Remarkable Selectivity and Photo-Cytotoxicity of an Oxidovanadium(IV) Complex of Curcumin in Visible Light

Oxidovanadium(IV) complexes of 2-(2'-pyridyl)-1,10-phenanthroline (pyphen), viz. VO(pyphen)(acac)](ClO4) (1), VO(pyphen)(anacac)](ClO4) (2) and VO(pyphen)(cur)](ClO4) (3), where acac is acetylacetonate (in 1), anacac is anthracenylacetylacetonate (in 2) and cur is curcumin monoanion (in 3) were synthesized, characterized and their photo-induced DNA cleavage activities and photo-cytotoxicities studied. The complexes are 1: 1 electrolytes in DMF. The one-electron paramagnetic complexes show a d-d band near 760 nm in DMF. Complexes 2 and 3 are blue and green emissive, respectively, in DMSO. The complexes exhibit irreversible V-IV/V-III reductive responses near -1.1 V and V-V/V-IV oxidative responses near 0.85 V vs. SCE in DMF-0.1 M TBAP. Complexes 2 and 3 display significant and selective photo-cytotoxicity upon irradiation with visible light giving an IC50 value of about 5 mu M against HeLa and MCF-7 cancer cells; they are significantly less-toxic against normal 3T3 control cells and in the absence of light. Complex 1 was used as a control. Both cytosolic and nuclear localization of the complexes were observed on the basis of fluorescence imaging. The complexes, avid binders to calf thymus (ct) DNA, were found to photocleave supercoiled pUC19 DNA upon irradiation with near-IR light (785 nm) by generating hydroxyl radical (OH) as the reactive oxygen species (ROS). Cell death events noted with HeLa and MCF-7 cell lines likely are attributable to apoptotic pathways involving light-assisted generation of intracellular ROS.

The phenanthroimidazole-based dizinc(II) complex as a fluorescent probe for the pyrophosphate ion as generated in polymerase chain reactions and pyrosequencing

A highly selective and sensitive phenanthroimidazole tagged Mannich base type dizinc(II) fluorescent probe (R-Zn2+) has been developed for the pyrophosphate ion (PPi) with a very low limit of detection (LOD) of 0.25 ppm; this also assesses PPi from DNA polymerization chain reaction (PCR).

Significant photocytotoxic effect of an iron(III) complex of a Schiff base ligand derived from vitamin B-6 and thiosemicarbazide in visible light

Iron(III)-Schiff base complexes, namely, Fe(tsc-py)(2)](NO3) (1), Fe(tsc-acpy)(2)](NO3) (2) and Fe(tsc-VB6)(2)](NO3) (3), where tsc-py, tsc-acpy and tsc-VB6 are the respective Schiff bases derived from thiosemicarbazide (tsc) and pyridine-2-aldehyde (tsc-py), 2-acetyl pyridine (tsc-acpy) and vitamin B-6 (pyridoxal, tsc-VB6), have been prepared, structurally characterized and their photocytotoxicity studied in cancer HeLa cells. The single crystal X-ray structures of the complexes 1 and 2 show a distorted octahedral geometry formed by the FeN4S2 core. The low-spin and 1 : 1 electrolytic complexes display a broad absorption band in the visible region. Complexes 1 and 2, without any VB6 moiety are not cytotoxic under light or dark conditions. Complex 3 is significantly photocytotoxic under visible light of 400-700 nm giving an IC50 value of 22.5 mu M in HeLa cells with no dark toxicity (IC50 > 100 mu M). The photo-induced cell death is attributable to apoptotic pathways involving photo-assisted generation of intracellular ROS. The observed photocytotoxicity of complex 3 could be the result of its better photosensitizing property combined with its enhanced uptake into cancer cells via a VB6 transporting membrane carrier (VTC) mediated diffusion pathway due to the presence of the VB6 moiety compared to the two non-vitamin B-6 analogues, complexes 1 and 2.

