Inhibition of peroxynitrite- and peroxidase-mediated protein tyrosine nitration by imidazole-based thiourea and selenourea derivatives

In the present study, the synthesis and characterization of a series of N-methylimidazole-based thiourea and selenourea derivatives are described. The new compounds were also studied for their ability to inhibit peroxynitrite (PN)- and peroxidase-mediated nitration of protein tyrosine residues. It has been observed that the selenourea derivatives are more efficient than the thiourea-based compounds in the inhibition of protein nitration. The higher activity of selenoureas as compared to that of the corresponding thioureas can be ascribed to the zwitterionic nature of the selenourea moiety. Single crystal X-ray diffraction studies on some of the thiourea and selenourea derivatives reveal that the C S bonds in thioureas possess more of double bond character than the C=Se bonds in the corresponding selenoureas. Therefore, the selenium compounds can react with PN or hydrogen peroxide much faster than their sulfur analogues. The reactions of thiourea and selenourea derivatives with PN or hydrogen peroxide produce the corresponding sulfinic or seleninic acid derivatives, which upon elimination of sulfurous/selenous acids produce the corresponding N-methylimdazole derivatives.

Characterization of Clean and Fouled Rail Track Ballast Subsurface Using Seismic Surface Survey Method: Model and Field Studies

The efficiency of track foundation material gradually decreases due to insufficient lateral confinement, ballast fouling, and loss of shear strength of the subsurface soil under cyclic loading. This paper presents characterization of rail track subsurface to identify ballast fouling and subsurface layers shear wave velocity using seismic survey. Seismic surface wave method of multi-channel analysis of surface wave (MASW) has been carried out in the model track and field track for finding out shear wave velocity of the clean and fouled ballast and track subsurface. The shear wave velocity (SWV) of fouled ballast increases with increase in fouling percentage, and reaches a maximum value and then decreases. This character is similar to typical compaction curve of soil, which is used to define optimum and critical fouling percentage (OFP and CFP). Critical fouling percentage of 15 % is noticed for Coal fouled ballast and 25 % is noticed for clayey sand fouled ballast. Coal fouled ballast reaches the OFP and CFP before clayey sand fouled ballast. Fouling of ballast reduces voids in ballast and there by decreases the drainage. Combined plot of permeability and SWV with percentage of fouling shows that after critical fouling point drainage condition of fouled ballast goes below acceptable limit. Shear wave velocities are measured in the selected location in the Wollongong field track by carrying out similar seismic survey. In-situ samples were collected and degrees of fouling were measured. Field SWV values are more than that of the model track SWV values for the same degree of fouling, which might be due to sleeper's confinement. This article also highlights the ballast gradation widely followed in different countries and presents the comparison of Indian ballast gradation with international gradation standards. Indian ballast contains a coarser particle size when compared to other countries. The upper limit of Indian gradation curve matches with lower limit of ballast gradation curves of America and Australia. The ballast gradation followed by Indian railways is poorly graded and more favorable for the drainage conditions. Indian ballast engineering needs extensive research to improve presents track conditions.

EPR, thermo and photoluminescence properties of ZnO nanopowders

Nanocrystalline ZnO powders have been synthesized by a low temperature solution combustion method. The photoluminescence (PL) spectrum of as-formed and heat treated ZnO shows strong violet (402, 421, 437, 485 nm) and weak green (520 nm) emission peaks respectively. The PL intensities of defect related emission bands decrease with calcinations temperature indicating the decrease of Zn(i) and V(o)(+) caused by the chemisorptions of oxygen. The results are correlated with the electron paramagnetic resonance (EPR) studies. Thermoluminescence (TL) glow curves of gamma irradiated ZnO nanoparticles exhibit a single broad glow peak at similar to 343 degrees C. This can be attributed to the recombination of charge carriers released from the surface states associated with oxygen defects, mainly interstitial oxygen ion centers. The trapping parameters of ZnO irradiated with various gamma-doses are calculated using peak shape method. It is observed that the glow peak intensity increases with increase of gamma dose without changing glow curve shape. These two characteristic properties such as TL intensity increases with gamma dose and simple glow curve structure is an indication that the synthesized ZnO nanoparticles might be used as good TL dosimeter for high temperature application. (C) 2011 Elsevier B.V. All rights reserved.

