Zoetic polymers

Conditions mediating the formation of biological polymers in situ are reviewed, and terminology suggested to differentiate polymers found in living cells from synthetic materials and polymers derived from biological sources that are modified or studied in a way that obscures their biological function. Methods currently used to characterize the mechanical properties of biopolymer networks in cells are briefly discussed.     

Large ring polymers align FtsZ polymers for normal septum formation

Cytokinesis in bacteria is initiated by polymerization of the tubulin homologue FtsZ into a circular structure at midcell, the Z-ring. This structure functions as a scaffold for all other cell division proteins. Several proteins support assembly of the Z-ring, and one such protein, SepF, is required for normal cell division in Gram-positive bacteria and cyanobacteria. Mutation of sepF results in deformed division septa. It is unclear how SepF contributes to the synthesis of normal septa. We have studied SepF by electron microscopy (EM) and found that the protein assembles into very large (～50 nm diameter) rings. These rings were able to bundle FtsZ protofilaments into strikingly long and regular tubular structures reminiscent of eukaryotic microtubules. SepF mutants that disturb interaction with FtsZ or that impair ring formation are no longer able to align FtsZ filaments in vitro, and fail to support normal cell division in vivo. We propose that SepF rings are required for the regular arrangement of FtsZ filaments. Absence of this ordered state could explain the grossly distorted septal morphologies seen in sepF mutants.     

Single-walled tubulin ring polymers

An unusual class of nanoscopic, ring-shaped, single-walled biopolymers arises when alphabeta-tubulin is mixed with certain small peptides obtained from various marine organisms and cyanobacteria. The single-ring structures, whose mean molecular weight depends on the specific peptide added to the reaction mixture, usually have sharp mass distributions corresponding, e.g., to rings containing eight tubulin dimers (when the added peptide is cryptophycin) and 14 dimers (e.g., with dolastatin). Although the ring-forming peptides have been shown to possess antimitotic properties when tested with cultured eukaryotic cells (and thus have generated considerable interest as possible agents to be used in the treatment of cancer), it is not our intention to extensively discuss the potential pharmacological properties of the peptides. Rather, we will review the polymeric structures that form and illustrate how certain physical techniques can be used to characterize their properties and interactions. The nanoscopic size and particular geometry of the individual rings make them appropriate targets for scattering and hydrodynamic techniques that provide details about their structure in solution, but it is necessary to relate measured data to postulated structures by nontrivial, albeit straight-forward, mathematical, and computational means. We will discuss how this is done when one uses such methods as small angle neutron scattering, dynamic light scattering, fluorescence correlation spectroscopy, and sedimentation velocity measurements. Moreover, we show that, by using several techniques, one can eliminate degeneracy to provide better discrimination between model structures.     

Lignin-based polymers and nanomaterials

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Chemoenzymatically synthesized glycoconjugate polymers

Glycoconjugate polymers with poly(vinyl alcohol) (PVA) backbone were synthesized via a chemoenzymatic method. The sugar alcohols of maltose and lactose were submitted to transesterification in the presence of lipases. The esterification was achieved with high selectivity and yield, and the resulting maltitol and lactitol 6-vinyl sebacates were polymerized by a conventional radical initiator with hydrogen peroxide and ascorbic acid. The glycoconjugate polymers carrying alpha-glucose and beta-galactose as recognition signals showed the biological activity such as lectin recognition abilities and hepatocyte adhension. The biodegradability of these polymers was modest but higher than PVA.     

Chiral liquid-crystalline side chain polymers by enantioselective modification of prochiral parent polymers

The preparation is reported of two side chain polyacrylate samples 1a , b containing a sulfide group linked to the mesogenic core. By oxidation with a preferentially chiral oxaziridine, samples 1a , b were chemoselectively and enantioselectively converted to the corresponding sulfoxide containing polymers 2a , b with an estimated 20% asymmetric induction. The mesophasic behaviour of the parent and oxidized polymer samples is analyzed by thermal and optical techniques. The modification of the prochiral sulfide groups into chiral sulfoxide groups slightly depresses the propensity of the resulting polymers to give stable and persistent mesophases.