meso-meso-Linked corrole dimers with modified cores: synthesis, characterization, and properties

The synthesis and characterization of the first examples of core-modified corrole dimers linked through the meso positions are described. The dimers are obtained by a simple Ag(I)- or Fe(III)-catalyzed coupling reaction in near-quantitative yields. The corroles obtained are metalated with metal ions, such as Cu(II) and Ni(II). The electronic-absorption spectral studies reveal weak electronic interaction between the two subunits and the exciton coupling observed for the free-base corrole dimer (1717 cm(-1)) is lower than that for the corresponding protonated derivative (4081 cm(-1)). The solution-state structure derived from (1)H and two-dimensional NMR spectral studies reveals a noncoplanar arrangement of two corrole units. Geometry optimization at the B3LYP-631G level also confirms the noncoplanar arrangement of corroles with a dihedral angle of 64.8 degrees between two corrole planes. The electron paramagnetic resonance (EPR) and magnetic characterization studies on the paramagnetic copper-metalated dimer indicate that both copper ions behave as independent spins without any noticeable interaction. Results of fluorescence studies reveal a bathochromic shift of about 60 nm upon dimerization. The first hyperpolarizability (beta) measured by using the hyper Rayleigh scattering (HRS) method reveals doubling of the beta values on progressing from monomer to dimer, attributed to enhanced pi conjugation. The use of copper dimers in the photocleavage of DNA is also explored. It is shown that the bimetallic copper dimer selectively cleaves the nucleic acids without affecting the proteins, suggesting a possible application of the copper complex in the removal of nucleic acid contaminants from protein extracts through a simple photolytic pathway.     

Evaporation-induced patterns from droplets containing motile and nonmotile bacteria

In this letter, we report the observations of specific pattern formation from the evaporation of aqueous droplets containing motile and nonmotile bacteria. We found that when motile bacteria were present the droplet evaporated into disclike patterned deposits of bacteria. However, when the bacteria were made nonmotile by treatment with liquid nitrogen, the droplet evaporated into ringlike deposits. We also observed that bacteria with higher motility produced more uniformly deposited disclike patterns. Furthermore, we propose a model with numerical simulations to explain the mechanism of formation of these patterns. The model is based on the advective fluid flow from the center of the droplet toward the edge due to enhanced evaporation from the edge of the pinned droplet in comparison to that from the free surface. For the case of motile bacteria, we have added another velocity parameter toward the axis of the droplet and directed against the fluid flow in order to account for the disclike pattern formation. The numerical simulations match the experimental observations well. The present work, by qualitative and quantitative understanding of the evaporation of bacteria droplets, demonstrates that the inherent bacterial motility is primarily responsible for the formation of these differential patterns.     

Growth, biochemical modifications and proline metabolism in Helianthus annuus L. as induced by drought stress

In the present investigation, two watering treatments, viz., 100% and 60% field capacity (FC) were used to understand the effects of water deficit on early growth, biomass allocation, pigment and biochemical constituents and proline metabolism of five varieties of Sunflower (Helianthus annuus L.) plants. We found that there was a significant difference in early growth, dry matter accumulation, pigment, biochemical constituents and proline metabolism among the five varieties. The root length, shoot length, total leaf area, fresh and dry weight, chlorophyll a, b, total chlorophyll and carotenoid were significantly reduced under water stress treatments. Water stress increased the proline, free amino acid and glycinebetaine contents along with increased activity of γ-glutamyl kinase but the activity of proline oxidase reduced as a consequence of water stress.     

Alterations in osmoregulation, antioxidant enzymes and indole alkaloid levels in Catharanthus roseus exposed to water deficit

Catharanthus roseus (L.) G. Don plants were grown in different water regimes in order to study the drought induced osmotic stress and proline (PRO) metabolism, antioxidative enzyme activities and indole alkaloid accumulation. The plants under pot culture were subjected to 10, 15 and 20 days interval drought (DID) stress from 30 days after sowing (DAS) and regular irrigation was kept as control. The plants were uprooted on 41 DAS (10 DID), 46 DAS (15 DID) and 51 DAS (20 DID). The drought stressed plants showed increased aminoacid (AA), glycine betaine (GB) and PRO contents and decreased proline oxidase (PROX) and increased γ-glutamyl kinase (γ-GK) activities when compared to control. The antioxidative enzymes like peroxidase (POX) and polyphenol oxidase (PPO) increased to a significant level in drought stressed plants when compared to control. The drought stressed C. roseus plants showed an increase in total indole alkaloid content in shoots and roots when compared to well-watered control plants. Our results suggest that the cultivation of medicinal plants like C. roseus in water deficit areas would increase its PRO metabolism, osmoregulation, defense system and the level of active principles.     