Field-induced dielectric properties of laser ablated antiferroelectric (Pb0.99Nb0.02)(Zr0.57Sn0.38Ti0.05)0.98O3 thin films

Niobium-modified lead zirconate stannate titanate antiferroelectric thin films with the chemical composition of (Pb0.99Nb0.02)(Zr0.57Sn0.38Ti0.05)0.98O3 were deposited by pulsed excimer laser ablation technique on Pt-coated Si substrates. Field-induced phase transition from antiferroelectric to ferroelectric properties was studied at different fields as a function of temperature. The field forced ferroelectric phase transition was elucidated by the presence of double-polarization hysteresis and double-butterfly characteristics from polarization versus applied electric field and capacitance and voltage measurements, respectively. The measured forward and reverse switching fields were 25 kV/cm and 77 kV/cm, respectively. The measured dielectric constant and dissipation factor were 540 and 0.001 at 100 kHz, respectively, at room temperature.

Chemistry and biology of DNA-binding small molecules

Regulation of the transcription machinery is one of the many ways to achieve control of gene expression. This has been done either at the transcription initiation stage or at the elongation stage. Different methodologies are known to inhibit transcription initiation via targeting of double-stranded (ds) DNA by: (i) synthetic oligonucleotides, (ii) ds-DNA-specific, sequenceselective minor-groove binders (distamycin A), intercalators (daunomycin) combilexins and (iii) small molecule (peptide or intercalator)-oligonucleotide conjugates. In some cases, instead of ds-DNA, higher order G-quadruplex structures are formed at the start site of transcription. In this regard G-quadruplex DNA-specific small molecules play a significant role towards inhibition of the transcription machinery. Different types of designer DNA-binding agents act as powerful sequence-specific gene modulators, by exerting their effect from transcription regulation to gene modification. But most of these chemotherapeutic agents have serious side effects. Accordingly, there is always a challenge to design such DNA-binding molecules that should not only achieve maximum specific DNA-binding affinity, and cellular and nuclear transport activity, but also would not interfere with the functions of normal cells.

Volume change behaviour of expansive soils

Understanding the volume change behaviour of expansive soils/clays becomes a dire necessity to obtain engineering solutions to structures founded on these soils. Behaviour of expansive soils does not conform to the natural behaviour of fine grained soils. Most of the cases, the permissible heave/settlement forms the design criteria. The paper discusses the basic properties, the role of effective stress concept, basic mechanism in controlling the volume change behaviour, the role of double layer repulsion and its validity and certain basic considerations of footing resting on an expansive soil with respect to heave or settlement and the soil reinforcement as a possible engineering solution.

Unzipping and binding of small interfering RNA with single walled carbon nanotube: A platform for small interfering RNA delivery

In an effort to design efficient platform for siRNA delivery, we combine all atom classical and quantum simulations to study the binding of small interfering RNA (siRNA) by pristine single wall carbon nanotube (SWCNT). Our results show that siRNA strongly binds to SWCNT surface via unzipping its base-pairs and the propensity of unzipping increases with the increase in the diameter of the SWCNTs. The unzipping and subsequent wrapping events are initiated and driven by van der Waals interactions between the aromatic rings of siRNA nucleobases and the SWCNT surface. However, molecular dynamics (MD) simulations of double strand DNA (dsDNA) of the same sequence show that the dsDNA undergoes much less unzipping and wrapping on the SWCNT in the simulation time scale of 70 ns. This interesting difference is due to smaller interaction energy of thymidine of dsDNA with the SWCNT compared to that of uridine of siRNA, as calculated by dispersion corrected density functional theory (DFT) methods. After the optimal binding of siRNA to SWCNT, the complex is very stable which serves as one of the major mechanisms of siRNA delivery for biomedical applications. Since siRNA has to undergo unwinding process with the effect of RNA-induced silencing complex, our proposed delivery mechanism by SWCNT possesses potential advantages in achieving RNA interference. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3682780]

EXIT Chart Based Design of Irregular LDPC Codes for Large-MIMO Systems

In this letter, we characterize the extrinsic information transfer (EXIT) behavior of a factor graph based message passing algorithm for detection in large multiple-input multiple-output (MIMO) systems with tens to hundreds of antennas. The EXIT curves of a joint detection-decoding receiver are obtained for low density parity check (LDPC) codes of given degree distributions. From the obtained EXIT curves, an optimization of the LDPC code degree profiles is carried out to design irregular LDPC codes matched to the large-MIMO channel and joint message passing receiver. With low complexity joint detection-decoding, these codes are shown to perform better than off-the-shelf irregular codes in the literature by about 1 to 1.5 dB at a coded BER of 10(-5) in 16 x 16, 64 x 64 and 256 x 256 MIMO systems.

