Synthesis of some 3,7-disubstituted quino[3,2-c][1,8]naphthyridines

The preparation of some 3,7-disubstituted-5,6-dihydroquino[3,2-c][1,8]naphthyridines ( 6 ) by the condensation of 7-substituted-2,3-dihydro-1,8-naphthyridin-4-(1H)ones ( 5 ) with o-aminoacetophenone or o-aminobenzophenone is described. All the 5,6-dihydroderivatives 6 were transformed into the fully aromatic compounds 7 by heating with nitrobenzene. Only a few quino[3,2-c][1,8]naphthyridines were previously described.     

An alternative multipolar expansion for intermolecular potential functions

We have derived a new multipolar expansion for intermolecular potential-energy functions with applications in molecular physics, theoretical chemistry, and mathematical physics. The new formulation employs a separation of radial and angular terms with a simple index structure that leads to computational efficiency and ease of physical interpretation. For the case of the Coulomb interaction, we compare the present formulation with two conventional multipole expansions: the Cartesian tensor and the irreducible spherical tensor expansions. The new formalism leads to efficient numerical algorithms that are useful for general applications beyond intermolecular potentials. In addition to the electrostatic Coulomb interaction, we illustrate the formalism with applications to special function theory and a bipolar expansion involved in potential theory.     

Stericaliy Congested Molecules: 2,2′-[(Biaryldiyl)bis(oxy)]bis[1,3,2-oxazaphospholidines]

The original suggestion that a through-space mechanism was operative in the seven-bond J(P, P) coupling constant of 30.3 Hz observed for 3.3′-bis(1,1-dimethylethyl)-2,2′-[3,3′,5,5′-tetrakis(1,1-dimethylethyl)-1,1′-biphenyl-2,2′-diyl]bis(oxy)}bis[1,3,2-oxazaphospholidine] ( 1a )) was investigated. In the solid-state CP-MAS ³¹PNMR spectrum of 1a , two nonequivalent P -atoms were observed; sufficient resolution could not be obtained to determine whether P, P coupling was present. The preparation and spectral data of the N-methyl analogue 1b and of the acyclic N-isopropyl analogue 6 (Scheme 1) provided evidence that a) the essentially exclusive formation (R*, R*,S*)- 1a in the reaction of the disodium biphenyldiolate 3a with the phosphorochloridite 4a is the result of significant differences in the free energy of activation (ΔG*) for the formation of the various diastereoisomers due to the steric congestion within the molecule and that b) the magnitude of the observed P,P coupling is dependent upon the degree of conformational freedom within the molecule. In the ³¹P-NMR spectrum of the P-sulfide 7 , which was prepared by the reaction of la with sulfur, 2s resonances were observed that strongly suggested that the lone electrons pair on P are involved in the mechanism for the transmission of coupling data. The (4S,5R) -12 and (4R, 5S) -12 of la were prepared in a three-step reaction sequence starting from the corresponding enantiomerically pure norephredine 8 (Scheme 2). Both (4S, 5R)- and (4R, 5S) -12 were obtained as a diastereoisomer mixture that differ by the configuration of the axis of chirality, i.e., (R*R*,R*)- and (R*,S*,R*) -12 were obtained. The major diastereoisomer was obtained upon recrystallization, and the atropisomers were observed to equilibrate in solution by monitoring the H? C(5) resonance in the ¹H-NMR with time (ΔG° = 0.4 kcal/mol; Fig. 2). The process observed corresponds to the restricted rotation about the central single bond of the biphenyl system. The isolation of an atropisomer with only a single ortho substituent on each aryl ring is quite rare. In the ¹³C-NMR spectrum of both (R*,R*,R*)- and (R*,S*,R*) -12 , C(5) is two-bond-coupled to the oxazaphospholidine P-atom (²J(C(5),P((2)) = 8.5 Hz) that is further virtually coupled to the P-atom of the other oxazaphospholidine ring (7J(P(2),P(2′)) = 30 Hz; ⁹J(C(5),P(2′)) = 0 Hz; δ(P(2)) = δ(P(2′)) = 136 ppm. In the ³¹P-NMR spectrum of (R*,R*,S*) -12 , which was prepared from the racemic chloridite (mixture of three diastereoisomers was obtained), a ⁷J(P(2),P(2′) of 36 Hz was observed. These observations provide strong evidence that seven-bond P,P coupling occurs in all three diastereoisomers of 12 . The observed P,P coupling is both independent of the configuration of the chiral axis and the configuration of the asymmetric P-centers. This independence of P,P coupling upon the configuration on P implies also the independence of the observed coupling upon the orientation of the lone-pair of electrons on P provided that the conformations of the diastereoisomers are similar in solution. The X-ray crystal structure of the complex formed from 1a and dichloro(cycloocta-1,5-diene)platinum(II) was obtained and the solid-state structure discussed. The major diastereoisomer of (4S,5R) -12 was used as a chiral ligand in asymmetric hydrosilylation and hydrogenation reactions (Scheme 3).     

