerogel fitting the Langmuir model with maximum adsorption capacities of 170.94, 147.28, and 129.87 mg/g for MB, RhB, and Cd2+, respectively. These results show that Amf-CNF/LS aerogel is a promising green and inexpensive adsorbent for MB, RhB, and Cd2+ removal from wastewater.

Amino-functionalized cross-linked cellulosic fabric with antibacterial, UV protection, and coloring effects using folic acid

The amino-functionalized cellulose with folic acid, via an esterification reaction between carboxylic acid of folic acid and hydroxyl groups of cellulose, can develop multifunctional products with new chemical and physical properties. Folic acid contains two carboxylic groups as well as an amine group that can be used as a coupling agent and provide suitable conditions for coupling hydroxyl-based compounds to cellulose. Also; the multi-functionalized cellulose with folic acid has no effects on the physical and mechanical properties and also has benefits such as antibacterial, UV protection, and wrinkle resistance. The FTIR-ATR and Raman analysis confirmed the amino functionalized-cellulosic fabric via an esterification reaction between cellulose and folic acid. The cell viability of L929 fibroblast (NCBI C161) and MCF-7 (NCBI C135) cancer cells indicated more effectiveness on MCF-7 cancer cells. Therefore; folic acid can be used as a biocompatible natural cross-linker to modify cellulose fabrics for apparel and medical applications.

Simultaneous and efficient removal of heavy metal ions and organophosphorus by amino-functionalized cellulose from complex aqueous media

Electroless plating occupies a vital position in the fields of metal anticorrosion while accompanied by a large amount of effluent containing organophosphorus (like phytic acid) and heavy metals ions {like Cu (II) and Ni (II)}. However, it was still remaining great challenges in how to simultaneously remove these organophosphorus and heavy metal ions with simple methods. This work prepared a green, clean and efficient adsorbent amino-functionalized cellulose (AFCA) for simultaneous removal of organophosphorus and metal ions from complex wastewater. Benefitting from its abundant amino groups, AFCA can rapidly remove organophosphorus and metal ions within 10 min. The theoretical maximum adsorption capacities of AFCA could also reach as high as 89.29 mg/g, 79.37 mg/g and 178.57 mg/g, respectively. Most importantly, for the mixed system of organophosphorus and Cu (II), the removal efficiency was increased by 5.66% and 30.23% compared with the individual system, respectively. High simultaneous removal capacity of AFCA was due to the hydrogen bond and electrostatic interactions with organophosphorus and the complexation interactions between abundant amino groups and metal ions. All of these results demonstrate that AFCA has enormous potential for the treatment of actual electroless plating effluents.

SalenCr Catalyst Immobilized on Amino-Functionalized Cellulose for the Copolymerization of SO2 with Cyclohexene Oxide

SalenCr Catalyst Immobilized on Amino-Functionalized Cellulose for the Copolymerization of SO2 with Cyclohexene Oxide

Enhancing Removal of Cr(VI), Pb2+, and Cu2+ from Aqueous Solutions Using Amino-Functionalized Cellulose Nanocrystal.

In this work, the amino-functionalized cellulose nanocrystal (ACNC) was prepared using a green route and applied as a biosorbent for adsorption of Cr(VI), Pb2+, and Cu2+ from aqueous solutions. CNC was firstly oxidized by sodium periodate to yield the dialdehyde nanocellulose (DACNC). Then, DACNC reacted with diethylenetriamine (DETA) to obtain amino-functionalized nanocellulose (ACNC) through a Schiff base reaction. The properties of DACNC and ACNC were characterized by using elemental analysis, Fourier transform infrared spectroscopy (FT-IR), Kaiser test, atomic force microscopy (AFM), X-ray diffraction (XRD), and zeta potential measurement. The presence of free amino groups was evidenced by the FT-IR results and Kaiser test. ACNCs exhibited an amphoteric nature with isoelectric points between pH 8 and 9. After the chemical modification, the cellulose I polymorph of nanocellulose remained, while the crystallinity decreased. The adsorption behavior of ACNC was investigated for the removal of Cr(VI), Pb2+, and Cu2+ in aqueous solutions. The maximum adsorption capacities were obtained at pH 2 for Cr(VI) and pH 6 for Cu2+ and Pb2+, respectively. The adsorption all followed pseudo second-order kinetics and Sips adsorption isotherms. The estimated adsorption capacities for Cr(VI), Pb2+, and Cu2+ were 70.503, 54.115, and 49.600 mg/g, respectively.