Optimisation of an asymmetric polymerase chain reaction assay for the amplification of single-stranded DNA from Wuchereria bancrofti for electrochemical detection

Single-stranded DNA (ssDNA) is a prerequisite for electrochemical sensor-based detection of parasite DNA and other diagnostic applications. To achieve this detection, an asymmetric polymerase chain reaction method was optimised. This method facilitates amplification of ssDNA from the human lymphatic filarial parasite Wuchereria bancrofti. This procedure produced ssDNA fragments of 188 bp in a single step when primer pairs (forward and reverse) were used at a 100:1 molar ratio in the presence of double-stranded template DNA. The ssDNA thus produced was suitable for immobilisation as probe onto the surface of an Indium tin oxide electrode and hybridisation in a system for sequence-specific electrochemical detection of W. bancrofti. The hybridisation of the ssDNA probe and target ssDNA led to considerable decreases in both the anodic and the cathodic currents of the system's redox couple compared with the unhybridised DNA and could be detected via cyclic voltammetry. This method is reproducible and avoids many of the difficulties encountered by conventional methods of filarial parasite DNA detection; thus, it has potential in xenomonitoring.

Infinitely divisible metrics and curvature inequalities for operators in the Cowen-Douglas class

The curvature (T)(w) of a contraction T in the Cowen-Douglas class B-1() is bounded above by the curvature (S*)(w) of the backward shift operator. However, in general, an operator satisfying the curvature inequality need not be contractive. In this paper, we characterize a slightly smaller class of contractions using a stronger form of the curvature inequality. Along the way, we find conditions on the metric of the holomorphic Hermitian vector bundle E-T corresponding to the operator T in the Cowen-Douglas class B-1() which ensures negative definiteness of the curvature function. We obtain a generalization for commuting tuples of operators in the class B-1() for a bounded domain in C-m.

Self propagating combustion synthesis and luminescent properties of nanocrystalline CeO2: Tb3+ (1-10 mol%) phosphors

Undoped and Tb3+ (1-10 mol%) doped CeO2 nanophosphors were synthesized by low temperature solution combustion method. The combustion derived products were well studied by Powder X-ray diffraction (PXRD), Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and Ultraviolet visible (UV-Vis) characterizations. The thermoluminescence (TL) glow curves of CeO2: Tb3+ (1-10 mol%) nanophosphors exposed to c source (60Co) for various doses were discussed for the first time. Two TL glow peaks recorded at 182 and 262 degrees C respectively. The TL intensity at 262 degrees C peak increases linearly in the dose range 0.5-7 kGy. Further, this peak was well defined, intense and glow peak structure does not change with c-dose as a result, it was quite useful in TL dosimetry of ionizing radiations. The kinetic parameters associated with the glow peak were estimated using Chen's half width method. The photoluminescence emission (PLE) spectra consists of characteristic peaks at 544 and 655 nm which were attributed to D-5(4) -> F-7(5) and D-5(4) -> F-7(2) transitions of Tb3+ ions. The optimal concentration of Tb3+ ions was found to be 7 mol%. The color co-ordinates of CeO2: Tb3+ (1-10 mol%) located in green region. Hence, this phosphor was quite useful for display applications. (C) 2013 Elsevier B. V. All rights reserved.

Glassy dielectric response in Tb2NiMnO6 double perovskite with similarities to a Griffiths phase

Results of frequency-dependent and temperature-dependent dielectric measurements performed on the double-perovskite Tb2NiMnO6 are presented. The real (epsilon(1)(f,T)) and imaginary (epsilon(2)(f,T)) parts of dielectric permittivity show three plateaus suggesting dielectric relaxation originating from the bulk, grain boundaries and the sample-electrode interfaces, respectively. The epsilon(1)(f,T) and epsilon(2)(f,T) are successfully simulated by a RC circuit model. The complex plane of impedance, Z'-Z `', is simulated using a series network with a resistor R and a constant phase element. Through the analysis of epsilon(f,T) using the modified Debye model, two different relaxation time regimes separated by a characteristic temperature, T*, are identified. The temperature variation of R and C corresponding to the bulk and the parameter alpha from modified Debye fit lend support to this hypothesis. Interestingly, the T* compares with the Griffiths temperature for this compound observed in magnetic measurements. Though these results cannot be interpreted as magnetoelectric coupling, the relationship between lattice and magnetism is markedly clear. We assume that the observed features have their origin in the polar nanoregions which originate from the inherent cationic defect structure of double perovskites. Copyright (C) EPLA, 2013

Molecular Basis for the Differential Quinolone Susceptibility of Mycobacterial DNA Gyrase

