Metal-metal charge transfer and interfacial charge transfer mechanism for the visible light photocatalytic activity of cerium and nitrogen co-doped TiO2

Nanosized cerium and nitrogen co-doped TiO2 (Ce-TiO2-xNx) was synthesized by sol gel method and characterized by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), FESEM, Fourier transform infrared, N-2 adsorption and desorption methods, photoluminescence and ultraviolet-visible (UV-vis) DRS techniques. PXRD analysis shows the dopant decreases the crystallite sizes and slows the crystallization of the titania matrix. XPS confirm the existence of cerium ion in +3 or +4 state, and nitrogen in -3 state in Ce-TiO2-xNx. The modified surface of TiO2 provides highly active sites for the dyes at the periphery of the Ce-O-Ti interface and also inhibits Ce particles from sintering. UV-visible DRS studies show that the metal-metal charge transfer (MMCT) of Ti/Ce assembly (Ti4+/Ce3+ -> Ti3+/Ce4+) is responsible for the visible light photocatalytic activity. Photoluminescence was used to determine the effect of cerium ion on the electron-hole pair separation between the two interfaces Ce-TiO2-xNx and Ce2O3. This separation increases with the increase of cerium and nitrogen ion concentrations of doped samples. The degradation kinetics of methylene blue and methyl violet dyes in the presence of sol gel TiO2, Ce-TiO2-xNx and commercial Degussa P25 was determined. The higher visible light activity of Ce-TiO2-xNx was due to the participation of MMCT and interfacial charge transfer mechanism.

Direct control of type IIA topoisomerase activity by a chromosomally encoded regulatory protein

Precise control of supercoiling homeostasis is critical to DNA-dependent processes such as gene expression, replication, and damage response. Topoisomerases are central regulators of DNA supercoiling commonly thought to act independently in the recognition and modulation of chromosome superstructure; however, recent evidence has indicated that cells tightly regulate topoisomerase activity to support chromosome dynamics, transcriptional response, and replicative events. How topoisomerase control is executed and linked to the internal status of a cell is poorly understood. To investigate these connections, we determined the structure of Escherichia coil gyrase, a type HA topoisomerase bound to YacG, a recently identified chromosomally encoded inhibitor protein. Phylogenetic analyses indicate that YacG is frequently associated with coenzyme A (CoA) production enzymes, linking the protein to metabolism and stress. The structure, along with supporting solution studies, shows that YacG represses gyrase by sterically occluding the principal DNA-binding site of the enzyme. Unexpectedly, YacG acts by both engaging two spatially segregated regions associated with small-molecule inhibitor interactions (fluoroquinolone antibiotics and the newly reported antagonist GSK299423) and remodeling the gyrase holo enzyme into an inactive, ATP-trapped configuration. This study establishes a new mechanism for the protein-based control of topoisomerases, an approach that may be used to alter supercoiling levels for responding to changes in cellular state.

Size Modulation of Colloidal Au Nanoparticles via Digestive Ripening in Conjunction with a Solvated Metal Atom Dispersion Method: An Insight Into Mechanism

Digestive ripening, a postsynthetic treatment of colloidal nanoparticles, is a versatile method to produce monodisperse nanoparticles and to prepare various bimetallic nanostructures. The mechanism of this process is largely unknown. Herein, we present a systematic study conducted using Au nanoparticles prepared by a solvated metal atom dispersion method to probe the mechanistic aspects of digestive ripening. In our study, experimental conditions such as concentration of capping agent, reaction time, and temperature, were found to influence the course of the digestive ripening process. Here it is shown that, during digestive ripening under reflux, nanoparticles within an optimum size window are conserved, and surface etching facilitated mass transfer resulted in monodisperse nanoparticles. Overall, digestive ripening can be considered as a kinetically controlled thermodynamic process.

Defect induced plasticity and failure mechanism of boron nitride nanotubes under tension

The effects of Stone-Wales (SW) and vacancy defects on the failure behavior of boron nitride nanotubes (BNNTs) under tension are investigated using molecular dynamics simulations. The Tersoff-Brenner potential is used to model the atomic interaction and the temperature is maintained close to 300 K. The effect of a SW defect is studied by determining the failure strength and failure mechanism of nanotubes with different radii. In the case of a vacancy defect, the effect of an N-vacancy and a B-vacancy is studied separately. Nanotubes with different chiralities but similar diameter is considered first to evaluate the chirality dependence. The variation of failure strength with the radius is then studied by considering nanotubes of different diameters but same chirality. It is observed that the armchair BNNTs are extremely sensitive to defects, whereas the zigzag configurations are the least sensitive. In the case of pristine BNNTs, both armchair and zigzag nanotubes undergo brittle failure, whereas in the case of defective BNNTs, only the zigzag ones undergo brittle failure. An interesting defect induced plastic behavior is observed in defective armchair BNNTs. For this nanotube, the presence of a defect triggers mechanical relaxation by bond breaking along the closest zigzag helical path, with the defect as the nucleus. This mechanism results in a plastic failure. (C) 2014 AIP Publishing LLC.

