Browsing by Subject "SPRUCE GALACTOGLUCOMANNANS"

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  • Morais de Carvalho, Danila; Lahtinen, Maarit; Bhattarai, Mamata; Lawoko, Martin; Mikkonen, Kirsi S. (2021)
    Hemicellulose-rich wood extracts show efficient capacity to adsorb at emulsion interfaces and stabilize them. Their functionality is enhanced by lignin moieties accompanying the hemicellulose structures, in the form of lignin-carbohydrate complexes (LCCs) and, potentially, other non-covalent associations. The formation and stability of emulsions is determined by their interfacial regions. These are largely unexplored assemblies when formed from natural stabilizers with a complex chemical composition. Understanding the structure of the interfacial region could facilitate both designing the extraction processes of abundant biomasses and unraveling a valuable industrial application potential for the extracts. Herein, we characterized the LCCs from the interface of oil-in-water emulsions stabilized by galactoglucomannan (GGM) or glucuronoxylan (GX)-rich wood extracts, using two-dimensional nuclear magnetic resonance (NMR) spectroscopy analysis. The type of covalent linkage between residual lignin and hemicelluloses determined their partitioning between the continuous and interfacial emulsion phases. Benzylether structures, only found in the interface, were suggested to participate in the physical stabilization of the emulsion droplets. In turn, the phenylglycosides, preferentially observed in the continuous phase, were suggested to interact with adsorbed stabilizers by electrostatic interaction. More hydrophobic lignin structures, such as guaiacyl lignin type, dibenzodioxocin substructures, and certain end groups also contributed to droplet stabilization. The elucidation of such attributes is of paramount importance for the biorefinery industry, enabling the optimization of extraction processes for the preparation of wood-based stabilizers and designed interfaces for novel and sustainable emulsion systems.
  • Valoppi, Fabio; Lahtinen, Maarit; Bhattarai, Mamata; Kirjoranta, Satu; Juntti, Venla; Peltonen, Leena; Kilpeläinen, Petri O.; Mikkonen, Kirsi S. (2019)
    With the emerging bio-based technologies, the fractionation of complex biomass is essential to obtain value-added functional molecules for material, chemical, and energy production. The refining process of biomasses often requires the use of solvents and hazardous chemicals, whose removal after fractionation decreases the eco-compatibility of the process and increases the cost and time of the refinement. Softwood extracts obtained through the environmentally friendly pressurized hot water extraction are heterogeneous mixtures rich in hemicelluloses and lignin. Here we developed a simple, fast, organic solvent-free, and sustainable method to fractionate softwood extracts using centrifugal forces. The characteristics of each obtained fraction in terms of composition, macromolecular properties (particle size, molar mass, charge), interfacial activity, and stabilization capacity were highly dependent on the centrifugal force and time applied. The hemicellulose and lignin contents in the fractions were balanced by centrifugal forces to obtain functional emulsifiers that efficiently stabilized the oil/water interface. Through fractionation of softwood extracts, we also found that both the hemicelluloses and lignin particles are involved in emulsion interface formation and stabilization. Centrifugation is a scalable concept that can be feasibly and easily introduced into the biorefinery system and used to optimize the composition of biomass fractions for targeted purposes.
  • Bhattarai, Mamata; Sulaeva, Irina; Pitkänen, Leena; Kontro, Inkeri; Tenkanen, Maija; Potthast, Antje; Mikkonen, Kirsi S. (2020)
    Development of a sustainable bioeconomy requires valorization of renewable resources, such as wood hemicelluloses. The intra- and inter-molecular associations of hemicelluloses within themselves or with other wood components can result in complex macromolecular features. These features exhibit functionality as hydrocolloids, however macromolecular characterization of these heterogeneous materials are challenging using conventional techniques such as size-exclusion chromatography. We studied galactoglucomannans (GGM) -rich softwood extracts at two grades of purity—as crude extract and after ethanol-precipitation. Asymmetrical flow field-flow fractionation (AF4) was optimized and utilized to fractionate size classes in GGM extracts, and subsequent characterization was performed with light scattering and microscopy techniques. Both GGM extracts contained polysaccharides of around 10,000 g/mol molar mass, and colloidal assemblies and/or particles in sub-micron size range. The optimized AF4 method facilitates the characterization of complex biomass-derived carbohydrates without pre-fractionation, and provides valuable understanding of their unique macromolecular features for their future application in food, pharmaceuticals, and cosmetics.
