Controlling the water content of never dried and reswollen bacterial cellulose by the addition of water-soluble polymers to the culture medium

For the modification of medically useful biomaterials from bacterially synthesized cellulose, fleeces of Acetobacter xylinum have been produced in the presence of 0.5, 1.0, and 2.0% (m/v) carboxymethylcellulose (CMC), methylcellulose (MC), and poly(vinyl alcohol) (PVA), respectively, in the Hestrin-Schramm culture medium. The incorporation of the water-soluble polymers into cellulose and their influence on the structure, crystal modifications, and material properties are described. With IR and solid-state ¹³C NMR spectroscopy of the fleeces, the presence of the cellulose ethers and an increase in the amorphous parts of the cellulose modifications (NMR results) have been detected. The incorporation is represented by a higher product yield, too. As demonstrated by scanning electron microscopy, a porelike cellulose network structure forms in the presence of CMC and MC. This modified structure increases the water retention ability (expressed as the water content), the ion absorption capacity, and the remaining nitrogen-containing residues from the culture medium or bacteria cells. The water content of bacterial cellulose (BC) in the never dried state and the freeze-dried, reswollen state can be controlled by the CMC concentration in the culture solution. The freeze-dried, reswollen BC-CMC (2.0%) contains 96% water after centrifugation, whereas standard BC has only 73%. About 98% water is included in a BC-MC composite in the wet state, and about 93% is included in the reswollen state synthesized in the presence of 0.5, 1.0, or 2.0% MC. These biomaterial composites can be stored in the dried state and reswollen before use, reaching a higher water absorption than pure, never dried BC. The copper ion capacity of BC-CMC composites increases proportionally with the added amount of CMC. BC-CMC (0.5%) can absorb 3 times more copper ions than original BC. In the case of 0.5 and 1.0% PVA additions to the culture solution, this polymer cannot be detected in the cellulose fleeces after they are washed. Nevertheless the presence of PVA in the culture medium effects a decreased product yield, a retention of nitrogen-containing residues in the material during purification, a reduced water absorption ability, and a slightly higher copper ion capacity in comparison with original BC. The water content of freeze-dried, reswollen BC-PVA (0.5%) is only 62%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 463–470, 2004     

Metallo‐supramolecular block copolymer micelles: Improved preparation and characterization

Micelles prepared from amphiphilic block copolymers in which a poly(styrene) segment is connected to a poly(ethylene oxide) block via a bis‐(2,2′:6′,2″‐terpyridine‐ruthenium) complex have been intensely studied. In most cases, the micelle populations were found to be strongly heterogeneous in size because of massive micelle/micelle aggregation. In the study reported in this article we tried to improve the homogeneity of the micelle population. The variant preparation procedure developed, which is described here, was used to prepare two “protomer”‐type micelles: PS₂₀‐[Ru]‐PEO₇₀ and PS₂₀‐[Ru]‐PEO₃₇₅. The dropwise addition of water to a solution of the compounds in dimethylformamide was replaced by the controlled addition of water by a syringe pump. The resulting micelles were characterized by sedimentation velocity and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission electron microscopy of negatively stained samples. Sedimentation analysis showed virtually unimodal size distributions, in contrast to the findings on micelles prepared previously. PS₂₀‐[Ru]‐PEO₇₀ micelles were found to have an average molar mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly less than after micelle preparation by the standard method) and an average hydrodynamic diameter (d_h) of 18 nm. For PS₂₀‐[Ru]‐PEO₃₇₅ micelles, the corresponding values were M = 603,000 g/mol (31 protomers per micelle) and d_h = 34 nm. The latter particles were found to be identical to the “equilibrium” micelles prepared in pure water. Both micelle types had a very narrow molar mass distribution but a much broader distribution of s values and thus of hydrodynamic diameters. This indicates a conformational heterogeneity that is stable on the time scale of sedimentation velocity analysis. The findings from electron microscopy were in disagreement with those from the sedimentation analysis both in average micelle diameter and in the width of the distributions, apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4458–4465, 2004     

Solid-State Thin-Film Sensors Based on Chalcogenide Materials Obtained by Planar Technology and Pulsed Laser Deposition

Methods of silicon planar technology and pulsed laser deposition were applied to fabricate fully solid-state chemical sensors for determining ions of copper, lead, cadmium, thallium, and also sulfide and chloride ions on the basis of thin chalcogenide films as ion-sensitive membranes.     

