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Adsorption is a relatively simple wastewater treatment method that has the potential to mitigate the impacts of pharmaceutical pollution. This requires the development of reusable adsorbents that can simultaneously remove pharmaceuticals of varying chemical structure and properties. Here, the adsorption potential of nanostructured wood-based adsorbents towards different pharmaceuticals in a multi-component system was investigated. The adsorbents in the form of macroporous cryogels were prepared by anchoring lignin nanoparticles (LNPs) to the nanocellulose network via electrostatic attraction. The naturally anionic LNPs were anchored to cationic cellulose nanofibrils (cCNF) and the cationic LNPs (cLNPs) were combined with anionic TEMPO-oxidized CNF (TCNF), producing two sets of nanocellulose-based cryogels that also differed in their overall surface charge density. The cryogels, prepared by freeze-drying, showed layered cellulosic sheets randomly decorated with spherical lignin on the surface. They exhibited varying selectivity and efficiency in removing pharmaceuticals with differing aromaticity, polarity and ionic characters. Their adsorption potential was also affected by the type (unmodified or cationic), amount and morphology of the lignin nanomaterials, as well as the pH of the pharmaceutical solution. Overall, the findings revealed that LNPs or cLNPs can act as functionalizing and crosslinking agents to nanocellulose-based cryogels. Despite the decrease in the overall positive surface charge, the addition of LNPs to the cCNF-based cryogels showed enhanced adsorption, not only towards the anionic aromatic pharmaceutical diclofenac but also towards the aromatic cationic metoprolol (MPL) and tramadol (TRA) and neutral aromatic carbamazepine. The addition of cLNPs to TCNF-based cryogels improved the adsorption of MPL and TRA despite the decrease in the net negative surface charge. The improved adsorption was attributed to modes of removal other than electrostatic attraction, and they could be 7C-7C aromatic ring or hydrophobic interactions brought by the addition of LNPs or cLNPs. However, significant improvement was only found if the ratio of LNPs or cLNPs to nanocellulose was 0.6:1 or higher and with spherical lignin nanomaterials. As crosslinking agents, the LNPs or cLNPs affected the rheological behavior of the gels, and increased the firmness and decreased the water holding capacity of the corresponding cryogels. The resistance of the cryogels towards disintegration with exposure to water also improved with crosslinking, which eventually enabled the cryogels, especially the TCNF-based one, to be regenerated and reused for five cycles of adsorption-desorption experiment for the model pharmaceutical MPL. Thus, this study opened new opportunities to utilize LNPs in providing nanocellulose-based adsorbents with additional functional groups, which were otherwise often achieved by rigorous chemical modifications, at the same time, crosslinking the nanocellulose network.

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.

Pharmaceuticals are emerging water pollutants that pose a global threat to the sustainability and safety of aquatic resources. To mitigate their potential hazardous impacts, one of the keys is to address the removal of pharmaceutical residues from wastewaters. In this study, adsorption utilizing nanostructured wood-based adsorbents is viewed as a simple and versatile wastewater treatment method that can be adapted to remove pharmaceutical pollutants. To realize this potential, there is a need to understand the interaction of wood-based nanomaterials towards various types of pharmaceuticals. Thus, this study characterized and investigated the adsorption potential of the two common wood-based nanomaterials, the nanocelluloses and lignin nanoparticles (LNPs), towards various types of pharmaceuticals. The unmodified and cationized LNPs from hardwood and softwood lignin and nanocelluloses (TEMPO-oxidized cellulose nanofibrils (TCNF), cellulose and lignocellulose nanofibrils) were characterized for their morphology, zeta potential and surface charge density at different pHs. The adsorption capacity was determined from a multi-analyte adsorption system consisting of seven pharmaceuticals with different chemical characteristics (aromatic, non-aromatic, anionic, cationic, and neutral). Overall, the LNPs, with their polyaromatic structure, adsorbed a wider range of pharmaceuticals than the nanocelluloses. Among the nanocelluloses, the TCNF exhibited the highest adsorption capacity for cationic pharmaceuticals. Based on these findings, LNPs and TCNF are promising materials that can be combined to construct novel nanostructured adsorbents for pharmaceutical pollutants in water. The interaction of different pharmaceuticals with LNPs and nanocelluloses as revealed in this study can also be beneficial in other applications, such as drug encapsulation and release.

