Cellulose Tosylate Research Articles

Novel cellulose derivative containing aminophenylacetic acid as sustainable adsorbent for removal of cationic and anionic dyes

The synthesis and characterization of a novel cellulose derivative as a potential sustainable adsorbent for cationic and anionic dyes are described through processing in ionic liquids. Cellulose was solubilized in ionic liquid with tosyl chloride to form tosyl cellulose which reacted with 4-aminophenylacetic acid through nucleophilic substitution mechanism. The new cellulose derivative was characterized and explored as an effective adsorbent for methylene blue (MB) and methyl orange (MO) removal, and the adsorption behaviors were investigated with various models. The adsorption behavior of the cellulose derivative followed Langmuir and pseudo-second-order models, and the maximum adsorption efficiency recorded 135 and 106 mg/g for MB and MO, respectively. There is possibility that the enhanced adsorption capacity of the cellulose derivative is due to the carboxylic and amino functional groups that provide sufficient active sites to enhance dye molecule affinity. The adsorption results demonstrate that the cellulose derivative containing aminophenylacetic acid was efficient adsorbent for removals of MB and MO.

Novel Cellulose/Silica Microspheres as Sustainable and Efficient Adsorbents for Methyl Orange Removal

The effective removal of organic dyes from aqueous solutions is essential for environmental protection and remediation. Hence, methods for fabricating efficient and sustainable adsorbents for removing toxic dyes are urgently desired. Here, new cellulose/silica microspheres containing amino groups were prepared and applied as functional materials for capturing anionic pollutants. Tosyl cellulose, which has a high degree of substitution, was prepared from cellulose using an ionic liquid as the solvent. Further, (3-aminopropyl)trimethoxysilane was utilized as a silica precursor to prepare the microhybrids via nucleophilic substitution, followed by the sol–gel process. The fabricated microhybrids exhibited an excellent capacity for methyl orange (MO) adsorption. Furthermore, the effects of different pH values, contact times, and initial dye concentrations on the MO adsorption capacity were evaluated. The Langmuir isotherm and pseudo-second-order kinetic models were effective for modeling the adsorption of MO on the cellulose/silica microspheres. Under the established optimal conditions, the cellulose/silica microspheres exhibited a higher adsorption capacity (588 mg/g) than those in previous reports. Therefore, the proposed cellulose/silica microspheres offer a promising platform for the sustainable development of water-purification systems.Graphical

Cellulose tosylate as support for α-amylase immobilization

Tremendous potential exists to use cellulose as a support for the immobilization of enzymes. In the current study, cellulose was transformed into cellulose tosylate, and α-Amylase was immobilized using the derivatized polymer. Techniques like Fourier transform infrared, scanning electron microscopy, thermogravimetric analysis, and X-ray diffraction methods were used to characterize the support. The support is a perfect illustration of how both covalent and hydrophobic/ionic types of immobilizations can be experimentally used on support. The support was found to show max degradation at 320.2 °C with 3.2 % residual substance and crystallinity of about 56.6 %. The support presented maximum enzyme loading at the support: enzyme ratio of 1:4. The immobilized enzyme displayed two ideal pH values (about 4.6 and 7) and two ideal temperatures (approximately 60 °C & 40 °C). It was discovered that the immobilized α-amylase could be used easily eight times with 9.9 % residual activity. The findings of this study show that the immobilized cellulose tosylate enzyme has the potential for application in both acidic and neutral pH environments with the best activity for commercial use.

Fibrous Polyethyleneimine‐Functionalized Cellulose Materials for CO2 Capture and Release

AbstractPoly(ethyleneimine) (PEI) immobilized on support materials are valuable alternatives to aqueous amine solutions for carbon dioxide (CO2) capture from the atmosphere since the thermal desorption of CO2 from these materials usually requires less energy. Herein, fibrous PEI‐functionalized carrier systems based on cellulose, cellulose tosylate (CT), and cellulose carbamate (CC) are described. Branched PEI is used for functionalization since higher CO2 sorption capacities compared to linear PEIs can be achieved. Under wet conditions, a PEI‐functionalized nonwoven material has a sorption capacity of 0.026 mg CO2/mg adsorbent; complete and reversible CO2 desorption is accomplished at 80 °C.