The convex hull property and topology of hypersurfaces with nonnegative curvature

We prove that, in Euclidean space, any nonnegatively curved, compact, smoothly immersed hypersurface lies outside the convex hull of its boundary, provided the boundary satisfies certain required conditions. This gives a convex hull property, dual to the classical one for surfaces with nonpositive curvature. A version of this result in the nonsmooth category is obtained as well. We show that our boundary conditions determine the topology of the surface up to at most two choices. The proof is based on uniform estimates for radii of convexity of these surfaces under a clipping procedure, a noncollapsing convergence theorem, and a gluing procedure.     

Über Effekte zweiter Ordnung bei Biegung und Torsion dünnwandiger Rohre elliptischen Querschnitts

Zusammenfassung Mittels einfacher Gleichgewichtsbetrachtungen wird gezeigt, daÜ bei der Biegung eines dünnwandigen Rohres von elliptischem Querschnitt neben den Längsspannungen der elementaren Biegungstheorie auch Biegungsspannungen auftreten, deren EinfluÜ bei geringer Wandstärke im Vergleich zu den Ellipsenachsen nicht zu vernachlässigen ist, vor allem wegen der Verformung des Querschnitts, den sie zur Folge haben. Diese Abplattung der Ellipse wird mit Hilfe des Castiglianoschen Satzes berechnet. Bei den zusätzlichen Biegungsspannungen und der zugeordneten Deformation handelt es sich um Effekte zweiter Ordnung, die eine Verminderung der Sicherheit gegen Einbeulen der Rohre verursachen. Entsprechende Betrachtungen werden für die Torsion angestellt, wobei gleichartige Ergebnisse erzielt werden. Die Aussage über die Herabsetzung der Instabilitätsgrenze ist nur qualitativer Art. Es wird eine einfache Anwendung auf das Bourdonsche Manometer gebracht und dabei die Erklärung der Tatsache gegeben, daÜ eine Röhrenfeder in den Endpunkten der groÜen Achse ihres Querschnittes zuerst aufreiÜt.Der Verfasser dankt Herrn Prof.L. Föppl für die Anregung dieser Arbeit, sowie für die überlassung der Gleichungen (25), (27), (36) aus unveröffentlichten Arbeiten.     

Metallo‐supramolecular micelles: Studies by analytical ultracentrifugation and electron microscopy

In aqueous solutions, amphiphilic block copolymers in which a polystyrene (PS) segment is connected to a poly(ethylene oxide) (PEO) block via a bis(2,2′:6′,2″‐ terpyridine ruthenium) complex can form micelles. Such micelles of the protomer type PS₂₀‐[Ru]‐PEO₇₀, according to the preparation procedure representing frozen micelles, were studied by sedimentation velocity and sedimentation equilibrium analysis in an analytical ultracentrifuge and by transmission electron microscopy, with different techniques applied for the sample preparation. The particles obtained were surprisingly multifarious in size. In ultracentrifugation experiments performed at relatively low salt concentrations, the distributions of the sedimentation coefficient s_20,w showed a pronounced peak at 9.6 S and a broad, only partly separated second peak around 14 S. The molar mass of the particles at the peak was around 430,000 g/mol, corresponding to an aggregation number of approximately 85. The average hydrodynamic diameter of the particles in the peak fraction was approximately 13 nm. In electron micrographs of negatively stained samples, spheres of diameters between 10 and 25 nm were the most abundant particles, but larger ones with a wide size range were also visible. The latter particles apparently were composed of smaller ones. The data from both sedimentation analysis and electron microscopy showed that (1) the studied compound formed primary micelles of diameters around 20 nm and (2) the primary micelles had a tendency toward aggregation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3159–3168, 2003     

Application of enzyme-field effect transistor sensor arrays as detectors in a flow-injection analysis system for simultaneous monitoring of medium components. Part II. Monitoring of cultivation processes

Glucose, maltose, sucrose, lactose, ethanol and urea concentrations were monitored simultaneously during the cultivation of Escherichia coli and Saccharomyces cerevisiae by means of enzyme field effect transistors (EnFETs) applying glucose dehydrogenase (GDH), maltase (MAL)/GDH, invertase (INV)/GDH, β-galactosidase (β-GAL)/galactosedehydrogenase (GALDH), alcoholdehydrogenase (ADH)/aldehydedehydrogenase (ALDH), and urease. These enzymes were (co)immobilized on the pH sensitive gates of an eight-FET array. The FET array was integrated in a commercial FIA system.