The interest on the digestive fate of oleogels, i.e., substitutes for solid fats rich in liquid oil, have pushed re-searchers to use the widely adopted INFOGEST protocol for static in vitro digestion. However, this protocol was originally designed to simulate the digestibility of conventional foods and to accommodate the large fraction of oil in oleogels, researchers have deliberately modified the INFOGEST protocol, inadvertently leading to results difficult to be compared. In this study, we highlighted possible problems that may arise during oleogel simulated digestion such as under-or overestimation of oleogel lipolysis. The effect of oleogel amount, oleogelator type and concentration, and shear applied during digestion on the rate and extent of oleogel digestion was studied. The release of fatty acids during the application of INFOGEST protocol was monitored using the pH-stat method and compared to those analyzed by HPLC-ELSD. Oleogels' structural information was obtained using brightfield, polarized, and fluorescence microscopy, and DSC. We determined that lipolysis of ethylcellulose oleogels follow the "interaction with enzymes and bile salts " pattern, whereas that of wax oleogels follow the "disintegration of oleogel and interaction with enzymes and bile salts ". We also observed that the chemical composition of wax, crystal morphology, and crystal distribution do not alter the lipolysis of oil entrapped inside the wax crystals. We finally recommended a few minimal but fundamental modifications to the INFOGEST protocol to achieve more reliable results from the static in vitro digestion of oleogels and possibly other lipid-based systems.

The most commonly-used and effective wall materials (WMs) for spray-dried microencapsulation of bioactive compounds are either costly, or derived from unsustainable sources, which lead to an increasing demand for alternatives derived from sustainable and natural sources, with low calories and low cost. Wood hemicelluloses obtained from by-products of forest industries appear to be attractive alternatives as they have been reported to have good emulsifying properties, low viscosity at high concentrations, high heat stability and low heat transfer. Here, we investigated the applicability of spruce galactoglucomannans (GGM) and birch glucuronoxylans (GX), to encapsulate flaxseed oil (FO, polyunsaturated fatty acid-rich plant based oil) by spray drying; and the results were compared to those of the highly effective WM, gum Arabic (GA). It was found that depending on solid ratios of WM:FO (1:1, 3:1 and 5:1), encapsulation efficiency of GGM was 88–96%, and GX was 63–98%. At the same encapsulation ratio, both GGM and GX had higher encapsulation efficiency than GA (49–92%) due to their ability to produce feed emulsions with a smaller oil droplet size and higher physical stability. In addition, the presence of phenolic residues in GGM and GX powders enabled them to have a greater ability to protect oil from oxidation during spray drying than GA. Physiochemical properties of encapsulated powders including thermal properties, morphology, molecular structure, particle size and water adsorption intake are also investigated. The study has explored a new value-added proposition for wood hemicelluloses which can be used as effective WMs in the production of microcapsules of polyunsaturated fatty acid-rich oils for healthy and functional products in food, pharmaceutical and cosmetic industries.

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.

