Summary: Nanocelluloses combine in a very exciting manner important properties of cellulose with amazing features of nano‐scale materials. With a view to the increasing discussion on the potential risks of nanoparticles and nanotechnology to human health and the environment, it is important to point out that the nanocellulose fibers are irreversibly networked in the supramolecular cellulose structure. This contribution assembles the current knowledge in research, development, and application in the field of nanocelluloses through examples. The topics combine selected results on nanocelluloses from bacteria and wood as well as the formation and in situ shaping of cellulose bodies, the coating of materials with nanosized cellulose networks/supports, and the preparation of nanocellulose composites as well as the use of bacterial cellulose as novel type of medical implants.

The biomaterial bacterial cellulose (BC) represents an innovative approach for overcoming reconstructive problems associated with extended vascular diseases by providing small caliber vascular grafts (diameter 1.0-3.7, length 5.0-10.0, and wallthickness 0.7 mm). In a first microsurgical study, the BC implants were attached in an artificial defect of the carotid artery of rats for 1 year. These long term results show the incorporation of the BC under formation of neointima and ingrowth of active fibroblasts. In a second study, the grafts were used to replace the carotid arteries of pigs. After 3 months, these grafts were removed and analyzed both macroand microscopically. Seven grafts (87.5%) were patent whereas one graft was found occluded. These data indicate that the innovative BC engineering technique results in the production of stable vascular conduits and confirm a highly attractive approach to in vivo tissue engineered blood vessels as part of programs in cardiovascular surgery.

Novel ligands have been obtained from the reaction of 4,4'-dibromomethyl-2,2'-bipyridine with 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosylthiol, 2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosylthiol or 2,3,4,6-tetra-O-acetyl-alpha-D-thioacetylmannopyranoside in which the sugar residues are thioglycosidically linked to the bipyridine in the 4,4'-position. Cleavage of the acetyl groups affords hydrophilic symmetric ligands with free hydroxyl groups. Reaction of the new glycoconjugated ligands (L) with [Re(CO)(5)Cl] yields fluorescent complexes of general formula [Re(L)(CO)(3)Cl], which were characterised by mass spectrometry, elemental analysis and (1)H and (13)C NMR, IR, UV/Vis and fluorescence spectroscopy. These complexes exhibit excellent solubility and stability in organic solvents or water, depending on the residues of the sugar. One complex, namely tricarbonyl-4,4'-bis[(2,3,4,6-tetra-O-acetyl-beta-D-glycopyranosyl)thiomethyl]-2,2'-bipyridinerheniumtricarbonylo chloride, has been characterised by X-ray crystallography. A non-symmetric structure of the complexes could be assigned. Radiolabelling of the unprotected ligands with [(99m)Tc(H(2)O)(3)(CO)(3)](+) affords the corresponding water-soluble technetium complexes (in quantitative yields), which were characterised by their HPLC radiation traces. The formed complexes are stable for several hours in the presence of histidine but show partial ligand-exchange after one day.

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Cisplatin analogue complexes with platinum(II) and palladium(II) starting from 3',5'-diamino-3',5'-dideoxy-thymidines were synthesized, both with the D-erythro- and D-threo configurations. Complexes of the general formula [MCl(2)L] were obtained and characterized. NMR spectroscopic measurements and single crystal X-ray structure analysis showed that the metal centers are coordinated to the ligands by the amino groups in 3'- and 5'-positions and not through the thymine moiety. All ligands and complexes showed no significant in vitro activities except thymiplatin (cis-dichloro(3',5'-diamino-3',5'-dideoxy-D-threo-thymidine)platinum(II)). Detailed in vitro studies on the apoptosis pathway in lymphoma (BJAB), leukemia (NALM-6), and melanoma cells (Mel-HO) as well as on transfected or resistant cell lines were carried out. Thymiplatin significantly induced an apoptotic response, which was found to be associated with the loss of mitochondrial membrane potential and with caspase activation. The activity was shown to be independent of Fas-associated protein with death domain (FADD), but dependent on Bcl-2 expression. As a consequence, for thymiplatin a mitochondrial mode of action could be assigned. Moreover, the compound showed activity in cells resistant to common drugs, such as daunorubicin and vincristin, and showed synergistic effects with doxorubicin, vincristin, cytarabin, and daunorubicin.

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We report the synthesis of the first 2',3'-diamino substituted uridine derivative with xylo-configuration, its use as starting material for the synthesis of salen-type ligands and the first structurally characterised copper(II) complex thereof.