Figure 4 - uploaded by Carina Olsson
Content may be subject to copyright.
Source publication
Corpora non agunt nisi solute (substances do not react unless dissolved) is a statement with roots in ancient alchemy, and still has some validity today. Unlike many petroleum based polymers, cellulose will not melt but decompose at elevated temperatures. To get the cellulose in liquid form, it has to be dissolved or chemically modified. Homogeneou...
Context in source publication
Context 1
... of the empirical Kamlet-Taft solvatochromic relationship are used to calculate the hydrogen bond donor (α), hydrogen bond acceptor (β), and dipolarity/polarizability (π*) properties of solvents as contributing to overall solvent polarity. This is done by UV/Vis spectroscopy to monitor the interactions of the substrate with chosen indicators of e.g. the ones shown in Figure 4. Numerous solvatochromic indicator dyes are available [25]. ...
Citations
... In addition, multitude number of direct solvents have been developed for analytical work as well as chemical modifications of cellulose and dissolution-coagulation processing., namely, alkali containing solvents e.g. NaOH(aq)/urea (Olsson & Westman, 2013), dimethylacetamide/lithium chloride (DMAc/LiCl) (Mccormick et al., 1985), phosphoric acid (Boerstoel et al., 2001), dimethyl sulfoxide/tetrabutylammonium fluoride (DMSO/TBAF) (Liebert & Heinze, 2001), ionic liquids (Zhu et al., 2006) and quaternary ammonium hydroxides (Kostag et al., 2018). Yet, low dissolution capacity, side reactions under required dissolution conditions and cellulose degradation are examples of set-backs which arise the need to actively develop new solvents for cellulose. ...
... However, the solubility of cel-lulose in conventional solvents is a challenge due to its extensive inter-and intramolecular hydrogen bonding. Industrially used derivatizing solvents such as carbon disulfide (CS 2 ) or N-methylmorpholine N-oxide (NMMO) have several disadvantages such as toxicity, insufficient solvent stability, degradation of both cellulose and solvent and significant stabilizer requirements (Azimi et al. 2022, Olsson andWestman 2013). A direct dissolution of raw cellulose not only simplifies the processing but also circumvents byproduct generation. ...
We present the extension of our all-atom force field BILFF (Bio-polymers in Ionic Liquids Force Field) to the co-solvent dimethyl sulfoxide (DMSO). BILFF already includes force field parameters for several imidazolium- and triazolium-based ionic liquids, water, and the bio-molecule cellulose. DMSO is known to increase the cellulose solubility of [EMIm][OAc] when applied as an additive. Our focus is on a correct reproduction of the hydrogen bonds in the ternary system of [EMIm]+\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^+$$\end{document}, [OAc]-\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^-$$\end{document}, water and DMSO compared to ab initio molecular dynamics simulations. For this purpose, the results from force field MD simulations such as radial and distance–angle distribution functions are compared with the reference AIMD simulation. Based on this, the force field parameters (starting from OPLS–AA) are iteratively adjusted. Four systems, pure and aqueous DMSO as well as DMSO in pure and aqueous [EMIm][OAc], are considered and additionally compared to DMSO-free [EMIm][OAc] systems. A very good agreement with respect to the microstructure of the quantum chemical reference simulations as well as to experimental data such as density, diffusion coefficients, enthalpy of vaporization, compressibility and thermal expansion coefficients can be observed over a wide temperature range. BILFF thus enables accurate simulations of larger systems of solvated cellulose in (aqueous) [EMIm][OAc] and the co-solvent DMSO.
... The regular assembly of cellobiose molecules gives native cellulose a certain chemical polarity. Indeed, the cellulose molecule has a relative polarity since its two ends have different chemical functionality: a non-reducing end in the C4 position and a reducing end in the Cl position due to a hemiacetal function of the terminal secondary alcohol ( Figure 5) (Olsson and Westm, 2013). (Olsson and Westm, 2013) The cellulose chain's polarity allows for the parallel or antiparallel arrangement of the chains within the cellulose crystal. ...
... Indeed, the cellulose molecule has a relative polarity since its two ends have different chemical functionality: a non-reducing end in the C4 position and a reducing end in the Cl position due to a hemiacetal function of the terminal secondary alcohol ( Figure 5) (Olsson and Westm, 2013). (Olsson and Westm, 2013) The cellulose chain's polarity allows for the parallel or antiparallel arrangement of the chains within the cellulose crystal. There are two conceivable layouts in the crystal: either all of the reducing ends are on the same side (organization in parallel chains) or they alternate (organization in antiparallel chains). ...
