Browsing by Author "Koso, Tetyana"
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Item 2D Assignment and quantitative analysis of cellulose and oxidized celluloses using solution-state NMR spectroscopy(SPRINGER, 2020-09-01) Koso, Tetyana; Rico del Cerro, Daniel; Heikkinen, Sami; Nypelö, Tiina; Buffiere, Jean; Perea-Buceta, Jesus E.; Potthast, Antje; Rosenau, Thomas; Heikkinen, Harri; Maaheimo, Hannu; Isogai, Akira; Kilpeläinen, Ilkka; King, Alistair W.T.; School services, CHEM; Department of Bioproducts and Biosystems; Biohybrid Materials; University of Helsinki; University of Natural Resources and Life Sciences, Vienna; VTT Technical Research Centre of Finland; University of Tokyo; Chalmers University of TechnologyThe limited access to fast and facile general analytical methods for cellulosic and/or biocomposite materials currently stands as one of the main barriers for the progress of these disciplines. To that end, a diverse set of narrow analytical techniques are typically employed that often are time-consuming, costly, and/or not necessarily available on a daily basis for practitioners. Herein, we rigorously demonstrate a general quantitative NMR spectroscopic method for structural determination of crystalline cellulose samples. Our method relies on the use of a readily accessible ionic liquid electrolyte, tetrabutylphosphonium acetate ([P-4444][OAc]):DMSO-d(6), for the direct dissolution of biopolymeric samples. We utilize a series of model compounds and apply now classical (nitroxyl-radical and periodate) oxidation reactions to cellulose samples, to allow for accurate resonance assignment, using 2D NMR. Quantitative heteronuclear single quantum correlation (HSQC) was applied in the analysis of key samples to assess its applicability as a high-resolution technique for following cellulose surface modification. Quantitation using HSQC was possible, but only after applying T(2)correction to integral values. The comprehensive signal assignment of the diverse set of cellulosic species in this study constitutes a blueprint for the direct quantitative structural elucidation of crystalline lignocellulosic, in general, readily available solution-state NMR spectroscopy. [GRAPHICS] .Item Bioactive Fiber Foam Films from Cellulose and Willow Bark Extract with Improved Water Tolerance(American Chemical Society, 2024-02-20) Lohtander, Tia; Koso, Tetyana; Huynh, Ngoc; Hjelt, Tuomo; Gestranius, Marie; King, Alistair W.T.; Österberg, Monika; Arola, Suvi; Department of Bioproducts and Biosystems; Bioproduct Chemistry; VTT Technical Research Centre of FinlandCellulose-based materials are gaining increasing attention in the packaging industry as sustainable packaging material alternatives. Lignocellulosic polymers with high quantities of surface hydroxyls are inherently hydrophilic and hygroscopic, making them moisture-sensitive, which has been retarding the utilization of cellulosic materials in applications requiring high moisture resistance. Herein, we produced lightweight all-cellulose fiber foam films with improved water tolerance. The fiber foams were modified with willow bark extract (WBE) and alkyl ketene dimer (AKD). AKD improved the water stability, while the addition of WBE was found to improve the dry strength of the fiber foam films and bring additional functionalities, that is, antioxidant and ultraviolet protection properties, to the material. Additionally, WBE and AKD showed a synergistic effect in improving the hydrophobicity and water tolerance of the fiber foam films. Nuclear magnetic resonance (NMR) spectroscopy indicated that the interactions among WBE, cellulose, and AKD were physical, with no formation of covalent bonds. The findings of this study broaden the possibilities to utilize cellulose-based materials in high-value active packaging applications, for instance, for pharmaceutical and healthcare products or as water-resistant coatings for textiles, besides bulk packaging materials.Item Challenges in Synthesis and Analysis of Asymmetrically Grafted Cellulose Nanocrystals via Atom Transfer Radical Polymerization(AMERICAN CHEMICAL SOCIETY, 2021-06-14) Delepierre, Gwendoline; Heise, Katja; Malinen, Kiia; Koso, Tetyana; Pitkänen, Leena; Cranston, Emily D.; Kilpeläinen, Ilkka; Kostiainen, Mauri A.; Kontturi, Eero; Weder, Christoph; Zoppe, Justin O.; King, Alistair W.T.; Department of Bioproducts and Biosystems; Materials Chemistry of Cellulose; Biorefineries; Biohybrid Materials; University of Fribourg; Aalto University; University of Helsinki; University of British Columbia; Polytechnic University of CataloniaWhen cellulose nanocrystals (CNCs) are isolated from cellulose microfibrils, the parallel arrangement of the cellulose chains in the crystalline domains is retained so that all reducing end-groups (REGs) point to one crystallite end. This permits the selective chemical modification of one end of the CNCs. In this study, two reaction pathways are compared to selectively attach atom-transfer radical polymerization (ATRP) initiators to the REGs of CNCs, using reductive