Efficient bacterial capture by amino-functionalized cellulose monolith

Efficient bacterial capture by amino-functionalized cellulose monolith

Upgrading Oryza sativa wastes into multifunctional antimicrobial and antibiofilm nominees; Ionic Metallo-Schiff base-supported cellulosic nanofibers

Biofilm formation acts as an important self-defense strategy used by bacteria to protect itself against external changes and antibiotics effects. Moreover, biofilms have serious environmental and health impacts. Potent and safe natural antimicrobials may offer an ideal solution to tackle this challenge. In this context, we have recycled rice wastes into amino-functionalized cellulose nanofibers (CNF-NH2), ammonium-based cellulosic nanofibers Schiff bases (CNFSBs), and their corresponding Ag(I)/Zn(II) complexes. The antibacterial study of new cellulosic specimens revealed that the grafting of CNF-NH2 with ammonium ionic liquids segments and metal ions has remarkably improved its antibacterial activity. CNFSB1-Ag was the most potent antibiotic candidate against common medically-relevant strains, methicillin-resistant S. aureus (MRSA) and E. coli (MICMRSA/E. coli = 0.19/0.65 µg/mL). Moreover, it is more active than the clinical drug (vancomycin) (MICMRSA/E. coli = 1.02/0.85 µg/mL). Also, CNFSB1-Ag was the most active in limiting of MRSA and E. coli biofilms formation with 97.9% and 81.0% biofilm reduction, respectively.

New insensitive nitrogen-rich energetic polymers based on amino-functionalized cellulose and microcrystalline cellulose: Synthesis and characterization

In this work, pristine cellulose amine nitrate (OCAN) and microcrystalline cellulose amine nitrate (MCCAN) as a new class of insensitive energetic nitrogen-rich polymers were successfully synthesized for the first time through chemical modification of pristine cellulose (OC) and microcrystalline cellulose (MCC). The synthesized energetic polymers and their precursors were deeply characterized using various analytical methods. Moreover, the energetic performances of the prepared nitrated polymers was predicted using the EXPLO5 V6.04 code. Their heats of combustion and mechanical sensitivities against impact and friction were also evaluated. Experimental results confirm the effectiveness of the functionalization process to synthesize OCAN and MCCAN with interesting features such as nitrogen content of 18.42% and 20.06%, density of 1.719 g/cm3 and 1.727 g/cm3, and detonation velocity of 7576 m/s and 7905 m/s, respectively, which are significantly better than those of the conventional nitrocellulose. In addition, the proposed approach allows the production of thermally stable energetic biopolymers with improved sensitivity characteristics. Thus, this investigation provides a novel and sustainable methodology to obtain a new class of insensitive energetic nitrogen-rich polymers based on cellulose, which may further promote their applications in explosives and high-performance propellants.

Amino-functionalized cellulose: a novel and high-efficiency scavenger for sodium cholate sorption

In this work, a novel and high-efficiency scavenger based on amino-functionalized cellulose was designed for sodium cholate sorption in vitro. To estimate the adsorption performance of the amino-functionalized cellulose for sodium cholate, various factors including sodium cholate concentration, contact time and electrolyte were investigated. The results suggested that amino-functionalization for cellulose regarding to hyperbranched polyethylenimine not only induce positive charge surface of cellulose but also provide abundant and special binding sites for sodium cholate sorption. The amino-functionalized cellulose displayed an excellent performance to sodium cholate sorption with a maximum adsorption capacity of 569.7 mg/g, higher than cholestyramine, a synthetic lipid-lowering drug in clinic. And the adsorption behavior was well fitted into the Langmuir isotherm model and pseudo-second-order kinetic model, suggesting a homogeneous monolayer chemisorption. Furthermore, the amino-functionalized cellulose presented the features of excellent anti-interferences, cytocompatibility and facile preparation process. All these results support amino-functionalized cellulose as a promising prospect for cholesterol elimination.

