Critical Region for Droplet Formation in the Two-Dimensional Ising Model

We study the formation/dissolution of equilibrium droplets in finite systems at parameters corresponding to phase coexistence. Specifically, we consider the 2D Ising model in volumes of size L ² , inverse temperature > _c and overall magnetization conditioned to take the value m L ² –2m v _L , where _c ^–1 is the critical temperature, m =m () is the spontaneous magnetization and v _L is a sequence of positive numbers. We find that the critical scaling for droplet formation/dissolution is when v _L ^3/2 L ^–2 tends to a definite limit. Specifically, we identify a dimensionless parameter , proportional to this limit, a non-trivial critical value _c and a function such that the following holds: For < _c , there are no droplets beyond log L scale, while for > _c , there is a single, Wulff-shaped droplet containing a fraction _c =2/3 of the magnetization deficit and there are no other droplets beyond the scale of log L. Moreover, and are related via a universal equation that apparently is independent of the details of the system.     

Water vapour sorption by the pedal mucus trail of a land snail

The hydrophilicity of pedal mucus trails deposited by snails influences the settlement of marine organisms and can potentially influence the trailing and homing mechanisms of terrestrial snails. The composition of pedal mucus deposited as a trail on a solid substrate by the giant African land snail (Achatina marginata) has been probed non-invasively using infrared ellipsometry. The primary chemical groups in the mucus (in its native state) have been identified through their characteristic infrared absorption frequencies. Water vapour sorption in the mucus trails in equilibrium with the atmosphere was measured as a function of the relative humidity (RH). When RH=84%, the mucus contains 53 volume percent water. The water sorption isotherm of the mucus trail can be described through a Flory–Huggins polymer/solvent interaction parameter of χ=0.54±0.1, which is comparable to the value for some synthetic hydrophilic polymers, such as poly(vinyl pyrrolidone).     

Enantioselective luminescence quenching of DNA light-switch [Ru(phen)2dppz]2+ by electron transfer to structural homologue [Ru(phendione)2dppz]2+

The quenching of the luminescence of [Ru(phen)(2)dppz](2+) by structural homologue [Ru(phendione)(2)dppz](2+), when both complexes are bound to DNA, has been studied for all four combinations of Delta and Lambda enantiomers. Flow linear dichroism spectroscopy (LD) indicates similar binding geometries for all the four compounds, with the dppz ligand fully intercalated between the DNA base pairs. A difference in the LD spectrum observed for the lowest-energy MLCT transition suggests that a transition, potentially related to the final localization of the excited electron to the dppz ligand in [Ru(phen)(2)dppz](2+), is overlaid by an orthogonally polarized transition in [Ru(phendione)(2)dppz](2+). This would be consistent with a low-lying LUMO of the phendione moiety of [Ru(phendione)(2)dppz](2+) that can accept the excited electron from [Ru(phen)(2)dppz](2+), thereby quenching the emission of the latter. The lifetime of excited Delta-[Ru(phen)(2)dppz](2+) is decreased moderately, from 664 to 427 ns, when bound simultaneously with the phendione complex to DNA. The 108 ns lifetime of opposite enantiomer, Lambda-[Ru(phen)(2)dppz](2+), is only shortened to 94 ns. These results are consistent with an average rate constant for electron transfer of approximately 1.10(6) s(-1) between the phenanthroline- and phendione-ruthenium complexes. At binding ratios close to saturation of DNA, the total emission of the two enantiomers is lowered equally much, but for the Lambda enantiomer, this is not paralleled by a decrease in luminescence lifetime. A binding isotherm simulation based on a generalized McGhee-von Hippel approach shows that the Delta enantiomer binds approximately 3 times stronger to DNA both for [Ru(phendione)(2)dppz](2+) and [Ru(phen)(2)dppz](2+). This explains the similar decrease in total emission, without the parallel decrease in lifetime for the Lambda enantiomer. The simulation also does not indicate any significant binding cooperativity, in contrast to the case when Delta-[Rh(phi)(2)bipy](3+) is used as quencher. The very slow electron transfer from [Ru(phen)(2)dppz](2+) to [Ru(phendione)(2)dppz](2+), compared to the case when [Rh(phi)(2)phen](3+) is the acceptor, can be explained by a much smaller driving free-energy difference.     

