Browsing by Author "Lintinen, Kalle"
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- Adsorption of Proteins on Colloidal Lignin Particles for Advanced Biomaterials
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä(2017-09-11) Leskinen, Timo; Witos, Joanna; Valle-Delgado, Juan José; Lintinen, Kalle; Kostiainen, Mauri; Wiedmer, Susanne K.; Österberg, Monika; Mattinen, Maija LiisaCoating of colloidal lignin particles (CLPs), or lignin nanoparticles (LNPs), with proteins was evaluated in order to establish a safe, self-assembly mediated modification technique to tune their surface chemistry. Gelatin and poly- l-lysine formed the most pronounced protein corona on the CLP surface, as determined by dynamic light scattering (DLS) and zeta potential measurements. Spherical morphology of individual protein coated CLPs was confirmed by transmission electron (TEM) and atomic force (AFM) microscopy. A mechanistic adsorption study with several random coiled and globular model proteins was carried out using quartz crystal microbalance with dissipation monitoring (QCM-D). The three-dimensional (3D) protein fold structure and certain amino acid interactions were decisive for the protein adsorption on the lignin surface. The main driving forces for protein adsorption were electrostatic, hydrophobic, and van der Waals interactions, and hydrogen bonding. The relative contributions of these interactions were highly dependent on the ionic strength of the surrounding medium. Capillary electrophoresis (CE) and Fourier transform infrared spectroscopy (FTIR) provided further evidence of the adsorption-enhancing role of specific amino acid residues such as serine and proline. These results have high impact on the utilization of lignin as colloidal particles in biomedicine and biodegradable materials, as the protein corona enables tailoring of the CLP surface chemistry for intended applications. - Antimicrobial Colloidal Silver-Lignin Particles via Ion and Solvent Exchange
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä(2019-09-16) Lintinen, Kalle; Luiro, Sanna; Figueiredo, Patrícia; Sakarinen, Ekaterina; Mousavi, Zekra; Seitsonen, Jani; Rivière, Guillaume N.S.; Mattinen, Ulriika; Niemelä, Matti; Tammela, Päivi; Österberg, Monika; Johansson, Leena Sisko; Bobacka, Johan; Santos, Hélder A.; Kostiainen, Mauri A.Acid-precipitated lignin nanoparticles with a cationic polymer coating exhibit antibacterial activity when infused with silver. While the use of such particles would be beneficial due to their high antibacterial activity with a low silver content, their production holds steps that are difficult to scale up to inexpensive industrial manufacture. For example, the production of acid-precipitated lignin nanoparticles requires the use of ethylene glycol, which is not easily recycled. Furthermore, the binding of silver to these particles is weak, and thus the particles need to be used rapidly after preparation. Here, we show that with a deprotonation reaction of an organic solution of anhydrous lignin and subsequent ion exchange with silver nitrate and colloid formation by solvent exchange, highly spherical silver carboxylate colloidal lignin particles (AgCLPs) can be prepared. Silver is not released from the particles in deionized water but can be released in physiological conditions, shown by their high antibacterial efficacy with low silver loading. In comparison to lignin nanoparticles with weakly bound silver, AgCLPs have high antibacterial activity even without cationic polyelectrolyte coating, and they retain their antibacterial activity for days. While the rapid depletion of silver from silver-infused lignin nanoparticles can be considered beneficial for some applications, the sustained antibacterial activity of the AgCLPs with ionically bound silver will enable their use in applications where silver nanoparticles have been previously used. Our results demonstrate that CLPs, which can be produced with a closed cycle process on a large scale, can be rapidly and quantitatively functionalized into active materials. - Calcium Chelation of Lignin from Pulping Spent Liquor for Water-Resistant Slow-Release Urea Fertilizer Systems
