A new formulation of the PCM solvation method: PCM-QINTn

A new formulation of the PCM electrostatic solution problem is proposed. Through a new derivation of the PCM-CLSn expression we propose an interpolation formula that improved the convergence: PCM-QINTn. All the available formulations are applied to the evaluation of the electrostatic component of the free energy of solvation for some molecular systems. In addition, PCM-QINT derivatives of G _el with respect to atomic coordinates are evaluated. The computational costs are compared with those of PCM-direct formulation. Received: 21 October 1996 / Accepted: 7 January 1997     

Molecular‐Dynamics‐Simulation‐Directed Rational Design of Nanoreceptors with Targeted Affinity

Here, we demonstrate the possibility of rationally designing nanoparticle receptors with targeted affinity and selectivity for specific small molecules. We used atomistic molecular‐dynamics (MD) simulations to gradually mutate and optimize the chemical structure of the molecules forming the coating monolayer of gold nanoparticles (1.7 nm gold‐core size). The MD‐directed design resulted in nanoreceptors with a 10‐fold improvement in affinity for the target analyte (salicylate) and a 100‐fold decrease of the detection limit by NMR‐chemosensing from the millimolar to the micromolar range. We could define the exact binding mode, which features prolonged contacts and deep penetration of the guest into the monolayer, as well as a distinct shape of the effective binding pockets characterized by exposed interacting points.     

Photoswitchable Dissipative Two‐Dimensional Colloidal Crystals

Control over particle interactions and organization at fluid interfaces is of great importance both for fundamental studies and practical applications. Rendering these systems stimulus‐responsive is thus a desired challenge both for investigating dynamic phenomena and realizing reconfigurable materials. Here, we describe the first reversible photocontrol of two‐dimensional colloidal crystallization at the air/water interface, where millimeter‐sized assemblies of microparticles can be actuated through the dynamic adsorption/desorption behavior of a photosensitive surfactant added to the suspension. This allows us to dynamically switch the particle organization between a highly crystalline (under light) and a disordered (in the dark) phase with a fast response time (crystallization in ≈10 s, disassembly in ≈1 min). These results evidence a new kind of dissipative system where the crystalline state can be maintained only upon energy supply.     

Tunable Fullerene Affinity of Cages,Bowls and Rings Assembled by PdII Coordination Sphere Engineering

For metal-mediated host compounds, the development of strategies to reduce symmetry and introduce multiple functionalities in a non-statistical way is a challenging task. We show that the introduction of steric stress around the coordination environment of square-planar Pd^II cations and bis-monodentate nitrogen donor ligands allows to control the size and shape of the assembled product, from [Pd₂L₄] cages over [Pd₂L₃] bowl-shaped structures to [Pd₂L₂] rings. Therefore, banana-shaped ligand backbones were equipped with pyridines, two different quinoline isomers and acridine, the latter three introducing steric congestion through hydrogen substituents on annelated benzene rings. Differing behavior of the four resulting hosts towards the binding of C₆₀ and C₇₀ fullerenes was studied and related to structural differences by NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction. The three cages based on pyridine, 6-quinoline or 3-quinoline donors were found to either bind C₆₀, C₇₀ or no fullerene at all.     

On the quenching of steel and zircaloy spheres in water-based nanofluids with alumina,silica and diamond nanoparticles

The quenching curves (temperature vs time) for small (∼1 cm) metallic spheres exposed to pure water and water-based nanofluids with alumina, silica and diamond nanoparticles at low concentrations (?0.1 vol%) were acquired experimentally. Both saturated (ΔT_sub = 0 °C) and highly subcooled (ΔT_sub = 70 °C) conditions were explored. The spheres were made of stainless steel and zircaloy, and were quenched from an initial temperature of ∼1000 °C. The results show that the quenching behavior in nanofluids is nearly identical to that in pure water. However, it was found that some nanoparticles accumulate on the sphere surface, which results in destabilization of the vapor film in subsequent tests with the same sphere, thus greatly accelerating the quenching process. The entire boiling curves were obtained from the quenching curves using the inverse heat transfer method, and revealed that alumina and silica nanoparticle deposition on the surface increases the critical heat flux and minimum heat flux temperature, while diamond nanoparticle deposition has a minimal effect on the boiling curve. The possible mechanisms by which the nanoparticles affect the quenching process were analyzed. It appears that surface roughness increase and wettability enhancement due to nanoparticle deposition may be responsible for the premature disruption of film boiling and the acceleration of quenching. The basic results were also confirmed by quench tests with rodlets.     

Fast–Slow Partially Hyperbolic Systems Versus Freidlin–Wentzell Random Systems

We consider a simple class of fast-slow partially hyperbolic dynamical systems and show that the (properly rescaled) behaviour of the slow variable is very close to a Freidlin–Wentzell type random system for times that are rather long, but much shorter than the metastability scale. Also, we show the possibility of a “sink” with all the Lyapunov exponents positive, a phenomenon that turns out to be related to the lack of absolutely continuity of the central foliation.     

Multipole expansions of the electrostatic molecular potential

Multipole expansions of the electrostatic molecular potential up to the hexadecapole terms are examined for H₂O, NH₃ and C₂H₄NH. A reasonable approximation to get unexpensive first order representations of the electrostatic potential for regions outside the van der Waals volume is found.     

Multiple functional group cooperation in phosphate diester cleavage promoted by Zn(II) complexes

Zn(II) complexes bearing multiple auxiliary organic groups greatly accelerate the cleavage of a phosphate diester.     

Quantum mechanical studies of environmental effects on biomolecules

Ab initia SCF calculations on the hydration of N-methylacetamide are reported and compared to the results previously obtained for formamide. The hydration energies are all slightly decreased. The angular positions of the two carbonyl sites are brought closer to the CO axis and the orientation of the water molecule on the NH site remains very flexible in spite of the a methyl group.