Second-order MS-MA calculations for the triplet state of H2 in the van der Waals region

Second-order MS-MA calculations by the variation-perturbation method for the triplet state of H₂ show that in the van der Waals region induction including exchange is practically negligible and the depth and position of the potential minimum are determined by the competition between repulsive first-order exchange and attractive Coulomb dispersion. Accurate interaction energies are obtained in second order only if all non-expanded multipoles up to the dipole-octupole term are properly accounted for.     

Synthesis,NMR spectra and X‐ray data of chloro and dichloro derivatives of 3‐hydroxy‐2‐phenylquinolin‐4(1H)‐ones and their cytostatic activity

As known, some derivatives of quinolin‐4(1H)‐one possess interesting biological properties. The biological and cytostactic activity of 2‐substituted 3‐hydroxyquinolin‐4(1H)‐ones has not been reported yet. In this paper the synthesis of a series of chloro and dichloro 2‐phenyl‐3‐hydroxyquinolin‐4(1H)‐ones and their characterization by NMR spectra and X‐ray data is described. Their cytostatic properties have been evaluated and the results are reported.     

Assessment of systematic errors in measurement of vapor pressures by thermogravimetric analysis

The present study explores the application of the diffusion limited evaporation theory to the estimation of vapor pressure from TG experimental data. A simplified method was developed to calculate the apparent values of the vapor pressure of pure substances from TG data, based on isothermal TG runs with crucibles having different surface areas available for evaporation. Antoine parameters are estimated through a numerical procedure based on a non-linear least square algorithm. The procedure also evaluates the substance diffusivity in nitrogen. The methodology developed might be used for a preliminary screening of the vapor pressure of pure compounds, due to the limited amounts of sample that are necessary and to the limited time frame required for the experimental runs. However, the estimation of diffusivity and vapor pressures values by the TG technique is possible with limited accuracy. Possible sources of error were thoroughly investigated and discussed.     

Pseudopeptide foldamers: the homo-oligomers of pyroglutamic acid

As a part of a program evaluating substituted gamma-lactams as conformationally constrained building blocks of pseudopeptide foldamers, we synthesized the homo-oligomers of L-pyroglutamic acid up to the tetramer level by solution methods. The preferred conformation of this pseudopeptide series in structure-supporting solvents was assessed by FT-IR absorption, 1H NMR and CD techniques. In addition, the crystal structure of the N alpha-protected dimer was established by X-ray diffraction. A high-level DFT computational modeling was performed based on the crystallographic parameters. In this analysis, we demonstrated that an alpha C-H...O=C intramolecular hydrogen bond is responsible for the stabilization of the s-trans L-pGlu-L-pGlu conformation by 1.4 kcal mol-1. This effect can be easily detected by 1H NMR spectroscopy, owing to the anomalous chemical shifts of the alpha CH protons present in all of the oligomers. In summary, we have developed a new polyimide-based, foldameric structure that, if appropriately functionalized, has promise as a rigid scaffold for novel functions and applications.     

Scalar field cosmology in phase space

Using dynamical systems methods, we describe the evolution of a minimally coupled scalar field and a Friedmann-Lemaître-Robertson-Walker universe in the context of general relativity, which is relevant for inflation and late-time quintessence eras. Focussing on the spatially flat case, we examine the geometrical structure of the phase space, locate the equilibrium points of the system (de Sitter spaces with a constant scalar field), study their stability through both a third-order perturbation analysis and Lyapunov functions, and discuss the late-time asymptotics. As we do not specify the scalar field’s origin or its potential, the results are independent of the high-energy model.     

Nanosphere lithography with variable deposition angle for the production of one‐directional transparent conductors

The production of high quality and cheap transparent electrodes is a fundamental step for a variety of optoelectronic devices. We present a method for the production of transparent conducting films optimised for electrical conduction in one direction. The deposition of a metal film through a perfectly aligned nanosphere‐lithography mask at variable incidence angle gave origin to parallel nanowires with thin interconnections. This structure showed excellent conductivity in one direction and high optical transparency.

Glass substrates under the crystalline areas of the polystyrene‐nanospheres mask.     

Excitonic effects in solids described by time-dependent density-functional theory

Starting from the many-body Bethe-Salpeter equation we derive an exchange-correlation kernel f(xc) that reproduces excitonic effects in bulk materials within time-dependent density functional theory. The resulting f(xc) accounts for both self-energy corrections and the electron-hole interaction. It is static, nonlocal, and has a long-range Coulomb tail. Taking the example of bulk silicon, we show that the -alpha/q(2) divergency is crucial and can, in the case of continuum excitons, even be sufficient for reproducing the excitonic effects and yielding excellent agreement between the calculated and the experimental absorption spectrum.     

Direct measurement of superluminal group velocity and signal velocity in an optical fiber

We present an easy way of observing superluminal group velocities using a birefringent optical fiber and other standard devices. In the theoretical analysis, we show that the optical properties of the setup can be described using the notion of "weak value." The experiment shows that the group velocity can indeed exceed c in the fiber; and we report the first direct observation of the so-called "signal velocity," the speed at which information propagates and that cannot exceed c.     

Model studies toward the synthesis of dihydropyrimidinyl and pyridyl alpha-amino acids via three-component Biginelli and Hantzsch cyclocondensations

A novel and versatile strategy for the synthesis of heterocyclic alpha-amino acids has been described. The use of components (aldehyde or beta-ketoester) bearing a masked glycinyl moiety in Biginelli and Hantzsch cyclocondensations allowed access to the 4-dihydropyrimidinyl-alpha-glycines, 4-dihydropyrimidinyl-alpha-alanines, 4-pyridyl-alpha-alanines, and 2-pyridyl-alpha-alanines classes. Dihydropyrimidinyl-amino acids were obtained as a mixture of diastereoisomers due to the formation of the stereocenter at C4 of the dihydropyrimidinone ring. Individual stereoisomers were isolated as pure compounds and their structures were assigned with the aid of X-ray crystallography and chiroptical properties. The enantiomeric purity of a representative selection of the above amino acids was greater than 96% as verified by derivatization to the corresponding Mosher's amides and subsequent (1)H and (19)F NMR spectroscopy. Incorporation of the 4-pyridyl-alpha-alanine derivative into a peptide chain is also described.