2-(4-Chlorobenzyl)-6-arylimidazo2,1-b]1,3,4]thiadiazoles: Synthesis, cytotoxic activity and mechanism of action

The cytotoxic activity of a new series of 2-(4'-chlorobenzyl)-5,6-disubstituted imidazo2,1-b]1,3,4]wthiadiazoles against different human and murine cancer cell lines is reported. Among the tested compounds, two derivatives namely 2-(4-chlorobenzyl)-6-(2-oxo-2H-chromen-3-yl)imidazo2,1-1)]1,3,4]th iadiazole-5-carbaldehyde 4i and 2-(4-chlorobenzyl)-6-(2-oxo-2H-chromen-3-ypimidazo2,1-1)]1,3,4]thi adiazol-5-yl thiocyanate 5i emerged as the most potent against all the cell lines. To investigate the mechanism of action, we selected compounds 4i for cell cycle study, analysis of mitochondrial membrane potential and Annexin V-FITC flow cytometric analysis and DNA fragmentation assay. Results showed that 4i induced cytotoxicity by inducing apoptosis without arresting the cell cycle. (C) 2014 Elsevier Masson SAS. All rights reserved.

Dual enzyme responsive and targeted nanocapsules for intracellular delivery of anticancer agents

We report the fabrication of dual enzyme responsive hollow nanocapsules which can be targeted to deliver anticancer agents specifically inside cancer cells. The enzyme responsive elements, integrated in the nanocapsule walls, undergo degradation in the presence of either trypsin or hyaluronidase leading to the release of encapsulated drug molecules. These nanocapsules, which were crosslinked and functionalised with folic acid, showed minimal drug leakage when kept in pH 7.4 PBS buffer, but released the drug molecules at a rapid rate in the presence of either one of the triggering enzymes. Studies on cellular interactions of these nanocapsules revealed that doxorubicin loaded nanocapsules were taken up by cervical cancer cells via folic acid receptor medicated endocytosis. Interestingly the nanocapsules were able to disintegrate inside the cancer cells and release doxorubicin which then migrated into the nucleus to induce cell death. This study indicates that these nanocapsules fabricated from biopolymers can serve as an excellent platform for targeted intracellular drug delivery to cancer cells.

Secondary instability as a possible mechanism for clear-air turbulence: a case study

Many theories and mechanisms have been proposed to explain the phenomenon of clear-air turbulence (CAT), and some of them have been successful in predicting light, moderate and, in some cases, severe turbulence. It is only recently that skill in the forecasting of the severe form of CAT, which could lead to injuries to passengers and damage to aircraft, has improved. Recent observations and simulations suggest that some severe to extreme turbulence could be caused by horizontal vortex tubes resulting from secondary instabilities of regions of high shear in the atmosphere. We have conducted direct numerical simulations to understand the scale relationship between primary structures (larger-scale structures related to one of the causes mentioned above) and secondary structures (smaller-sized, shear structures of the size of aircraft). From shear layer simulations, we find that the ratio of sizes of primary and secondary vortices is of the right order to generate aircraft-scale vortex tubes from typical atmospheric shear layers. We have also conducted simulations with a mesoscale atmospheric model, to understand possible causes of turbulence experienced by a flight off the west coast of India. Our simulations show the occurrence of primary flow structures related to synoptic conditions around the time of the incident. The evidence presented for this mechanism also has implications for possible methods of detection and avoidance of severe CAT.

The interaction of N-trifluoroacetylgalactosamine and its derivatives with winged bean (Psophocarpus tetragonolobus) basic agglutinin reveals differential mechanism of their recognition: a fluorine-19 nuclear magnetic resonance study

Here, we show the binding results of a leguminosae lectin, winged bean basic agglutinin (WBA I) to N-trifluoroacetylgalactosamine (NTFAGalN), methyl-alpha-N-trifluoroacetylgalactosamine (Me alpha NTFAGalN) and methyl-beta-tifluoroacetylgalactosamine (Me beta NTFAGalN) using (19) F NMR spectroscopy. No chemical shift difference between the free and bound states for NTFAGalN and Me beta NTFAGalN, and 0.01-ppm chemical shift change for Me alpha NTFAGalN, demonstrate that the Me alpha NTFAGalN has a sufficiently long residence time on the protein binding site as compared to Me beta NTFAGalN and the free anomers of NTFAGalN. The sugar anomers were found in slow exchange with the binding site of agglutinin. Consequently, we obtained their binding parameters to the protein using line shape analyses. Aforementioned analyses of the activation parameters for the interactions of these saccharides indicate that the binding of alpha and beta anomers of NTFAGalN and Me alpha NTFAGalN is controlled enthalpically, while that of Me beta NTFAGalN is controlled entropically. This asserts the sterically constrained nature of the interaction of the Me beta NTFAGalN with WBA I. These studies thus highlight a significant role of the conformation of the monosaccharide ligands for their recognition by WBA I.

