Antifouling coating of cellulose acetate thin films with polysaccharide multilayers.

In this investigation, partially deacetylated cellulose acetate (DCA) thin films were prepared and modified with hydrophilic polysaccharides with the layer-by-layer (LbL) technique. As polysaccharides, chitosan (CHI) and carboxymethyl cellulose (CMC) were used. DCA thin films were manufactured by exposing spin coated cellulose acetate to potassium hydroxide solutions for various times. The deacetylation process was monitored by attenuated total reflectance-infrared spectroscopy, film thickness and static water contact angle measurements. A maximum of three bilayers was created from the alternating deposition of CHI and CMC on the DCA films under two different conditions namely constant ionic strengths and varying pH values of the CMC solutions. Precoatings of CMC at pH 2 were used as a base layer. The sequential deposition of CMC and CHI was investigated with a quartz crystal microbalance with dissipation, film thickness, static water contact angle and atomic force microscopy (AFM) measurements. The versatility and applicability of the developed functional coatings was shown by removing the multilayers by rinsing with mixtures containing HCl/NaCl. The developed LbL coatings are used for studying the fouling behavior of bovine serum albumin (BSA).

Adsorption of carboxymethyl cellulose on polymer surfaces: evidence of a specific interaction with cellulose.

The adsorption of carboxymethyl cellulose (CMC), one of the most important cellulose derivatives, is crucial for many scientific investigations and industrial applications. Especially for surface modifications and functionalization of materials, the polymer is of interest. The adsorption properties of CMC are dependent not only on the solutions state, which can be influenced by the pH, temperature, and electrolyte concentration, but also on the chemical composition of the adsorbents. We therefore performed basic investigation studies on the interaction of CMC with a variety of polymer films. Thin films of cellulose, cellulose acetate, deacetylated cellulose acetate, polyethylene terephthalate, and cyclo olefin polymer were therefore prepared on sensors of a QCM-D (quartz crystal microbalance) and on silicon substrates. The films were characterized with respect to the thickness, wettability, and chemical composition. Subsequently, the interaction and deposition of CMC in a range of pH values without additional electrolyte were measured with the QCM-D method. A comparison of the QCM-D results showed that CMC is favorably deposited on pure cellulose films and deacetylated cellulose acetate at low pH values. Other hydrophilic surfaces such as silicon dioxide or polyvinyl alcohol coated surfaces did not adsorb CMC to a significant extent. Atomic force microcopy confirmed that the morphology of the adsorbed CMC layers differed depending on the substrate. On hydrophobic polymer films, CMC was deposited in the form of larger particles in lower amounts whereas hydrophilic cellulose substrates were to a high extent uniformly covered by adsorbed CMC. The chemical similarity of the CMC backbone seems to favor the irreversible adsorption of CMC when the molecule is almost uncharged at low pH values. A selectivity of the cellulose CMC interaction can therefore be assumed. All CMC treated polymer films exhibited an increased hydrophilicity, which confirmed their modification with the functional molecule.

Nitrilases catalyze key step to conformationally constrained GABA analogous gamma-amino acids in high optical purity.

Five- and six-membered carbocyclic gamma-amino acids were prepared in high enantiomeric purity by nitrilase-mediated transformation of hitherto unreported gamma-amino nitriles. The nitrilases investigated reveal a strong enantiopreference for cis-isomers (up to 99% ee), whereas trans-isomers were available in up to 86% ee. The biocatalytic enantioselective syntheses of cis-3-aminocyclohexanecarboxylic acid (3b), trans-3-aminocyclohexanecarboxylic acids (4b, 6b, 8b) as well as trans-3-aminocylopentanecarboxylic acid (2b) are hereby reported for the first time.