Ritva Serimaa

Crystallinity of wood and the size of cellulose crystallites in Norway spruce (Picea abies)

X-ray diffraction was used to study variations in the crystallinity of wood and the average thickness and length of the crystallites of cellulose as a function of the number of the year ring in Norway spruce [Picea abies (L.) Karst.]. The crystallinity increased from ring 4 to ring 10 from the pith and was constant after ring 10. The crystallinity of mature wood was about 30% ± 5%. The average thickness and average length of the crystallites were 3.2 ± 0.1 nm and 28 ± 2 nm, respectively; and no systematic variation of these values with the number of the year ring was observed. The mean microfibril angle decreased near the pith but was constant in the mature wood.

A Fast Method to Produce Strong NFC Films as a Platform for Barrier and Functional Materials

In this study, we present a rapid method to prepare robust, solvent-resistant, nanofibrillated cellulose (NFC) films that can be further surface-modified for functionality. The oxygen, water vapor, and grease barrier properties of the films were measured, and in addition, mechanical properties in the dry and wet state and solvent resistance were evaluated. The pure unmodified NFC films were good barriers for oxygen gas and grease. At a relative humidity below 65%, oxygen permeability of the pure and unmodified NFC films was below 0.6 cm(3) μm m(-2) d(-1) kPa(-1), and no grease penetrated the film. However, the largest advantage of these films was their resistance to various solvents, such as water, methanol, toluene, and dimethylacetamide. Although they absorbed a substantial amount of solvent, the films could still be handled after 24 h of solvent soaking. Hot-pressing was introduced as a convenient method to not only increase the drying speed of the films but also enhance the robustness of the films. The wet strength of the films increased due to the pressing. Thus, they can be chemically or physically modified through adsorption or direct chemical reaction in both aqueous and organic solvents. Through these modifications, the properties of the film can be enhanced, introducing, for example, functionality, hydrophobicity, or bioactivity. Herein, a simple method using surface coating with wax to improve hydrophobicity and oxygen barrier properties at very high humidity is described. Through this modification, the oxygen permeability decreased further and was below 17 cm(3) μm m(-2) d(-1) kPa(-1) even at 97.4% RH, and the water vapor transmission rate decreased from 600 to 40 g/m(2) day. The wax treatment did not deteriorate the dry strength of the film. Possible reasons for the unique properties are discussed. The developed robust NFC films can be used as a generic, environmentally sustainable platform for functional materials.

Drug release from nanoparticles embedded in four different nanofibrillar cellulose aerogels

Highly porous nanocellulose aerogels prepared by freeze-drying from various nanofibrillar cellulose (NFC) hydrogels are introduced as nanoparticle reservoirs for oral drug delivery systems. Here we show that beclomethasone dipropionate (BDP) nanoparticles coated with amphiphilic hydrophobin proteins can be well integrated into the NFC aerogels. NFCs from four different origins are introduced and compared to microcrystalline cellulose (MCC). The nanocellulose aerogel scaffolds made from red pepper (RC) and MCC release the drug immediately, while bacterial cellulose (BC), quince seed (QC) and TEMPO-oxidized birch cellulose-based (TC) aerogels show sustained drug release. Since the release of the drug is controlled by the structure and interactions between the nanoparticles and the cellulose matrix, modulation of the matrix formers enable a control of the drug release rate. These nanocomposite structures can be very useful in many pharmaceutical nanoparticle applications and open up new possibilities as carriers for controlled drug delivery.

Small-angle x-ray scattering studies of human breast tissue samples

Small-angle x-ray scattering (SAXS) patterns are recorded from thin breast tissue samples containing healthy and cancerous regions. The SAXS patterns are compared with histo-pathological observations. The information available from SAXS is reviewed, and a model for scattering from collagen is presented. Scattering patterns of collagen at regions far from the tumours are essentially different from those at tumours. The axial period of collagen fibrils is 65.0 +/- 0.1 nm in healthy regions, and 0.3 nm larger in cancer-invaded regions. The average intensity of scattering from cancerous regions is an order of magnitude higher than the intensity from healthy regions. This is interpreted to arise from an increase of the specific surface area of the scatterers, which is due to a disruption of the molecular and supra-molecular structures in cancerous regions and invasion of new types of cells. The differences of the SAXS patterns are large and distinctive enough to suggest that these phenomena may be utilized in mammography.

Aggregation and self-assembly of hydrophobins from Trichoderma reesei: low-resolution structural models

Hydrophobins are secreted fungal proteins, which have diverse roles in fungal growth and development. They lower the surface tension of water, work as adhesive agents and coatings, and function through self-assembly. One of the characteristic properties of hydrophobins is their tendency to form fibrillar or rod-like aggregates at interfaces. Their structure is still poorly known. In a step to elucidate the structure/function relation of hydrophobin self-assembly, we present the low-resolution structure of self-assembled fibrils of the class II hydrophobin HFBII from Trichoderma reesei based on small and wide-angle x-ray scattering. We first studied the solution state (10 mg/mL) of both HFBI and HFBII and showed that they formed assemblages in aqueous solution, which have a radius of gyration of ~24 A and maximum dimension of ~65 A, corresponding to the size of a tetramer. This result was supported by size-exclusion chromatography. Undried samples of HFBII fibrils had a monoclinic crystalline structure, which changed to hexagonal when the material was dried. A low-resolution structure for the HFBII fibrils is suggested. There are data in the literature based on staining properties suggesting that hydrophobins of class I form assemblies with an amyloid structure. Comparison of the HFBII data (x-ray results, staining with thioflavin T) to published data showed that the HFBII assemblages are not amyloid.