Implication of a sigma-Methane Complex en Route to Elimination of Methane from a Ruthenium Complex: An Experimental and Theoretical Investigation

The five-coordinated 16-electron complex Ru(Me)(dppe)(2)]OTf] (3) undergoes methane elimination at room temperature to afford the ortho-metalated species (dppe){(C6H5)(C6H4)PCH2CH2P(C6H5)(2)}Ru]OTf] (7). Methane elimination, monitored using NMR spectroscopy, revealed no intermediate throughout the reaction. The NOE between Ru-Me protons and ortho phenyl protons and an agostic interaction trans to the methyl group were found in complex 3 by NMR spectroscopy, which form the basis for three plausible pathways for methane elimination and ortho metalation: pathway I (through spatial interaction), pathway II (through oxidative addition and reductive elimination), and pathway III (through agostic interaction). Methane elimination from complex 3 via pathway I was discounted, since it involves interactions through space and not through bonds. Moreover, the calculated energy barrier for the pathway I transition state was quite high (71.3 kcal/mol), which also indicates that this pathway is very unlikely. Furthermore, no spectroscopic evidence for oxidatively added seven-coordinated Ru(IV) species was found and the computed energy barrier of the transition state for pathway II was moderately high (41.1 kcal/mol), which suggests that this cannot be the right pathway for methane elimination and ortho-metalation of complex 3. On the other hand, indirect evidence in the form of chemical reactions point to the most plausible pathway for methane elimination, pathway III, via the intermediacy of a sigma-CH4 complex that could not be found spectroscopically. DFT calculations at several levels on this pathway showed an initial low-barrier rearrangement through TS1 to a square-pyramidal intermediate wherein methyl and agostic C-H are cis to each other. Migration of hydrogen from agostic C-H and elimination of methane proceed through the transition state TS2, which retains a weak metal-H bonding through most parts of the reaction coordinate. Upon comparison of all three pathways, pathway III was found to be the most likely for methane elimination and ortho-metalation of complex 3.

Piezoelectric properties of individual nanocrystallites of Ba0.85Ca0.15Zr0.1Ti0.9O3 obtained by oxalate precursor route

Nanocrystalline Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) powder was synthesized via the complex oxalate precursor route at a relatively low temperature (800 degrees C/5 h). The phase formation temperature of BCZT at nanoscale was confirmed by thermogravimetric (TG), differential thermal analysis (DTA) followed by X-ray powder diffraction (XRD) studies. Fourier transform infrared (FTIR) spectroscopy was carried out to confirm the complete decomposition of oxalate precursor into BCZT phase. The XRD and profile fitting revealed the coexistence of cubic and tetragonal phases and was corroborated by Raman study. Transmission electron microscopy (TEM) carried out on 800 degrees C and 1000 degrees C/5 h heat treated BCZT powder revealed the crystallite size to be in the range of 20-50 nm and 40-200 nm respectively. The optical band gap for BCZT nanocrystalline powder was obtained using Kubelka Munk function and was found to be around 3.12 +/- 0.02 eV and 3.03 +/- 0.02 eV respectively for 800 degrees C (20-50 nm) and 1000 degrees C/5 h (40-200 nm) heat treated samples. The piezoelectric properties were studied for two different crystallite sizes (30 and 70 nm) using a piezoresponse force microscope (PFM). The d(33) coefficients obtained for 30 nm and 70 nm sized crystallites were 4 pm V-1 and 47 pm V-1 respectively. These were superior to that of BaTiO3 nanocrystal (approximate to 50 nm) and promising from a technological/industrial applications viewpoint.

Impacts of climate change and management responses in tropical forests depend on complex frugivore-mediated seed dispersal

