Thin Films of Zinc Oxide Nanoparticles and Poly(acrylic acid) Fabricated by the Layer-by-Layer Technique: a Facile Platform for Outstanding Properties

The incorporation of nanoparticles into polyelectrolytes thin films opens the way to a broad range of applications depending on the functionality of the nanoparticles. In this work, thin films of ZnO nanoparticles and poly­(acrylic acid) (PAA) were built up using the layer-by-layer technique. The thickness of a 20-bilayer film is about 120 nm with a surface roughness of 22.9 nm as measured by atomic force microscopy (AFM). Thin ZnO/PAA films block UV radiation starting at a wavelength of 361 nm due to absorption by ZnO although the films are highly transparent. Due to their high porosity, these thin films show a broadband antireflection in the visible region, and thus they provide selective opacity in the UV region and enhanced transmittance in the visible region up to the near-infrared region. They are also superhydrophilic due to their high porosity and surface roughness

Influence of Surface Charge Density and Morphology on the Formation of Polyelectrolyte Multilayers on Smooth Charged Cellulose Surfaces

To clarify the importance of the surface charge for the formation of polyelectrolyte multilayers, layer-by-layer (LbL) assemblies of polydiallyldimethylammonium chloride (pDADMAC) and polystyrenesulfonate (PSS) have been investigated on cellulose films with different carboxylic acid contents (20, 350, 870, and 1200 μmol/g) regenerated from oxidized cellulose. The wet cellulose films were thoroughly characterized prior to multilayer deposition using quantitative nanomechanical mapping (QNM), which showed that the mechanical properties were greatly affected by the degree of oxidation of the cellulose. Atomic force microscopy (AFM) force measurements were used to determine the surface potential of the cellulose films by fitting the force data to the DLVO theory. With the exception of the 1200 μmol/g film, the force measurements showed a second-order polynomial increase in surface potential with increasing degree of oxidation. The low surface potential for the 1200 μmol/g film was attributed to the low degree of regeneration of the cellulose film in aqueous media due to increasing solubility with increasing charge. The multilayer formation was characterized using a quartz crystal microbalance with dissipation (QCM-D) and stagnation-point adsorption reflectometry (SPAR). Extensive deswelling was observed for the charged films when pDADMAC was adsorbed due to the reduced osmotic pressure when ions inside the film were released, and the 1:1 charge compensation showed that all the charges in the films were reached by the pDADMAC. The multilayer formation was not significantly affected by the charge density above 350 μmol/g due to interlayer repulsions, but it was strongly affected by the salt concentration during the layer build-up

Nanometer Smooth, Macroscopic Spherical Cellulose Probes for Contact Adhesion Measurements

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 ∼1 mm and a root-mean-square surface roughness of ∼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

Immunoselective Cellulose Nanospheres: A Versatile Platform for Nanotheranostics

This paper describes a novel route for the preparation and functionalization of perfectly spherical cellulose nanospheres (CNSs), ranging from 100 to 400 nm with a typical diameter of 160–170 nm, 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

Spin-Assisted Multilayers of Poly(methyl methacrylate) and Zinc Oxide Quantum Dots for Ultraviolet-Blocking Applications

Thin UV-blocking films of poly­(methyl methacrylate) (PMMA) and ZnO quantum dots (QDs) were built-up by spin-coating. Ellipsometry reveals average thicknesses of 9.5 and 8.6 nm per bilayer before and after heating at 100 °C for one hour, respectively. The surface roughness measured by Atomic force microscopy (AFM) was 3.6 and 8.4 nm for the one and ten bilayer films, respectively. The linear increase in thickness as well as the low surface roughness increment per bilayer indicates a stratified multilayer structure and a smooth interface without aggregation. The absorption of UV radiation increased with increasing number of bilayers. At the same time, transmission was damped at wavelengths shorter than 375 nm. The thin films had a high and constant transparency in the visible region. Green-light emitting QDs could be detected by confocal microscopy at a concentration of 20% in a single layer of PMMA/ZnO. PMMA/ZnO QDs thin films are hydrophobic, as indicated by contact angle measurements

Rapid Development of Wet Adhesion between Carboxymethylcellulose Modified Cellulose Surfaces Laminated with Polyvinylamine Adhesive

The surface of regenerated cellulose membranes was modified by irreversible adsorption of carboxymethylcellulose (CMC). Pairs of wet CMC-modified membranes were laminated with polyvinylamine (PVAm) at room temperature, and the delamination force for wet membranes was measured for both dried and never-dried laminates. The wet adhesion was studied as a function of PVAm molecular weight, amine content, and deposition pH of the polyelectrolyte. Surprisingly the PVAm–CMC system gave substantial wet adhesion that exceeded that of TEMPO-oxidized membranes with PVAm for both dried and never-dried laminates. The greatest wet adhesion was achieved for fully hydrolyzed high molecular weight PVAm. Bulk carboxymethylation of cellulose membranes gave inferior wet adhesion combined with PVAm as compared to CMC adsorption which indicates that a CMC layer of the order of 10 nm was necessary. There are no obvious covalent cross-linking reactions between CMC and PVAm at room temperature, and on the basis of our results, we are instead attributing the wet adhesion to complex formation between the PVAm and the irreversibly adsorbed CMC at the cellulose surface. We propose that interdigitation of PVAm chains into the CMC layer is responsible for the high wet adhesion values