amination. This modification further enabled the site-specific grafting of the anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS) from the CNCs. Different analytical methods, including colorimetry and solution-state NMR analysis, were combined to confirm the REG-modification with ATRP-initiators and PSS. The achieved grafting yield was low due to either a limited conversion of the CNC REGs or side reactions on the polymerization initiator during the reductive amination. The end-tethered CNCs were easy to redisperse in water after freeze-drying, and the shear birefringence of colloidal suspensions is maintained after this process.Item Highly regioselective surface acetylation of cellulose and shaped cellulose constructs in the gas-phase(Royal Society of Chemistry, 2022-07-21) Koso, Tetyana; Beaumont, Marco; Tardy, Blaise L.; Rico del Cerro, Daniel; Eyley, Samuel; Thielemans, Wim; Rojas, Orlando J.; Kilpeläinen, Ilkka; King, Alistair W.T.; Department of Bioproducts and Biosystems; Bio-based Colloids and Materials; University of Helsinki; KU LeuvenGas-phase acylation is an attractive and sustainable method for modifying the surface properties of cellulosics. However, little is known concerning the regioselectivity of the chemistry, i.e., which cellulose hydroxyls are preferentially acylated and if acylation can be restricted to the surface, preserving crystallinities/morphologies. Consequently, we reexplore simple gas-phase acetylation of modern-day cellulosic building blocks - cellulose nanocrystals, pulps, dry-jet wet spun (regenerated cellulose) fibres and a nanocellulose-based aerogel. Using advanced analytics, we show that the gas-phase acetylation is highly regioselective for the C6-OH, a finding also supported by DFT-based transition-state modelling on a crystalloid surface. This contrasts with acid- and base-catalysed liquid-phase acetylation methods, highlighting that gas-phase chemistry is much more controllable, yet with similar kinetics, to the uncatalyzed liquid-phase reactions. Furthermore, this method preserves both the native (or regenerated) crystalline structure of the cellulose and the supramolecular morphology of even delicate cellulosic constructs (nanocellulose aerogel exhibiting chiral cholesteric liquid crystalline phases). Due to the soft nature of this chemistry and an ability to finely control the kinetics, yielding highly regioselective low degree of substitution products, we are convinced this method will facilitate the rapid adoption of precisely tailored and biodegradable cellulosic materials.Item Microwave hydrolysis, as a sustainable approach in the processing of seaweed for protein and nanocellulose management(Elsevier, 2024-03) Trubetskaya, Anna; Lê, Huy Quang; Leppiniemi, Jenni; Koso, Tetyana; Välisalmi, Teemu; Linder, Markus B.; Pisano, Italo; Dou, Jinze; Leahy, J. J.; Kontturi, Eero; Department of Bioproducts and Biosystems; Wood Chemistry; Biopolymer Chemistry and Engineering; Biomolecular Materials; Materials Chemistry of Cellulose; Tampere University; VTT Technical Research Centre of Finland; University of Limerick; Nord UniversityThe nature of marine biomass is very complex for a material scientist due to the large seasonal variation in the chemical composition that makes it difficult to prepare standardized products. A systematic investigation of the interaction of microwave irradiation with seaweed from Norway and Caribbean region was performed, covering a broad temperature range (130 → 170 °C) and without and with addition of ℽ-valerolactone (GVL) in ratios of 1:4 and 1:2. The temperatures above 150 °C and without addition of GVL led to the closure of mass balances up to 90 % that includes polysaccharides, “pseudo-lignin” fraction, fatty acids, and proteins. Fucoidan and mannose represented >50 % of all detected polysaccharides in ascophyllum nodosum (AN), while aegagropila linnaei (AL) contained mostly glucose. The presence of arabinose and rhamnose in the upper surface of the cell wall hinders the glucose release during microwave treatment. The differences in the polysaccharide composition among both algae samples hindered the definition of a parameters set that can be used in microwave treatment of various seaweed species. A large fraction of protein (> 95 %) remained in the seaweed solid residue. Higher amount of protein was determined in AL, which was dominated by leucine and lysine. Another potential barrier to the application of seaweed in industry is the limited knowledge on the chemical composition of “pseudo-lignin” and extractives. The total amino acid analysis was identified as the most accurate to characterize the protein yield and composition. The results showed that microwave treatment of seaweed is indeed a viable method for producing bioactives in the temperature range 120–150 °C, and proteins and nanocellulose at temperatures above 170 °C without using GVL. The microwave temperature and seaweed type played a dominating role in the mass closure balances leading to >95 % identified compound.Item Solution-state