Random Copolymers of 1,5-Dioxepan-2-one

ABSTRACT

Copolymers of 1,5-dioxepan-2-one (DXO) and e-caprolactone (?-CL), δ-valerolactone (δ-VL) or L-lactide (LLA) have been synthesized and characterized. High molecular weight copolymers were obtained using stannous-2-ethyl hexanoate as catalyst in bulk. Reactivity ratios for the copolymerization of DXO and δ-VL were determined at 110°C as r_VL=0.5 and r_DXO=2.3. At high conversion, depolymerization of δ-VL occurred, resulting in lower molecular weight and variations in the copolymer composition.

Physical properties, such as crystallinity and melting temperature of the DXO-copolymers proved to be strongly dependent on the choice of comonomer and on the molar composition of the copolymers. DXO appears to be incorporated into the poly-?-caprolactone (PCL) crystals and to some extent into the poly-δ-valerolactone (PVL) crystals, resulting in a more gradual decrease in crystallinity with increasing amount of DXO.     

Microscopic reversibility and reciprocal relations for Brownian molecular machines

Chemists have made great progress in synthesizing molecules that emulate in part the remarkable properties of biological molecular motors, most especially the ability to use chemical energy to drive directed motion and do mechanical work. Here the mechanism of a molecular motor is treated as a renewal process in which the motor molecule fluctuates away from, and then returns to some arbitrary initial configurational state. During this excursion, some number of fuel molecules will have been catalytically converted to product, and the motor will have undergone some number of mechanical cycles in which work is done on the environment. The dependences of the number of catalytic and mechanical processes per renewal obey reciprocal relations for arbitrarily strong load force and chemical driving force. These relations characterize the behavior of the system far from thermodynamic equilibrium in the same way that the Onsager reciprocal relations characterize the system close to thermodynamic equilibrium.     

Protein conformational fluctuations and free-energy transduction

Non-equilibrium fluctuations, whether imposed externally or driven by an energy-releasing chemical reaction, can cause a protein to cycle through several conformations. This cycling can drive a process thermodynamically uphill even though any one conformation considered independently catalyzes the process in the downhill direction. This is because the different conformations have different rate constants (energy barriers) between the states in the catalytic cycle. Even though each conformation individually obeys detailed balance, the flashing between different energy profiles gives rise to a ratchet effect. Further, by exploiting protein conformational dynamics, a single stochastic input can be converted into two phase-shifted internal parameters (e.g. a kinetic barrier height and a binding well energy). This allows the output process to be driven nearly adiabatically, explaining in part the very high efficiencies observed for some biological energy-transduction processes. The results apply equally to driving a biochemical reaction away from equilibrium by an enzyme, to formation of an osmotic gradient across a membrane by a molecular pump, or to motion and generation of force by a molecular motor. Received: 8 February 2002 / Accepted: 4 March 2002 / Published online: 22 April 2002     

Design principles for Brownian molecular machines: how to swim in molasses and walk in a hurricane

Protein molecular motors-perfected over the course of millions of years of evolution-play an essential role in moving and assembling biological structures. Recently chemists have been able to synthesize molecules that emulate in part the remarkable capabilities of these biomolecular motors (for extensive reviews see the recent papers: E. R. Kay, D. A. Leigh and F. Zerbetto, Angew. Chem., Int. Ed., 2006, 46, 72-191; W. R. Browne and B. L. Feringa, Nat. Nanotechnol., 2006, 1, 25-35; M. N. Chatterjee, E. R. Kay and D. A. Leigh, J. Am. Chem. Soc., 2006, 128, 4058-4073; G. S. Kottas, L. I. Clarke, D. Horinek and J. Michl, Chem. Rev., 2005, 105, 1281-1376; M. A. Garcia-Garibay, Proc. Natl. Acad. Sci., U. S. A., 2005, 102, 10771-10776)). Like their biological counterparts, many of these synthetic machines function in an environment where viscous forces dominate inertia-to move they must "swim in molasses". Further, the thermal noise power exchanged reversibly between the motor and its environment is many orders of magnitude greater than the power provided by the chemical fuel to drive directed motion. One might think that moving in a specific direction would be as difficult as walking in a hurricane. Yet biomolecular motors (and increasingly, synthetic motors) move and accomplish their function with almost deterministic precision. In this Perspective we will investigate the physical principles that govern nanoscale systems at the single molecule level and how these principles can be useful in designing synthetic molecular machines.     

Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

Great expectations: can artificial molecular machines deliver on their promise?

The development and fabrication of mechanical devices powered by artificial molecular machines is one of the contemporary goals of nanoscience. Before this goal can be realized, however, we must learn how to control the coupling/uncoupling to the environment of individual switchable molecules, and also how to integrate these bistable molecules into organized, hierarchical assemblies that can perform significant work on their immediate environment at nano-, micro- and macroscopic levels. In this tutorial review, we seek to draw an all-important distinction between artificial molecular switches which are now ten a penny-or a dime a dozen-in the chemical literature and artificial molecular machines which are few and far between despite the ubiquitous presence of their naturally occurring counterparts in living systems. At the single molecule level, a prevailing perspective as to how machine-like characteristics may be achieved focuses on harnessing, rather than competing with, the ineluctable effects of thermal noise. At the macroscopic level, one of the major challenges inherent to the construction of machine-like assemblies lies in our ability to control the spatial ordering of switchable molecules-e.g., into linear chains and then into muscle-like bundles-and to influence the cross-talk between their switching kinetics. In this regard, situations where all the bistable molecules switch synchronously appear desirable for maximizing mechanical power generated. On the other hand, when the bistable molecules switch "out of phase," the assemblies could develop intricate spatial or spatiotemporal patterns. Assembling and controlling synergistically artificial molecular machines housed in highly interactive and robust architectural domains heralds a game-changer for chemical synthesis and a defining moment for nanofabrication.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

Towards a chemically driven molecular electron pump

Charge can be pumped through a tiny gated portal from a reservoir at low electrochemical potential to one at the same or higher electrochemical potential by cyclically modulating the portal and gate energies. A theoretically and experimentally well established mechanism is Thouless adiabatic pumping, achieved by a precisely timed out-of-phase modulation of at least two parameters of the system. Here we show that stochastic modulation between two configurations of gate and portal energies can drive efficient pumping by a different, nonadiabatic, mechanism that may provide a basis for chemically driven electron pumping through a molecular wire.     

Detection of weak electric fields by sharks,rays, and skates

The elasmobranchs-sharks, rays, and skates-can detect very weak electric fields in their aqueous environment through a complex sensory system, the ampullae of Lorenzini. The ampullae are conducting tubes that connect the surface of the animal to its interior. In the presence of an electric field, the potential of the surface of the animal will differ from that of the interior and that potential is applied across the apical membrane of the special sensory cells that line the ampullae. The firing rate of the afferent neurons that transmit signals from the ampullae has been shown to vary with that potential. We show that those firing rates can be described quantitatively in terms of synchronous firing of the sensory cells that feed the neurons. We demonstrate that such synchronism follows naturally from a hypothetical weak cell-to-cell interaction that results in a self-organization of the sensory cells. Moreover, the pulse rates of those cells-and the neurons that service the cells-can be expected to vary with the imposed electric fields in accord with measured values through actions of voltage gated transmembrane proteins in the apical sector of the cell membranes that admit Ca(++) ions. We also present a more conjectural model of signal processing at the neuron level that could exploit small differences in firing rates of nerve fibers servicing different ampullae to send an unambiguous signal to the central nervous system of the animal. (c) 1998 American Institute of Physics.