Kalle Lintinen

A simple process for lignin nanoparticle preparation

A 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 lignins 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).

Structural diversity in metal–organic nanoparticles based on iron isopropoxide treated lignin

The magnetic nature of iron-containing nanoparticles enables multiple high-end applications. Metal alkoxides are a highly reactive chemical species, which are widely used in ceramics and sol–gel manufacture. However, their use with organic molecules has been mostly limited to catalytic purposes due to their highly reactive nature. Lignin is the second most abundant biopolymer in the world-rich in OH groups and amenable to highly stable colloid nanoparticle formation by a simple solvent exchange process. Here we show that the reaction between iron isopropoxide and lignin in tetrahydrofuran (THF) solution produces metal–organic nanoparticles with tunable morphologies, ranging from hollow and solid nanospheres to open network structures. The immediate condensation reaction between lignin and iron isopropoxide as well as the resulting structure morphology can be controlled by varying the reaction parameters. Despite iron isopropoxide being highly water sensitive, the formed structures are stable as water suspensions. Our results demonstrate that solution processable metal–organic nanoparticles can be easily produced with macromolecular polyols in an inert solvent, such as THF. This presents a facile method of obtaining various metal–organic nanomaterials, with a wide range of metal alkoxides and organic polyols to choose from. We anticipate that metal–bioorganic sol–gel reactions will produce biocompatible materials with enhanced functionality, such as magnetic, antibacterial and catalytic properties depending on the chosen metal and polyol.

Adsorption of Proteins on Colloidal Lignin Particles for Advanced Biomaterials

Coating 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.

Closed cycle production of concentrated and dry redispersible colloidal lignin particles with a three solvent polarity exchange method

Lignin, 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.

Enzymatically and chemically oxidized lignin nanoparticles for biomaterial applications

Cross-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.

Techno-economic assessment for the large-scale production of colloidal lignin particles

The 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.