Ionic Liquid Chitosan Research Articles

Chemometrics and electrochemistry joined hands to develop a novel and intelligent electronic device for simultaneous determination of malathion and diazinon in fruit juices: A progress in multidisciplinary studies

In this work, chemometrics and electrochemistry connected to each other to open a new way for assisting food industry specialists based on developing a novel electrochemical sensor for simultaneous determination of malathion (MT) and diazinon (DZ) in the presence of patulin (PT) and citrinin (CT) as uncalibrated interference in fruit juices. The sensor was fabricated based on modification of a glassy carbon electrode (GCE) by chitosan-ionic liquid (Ch-IL), electrodeposition of gold nanoparticles (Au NPs), drop-casting of multiwalled carbon nanotubes-IL (MWCNTs-IL), and electrochemical synthesis of dual templates molecularly imprinted polymers (DTMIPs) in which MT and DZ were used as templates. Effects of experimental variables on structure and response of the sensor were screened and optimized by Min Run screening and central composite design, respectively. After optimization, the third-order hydrodynamic differential pulse voltammetric (HDPV) data were generated based on changing modulation times and modulation amplitudes as instrumental parameters and modeled by N-PLS/RTL, U-PLS/RTL, U-PCA/RTL, APARAFAC, PARAFAC2 and MCR-ALS to select the best one to assist the sensor for ultra selective simultaneous determination of MT and DZ in the presence of PT and CT as uncalibrated interference in fruit samples. The results confirmed the MCR-ALS was the best assistance for DTMIPs/MWCNTs-IL/Au NPs/Ch-IL/GCE for simultaneous determination of MT and DZ in the presence of PT and CT as uncalibrated interference in both synthetic and real samples. Performance of the sensor assisted by MCR-ALS for ultra selective simultaneous determination of MT (0.1 pM–12.5 pM, LOD = 0.01 pM) and DZ (0.25 pM–8.5 pM, LOD = 0.15 pM) was really admirable which was comparable with HPLC with UV detection while it was faster, simpler and low-cost in comparison to HPLC-UV which motivated us to introduce it as a reliable method to assist food industry specialists for quality assurance purposes.

Engagement of computerized and electrochemical methods to develop a novel and intelligent electronic device for detection of heroin abuse

In this work, a novel biosensing platform was fabricated based on modification of a rotating glassy carbon electrode (GCE) with chitosan-ionic liquid (Ch-IL) composite film, electrochemical synthesis of gold palladium platinum trimetallic three metallic alloy nanoparticles (AuPtPd NPs) onto its surface, and electrosynthesis of dual templates molecularly imprinted polymers (MIPs) where morphine (MO) and codeine (COD) used as template molecules. The AuPtPd NPs were synthesized under different electrochemical conditions, and surfaces of electrodes were investigated by digital image processing, and the best electrode was chosen. Effects of experimental variables on response of the biosensor to MO and COD were optimized by a central composite design (CCD), and under optimized conditions (concentration of the phosphate buffered solution (PBS): 0.09 M, pH of the PBS: 3.21–3.2, time of immersion: 204.8–205 s, and rotation rate: 2993.51–3000 rpm) the biosensor responses to MO and COD were individually calibrated (1–20 pM for MO and 0.5–12 pM for COD), three-way calibrated by PARASIAS, PARAFAC2, and MCR-ALS, and validated in the presence of ascorbic acid and uric acid as uncalibrated interference. Finally, performance of the biosensor in simultaneous determination of MO and COD in the presence of ascorbic acid and uric acid as uncalibrated interference in human serum samples were verified and compared with the results of HPLC-UV as the reference method which guaranteed it as a reliable method.

