Self-assembly of nanoparticles into rings: a lattice-gas model

A coarse-grained lattice-gas model in three dimensions is developed to study the self-assembly of nanoparticles into micrometer-sized rings from a thin liquid film containing the nanoparticles. The model describes the nanoparticles as well as the solvent on length scales that are typical of the solvent bulk correlation length. Morphologies obtained from simulations of the model resemble recent experiments and provide a microscopic picture for the formation of nanoparticle rings. The role of evaporation rate, film thickness, diffusion rate, and nanoparticle coverage is discussed and compared to other continuum theories. Predictions of novel structures resulting from low nanoparticle mobility are analyzed.     

Synthesis,characterization, aggregation and thermal properties of a novel polymeric metal-free phthalocyanine and its metal complexes

A novel polymeric metal-free phthalocyanine (M = 2H) and its metal complexes (M = Zn, Cu, Co and Ni) were prepared by the tetramerization reaction of 3,6,9-Tris(p-tolylsulfonyl)-1,11-bis(3,4-dicyanophenoxy)-3,6,9-triazaundecane 5 with the appropriate materials. The electrical conductivities of the metal-free phthalocyanine and the metal complexes, measured in air, were found to be ∼10⁻⁶–10⁻⁵ S m⁻¹. The aggregation property of the zinc complex 7 was investigated with Ni²⁺, Cu²⁺, Co²⁺, Pb²⁺, Cd²⁺ and Ag⁺ cations. Thermal analysis of the polymers were done by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) at a heating rate of 10 °C min⁻¹ under a nitrogen atmosphere. All the novel compounds were characterized by using elemental analysis, UV–Vis, FT–IR, NMR and MS spectral data and DSC, DTA/TG techniques.     

Adiabatic pumping in interacting systems

A dc current can be pumped through an interacting system by periodically varying two independent parameters such as the magnetic field and a gate potential. We present a general expression for the adiabatic pumping current in interacting systems, written in terms of instantaneous properties of the system at equilibrium, and find the limits of its applicability. This expression generalizes the scattering approach for noninteracting particles. We apply our formula for a quantum critical system that exhibits the two-channel Kondo effect, where single particle excitations are not well defined. We find that if the quantum critical point is contained in the pumping trajectory, the pumped spin between the channels approaches h, and if it is not contained in the trajectory, the spin approaches zero when the temperature T --> 0. We discuss the non-Fermi liquid features of this system at finite T.     

Spectral techniques applied to sparse random graphs

We analyze the eigenvalue gap for the adjacency matrices of sparse random graphs. Let λ₁ ≥ … ≥ λ_n be the eigenvalues of an n‐vertex graph, and let λ = max[λ₂,|λ_n|]. Let c be a large enough constant. For graphs of average degree d = c log n it is well known that λ₁ ≥ d, and we show that . For d = c it is no longer true that , but we show that by removing a small number of vertices of highest degree in G, one gets a graph G′ for which . Our proofs are based on the techniques of Friedman Kahn and Szemeredi from STOC 1989, who proved similar results for regular graphs. Our results are useful for extending the analysis of certain heuristics to sparser instances of NP‐hard problems. We illustrate this by removing some unnecessary logarithmic factors in the density of k‐SAT formulas that are refuted by the algorithm of Goerdt and Krivelevich from STACS 2001. © 2005 Wiley Periodicals, Inc. Random Struct. Alg., 2005     

Depth-resolved multiphoton polarization microscopy by third-harmonic generation

We achieve depth-resolved polarization microscopy by measuring third-harmonic generation induced by a tightly focused circularly polarized beam. In crystals exhibiting strong birefringence this signal is dominated by positively phase-matched third-harmonic generation. This process occurs in only optically anisotropic media, in which the birefringence compensates for the phase mismatch between the fundamental and the third harmonic induced by dispersion. Both the intensity and the polarization of the emitted signal provide information on the local optical anisotropy. We demonstrate the technique by imaging biogenic crystals in sea urchin larval spicules.     

