Synthesis of lariat organochalcogenoethers based on azacalix[3]arenes for the potentiometric detection of [UO2] ions

The syntheses of organochalcogen-supported azacalix[3]arenes are described in a one-pot manner in satisfactory yields. A remarkably selective potentiometric response was accomplished for uranyl ions over a variety of other metal ions, including alkali (Na⁺, K⁺), alkaline-earth (Mg²⁺, Ca²⁺, Ba²⁺), transition and heavy metal ions (Co²⁺, Ni²⁺, Cu²⁺, Ag⁺, Fe³⁺, Zn²⁺, Cd²⁺ and Pb²⁺) using an ion-selective electrode based on compound 3 incorporated into a polymeric (PVC) membrane.     

Reproducible SERRS from structured gold surfaces

Metallic substrates with ordered spherical cavities have been shown to be very effective for surface-enhanced Raman scattering (SERS) and can be fabricated reproducibly using electrodeposition. The sensitivity of detection is increased by several orders of magnitude by using surface-enhanced resonance Raman scattering (SERRS). In this report we demonstrate SERRS for the first time on electrodeposited gold films templated with colloidal spheres and demonstrate the reproducibility of the response. We also obtain a direct comparison between SERRS and SERS by choosing two dyes, Cy5 and Cy3, which are similar in structure but differ in their excitation maxima, such that one is resonant and the other non-resonant with our laser excitation. As expected, the resonant enhancement is found to be of the order of 10(3) over and above that for SERS. The net SERRS enhancements are shown to be of the order of 10(9). We also find that the resonant enhancement profile of the different peaks for the chromophore follows the plasmonic resonance absorption spectrum obtained for the structured surface.     

The versatility of salicylaldehyde thiosemicarbazone in the determination of copper in blood using adsorptive stripping voltammetry

The adsorptive cathodic stripping voltammetry technique (AdCSV) is used to determine copper(II) using salicylaldehyde thiosemicarbazone (N, S- donor) as a complexing agent on hanging mercury drop electrode at pH 9.3. Variable factors affecting the response, i.e. the concentration of ligand, pH, adsorption potential and adsorption time are assessed and optimized. The adsorbed complex of copper(II) and salicylaldehyde thiosemicarbazone gives a well defined cathodic stripping peak current at −0.35 V, which has been used for the determination of copper in the concentration range of 7.85 × 10⁻⁹ to 8.00 × 10⁻⁶ M with accumulation time of 360 s at −0.1 V versus Ag/AgCl. This technique has been applied for the determination of copper in various digested samples of whole blood at trace levels.     

Isocytosine as a hydrogen-bonding partner and as a ligand in metal complexes

Isocytosine (ICH; 1) exists in solution in an equilibrium of tautomers 1a and 1b with the N1 and N3 positions carrying the acidic proton, respectively. In the solid state, both tautomers coexist in a 1:1 ratio. As we show, the N3H tautomer 1b can selectively be crystallized in the presence of the model nucleobase 1-methylcytosine (1-MeC). The complex 1b x (1-MeC)2 x H2O (2) forms pairs through three hydrogen bonds between the components; hydrogen bonds between identical molecules are also formed, leading to an infinite tape structure. On the other hand, the N1H tautomer 1a co-crystallizes with protonated ICH to give [1a x ICH2]NO3 (3), again with three hydrogen bonds between the partners, yet the acidic proton is disordered over the two entities. With M(II)(dien) (M=Pt, Pd; dien=diethylenetriamine) preferential coordination of tautomer 1a through the N3 position is observed. DFT calculations, which were also extended to Pt(II)(tmeda) linkage isomers (tmeda=N,N,N',N'-tetramethylethylenediamine), suggest that intramolecular hydrogen bonding between the ICH tautomers and the co-ligands at M, while adding to the preference for N3 coordination, is not the major determining factor. Rather it is the inherently stronger Pt-N3 bond which favors complexation of 1a. With an excess of M(II)(dien), dinuclear species [M2(dien)2(IC-N1,N3)]3+ (M=Pd(II), 4 and Pt(II), 5) also form and were isolated as their ClO4(-) salts and structurally characterized. In strongly acidic medium 5 is converted to [Pt(dien)(ICH-N1)]2+ (6), that is, to the Pt(II) complex of tautomer 1b.     