Development of a three-dimensional porous ionic liquid-chitosan-graphene oxide aerogel for efficient extraction and detection of polyhalogenated carbazoles in sediment samples

The three-dimensional porous ionic liquid-chitosan-graphene oxide aerogel (IL–CS–GOA) monolithic adsorbent with a through-hole structure was prepared using natural chitosan (CS) as the skeletal framework, graphene oxide (GO) as the support to provide mechanical strength, and ionic liquid (IL) as the porogen and modifier. The resulting IL–CS–GOA demonstrated a fluffy and porous structure with various pore sizes and excellent regeneration capability (over six cycles). Its specific surface area exceeded that of CS-GOA and IL-GOA by more than 7 times, enhancing its polyhalogenated carbazoles (PHCZs) adsorption capacity. Within 5 min, IL–CS–GOA (1.0 mg) exhibited adsorption amounts of 539 ng mg−1 for 3-bromocarbazole (3-BCZ), 716 ng mg−1 for 2,7-dibromocarbazole (2,7-BCZ), and 798 ng mg−1 for 1,3,6,8-tetrabromocarbazole (1,3,6,8-BCZ), showcasing its rapid mass transfer and high adsorption capabilities. IL–CS–GOA was utilized as the adsorbent for glass dropper extraction (GDE) in conjunction with gas chromatography-mass spectrometry (GC-MS/MS), to develop a highly efficient and accurate method for determining PHCZs in sediments. Under optimal conditions, the established method exhibited a wide linear range (0.4–250 ng g−1, r ≥ 0.9990), low detection limits (0.04–0.24 ng g−1), and satisfactory recoveries (80.5 %–93.8 %), enabling the accurate and rapid detection of PHCZs in sediment samples. This study presents a novel approach for creating three-dimensional porous aerogels, introduces a new form of sample pretreatment using GDE with a monolithic adsorbent, and offers a new method for the determination of PHCZs in environmental matrices.

Preparation and corrosion inhibition mechanism of a chitosan ionic liquid Schiff base for the protection of N80 in HCl solution

Three chitosan ionic liquid type Schiff bases (CS-IL-SBs) were synthesized by grafting three aldehydes (vanillin, cinnamaldehyde, and pyridine-4-carboxaldehyde) on CS-IL (chitosan grafted with p-toluene sulfonic acid) through a Schiff base reaction.

Exploiting second-order advantage for simultaneous biosensing of romidepsin and vorinostat in the presence of belinostat as uncalibrated interference in human serum samples

In this work, a novel, ultra-sensitive, selective, and multi-electrochemical techniques biosensor was fabricated for simultaneous determination of romidepsin (RD) and vorinostat (VN) in the presence of belinostat (BS) as uncalibrated interference in human serum samples. A glassy carbon electrode (GCE) was modified with chitosan-ionic liquid (CS-IL) which was used as a platform to immobilize histone deacetylase (HDAC) by the use of glutaraldehyde. The RD and VN as inhibitors of the HDAC were trapped by the HDAC onto the biosensor surface which didn’t show any response at the surface of the CS-IL/GCE. In order to simultaneous biosensing of RD and VN, the biosensor was immersed into a probe solution to get a response from the biosensor. By individual immersion of the biosensor into RD and VN solutions different steric hindrances were occurred at the biosensor surface which caused generation of two different responses from the biosensor. The biosensor responses were individually calibrated and used to develop second-order calibration models to support the biosensor for simultaneous determination of RD and VN. Second-order hydrodynamic square wave voltammetric (HSWV) data were generated and modeled by PARAFAC2, MCR-ALS, PARASIAS, and U-PCA/RBL to find the best method to couple with outputs of the biosensor. The results confirmed the best performance for the biosensor- U-PCA/RBL for simultaneous determination of RD and VN in the presence of BS in artificial human serum samples. The biosensor-U-PCA/RBL combinatorial method was also successful in simultaneous determination of RD and VN in the presence of BS in real human serum samples with a comparable performance with HPLC as the reference method.

