A synthesis protocol was identified to produce covalent grafting of poly(dimethyl siloxane) from cellulose, based on prior studies of analogous ring opening polymerizations. Following this polymer modification of cellulose, the contact adhesion was anticipated to be modified and varied as a function of the polymer molecular mass. The synthetic details were optimized for a filter paper surface before grafting the polymer from bulk cellulose spheres. The adhesion of the unmodified and grafted, bulk cellulose spheres were evaluated using the Johnson-Kendall-Roberts (JKR) theory with a custom build contact adhesion testing setup. We report the first example of grafting poly(dimethyl siloxane) directly from bulk cellulose using ring opening polymerization. For short grafting lengths, both the JKR work of adhesion and the adhesion energy at the critical energy release rate (G(c)) were comparable to unmodified cellulose beads. When polymer grafting lengths were extended sufficiently where chain entanglements occur, both the JKR work of adhesion and G(c) were increased by as much as 190%. Given the multitude of options available to graft polymers from cellulose, this study shows the potential to use this type of cellulose spheres to study the interaction between different polymer surfaces in a controlled manner. [GRAPHICS] .

This paper describes a novel route for the preparation and functionalization of perfectly spherical cellulose nanospheres (CNSs), ranging from 100 to 400 nrn with a typical diameter of 160-170 nrn,for use in theranostics. The method of preparation enables both surface and interior bulk functionalization, and this presumably also makes the CNSs suitable for use in end-use applications other than theranostics. Surface functionalization was here demonstrated by antibody conjugation with an antibody specific toward the epidermal growth factor receptor (EGFR) protein, i.e., facilitating interaction with cancer cells having the EGFR. Besides showing specificity, the CNS-antibody conjugates showed a very low nonspecific binding. The CNSs could easily be bulk functionalized by embedding gold nanoparticles in the cellulose sphere matrix during CNS preparation to provide imaging contrast for diagnostic purposes.

We demonstrate how to prepare extraordinarily deformable, gas-filled, spherical capsules from nonmodified cellulose. These capsules have a low nominal density, ranging from 7.6 to 14.2 kg/m(3), and can be deformed elastically to 70% deformation at 50% relative humidity. No compressive strain-at-break could be detected for these dry cellulose capsules, since they did not rupture even when compressed into a disk with pockets of highly compressed air. A quantitative constitutive model for the large deformation compression of these capsules is derived, including their high-frequency mechanical response and their low-frequency force relaxation, where the latter is governed by the gas barrier properties of the dry capsule. Mechanical testing corroborated these models with good accuracy. Force relaxation measurements at a constant compression rendered an estimate for the gas permeability of air through the capsule wall, calculated to 0.4 mL mu m/m(2) days kPa at 50% relative humidity. These properties taken together open up a large application area for the capsules, and they could most likely be used for applications in compressible, lightweight materials and also constitute excellent model materials for adsorption and adhesion studies.

The structure of a polymeric material has a great influence in many fundamental scientific areas as well as in more applied science, since it affects the diffusion, permeability, mechanical strength, elasticity, and colloidal properties of the materials. The results in this thesis demonstrate that it is possible to fabricate solid and hollow cellulose spheres with a cellulose shell and encapsulated gas, liquid or solid particles and with a sphere size ranging from a few hundreds of nanometres to several millimetres, all with a tailored design and purpose.

The sizes of the different spheres have been controlled by three different preparation methods: large cellulose macrospheres by a solution solidification procedure, hollow micrometre-sized cellulose spheres by a liquid flow-focusing technique in microchannels, and nanometre-sized cellulose spheres by a membrane emulsification technique. 

The spheres were then modified in different ways in order to functionalize them into more advanced materials. This thesis demonstrates how to control the cellulose sphere dimensions and the wall-to-void volume ratio, the elasticity and the functionality of the spheres as such, where they were prepared to be pH-responsive, surface specific and X-ray active. These modifications are interesting in several different types of final materials such as packaging materials, drug release devices or advanced in vivo diagnostic applications.

In the more fundamental science approach, surface-smooth solid cellulose spheres were prepared for characterization of the macroscopic work of adhesion when a cellulose surface is separated from another material. Using these ultra-smooth macroscopic cellulose probes, it is possible to measure the compatibility and the surface interactions between cellulose and other materials which provide an important tool for incorporating cellulose into different composite materials. 

