Dinitroaliphatics as linkers: application in the synthesis of novel artemisinin carba-dimer

Abstract  

The versatility of nitroaliphatics is demonstrated by using it in the syntheses of artemisinin derived dimers. A few novel artemisinin derived dimer and monomer have been synthesized using nitroalkane as linker.     

Magnetodielectric effect in Co3O4 nanoparticles grown within a silica glass

Co₃O₄ nanocrystals of sizes in the range 17.5-33.1 nm were grown within a sol-gel-derived silica glass matrix. Rietveld analysis of the X-ray diffraction data showed that the crystals had tetragonal symmetry. This was explained as arising due to a tensile strain induced at the glass-crystal interface as a result of thermal expansion mismatch between the phases. The crystals showed ferromagnetic behaviour with superparamagnetism setting-in at temperatures above 15 K. They also exhibited ferroelectric characteristics with large remanent polarization. Change in dielectric constant as a function of magnetic field was observed in these nanocomposites. This was discussed on the basis of magnetostriction effect.     

Component Selection in the Self‐Assembly of Palladium(II) Nanocages and Cage‐to‐Cage Transformations

Dynamic supramolecular systems involving a tetratopic palladium(II) acceptor and three different pyridine‐ and imidazole‐based donors have been used for self‐selection by a synergistic effect of morphological information and coordination ability of ligands through specific coordination interactions. Three different cages were first synthesized by two‐component self‐assembly of individual donor and acceptor. When all four components were allowed to interact in a reaction mixture, only one out of three cages was isolated. The preferential binding affinity towards a particular partner was also established by transforming a non‐preferred cage into a preferred cage by interaction with the appropriate ligand. Computational studies further supported the fact that coordination interaction of imidazole moiety to Pd^II is enthalpically more preferred compared to pyridine, which drives the selection process. Analysis of crystal packing of both complexes indicated the presence of strong hydrogen bonds between nitrate and water molecules and also H‐bonded 3D networks of water. Both complexes exhibit promising proton conductivity (10^?5 to ca. 10^?3 S cm^?1) at ambient temperature under a relative humidity of circa 98 % with low activation energy.     

Super Sensitization: Grand Charge (Hole/Electron) Separation in ATC Dye Sensitized CdSe,CdSe/ZnS Type‐I,and CdSe/CdTe Type‐II Core–Shell Quantum Dots

Ultrafast charge‐transfer dynamics has been demonstrated in CdSe quantum dots (QD), CdSe/ZnS type‐I core–shell, and CdSe/CdTe type‐II core–shell nanocrystals after sensitizing the QD materials by aurin tricarboxylic acid (ATC), in which CdSe QD and ATC form a charge‐transfer complex. Energy level diagrams suggest that the conduction and valence band of CdSe lies below the LUMO and the HOMO level of ATC, respectively, thus signifying that the photoexcited hole in CdSe can be transferred to ATC and that photoexcited ATC can inject electrons into CdSe QD, which has been confirmed by steady state and time‐resolved luminescence studies and also by femtosecond time‐resolved absorption measurements. The effect of shell materials (for both type‐I and type‐II) on charge‐transfer processes has been demonstrated. Electron injection in all the systems were measured to be <150 fs. However, the hole transfer time varied from 900 fs to 6 ps depending on the type of materials. The hole‐transfer process was found to be most efficient in CdSe QD. On the other hand, it has been found to be facilitated in CdSe/CdTe type‐II and retarded in CdSe/ZnS type‐I core–shell materials. Interestingly, electron injection from photoexcited ATC to both CdSe/CdTe type‐II and CdSe/ZnS type‐I core–shell has been found to be more efficient as compared to pure CdSe QD. Our observation suggests the potential of quantum dot core–shell super sensitizers for developing more efficient quantum dot solar cells.     

Metriplectic structure, Leibniz dynamics and dissipative systems

A metriplectic (or Leibniz) structure on a smooth manifold is a pair of skew-symmetric Poisson tensor P and symmetric metric tensor G. The dynamical system defined by the metriplectic structure can be expressed in terms of Leibniz bracket. This structure is used to model the geometry of the dissipative systems. The dynamics of purely dissipative systems are defined by the geometry induced on a phase space via a metric tensor. The notion of Leibniz brackets is extendable to infinite-dimensional spaces. We study metriplectic structure compatible with the Euler-Poincaré framework of the Burgers and Whitham-Burgers equations. This means metriplectic structure can be constructed via Euler-Poincaré formalism. We also study the Euler-Poincaré frame work of the Holm-Staley equation, and this exhibits different type of metriplectic structure. Finally we study the 2D Navier-Stokes using metriplectic techniques.     