Potential of amino-functionalized cellulose as an alternative sorbent intended to remove anionic dyes from aqueous solutions

Adsorption has been explored to minimize the pollution caused by dyes. This work relates the preparation of diethylenetriamine-modified cellulose (DetaCel) by reacting phthalic anhydride-modified cellulose (PhCel) with diethylenetriamine (Deta). Materials were characterized by Elemental Analysis and results showed a degree of incorporation of 5.55 ± 0.02 mmol of nitrogen per gram of modified material. The main bands observed for DetaCel by Fourier-Transform Infrared Spectroscospy (FTIR) were attributed to CN deformation (1330 cm−1) and NH stretching of amide (3400 cm−1), while Solid State Nuclear Magnetic Resonance of 13C (13C{1H}CP-MAS NMR) showed a signal at 164.6 ppm characteristic of amide group. Crystallinity index (CrI) obtained by X-Ray Diffraction (XRD) was 74.99 (Cel), 58.64 (PhCel) and 46.12% (DetaCel). Adsorbent matrices were employed to remove methyl orange (MO) and eosin (EY) dyes in aqueous medium. Data obtained experimentally from kinetic study had a better fit to the pseudo-first order, thus the adsorption process occurs in monolayer, with MO adsorption capacity by Cel and DetaCel of 2.19 and 65.45 mg g−1, respectively. For EY adsorption by Cel and DetaCel was 1.30 and 56.69 mg g−1, respectively. These results suggest that DetaCel can be used as an alternative potential for removal dyes in aqueous solution.

Covalently anchored sulfamic acid on cellulose as heterogeneous solid acid catalyst for the synthesis of structurally symmetrical and unsymmetrical 1,4-dihydropyridine derivatives

A novel heterogeneous solid acid catalyst has been prepared by covalent grafting of chlorosulphonic acid on amino-functionalized cellulose (Cell–Pr-NHSO3H).

Macromol. Rapid Commun. 22/2013

Front Cover: The electro-spinning of amino-functionalized cellulose yielding nanofibrous materials opens up new fields of applications for this interesting class of cellulose derivatives. The 6-deoxy-6-triaminotriethylamino (TEAE) cellulose based nanofiber webs exhibit a strong reduction or a significant antibacterial efficiency depending on the type. Further details can be found in the article by K. Roemhild, C. Wiegand, U.-C. Hipler, and T. Heinze* on page 1767.

Amino‐Functionalized Cellulose Nanoparticles: Preparation, Characterization, and Interactions with Living Cells

Spherical nanoparticles with sizes from 80 to 200 nm are obtained by self-assembly of highly functionalized 6-deoxy-6-(ω-aminoalkyl)aminocellulosecarbamates. The particles are very stable, nontoxic, and possess primary amino groups that are accessible to further modifications in aqueous suspension. The particles can be labeled with rhodamine B isothiocyanate without changing their size, stability, and shape. The nanoparticles obtained are investigated by means of photo correlation spectroscopy, zeta potential measurements, SEM and fluorescence spectroscopy. Incorporation of the nanoparticles in human foreskin fibroblasts BJ-1-htert and breast carcinoma MCF-7 cells without any transfection reagent is proved by means of confocal laser scanning microscopy.

Efficient assembly of peptomers on continuous surfaces

The SPOT synthesis technique, originally developed for peptide synthesis on continuous surfaces, was adapted for high-throughput parallel solid phase synthesis of peptomers (peptide-peptoid-hybrids) using amino-functionalized cellulose membranes, a linker cleavable under dry conditions and modified synthesis protocols.