Circular dichroism and theoretical studies on the inclusion of the antimalarian drug Licochalcone-A in β-cyclodextrin

The Induced Circular Dichroism of the complex formed by inclusion of Licochalcone-A (a powerful antimalarian of natural origin) and β-cyclodextrin was measured and calculated. The association constant was determined by titration experiments of ICD and fluorescence. The lowest energy conformations of the complex were obtained through docking procedures and their Circular Dichroism was evaluated within the Tinoco framework. The geometry of the complex was found to be consistent with the main experimental features.     

Novel scaling behavior of directed polymers: Disorder distribution with long tails

We study the problem of directed polymers (DP) on a square lattice. The distribution of disorder is assumed to be independent but non-Gaussian. We show that for distributions with a power-law tailP() 1/||¹⁺ , where>2, so that the mean and variance are well defined, the scaling exponentv of the DP model depends on in a continuous fashion.     

The inelastic hard dimer gas: a nonspherical model for granular matter

We study a two-dimensional gas of inelastic smooth hard dimers. Since the collisions between dimers are dissipative, being characterized by a coefficient of restitution alpha<1, and no external driving force is present, the energy of the system decreases in time and no stationary state is achieved. However, the resulting nonequilibrium state of the system displays several interesting properties in close analogy with systems of inelastic hard spheres, whose relaxational dynamics has been thoroughly explored. We generalize to inelastic systems a recently method introduced [G. Ciccotti and G. Kalibaeva, J. Stat. Phys. 115, 701 (2004)] to study the dynamics of rigid elastic bodies made up of different spheres held together by rigid bonds. Each dimer consists of two hard disks of diameter d, whose centers are separated by a fixed distance a. By describing the rigid bonds by means of holonomic constraints and deriving the appropriate collision rules between dimers, we reduce the dynamics to a set of equations which can be solved by means of event-driven simulation. After deriving the algorithm we study the decay of the total kinetic energy, and of the ratio between the rotational and the translational kinetic energy of inelastic dimers. We show numerically that the celebrated Haff's homogeneous cooling law t(-2), describing how the kinetic energy of an inelastic hard-sphere system with a constant coefficient of restitution decreases in time, holds even in the case of these nonspherical particles. We fully characterize this homogeneous decay process in terms of appropriate decay constants and confirm numerically the scaling behavior of the velocity distributions.     

Circular‐Dichroism Studies on Artemisinin and Epiartemisinin and Their β‐Cyclodextrin Complexes in Solution

The circular dichroism (CD) spectra of the powerful antimalarian active principle artemisinin (ART; 1 ) from Artemisia annua, and of epiartemisinin (EPI, 2), its C(7) epimer, were studied in solution in the presence and absence of β‐cyclodextrin (β‐cd). A significant inversion of sign in the region of the second electronic transition was detected. The rotational strengths were successfully calculated within the time‐dependent density functional theory (DFT), which enabled us to establish a correlation between the molecular recognition and the biological acitivities of the two isomers.     

Charge-transfer interactions in face-to-face porphyrin-fullerene systems: solvent-dependent luminescence in the infrared spectral region

The cyclophane-type molecular dyads 1 x 2H and 1 x Zn, in which a doubly bridged porphyrin donor adopts a close, tangential orientation relative to the surface of a fullerene acceptor, were prepared by Bingel macrocylization. The porphyrin derivatives 2 x 2H and 2 x Zn with two appended, singly linked C60 moieties were also formed as side products. NMR investigations revealed that the latter compounds strongly prefer conformations with one of the carbon spheres nesting on the porphyrin surface, thereby taking a similar orientation to that of the fullerene moiety in the doubly bridged systems. Cyclic voltammetric measurements showed that the mutual electronic effects exerted by the fullerene on the porphyrin and vice versa are only small in all four dyads, despite the close proximity of the donor and acceptor components. The steady-state and time-resolved absorption and luminescence properties of 1 x Zn and 2 x Zn were investigated in toluene solution and it was shown that, upon light excitation, both the porphyrin- and the fullerene-centered excited states are deactivated to a lower-lying CT state, emitting in the IR spectral region (lambda max = 890 and 800 nm at 298 and 77 K, respectively). In the more polar solvent benzonitrile, this CT state is still detected but, owing to its very low energy (below 1.4 eV), is not luminescent and shorter-lived than in toluene. The remarkable observation of similar photophysical behavior of 1 x Zn and 2 x Zn suggests that a tight donor-acceptor distance cannot only be established in doubly bridged cyclophane-type structures but also in singly bridged dyads, by taking advantage of favourable fullerene-porphyrin ground-state interactions.     