Structural investigation of radiation grafted and sulfonated poly(vinylidene fluoride), PVDF, membranes

Radiation grafted and sulfonated poly(vinylidene fluoride), PVDF, membranes have been studied by thermal analysis and X-ray diffraction to determine the changes in membrane crystallinity and structure during preparation. Commercial PVDF films were irradiated with an electron beam, grafted with styrene and finally sulfonated. Both the crystallinity and the size of the crystallites of PVDF decrease in the grafting reaction. A further decrease in crystallinity is observed in the sulfonation reaction. The residual crystallinity of PVDF was considerable (10–20%) even in membranes which had been subjected to severe reaction conditions. These results can be explained by assuming that the grafting takes place mainly in the amorphous region of the PVDF, and close to the surfaces of the crystals, but that grafts do not penetrate into the crystals. The proton conductivity of the grafted and sulfonated PVDF membranes reached values comparable to those of Nafion membranes.

Structure and properties of sulfonated poly [(vinylidene fluoride)–g-styrene] norous membranes porous membranes

The possibility of developing polyfvinylidene fluoride (PVDF)-based membranes as proton conductors has been investigated. Using electron beam radiation grafting and functionalisation, the composition of the membranes can be controlled. Membranes have been prepared from porous films of PVDF, and their structure and properties have been studied with Raman spectroscopy, wide angle X-ray scattering (WAXS), small angle X-ray scattering (SAXS), swelling tests, and by impedance spectroscopy. The grafting reaction of styrene, initiated in the amorphous regions and at the surfaces of the crystallites in the partly crystalline PVDF matrix, is very efficient, and high degrees of grafting can be achieved. Grafts are formed both from C–H and C–F branch pointsl Sulfonation can be accomplished to ca. 100%, and occurs mainly at the para-position of the phenyl rings. The hydration number was found to be independent of the degree of grafting, degree of sulfonation and crystallinity. The overall crystallinity decreased in the structure with the degree of grafting and sulfonation, partly owing to the diluting effect of the grafts, partly owing to efficient penetration of the grafts in the crystallites. The conductivity increased with the content of sulfonic acid groups and, in particular, with decreasing crystallinity. In the case of fully sulfonated membranes, a levelling-out of the conductivity was found at a degree of grafting of around 200%. Conductivities up to 120 mS cm–1 at room temperature were achieved.

Self-assembled films of hydrophobin proteins HFBI and HFBII studied in situ at the air/water interface.

Hydrophobins are a group of surface-active fungal proteins known to adsorb to the air/water interface and self-assemble into highly crystalline films. We characterized the self-assembled protein films of two hydrophobins, HFBI and HFBII from Trichoderma reesei, directly at the air/water interface using Brewster angle microscopy, grazing-incidence X-ray diffraction, and reflectivity. Already in zero surface pressure, HFBI and HFBII self-assembled into micrometer-sized rafts containing hexagonally ordered two-dimensional crystallites with lattice constants of 55 A and 56 A, respectively. Increasing the pressure did not change the ordering of the proteins in the crystallites. According to the reflectivity measurements, the thicknesses of the hydrophobin films were 28 A (HFBI) and 24 A (HFBII) at 20 mN/m. The stable films could also be transferred to a silicon substrate. Modeling of the diffraction data indicated that both hydrophobin films contained six molecules in the unit cell, but the ordering of the molecules was somewhat different for HFBI and HFBII, suggesting specific protein-protein interactions.

Hydrophobin film structure for HFBI and HFBII and mechanism for accelerated film formation.

Hydrophobins represent an important group of proteins from both a biological and nanotechnological standpoint. They are the means through which filamentous fungi affect their environment to promote growth, and their properties at interfaces have resulted in numerous applications. In our study we have combined protein docking, molecular dynamics simulation, and electron cryo-microscopy to gain atomistic level insight into the surface structure of films composed of two class II hydrophobins: HFBI and HFBII produced by Trichoderma reesei. Together our results suggest a unit cell composed of six proteins; however, our computational results suggest P6 symmetry, while our experimental results show P3 symmetry with a unit cell size of 56 Å. Our computational results indicate the possibility of an alternate ordering with a three protein unit cell with P3 symmetry and a smaller unit cell size, and we have used a Monte Carlo simulation of a spin model representing the hydrophobin film to show how this alternate metastable structure may play a role in increasing the rate of surface coverage by hydrophobin films, possibly indicating a mechanism of more general significance to both biology and nanotechnology.

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.