Syntheses,characterization, X-ray crystal structures and emission properties of copper(II), zinc(II) and cadmium(II) complexes of pyridyl–pyrazole derived Schiff base ligand – Metal selective ligand binding modes

The varying coordination modes of the title ligand, L [5-methyl-1-(pyridin-2-yl)-N′-[pyridin-2-ylmethylidene]pyrazole-3-carbohydrazide] towards the different metal centers is reported by preparation and characterization of Cu(II), Zn(II) and Cd(II) complexes, [Cu(L)NO₃.H₂O](NO₃) (1) [Zn(L)₂](ClO₄)₂·2DMF (2) and [Cd(L)(I)₂] (3) respectively. In 1, the neutral ligand serves as tetradentate 4 N donor where both pyridine and pyrazole nitrogen atoms of pyridyl–pyrazole part are coordinatively active, leaving the carbonyl oxygen of the carbohydrazide part inactive. The same pyridine and pyrazole N atoms remain abstained from the coordination process towards the Zn(II) and Cd(II) metal centers. For 2 and 3 the ligand behaves as a tridentate NNO donor where the two nitrogen atoms come from azomethine, pyridine of pyridine-2-carbaldehyde parts and O from carbonyl oxygen atoms (carbohydrazide part). The complex 1 and 2 are distorted octahedral while complex 3 adopts distorted square pyramidal geometry. All the complexes are X-ray crystallographically characterized.     

Synthesis and reactivity of N-aryl substituted N-heterocyclic silylenes

The synthesis of two N-aryl substituted 2-silaimidazolidenes 9a, b by metal-reduction of the appropriate silicon(IV) heterocycles is reported. Structural as well as spectroscopic data obtained for the N-aryl substituted N-heterocyclic silylenes (NHSi) are very close to those obtained previously for their N-alkyl substituted counterparts. NHSis 9a, b are used as starting materials for the synthesis of a series of dichalcogenadisiletanes 19-24 and for of a mono silylene tungsten complex 29. The reactivity studies revealed only marginally differences between the N-aryl substituted NHSis 9a, b and previously described N-alkyl substituted silylenes.     

Macroscopic Form of the First Law of Thermodynamics for an Adibatically Evolving <Emphasis Type="Italic">Non-singular</Emphasis> Self-gravitating Fluid

We emphasize that the pressure related work appearing in a general relativistic first law of thermodynamics should involve proper volume element rather than coordinate volume element. This point is highlighted by considering both local energy momentum conservation equation as well as particle number conservation equation. It is also emphasized that we are considering here a non-singular fluid governed by purely classical general relativity. Therefore, we are not considering here any semi-classical or quantum gravity which apparently suggests thermodynamical properties even for a (singular) black hole. Having made such a clarification, we formulate a global first law of thermodynamics for an adiabatically evolving spherical perfect fluid. It may be verified that such a global first law of thermodynamics, for a non-singular fluid, has not been formulated earlier.     

Dynamic multiscaling in two-dimensional fluid turbulence

We obtain, by extensive direct numerical simulations, time-dependent and equal-time structure functions for the vorticity, in both quasi-Lagrangian and Eulerian frames, for the direct-cascade regime in two-dimensional fluid turbulence with air-drag-induced friction. We show that different ways of extracting time scales from these time-dependent structure functions lead to different dynamic-multiscaling exponents, which are related to equal-time multiscaling exponents by different classes of bridge relations; for a representative value of the friction we verify that, given our error bars, these bridge relations hold.     

Persistence problem in two-dimensional fluid turbulence

We present a natural framework for studying the persistence problem in two-dimensional fluid turbulence by using the Okubo-Weiss parameter Λ to distinguish between vortical and extensional regions. We then use a direct numerical simulation of the two-dimensional, incompressible Navier-Stokes equation with Ekman friction to study probability distribution functions (PDFs) of the persistence times of vortical and extensional regions by employing both Eulerian and Lagrangian measurements. We find that, in the Eulerian case, the persistence-time PDFs have exponential tails; by contrast, this PDF for Lagrangian particles, in vortical regions, has a power-law tail with an exponent θ=2.9±0.2.     

Mode-coupling-induced dissipative and thermal effects at long times after a quantum quench

An interaction quench in a Luttinger liquid can drive it into an athermal steady state. We analyze the effects on such an out of equilibrium state of a mode coupling term due to a periodic potential. Employing a perturbative renormalization group approach we show that even when the periodic potential is an irrelevant perturbation in equilibrium, it has important consequences on the athermal steady state as it generates a temperature as well as a dissipation and hence a finite lifetime for the bosonic modes.     

High sensitivity (1 ppm) hydrogen detection using an unconventional Pd/n-InP Schottky device

Hydrogen is detected using a Pd/n-InP Schottky diode in which the elongated, very thin Pd electrode is of greater resistance than the underlying semiconductor substrate. Four-probe measurements of the device resistance, as a function of hydrogen concentration, are made by contacting only the Pd electrode, with a sensitivity of 1 ppm being achieved. On hydrogen exposure the device resistance drops from an initial high value, characteristic of the Pd electrode alone, to a lower value due to a hydrogen-induced lowering of the Schottky barrier that opens up the InP substrate as a parallel current carrying channel.     

Diffusion of water in molecular magnet Cu(0.75)Mn(0.75)[Fe(CN)6]·7H2O

Here we report the dynamical behaviour of water in Prussian blue analogue (PBA) Cu(0.75)Mn(0.75)[Fe(CN)(6)]·7H(2)O molecular magnet in the temperature range 260-360 K as studied using the quasielastic neutron scattering technique. While significant quasielastic broadening is observed in the hydrated sample, no broadening was observed in the dehydrated one. Data analysis showed that the observed quasielastic broadening in Cu(0.75)Mn(0.75)[Fe(CN)(6)]·7H(2)O corresponds to the dynamics of the non-coordinated water molecules at the 32f site and the coordinated water molecules at the 24e site, existing in the cavities created by the absence of Fe(CN)(6) units. The non-coordinated water molecules at 8c interstitial sites do not contribute to the broadening, suggesting that they are immobile at least within the time window of the spectrometer used. Behaviour of the elastic incoherent structure factor is consistent with the model where the water molecules undergo translational diffusion localized within the cavity of 5.1 ?. While all the non-coordinated water molecules at the 32f site are dynamic over the entire range of temperatures, the coordinated ones at the 24e site become progressively dynamic with temperature. The water molecules were found to undergo hindered (~1.16 × 10(-5) cm(2) s(-1) at 300 K) diffusion compared to bulk water and the diffusivity followed Arrhenius behaviour within the measured temperature range with an activation energy of 1.26 kcal mol(-1).     

Microscale membrane extraction of diverse antibiotics from water

Antibiotics include a wide range of compounds that in addition to having high solubility in water may be basic, acidic or neutral. Therefore, it is anticipated that no single method would be effective in simultaneously extracting all of these compounds. In recent times, microscale membrane extraction has evolved as a viable sample preparation alternative. The two major approaches are microscale supported liquid membrane extraction (μ-SLME) and microscale liquid-liquid membrane extraction (μ-LLME). An approach that includes μ-LLME as well as μ-SLME for acidic and basic compounds is presented for the extraction and concentration of diverse antibiotics in water. Enrichment factors as high as 2700 were achieved. Relative standard deviations ranged from 1.5% to 2.0%, and detection limits were as low as 92 ng/L.