Eero Kontturi

SEM imaging of chiral nematic films cast from cellulose nanocrystal suspensions

The chiral nematic self-assembly of aqueous suspensions of cellulose nanocrystals is partially preserved on evaporation of water, but the ordering of the rod-like nanoparticles may become distorted by changes in volume, ionic strength and surface and convective forces during evaporation, thus affecting the morphology and optical properties of the dried film. Proposed applications for these solids with chiral nematic order require confirmation of their structure. A SEM examination of the fracture surface of a slowly-dried film showed a surprisingly regular fan-like pattern which is shown to be characteristic of cross-sections of the left-handed helicoidal arrangement of nanocrystals, where the helicoidal axis was almost perpendicular to the film surfaces. Superimposed on this pattern was what appeared to be a regular porosity, which is postulated to result from pull-out of the nanocrystals oriented orthogonal to the fracture surface.

Polyelectrolyte Brushes Grafted from Cellulose Nanocrystals Using Cu-Mediated Surface-Initiated Controlled Radical Polymerization

Herein we report the synthesis of cellulose nanocrystals (CNCs) grafted with poly(acrylic acid) (PAA) chains of different lengths using Cu-mediated surface initiated-controlled radical polymerization (SI-CRP). First, poly(tert-butylacrylate) (PtBA) brushes were synthesized; then, subsequent acid hydrolysis was used to furnish PAA brushes tethered onto the CNC surfaces. The CNCs were chemically modified to create initiator moieties on the CNC surfaces using chemical vapor deposition (CVD) and continued in solvent phase in DMF. A density of initiator groups of 4.6 bromine ester groups/nm(2) on the CNC surface was reached, suggesting a dense functionalization and a promising starting point for the controlled/living radical polymerization. The SI-CRP of tert-butylacrylate proceeded in a well-controlled manner with the aid of added sacrificial initiator, yielding polymer brushes with polydispersity values typically well below 1.12. We calculated the polymer brush grafting density to almost 0.3 chains/nm(2), corresponding to high grafting densities and dense polymer brush formation on the nanocrystals. Successful rapid acid hydrolysis to remove the tert-butyl groups yielded pH-responsive PAA-polyelectrolyte brushes bound to the CNC surface. Individually dispersed rod-like nanoparticles with brushes of PtBA or PAA were clearly visualized by AFM and TEM imaging.

Amorphous Characteristics of an Ultrathin Cellulose Film

Swelling behavior and rearrangements of an amorphous ultrathin cellulose film (20 nm thickness) exposed to water and subsequently dried were investigated with grazing incidence X-ray diffraction, neutron reflectivity, atomic force microscopy, and surface energy calculations obtained from contact angle measurements. The film swelled excessively in water, doubling its thickness, but shrunk back to the original thickness upon water removal. Crystallinity (or amorphousness) and morphology remained relatively unchanged after the wetting/drying cycle, but surface free energy increased considerably (ca. 15%) due to an increase in its polar component, that is, the hydrophilicity of the film, indicating that rearrangements occurred during the films exposure to water. Furthermore, stability of the films in aqueous NaOH solution was investigated with quartz crystal microbalance with dissipation monitoring. The films were stable at 0.0001 M NaOH but already 0.001 M NaOH partially dissolved the film. The surprising susceptibility to dissolve in dilute NaOH was hypothetically attributed to the lack of hierarchical morphology in the amorphous film.

Quantitative Assessment of the Enzymatic Degradation of Amorphous Cellulose by Using a Quartz Crystal Microbalance with Dissipation Monitoring