Synthesis and structure characterization of novel polyampholytes based on cellulose

Sulfobetainic polymers were synthesized by polymeranalogous reaction of new amino celluloses starting from cellulose tosylate. To obtain different amino celluloses as starting building blocks, a comprehensive study with a selection of asymmetric and symmetric N-alkylated diamines was performed. For reaction with asymmetric diamines, it turned out that the primary amino moiety reacts preferably. Derivatives thus obtained consist in a neutral main structural unit and a cationic side structural unit, which is not described up to now. In order to investigate the reactivity of the amino celluloses 6-deoxy-6-(N,N,N′,N′-tetramethylethylenediamino) cellulose was used as uniform starting material for the design of novel polyampholytes by conversion with 1,3-propansultone. Detailed structure characterization was implemented by means of 1D and 2D-NMR spectroscopy.

Nucleophilic Displacement Reaction on Tosyl Cellulose by L-Methionine to the Synthesis of Novel Water-Soluble Cellulose Derivative and Its Antibacterial Activity

A novel ampholytic cellulose derivative, cellulose-L-methionine, has been synthesized by means of an esterification reaction of microcrystalline cellulose with tosyl chloride (p-TsCl) in DMAc/LiCl (8%) at 8°C that was followed by nucleophilic displacement (SN) of the tosyl group by the L-methionine amino acid. The resulting structure of cellulose-L-methionine has been characterized by elemental analysis (CHNSO), Fourier-transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H-NMR), and scanning electron microscopy (SEM). The antibacterial activity of the synthesized product was screened against Gram-positive and Gram-negative microbial strains such as Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa, by the agar well diffusion method, and compared with commercial antibiotics such as ampicillin and chloramphenicol. It was found that antibacterial experiment revealed excellent antibacterial activity of the cellulose-methionine with respect to a minimal inhibitory concentration (MIC) reference.

Tosylation Optimization, Characterization and Pyrolysis Kinetics of Cellulose Tosylate

AbstractCellulose tosylates with different degree of substitution (DS) were prepared by reacting cellulose in DMAc/LiCl with p‐tosyl chloride at 8 °C in the presence of triethylamine. The effects of number of mole of tosyl chloride (A), number of mole of base (triethylamine) (B) and reaction time (C) on DS were studied by Response Surface Methodology (RSM) known as Box‐Behnken Design (BBD). It was found that A is the main factor influencing DS and the interaction between B and C is negligible. An optimal DS value of 2.79 was obtained with A=6.96 and B=2.99 mol eq. at a reaction time C=24 h. The synthetic polymers were characterized by elemental analyses, FT‐IR, NMR and SEM spectroscopy. The results indicated that the cellulose was successfully tosylated with various DS. Cellulose tosylate with DS=0.5 and DS=2 were subjected to thermo‐gravimetric analysis under inert atmosphere. The kinetic parameters were determined by Coats‐Redfern method. Thermal analyses and kinetics indicates that the lower DS of tosyl group the higher thermal stability is. Thus, cellulose lose its stability after esterification with p‐tosyl chloride.

SYNTHESIS AND ANTIRADICAL ACTIVITY OF HINDERED PHENOLIC DERIVATIVES OF FLAX CELLULOSE

The modification of powdered ultradisperse cellulose by hindered phenol fragments was carried out. The modification was carried out by reacting cellulose tosylate with 3-(3',5'-ditert-butyl-4'-hydroxyphenyl) propionic acid hydrazide and 3,5-ditert-butyl-4-hydroxybenzyl dimethylamine in DMF at 100 ○C for 16–30 hours. Samples of modified cellulose were characterized by spectroscopy IR and 1H NMR. From the of elemental analysis data, the degree of substitution of cellulose derivatives by hindered phenol units was calculated. The antiradical activity of the obtained samples in their reactions with a stable radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) was determined. The reactions of modified cellulose with DPPH were carried out under the pseudo first-order conditions with respect to the radical. From the values of the effective constants, the second-order rate constants were calculated. It was established that the modification of cellulose by hindered phenol fragments leads to a sharp increase in its antiradical activity, which depends on the degree of substitution of the sample and the method of substitution. The difference in the activity of hydrazide and benzyl derivatives of cellulose may indicate their different spatial structure, resulting in different availability of phenol fragments. The antiradical activity of the hydrazide derivative of cellulose exceeds that of the antioxidant Ionol (2,6-ditert-butyl-4-methylphenol).