Unusual Electro‐Optic Kerr Response in a Self‐Stabilized Amorphous Blue Phase with Nanoscale Smectic Clusters

We investigated the electro‐optic response in the “foggy” amorphous blue phase (BPIII) as well as in the isotropic phase. To the best of our knowledge, such a study has not yet been performed due to the very limited thermal range of BPIII. In this study, we used a single‐component chiral bent‐core liquid crystal with a self‐stabilized BPIII, which is stable over a wide temperature range. The results show that the response time is on the order of hundreds of microseconds in the isotropic phase and increases to 1–2 ms in the BPIII (at T_I?BP–T <1), then drastically increases up to a few tens of milliseconds upon further cooling in BPIII. Such an unusual behavior was explained on the basis of the high rotational viscosity and/or the existence of nanoscale smectic (Sm) clusters. The Kerr constant was also measured and found to be ～500 pm V^?2, which is the largest among bent‐core BP systems reported so far and comparable with that of polymer‐stabilized BPs.     

Importance of solvent accessibility and contact surfaces in modeling side-chain conformations in proteins

Contact surface area and chemical properties of atoms are used to concurrently predict conformations of multiple amino acid side chains on a fixed protein backbone. The combination of surface complementarity and solvent-accessible surface accounts for van der Waals forces and solvation free energy. The scoring function is particularly suitable for modeling partially buried side chains. Both iterative and stochastic searching approaches are used. Our programs (Sccomp-I and Sccomp-S), with relatively fast execution times, correctly predict chi1 angles for 92-93% of buried residues and 82-84% for all residues, with an RMSD of approximately 1.7 A for side chain heavy atoms. We find that the differential between the atomic solvation parameters and the contact surface parameters (including those between noncomplementary atoms) is positive; i.e., most protein atoms prefer surface contact with other protein atoms rather than with the solvent. This might correspond to the driving force for maximizing packing of the protein. The influence of the crystal packing, completeness of rotamer library and precise positioning of Cbeta atoms on the accuracy of side-chain prediction are examined. The Sccomp-S and Sccomp-I programs can be accessed through the Web (http://sgedg.weizmann.ac.il/sccomp.html) and are available for several platforms.     

Mode-coupling theory for reaction dynamics in liquids

A theory for chemical reaction dynamics in condensed phase systems based on the generalized Langevin formalism of Grote and Hynes [J. Chem. Phys. 73, 2715 (1980)] is presented. A microscopic approach to calculate the dynamic friction is developed within the framework of a combination of kinetic and mode-coupling theories. The approach provides a powerful analytic tool to study chemical reactions in realistic condensed phase environments. The accuracy of the approach is tested for a model isomerization reaction in a Lennard-Jones fluid. Good agreement is obtained for the transmission coefficient at different solvent densities, in comparison with numerical simulations based on the reactive-flux approach.     

Liquid phase equilibria of (water + propionic acid + oleyl alcohol) ternary system at several temperatures

(Liquid–liquid) equilibrium (LLE) data are investigated for mixtures of (water + propionic acid + oleyl alcohol) at 298.15, 308.15 and 318.15 K and atmospheric pressure. The solubility curves and the tie-line end compositions of liquid phases at equilibrium were determined, and the tie-line results were compared with the data predicted by the UNIFAC method. The phase diagrams for the ternary mixtures including both the experimental and correlated tie-lines are presented. The distribution coefficients and the selectivity factors for the immiscibility region are calculated to evaluate the effect of temperature change. The reliability of the experimental tie-lines was confirmed by using Othmer–Tobias correlation. It is concluded that oleyl alcohol may serve as an adequate solvent to extract propionic acid from its dilute aqueous solutions. The UNIFAC model correlates the LLE data for 298.15, 308.15 and 318.15 K with a root mean square deviation of 5.89, 6.46, and 6.69%, respectively, between the observed and calculated mole concentrations.