AimBiodiversity outcomes under global change will be influenced by a range of ecological processes, and these processes are increasingly being considered in models of biodiversity change. However, the level of model complexity required to adequately account for important ecological processes often remains unclear. Here we assess how considering realistically complex frugivore-mediated seed dispersal influences the projected climate change outcomes for plant diversity in the Australian Wet Tropics (all 4313 species). LocationThe Australian Wet Tropics, Queensland, Australia. MethodsWe applied a metacommunity model (M-SET) to project biodiversity outcomes using seed dispersal models that varied in complexity, combined with alternative climate change scenarios and habitat restoration scenarios. ResultsWe found that the complexity of the dispersal model had a larger effect on projected biodiversity outcomes than did dramatically different climate change scenarios. Applying a simple dispersal model that ignored spatial, temporal and taxonomic variation due to frugivore-mediated seed dispersal underestimated the reduction in the area of occurrence of plant species under climate change and overestimated the loss of diversity in fragmented tropical forest remnants. The complexity of the dispersal model also changed the habitat restoration approach identified as the best for promoting persistence of biodiversity under climate change. Main conclusionsThe consideration of complex processes such as frugivore-mediated seed dispersal can make an important difference in how we understand and respond to the influence of climate change on biodiversity.

A rhodamine-based `turn-on' Al3+ ion-selective reporter and the resultant complex as a secondary sensor for F- ion are applicable to living cell staining

A newly designed fluorescent aluminum(III) complex (L'-Al; 2) of a structurally characterized non-fluorescent rhodamine Schiff base (L) has been isolated in pure form and characterized using spectroscopic and physico-chemical methods with theoretical density functional theory (DFT) support. On addition of Al(III) ions to a solution of L in HEPES buffer (1 mM, pH 7.4; EtOH-water, 1 : 3 v/v) at 25 degrees C, the systematic increase in chelation-enhanced fluorescence (CHEF) enables the detection of Al(III) ions as low as 60 nM with high selectivity, unaffected by the presence of competitive ions. Interestingly, the Al(III) complex (L'-Al; 2) is specifically able to detect fluoride ions by quenching the fluorescence in the presence of large amounts of other anions in the HEPES buffer (1 mM, pH 7.4) at 25 degrees C. On the basis of our experimental and theoretical findings, the addition of Al3+ ions to a solution of L helps to generate a new fluorescence peak at 590 nm, due to the selective binding of Al3+ ions with L in a 1 : 1 ratio with a binding constant (K) of 8.13 x 10(4) M-1. The Schiff base L shows no cytotoxic effect, and it can therefore be employed for determining the intracellular concentration of Al3+ and F-ions by 2 in living cells using fluorescence microscopy.

Deciphering complex patterns of class-I HLA-peptide cross-reactivity via hierarchical grouping

T-cell responses in humans are initiated by the binding of a peptide antigen to a human leukocyte antigen (HLA) molecule. The peptide-HLA complex then recruits an appropriate T cell, leading to cell-mediated immunity. More than 2000 HLA class-I alleles are known in humans, and they vary only in their peptide-binding grooves. The polymorphism they exhibit enables them to bind a wide range of peptide antigens from diverse sources. HLA molecules and peptides present a complex molecular recognition pattern, as many peptides bind to a given allele and a given peptide can be recognized by many alleles. A powerful grouping scheme that not only provides an insightful classification, but is also capable of dissecting the physicochemical basis of recognition specificity is necessary to address this complexity. We present a hierarchical classification of 2010 class-I alleles by using a systematic divisive clustering method. All-pair distances of alleles were obtained by comparing binding pockets in the structural models. By varying the similarity thresholds, a multilevel classification was obtained, with 7 supergroups, each further subclassifying to yield 72 groups. An independent clustering performed based only on similarities in their epitope pools correlated highly with pocket-based clustering. Physicochemical feature combinations that best explain the basis of clustering are identified. Mutual information calculated for the set of peptide ligands enables identification of binding site residues contributing to peptide specificity. The grouping of HLA molecules achieved here will be useful for rational vaccine design, understanding disease susceptibilities and predicting risk of organ transplants.

Biodiesel Exhaust Treatment with Dielectric Barrier Discharges Coupled with Industrial Waste Byproducts

Biodiesel run engines are gaining popularity since the last few years as a viable alternative to conventional petro-diesel based engines. In biodiesel exhaust the content of volatile organic compounds, oil mist, and mass of particulate matter is considerably lower. However, the concentration of oxides of nitrogen (NOx) is relatively higher. In this paper the biodiesel exhaust from a stationary engine is treated under controlled laboratory conditions for removal of NOx using dielectric barrier discharge plasma in cascade with adsorbents prepared from abundantly available industrial waste byproducts like red mud and copper slag. Results were compared with gamma-alumina, a commercial adsorbent. Two different dielectric barrier discharge (DBD) reactors were tested for their effectiveness under Repetitive pulses /AC energization. NOx removal as high as 80% was achieved with pulse energized reactors when cascaded with red mud as adsorbent.