Every year, around 140 million tons of synthetic polymers are produced worldwide. Because of their non-degradability in landfills, traditional plastics made with petroleum-based synthetic polymers have caused considerable environmental difficulties. Aware of the growing concern, the proactive approach involves the investigation of polymers derived from renewable and sustainable materials for the production of bioproducts. This strategy provides a viable and novel alternative for reducing greenhouse gas and hazardous emissions, increasing energy efficiency, and reducing the use of nonrenewable resources. As a result, much study has been conducted on numerous types of biopolymers, examining their characteristics and potential medical applications. The results of this research show that cellulose is the most used biopolymer thanks to its biodegradability and various biological properties. To improve these properties, it is desirable to combine cellulose with biomass which bears important biological properties. The choice was the use of Moroccan natural phosphate thanks to the important reserves of phosphate rocks in Morocco, for the preparation of hydroxyapatite and combining them with the prepared cellulose, and then the elaboration of HAp-Cellulose biocomposite, by the method of 3D printing. this biocomposite will be used in the biomedical field.
... Cellulose was first brought to light by French chemist Payen (1838) by providing the first explanation of the chemical structure of cellulose (Olsson and Westman 2013). Subsequently, the chemical and physical attributes of cellulose have been studied thoroughly. ...
All plants naturally contain cellulose which is a linear biopolymer. In addition to being the most common natural polymeric material on the global scale, it also has numerous advantages, such as comparatively low density, good biocompatibility, as well as noteworthy mechanical strength at a reasonable price. Lignocellulosic materials are generally converted into cellulose nanofibers or cellulose nanocrystals, commonly known as nanocellulose using mechanical or chemical or a combination of both the methods. In recent years, nanocellulose has appeared as one of the most notable green materials for diverse applications. Nanoscaled cellulose has also achieved commendable recognition owing to its intrinsic properties like more surface area, high mechanical strength, abundance and renewability, less toxicity, biocompatibility, decomposability making it a perfect and ideal nanomaterial. This review provides a broad introduction to nanocellulose, its types and various methods of extraction. In addition, a number of recent and forthcoming applications for nanocellulose have also been discussed, including wood adhesives, surface coatings, biomedical, wastewater treatment and in developing novel bio-based nanocomposites.
... Intramolecular hydrogen bonding stiffens the polymer chains, while intermolecular hydrogen bonding facilitates the arrangement of these linear polymers into sheet-like structures. These sheets are densely packed together through hydrophobic interactions and form crystalline structures [22,23]. To dissolve cellulose in ILs, the intermolecular hydrogen bonds between the cellulose strands must be disrupted and replaced by interactions with the solvent. ...
We present an extension of our previously developed all-atom force field BILFF (Bio-polymers in Ionic Liquids Force Field) to three different ionic liquids: 1-ethyl-3-methyl-1,2,3-triazolium acetate ([EMTr][OAc]), 1-ethyl-3-methyl-1,2,3-triazolium benzoate ([EMTr][OBz]), and 1-ethyl-3-methylimidazolium benzoate ([EMIm][OBz]). These ionic liquids are of practical importance as they have the ability to dissolve significant amounts of cellulose even at room temperature. Our force field is optimized to accurately reproduce the strong hydrogen bonding in the system with nearly quantum chemical accuracy. A very good agreement between the microstructure of the quantum chemical simulations over a wide temperature range and experimental density data with the results of BILFF were observed. Non-trivial effects, such as the solvation shell structure and π–π stacking of the cations, are also accurately reproduced. Our force field enables accurate simulations of larger systems, such as solvated cellulose in different (aqueous) ionic liquids, and is the first to present the optimized parameters for mixtures of these solvents and water.
... These results showed that increasing CMC concentration decreased the resistance of bioplastics in acidic environments. CMC was known to enable swelling within water or solutions, thereby permitting the penetration of strong acids into the cellulose structure, leading to its dissolution (Olsson and Westm, 2013). Fig. 10 shows the results of the chemical resistance testing of bioplastics in an alkaline environment. ...