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä(2017-01) Sipponen, Mika Henrikki; Rojas, Orlando J.; Pihlajaniemi, Ville; Lintinen, Kalle; Österberg, MonikaSlow-release fertilizers represent a possible large-scale application for plant polymers. Here we show a facile way to stabilize urea in fertilizer systems by lignin. Chelation of kraft black liquor with calcium acetate at pH 13 precipitated lignin as a calcium complex (Ca-lignin), which offered beneficial effects if compared to those from lignin obtained by precipitation at low pH (Acid-lignin). The reduced affinity of water to Ca-lignin was exploited in the formulation of slow release fertilizers comprising wheat straw sections impregnated with Ca-lignin in molten urea. Compared to the case of Acid-lignin, immersion in water was slowed down more extensively by Ca-lignin. After 24 h incubation at low moisture conditions, the highest proportion of urea retained in the Ca-lignin/straw fertilizer system was 58%. The water resistance of Ca-lignin was explained by a lower aqueous solubility that differed from the typical pH-dependent solubility of Acid-lignin. Electron microscopy, infrared spectroscopy, and accessible surface areas suggested that Ca-lignin consisted of less densely packed molecules organized as calcium-chelated chains. Overall, the controlled water-solubility of lignin precipitated by metal cations is greatly beneficial in fertilizer systems and can open new opportunities in material development (permeable films and others). - Closed cycle production of concentrated and dry redispersible colloidal lignin particles with a three solvent polarity exchange method
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä(2018) Lintinen, Kalle; Xiao, Yao; Bangalore Ashok, Rahul; Leskinen, Timo; Sakarinen, Ekaterina; Sipponen, Mika; Muhammad, Farooq; Oinas, Pekka; Österberg, Monika; Kostiainen, MauriLignin, an aromatic biopolymer, is the main by-product of pulp manufacture, and has been under intense study, as it offers great promise as an alternative for petrochemical polymers. However due to its heterogeneity, the applications where lignin can be used have been limited, leading to the vast majority of it being burned for fuel. Colloidal lignin particles (CLPs) offer a means to disperse lignin homogenously into both water and other media, such as polymers. However, no means thus far have been presented that would allow for a large-scale production of CLPs. Herein we show an industrially scalable closed cycle process of CLP production. In the process, a concentrated solution of lignin in tetrahydrofuran (THF) and ethanol (EtOH) is added into the non-solvent water, instantaneously forming CLPs through self-assembly. The organic solvents are recovered and reused in the process. The aqueous CLPs are concentrated by ultrafiltration and the concentrated particles are spray dried, leading to redispersible microclusters. CLPs can be used in multiple applications, such as Pickering emulsions and composite materials. A significant portion of the 50 million tons of lignin produced by the pulp industry could be made into CLPs with this low cost process, which would open a whole new class of materials for industrial applications. - Collodial lignin particles in wood adhesives
Kemian tekniikan korkeakoulu | Master's thesis(2020-08-18) Tuominen, NikoReplacing environmentally toxic materials with greener and naturally safe solutions has gained increasing interest among scientists. One area of interest has been the possibility to replace part of the toxic compounds in wood adhesives with more environmentally friendly solutions. The aim of this master’s thesis was to test how colloidal lignin particles could be used in wood adhesives both in wet and dry conditions. To achieve this goal, various batches of adhesives were manufactured, and finally the adhesives were tested with Automated bonding evaluation system (ABES) to determine the shear strengths of the glue joints. Adhesives had several different ratios of solid contents and were either combinations of CLP:PDADMAC+TONFC, CLP+CLP:PDADMAC or Dirty Lignoboost+PF. The ABES tests had various parameters, including temperature and adhesive dosage. Based on the ABES tests, all adhesives had weaker shear strength properties compared to PF reference. However, the TONFC+CLP:PDADMAC adhesives had weaker glue joint strength in overall compared to CLP+CLP:PDADMAC samples. The combination of Dirty Lignoboost and PF had most promising results of all adhesives. By substituting either 20% or 40% of the PF with Dirty Lignoboost, resulted as higher shear strength results in wet samples compared to PF reference. The results indicate in overall that although PF reference has higher shear strength compared to other tested adhesives, there is room for further investigation of as an example whether the adhesive bonding could be improved in wet samples. In addition, it should be studied if the dry content ratios of the adhesives could be increased without making the adhesives too solid for application with pipette. - Enzymatically and chemically oxidized lignin nanoparticles for biomaterial applications