Tree bark is a highly specialized array of tissues that plays important roles in plant protection and development. Bark tissues develop from two lateral meristems; the phellogen (cork cambium) produces the outermost stem-environment barrier called the periderm, while the vascular cambium contributes with phloem tissues. Although bark is diverse in terms of tissues, functions and species, it remains understudied at higher resolution. We dissected the stem of silver birch (Betula pendula) into eight major tissue types, and characterized these by a combined transcriptomics and metabolomics approach. We further analyzed the varying bark types within the Betulaceae family. The two meristems had a distinct contribution to the stem transcriptomic landscape. Furthermore, inter- and intraspecies analyses illustrated the unique molecular profile of the phellem. We identified multiple tissue-specific metabolic pathways, such as the mevalonate/betulin biosynthesis pathway, that displayed differential evolution within the Betulaceae. A detailed analysis of suberin and betulin biosynthesis pathways identified a set of underlying regulators and highlighted the important role of local, small-scale gene duplication events in the evolution of metabolic pathways. This work reveals the transcriptome and metabolic diversity among bark tissues and provides insights to its development and evolution, as well as its biotechnological applications. Published version

The increasing public awareness of health and sustainability has prompted the development of functional foods rich in health-promoting ingredients. Processing technologies and sustainable multifunctional ingredients are needed for structuring these formulations. Spruce galactoglucomannan (GGM), the main hemicelluloses in softwood cell walls, are an abundantly available, emerging sustainable food hydrocolloid that have the ability to efficiently emulsify and stabilize oil-in-water emulsions. In this study, we illustrate how this lignocellulosic stabilizer affects the digestion of polyunsaturated fatty acids (PUFAs) in vitro. A 100% decrease in the initial TAG content was observed during the in vitro digestion, suggesting that complete hydrolysis of the TAGs was achieved by the digestive enzymes. Besides, no release of mono-, di-, and oligosaccharides or phenolic compounds from GGM was detected. Our results demonstrate that the GGM-stabilized emulsion could potentially deliver lipophilic bioactive ingredients and enhance their bioaccessibility. In addition, this bio-stabilizer itself would remain stable in the upper gastrointestinal track and serve as a prebiotic for gut microbiota. We anticipate GGM to complement or even replace many of the conventional carriers of bioactive components in future health care products and functional foods.

Hypothesis: Amphiphilic character of surfactants drives them at the interface of dispersed systems, such as emulsions. Hemicellulose-rich wood extracts contain assemblies (lignin-carbohydrate complexes, LCC) with natural amphiphilicity, which is expected to depend on their chemical composition resulting from the isolation method. Lignin-derived phenolic residues associated with hemicelluloses are hypothesized to contribute to emulsions' interfacial properties and stability. Experiments: We investigated the role of phenolic residues in spruce hemicellulose extracts in the stabilization of oil-in-water emulsions by physical and chemical approach. Distribution and changes occurring in the phenolic residues at the droplet interface and in the continuous phase were studied during an accelerated storage test. Meanwhile, the physical stability and lipid oxidation in emulsions were monitored. Findings: Naturally associated lignin residues in GGM act as vehicles for anchoring these hemicelluloses into the oil droplet interface and further enable superior stabilization of emulsions. By adjusting the isolation method of GGM regarding their phenolic profile, their functionalities, especially interfacial behavior, can be altered. Retaining the native interactions of GGM and phenolic residues is suggested for efficient physical stabilization and extended protection against lipid oxidation. The results can be widely applied as guidelines in tailoring natural or synthetic amphiphilic compounds for interfacial stabilization. (C) 2017 Elsevier Inc. All rights reserved.

Highlights • Emulgels with high oil content were converted to aerogels. • Hexanal production in aerogels was initiated by enzymes or photosensitizers. • Hexanal was produced and released from aerogels continuously up to three weeks. • The developed aerogels extend the shelf life of fresh plant products., Transportation and storage of vegetables and fruits, including berries, is increasing to meet growing consumer demand for fresh foods. Ripening and softening of plant tissues may be slowed down by hexanal, a safe volatile compound that also has antimicrobial properties. Thus hexanal could be applied during the food distribution chain to slow down the spoilage of plant-based products and reduce food waste. Nonetheless, due to the rapid evaporation of hexanal, a constant supply is needed. Our aim was to develop a concept to incorporate food-grade sunflower oil in a polysaccharide aerogel matrix for controlled in situ production and release of hexanal. We compared enzyme- and light-catalyzed lipid oxidation reactions, determined the release of hexanal at different conditions, and performed storage stability tests of blueberries and cherry tomatoes. The lipid-loaded aerogels assessed here are a potential novel delivery matrix for controlled hexanal formation to extend the shelf life of plant-based products.

