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.     

A New Definition of the Term “High-Phenolic Olive Oil” Based on Large Scale Statistical Data of Greek Olive Oils Analyzed by qNMR

In the last few years, a new term, “High-phenolic olive oil”, has appeared in scientific literature and in the market. However, there is no available definition of that term regarding the concentration limits of the phenolic ingredients of olive oil. For this purpose, we performed a large-scale screening and statistical evaluation of 5764 olive oil samples from Greece coming from >30 varieties for an eleven-year period with precisely measured phenolic content by qNMR. Although there is a large variation among the different cultivars, the mean concentration of total phenolic content was 483 mg/kg. The maximum concentration recorded in Greece reached 4003 mg/kg. We also observed a statistically significant correlation of the phenolic content with the harvest period and we also identified varieties affording olive oils with higher phenolic content. In addition, we performed a study of phenolic content loss during usual storage and we found an average loss of 46% in 12 months. We propose that the term high-phenolic should be used for olive oils with phenolic content > 500 mg/kg that will be able to retain the health claim limit (250 mg/kg) for at least 12 months after bottling. The term exceptionally high phenolic olive oil should be used for olive oil with phenolic content > 1200 mg/kg (top 5%).     

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.     

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.     

Perturbation solution of Poiseuille flow of a weakly compressible Oldroyd-B fluid

The isothermal, planar Poiseuille flow of a weakly compressible Oldroyd-B fluid is considered under the assumption that the density of the fluid obeys a linear equation of state. A perturbation analysis for all the primary flow variables is carried out with the isothermal compressibility serving as the perturbation parameter. The sequence of partial differential equations which results from the perturbation procedure is solved analytically up to second order. The effects of the compressibility parameter, the aspect ratio, and the Weissenberg number are discussed. In particular, it is demonstrated that compressibility has a significant effect on the transverse velocity and the first normal stress difference.     

Double large field stereoscopic PIV in a high Reynolds number turbulent boundary layer

An experiment on a flat plate turbulent boundary layer at high Reynolds number has been carried out in the Laboratoire de Mecanique de Lille (LML, UMR CNRS 8107) wind tunnel. This experiment was performed jointly with LEA (UMR CNRS 6609) in Poitiers (France) and Chalmers University of Technology (Sweden), in the frame of the WALLTURB European project. The simultaneous recording of 143 hot wires in one transverse plane and of two perpendicular stereoscopic PIV fields was performed successfully. The first SPIV plane is 1?cm upstream of the hot wire rake and the second is both orthogonal to the first one and to the wall. The first PIV results show a blockage effect which based on both statistical results (i.e. mean, RMS and spatial correlation) and a potential model does not seem to affect the turbulence organization.     

Inclusion compounds of plant growth regulators in cyclodextrins, part VII: study of the crystal structures of 2-naphthylacetic acid encapsulated in β-cyclodextrin and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin complexes by X-ray crystallography

The crystal structures of the β-naphthylacetic acid (2NAA)/β-cyclodextrin (β-CD) and the 2NAA/heptakis(2,3,6-tri-O-methyl)-β-CD (TMβCD) complexes are reported. The 2NAA/β-CD complex crystallizes in the triclinic system forming a dimer inside the cavity of which two 2NAA molecules disordered over two sites are located. The dimers are stacked along the c axis according to the channel packing mode forming a nanotube which resembles a wireway as it contains guest molecules linked by π–π interactions inside each dimeric cavity and by H-bonds between the adjacent dimers. The 2NAA/TMβCD complex crystallizes in the orthorhombic space group P2₁2₁2₁. Its asymmetric unit contains one host, one guest distributed over two sites and one water molecule having a low occupancy factor. The complexes are packed in a head-to-tail mode forming a screw channel along the b axis. The carboxyl group of the guest protrudes towards the “free” space between the complexes and is H-bonded to the water molecule which in turn is H-bonded to the O5n atom of the host of the subsequent complex. The orientation of the guest molecule in the 2NAA/β-CD complex has been found opposite to that of the guest in the 2NAA/TMβCD complex probably due to the formation of dimers and the π–π interactions between the naphthalene moieties of the encapsulated molecules inside the dimeric cavity.     

Formation of reactive o-quinone methides from the reaction of trimethylsilyl(methyl)-substituted 1,4-benzoquinones with nucleophiles

o-Quinone methides are formed from the reaction of nucleophiles with trimethylsilyl(methyl)-1,4-benzoquinones. These reactive intermediates are trapped by excess nucleophile to form substituted quinones following oxidation. In addition, varying amounts of a symmetrical dimer and a xanthen derivative were observed. The influence of different nucleophiles and ring substituents on the rate of reaction have been studied, and are consistent with rate-limiting formation of a vinylogous enolate initiated by attack of the nucleophile on the silyl group.     

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.