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä(2018-04-01) Mattinen, Maija Liisa; Valle-Delgado, Juan José; Leskinen, Timo; Anttila, Tuomas; Riviere, Guillaume; Sipponen, Mika; Paananen, Arja; Lintinen, Kalle; Kostiainen, Mauri; Österberg, MonikaCross-linked and decolorized lignin nanoparticles (LNPs) were prepared enzymatically and chemically from softwood Kraft lignin. Colloidal lignin particles (CLPs, ca. 200 nm) in a non-malodorous aqueous dispersion could be dried and redispersed in tetrahydrofuran (THF) or in water retaining their stability i.e. spherical shape and size. Two fungal laccases, Trametes hirsuta (ThL) and Melanocarpus albomyces (MaL) were used in the cross-linking reactions. Reactivity of ThL and MaL on Lignoboost™ lignin and LNPs was confirmed by high performance size exclusion chromatography (HPSEC) and oxygen consumption measurements with simultaneous detection of red-brown color due to the formation of quinones. Zeta potential measurements verified oxidation of LNPs via formation of surface-oriented carboxylic acid groups. Dynamic light scattering (DLS) revealed minor changes in the particle size distributions of LNPs after laccase catalyzed radicalization, indicating preferably covalent intraparticular cross-linking over polymerization. Changes in the surface morphology of laccase treated LNPs were imaged by atomic force (AFM) and transmission emission (TEM) microscopy. Furthermore, decolorization of LNPs without degradation was obtained using ultrasonication with H2O2 in alkaline reaction conditions. The research results have high impact for the utilization of Kraft lignin as nanosized colloidal particles in advanced bionanomaterial applications in medicine, foods and cosmetics including different sectors from chemical industry. - The Influence of Solvents on Lignin in General and on Colloidal Lignin Particles in Specific
Kemiantekniikan korkeakoulu | Bachelor's thesis(2021-06-03) Tynkkynen, Milla - Lignin nanoparticles modified with tall oil fatty acid for cellulose functionalization
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä(2020-01-01) Setala, Harri; Alakomi, Hanna-Leena; Paananen, Arja; Szilvay, Geza R.; Kellock, Miriam; Lievonen, Miikka; Liljestrom, Ville; Hult, Eva-Lena; Lintinen, Kalle; Osterberg, Monika; Kostiainen, MauriIn this study, tall oil fatty acid ester of softwood kraft lignin (TOFA-L) was used to prepare TOFA lignin nanoparticles (TLNP) in water. The average diameters for two prepared TLNPs in 0.1 mg/ml concentration were 140 nm and 160 nm. TLNPs were attached covalently onto modified and unmodified cellulose fibres to form an antimicrobial composite material. The modified cellulose fibres contained reactive allylic double bonds with a degree of substitution of 0.05. The antimicrobial properties of both TLNPs and TLNP coated fibres (TLNP-C) were studied against Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa using silver nanospheres (average size 10 nm) and Lignoboost lignin particles with 300 and 400 nm sizes as references. Antimicrobial activity of the samples was stronger against Gram-positive S. aureus cells than against Gram-negative target microbes E. coli and P. aeruginosa. - Nanocellulose-titanium for the preparation of oxygen barrier films
Kemian tekniikan korkeakoulu | Master's thesis(2016-08-23) Asad, Muhammad FaizanCellulose is one of the most abundant polymers in nature. Researchers are keen to find different ways to develop more practical applications of cellulose. An important form of cellulose is Nanofribrillar cellulose, which has already been investigated for barrier properties. This study is about the preparation of transparent NFC-OTi composite films, through the reaction of nanocellulose and metal alkoxides. These transparent films could be used as barrier materials for moisture and oxygen. Moreover, the transparent and barrier property of NFCOTi films make it suitable for many applications such as food packaging. - Radiolabeled Molecular Imaging Probes for the In Vivo Evaluation of Cellulose Nanocrystals for Biomedical Applications
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä(2019-02-11) Imlimthan, Surachet; Otaru, Sofia; Keinänen, Outi; Correia, Alexandra; Lintinen, Kalle; Santos, Helder A.; Airaksinen, Anu J.; Kostiainen, Mauri; Sarparanta, MirkkaCellulose nanocrystals (CNCs) have remarkable potential to improve the delivery of diagnostic and therapeutic agents to tumors; however, the in vivo studies on CNC biodistribution are still limited. We developed CNC-based imaging probes for the in vitro and in vivo evaluation using two labeling strategies: site-specific hydrazone linkage to the terminal aldehyde of the CNC and nonsite-specific activation using 1,1′-carbonyldiimidazole (CDI). The in vivo behavior of unmodified CNC, DOTA-CNC (ald.), and DOTA-CNC (OH) was investigated in healthy and 4T1 breast cancer mouse models. They displayed good biocompatibility in cell models. Moreover, the biodistribution profile and SPECT/CT imaging confirmed that the accumulation of 111 In-labeled DOTA-CNC (ald.) and 111 In-DOTA-CNC (OH) was primarily in hepatic, splenic, and pulmonary ducts in accordance with the clearance of nontargeted nanoparticles. The developed CNC imaging probes can be used to obtain information with noninvasive imaging on the behavior in vivo to guide structural optimization for targeted delivery. - Scaling up production of colloidal lignin particles
