Mononuclear manganese carboxylate complexes: Synthesis and structural studies

Several manganese carboxylates complexes having Pz^iPr2H (3,5-diisopropylpyrazole), Tp^Ph,Me (hydrotris(3-phenyl,5-methyl-pyrazol-1-yl)borate), Tp^ipr2 (hydrotris(3,5-diisopropyl-pyrazol-1-yl)borate) as supporting ligands have been synthesised and structurally characterized. Single-crystal X-ray diffraction studies suggest that the manganese center in complexes (Pz^iPr2H)₄Mn(NO₂–OBz)₂ (5) and (Pz^iPr2H)₄Mn(F–OBz)₂ (6) have same coordination environment and geometry whereas the complex [Tp^Ph,MeMn(OAc)Pz^Ph,MeH] (7) has a five coordinate manganese center. In all these complexes, the carboxylate groups are coordinated as monodentate and the uncoordinated oxygen atom of the carboxylate groups form intramolecular hydrogen bonds with the NH group of the corresponding coordinated pyrazole (Pz^iPr2H/Pz^Ph,MeH). The complexes 5–8 and 10 were tested for their superoxide dismutase activity and it was found that only complex 7 has SOD activity as its structure is very similar to the active site structure of the native Mn–SOD enzyme. The SOD activity studies on these carboxylate complexes suggest that any model compound with analogous active site structure and intramolecular hydrogen bonding may be a suitable mimic for the Mn–SOD enzyme.     

Room-Temperature Ionic Liquid–DMSO Promoted and Improved One-Pot Synthesis of 5,6-Diaryl-1,2,4-triazines

An improved and rapid one-pot synthesis of 5,6-diarylsubstituted-1,2,4-triazines in a mixture of room-temperature ionic liquid 1,3-dibutylimidazolium bromide [Bbim]⁺Br^? and dimethylsulfoxide (DMSO) is described without the need for any added catalyst. Different polar aprotic solvents were screened along with ionic liquids and a synergistic effect with DMSO has been found. The predominance of one regioisomer over the other has also been studied with varying reaction temperatures. The one-pot methodology leading to excellent isolated yields in short span of time is achieved by simple workup procedure. The ionic liquid was efficiently recovered and reused three times without the loss of catalysis. All the compounds were characterized by infrared, NMR, mass spectrometry, and elemental analysis.     

Photoinduced charge transfer mechanism in PPV [poly(p-phenylinevinylene)] polymer: role of iodide species

The photophysical and photochemical behavior of poly(p-phenylinevinylene (PPV) polymers in different solvents (toluene and Triton X-100) and in thin form [PPV/optical transparent electrode (OTE)] has been investigated by emission and transient absorption spectroscopies. The absorption and emission studies strongly indicate the presence of dynamic quenching for PPV polymers in different solvents (toluene and Triton X-100) in the presence of LiI/I₂. The fluorescence quenching of the PPV polymer by iodide obeys the linear Stern–Volmer equation for PPV/toluene/LiI system. The positive deviation from Stern–Volmer observed in PPV/Triton X-100/I₂ system may be accounted for by the “quenching sphere of action model”. Emission studies indicated an increased conjugation length for PPV polymers on going from solution to the solid state. The emission of PPV was readily quenched by hole scavengers such as I⁻ (LiI, I₂). The photoinduced charge transfer to these hole scavengers was studied by laser flash photolysis. The transient absorption measurements confirm the formation of I⁻ and subsequent formation of which has been reported for the first time for PPV/I₂ system.     

Minimisation of palladium content in Suzuki cross-coupling reactions

A protocol for conducting Suzuki reactions in a plate format amenable to use in library synthesis of biaryl compounds has been developed. A key objective was to determine reaction conditions which give biaryl products containing <10 ppm of Pd for a wide variety of building blocks. A Design of Experiments (DoE) approach for the identification of an optimised set of reaction conditions was successfully applied. The utility of the protocol developed has been demonstrated by preparation of an array of 96 biaryl compounds in a parallel fashion.     

