An efficient Monte Carlo algorithm for the fast equilibration and atomistic simulation of alkanethiol self-assembled monolayers on a Au(111) substrate

A new Monte Carlo algorithm is presented for the simulation of atomistically detailed alkanethiol self-assembled monolayers (R-SH) on a Au(111) surface. Built on a set of simpler but also more complex (sometimes nonphysical) moves, the new algorithm is capable of efficiently driving all alkanethiol molecules to the Au(111) surface, thereby leading to full surface coverage, irrespective of the initial setup of the system. This circumvents a significant limitation of previous methods in which the simulations typically started from optimally packed structures on the substrate close to thermal equilibrium. Further, by considering an extended ensemble of configurations each one of which corresponds to a different value of the sulfur-sulfur repulsive core potential, sigmass, and by allowing for configurations to swap between systems characterized by different sigmass values, the new algorithm can adequately simulate model R-SH/Au(111) systems for values of sigmass ranging from 4.25 A corresponding to the Hautman-Klein molecular model (J. Chem. Phys. 1989, 91, 4994; 1990, 93, 7483) to 4.97 A corresponding to the Siepmann-McDonald model (Langmuir 1993, 9, 2351), and practically any chain length. Detailed results are presented quantifying the efficiency and robustness of the new method. Representative simulation data for the dependence of the structural and conformational properties of the formed monolayer on the details of the employed molecular model are reported and discussed; an investigation of the variation of molecular organization and ordering on the Au(111) substrate for three CH3-(CH2)n-SH/Au(111) systems with n=9, 15, and 21 is also included.     

Tissue distribution and urinary excretion of intravenously administered chemically functionalized graphene oxide sheets

The design of graphene-based materials for biomedical purposes is of great interest. Graphene oxide (GO) sheets represent the most widespread type of graphene materials in biological investigations. In this work, thin GO sheets were synthesized and further chemically functionalized with DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid), a stable radiometal chelating agent, by an epoxide opening reaction. We report the tissue distribution of the functionalized GO sheets labeled with radioactive indium (¹¹¹In) after intravenous administration in mice. Whole body single photon emission computed tomography (SPECT/CT) imaging, gamma counting studies, Raman microscopy and histological investigations indicated extensive urinary excretion and predominantly spleen accumulation. Intact GO sheets were detected in the urine of injected mice by Raman spectroscopy, high resolution transmission electron microscopy (HR-TEM) and electron diffraction. These results offer a previously unavailable pharmacological understanding on how chemically functionalized GO sheets transport in the blood stream and interact with physiological barriers that will determine their body excretion and tissue accumulation.     

Corrole and Porphyrin Amino Acid Conjugates: Synthesis and Physicochemical Properties

A series of conjugates of amino acids with porphyrins and corroles was synthesized. Their self‐assembling ability under defined conditions was investigated by scanning electron microscopy. The morphology and photophysical properties of these molecules were studied by absorption and fluorescence spectroscopy in solid, liquid, and self‐assembled forms. We observed that both corrole and porphyrin conjugated with the l ‐phenylalanine–l ‐phenylalanine peptide to form spherical nanostructures with bathochromic shifts in the emission spectra, indicating the formation of aggregates. These aggregates are characterized by the impressive absorption of light over nearly the whole visible range. The broadening of all bands was particularly strong in the case of corroles. The fluorescence lifetimes of self‐assembled species were longer as compared to the solid‐state form.     

A differential model for the rheological properties of concentrated suspensions with weakly viscoelastic matrices

A model for the rheological properties of a concentrated suspension in weakly viscoelastic fluid matrices is proposed. The model is derived according to the Roscoe differential procedure described in 1952. The analytical results produced recently by Greco et al. (J Non-Newton Fluid Mech 147:1–10, 2007) and Housiadas and Tanner (J Non-Newton Fluid Mech 162:88–92, 2009) for dilute suspensions of neutrally buoyant, non-Brownian rigid spheres in weakly viscoelastic matrix fluids are the key results which are used as a base to predict the properties of concentrated suspensions. The results are compared with the few available experimental data from the literature, showing promising trends for the viscometric properties of the suspensions. In particular, one sees the rapidly increasing value of −N₂/N₁ as concentration increases.     