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä(2017) Leskinen, Timo; Smyth, Matthew; Xiao, Yao; Lintinen, Kalle; Mattinen, Maija-Liisa; Kostiainen, Mauri A.; Oinas, Pekka; Osterberg, MonikaFundamentals of nanoprecipitation process to form colloidal lignin particles (CLPs) from tetrahydrofuran (THF)-water solvent system were studied, and applied in establishment of a robust reactor design for scaled-up CLP production. Spherical lignin particles with an average diameter of 220 nm could be produced by the new reactor design. Evaporation was applied for removal of THF, concentration of the CLP dispersions, and finally for drying of the CLPs into flake like dry form. The dried CLPs could be re-dispersed in water to restore their colloidal form by applying short physical agitation. Salt triggered sedimentation of the particles was also investigated as a way for reducing the energy consumption related to water evaporation from the CLP dispersions. Aqueous thermal post-treatments were demonstrated to yield structural reinforcement of the CLP structure against solvation in various lignin solvents. In summary, the presented work pushes forward the conceptual design of large-scale CLP production, and addresses some of the foreseen technical challenges. - Self-assembly of colloidal lignin particles in a continuous flow tubular reactor
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä(2020-02-20) Bangalore Ashok, Rahul; Xiao, Yao; Lintinen, Kalle; Oinas, Pekka; Kostiainen, Mauri; Österberg, MonikaA scalable tubular flow reactor was designed and developed for the continuous formation of colloidal lignin particles (CLPs). The reactor consists of a series of tubes, inside which many static mixing elements are equipped to aid in the formation of a homogeneous dispersion of CLPs. The colloids were formed instantaneously through self-assembly upon the addition of the lignin solution into water. The effects of flowrate, length of the tubes and static mixing elements on the particle size, stability and CLP yield after drying were determined. It was found that a higher flowrate of lignin solution within the testing range of 32-240 mL/min resulted in smaller sized CLPs. Optimizations of the mixing length and the static mixing elements to 3 m and at least 1 m, respectively, could ensure an efficient mixing, thus resulting in CLP dispersions with smaller size of lignin particles (200 nm – 400 nm) and high lignin concentrations (up to 2.8 wt. %) along with yields up to 95 %. The TEM images indicated that the formed colloids are composed of lignin particles of regular sphere shape and with good stability. The tubular reactor offers better control of particle size which ensures the formation of colloidal dispersions with narrower particle size distribution in comparison to a stirred mixer reactor. Furthermore, using a tubular reactor enables the continuous production of CLPs, making it suitable for scale up and industrial applications. - Silver containing colloidal lignin
Kemian tekniikan korkeakoulu | Master's thesis(2017-04-24) Luiro, SannaSilver containing colloidal lignin particles are an environmentally friendly alternative for silver nanoparticles in antimicrobial applications. The only reported method for preparing these particles however includes a 72 hour dialysis step and the particles release over 95% of the silver within the first 24 hours. The aim of this thesis was to circumvent the dialysis step by utilizing volatile organic solvents and to possibly modify the silver release profile with a novel way of binding silver. The preparation method was based on treating the phenolic hydroxyl and carboxylic acid groups of lignin with sodium methylate and introducing the silver nitrate in organic phase. The colloid formation into water then followed. The preparation steps were primarily assessed based on the visual appearance of the products. Furthermore, the inclusion of silver in the particles was studied with energy dispersive X-ray spectroscopy, the size distribution and zeta potential were determined with dynamic light scattering and the morphology and structural composition were analysed with transmission electron microscopy. Additionally, the release of silver ions from the particles was studied with ion selective electrode (ISE) and the antibacterial activity of the particles was tested against Escherichia coli. Silver was successfully included in the particles with this method. The silver was considered to occur as silver nanoparticles and as bound to the targeted groups. The most significant challenges in the method development were the heterogeneous size distribution and especially aggregation. These challenges remained unsolved. It was shown that by coating with poly (diallyldimethylammonium chloride) (PDAC) the surface charge of these particles can be reversed from negative to positive. Moreover, the ISE measurement revealed free silver ions in the dispersions and their concentrations correlated with the results of the antibacterial assay. The dispersions with the highest silver concentrations significantly inhibited the growth of E. coli. - A simple process for lignin nanoparticle preparation
