A role for confined water in chaperonin function

Chaperonins engulf other proteins and accelerate their folding by an unknown mechanism. Here, we combine all-atom molecular dynamics simulations with data from experimental assays of the activity of the bacterial chaperonin GroEL to demonstrate that a chaperonin's ability to facilitate folding is correlated with the affinity of its interior surface for water. Our results suggest a novel view of the behavior of confined water for models of in vivo protein folding scenarios.     

Theory for an order-driven disruption of the liquid state in water

Water is known to exhibit a number of peculiar physical properties because of the strong orientational dependence of the intermolecular hydrogen bonding interactions that dominate its liquid state. Recent full-atom simulations of water in a nanolayer between graphite plates submersed in an aqueous medium have raised the possibility of a new addition to this list of peculiarities: they show that application of a strong, uniform electric field normal to and between the plates can cause a pronounced decrease in particle density, rather than the increase expected from electrostriction theory for polarizable fluids [Vaitheeswaran et al., J. Phys. Chem. B 70, 6629 (2005)]. However, in seeming contradiction to this result, another study that simulated a range of similar systems has reported a less surprising electrostrictive increase in particle density upon application of the field [Bratko et al., J. Am. Chem. Soc. 129, 2504 (2007)]. In this work, we attempt to reconcile these conflicting simulation phenomena using a statistical mechanical lattice liquid model of water in an applied field. By solving the model using mean-field theory, we show that a field-induced transition to a markedly lower-density phase such as that observed in recent simulations is possible within a certain parameter regime, but that outside of this regime, the more conventional electrostrictive result should be obtained. Upon modifying the model to treat the case of bulk water under constant pressure in an applied field, we predict a density drop with rising field, and subsequently observe the predicted behavior in our own molecular dynamics simulations of liquid water. Our findings lead us to propose that the model considered here may be useful in a variety of contexts for describing the trade-off between orientational ordering of water molecules and their participation in the liquid phase.     

Iron(II), manganese(II) and cobalt(II) complexes containing tetradentate biphenyl-bridged ligands and their application in alkane oxidation catalysis

A series of manganese(II), iron(II) and cobalt(II) bis(triflate) complexes containing linear tetradentate bis(imine) and bis(amine) ligands with a biphenyl bridge have been synthesized. The twist in the ligand backbone due to the biphenyl unit leads in the case of the bis(imine) ligands (1 and 2) containing sp2 hybridised N donors, to a distorted cis-alpha coordination geometry, whereas in the case of the biphenyl- and biphenylether-bridged bis(amine) ligands (7 - 9 and 12), a trans coordination geometry is observed. The catalytic properties of the complexes for the oxidation of cyclohexane, using H2O2 as the oxidant, have been evaluated. Only the iron complexes show any catalytic activity under the conditions used, but the low conversions and selectivies observed indicate that these catalysts lead predominantly to free radical auto-oxidation.     

Synthesis of the western half of the lolicines and lolitrems

[reaction: see text] The synthesis of the highly substituted indole portion of the complex tremorgenic natural products lolicine A and B is presented. The Diels-Alder reaction of a quinone monoimine enables the synthesis of an appropriately substituted indole. The key step in the synthesis is a tandem isopropenyl cuprate addition/aldol cyclocondensation which provides the necessary functionality for elaboration to the 2,2,5,5-tetramethyltetrahydrofuran.     

Mechanistic studies of an unusual epoxide-forming elimination of a beta-hydroxyalkyl rhodium porphyrin

A new and remarkably facile sp3-C-O bond forming reaction of beta-hydroxyalkyl Rh porphyrins to form epoxides has been discovered and its mechanism investigated.     

A Synthetic High‐Spin Oxoiron(IV) Complex: Generation,Spectroscopic Characterization,and Reactivity

High versus low : The high‐yield generation of a synthetic high‐spin oxoiron(IV) complex, [Fe^IV(O)(TMG₃tren)]²⁺ (see picture, TMG₃tren = 1,1,1‐tris{2‐[N2‐(1,1,3,3‐tetramethylguanidino)]ethyl}amine), has been achieved by using the very bulky tetradentate TMG₃tren ligand, in order to both sterically protect the oxoiron(IV) moiety and enforce a trigonal bipyramidal geometry at the iron center, for which an S=2 ground state is favored.

     

Generalised elliptic functions

We consider multiply periodic functions, sometimes called Abelian functions, defined with respect to the period matrices associated with classes of algebraic curves. We realise them as generalisations of the Weierstraß ?-function using two different approaches. These functions arise naturally as solutions to some of the important equations of mathematical physics and their differential equations, addition formulae, and applications have all been recent topics of study.The first approach discussed sees the functions defined as logarithmic derivatives of the σ-function, a modified Riemann θ-function. We can make use of known properties of the σ-function to derive power series expansions and in turn the properties mentioned above. This approach has been extended to a wide range of non hyperelliptic and higher genus curves and an overview of recent results is given.The second approach defines the functions algebraically, after first modifying the curve into its equivariant form. This approach allows the use of representation theory to derive a range of results at lower computational cost. We discuss the development of this theory for hyperelliptic curves and how it may be extended in the future. We consider how the two approaches may be combined, giving the explicit mappings for the genus 3 hyperelliptic theory. We consider the problem of generating bases of the functions and how these decompose when viewed in the equivariant form.     

Sensitive resist systems based on acid-catalyzed polymer reactions

Acid-catalyzed polymer reactions have been successfully utilized in the design of chemical amplification resist systems for semiconductor manufacturing. In this paper are described preparation and acid-catalyzed depolymerization reactions of α-substituted polystyrenes.