Long-range attraction between charge-mosaic surfaces across water

We have measured directly the forces across water between hydrophilic surfaces covered with a random mosaic of positive and negative charged domains. We find a strong, long-ranged attraction between them at a surface separation comparable with the charge domain size (many tens of nanometers). This attraction persists at higher salt concentration, but its range then becomes comparable to the Debye screening length. We attribute the attraction to correlation between negative and positive regions on opposing surfaces, facilitated by the lateral mobility of the charge patches on the surfaces.     

Stallings’ folds for cube complexes

We describe a higher dimensional analogue of Stallings’ folding sequences for group actions on CAT(0) cube complexes. We use it to give a characterization of quasiconvex subgroups of hyperbolic groups that act properly and cocompactly on CAT(0) cube complexes via finiteness properties of their hyperplane stabilizers.     

Subtle differences in structural transitions between poly-L- and poly-D-amino acids of equal length in water

Mirror-image asymmetric molecules, i.e., chiral isomers or enantiomers, are classically considered as chemically identical. Recent studies, however, have indicated that parity violation by the nuclear weak force induces a tiny energy difference between chiral isomers. Upon combination with a massive amplification process, expansion of this difference to a detectable macroscopic level may be achieved. Yet, experimental tests of this possibility, where one enantiomer is compared to the other in solution, are hampered by the possible presence of undetectable impurities. In this study we have overcome this problem by comparing structural and dynamic features of synthetic D- and L-polyglutamic acid and polylysine molecules each of 24 identical residues. In these water-soluble polypeptides helix formation is an intramolecular autocatalytic process amplified by each turn, which is actually unaffected by low level of putative impurities in the solvent. The helix and random coil configurations and their transition were determined in this study by circular dichroism (CD) and isothermal titration calorimetry (ITC) in water and deuterium oxide. Distinct differences in structure and transition energies between the enantiomeric polypeptides were detected by both CD and ITC when dissolved in water. Intriguingly, these differences were by and large abolished in deuterium oxide. Our findings suggest that deviation from physical invariance between the D- and L-polyamino acids is induced in part by different hydration in water which is eliminated in deuterium oxide. Based on the recent findings by Tikhonov and Volkov (V. I. Tikhonov and A. A. Volkov, Science 2002, 296, 2363) we suggest that ortho-H(2)O, which constitutes 75% of bulk H(2)O, has a preferential affinity to L-enantiomers. Differential hydration of enantiomers may have played a role in the selection of L-amino acids by early forms of life.     

Photocycles of Channelrhodopsin-2

Recent developments have used light-activated channels or transporters to modulate neuronal activity. One such genetically-encoded modulator of activity, channelrhodopsin-2 (ChR2), depolarizes neurons in response to blue light. In this work, we first conducted electrophysiological studies of the photokinetics of hippocampal cells expressing ChR2, for various light stimulations. These and other experimental results were then used for systematic investigation of the previously proposed three-state and four-state models of the ChR2 photocycle. We show the limitations of the previously suggested three-state models and identify a four-state model that accurately follows the ChR2 photocurrents. We find that ChR2 currents decay biexponentially, a fact that can be explained by the four-state model. The model is composed of two closed (C1 and C2) and two open (O1 and O2) states, and our simulation results suggest that they might represent the dark-adapted (C1-O1) and light-adapted (C2-O2) branches. The crucial insight provided by the analysis of the new model is that it reveals an adaptation mechanism of the ChR2 molecule. Hence very simple organisms expressing ChR2 can use this form of light adaptation.     

Adsorption isotherms and Sips models of nitrogen,methane, ethane,and propane on commercial activated carbons and polyvinylidene chloride

In this paper we present the measured isotherms of nitrogen, methane, ethane, and propane on three carbons: Norit RB2, Chemviron AP 4-60, and highly activated Saran. The measurements are taken at temperatures between 300 and 400 K, in 20 K steps. The measured data is fitted to the Sips adsorption model, where the Sips parameters are determined by a linearization method. The Sips parameters are further adjusted to realize a logic dependence on temperature and the parameter characteristics are discussed. Subsequently, the Sips model is modified to incorporate the temperature dependence. Including the temperature dependence results in a slightly higher error relative to the experimental results (typically 10 % as compared to 6 %). The immediate research product is a convenient expression for every adsorbate-adsorbent system which is discussed in this paper, for calculating the adsorption concentration as a function of temperature and pressure. A more general research product is a better understanding of the Sips parameter characteristics that should help in developing future adsorbents on demand.     

K-region oxides and imines of benzo[b]phenanthro[2,3-d]thiophene and benzo[b]phenanthro[3,2-d]thiophene

The syntheses of the K-oxides and K-imine derivatives of benzo[b]phenanthro[2,3-d]thiophene and benzo-[b]phenanthro[3,2-d]thiophene are described. The parent hydrocarbons 1 and 2 were oxidized with osmium tetroxide and sodium metaperiodate, and the dialdehydes 12 and 18 so formed, cyclized to the corresponding epoxides 1a,12b-dihydrobenz[b]oxireno[9,10]phenanthro[2,3-d]thiophene ( 7 ) and 1a,12b-dihydrobenz-[b]oxireno[9,10]phenanthro[3,2-d]thiophene ( 13 ). Reaction of the oxiranes with sodium azide gave mixtures of azido-alcohols that, in turn, were transformed to the thiaarene imines 1a,12b-dihydro-1H-benz[b]azirino-[9,10]phenanthro[2,3-d]thiophene ( 8 ) and 1a,12b-dihydro-1H-benz[b]azirino[9,10]phenanthro[3,2-d]thiophene ( 14 ), respectively, with the aid of tri-n-butylphosphine.     

Elucidating the role of many-body forces in liquid water. I. Simulations of water clusters on the VRT(ASP-W) potential surfaces

We test two new potentials for water, fit to vibration-rotation tunneling (VRT) data by employing diffusion quantum Monte Carlo simulations to calculate the vibrational ground-state properties of water clusters. These potentials, VRT(ASP-W)II and VRT(ASP-W)III, are fits of the highly detailed ASP-W (anisotropic site potential with Woermer dispersion) ab initio potential to (D(2)O)(2) microwave and far-infrared data, and along with the SAPT5s (five-site symmetry adapted perturbation theory) potentials, are the most accurate water dimer potential surfaces in the literature. The results from VRT(ASP-W)II and III are compared to those from the original ASP-W potential, the SAPT5s family of potentials, and several bulk water potentials. Only VRT(ASP-W)III and the spectroscopically "tuned" SAPT5st (with N-body induction included) accurately reproduce the vibrational ground-state structures of water clusters up to the hexamer. Finally, the importance of many-body induction and three-body dispersion are examined, and it is shown that the latter can have significant effects on water cluster properties despite its small magnitude.     

Perturbation theories and wave functions for calculation of electronic polarizabilities application to DNA bases

Three different forms of perturbation theories, variational perturbation, finite perturbation and second-order, are evaluated regarding their value for calculation of electronic polarizabilities of small and intermediate size molecules. It is concluded that with the practical constraint of a small basis set the variational perturbation method is the most promising alternative for calculation of polarizabilities. For several small molecules, our calculated polarizabilities indicate that both IEHT and ab initio wave functions give values in close agreement with each other. Variational perturbation calculations of polarizabilities with IEHT wave functions also include the DNA bases.