Nanometer-Thick Hyaluronic Acid Self-Assemblies with Strong Adhesive Properties

The adhesive characteristics of poly­(allylamine hydrochloride) (PAH)/hyaluronic acid (HA) self-assemblies were investigated using contact adhesion testing. Poly­(dimethylsiloxane) spheres and silicon wafers were coated with layer-by-layer (LbL) assemblies of PAH/HA. No increase in adhesion was observed when surfaces covered with dried LbL films were placed in contact. However, bringing the coated surfaces in contact while wet and separating them after drying resulted in an increase by a factor of 100 in the work of adhesion (from one to three bilayers). Herein we discuss the adhesion in PAH/HA and PAH/poly­(acrylic acid) assemblies. PAH/HA assemblies have potential application as strong biomedical adhesives

Adhesive Layer-by-Layer Films of Carboxymethylated Cellulose Nanofibril–Dopamine Covalent Bioconjugates Inspired by Marine Mussel Threads

The preparation of multifunctional films and coatings from sustainable, low-cost raw materials has attracted considerable interest during the past decade. In this respect, cellulose-based products possess great promise due not only to the availability of large amounts of cellulose in nature but also to the new classes of nanosized and well-characterized building blocks of cellulose being prepared from trees or annual plants. However, to fully utilize the inherent properties of these nanomaterials, facile and also sustainable preparation routes are needed. In this work, bioinspired hybrid conjugates of carboxymethylated cellulose nanofibrils (CNFC) and dopamine (DOPA) have been prepared and layer-by-layer (LbL) films of these modified nanofibrils have been built up in combination with a branched polyelectrolyte, polyethyleneimine (PEI), to obtain robust, adhesive, and wet-stable nanocoatings on solid surfaces. It is shown that the chemical functionalization of CNFCs with DOPA molecules alters their conventional properties both in liquid dispersion and at the interface and also influences the LbL film formation by reducing the electrostatic interaction. Although the CNFC–DOPA conjugates show a lower colloidal stability in aqueous dispersions due to charge suppression, it was possible to prepare the LbL films through the consecutive deposition of the building blocks. Adhesive forces between multilayer films prepared using chemically functionalized CNFCs and a silica probe are much stronger in the presence of Fe³⁺ than those between a multilayer film prepared from unmodified nanofibrils and a silica probe. The present work demonstrates a facile way to prepare chemically functionalized cellulose nanofibrils whereby more extended applications can produce novel cellulose-based materials with different functionalities

Formation of Colloidal Nanocellulose Glasses and Gels

Nanocellulose (NC) suspensions can form rigid volume-spanning arrested states (VASs) at very low volume fractions. The transition from a free-flowing dispersion to a VAS can be the result of either an increase in particle concentration or a reduction in interparticle repulsion. In this work, the concentration-induced transition has been studied with a special focus on the influence of the particle aspect ratio and surface charge density, and an attempt is made to classify these VASs. The results show that for these types of systems two general states can be identified: glasses and gels. These NC suspensions had threshold concentrations inversely proportional to the particle aspect ratio. This dependence indicates that the main reason for the transition is a mobility constraint that, together with the reversibility of the transition, classifies the VASs as colloidal glasses. If the interparticle repulsion is reduced, then the glasses can transform into gels. Thus, depending on the preparation route, either soft and reversible glasses or stiff and irreversible gels can be formed

Direct Adhesive Measurements between Wood Biopolymer Model Surfaces

For the first time the dry adhesion was measured for an all-wood biopolymer system using Johnson–Kendall–Roberts (JKR) contact mechanics. The polydimethylsiloxane hemisphere was successfully surface-modified with a Cellulose I model surface using layer-by-layer assembly of nanofibrillated cellulose and polyethyleneimine. Flat surfaces of cellulose were equally prepared on silicon dioxide substrates, and model surfaces of glucomannan and lignin were prepared on silicon dioxide using spin-coating. The measured work of adhesion on loading and the adhesion hysteresis was found to be very similar between cellulose and all three wood polymers, suggesting that the interaction between these biopolymers do not differ greatly. Surface energy calculations from contact angle measurements indicated similar dispersive surface energy components for the model surfaces. The dispersive component was dominating the surface energy for all surfaces. The JKR work of adhesion was lower than that calculated from contact angle measurements, which partially can be ascribed to surface roughness of the model surfaces and overestimation of the surface energies from contact angle determinations