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä(2016-03-07) Lievonen, Miikka; Valle-Delgado, Juan José; Mattinen, Maija Liisa; Hult, Eva Lena; Lintinen, Kalle; Kostiainen, Mauri A.; Paananen, Arja; Szilvay, Géza R.; Setälä, Harri; Österberg, MonikaA lack of renewable resources and their inefficient use is a major challenge facing the society. Lignin is a natural biopolymer obtained mainly as a by-product from the pulp- and paper-making industries, and is primarily burned to produce energy. However, interest for using lignin in more advanced applications has increased rapidly. In particular, lignin based nanoparticles could find potential use in functional surface coatings, nanoglue, drug delivery, and microfluidic devices. In this work, a straightforward method to produce lignin nanoparticles from waste lignin obtained from kraft pulping is introduced. Spherical lignin nanoparticles were obtained by dissolving softwood kraft lignin in tetrahydrofuran (THF) and subsequently introducing water into the system through dialysis. No chemical modification of lignin was needed. Water acts as a non-solvent reducing lignin's degrees of freedom causing the segregation of hydrophobic regions to compartments within the forming nanoparticles. The final size of the nanoparticles depended on the pre-dialysis concentration of dissolved lignin. The stability of the nanoparticle dispersion as a function of time, salt concentration and pH was studied. In pure water and at room temperature the lignin nanoparticle dispersion was stable for over two months, but a very low pH or high salt concentration induced aggregation. It was further demonstrated that the surface charge of the particles could be reversed and stable cationic lignin nanoparticles were produced by adsorption of poly(diallyldimethylammonium chloride) (PDADMAC). - Synthetic functionalization of colloidal lignin particles for wood adhesive applications
Kemian tekniikan korkeakoulu | Master's thesis(2020-08-18) Fusi, Alexander - Techno-economic assessment for the large-scale production of colloidal lignin particles
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä(2018-10-02) Bangalore Ashok, Rahul; Oinas, Pekka; Lintinen, Kalle; Sarwar, Golam; Kostiainen, Mauri; Österberg, MonikaThe purpose of this study is to investigate the techno-economic feasibility of an environmentally sustainable and green process for the cost-effective large-scale manufacturing of colloidal lignin particles. The process involves the instantaneous formation of colloidal lignin particles (CLPs) through self-assembly when a concentrated solution of lignin in tetrahydrofuran (THF) and ethanol is introduced into water. The capacity of the plant is assumed to be 50 kt per year of dry colloidal lignin and Aspen plus simulation program is used for the mass and energy balance calculations. The process equipment design and pricing are carried out based on relevant literature and vendor data. Results show that the total investment cost for a plant integrated with an existing pulp mill or bio-refinery is 36 M€ and the annual operating cost is 46 M€. The project lifetime is assumed as 20 years and the cost of production of colloidal lignin is found to be 0.99 € kg−1 (in case of integration) and 1.59 € kg−1 (without integration). The revenue for the process comes mainly from selling the colloidal lignin particles and additional revenue is generated from high pressure and low-pressure steam condensate sold as district heat. The payback period with a CLP selling price of 1.10 € kg−1 is found to be roughly 5 years. A minimum profitability requirement of 10% is considered for the techno-economic analysis and the internal rate of return (IRR) is calculated as 17% making the process viable and profitable. In addition, a sensitivity analysis is carried out to evaluate the effect of raw material price and ethanol recovery on the operating cost. Colloidal lignin has the potential to compete favorably as a renewable replacement for petroleum based feedstock like polyethylene, polypropylene, polyethylene terephthalate (PET) and phenol and can be used in attractive applications like phenol formaldehyde (PF) resins, foams, carbon fillers, bactericides and composites.