Aminated cellulose as a versatile adsorbent for batch removal of As(V) and Cu(II) from mono- and multicomponent aqueous solutions

A bioadsorbent (CEDA) capable of adsorbing As(V) and Cu(II) simultaneously was prepared by tosylation of microcrystalline cellulose (MC) and nucleophilic substitution of the tosyl group by ethylenediamine. MC, tosyl cellulose, and CEDA were characterized by elemental C, H, N, and S analysis, infrared spectroscopy, and 13C solid-state nuclear magnetic resonance spectroscopy. The adsorption of As(V) and Cu(II) on CEDA was evaluated as a function of solution pH, contact time, and initial solute concentration. The maximum adsorption capacities of CEDA for As(V) and Cu(II) were 1.62 and 1.09 mmol g−1, respectively. The interactions of As(V) and Cu(II) with CEDA were elucidated using thermodynamic parameters, molecular quantum mechanics calculations, and experiments with ion exchange of Cd(II) by Cu(II), and As(V) by SO42−. Adsorption enthalpies were determined as a function of surface coverage of the CEDA, using isothermal titration calorimetry, with ΔadsH° values of −32.24 ± 0.07 and −93 ± 2 kJ mol−1 obtained for As(V) and Cu(II), respectively. The potential to reuse CEDA was evaluated and the interference of other ions in the adsorption of As(V) and Cu(II) was investigated. Multi-component experiments showed that Cd(II), Co(II), Ni(II), and Pb(II) did not interfere in the adsorption of Cu(II), while SO42− inhibited As(V) adsorption.

N-Hydroxysuccinimide-activated esters as a functionalization agent for amino cellulose: synthesis and solid-state NMR characterization

We propose a mild and versatile synthesis protocol based on N-hydroxysuccinimide-activated esters for the introduction of new functionalities to cellulose, using as starting point established protocols for the tosylation of cellulose and its subsequent reaction with a diamine linker. As a proof of concept, we describe the functionalization of microcrystalline cellulose with a N-hydroxysuccinimide-activated ester of benzophenone, a photoreactive functional group. Irradiation of the final product with UV light yields a self-standing polymer film and is expected to result in cross-linking among cellulose chains. To monitor structural changes at the molecular level, each functionalization step is characterized by a multinuclear solid-state NMR approach. DNP-enhanced 15N CP MAS NMR experiments reveal the formation of the amide bond to the photoreactive linker and deliver further information about the binding situation of nitrogen-containing groups in these materials. The flexible synthesis protocol described here can be easily extended to a broad range of other functionalities of interest, both for the cellulose and macromolecular research.

New approach for immobilization of 3-aminopropyltrimethoxysilane and TiO2 nanoparticles into cellulose for BJ1 skin cells proliferation

In the present study, tosylcellulose (TC) was used as a key intermediate for the selective coupling with 3-aminopropyltrimethoxysilane (APTMS) affording amino-propylsilane-grafted tosylcellulose (TC-Si). Solid state 13C NMR and FT-IR analyses confirmed the coupling and self-condensation of APTMS along TC. The changes in the surface morphology of the functionalized cellulose were identified by SEM imaging. The thermal stability of TC-Si was significantly improved as compared to MCC and TC. A new organic/inorganic hybrid cellulosic material was fabricated by embedding TiO2 nanoparticles into TC-Si network. The new cellulose polymers were investigated for their ability to promote the proliferation of human skin fibroblast (BJ1). The cell cytotoxicity assay showed that both TC and TC-Si possessed moderate toxicity to BJ1 cells by 17% and 23.8%, respectively at 20 μM. Meanwhile, TC-Si/TiO2 hybrid enhanced the proliferation of BJ1 by 42%. Additionally TC-Si/TiO2 hybrid demonstrated promising antimicrobial activity against Staphylococcus aureus, Pseudomonas aeruginosa, and Candida albicans.