Synthetic plastics are generally challenging to degrade in the environment and capable of releasing harmful chemicals upon improper disposal, endangering both wildlife and humans. Therefore, this study aimed to develop cellulose-based bioplastics from corn husk waste and carboxymethyl cellulose (CMC) using sorbitol as a plasticizer. The effect of corn husk delignification, CMC addition, and variations in sorbitol concentration were investigated. The results of Chesson's test showed that the delignification process increased cellulose content to 77.30% and decreased lignin content to 3.6%. Additionally, Fourier-transform infrared (FTIR) demonstrated the effective removal of lignin and hemicellulose components from corn husk fibers. X-ray diffraction (XRD) analysis indicated the elevation of corn husk crystallinity from 63.97% to 80.83% after the treatment. Scanning electron microscopy (SEM) revealed bioplastic morphologies featuring porous and smooth surfaces juxtaposed with uneven and lumpy characteristics. Biodegradation assessment yielded a peak value of 33.4% under a composition comprising 3% CMC and 1.5% sorbitol. The swelling test performed on corn husk bioplastic samples produced values ranging from 52.89 to 66%, with the highest value recorded at 66% for the bioplastic formulation consisting of 3% CMC and 1.5% sorbitol. Resistance testing on samples containing 3% CMC, with a soaking time of four days in acidic environments, indicated a maximum weight loss of 61.3% (10% H 2 SO 4) and 62.5% (20% H 2 SO 4). Alkaline resistance tests displayed a 95.6% (10% NaOH) and 94.6% (20% NaOH) weight loss under similar conditions. These results suggested the potential utility of corn husk waste as a viable bioplastic source, promoting the circular economy concept in Indonesia while mitigating greenhouse gas emissions, reducing waste volume, and increasing rural economic growth.
... This is because of the toxic nature of the used organic solvent in SOPOS. When DMAc is combined with LiCl, it becomes highly toxic, corrosive, and volatile, increasing health and safety risks and concerns [42,43]. ...
Oil spill remediation plays a vital role in mitigating the environmental impacts caused by oil spills. The chemical method is one of the widely recognized approaches in chemical surfactants. However, the most commonly used chemical surfactants are toxic and non-biodegradable. Herein, two biocompatible and biodegradable surfactants were synthesized from orange peel using the ionic liquid 1-butyl-3-methylimidazolium chloride (BMIMCl) and organic solvent dimethylacetamide (CH3CN(CH3)2) as reaction media. The acronyms SOPIL and SOPOS refer to the surfactants prepared with BMIMCl and dimethylacetamide, respectively. The surface tension, dispersant effectiveness, optical microscopy, and emulsion stability test were conducted to examine the comparative performance of the synthesized surfactants. The Baffled flask test (BFT) was carried out to determine the dispersion effectiveness. The toxicity test was performed against zebrafish (Danio rerio), whereas the closed bottle test (CBT) evaluated biodegradability. The results revealed that the critical micelle concentration (CMC) value of SOPIL was lower (8.57 mg/L) than that of SOPOS (9.42 mg/L). The dispersion effectiveness values for SOPIL and SOPOS were 69.78% and 40.30%, respectively. The acute toxicity test demonstrated that SOPIL was ‘practically non-toxic’ with a median lethal concentration of more than 1000 mg/L after 96 h. The biodegradation rate was recorded as higher than 60% for both surfactants within 28 days, demonstrating their readily biodegradable nature. Considering these attributes, biocompatible and biodegradable surfactants derived from orange peel emerge as a promising and sustainable alternative for oil spill remediation.
... Direct dissolution of cellulose, without derivatization, may simplify the production of cellulose hydrogels because many steps are omitted. A direct solvent is also considerably straightforward to recycle because no by products are generated (Olsson and Westman 2013). Among all solvents used to dissolve cellulose, aqueous sodium hydroxide (NaOH)/urea solution is gaining increased attention owing to its environment friendliness, simplicity, low cost, and low toxicity (Yang et al., 2020;Zainal et al., 2020). ...