The systematic evaluation of the degradation of an amorphous cellulose film by a monocomponent endoglucanase (EG I) by using a quartz crystal microbalance with dissipation monitoring (QCM-D) identified several important aspects relevant to the study the kinetics of cellulose degradation by enzymes. It was demonstrated that, to properly evaluate the mechanism of action, steady state conditions in the experimental set up need to be reached. Rinsing or diluting the enzyme, as well as concentration of the enzyme, can have a pronounced effect on the hydrolysis. Quantification of the actual hydrolysis was carried out by measuring the film thickness reduction by atomic force microscopy after the enzymatic treatment. The values correlated well with the frequency data obtained by QCM-D measurement for corresponding films. This demonstrated that the evaluation of hydrolysis by QCM-D can be done quantitatively. Tuning of the initial thickness of films enabled variation of the volume of substrate available for hydrolysis which was then utilized in establishing a correlation between substrate volume and hydrolytic activity of EG I as measured by QCM-D. It was shown that, although the amount of substrate affects the absolute rate of hydrolysis, the relative rate of hydrolysis does not depend on the initial amount of substrate in steady state system. With this experimental setup it was also possible to demonstrate the impact of concentration on crowding of enzyme and subsequent hydrolysis efficiency. This effort also shows the action of EG I on a fully amorphous substrate as observed by QCM-D. The enzyme was shown to work uniformly within the whole volume of swollen film, however being unable to fully degrade the amorphous film.

Impact of Drying on Wood Ultrastructure Observed by Deuterium Exchange and Photoacoustic FT-IR Spectroscopy

The impact of drying on the ultrastructure of fresh wood was studied by deuterium exchange coupled with FT-IR analysis. This fundamental investigation demonstrated that water removal leads to irreversible alterations of the wood structure, namely, supramolecular rearrangements between wood polymers. The deuteration of fresh wood was shown to be fully reversible by a subsequent exposure of the deuterated sample to water (reprotonation). Therefore, the presence of any OD groups in deuterated and then dried wood samples after reprotonation is a clear indicator of reduced accessibility. The extent of changes was affected by drying temperature and relative humidity. Application of this methodology for the evaluation of chemical pulp sample (reference material) resulted in similar response, only more pronounced. Two hypothetical alternatives were proposed for accessibility reduction in dried wood: (i) irreversible aggregation of cellulose microfibrils and (ii) irreversible stiffening of the hemicellulose/lignin matrix that extensively swells when exposed to water.

Transition to Reinforced State by Percolating Domains of Intercalated Brush-Modified Cellulose Nanocrystals and Poly(butadiene) in Cross-Linked Composites Based on Thiol–ene Click Chemistry

The classic nanocomposite approach aims at percolation of low fraction of exfoliated individual reinforcing nanoscale elements within a polymeric matrix. By contrast, many of the mechanically excellent biological nanocomposites involve self-assembled and space-filled structures of hard reinforcing and soft toughening domains, with high weight fraction of reinforcements. Here we inspect a new concept toward mimicking such structures by studying whether percolation of intercalated domains consisting of alternating rigid and reinforcing, and soft rubbery domains could allow a transition to a reinforced state. Toward that, we present the functionalization of rigid native cellulose nanocrystals (CNCs) by esterification with a dense hydrocarbon chain brush containing cross-linkable double bonds. Composite films with 0-80 wt % of such modified CNCs (mCNCs) within a poly(butadiene) (PBD) rubber matrix were prepared via cross-linking by UV-light initiated thiol-ene click reaction. Transmission electron microscopy showed structures at two length scales, where the mCNCs and PBD form domains having internal aligned self-assemblies of alternating hard mCNCs and soft PBD with periodicity of ca. 40 nm, and where additional PBD connects such domains. Increasing the weight fraction of mCNCs causes an uncommon abrupt transition from PBD-dominated soft materials to significantly reinforced mCNC-dominated mechanical properties, suggesting that the intercalated self-assembled mCNC/PBD domains percolate in PBD upon passing 30-35 wt % of mCNCs. Maximum stress of 16 MPa at mCNC fraction of 80 wt % was obtained. The mechanical properties of the composites show exceptional insensitivity to air humidity. The shown simple concept of percolative intercalated nanocomposites suggests searching for more general biomimetic compositions involving several deformation mechanisms for improved mechanical properties.

Impact of drying on wood ultrastructure: similarities in cell wall alteration between native wood and isolated wood-based fibers.