Stepwise retro 1,3-dipolar cycloaddition induced by electron. Impact on 3,5-diphenyl-1,2,4-oxadiazole

The retro 1,3-dipolar cycloaddition induced by electron impact on 3,5-diphenyl-1,2,4-oxadiazole is interpreted as a two-step process on the basis of the energetics and kinetics of the fragments [C₇H₅NO]⁺., [C₆H₅CN]⁺. and [C₆H₅CO]⁺.     

Anion-pi interactions in cyanuric acids: a combined crystallographic and computational study

Several structures of pi complexes of isocyanuric acid and of several thio derivatives with anions have been computed by using high level ab initio calculations. The nature of the complexes has been studied by means of the method of molecular interaction potential with polarization (MIPp) and Bader's theory of atoms-in-molecules. These molecules form favorable complexes with anions and can be used as binding units for building receptors for the molecular recognition of anions. In several cases, the anion-pi interaction has been demonstrated experimentally by means of X-ray crystallography.     

Phase diagram of the ANNNI model in the Hamiltonian limit

The Hamiltonian limit of the ANNNI model in (1+1) dimensions is studied by using the Quantum Statistical Monte Carlo method. Even if recent results suggest that Monte Carlo calculations may prove unreliable in the study of this system, the phase diagram of the quantum version of the model was successfully obtained. In particular, the clusive transitions between the disordered, the floating incommensurate and the degenerate 2, 2 are determined by analysing the correlation length behaviour in finite lattices.Partially supported by CONICET Argentina     

Hyperovals and Hadamard designs

In this paper, we investigatec-sets in 2-designs, with particular regard to sets of type (0,n) in projective planes. In particular, we associate a Hadamard design to a hyperoval of a projective plane of even orderq and we investigate some properties of its lines. This gives information on the order of the projective plane.     

GO-SWCNT Buckypapers as an Enhanced Technology for Water Decontamination from Lead

Water decontamination is an important challenge resulting from the incorrect disposal of heavy metal waste into the environment. Among the different available techniques (e.g., filtration, coagulation, precipitation, and ion-exchange), adsorption is considered the cheapest and most effective procedure for the removal of water pollutants. In the last years, several materials have been tested for the removal of heavy metals from water, including metal-organic frameworks (MOFs), single-walled carbon nanotubes (SWCNTs), and graphene oxide (GO). Nevertheless, their powder consistency, which makes the recovery and reuse after adsorption difficult, is the main drawback for these materials. More recently, SWCNT buckypapers (SWCNT BPs) have been proposed as self-standing porous membranes for filtration and adsorption processes. In this paper, the adsorption capacity and selectivity of Pb²⁺ (both from neat solutions and in the presence of other interferents) by SWCNT BPs were evaluated as a function of the increasing amount of GO used in their preparation (GO-SWCNT buckypapers). The highest adsorption capacity, 479 ± 25 mg g⁻¹, achieved for GO-SWCNT buckypapers with 75 wt.% of graphene oxide confirmed the effective application of such materials for cheap and fast water decontamination from lead.     

Comparative Effect of UV,UV/H2O2 and UV/H2O2/Fe on Terbuthylazine Degradation in Natural and Ultrapure Water

Different advanced oxidation processes (AOPs) (ultraviolet radiation, hydrogen peroxide photolysis and photo-Fenton) were applied to test the degradation of terbuthylazine in three types of water: (a) ultrapure water, (b) surface water from the Gaditana area (Los Hurones reservoir, Cádiz, Spain) and (c) groundwater from the Tempul spring in Jerez de la Frontera (Cádiz, Spain). The experiments were carried out on a laboratory scale, using two different types of reactors, batch and semi-continuous. In batch reactors, the most efficient process for the experiments carried out with both ultrapure water and underground groundwater was ultraviolet radiation, whereas for surface water from the Gaditana area, the process that obtained the best results was the photolysis of hydrogen peroxide with 2.5 mg L⁻¹ of H₂O₂. In semi-continuous reactors, the most efficient process was the photolysis of hydrogen peroxide with 2.5 mg L⁻¹ of H₂O₂ for all the matrices studied. In both types of reactors, terbuthylazine degradation percentages higher than 90% were achieved; the main difference was in the reaction time, which varied from minutes in the batch reactor to seconds in the semi-continuous reactor. In all the applied AOPs, N-terbutyl-6-hydroxy-N′ethyl-1,3,5-triazine-2,4-diamine (TBA-212) was generated as a reaction intermediate.     

Drying of solids with irregular geometry: numerical study and application using a three-dimensional model

This article proposes a numerical solution for the diffusion equation applied to solids with arbitrary geometry using non-orthogonal structured grids for the boundary condition of the first kind. A transient three-dimensional mathematical formulation written in boundary fitted coordinates and numerical formalism to discretize the diffusion equation by using the finite volume method, including numerical analysis of the computational solution are presented. To validate the proposed solution, the results obtained in this work were compared with well-known numerical solution available in literature and good agreement was observed. In order to verify the potential of the proposed numerical solution, it was applied to describe mass transfer inside ceramic roof tiles during drying. For that, it was used experimental data of the drying kinetics at the following temperatures: 55.6; 69.7; 82.7 and 98.6 °C. An optimization technique using experimental dataset has been presented to estimation of transport properties. The obtained statistical indicators enable to conclude that the numerical solution satisfactorily describes the drying processes.