B Lee

We have measured the repulsive force between B-form double helices in parallel packed arrays of polymer-condensed DNA in the presence of 0.005-1.0 M ionic solutions. Molecular repulsion is consistently exponential with a 2.5-3.5 A decay distance, when the separation between DNA surfaces is 5-15 A. Only weakly dependent on ionic strength and independent of molecular size, this intermolecular repulsion does not obey the predictions of electrostatic double-layer theory. Rather, it strongly resembles the "hydration force" first recognized and quantified between phospholipid bilayers. Only beyond 15 A separation between molecules is there evidence of electrostatic double-layer forces. The quantitative failure of electrostatic double-layer theory seen here must gravely affect accepted analyses of other polyelectrolyte systems. Because the packing of condensed DNA resembles the spacings of DNA in many bacteriophages, our results permit estimation of the "DNA pressure" in phage heads.

Photoresponsive polymers convert a light stimulus input into a mechanical output (work). Photoinduced conformational changes, such as within azobenzene, dictate molecular-level distortions that summate into a macroscopic strain, which often manifests as a shape change or motion. The transduction of the molecular-level response to a macroscale effect is regulated by mesoscopic features, such as chain packing, free volume, and local molecular order—factors which depend on chemical composition as well as the process history of the material. Herein, we demonstrate the ability to widely tailor the photomechanical response of a photoresponsive polymer by manipulating the energy state of the glass, rather than formulating new chemical compositions. Physical aging increases the density of the glass, reduces local free volume, and thus reduces the minima in local conformation space, thereby strongly influencing the azobenzene photochemistry (trans–cis–trans isomerization). The subsequent change in the energy landscape of the system reduces the fraction of azobenzene able to undergo reconfiguration as well as increases the probability that those photoinduced conformations will relax back to the initial local environment. The result is a tuning of the magnitude of macroscopic strain and the ability to shift from shape fixing to shape recovery, respectively.

Analyses of the x-ray diffraction intensity data by the Patterson synthesis and rotation function techniques show that the true space group of the monoclinic crystals of L-asparaginase (L-asparagine amidohydrolase, EC 3.5.1.1) from Proteus vulgaris is P21, that the molecular centers lie at x = 0.054, y = 0, z = 0.256, and its symmetry related positions, and that the tetramer molecules possess three approximate, mutually perpendicular 2-fold rotational symmetries, the axes of which run along the directions of the crystallographic a*-, b-, and c-axes. In addition, an investigation of the molecular packing arrangement in the crystal indicates that the tetramer molecules possess an approximately regular tetrahedral subunit structure.