  • Aaen, Ragnhild; Lehtonen, Mari; Mikkonen, Kirsi S.; Syverud, Kristin (2021)
    The use of wood-derived cellulose nanofibrils (CNFs) or galactoglucomannans (GGM) for emulsion stabilization may be a way to obtain new environmentally friendly emulsifiers. Both have previously been shown to act as emulsifiers, offering physical, and in the case of GGM, oxidative stability to the emulsions. Oil-in-water emulsions were prepared using highly charged (1352 ± 5 µmol/g) CNFs prepared by TEMPO-mediated oxidation, or a coarser commercial CNF, less charged (≈ 70 µmol/g) quality (Exilva forte), and the physical emulsion stability was evaluated by use of droplet size distributions, micrographs and visual appearance. The highly charged, finely fibrillated CNFs stabilized the emulsions more effectively than the coarser, lower charged CNFs, probably due to higher electrostatic repulsions between the fibrils, and a higher surface coverage of the oil droplets due to thinner fibrils. At a constant CNF/oil ratio, the lowest CNF and oil concentration of 0.01 wt % CNFs and 5 wt % oil gave the most stable emulsion, with good stability toward coalescence, but not towards creaming. GGM (0.5 or 1.0 wt %) stabilized emulsions (5 wt % oil) showed no creaming behavior, but a clear bimodal distribution with some destabilization over the storage time of 1 month. Combinations of CNFs and GGM for stabilization of emulsions with 5 wt % oil, provided good stability towards creaming and a slower emulsion destabilization than for GGM alone. GGM could also improve the stability towards oxidation by delaying the initiation of lipid oxidation. Use of CNFs and combinations of GGM and CNFs can thus be away to obtain stable emulsions, such as mayonnaise and beverage emulsions.
  • Mikkonen, Kirsi S.; Kirjoranta, Satu; Xu, Chunlin; Hemming, Jarl; Pranovich, Andrey; Bhattarai, Mamata; Peltonen, Leena; Kilpeläinen, Petri; Maina, Ndegwa; Tenkanen, Maija; Lehtonen, Mari; Willför, Stefan (2019)
    Wood biorefining currently involves large-scale industrial processes where a notable portion of raw materials, namely hemicelluloses and lignin, are either lost with the process water, degraded, or burnt for energy. Value added utilization of polymeric hemicelluloses is challenging due to their intermediate molar mass and the presence of other wood components, such as phenolic residues or wood extractives. Oil-in-water (O/W) emulsions represent a diverse and abundant class of applications in which the natural properties of wood hemicelluloses are beneficial. In the current work, we present highly promising new technical alkyd paint emulsion systems stabilized with hardwood glucuronoxylans (GX) and softwood galactoglucomannans (GGM). Samples from three isolation methods and their further fractionation by ethanol precipitation were systematically compared with regard to hemicellulose composition, interfacial activity, and functionality in emulsions. Emulsification of alkyd resins was successful with both GX and GGM obtained by various biorefining strategies. The highest emulsion stability over storage was achieved using crude non-purified GX and GGM fractions, and was correlated with the presence of phenolic compounds and extractives, interfacial activity, and small droplet size. Hardwood GX and softwood GGM are envisioned as natural emulsifiers of alkyd O/W emulsions, which are examples of diverse and abundantly-used technical dispersions. This study can be utilized as a guideline for targeted extraction of hemicelluloses with desired functionality, and as a protocol for developing environmentally-compatible industrial dispersions.
  • Kirjoranta, Satu; Knaapila, Antti; Kilpelainen, Petri; Mikkonen, Kirsi S. (2020)
    Wood is an abundant and sustainable source of emerging food ingredients, namely hemicelluloses that fulfil a number of requirements for functional hydrocolloids. Hemicelluloses, especially spruce galactoglucomannans (GGM) and birch glucuronoxylans (GX), have potential to be used as stabilizers in various foods such as yogurts, beverages, dressings, and desserts. However, in addition to good technological functionality, safety, and low price, the applicability and market potential of new hydrocolloids is determined by their sensory properties. The present study reports, for the first time, the sensory profile of spruce GGM and birch GX in food. Sensory profiles from generic descriptive analysis of GGM- and GX-rich extracts, processed by spray drying or ethanol precipitation, were compared in three types of model food systems: water solutions, yogurt with solutions, and yogurt with emulsions stabilized by GGM or GX. Gum Arabic was included for comparison with a commercial ingredient known to have a mild flavor. The results showed that GGM and GX have a woody flavor, which can be reduced by ethanol precipitation and, in yogurt, masked by other food ingredients.
  • Mikkonen, Kirsi S. (2020)
    Wood biomass is an abundant renewable source of materials, but due to the accelerating depletion of natural resources, it is important to explore new ways to use it in a more sustainable manner. Modern technologies enable the recovery and valorization of the main components of wood—namely, cellulose, lignin, and hemicelluloses—contributing to sustainability. However, the method of isolation and resulting structure and purity of lignocellulosic materials determine their functionality and applicability. This review discusses the properties of all three main wood-based compounds that can stabilize emulsions, a class of industrial dispersions that are widely used in life science applications and chemicals. Due to the multi-billion-dollar annual market for hydrocolloids, the food, pharmaceutical, cosmetic, coating, and paint industries are actively seeking new sustainable emulsion stabilizers that fulfill the demanding requirements regarding safety and functionality. Wood-derived stabilizers facilitate various mechanisms involved in emulsion stabilization: (1) development of amphiphilic structures that decrease interfacial tension, (2) stabilization of interfaces by particles according to the Pickering theory, and (3) increase in the viscosity of emulsions’ continuous phase. This review presents pathways for treating cellulose, lignin, and hemicelluloses to achieve efficient stabilization and provides suggestions for their broad use in emulsions.