David Reishofer

Designing Hydrophobically Modified Polysaccharide Derivatives for Highly Efficient Enzyme Immobilization.

In this contribution, a hydrophobically modified polysaccharide derivative is synthesized in an eco-friendly solvent water by conjugation of benzylamine with the backbone of the biopolymer. Owing to the presence of aromatic moieties, the resulting water-soluble polysaccharide derivative self-assembles spontaneously and selectively from solution on the surface of nanometric thin films and sheets of polystyrene (PS). The synthetic polymer modified in this way bears a biocompatible nanolayer suitable for the immobilization of horseradish peroxidase (HRP), a heme-containing metalloenzyme often employed in biocatalysis and biosensors. Besides the detailed characterization of the polysaccharide derivative, a quartz crystal microbalance with dissipation (QCM-D) and atomic force microscopy (AFM) are used to investigate the binding efficiency and interaction of HRP with the tailored polysaccharide interfaces. Subsequent enzyme activity tests reveal details of the interaction of HRP with the solid support. The novel polysaccharide derivative and its use as a material for the selective modification of PS lead to a beneficial, hydrophilic environment for HRP, resulting in high enzymatic activities and a stable immobilization of the enzyme for biocatalytic and analytic purposes.

Interaction of Tissue Engineering Substrates with Serum Proteins and Its Influence on Human Primary Endothelial Cells

Polymer-based biomaterials particularly polycaprolactone (PCL) are one of the most promising substrates for tissue engineering. The surface chemistry of these materials plays a major role since it governs protein adsorption, cell adhesion, viability, degradation, and biocompatibility in the first place. This study correlates the interaction of the most abundant serum proteins (albumin, immunoglobulins, fibrinogen) with the surface properties of PCL and its influence on the morphology and metabolic activity of primary human arterial endothelial cells that are seeded on the materials. Prior to that, thin films of PCL are manufactured by spin-coating and characterized in detail. A quartz crystal microbalance with dissipation (QCM-D), a multiparameter surface plasmon resonance spectroscopy instrument (MP-SPR), wettability data, and atomic force microscopy are combined to elucidate the pH-dependent protein adsorption on the PCL substrates. Primary endothelial cells are cultured on the protein modified polymer, and conclusions are drawn on the significant impact of type and form of proteins coatings on cell morphology and metabolic activity.

Reactive cellulose-based thin films – a concept for multifunctional polysaccharide surfaces

Reactive coatings of hydroxyethyl cellulose furoate in the form of thin films, suitable for the covalent immobilization of functional molecules, were developed and characterized in this work. The cellulose furoate derivatives were synthesized under homogeneous conditions by esterification of hydroxyethyl cellulose with 2-furoic acid. Reactive platform layers of these furoates were obtained by chemical surface modification of spin coated thin films with N,N′-carbonyldiimidazole. This chemistry allowed the covalent immobilization of functional molecules bearing primary and secondary amines on the films. The degree of substitution of the furoate thin films and their amino functionalized counterparts was determined gravimetrically by a quartz crystal microbalance (QCM-D) and correlated with infrared and X-ray photoelectron spectroscopy and zeta-potential measurements. Scanning electron- and atomic force microscopy showed changes in the morphologies that were influenced by the chemical reactions on the surface. The concept presented can be seen as a versatile method for immobilizing amine-containing (bio-)molecules to polysaccharide surfaces with the furoates having the potential for further reversible cross-linking in Diels–Alder reactions.

Pulp Fines—Characterization, Sheet Formation, and Comparison to Microfibrillated Cellulose

In the pulp and paper industry different types of pulp or fiber fines are generated during the pulping (primary fines, mechanical fines), and/or the refining process (secondary fines). Besides fibers, these cellulosic microparticles are a further component of the paper network. Fines, which are defined as the fraction of pulp that is able to pass through a mesh screen or a perforated plate having a hole diameter of 76 μm, are known to influence the properties of the final paper product. To better understand the effect and properties of this material, fines have to be separated from the pulp and investigated as an independent material. In the present study, fines are isolated from the pulp fraction by means of a laboratory pressure screen. To allow for further processing, the solids content of the produced fines suspension was increased using dissolved air flotation. Morphological properties of different types of fines and other cellulosic microparticles, such as microfibrillated celluloses (MFC) are determined and compared to each other. Furthermore, handsheets are prepared from these materials and properties, such as apparent density, contact angle, modulus of elasticity, and strain are measured giving similar results for the analyzed types of fines in comparison to the tested MFC grades. The analysis of the properties of fiber fines contributes on the one hand to a better understanding of how these materials influences the final paper products, and on the other hand, helps in identifying other potential applications of this material.

