The TACO Puzzle: A Phase-Transition Mystery Revisited

The organic salt (5-methyl-1-thia-5-azacyclo-octane-1-oxide) perchlorate (TACO) is known to undergo a single-crystal-to-single-crystal phase transition in the 276-298 K T range without a change in the external shape of the sample. Despite extensive computational and experimental investigations, no safe conclusions about the transition mechanism could be drawn till now. The two packing patterns are very similar, and symmetry is conserved, apart from an interchange of cell axes from P21/c (\u3b1-TACO, low-T) to P21/a (\u3b2-TACO, high-T). Yet, the phase transition implies a significant conformational rearrangement, coupled with 3c180\ub0-wide rotations, of 1/2 of the cations, in conjunction with reorientation of the anions. Here, we analyze the crystal packing of the two phases in terms of pairwise molecule-molecule interaction energies, as derived from the PIXEL approach. Rigid-body molecular reorientations are simulated by solid-state Monte Carlo calculations, while the likelihood of conformational rearrangements is estimated through gas-phase density functional theory M06/6-311G(p,d) simulations. We demonstrate that rotational motion of the cations is not hampered by substantial energetic barriers, while the ring flip can be described as a two-step process with a main kinetic barrier of 3c45 kJ\ub7mol-1, which might explain the metastable behavior of the \u3b2 phase at low T. A possible mechanism of the phase transition is proposed, accounting for the present computational evidences in the context of the former experimental findings

Alternate islands of multiple isochronous chains in wave-particle interactions

We analyze the dynamics of a relativistic particle moving in a uniform magnetic field and perturbed by a standing electrostatic wave. We show that a pulsed wave produces an infinite number of perturbative terms with the same winding number, which may generate islands in the same region of phase space. As a consequence, the number of isochronous island chains varies as a function of the wave parameters. We observe that in all the resonances, the number of chains is related to the amplitude of the various resonant terms. We determine analytically the position of the periodic points and the number of island chains as a function of the wave number and wave period. Such information is very important when one is concerned with regular particle acceleration, since it is necessary to adjust the initial conditions of the particle to obtain the maximum acceleration.Comment: Submitte

On the molecular basis of the activity of the antimalarial drug chloroquine : EXAFS-assisted DFT evidence of a direct Fe–N bond with free heme in solution

4-aminoquinoline antiplasmodials interfere with the biocrystallization of the malaria pigment, a key step of the malaria parasite metabolism. It is commonly believed that these drugs set stacking \u3c0 \ub7\ub7\ub7 \u3c0 interactions with the Fe-protoporphyrin scaffold of the free heme, even though the details of the heme:drug recognition process remain elusive. In this work, the local coordination of Fe(III) ions in acidic solutions of hematin at room temperature was investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy in the 4.0\u20135.5 pH range, both in the presence and in the absence of the antimalarial drug chloroquine. EXAFS results were complemented by DFT simulations in polarizable continuum media to model solvent effects. We found evidence that a complex where the drug quinoline nitrogen is coordinated with the iron center might coexist with formerly proposed adduct geometries, based on stacking interactions. Charge-assisted hydrogen bonds among lateral chains of the two molecules play a crucial role in stabilizing this complex, whose formation is favored by the presence of lipid micelles. The direct Fe\u2013N bond could reversibly block the axial position in the Fe 1st coordination shell in free heme, acting as an inhibitor for the crystallization of the malaria pigment without permanently hampering the catalytic activity of the redox center. These findings are discussed in the light of possible implications on the engineering of drugs able to thwart the adaptability of the malaria parasite against classical aminoquinoline-based therapies

Correlations of Crystal Structure and Solubility in Organic Salts: The Case of the Antiplasmodial Drug Piperaquine