Multiobjective Optimization Based on “Distance-to-Target” Approach of Membrane Units for Separation of CO2/CH4

The effective separation of CO2 and CH4 mixtures is essential for many applications, such as biogas upgrading, natural gas sweetening or enhanced oil recovery. Membrane separations can contribute greatly in these tasks, and innovative membrane materials are being developed for this gas separation. The aim of this work is the evaluation of the potential of two types of highly CO2-permeable membranes (modified commercial polydimethylsiloxane and non-commercial ionic liquid–chitosan composite membranes) whose selective layers possess different hydrophobic and hydrophilic characteristics for the separation of CO2/CH4 mixtures. The study of the technical performance of the selected membranes can provide a better understanding of their potentiality. The optimization of the performance of hollow fiber modules for both types of membranes was carried out by a “distance-to-target” approach that considered multiple objectives related to the purities and recovery of both gases. The results demonstrated that the ionic liquid–chitosan composite membranes improved the performance of other innovative membranes, with purity and recovery percentage values of 86 and 95%, respectively, for CO2 in the permeate stream, and 97 and 92% for CH4 in the retentate stream. The developed multiobjective optimization allowed for the determination of the optimal process design and performance parameters, such as the membrane area, pressure ratio and stage cut required to achieve maximum values for component separation in terms of purity and recovery. Since the purities and recoveries obtained were not enough to fulfill the requirements imposed on CO2 and CH4 streams to be directly valorized, the design of more complex multi-stage separation systems was also proposed by the application of this optimization methodology, which is considered as a useful tool to advance the implementation of the membrane separation processes.

Reaction kinetics of glycidyl trimethyl ammonium chloride and chitosan in 1-allyl-3-methylimidazolium chloride

The modification of chitosan in ionic liquids through homogeneous reactions has advantages including shorter time and simple post-treatment and the generated chitosan derivatives have high degrees of subsititution and good reproducibility. In this paper, we studied the reaction kinetics of glycidyl trimethyl ammonium chloride and chitosan in 1-allyl-3-methylimidazolium chloride. Chitosan concentration, temperature, and reaction time were studied to determine their influence on reaction kinetics. The results indicated that reaction rate increased with increases of both chitosan concentration and temperature. A first-order kinetics equation was generated, where the relationship between reaction rate constant and temperature was determined.

Effect of Water and Organic Pollutant in CO2/CH4 Separation Using Hydrophilic and Hydrophobic Composite Membranes.

Membrane technology is a simple and energy-conservative separation option that is considered to be a green alternative for CO2 capture processes. However, commercially available membranes still face challenges regarding water and chemical resistance. In this study, the effect of water and organic contaminants in the feed stream on the CO2/CH4 separation performance is evaluated as a function of the hydrophilic and permselective features of the top layer of the membrane. The membranes were a commercial hydrophobic membrane with a polydimethylsiloxane (PDMS) top layer (Sulzer Chemtech) and a hydrophilic flat composite membrane with a hydrophilic [emim][ac] ionic liquid–chitosan (IL–CS) thin layer on a commercial polyethersulfone (PES) support developed in our laboratory. Both membranes were immersed in NaOH 1M solutions and washed thoroughly before characterization. The CO2 permeance was similar for both NaOH-treated membranes in the whole range of feed concentration (up to 250 GPU). The presence of water vapor and organic impurities of the feed gas largely affects the gas permeance through the hydrophobic PDMS membrane, while the behavior of the hydrophilic IL–CS/PES membranes is scarcely affected. The effects of the interaction of the contaminants in the membrane selective layer are being further evaluated.