On the formation of Bi2S3-cellulose nanocomposite films from bismuth xanthates and trimethylsilyl-cellulose

The synthesis and characterization of bismuth sulfide-cellulose nanocomposite thin films was explored. The films were prepared using organosoluble precursors, namely bismuth xanthates for Bi2S3 and trimethylsilyl cellulose (TMSC) for cellulose. Solutions of these precursors were spin coated onto solid substrates yielding homogeneous precursor films. Afterwards, a heating step under inert atmosphere led to the formation of thin nanocomposite films of bismuth sulfide nanoparticles within the TMSC matrix. In a second step, the silyl groups were cleaved off by vapors of HCl yielding bismuth sulfide/cellulose nanocomposite films. The thin films were characterized by a wide range of surface sensitive techniques such as atomic force microscopy, attenuated total reflection infrared spectroscopy, transmission electron microscopy and wettability investigations. In addition, the formation of the nanoparticle directly in the TMSC matrix was investigated in situ by GI-SWAXS using a temperature controlled sample stage.

Direct-Write Fabrication of Cellulose Nano-Structures via Focused Electron Beam Induced Nanosynthesis

In many areas of science and technology, patterned films and surfaces play a key role in engineering and development of advanced materials. Here, we introduce a new generic technique for the fabrication of polysaccharide nano-structures via focused electron beam induced conversion (FEBIC). For the proof of principle, organosoluble trimethylsilyl-cellulose (TMSC) thin films have been deposited by spin coating on SiO2 / Si and exposed to a nano-sized electron beam. It turns out that in the exposed areas an electron induced desilylation reaction takes place converting soluble TMSC to rather insoluble cellulose. After removal of the unexposed TMSC areas, structured cellulose patterns remain on the surface with FWHM line widths down to 70 nm. Systematic FEBIC parameter sweeps reveal a generally electron dose dependent behavior with three working regimes: incomplete conversion, ideal doses and over exposure. Direct (FT-IR) and indirect chemical analyses (enzymatic degradation) confirmed the cellulosic character of ideally converted areas. These investigations are complemented by a theoretical model which suggests a two-step reaction process by means of TMSC → cellulose and cellulose → non-cellulose material conversion in excellent agreement with experimental data. The extracted, individual reaction rates allowed the derivation of design rules for FEBIC parameters towards highest conversion efficiencies and highest lateral resolution.

Deuterium and Cellulose: A Comprehensive Review

This contribution summarizes achievements in the understanding of cellulose accessibility, structure, and function with a particular focus on its interactions with deuteration. This review is the first to explicitly devote a discussion to deuteration of cellulose and highlights remarkable new findings in cellulose research as a result of the development of new experimental approaches, from simple weighing of deuterated samples to sophisticated techniques such as small angle neutron scattering and 2H-NMR spectroscopy.

Novel protein-repellent and antimicrobial polysaccharide multilayer thin films

Abstract Nanostructured and bio-active polysaccharide-based thin films were manufactured by means of subsequent spin-coated deposition of a regenerated cellulose (RC) layer and a 2,2,6,6-Tetramethylpiperidine-1-oxyl radical (TEMPO) oxidised cellulose nanofibril (TOCN) layer. The bio-activity of the bilayer was achieved by addition of chitosan (CS). The chitosan was either mixed with the TOCN (TOCN+CS) and deposited on the RC layer by spin-coating, or deposited on the RC and TOCN bilayer by pumping its aqueous solution with various pH over the surface of the bilayer. The water content of the thin films and the CS interactions with the bilayer during deposition were studied in situ by means of a quartz crystal microbalance with dissipation (QCM-D). The pH dependent charging behaviour of the TOCN, TOCN+CS and CS dispersions was evaluated by pH-potentiometric titrations. The surface morphology of the thin films was characterised by atomic force microscopy (AFM). The bio-activity of the thin films was evaluated by studying their protein-repellent properties in situ with a continuous flow of bovine serum albumin (BSA) by means of QCM-D and by evaluating their antibacterial properties in vitro against Staphylococcus aureus and Escherichia coli. These polysaccharide-based thin films are high value-added products because of their multifunctionality, high water absorbance capacity, protein-repellence and antimicrobial activity, and have the potential for medical application as a wound dressing material.