Five organic salts of the antiplasmodial drug piperaquine (PQ, C29H32Cl2N6) were synthesized and characterized by X-ray diffraction methods. The corresponding solubilities in water and acetic acid solutions were evaluated in the 20-50 \ub0C (293-323 K) T range by UV-vis spectroscopy, with the aim of elucidating how they depend on chemical, structural, and thermodynamic factors. Experiments were complemented by DFT calculations, both in vacuo and in the solid state, to estimate changes in thermodynamic state functions related to the solvation process. It is demonstrated that solubility is mainly governed by the electronic and chemical properties of the anion, while lattice energies and packing effects, including in-crystal conformational changes of the drug, play a less important role. PQ salts generally conform to the predictions of hard and soft acid and bases (HSAB) theory, as less soluble compounds bear ions of comparable hardness, and vice versa. A remarkable exception is the PQ hydrogen sulfate salt, whose poor solubility can be ascribed to an exceptionally stable crystal lattice. Other factors, such as entropic effects related to solid-state disorder, can influence the response of solubility to temperature

Porosity and crystal morphology of heterometallic coordination networks from β-diketonate ligands

Porous coordination polymers (PCPs) or metal-organic-frameworks (MOFs) are considered very promising porous materials that can be exploited in many different technological fields such as gas storage, heterogeneous catalysis and separation of mixtures. In the field of MOF materials, many efforts are devoted to the search of rational synthetic procedures. Among others, a useful synthetic strategy is the so-called Metalloligand (MLs) approach. MLs are coordination complexes containing suitably oriented exo donor-groups that, used in place of organic linkers, can orient the formation of desired homo and heterometallic polymeric architectures [1]. Functionalized chelating ligands suited to obtain useful MLs are \uf062-diketonate molecules.[2] We report the synthesis and the structural characterization of two families of coordination frameworks obtained through the use of different \uf062-diketonate ligands with copper salts of several counter-ions. The first family of polymers have a two-dimensional layered structure whereas the members of the second family adopt a three-dimensional flexible framework structure. We have focused our attention to the correlations between the crystal structure, the dimensionality, the topology and porosity of the networks and the crystal morphologies, as well as to the investigation of the surface phenomena during the crystal growing process. Moreover, we have mapped a continuous set of crystal morphologies by controlling experimental variables such as the solvent system, the metal-ligand molar ratio and the nature of the counter-anion. The aim is to develop a method to tune the crystal habit according to the specific requirement of some important applications.[3] [1] S. Kitagawa, R. Kitaura, S. Noro Angew. Chem., Int. Ed., 43 (2004) 2334. [2] L. Carlucci, G. Ciani, S. Maggini, D.M. Proserpio, M. Visconti, Chem. Eur. J, 16 (2010) 12328. [3] L. Carlucci, G. Ciani, J. M. Garc\ueca-Ruiz, M. Moret, D. M. Proserpio and S. Rizzato , Cryst. Growth Des., 2009, 9(12), 5024-5034

Unravelling the Chemistry of the [Cu(4,7-Dichloroquinoline)2Br2]2 Dimeric Complex through Structural Analysis: A Borderline Ligand Field Case

Large dark prismatic crystals (P 1\uaf ) consisting of closely packed centrosymmetric [Cu(4,7-dichloroquinoline)2]2Br4 binuclear units are formed when 4,7-dichloroquinoline (DCQ, C9H5NCl2) binds copper(II). Cu2+ adopts a strongly distorted square pyramidal coordination geometry, perturbed by electrostatic interactions with two axial \u3bc\u2013Br ligands acting as highly asymmetric bridges. It is shown that, as electronic states of ligands are higher in energy than the metal ones, antibonding orbitals bear significant ligand-like character and electronic charge is partially transferred from inner-sphere coordinated halogen atoms to copper. Overall, the title compound sits on the Hoffman\u2019s border between main group and transition chemistry, with non-negligible contributions of the ligands to the frontier orbitals. The relative energy placement of metal and ligand states determines an internal redox process, where the metal is slightly reduced at the expense of partial oxidation of the bromide ligands. In fact, the crystal structure is partially disordered due to the substitution of some penta-coordinated Cu(II) centers with tetra-coordinated Cu(I) ions. The geometry of the complex is rationalized in terms of electrostatic-driven distortions from an ideal octahedral prototype. Implications on the reactivity of Cu(II)\u2013quinoline complexes are discusse

Gate stability of GaN-Based HEMTs with P-Type Gate

status: publishe