Particle creation in a time-dependent electric field revisited

We adopt the general formalism for analyzing evolution of gaussian states of quantized fields in time-dependent backgrounds in the Schrodinger picture (presented in detail in Mahajan and Padmanabhan [G. Mahajan, T. Padmanabhan, Gen. Rel. Grav. 40 (2008) 661]) to study the example of a spatially uniform electric field background (in a time-dependent gauge) which is kept turned on for a finite duration of time. In particular, we study the time-dependent particle content, defined in terms of the concept of instantaneous eigenstates, and describe how it captures the time evolution of the quantized field modes. The actual particle creation process occurs over a relatively short interval in time, and the particle content saturates rather quickly. We also compare the power spectrum of the field modes, computed in the asymptotic limit, with the corresponding situation in a cosmological de Sitter background. Particle creation under the influence of a spiked electric field localized in time, as a particular limiting case of the above general model, is also considered.     

Synthesis and characterization of K2NiF4-type phases Ln0.5Sr1.5Mn0.5Fe0.5O4 (Ln = La, Nd, Gd, and Dy)

A systematic investigation of layered perovskite oxides with general formula Ln_0.5Sr_1.5Mn_0.5Fe_0.5O₄ (Ln?=?La, Nd, Gd, and Dy) has been undertaken mainly to understand their structural, magnetic, as well as electrical behavior. The materials were prepared by the ceramic method. X-ray data have been analyzed by using program Checkcell and the variations of various parameters are explained. It has been concluded that not only A-site cation radius, <r _A>, but also the size variance factor (σ ²) influence electrical and magnetic properties. A systematic study of electrical resistivity of all the four materials was undertaken as a function of temperature to understand the conduction mechanism. On analyzing the electrical resistivity data, it has been concluded that variable range hopping model is found to fit well. The magnetic studies suggest that the phases are antiferromagnetic and this behavior could arise from Mn⁴⁺–O–Mn⁴⁺, and Fe³⁺–O–Fe³⁺ superexchange interaction.     

Complex Classical Mechanics of a QES Potential

We study a combined parity (P) and time reversal (T) invariant non-Hermitian quasi-exactly solvable (QES) potential, which exhibits PT phase transition, in the complex plane classically to demonstrate different quantum effects. The particle with real energy makes closed orbits around one of the periodic wells of the complex potential depending on the initial condition. However interestingly the particle escapes to an open orbits even with real energy if it is placed beyond a certain distance from the center of the well. On the other hand when the particle energy is complex the trajectory is open and the particle tunnels back and forth between two wells which are separated by a classically forbidden path. The tunneling time is calculated for different pair of wells and is shown to vary inversely with the imaginary component of energy. Our study reveals that spontaneous PT symmetry breaking does not affect the qualitative features of the particle trajectories in the analogous complex classical model.     

Vortical dynamics of spinning quantum plasmas: helicity conservation

It is shown that a vorticity, constructed from the spin field of a quantum spinning plasma, combines with the classical generalized vorticity (representing the magnetic and the velocity fields) to yield a new grand generalized vorticity that obeys the standard vortex dynamics. Expressions for the quantum or spin vorticity and for the resulting generalized helicity invariant are derived. Reduction of the rather complex spinning quantum system to a well known and highly investigated classical form opens familiar channels for the delineation of physics peculiar to dense plasmas spanning solid state to astrophysical objects. A simple example is worked out to show that the magnetics of a spinning plasma can be much richer than that of the corresponding classical system.     

Microwave‐assisted synthesis,characterization, biotoxicity and antispermatogenic activity of some antimony(III) complexes with N∩O and N∩S donor ligands

New series of phenylantimony chloride and antimony chloride with Schiff base ligands, L¹H and L²H having N^∩S and N^∩O donor systems were synthesized under microwave irradiation using a domestic microwave oven. The reaction time was brought down from hours to a few seconds with improved yield as compared with conventional heating. All the ligands and their antimony(III) derivatives were characterized on the basis of microanalysis, elemental analyses, molecular weight determinations and spectral studies including IR, NMR (¹H and ¹³C) and electronic spectral studies. A distorted trigonal bipyramidal and pseudo‐octahedral geometry around the antimony atom was tentatively proposed for these derivatives. The compounds were screened in vitro against bacteria and fungi to test their antimicrobial property and in vivo in male albino rats to test their antifertility properties. The treatment with the ligands and their phenylantimony derivatives at dose levels of 20 mg per rat per day did not cause any significant change in body weight, but a significant reduction in the weights of reproductive organs was observed. Arrest of spermatogenesis was noted at various stages with production of primary spermatocytes (preleptotene and pachytene), secondary spermatocytes and step‐19 spermatids found to be decreased. Biochemical parameters of tissues, i.e. protein, sialic acid, cholesterol content of testes and seminal vesicular fructose also showed significant reduction. Further, the serum testosterone concentrations were also decreased after treatment with ligands and their antimony(III) derivatives. Copyright © 2008 John Wiley & Sons, Ltd.