Exploiting C3-symmetry in the dynamic coordination of a chiral trisoxazoline to copper(II): improved enantioselectivity, and catalyst stability in asymmetric lewis acid catalysis

Chiral C3-symmetric trisoxazolines are highly efficient stereodirecting ligands in enantioselective Cu(II) Lewis acid catalysis which is based on the concept of a stereoelectronic hemilability of the divalent copper; in direct comparison with the analogous bisoxazoline systems they are more efficient in the enantioselective alpha-amination as well as the enantioselective Mannich reaction of prochiral beta-ketoesters.     

Fluid-like behavior of a one-dimensional granular gas

We study the properties of a one-dimensional (1D) granular gas consisting of N hard rods on a line of length L (with periodic boundary conditions). The particles collide inelastically and are fluidized by a heat bath at temperature Tb and viscosity gamma. The analysis is supported by molecular dynamics simulations. The average properties of the system are first discussed, focusing on the relations between granular temperature Tg=mv2, kinetic pressure, and density rho=N/L. Thereafter, we consider the fluctuations around the average behavior obtaining a slightly non-Gaussian behavior of the velocity distributions and a spatially correlated velocity field; the density field displays clustering: this is reflected in the structure factor which has a peak in the k approximately 0 region suggesting an analogy between inelastic hard core interactions and an effective attractive potential. Finally, we study the transport properties, showing the typical subdiffusive behavior of 1D stochastically driven systems, i.e., approximately Dt(1/2), where D for the inelastic fluid is larger than the elastic case. This is directly related to the peak of the structure factor at small wave vectors.     

Soft-x-ray laser interferometry of a plasma with a tabletop laser and a Lloyd's mirror

We report what is believed to be the first demonstration of soft-x-ray interferometry of a plasma with a tabletop soft-x-ray laser. A Lloyd's mirror interferometer was used in combination with a very compact lambda = 46.9 nm capillary-discharge-pumped laser to map the electron density in the cathode region of a pinch plasma.     

The structure of higher order C60-fullerene-γ-cyclodextrin complexes

C₆₀ inclusion complexes in γ-cyclodextrin are studied by molecular mechanics and semi-empirical methods with the aim of comparing measured and calculated induced circular dichroism (ICD) spectra. Low energy geometries of the complexes are generated by Monte Carlo simulations, also accounting for solvation effects by an aqueous environment. The ICD spectrum of the complex is then obtained from an exciton model based on semi-empirical calculations of the transition energies and the corresponding transition moments. Highly symmetric, tightly bound complexes of two γ-cyclodextrins and buckminsterfullerene are found as the most probable structures. The main bands of the experimentally derived ICD spectrum are assigned to the excitation transitions of the chromophore and are discussed in comparison to calculations on the magnetic circular dichroism (MCD) spectrum of C₆₀.     

Isotope shift in the proton magnetic resonance of deuterated methanes

The isotope shift in the proton magnetic resonance of deuteromethanes has been examined. By the use of Pople's formula for the chemical shift, it has been shown that the effect is due to vibronic coupling from the bending modes S₄. The chemical shift was evaluated under the assumption that the hydrogen population is linearly dependent on the 2S character of the bonded carbon hybrid. Satisfactory agreement between theoretical and experimental results was obtained.