For a sustainable food chain, the demand for plant-based, functional, and cost-effective food hydrocolloids is on a high-rise. Hemicelluloses from the renewable lignocellulosic biomass are available in abundance from side-streams of the forestry industry to fulfill this demand. Their effective valorization requires a safe, economic extraction method that can be up-scaled to an industrial scale and, simultaneously, understanding of their functionality to develop applications. In this study, an aqueous-based extraction method, pressurized hot water extraction (PHWE) of spruce saw meal was used to obtain galactoglucomannans (GGM), "spruce gum". Ethanol precipitation was performed to remove non-polysaccharide extractives such as free phenolic compounds, and the emulsion component ratio-dependent interfacial saturation capacity of the remaining purified fraction was studied to understand its functionality. GGM resulted in good to excellent emulsification and stabilization of oil-in-water emulsions and exhibited adsorption at the oil droplet interface, which depended on the amount of oil and droplet size of emulsions. The adsorbed GGM content was determined by gas chromatography after acid methanolysis, and their macromolecular characteristics were studied by size-exclusion chromatography. At GGM to oil ratios 2, 1, and 0.4, stable emulsions with predicted several months of shelf life at room temperature were achieved. The results indicated mechanisms affecting the physical stabilization and breakdown of emulsions containing spruce gum, a novel sustainable hydrocolloid. (C) 2018 Elsevier Ltd. All rights reserved.

Nowadays, several types of food products are fortified with plant sterols because of their cholesterol-lowering properties. Therefore, it is also important to study the oxidation behaviour of sterols and their conjugates. In the present study, the autoxidation of intact steryl fatty acyl esters was investigated by following the formation and decomposition of these esters’ primary hydroperoxides. The effects of the unsaturation of the acyl moiety on the sterol oxidation were investigated by oxidising pure cholesteryl fatty acyl esters at 100 °C. A previously introduced HPLC-ELSD method was further developed in order to follow the primary oxidation of steryl and acyl moieties individually. Peroxide values and secondary oxidation products of sterol were determined to confirm the obtained results and to follow further reactions. In the case of cholesteryl oleate and linoleate, the primary hydroperoxides of the steryl and acyl moieties were initially measurable at the same time point. As the unsaturation of the acyl moiety was increased, the induction period of the sterol oxidation was shortened and the rate of hydroperoxide formation increased. Moreover, the hydroperoxides started to decompose earlier. The maximum content of primary hydroperoxides was higher in cholesteryl stearate (64 mg/g) and oleate (78 mg/g) than in cholesteryl linoleate (40 mg/g). Thus, the degree of unsaturation of the acyl moiety also clearly affects the oxidation behaviour of the steryl moiety.