Vibronic interaction and triplet state photophysics of phenylisatin and oxindole

Photophysical study of phenylisatin and oxindole triplet states have been made at room temperature and in different glasses at 77K. Qualitatively, in all respects the compounds have identical spectroscopic characteristics. Phosphorescence emission, excitation along with their polarization and lifetime suggest that a perturbation of the zero-point level of emitting state (³ππ*) by a close-lying triplet state (³nπ*) leads to a number of new spectral features. The experimental observations have been interpreted satisfactorily in terms of a switch (³ππ* state to ³nπ*) in the character of the lowest triplet states (T₁ and T₂) and also a similar switch in the character of the excited singlet states S₁ and S₂ for a change of glass matrix from MCH to ethanol. Invoking of first order and second order spin-orbit coupling explains the phosphorescence emission unambiguously.     

Synthesis and characterization of Ni1−xCoxFe2O4 nanoparticles

Ni_1−xCo_xFe₂O₄ (x=0.6, 0.8 and 0.9) nanoparticles have been synthesized with various crystallite sizes depending on the thermal treatments and composition (cobalt content) using the sol-gel combustion method. The size of nanoparticles has been controlled by thermal treatment. On the other hand, the magnetic property of the ferrite has been controlled by changing the heat treatment. Morphology and particle sizes of Ni_1−xCo_xFe₂O₄ have been studied using atomic force microscopy (AFM) and transmission electron microscopy (TEM). The presence of functional group has been identified by Fourier Transform Infrared (FTIR) spectra. From TGA-DTA studies, the weight gains of Ni_1−xCo_xFe₂O₄ nanoparticles have been observed and it might be due to capping organic molecules with oxygen at temperatures above 200 °C. Magnetic properties of Ni_1−xCo_xFe₂O₄ particles have been analysed using VSM and it is found that saturation magnetization (M_s) has increased with particle size and has coercivity (H_c) increased initially and then decreased. The M_s and H_c values decreased with the increase of content of cobalt in Ni_1−xCo_xFe₂O₄.     

3D zinc(II) coordination polymers built up by triazole and benzene-polycarboxylate anions: Synthesis,crystal structure,thermal and photoluminescence characterization

Two coordination polymers of the formula [Zn₅(tmaH)₄(trz)₂(H₂O)₄] (1) and [Zn₃(bta)(trz)₂(H₂O)₄]·2H₂O (2) [tmaH₃ = benzene-1,3,5-tricarboxylic acid/trimesic acid, trzH = 1,2,4-triazole, btaH₄ = benzene-1,2,4,5-tetracarboxylic acid] have been synthesized and structurally characterized by X-ray single crystal diffraction analysis. Both complexes are 3D coordination polymers containing [Zn₄(trz)₂] units connected by benzene-carboxylate anions. In particular, an undulated layer containing 6- and 18-membered rings is outlined in the network of 1. Hydrogen bonds, involving the coordinated and lattice water molecules with carboxylate oxygen atoms, contribute to the stabilization of the networks. Their thermal stability was investigated by thermogravimetric analysis. The fluorescence spectrum of 1 features two peaks at 419 and 323 nm, originating from a π–π∗ intraligand transition and LMCT, respectively. For 2 a broad band at 410 nm is assigned solely as a π–π∗ intraligand transition.     

LC–MS Simultaneous Determination of Itopride Hydrochloride and Domperidone in Human Plasma

A rapid, simple, sensitive and specific liquid chromatography–tandem mass spectrometry method was developed and validated for simultaneous quantification of itopride hydrochloride and domperidone in human plasma. Both drugs were extracted by liquid–liquid extraction with ethyl acetate and saturated borax solution. The chromatographic separation was performed on a reversed-phase C18 column with a mobile phase of water–methanol (2:98, v/v) containing 0.5% formic acid. The protonated analyte was quantitated in positive ionization by multiple reaction monitoring with a mass spectrometer. The assay exhibited linearity over the concentration range of 3.33–500 ng mL^?1 for itopride hydrochloride and 3.33–100 ng mL^?1 for domperidone in human plasma. The precursor to product ion transitions of m/z 359.1–72.3 and 426.0–147.2 were used to measure itopride hydrochloride and domperidone respectively. The method was found suitable for the analysis of plasma samples collected during phase 1 pharmacokinetics study of itopride HCl 50 mg and domperidone 20 mg in 12 healthy volunteers after single oral doses of the combination drug.