Highly Transparent All‐Polysaccharide Composite Films with Tailored Transmission Haze for Light Manipulation

AbstractLow‐cost light management films that completely originate from natural polymers for biodegradable optoelectronics are a growing trend with great demand in the near future, for example, highly transparent and hazy films. Herein, a novel green method simply based on the solubility difference between cellulose and chitosan in ionic liquid is proposed to cast all‐polysaccharide transparent films with customized transmission haze. The dissolved cellulose in 1‐Allyl‐3‐methylimidazolium chloride (AmimCl) ionic liquid serves as matrix. The insoluble chitosan is deliberately dispersed in the matrix, which can maintain its original particle size due to its poor solubility in AmimCl and can significantly increase the surface roughness of the composite film and hence functions as the light scatterer. Eventually, an all‐polysaccharide composite film (Cel/CS) with high transmittance (>84.8%) and tunable haze (10–93%) is prepared using different coagulating bath and drying methods. The film is highly suitable for large‐scale continuous production and sufficient to satisfy the varying haze requirements of different applications, including flexible lighting and displays, antireflection and anti‐glare coatings, and privacy protection.

Ecofriendly Method to Dissolve Chitosan in Plain Water.

Chitosan is an important and abundant natural-based polymer, and it has broad applications. However, dissolving chitosan in plain water is a challenge, which mostly limits the biomedical applications of chitosan materials. Herein, we report an ecofriendly dissolution method to obtain a plain water-based chitosan solution for the first time. In this method, dissolving chitosan in ionic liquid followed by overnight freezing at -20 °C and subsequent solvent exchange with plain water at room temperature results in a stable chitosan dispersion in water with nanosize, namely water-based, chitosan pseudosolution. The overall process is ecofriendly. This new method augments the quality and processability of chitosan solutions used in manufacturing and bioprocessing and promotes the biomedical applications of chitosan-based products.

Dissolution, materialization and derivatization of chitin and chitosan in ionic liquids

Chitin and chitosan are renewable biomass resources with macromolecular structures. Due to the strong intra- and inter-molecular hydrogen bonds, chitin and chitosan cannot be dissolved in water or traditional organic solvents, which tremendously limit their applications in many fields. Ionic liquid, as a novel green solvent, provides excellent solubility to chitin and chitosan. In this paper, the research progress on dissolution performance and dissolution mechanism of chitin and chitosan in ionic liquids is reviewed. Materials including fibers, films and gels created from the homogeneous solutions are summarized; meanwhile, the chemical derivatization of chitin and chitosan in ionic liquids are also discussed. Finally, the challenges and future development of ionic liquids in chitin and chitosan chemistry are proposed.

Multi-branched ionic liquid-chitosan as a smart and biocompatible nano-vehicle for combination chemotherapy with stealth and targeted properties

A possible approach for clinical cancer treatment is combination chemotherapy. To address this issue, many anticancer agents have been used simultaneously to achieve synergistic effects with the different mechanism of actions, however, their toxic side effects are still a big challenge. In this study, a smart, biocompatible, magnetic nanocarrier composed of multi-branched ionic liquid-chitosan grafted mPEG was designed and used for targeted multidrug delivery of DOX and MTX as model anticancer agents to MCF7 breast cancer cells. The results of hemolysis assay on human red blood cells and cytotoxicity studies indicated that blank nanocarrier has no significant hemolytic and cytotoxic effects in MCF7 cells as observed in the results of MTT assay, however, drugs-loaded nanocarrier could decrease the viability of MCF7 cells in a dose-dependent manner. To further simulate the interaction of nanocarrier with plasma proteins, the SDS-PAGE assay was performed after the nanocarrier was incubated with human plasma and the results indicated that a series of proteins were attached to the surface of nanocarrier leading protein-particle corona complex. This complex gives a stealth property as well as increasing cellular uptake process due to the presence of proteins acting as ligands for receptors in the surface of cancer cells that are suitable for drug delivery systems. The efficiency of dual-drug delivery was also confirmed by cellular uptake and DAPI staining. All these results persuade us, this nanocarrier is suitable for use in further animal studies in future investigations.

Aerogels from Chitosan Solutions in Ionic Liquids.