Synthesis and characterization of polyaniline/tosylcellulose stearate composites as promising semiconducting materials

Tosylcellulose stearate (TCSt) as a thermoplastic polymer has been prepared starting from microcrystalline cellulose (MCC) which was converted into a more reactive and solvent soluble tosylcellulose (TC) with degree of substitution = 0.45 under homogenous conditions. Then, tosylcellulose underwent esterification reaction through its reaction with stearic anhydride in DMF/DCM to afford tosylcellulose stearate. FT-IR, 13C NMR, and elemental analyses confirmed the chemical structure of both tosylcellulose and tosylcellulose stearate. TCSt fibers were used as matrix for polyaniline (PANI) which had been prepared via in situ oxidative polymerization of aniline hydrochloride using hydrochloric acid as dopant and ammonium persulfate as an oxidizing agent. PANI/TCSt composites with loading ratios of 75:25, 50:50, and 25:75 wt/wt were fabricated. The thermal stability, degree of crystallinity, and surface morphology of the prepared composites were characterized. The presence of PANI improved the thermal stability of the PANI/TCSt composites with (50:50 wt:wt). The electrical conductivity for PANI/TCSt composites was measured by Broadband Dielectric Spectrometer, and the conductivity values of PANI/TCSt composite prepared at weight ratio 75:25 wt% was coincided with those of PANI alone. Increasing the temperature from −40 to +50 °C increased the conductivity of the composites by about two orders of magnitudes for all investigated samples. The films prepared from TCSt and PANI/TCSt composite (50:50 wt:wt) displayed improved mechanical properties when compared with the films prepared from cellulose acetate (CA) and CA/PANI composite (50:50 wt:wt).

Facile synthesis of novel soluble cellulose-grafted hyperbranched polymers as potential natural antimicrobial materials

A new class of soluble cellulose-grafted hyperbranched polymers has been synthesized by a facile “hypergrafting” reaction using bis(2-chloroethyl)amine and soluble cellulose tosylates. The molecular structures of the obtained new materials were characterized by 13C NMR, FTIR spectroscopy, and elemental analysis. The degree of substitution of the hyperbranched cellulose derivatives ranges between 0.13–0.53. The new cellulose-based materials were soluble in various polar aprotic organic solvents. The thermal properties of the new cellulose materials were investigated by thermal gravimetric analysis. Antibacterial activity of the new cellulose derivatives was evaluated by diffusion disk tests against various gram negative and positive bacteria. Our results suggested that the obtained natural cellulosic materials can act as effective polymeric biocides, and may have great potential in various antimicrobial materials applications.

Solvent‐free synthesis of 6‐deoxy‐6‐(ω‐aminoalkyl)amino cellulose

ABSTRACTCellulose p‐toluenesulfonic acid esters (TosCell) with degree of substitution (DSTos) between 0.8 and 1.4 were converted with ethylene diamine or tris(2‐aminoethyl)amine. In contrast to procedures published, the conversion was carried out without any solvent, i.e., the reagent (amines) was used as reaction medium yielding readily soluble products. Moreover, the absence of an additional solvent makes the recycling of both not‐consumed amine and precipitant easy. Recycling experiments proofed the possibility of reusing the isolated ethylene diamine. The DS of 6‐deoxy‐6‐(ω‐aminoalkyl)amino groups is between 0.71 and 0.93, which is in accordance with the functionalization pattern of tosyl cellulose and the ability of amines to displace primary tosylate moieties only. Attention must be paid to the precipitant used for the workup procedure; 13C NMR measurements revealed a formation of imine structures in case of precipitation with acetone. Precipitation in 2‐propanol did not lead to any side product. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43987.

Cellulose carboxylate/tosylate mixed esters: Synthesis, properties and shaping into microspheres

Cellulose carboxylate/tosylate mixed esters (Cel-Carboxy/Ts) were synthesized with constant degree of tosylation, DSTs=0.98 and variable degree of acylation, DSCarboxy; acetate, butanoate, and hexanoate. The tosylate (Cel-Ts) was prepared by reacting cellulose with tosyl chloride in presence of trimethylamine. The mixed esters were obtained by reacting Cel-Ts with carboxylic acid anhydride. The dependence of the following on DSCarboxy was investigated: IR data, including νCO, νSO and peak area (CO); empirical polarity of the films, determined by an adsorbed perichromic dye. We employed these parameters to determine DSCarboxy. Relative to ester saponification, these spectroscopic methods are convenient, expedient, and require much less sample. Mixed esters prepared physically from cellulose tosylate and tosylate/acetate behave only qualitatively similar to (Cel-Carboxy/Ts). The mixed esters were dissolved in acetone and regenerated in water as homogeneous microspheres.