nuclear magnetic resonance spectroscopy of crystalline cellulosic materials using a direct dissolution ionic liquid electrolyte(Nature Publishing Group, 2023-07) Fliri, Lukas; Heise, Katja; Koso, Tetyana; Todorov, Aleksandar R.; del Cerro, Daniel Rico; Hietala, Sami; Fiskari, Juha; Kilpeläinen, Ilkka; Hummel, Michael; King, Alistair W.T.; Department of Bioproducts and Biosystems; Biopolymer Chemistry and Engineering; Materials Chemistry of Cellulose; University of Helsinki; Mid Sweden UniversityOwing to its high sustainable production capacity, cellulose represents a valuable feedstock for the development of more sustainable alternatives to currently used fossil fuel-based materials. Chemical analysis of cellulose remains challenging, and analytical techniques have not advanced as fast as the development of the proposed materials science applications. Crystalline cellulosic materials are insoluble in most solvents, which restricts direct analytical techniques to lower-resolution solid-state spectroscopy, destructive indirect procedures or to ‘old-school’ derivatization protocols. While investigating their use for biomass valorization, tetralkylphosphonium ionic liquids (ILs) exhibited advantageous properties for direct solution-state nuclear magnetic resonance (NMR) analysis of crystalline cellulose. After screening and optimization, the IL tetra-n-butylphosphonium acetate [P4444][OAc], diluted with dimethyl sulfoxide-d 6, was found to be the most promising partly deuterated solvent system for high-resolution solution-state NMR. The solvent system has been used for the measurement of both 1D and 2D experiments for a wide substrate scope, with excellent spectral quality and signal-to-noise, all with modest collection times. The procedure initially describes the scalable syntheses of an IL, in 24–72 h, of sufficient purity, yielding a stock electrolyte solution. The dissolution of cellulosic materials and preparation of NMR samples is presented, with pretreatment, concentration and dissolution time recommendations for different sample types. Also included is a set of recommended 1D and 2D NMR experiments with parameters optimized for an in-depth structural characterization of cellulosic materials. The time required for full characterization varies between a few hours and several days.Item Spatioselective surface chemistry for the production of functional and chemically anisotropic nanocellulose colloids(Royal Society of Chemistry, 2022-11-28) Heise, Katja; Koso, Tetyana; King, Alistair W.T.; Nypelö, Tiina; Penttilä, Paavo; Tardy, Blaise L.; Beaumont, Marco; Department of Bioproducts and Biosystems; Materials Chemistry of Cellulose; Wood Material Science; University of Helsinki; VTT Technical Research Centre of Finland; Chalmers University of Technology; Khalifa University of Science and Technology; University of Natural Resources and Life Sciences, ViennaMaximizing the benefits of nanomaterials from biomass requires unique considerations associated with their native chemical and physical structure. Both cellulose nanofibrils and nanocrystals are extracted from cellulose fibers via a top-down approach and have significantly advanced materials chemistry and set new benchmarks in the last decade. One major challenge has been to prepare defined and selectively modified nanocelluloses, which would, e.g., allow optimal particle interactions and thereby further improve the properties of processed materials. At the molecular and crystallite level, the surface of nanocelluloses offers an alternating chemical structure and functional groups of different reactivity, enabling straightforward avenues towards chemically anisotropic and molecularly patterned nanoparticles via spatioselective chemical modification. In this review, we will explain the influence and role of the multiscale hierarchy of cellulose fibers in chemical modifications, and critically discuss recent advances in selective surface chemistry of nanocelluloses. Finally, we will demonstrate the potential of those chemically anisotropic nanocelluloses in materials science and discuss challenges and opportunities in this field.Item Stable glycosylamines at the reducing ends of cellulose nanocrystals(Royal Society of Chemistry, 2023-08-07) Xia, Jingwen; Koso, Tetyana; Heise, Katja; Fliri, Lukas; Ressouche, Emilie; Majoinen, Johanna; Kostiainen, Mauri A.; Hietala, Sami; Hummel, Michael; Aseyev, Vladimir; Kilpeläinen, Ilkka; King, Alistair W.T.; Department of Bioproducts and Biosystems; Materials Chemistry of Cellulose; Biopolymer Chemistry and Engineering; Bio-based Colloids and Materials; Biohybrid Materials; University of Helsinki; VTT Technical Research Centre of FinlandThe reaction of reducing end groups in cellulose nanocrystals with dodecylamine was examined. Using a direct-dissolution solution-state NMR protocol, the regioselective formation of glucosylamines was shown. This provides an elegant approach to sustainably functionalize these bio-based nanomaterials, that may not require further reduction to more stable secondary amines.