Cellulose spheres were prepared by dissolving cellulose fibers and subsequently solidifying the solution in a nonsolvent. Three different solution concentrations were tested and several nonsolvents were evaluated for their effect on the formation of spheres. Conditions were highlighted to create cellulose spheres with a diameter of similar to 1 mm and a root-mean-square surface roughness of similar to 1 nm. These solid spheres were shown to be easily chemically modified without changing the mechanical properties significantly. Contact adhesion measurements were then implemented with these spheres against a poly(dimethylsiloxane) (PDMS) elastomer in order to quantify the adhesion. Using Johnson-Kendall-Roberts (JKR) theory, we quantified the adhesion for unmodified cellulose and hydrophobic cellulose spheres. We highlight the ability of these spheres to report more accurate adhesion information, compared to spin-coated thin films. The application of these new cellulose probes also opens up new possibilities for direct, accurate measurement of adhesion between cellulose and other materials instead of using uncertain surface energy determinations to calculate the theoretical work of adhesion between cellulose and different solid materials.

Cellulose capsules with average outer and inner radii of approximately 44 mu m and 29 mm respectively were prepared from cellulose dissolved in a mixture of lithium chloride and dimethylacetamide using a microfluidic flow focusing device (MFFD). The MFFD had three inlets where octane oil in a cellulose solution in silicone oil was used to produce a double emulsion containing a cellulose capsule. This technique enables the formation of capsules with a narrow size distribution which can be beneficial for drug delivery or controlled release capsules. In this respect, cellulose is a highly interesting material since it is known to cause no autoimmune reactions when used in contact with human tissue. Furthermore, by controlling the chemical properties of the cellulose, it is possible to trigger a swelling of the capsules and consequentially the release of an encapsulated substance, e. g. a model drug, when the capsule becomes exposed to an external stimulus. To demonstrate this, capsules were functionalized by carboxymethylation to be pH- responsive and to expand approximately 10% when subjected to a change in pH from 3 to 10. The diffusion constant of a model drug, a 4 kDa fluorescently labelled dextran, through the native capsule wall was estimated to be 6.5 X 10(-14) m(2) s(-1) by fitting fluorescence intensity data to Fick's second law.

A new material consisting of mm-sized hollow cellulose spheres, for biomedical applications or for the preparation of low weight porous materials has been prepared by a unique solution precipitation (SP) method. The technique is based on three separate steps. In the first step, high molecular mass, non-modified cellulose is dissolved in a suitable solvent. This cellulose solution is then saturated with a suitable gas (CO2 or N2 in the present work) and finally this gas-saturated solution is drop-wise added to a water reservoir. In this step, the cellulose is precipitated and a gas bubble is nucleated in the center of the cellulose sphere. When stored in water, the hollow center is filled with water, indicating that the capsule wall is porous in nature. This was also supported by BET-area measurements as well as by high resolution SEM-images of broken capsule walls. The internal void volume of a capsule was about 5 μl and the wall volume was about 8 μl. It was also established that the properties of the cellulose capsules, i.e. wall and void volume, the specific surface area, the average pore size of the capsule wall, the wall density, and the compressive load capacity could be tuned by the choice of cellulose concentration in the solution before precipitation. The capsule wall volume and void volume were also affected by the choice of gas, the gas pressure and the gas dissolution time during the gas saturation step. The response of the cellulose wall of the prepared capsules to changes in pH and ion concentration in the surrounding solution was also investigated. The swelling-shrinking behavior was further investigated by introducing more charges to the capsule wall, via carboxymethylation of the cellulose. This was achieved by using carboxymethylated cellulose which increased the swelling-shrinking effect. The results show a typical polyelectrolyte gel behavior of the capsule wall and the wet modulus of the cellulose wall was determined to be between 0.09-0.2 MPa depending on the charge of the cellulose in the capsule wall. Furthermore, the freeze dried cellulose spheres had a modulus of 1.9-7.4 MPa, depending on the cellulose concentration during the preparation of the spheres. These cellulose capsules are suitable both for the preparation of porous materials, where these larger spheres are joined together in 3D-shaped materials, and for controlled release where the interior of the capsules is filled with active substances and these substances are released by controlling the pores in the capsule walls.