Spectrophotometric determination of molybdenum with Syzygium jambolanum DC leaf extracts

A new spectrophotometric method for the determination of molybdenum in industrial materials has been developed using the leaf extract of Syzygium jambolanum DC based on the reaction of Mo (VI) at pH 7.0 to produce an orange-yellow complex with an absorption maximum at 426 nm. The molar absorptivity of the complex is 4.27 x 10(4) l mol(-1) cm(-1) and the absorbance, is linear in the range 0.05-0.8 ppm. Sandell sensitivity coefficient was found to be 2.25 x 10(-3) mu g/cm(2). The method is ten times more sensitive than the aqueous thiocyanate system. It has been applied successfully in micronutrient fertilizer, artificial freshwater and sea-water analyses.

An enolato-bridged dinuclear Cu(II) complex with a coumarin-assisted precursor: a spectral, magnetic and biological study

A new, phenoxo-bridged Cu-II dinuclear complex Cu-2(L)(2)(DMF)(2)] (1) has been obtained by employing the coumarin-assisted tridentate precursor, H2L, benzoic acid(7-hydroxy-4-methyl-2-oxo-2H-chromen-8-ylmethylene)-hydrazide]. Complex 1 has been systematically characterized by FTIR, UV-Vis, fluorescence and PR spectrometry. The single crystal X-ray diffraction analysis of 1 shows that the geometry around each copper ion is square pyramidal, comprising two enolato oxygen atoms belonging to different ligands (which assemble the dimer bridging the two metal centers), one imine-N and one phenolic-O atoms of the Schiff base and one oxygen atom from the DMF molecule. The temperature dependent magnetic interpretation agrees with the existence of weak ferromagnetic interactions between the bridging dinuclear Cu(II) ions. Both the ligand and complex 1 exhibit anti-mycobacterial activity and considerable efficacy towards M. tuberculosis H37Rv ATCC 27294 and M. tuberculosis H37Ra ATCC 25177 strains. The cytotoxicity study on human adenocarcinoma cell lines (MCF7) suggests that the ligand and complex 1 have potential anticancer properties. Molecular docking of H2L with the enoyl acyl carrier protein reductase of M. tuberculosis H37R(v) (PDB ID: 4U0K) is examined and the best docked pose of H2L shows one hydrogen bond with Thr196 (1.99 angstrom).

Differential expression of estrogen receptor alpha in the embryonic adrenal-kidney-gonadal complex of the oviparous lizard, Calotes versicolor (Daud.)

Estrogen signalling is critical for ovarian differentiation in reptiles with temperature-dependent sex determination (TSD). To elucidate the involvement of estrogen in this process, adrenal-kidney-gonadal (AKG) expression of estrogen receptor (ER alpha) was studied at female-producing temperature (FPT) in the developing embryos of the lizard, Calotes versicolor which exhibits a distinct pattern of TSD. The eggs of this lizard were incubated at 31.5 +/- 0.5 degrees C (100% FPT). The torso of embryos containing adrenal-kidney-gonadal complex (AKG) was collected during different stages of development and subjected to Western blotting and immunohistochemistry analysis. The ER alpha, antibody recognized two protein bands with apparent molecular weight similar to 55 and similar to 45 kDa in the total protein extracts of embryonic AKG complex of C. versicolor. The observed results suggest the occurrence of isoforms of ER alpha. The differential expression of two different protein isoforms may reveal their distinct role in cell proliferation during gonadal differentiation. This is the first report to reveal two isoforms of the ER alpha in a reptile during development. Immunohistochemical studies reveal a weak, but specific, cytoplasmic ER alpha immunostaining exclusively in the AKG during late thermo-sensitive period suggesting the responsiveness of AKG to estrogens before gonadal differentiation at FPT. Further, cytoplasmic as well as nuclear expression of ER alpha in the medulla and in oogonia of the cortex (faint activity) at gonadal differentiation stage suggests that the onset of gonadal estrogen activity coincides with sexual differentiation of gonad. Intensity and pattern of the immunoreactions of ER alpha in the medullary region at FPT suggest endogenous production of estrogen which may act in a paracrine fashion to induce neighboring cells into ovarian differentiation pathway. (C) 2014 Elsevier Inc. All rights reserved.