Effect of the type of alkylammonium ion clay modifier on the structure and thermal/mechanical properties of glassy and rubbery epoxy-clay nanocomposites

Glassy and rubbery epoxy-clay nanocomposites were synthesized by using various montmorillonite organoclays in order to investigate and compare the effect of the type of alkylammonium ion clay modifier on the structure and properties of the nanocomposites. The organoclays studied were the Nanomer I.28E and I.30E and the Cloisite C10A, C15A and C20A. The functionality (acidity), size and shape of backbone chain, hydrophobicity and polarity were the varying parameters of the organic modifiers that were correlated to the ability of the organoclays to form highly intercalated or exfoliated nanocomposites and to the changes observed in the mechanical (tensile measurements), thermo-mechanical (DMA) and thermal (TGA) properties of the epoxy nanocomposites. The primary alkylammonium ion modifiers with reactive/acidic hydrogen atoms, compared to the quaternary octadecyl, dihydrogenated tallow and benzyl-substituted hydrogenated tallow ammonium ions, were the most effective for the formation of exfoliated clay glassy and rubbery epoxy nanocomposites which exhibited improved properties compared to the pristine epoxy polymers.     

Modeling local flotation frequency in a turbulent flow field

Despite the significance of turbulent fluid motion for enhancing the flotation rate in several industrial processes, there is no unified approach to the modeling of the flotation rate in a turbulent flow field. Appropriate modeling of the local flotation (bubble-particle attachment) rate is the basic constituent for global modeling and prediction of flotation equipment efficiency. Existing approaches for the local flotation rate are limited to specific set of conditions like high or low turbulence. In addition, the combined effects of buoyant bubble rise and/or particle gravity settling are usually ignored. The situation is even vaguer for the computation of collision and attachment efficiencies which are usually computed using the gravity induced velocities although the dominant mode of flotation is the turbulent one. The scope of this work is clear: the development of a general expression for the flotation rate in a turbulent flow field which will cover in a unified and consistent way all possible sets of the problem parameters. This is achieved by using concepts from statistical approach to homogeneous turbulence and gas kinetic theory.     

Charged cosmic strings interacting with gravitational and electromagnetic waves

Under a particular choice of the Ernst potential, we solve analytically the Einstein–Maxwell equations to derive a new exact solution depending on five parameters: the mass, the angular-momentum (per unit mass), α, the electromagnetic-field strength, k, the parameter-p and the Kerr-NUT parameter, l. This (Petrov Type D) solution is cylindrically symmetric and represents the curved background around a charged, rotating cosmic string, surrounded by gravitational and electromagnetic waves, under the influence of the Kerr-NUT parameter. A C-energy study in the radiation zone suggests that both the incoming and the outgoing radiation is gravitational, strongly focused around the null direction and preserving its profile. In this case, the absence of the k-parameter from the C-energy implies that, away from the linear defect the electromagnetic field is too weak to contribute to the energy-content of the cylindrically symmetric space-time under consideration. In order to explain this result, we have evaluated the Weyl and the Maxwell scalars near the axis of the linear defect and at the spatial infinity. Accordingly, we have found that the electromagnetic field is concentrated (mainly) in the vicinity of the axis, while falling-off prominently at large radial distances. However, as long as k ≠ 1, the non-zero Kerr-NUT parameter enhances those scalars, both near the axis and at the spatial infinity, introducing some sort of gravitomagnetic contribution.     

P.‐O. Löwdin and the International Journal of Quantum Chemistry: A kaleidoscopic agenda for quantum chemistry

This is a article about P.‐O. Löwdin's life, his work in shaping quantum chemistry into a mature discipline at the intersection of mathematics, physics, chemistry, and biology, and his founding of the International Journal of Quantum Chemistry in 1967. Unavoidably, it is, also, a article reflecting our views about the history of quantum chemistry. We attempt to convey the complexities in the becoming of a subdiscipline, like quantum chemistry, where a variety of factors will have to be taken into consideration for a comprehensive understanding of its historical developments: the relations of chemists to the Heisenberg‐Schrödinger formulation of quantum mechanics after 1926, the institutional dynamics centered around the establishment of new courses and chairs, the research agendas and the vying for dominance within the community of quantum chemists, the methodological, and philosophical issues that have never left the quantum chemists indifferent, and, of course, the dramatic role of the computer in transforming the culture for actually practicing quantum chemistry. Furthermore, attracted by American history, culture, and ways of life, Löwdin suggested in the late 1970s that the post‐WWII character of quantum chemistry was dependent on its ability to hub a “scientific melting pot,” much like the United States of America which he viewed as a fusion of people from diverse provenances and cultures. In this article, we attempt to investigate another metaphor, that of the “kaleidoscope.” Löwdin believed that quantum chemistry's strength arose from its ability to nurture a multiplicity of heterogeneous cultural elements/subcultures and practices, interacting with each other, exchanging perspectives and modes of action, which circulated in an increasingly extended network of actors and institutional frameworks. © 2013 Wiley Periodicals, Inc.