Characterization of a dual-active enzyme, DcpA, involved in cyclic diguanosine monophosphate turnover in Mycobacterium smegmatis

We have reported previously that the long-term survival of Mycobacterium smegmatis is facilitated by a dual-active enzyme MSDGC-1 (renamed DcpA), which controls the cellular turnover of cyclic diguanosine monophosphate (c-di-GMP). Most mycobacterial species possess at least a single copy of a DcpA orthologue that is highly conserved in terms of sequence similarity and domain architecture. Here, we show that DcpA exists in monomeric and dimeric forms. The dimerization of DcpA is due to non-covalent interactions between two protomers that are arranged in a parallel orientation. The dimer shows both synthesis and hydrolysis activities, whereas the monomer shows only hydrolysis activity. In addition, we have shown that DcpA is associated with the cytoplasmic membrane and exhibits heterogeneous cellular localization with a predominance at the cell poles. Finally, we have also shown that DcpA is involved in the change in cell length and colony morphology of M. smegmatis. Taken together, our study provides additional evidence about the role of the bifunctional protein involved in c-di-GMP signalling in M. smegmatis.

Direct regulation of topoisomerase activity by a nucleoid-associated protein

The topological homeostasis of bacterial chromosomes is maintained by the balance between compaction and the topological organization of genomes. Two classes of proteins play major roles in chromosome organization: the nucleoid-associated proteins (NAPs) and topoisomerases. The NAPs bind DNA to compact the chromosome, whereas topoisomerases catalytically remove or introduce supercoils into the genome. We demonstrate that HU, a major NAP of Mycobacterium tuberculosis specifically stimulates the DNA relaxation ability of mycobacterial topoisomerase I (TopoI) at lower concentrations but interferes at higher concentrations. A direct physical interaction between M. tuberculosis HU (MtHU) and TopoI is necessary for enhancing enzyme activity both in vitro and in vivo. The interaction is between the amino terminal domain of MtHU and the carboxyl terminal domain of TopoI. Binding of MtHU did not affect the two catalytic trans-esterification steps but enhanced the DNA strand passage, requisite for the completion of DNA relaxation, a new mechanism for the regulation of topoisomerase activity. An interaction-deficient mutant of MtHU was compromised in enhancing the strand passage activity. The species-specific physical and functional cooperation between MtHU and TopoI may be the key to achieve the DNA relaxation levels needed to maintain the optimal superhelical density of mycobacterial genomes.

Charge density distribution and electrostatic interactions of ethionamide: an inhibitor of the enoyl acyl carrier protein reductase (inhA) enzyme of Mycobacterium tuberculosis

An experimental charge density analysis of an anti-TB drug ethionamide was carried out from high resolution X-ray diffraction at 100 K to understand its charge density distribution and electrostatic properties. The experimental results were validated from periodic theoretical charge density calculations performed using CRYSTAL09 at the B3LYP/6-31G** level of theory. The electron density rho(bcp)(r) and the Laplacian of electron density del(2)(rho bcp)(r) of the molecule calculated from both the methods display the charge density distribution of the ethionamide molecule in the crystal field. The electrostatic potential map shows a large electropositive region around the pyridine ring and a large electronegative region at the vicinity of the thiol atom. The calculated experimental dipole moment is 10.6D, which is higher than the value calculated from theory (8.2D). The topological properties of C-H center dot center dot center dot S, N-H center dot center dot center dot N and N-H center dot center dot center dot S hydrogen bonds were calculated, revealing their strength. The charge density analysis of the ethionamide molecule determined from both the experiment and theory gives the topological and electrostatic properties of the molecule, which allows to precisely understand the nature of intra and intermolecular interactions.

Direct correlation between non-random distribution of cations and ion transport mechanism in soda-lime silicate glasses

We report a direct correlation between dissimilar ion pair formation and alkali ion transport in soda-lime silicate glasses established via broad band conductivity spectroscopy and local structural probe techniques. The combined Raman and Nuclear Magnetic Resonance (NMR) spectroscopy techniques on these glasses reveal the coexistence of different anionic species and the prevalence of Na+-Ca2+ dissimilar pairs as well as their distributions. The spectroscopic results further confirm the formation of dissimilar pairs atomistically, where it increases with increasing alkaline-earth oxide content These results, are the manifestation of local structural changes in the silicate network with composition which give rise to different environments into which the alkali ions hop. The Na+ ion mobility varies inversely with dissimilar pair formation, i.e. it decreases with increase of non-random formation of dissimilar pairs. Remarkably, we found that increased degree of non-randomness leads to temperature dependent variation in number density of sodium ions. Furthermore, the present study provides the strong link between the dynamics of the alkali ions and different sites associated with it in soda-lime silicate glasses. (C) 2014 Elsevier B.V. All rights reserved.