Darstellung und Kristallstrukturen von Dicyanamido(triphenylphosphan)gold(I) und Nitrosodicyanmethanido(triphenylphosphan)gold(I)

Preparation and Crystal Structures of Dicyanamido(triphenylphosphane)gold(I) and Nitrosodicyanomethanido(triphenylphosphane)gold(I) The coordination compounds [(Ph₃P)Au{N(CN)₂}] ( 1 ) and [(Ph₃P)Au{ONC(CN)₂}] ( 2 ) are obtained by the reaction of [Au(PPh₃)]NO₃ with Na[N(CN)₂] or K[ONC(CN)₂] in CH₂Cl₂. The compounds are characterized by IR spectroscopy and by crystal structure determination. 1 crystallizes triclinic in the space group P 1 with a = 930.16(4), b = 1011.89(13), c = 1118.35(16) pm, α = 115.327(10), β = 90.899(8), γ = 103.394(8)°, Z = 2. 2 crystallizes monoclinic in the space group P2₁/n with a = 832.59(10), b = 1139.30(16), c = 2078.9(4) pm, β = 99.84(2)°, Z = 4. The crystal structures of both compounds are built up by pairs of antiparallel oriented molecules with linear coordinated gold atoms and weak intermolecular Au–N‐interactions.     

Improved measurement of B(D+ --> mu+nu) and the pseudoscalar decay constant fD+

We extract a relatively precise value for the decay constant of the meson by measuring B(D+ --> mu+nu) = (4.40 +/-0.66(+0.09)(-0.12) x 10(-4) using 281 pb(-1) of data taken on phi(3770) the resonance with the CLEO-c detector. We find fD+ = (222.6 +/- 16.7(+2.8)(-3.4)) MeV, and compare with current theoretical calculations. We also set a 90% confidence upper limit on B(D+e+nu)< 2.4 x 10(-5) which constrains new physics models.     

Monitoring the DNA binding kinetics of a binuclear ruthenium complex by energy transfer: evidence for slow shuffling

The semirigid binuclear ruthenium complex Delta,Delta-[mu-(11,11'-bidppz)(phen)(4)Ru(2)](4+) has been shown to rearrange slowly from an initial groove-bound nonluminescent state to a final intercalated emissive state by threading one of its bulky Ru(phen)(2) moieties through the DNA base stack. When this complex binds to poly[d(A-T)(2)], a further increase in emission from the complex is observed after completion of the intercalation, assigned to reorganization of the intercalated complex. We here report a study of the threading process in poly[d(A-T)(2)], in which the minor groove binding dye DAPI is used as an energy transfer probe molecule to assess the distribution of ruthenium complex during and also after the actual threading phase. The emission from DAPI is found to change with the same rate as the emission from the ruthenium complex, and furthermore, DAPI does not disturb the binding kinetics of the latter, justifying it as a good probe of both the threading and the reorganization processes. We conclude from the change in the emission from both DAPI and the ruthenium complex with time that DAPI-ruthenium interactions are most pronounced during the process of threading of the complex, suggesting that the complexes are initially threaded slightly anticooperatively and thereafter redistribute along the DNA to reach their thermodynamically most favorable distribution. The final distribution is characterized by a small but significant binding cooperativity, probably as a result of hydrophobic interactions between the complex ions despite their tetravalent positive charges. The mechanism of "shuffling" the complex along the DNA chain is discussed, i.e., whether the ruthenium complex remains threaded (requiring sequential base-pair openings) or if unthreading followed by lateral diffusion within the ionic atmosphere of the DNA and rethreading occurs.