Chitosan aerogels conjugates the characteristics of nanostructured porous materials, i.e., extended specific surface area and nano scale porosity, with the remarkable functional properties of chitosan. Aerogels were obtained from solutions of chitosan in ionic liquids (ILs), 1-butyl-3-methylimidazolium acetate (BMIMAc), and 1-ethyl-3-methyl-imidazolium acetate (EMIMAc), in order to observe the effect of the solvent in the structural characteristics of this type of materials. The process of elaboration of aerogels comprised the formation of physical gels through anti-solvent vapor diffusion, liquid phase exchange, and supercritical CO2 drying. The aerogels maintained the chemical identity of chitosan according to Fourier transform infrared spectrophotometer (FT-IR) spectroscopy, indicating the presence of their characteristic functional groups. The internal structure of the obtained aerogels appears as porous aggregated networks in microscopy images. The obtained materials have specific surface areas over 350 m2/g and can be considered mesoporous. According to swelling experiments, the chitosan aerogels could absorb between three and six times their weight of water. However, the swelling and diffusion coefficient decreased at higher temperatures. The structural characteristics of chitosan aerogels that are obtained from ionic liquids are distinctive and could be related to solvation dynamic at the initial state.

Adsorption of malachite green from aqueous solution by using novel chitosan ionic liquid beads

Chitosan ionic liquid beads were prepared from chitosan and 1-butyl-3-methylimidazolium based ionic liquids to remove Malachite Green (MG) from aqueous solutions. Batch adsorption experiments were carried out as a function of initial pH, adsorbent dosage, agitation time and initial MG concentration. The optimum conditions were obtained at pH 4.0, 0.008g of adsorbent dosage and 20min of agitation time were utilized in the kinetic and isotherm studies. Three kinetic models were applied to analyze the kinetic data and pseudo-second order was found to be the best fitted model with R2>0.999. In order to determine the adsorption capacity, the sorption data were analyzed using the linear form of Langmuir, Freundlich and Temkin equations. The isotherm was best fitted by Langmuir isotherm model. The maximum adsorption capacity (qmax) obtained from Langmuir isotherm for two chitosan beads 1-butyl-3-methylimidazolium acetate A and 1-butyl-3-methylimidazolium B are 8.07mgg−1 and 0.24mgg−1 respectively.

Facile synthesis of water-soluble graphene-based composite: Non-covalently functionalized with chitosan-ionic liquid conjugation

Chitosan-ionic liquid conjugation (CILC), which was prepared through the reaction of 1-(4-bromobutyl)-3-methylimidazolium bromide (BBMIB) with chitosan, was firstly used to prepare functionalized graphene composite via the chemical reduction of graphene oxide (GO). The obtained water soluble graphene-based composite was characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), ultraviolet-visible (UV–Vis) spectroscopy and so on. CILC-RGO showed excellent dispersion stability in water at the concentration of 2.0 mg/mL, which was stable for several months without any precipitate. This may be ascribed to the electrostatic attraction and [Formula: see text]–[Formula: see text] interaction between CILC and graphene.

Development of sensitive amperometric hydrogen peroxide sensor using a CuNPs/MB/MWCNT-C60-Cs-IL nanocomposite modified glassy carbon electrode

A sensitive hydrogen peroxide (H2O2) sensor was constructed based on copper nanoparticles/methylene blue/multiwall carbon nanotubes–fullerene–chitosan–ionic liquid (CuNPs/MB/MWCNTs–C60–Cs–IL) nanocomposites. The MB/MWCNTs–C60–Cs–IL and CuNPs were modified glassy carbon electrode (GCE) by the physical adsorption and electrodeposition of copper nitrate solution, respectively. The physical morphology and chemical composition of the surface of modified electrode was investigated by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), respectively. The electrochemical properties of CuNPs/MB/MWCNTs–C60–Cs–IL/GCE were investigated by cyclic voltammetry (CV) and amperometry techniques and the sensor exhibited remarkably strong electrocatalytic activities toward the reduction of hydrogen peroxide. The peak currents possess a linear relationship with the concentration of H2O2 in the range of 0.2μM to 2.0mM, and the detection limit is 55.0nM (S/N=3). In addition, the modified electrode was used to determine H2O2 concentration in human blood serum sample with satisfactory results.