On the Two-Step Mechanism for Synthesis of Transition-Metal Nanoparticles

The two-step particle synthesis mechanism, also known as the Finke-Watzky (1997) mechanism, has emerged as a significant development in the field of nanoparticle synthesis. It explains a characteristic feature of the synthesis of transition metal nanoparticles, an induction period in precursor concentration followed by its rapid sigmoidal decrease. The classical LaMer theory (1950) of particle formation fails to capture this behavior. The two-step mechanism considers slow continuous nucleation and autocatalytic growth of particles directly from precursor as its two kinetic steps. In the present work, we test the two-step mechanism rigorously using population balance models. We find that it explains precursor consumption very well, but fails to explain particle synthesis. The effect of continued nucleation on particle synthesis is not suppressed sufficiently by the rapid autocatalytic growth of particles. The nucleation continues to increase breadth of size distributions to unexpectedly large values as compared to those observed experimentally. A number of variations of the original mechanism with additional reaction steps are investigated next. The simulations show that continued nucleation from the beginning of the synthesis leads to formation of highly polydisperse particles in all of the tested cases. A short nucleation window, realized with delayed onset of nucleation and its suppression soon after in one of the variations, appears as one way to explain all of the known experimental observations. The present investigations clearly establish the need to revisit the two-step particle synthesis mechanism.

Absolute/Convective Instability Transition in a Backward Facing Step Combustor: Fundamental Mechanism and Influence of Density Gradient

Hydrodynamic instabilities of the flow field in lean premixed gas turbine combustors can generate velocity perturbations that wrinkle and distort the flame sheet over length scales that are smaller than the flame length. The resultant heat release oscillations can then potentially result in combustion instability. Thus, it is essential to understand the hydrodynamic instability characteristics of the combustor flow field in order to understand its overall influence on combustion instability characteristics. To this end, this paper elucidates the role of fluctuating vorticity production from a linear hydrodynamic stability analysis as the key mechanism promoting absolute/convective instability transitions in shear layers occurring in the flow behind a backward facing step. These results are obtained within the framework of an inviscid, incompressible, local temporal and spatio-temporal stability analysis. Vorticity fluctuations in this limit result from interaction between two competing mechanisms-(1) production from interaction between velocity perturbations and the base flow vorticity gradient and (2) baroclinic torque in the presence of base flow density gradients. This interaction has a significant effect on hydrodynamic instability characteristics when the base flow density and velocity gradients are colocated. Regions in the space of parameters characterizing the base flow velocity profile, i.e., shear layer thickness and ratio of forward to reverse flow velocity, corresponding to convective and absolute instability are identified. The implications of the present results on understanding prior experimental studies of combustion instability in backward facing step combustors and hydrodynamic instability in other flows such as heated jets and bluff body stabilized flames is discussed.

An insight to the low temperature conduction mechanism of c-axis grown Al-doped ZnO, a widely used transparent conducting oxide

Al-doped ZnO thin films were synthesized from oxygen reactive co-sputtering of Al and Zn targets. Explicit doping of Al in the highly c-axis oriented crystalline films of ZnO was manifested in terms of structural optical and electrical properties. Electrical conduction with different extent of Al doping into the crystal lattice of ZnO (AZnO) were characterized by frequency dependent (40 Hz-50 MHz) resistance. From the frequency dependent resistance, the ac conduction of them, and correlations of localized charge particles in the crystalline films were studied. The dc conduction at the low frequency region was found to increase from 8.623 mu A to 1.14 mA for the samples AZnO1 (1 wt% Al) and AZnO2 (2 wt% Al), respectively. For the sample AZnO10 (10 wt% Al) low frequency dc conduction was not found due to the electrode polarization effect. The measure of the correlation length by inverse of threshold frequency (omega(0)) showed that on application of a dc electric field such length decreases and the decrease in correlation parameter(s) indicates that the correlation between potentials wells of charge particles decreases for the unidirectional nature of dc bias. The comparison between the correlation length and the extent of correlation in the doped ZnO could not be made due to the observation of several threshold frequencies at the extent of higher doping. Such threshold frequencies were explained by the population possibility of correlated charge carriers that responded at different frequencies. For AZnO2 (2% Al), the temperature dependent (from 4.5 to 288 K) resistance study showed that the variable range hopping mechanism was the most dominating conduction mechanism at higher temperature whereas at low temperature region it was influenced by the small polaronic hopping conduction mechanism. There was no significant influence found in these mechanisms on applications of 1, 2 and 3 V as biases.