Rhizoctonia solani causes stem canker and black scurf diseases on potato and negatively affects the yield in all potato-growing areas. While seed-borne infection can be efficiently controlled by dressing with fungicides, few means of effective control are available against soil-borne infection. In this study, commercially available antagonistic fungi and bacteria, and the combination of antagonistic Trichoderma harzianum and seed dressing with flutolanil, were tested for their efficacy in the control of soil-borne infection of R. solani in the field. Combined use of flutolanil and T. harzianum was found feasible because even the highest tested concentration of flutolanil [13.0 lg active ingredient (a.i.) mL 21 ] had little effect on the growth of T. harzianum in vitro, whereas over 100-fold lower concentrations (0.1 lg a.i. mL 21 ) were sufficient to strongly inhibit the growth of R. solani (EC50 0.045 0.0068 lg a.i. mL 21 1 ). The variables under focus in plants inoculated with R. solani were the relative stem lesion index; sprout/stem number; stolon number, weight and incidence of symptoms on stolons; total yield and the yield of marketable sized tubers and incidence of black scurf on the marketable-sized tubers. Flutolanil and its combined application with T. harzianum reduced the damage to sprouts and severity of stem canker at the early stages of growth (up to 30 days postplanting). Towards the end of the growing season, T. harzianum was required to reduce disease severity. When applied in-furrow alone or in combination with flutolanil-dressed seed potatoes, T. harzianum increased the proportion of marketable-sized tubers in yield from 35% to 60% and decreased the incidence of black scurf on progeny tubers from 31% to 11%, which was not achieved using flutolanil alone. The number and weight of stolons and the yield of plants remained lower in the inoculated plants than un-inoculated control plants regardless of the method of control used. The other two antagonists tested, Streptomyces griseoviridis and Gliocladium catenulatum, showed no consistent control of R. solani. Taken together, the results suggest that combining the application of the antagonist T. harzianum with seed dressing with flutolanil may provide the best protection of the potato crop against damage caused by R. solani throughout the growing season.

Comprehensive two-dimensional gas chromatography utilising a semi-rotating cryogenic modulator was applied to the analysis of dietary milk derived fatty acids. Four column combinations were tested: two polar-nonpolar and two different nonpolarpolar column combinations. Best results were obtained with a nonpolar-polar column set, with narrow-bore (50 microm ID) Carbowax column as the second column. The GC x GC method clearly improved the separation efficiency of the fatty acids in comparison with one-dimensional GC analysis and proved to be suitable for the quantification of the analytes. The relative standard deviations (RSD) of the retention times in the first and second dimensions were on average 0.06% and 4.9%, respectively. The relative RSD for peak volumes was on average 2.9%.

In the present study, the formation and further reactions of intact steryl ester hydroperoxides were followed in a tripalmitin matrix maintained at 100°C. The effects of the acyl moiety and its unsaturation degree, and of the sterol structure were investigated. Intact steryl ester hydroperoxides were isolated from the lipid matrix by a developed solid-phase extraction (SPE) method and were determined by HPLC-ELSD. Further reactions of hydroperoxides were followed by determining secondary oxidation products of sterol by GC-FID/MS and oligomers by HPSEC-RI. The oxidation of sterol decreased when its solubility in the lipid medium was increased by introduction of acyl moiety. Increased unsaturation of the acyl or steryl moiety of steryl ester shortened the induction period and increased the oxidation of both steryl and acyl moieties. Thus, by changing the chemical and physical properties of sterols, their oxidation may be greatly affected.

Comprehensive two-dimensional gas chromatography utilising a semi-rotating cryogenic modulator was applied to the analysis of urban aerosols. Samples were collected onto glass fibre filters using a high-volume sampler in Helsinki, Finland. Sample preparation included extraction into n -hexane–acetone mixture and clean-up on silver-impregnated silica column. Analyses were performed with GC×GC–FID and GC×GC–QMS equipment. Linearity of the method was good with R 2 values greater than 0.994 for all analytes. Polycyclic aromatic hydrocarbons (PAHs) and oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) were identified and quantified in urban particulates. PAH and oxy-PAH concentrations ranged from 0.5 to 5.5 ng/m 3 .

It is well known that the dynamics in business are changing. Companies need to be aware of changes in their business environment, and must be able to recognise and exploit opportunities through their rare and distinctive resources and capabilities. This depends on their dynamic ability to reinvent their capabilities, business models, and strategies as circumstances for ongoing change. This paper studies the framework for sustaining the renewal of core capabilities in an inter-organisational context. Firstly, the dynamic capability view is introduced. Secondly, organisational knowledge creation through communication and learning are examined, and the basis of future-oriented knowledge is explained. This study demonstrates the knowledge creation process in an inter-industry context. The paper clarifies the real advantages and problems of the process by introducing the framework for creating future capabilities.