Ultrastructural alterations of fresh wood caused by initial drying were compared to changes incurred during drying of never-dried wood pulp fibers of different macromolecular composition. Drying induced inaccessibility of a native wood sample exhibited remarkable similarity to wood pulp samples of different lignin contents. The results suggest that the supramolecular rearrangements in native wood matrix upon dehydration are qualitatively identical to the well-known changes occurring in pulp fibers after drying, although the changes are considerably different in quantity. The alterations were observed and quantified by monitoring the conversion of accessible deuterium exchanged OH groups in fresh wood and wood pulp fibers to inaccessible, reprotonation resistant OD groups during drying. The deuteration/FT-IR measurements correlated well with the water retention measurement of the pulp samples. Irreversible reduction of water retention due to the supramolecular changes implies reduced accessibility of wood polymers in various chemical and mechanical treatments, such as enzymatic conversion of biomass or preparation of cellulosic nano-objects for diverse applications.

Supracolloidal Multivalent Interactions and Wrapping of Dendronized Glycopolymers on Native Cellulose Nanocrystals

Cellulose nanocrystals (CNCs) are high aspect ratio colloidal rods with nanoscale dimensions, attracting considerable interest recently due to their high mechanical properties, chirality, sustainability, and availability. In order to exploit them for advanced functions in new materials, novel supracolloidal concepts are needed to manipulate their self-assemblies. We report on exploring multivalent interactions to CNC surface and show that dendronized polymers (DenPols) with maltose-based sugar groups on the periphery of lysine dendrons and poly(ethylene-alt-maleimide) polymer backbone interact with CNCs. The interactions can be manipulated by the dendron generation suggesting multivalent interactions. The complexation of the third generation DenPol (G3) with CNCs allows aqueous colloidal stability and shows wrapping around CNCs, as directly visualized by cryo high-resolution transmission electron microscopy and electron tomography. More generally, as the dimensions of G3 are in the colloidal range due to their ~6 nm lateral size and mesoscale length, the concept also suggests supracolloidal multivalent interactions between other colloidal objects mediated by sugar-functionalized dendrons giving rise to novel colloidal level assemblies.

Distribution of lignin and its coniferyl alcohol and coniferyl aldehyde groups in Picea abies and Pinus sylvestris as observed by Raman imaging

Wood cell wall consists of several structural components, such as cellulose, hemicelluloses and lignin, whose concentrations vary throughout the cell wall. It is a composite where semicrystalline cellulose fibrils, acting as reinforcement, are bound together by amorphous hemicelluloses and lignin matrix. Understanding the distribution of these components and their functions within the cell wall can provide useful information on the biosynthesis of trees. Raman imaging enables us to study chemistry of cell wall without altering the structure by staining the sample or fractionating it. Raman imaging has been used to analyze distributions of lignin and cellulose, as well as the functional groups of lignin in wood. In our study, we observed the distribution of cellulose and lignin, as well as the amount of coniferyl alcohol and aldehyde groups compared to the total amount of lignin in pine (Pinus sylvestris) and spruce (Picea abies) wood samples. No significant differences could be seen in lignin and cellulose distribution between these samples, while clear distinction was observed in the distribution of coniferyl alcohols and coniferyl aldehyde in them. These results could provide valuable insight on how two similar wood species control biosynthesis of lignin differently during the differentiation of cell wall.

Molecular Engineering of Fracture Energy Dissipating Sacrificial Bonds Into Cellulose Nanocrystal Nanocomposites

Even though nanocomposites have provided a plethora of routes to increase stiffness and strength, achieving increased toughness with suppressed catastrophic crack growth has remained more challenging. Inspired by the concepts of mechanically excellent natural nanomaterials, one-component nanocomposites were fabricated involving reinforcing colloidal nanorod cores with polymeric grafts containing supramolecular binding units. The concept is based on mechanically strong native cellulose nanocrystals (CNC) grafted with glassy polymethacrylate polymers, with side chains that contain 2-ureido-4[1H]-pyrimidone (UPy) pendant groups. The interdigitation of the grafts and the ensuing UPy hydrogen bonds bind the nanocomposite network together. Under stress, UPy groups act as sacrificial bonds: simultaneously providing adhesion between the CNCs while allowing them to first orient and then gradually slide past each other, thus dissipating fracture energy. We propose that this architecture involving supramolecular binding units within side chains of polymer grafts attached to colloidal reinforcements opens generic approaches for tough nanocomposites.