Hydrogels are modern dermal drug-delivery media which can hold a huge amount of water and modify their structure to enable spontaneous response to temperature change and are thus attractive to overcome the limitations of conventional drug-delivery media. In this study, a sustainable method was developed to synthesize thermoresponsive Pluronic F127 (PF127) composite hydrogel reinforced by cellulose extracted from oil palm empty fruit bunches (OPEFBs). The thermoresponsive cellulose/PF127 composite hydrogels were formulated by dissolving OPEFB-extracted cellulose in aqueous sodium hydroxide/urea solution prior to mixing with PF127 polymer at low temperature. The performance of the synthesized thermoresponsive cellulose/PF127 composite hydrogels was evaluated in terms of their swelling ratio, percentage of degradation, and in vitro silver sulfadiazine (AgSD) drug release. PCT20 thermoresponsive cellulose/PF127 composite hydrogel with 20 w/v% PF127 and 3 w/v% OPEFB cellulose showed high mechanical strength (storage modulus and complex viscosity values of 20.90 kPa and 2.09 kPa s, respectively), relatively high swelling ratio (3.63 ± 0.43), and prolonged release of AgSD (t50% value of 4 h) compared with PCT17-PCT19 thermoresponsive cellulose/PF127 composite hydrogels. Besides, AgSD-loaded thermo-responsive cellulose/PF127 composite hydrogels showed relatively good inhibitory activity against the Staphylococcus aureus, Escherichia coli, Enterococcus faecalis, Enterococcus faecium, Streptococcus pyogenes, and Klebsiella pneumoniae bacteria. The exploration of thermoresponsive cellulose/PF127 composite hydrogel from OPEFBs can promote sustainable, environment-friendly, and cost-effective drug delivery systems by using abundant agricultural biomass.
... At the same time, stacking the sheets into the three-dimensional crystal structures of the cellulose material involves hydrophobic interactions. Therefore, it has been suggested that hydrophobic interactions contribute favorably to stabilizing a crystal-like stacked structure (Bergenstråhle et al. 2010;Olsson and Westman 2013). It is evidenced in Table 2 that the interplanar distances and apparent crystal size belonging to the three reflections do not present significant changes. ...
Cellulose from vegetable sources is the most abundant biopolymer on earth. In plants, cellulose is a reinforcement element that conforms to a hierarchical structure. Cellulose micro-/nanofibers can be isolated from the cell wall by top-down strategies involving mechanical processes to be used in applications as a reinforcing material. Nonetheless, its use has been limited as its extraction in an aqueous medium is unfavorable when employed in low-hydrophilic matrices. Therefore, this work proposes a novel homogenization route in which cellulose micro-/nanofibers are directly obtained and dispersed in propylene glycol (PG), which generates more possibilities for these (nano) structures in applications that require water-free environments. Moreover, the influence on the cycle numbers in the morphological, chemical, thermal, and rheological properties was researched. Thus, the obtained micro-/nanofibers presented TEM diameters even below 20 nm. XRD analysis evidenced crystalline planes located at $$1\overline{1 }0$$ 1 1 ¯ 0 , 110, and 200, and crystallinity degree values up to 80%. Also, FTIR spectra bands in 3340 cm ⁻¹ , 2890 cm ⁻¹ , 1314 cm ⁻¹ , and in the fingerprint region corresponded to native cellulose Iβ. FTIR and TGA confirmed no influence of mechanical cycles on cellulose fibers’ chemical and thermal properties. Furthermore, the increase in the cycle number evidenced a shear-thinning rheological behavior of the suspensions. Considering the above results, it was concluded that the proposed high-pressure homogenization within PG is an approach for vegetable nanocellulose homogenization while maintaining high crystallinity, thermal, and chemical features with huge importance for subsequent processes in the development of nanocomposites with hydrophilic matrices for industrial applications.
Graphical abstract
... The most signi cant advantage is the easy availability in nature, from which a relatively low product price comes. Another advantage is cellulose properties, which meet three fundamental requirements for biomaterials -biocompatibility, bioactivity and biomechanics (Hickey & Pelling, 2019;Olsson & Westm, 2013). Carboxymethyl cellulose (CMC) is an anionic, water-soluble cellulose derivative. ...
Bleeding is one of the most commonly occurring injuries; it can be painful and even life-threatening condition. The hemostats are substances that promote blood clotting and fasten hemostasis. In this paper, we evaluated the hemostatic effect of freeze-dried wound dressings based on equine collagen, porcine collagen, fibrous carboxymethyl cellulose (CMC) and their mixtures. The wound dressings were investigated for their morphological structure, chemical structure, absorption properties, in vitro hemostasis, cytotoxicity assay and lastly, for i n vivo hemostasis. We have found out that adding fibrous CMC into collagen-based hemostatic wound dressings creates a strong synergistic effect, which significantly improves absorption capacity by almost doubling it, as well as supports clotting time. Based on the in vivo studies on partial nephrectomy in rats, the time needed for achieving hemostasis was significantly lower due to the synergy of collagen and CMC. Our materials were compared to the commonly used hemostatic sealing patch on the market (Tachosil) during the in vivo testing, and sample of a mixture of equine collagen and CMC showed better hemostatic efficacy.