Preparation of chitosan fibers using aqueous ionic liquid as the solvent

In this work, acidic ionic liquid glycine hydrochloride (Gly·HCl) is reported as a new solvent for dissolving chitosan. The regenerated chitosan fibers were fabricated by a wet spinning process and characterized by scanning electronic microscopy, fourier transform infrared spectroscopy, wide-angle X-ray diffraction and thermal gravimetric analysis. The result shows that the regenerated chitosan fibers had the same chemical structure as the raw chitosan flake, however, its thermal stability and crystallinity is a little low. Furthermore, a new mechanism of dissolving chitosan in ionic liquid was proposed. The chitosan fibers had soft feeling, excellent antibacterial property and have huge potential application in biomaterials.

Using electrochemical oxidation of Rutin in modeling a novel and sensitive immunosensor based on Pt nanoparticle and graphene–ionic liquid–chitosan nanocomposite to detect human chorionic gonadotropin

This study aims at developing an innovative electrochemical immunoassay system for an ultrasensitive detection of human chorionic gonadotropin (hCG). hCG is a secretion of the placenta during pregnancy and gestational trophoblastic diseases. It increases as a consequence of abnormal placental invasion and placental immaturity. Thus, an exact diagnosis of the concentration of hCG in urine or serum plays an important role in monitoring trophoblastic diseases in all modern immunological pregnancy tests. In this work, a novel immunosensor is constructed by covalent immobilization of Pt nanoparticles (PtNPs) onto robust nanocomposite containing graphene (Gr), chitosan (Chit) and 1-methyl-3-octyl imidazolium tetrafluoroborate as ionic liquid (IL) (Gr–IL–Chit). The nanocomposite not only led to increase the electrode surface area and accelerate the electron transfer kinetics, but also it could provide a highly stable matrix to enhance the loading amount of the nanoparticles. PtNPs acts as a linker to immobilize hCG antibody onto the modified electrode. The amine groups of the antibody are covalently attached to PtNPs. Cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) were employed to trace the assembly process of the immunosensor. In this study, we used Rutin (RU) for the first time as the redox probe in the development of the electrochemical immunosensor. Upon biorecognition hCG to its antibody, peak current of RU decreased due to the formation of hCG–anti hCG complex. Through differential pulse voltammetry (DVP) experiments, it was found that proposed immunosensor could detect hCG at two broad linear ranges: 0.00106–2.12 and 2.12–350mIU/mL and a low detection limit of 0.00035mIU/mL. The immunosensor was found stable, reproducible, and highly specific for hCG detection.

Influence of Green Corrosion Inhibitor based on Chitosan Ionic Liquid on the Steel Corrodibility in Chloride Solution

Influence of Green Corrosion Inhibitor based on Chitosan Ionic Liquid on the Steel Corrodibility in Chloride Solution

Chitosan–ionic liquid modified single-use sensor for electrochemical monitoring of sequence-selective DNA hybridization

Chitosan-(CHIT) and ionic liquid- (1-butyl-3-methylimidazolium hexafluorophosphate (IL)) modified single-use graphite electrodes (PGEs) were developed for the first time in the present study for the enhanced monitoring of DNA, and also for sequence-selective DNA hybridization by measuring the guanine oxidation signal. The electrochemical behaviour of the CHIT–IL modified electrodes was first investigated (with unmodified electrodes as controls) using electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV). Sequence-selective DNA hybridization related to Hepatitis B virus (HBV) was also evaluated in the case of hybridization between amino-linked HBV probe and its complementary (target), a noncomplementary (NC) sequence, single base mismatch (MM), and also in the medium of target/mismatch (MM) mixtures (1:1). CHIT–IL modified PGEs presented a very effective discrimination of DNA hybridization owing to their superior selectivity and sensitivity.