Hawking radiation and near horizon universality of chiral Virasoro algebra

We show that the diffeomorphism anomaly together with the trace anomaly reveal a chiral Virasoro algebra near the event horizon of a black hole. This algebra is the same irrespective of whether the anomaly is covariant or consistent, thereby manifesting its universal character and the fact that only the outgoing modes are relevant near the horizon. Our analysis therefore clarifies the role of the trace anomaly in the diffeomorphism anomaly approach [Robinson and Wilczek in Phys. Rev. Lett. 95:011303, 2005; Iso et al. in Phys. Rev. Lett. 96:151302, 2006; Banerjee and Kulkarni in Phys. Rev. D 77:024018, 2008; Gangopadhyay and Kulkarni in Phys. Rev. D 77:024038, 2008] to the Hawking radiation.     

Quantum phase transition and emergent symmetry in a quadruple quantum dot system

We propose a system of four quantum dots designed to study the competition between three types of interactions: Heisenberg, Kondo, and Ising. We find a rich phase diagram containing two sharp features: a quantum phase transition (QPT) between charge-ordered and charge-liquid phases and a dramatic resonance in the charge liquid visible in the conductance. The QPT is of the Kosterlitz-Thouless type with a discontinuous jump in the conductance at the transition. We connect the resonance phenomenon with the degeneracy of three levels in the isolated quadruple dot and argue that this leads to a Kondo-like emergent symmetry from left-right Z2 to U(1).     

Quantum phase transitions of hard-core bosons in background potentials

We study the zero temperature phase diagram of hard-core bosons in two dimensions subjected to three types of background potentials: staggered, uniform, and random. In all three cases there is a quantum phase transition from a superfluid (at small potential) to a normal phase (at large potential), but with different universality classes. As expected, the staggered case belongs to the XY universality, while the uniform potential induces a mean field transition. The disorder driven transition is clearly different from both; in particular, we find z approximately 1.4, nu approximately 1, and beta approximately 0.6.     

Effect of ratios of Cd:Se in CdSe nanoparticles on optical edge shifts and photoluminescence properties

This paper addresses the issue related to morphology of CdSe nanoparticles capped with organic molecules. Semiconducting CdSe nanoparticles of 5–16 nm are synthesized using CdO precursor, capped with trioctyl phosphine (TOP)/trioctyl phosphine oxide (TOPO) using different starting precursor ratios of Cd:Se. At an optimum ratio of Cd/Se-2:1, highly luminescent and small sized (5 nm) nanoparticles are obtained. At other Cd/Se precursor ratios (0.5:1, 1:1, 3:1) larger particles are formed with varying photoluminescence (PL) intensity and optical absorption (UV–VIS). X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) are used to determine the crystallinity and stoichiometry of the system, respectively. It is shown that the blue shifts of the optical absorption edge concurrent with the CdSe nanocrystal size reduction, for sizes measured by XRD with respect to the bulk semiconductor, agree perfectly with the strong quantum confinement model. The optical edge shifts are significantly higher for CdSe nanocrystallite as measured by transmission electron microscopy (TEM) than the theoretical prediction based on the strong quantum confinement model. This is understood on the basis of agglomeration effects as observed by TEM for CdSe nanocrystallites. The nano-sized CdSe growth island thus formed comprises of several TOP/TOPO passivated nanocrystals.     

Failure of mean field theory at large N

We study strongly coupled lattice QCD with N colors of staggered fermions in 3+1 dimensions. While mean field theory describes the low temperature behavior of this theory at large N, it fails in the scaling region close to the finite temperature second order chiral phase transition. The universal critical region close to the phase transition belongs to the 3D XY universality class even when N becomes large. This is in contrast to Gross-Neveu models where the critical region shrinks as N (the number of flavors) increases and mean field theory is expected to describe the phase transition exactly in the limit of infinite N. Our work demonstrates that infrared fluctuations can be important close to second order phase transitions even when N is strictly infinite.