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     

Generic Transport Aft-body Drag Reduction using Active Flow Control

Active flow-separation control is an effective and efficient mean for drag reduction and unsteady load alleviation resulting from locally or massively separated flow. Such a situation occurs in configurations where the aerodynamic performance is of secondary importance to functionality. The performance of heavy transport helicopters and aeroplanes, having a large, and almost flat, aft loading ramp suffer from the poor aerodynamics of the aft body. Hence, a combined experimental and numerical investigation was undertaken on a generic transport aeroplane/helicopter configuration. The experimental study provided surface pressures, direct drag measurements, surface and smoke flow visualization. The baseline flow was numerically analyzed, using finite volume solutions of the RANS equations. The baseline flow around the model was insensitive to the Reynolds number in the range it was tested. The flow separating from the aft body was characterized by two main sources of drag and unsteadiness. The first is a separation bubble residing at the lower ramp corner and the second is a pair of vortex systems developing and separating from the sides of the ramp. As the model incidence is decreased, the pair of vortex systems also penetrates deeper towards the centerline of the ramp, decreasing the pressure and increasing the drag. As expected, the ramp lower corner bubble was highly receptive to periodic excitation introduced from four addressable piezo-fluidic actuators situated at the ramp lower corner. Total drag was reduced by 3–11%, depending on the model incidence. There are indications that the flow in the wake of the model is also significantly steadier when the bubble at the lower ramp corner is eliminated. The vortex system is tighter and steadier when the ramp-corner bubble is eliminated.     

The ternary system CsCl−NaCl−LaCl3

The ternary system CsCl?NaCl?LaCl₃ was investigated by means of differential thermal analysis and X-ray powder diffraction analysis. There exists one congruently melting compound, Cs₂NaLaCl₆, crystallizing with the cubic elpasolite structure. No quasi-binary section exists for the whole system, however three binaries range from the ternary compound Cs₂NaLaCl₆ to NaCl, CsLa₂Cl₇ and Cs₃LaCl₆ resp., dividing the system in three areas of composition: one triangle, Cs₃LaCl₆?Cs₂NaLaCl₆?CsLa₂Cl₇, containing additionally a compound Cs₂LaCl₅ below 510°C, and the two areas CsCl?NaCl?Cs₂NaLaCl₆?Cs₃LaCl₆ and Cs₂NaLaCl₆?NaCl?LaCl₃?CsLa₂Cl₇, containing a mixed crystal range between LaCl₃ and Na₃La₅Cl₁₈. These areas could be further divided in five triangles, so that the whole system contains six Alkemade triangles.     

1.2 Anorganische analyse

Ohne Zusammenfassung     

Buchbesprechungen

Ohne Zusammenfassung     

Anion-assisted trans-cis isomerization of palladium(II) phosphine complexes containing acetanilide functionalities through hydrogen bonding interactions

The anion-assisted shift of trans-cis isomerization equilibrium of a palladium(II) complex containing acetanilide functionalities brought about by allosteric hydrogen bonding interactions has been established by UV/Vis, 1H NMR, 31P NMR and ESI-MS studies.     

Total Synthesis of Cyclothialidine

A total synthesis of cyclothialidine ( 1 ), a new DNA gyrase inhibitor isolated from Streptomyces filipinensis, is described. The synthetic concept was tested by preparing the lactone 13 (Scheme 2) which contains the characteristic bicyclic core entity of 1 . Key features of the synthesis of 1 are: preparation of 3,5-dihydroxy-2,6-dimethylbenzoic acid ( 23 ) from 3,5-dihydroxybenzoic acid ( 19 ) by two consecutive Mannich aminomethylation/hydrogenation sequences; benzylic N-bromosuccinimide bromination of an ester derivative 25 thereof and its subsequent coupling with Boc-Ser-Cys-OMe ( 11 ); cyclization of the ω-hydroxy acid 29 29 to the 12-membered lactone 30 using preferably Mitsunobu conditions; completion of the peptidic side chains of 1 using Boc strategy (Scheme 4). Optically pure cis-N-(tert-butoxycarbonyl)-3-hydroxy-L -proline ((–)- 14 ) was obtained by resolution of the racemate via an efficient reaction sequence containing a lipase-catalyzed enantiospecific acetate hydrolysis (Scheme 3). The structure of natural 1 was confirmed by comparison with the synthetic material. The synthetic route described provides also easy access to analogues of 1 , e.g., via the intermediate 30 .     

1,6-dithia-spiro[4.4]nonadiene aus 2-thiazolin-5-thionen

4,4-Dimethyl-2-phenyl-2-thiazolin-5-thione ($\text{4}$) reacts with 2,3-diphenylcyclopropenone ($\text{2a}$) at 145°C and with benzonitrilio-2-propanide ($\text{6}$) at room temperature to yield the 1,6-dithia-spiro[4.4]nonadienes $\text{5}$ and $\text{7}$, respectively.