Implementation of tristate logic based all optical flip-flop with nonlinear material

The advantages of multivalued logic in optical parallel computation need no introduction. There are lots of proposals, already reported, where tristate, quarternary state logic operations can be performed with optics. Here we report a new approach to implement tristate logic based all optical flip-flop using optical nonlinear material. The concept and the principle of operation of this type of flip-flop are different from that of the conventional binary one.     

Implicit solitary wave solutions of the generalized magma equation

The generalized magma equation, in which dispersion and nonlinearity are coupled together in a manner reminiscent of the Harry-Dym equation, is solved to indicate both periodic and aperiodic implicit solitary wave solutions. It is argued that the presence of an additional spatial derivative in the magma equation also permits explicit solitary wave solutions, a feature not shared by the Harry-Dym equation.     

Isomerization and fluorescence depolarization of merocyanine 540 in polyacrylic acid. Effect of p H

Dynamics of isomerization and fluorescence depolarization of merocyanine 540 (MC540) in an aqueous solution of polyacrylic acid (PAA) have been studied using picosecond time resolved fluorescence spectroscopy. It is observed that the dynamics of isomerization and depolarization are sensitive enough to monitor the uncoiling of PAA at high pH (> 6). At low pH (< 3), when the polymer remains in a hypercoiled form, polymer bound MC540 experiences very high microscopic friction and, hence, the isomerization and depolarization processes are very slow. At high pH (> 6) a polyanion is formed and the polymer assumes an extended configuration due to electrostatic repulsion. At high pH (> 6), the anionic probe MC540 is expelled from the polyanion to bulk water and the dynamics of isomerization and fluorescence depolarization become faster by 12 and 5 times respectively, compared to those at low pH.     

On the incompatibility of standard quantum mechanics and conventional de Broglie-Bohm theory

It is shown that conventional de Broglie-Bohm quantum theory is incompatible with the standard quantum theory of a system unless the former is ergodic.     

Born-Oppenheimer symmetry breaking in the C state of NO2: importance of static and dynamic correlation effects

A systematic theoretical treatment is performed with highly correlated ab initio theoretical methods to establish the structural nature of the C state of NO2. We predict the C state to have an asymmetric structure (point group C(s)). Spin-restricted and spin-unrestricted configuration interaction (CISD), coupled cluster [CCSD and CCSD(T)], multireference complete active space self-consistent field (CASSCF), and internally contracted multireference configuration interaction (ICMRCI) methods were used in conjunction with very large correlation-consistent polarized valence zeta cc-pVXZ and aug-cc-pVXZ [X = T, Q, 5] basis sets. The asymmetric C 2A' state is predicted to lie T(e) = 47.5 kcal/mol (2.06 eV, 16,600 cm(-1)) above the X 2A1 state at the aug-cc-pV5Z/UCCSD(T) level of theory, with T0 = 46.0 kcal/mol (2.00 eV, 16,100 cm(-1)), in good agreement with the experimental values of 46.77 kcal/mol (2.028 eV, 16,360 cm(-1)) by Weaver and 46.42 kcal/mol (2.013 eV, 16,234 cm(-1)) by Aoki. The symmetric structure (in C(2v) symmetry) with re(NO) = 1.274 A and theta(e) (ONO) = 109.9 degrees is a transition state between the two equivalent asymmetric (in C(s) symmetry) structures and is located only 1.53 kcal/mol (0.066 eV, 540 cm(-1)) above the asymmetric structure. The asymmetric structure is predicted to have structural parameters r(e)(NOl) = 1.489 A, r(e)(NOs) = 1.169 A, and theta(e)(ONO) = 109.7 degrees with the same method, aug-cc-pV5Z/UCCSD(T). The averaged NO bond distance is 1.329 A, and the difference between the two NO bond distances is 0.320 A. The three harmonic vibrational frequencies for the C 2A' state are 1656 (in-phase stretch), 759 (bend), and 378 (out- of-phase stretch) cm(-1). While these theoretical results further corroborate the previous predictions concerning the asymmetric nature of the C state, there remains discrepancy between the theoretical and experimental symmetric stretching mode omega1 (1656 and 923 cm(-1), respectively). It is possible, however, that this disagreement could be resolved by a reassignment of the corresponding lines in the experimental spectrum, though additional vibronic simulations of the spectrum are required to confirm this proposition.