Synthesis and Characterization of Cellulose Tosylate in an Ionic Liquid 1-Butyl-3-Methylimidazolium Chloride

Synthesis and Characterization of Cellulose Tosylate in an Ionic Liquid 1-Butyl-3-Methylimidazolium Chloride

UV-Induced [2+2] Grafting-To Reactions for Polymer Modification of Cellulose.

Benzaldehyde-functional cellulose paper sheets have been synthesized via tosylation of cellulose (Whatman No 5) followed by addition of p-hydroxy benzaldehyde. Via UV-induced Paterno-Büchi [2+2] cycloaddition reactions, these aldehyde functional surfaces are grafted with triallylcyanurate, trimethylolpropane allyl ether, and vinyl chloroacetate. In the following, allyl-functional polymers (poly(butyl acrylate), pBA, Mn = 6990 g mol(-1) , Đ = 1.12 and poly(N-isopropyl acrylamide), pNIPAAm, Mn = 9500 g mol(-1) , Đ = 1.16) synthesized via reversible addition fragmentation chain transfer polymerization are conjugated to the celloluse surface in a UV-induced grafting-to approach. With pBA, hydrophobic cellulose sheets are obtained (water contact angle 116°), while grafting of pNIPAAm allows for generation of "smart" surfaces, which are hydrophilic at room temperature, but that become hydrophobic when heated above the characteristic lower critical solution temperature (93° contact angle). The Paterno-Büchi reaction has been shown to be a versatile synthetic tool that also performs well in grafting-to approaches whereby its overall performance seems to be close to that of radical thiol-ene reactions.

6-Deoxy-6-aminoethyleneamino cellulose: synthesis and study of hemocompatibility

Hemocompatibility of aqueous solutions of antimicrobial 6-deoxy-6-aminoethyleneamino (AEA) cellulose with different degrees of substitution (DS, 0.54–0.92) was investigated in vitro. The AEA cellulose derivatives were synthesized by tosylation of cellulose and subsequent nucleophilic substitution with 1,2-diaminoethane. The structure was confirmed by elemental analysis as well as by FTIR and NMR spectroscopies. Markers for coagulation (thrombin generation, aPTT, PT, blood clotting, thrombocyte activation) and membrane integrity (hemolysis) were measured in human whole blood, human platelet-rich plasma, human pooled plasma, and erythrocytes suspension. AEA cellulose with a low DS of 0.54 showed the highest hemocompatibility in vitro, suggesting the possibility of biomedical applications.

Role of Tosyl Cellulose Acetate as Potential Carrier for Controlled Drug Release

Cellulose is a naturally occurring organic polymer. The chemical functionalization of cellulose is conducted to adjust its properties for different purposes. In the present study, cellulose was extracted from bagasse, derivatized to acetate, and chemically modified again to prepare tosylated cellulose acetate. The prepared cellulose derivatives were investigated by Fourier transform infrared spectroscopy and scanning electron microscopy. Tosyl cellulose acetate was evaluated as a potential carrier for the controlled release of pH-sensitive drugs. The release was investigated as a function of pH and time at various pH values. The results find their use in controlled release applications.

New carboxymethyl cellulose tosylate with low biodeterioration

Microbial biodegradation and biodeterioration of cellulose based thickeners is a serious problem in industry. A new tosylic ester of carboxymethyl cellulose (TsCMC) was prepared with anhydride of p-toluensulphonic acid. The TsCMC has improved rheological properties, higher viscosity and pseudoplasticity, superior emulsification properties and decreased wettability compared to parental CMC. The biodeterioration of TsCMC was significantly reduced compared to parental CMC or other commercially used modified cellulose thickeners in water based paint industry. Improved rheological properties combined with low biodeterioration make TsCMC a promising new material for industrial applications with a potential to reduce the use of hazardous antimicrobial agents.