Microwave spectroscopic and theoretical investigations of the strongly hydrogen bonded hexafluoroisopropanol...water complex

This paper reports microwave spectroscopic and theoretical investigations on the interaction of water with hexafluoroisopropanol (HFIP). The HFIP monomer can exist in two conformations, antiperiplanar (AP) and synclinical (SC). The former is about 5 kJ mol(-1) more stable than the latter. Theoretical calculations predicted three potential minima for the complex, two having AP and one having SC conformations. Though, the binding energy for the HFIP(SC)...H2O turned out to be larger than that for the other two conformers having HFIP in the AP form, the global minimum for the complex in the potential energy hypersurface had HFIP in the AP form. Experimental rotational constants for four isotopologues measured using a pulsed nozzle Fourier transform microwave spectrometer, correspond to the global minimum in the potential energy hypersurface. The structural parameters and the internal dynamics of the complex could be determined from the rotational spectra of the four isotopologues. The global minimum has the HFIP(AP) as a hydrogen bond donor forming a strong hydrogen bond with H2O. To characterize the strength of the bonding and to probe the other interactions within the complex, atoms in molecules, non-covalent interaction index and natural bond orbital theoretical analyses have been performed.

Probing complex heterostructures using hard X-ray photoelectron spectroscopy (HAXPES)

X-ray Photoelectron Spectroscopy (XPS) plays a central role in the investigation of electronic properties as well as compositional analysis of almost every conceivable material. However, a very short inelastic mean free path (IMFP) and the limited photon flux in standard laboratory conditions render this technique very much surface sensitive. Thus, the electronic structure buried below several layers of a heterogeneous sample is not accessible with usual photoemission techniques. An obvious way to overcome this limitation is to use a considerably higher energy photon source, as this increases the IMFP of the photo-ejected electron, thereby making the technique more depth and bulk sensitive. Due to this obvious advantage, Hard X-ray Photo Electron Spectroscopy (HAXPES) is rapidly becoming an extremely powerful tool for chemical, elemental, compositional and electronic characterization of bulk systems, more so with reference to systems characterized by the presence of buried interfaces and other types of chemical heterogeneity. The relevance of such an investigative tool becomes evident when we specifically note the ever-increasing importance of heterostructures and interfaces in the context of a wide range of device applications, spanning electronic, magnetic, optical and energy applications. The interest in this nondestructive, element specific HAXPES technique has grown rapidly in the past few years; we discuss critically its extensive use in the study of depth resolved electronic properties of nanocrystals, multilayer superlattices and buried interfaces, revealing their internal structures. We specifically present a comparative discussion, with examples, on two most commonly used methods to determine internal structures of heterostructured systems using XPS. (C) 2015 Elsevier B.V. All rights reserved.

Estimation of Power Input to Complex Dielectric Barrier Discharge Reactor Geometries used in NOx Cleaning

Studies were carried out to estimate the power input to Dielectric Barrier Discharge (DBD) reactors powered by AC high voltage in the context of their application in non-thermal plasma cleaning of exhaust gases. Power input to the reactors was determined both theoretically and experimentally. Four different reactor geometries energized with 50 Hz and 1.5 kHz AC excitation were considered for the study. The theoretically estimated power using Manley's equation was found to agree with the experimental results. Results show that the analytically computed capacitance, without including the electrode edge effects, gives sufficiently good results that are matching with the measured values. For complex geometries where analytical calculation of capacitance is often difficult, a novel method of estimating the reactor capacitance, and hence the power input to the reactor, was introduced in this paper. The predicted results were validated with experiments.