DNA gyrase is a type II topoisomerase that catalyzes the introduction of negative supercoils in the genomes of eubacteria. Fluoroquinolones (FQs), successful as drugs clinically, target the enzyme to trap the gyrase-DNA complex, leading to the accumulation of double-strand breaks in the genome. Mycobacteria are less susceptible to commonly used FQs. However, an 8-methoxy-substituted FQ, moxifloxacin (MFX), is a potent antimycobacterial, and a higher susceptibility of mycobacterial gyrase to MFX has been demonstrated. Although several models explain the mechanism of FQ action and gyrase-DNA-FQ interaction, the basis for the differential susceptibility of mycobacterial gyrase to various FQs is not understood. We have addressed the basis of the differential susceptibility of the gyrase and revisited the mode of action of FQs. We demonstrate that FQs bind both Escherichia coli and Mycobacterium tuberculosis gyrases in the absence of DNA and that the addition of DNA enhances the drug binding. The FQs bind primarily to the GyrA subunit of mycobacterial gyrase, while in E. coli holoenzyme is the target. The binding of MFX to GyrA of M. tuberculosis correlates with its effectiveness as a better inhibitor of the enzyme and its efficacy in cell killing.

GdAlO3:Eu3+:Bi3+ nanophosphor: Synthesis and enhancement of red emission for WLEDs

GdAlO3, GdAlO3:Eu3+ and GdAlO3:Eu3+:Bi3+ nanophosphors were synthesised by solution combustion technique. Pure orthorhombic phase was obtained from powder X-ray diffraction (PXRD) studies. Scanning electron microscopy (SEM) micrographs showed the porous, agglomerated and irregular shaped particles. The particle size obtained by transmission electron microscopy (TEM) measurement was in good agreement with the values obtained by Debye Scherrer's and W-H plots. The selected area electron diffraction (SAED) pattern show single crystalline nature of the sample. Photoluminescence (PL) measurements were carried out for GdAlO3:Eu3+ and GdAlO3:Eu3+:Bi3+ phosphors excited at a wavelength of 274 nm. The characteristic emission peaks of Eu3+ ions were recorded at 590, 614, 655 and 695 nm corresponding to D-5(0) -> F-7(J) (J = 1, 2, 3, 4) transitions respectively. However, with addition of Bi3+ ions in GdAlO3:Eu3+, PL intensity drastically enhanced. Orange red color was tuned to deep red color with the addition of Bi3+ ions in GdAlO3:Eu3+ phosphor. Therefore, the phosphor was highly useful as red component in WLEDs. A single well resoled glow peak at 225 degrees C was recorded in GdAlO3 and GdAlO3:Eu3+. Further, with addition of Bi3+ ions, an additional peak at 300 degrees C was recorded. TL glow curves of different UV-exposed GdAlO3:Eu3+:Bi3+ show two TL peaks at 207 and 300 degrees C respectively. The 207 degrees C peak show simple glow peak structure and its intensity increases linearly up to 25 mm and after that it decrease. (C) 2014 Elsevier B.V. All rights reserved.

Photoluminescence, photocatalysis and Judd-Ofelt analysis of Eu3+-activated layered BiOCl phosphors

Eu3+-activated layered BiOCl phosphors were synthesized by the conventional solid-state method at relatively low temperature and shorter duration (400 degrees C for 1 h). All the samples were crystallized in the tetragonal structure with the space group P4/nmm (no. 129). Field emission scanning electron microscopy (FE-SEM) studies confirmed the plate-like morphology. Photoluminescence spectra exhibit characteristic luminescent D-5(0) -> F-7(J) (J = 0-4) intra-4f shell Eu3+ ion transitions. The electric dipole transition located at 620 nm (D-5(0) -> F-7(2)) was stronger than the magnetic dipole transition located at 594 nm (D-5(0) -> F-7(1)). The evaluated Commission International de l'Eclairage (CIE) color coordinates of Eu3+-activated BiOCl phosphors were close to the commercial Y2O3:Eu3+ and Y2O2S:Eu3+ red phosphors. Intensity parameters (Omega(2), Omega(4)) and various radiative properties such as transition probability (A(tot)), radiative lifetime (tau(rad)), stimulated emission cross-section (sigma(e)), gain bandwidth (sigma(e) x Delta lambda(eff)) and optical gain (sigma(e) x tau(rad)) were calculated using the Judd-Ofelt theory. The experimental decay curves of the D-5(0) level in Eu3+-activated BiOCl have a single exponential profile. In comparison with other Eu3+ doped materials, Eu3+-activated BiOCl phosphors have a long lifetime (tau(exp)), low non-radiative relaxation rate (W-NR), high quantum efficiency (eta) and better optical gain (sigma(e) x tau(rad)). The determined radiative properties revealed the usefulness of Eu3+-activated BiOCl in developing red lasers as well as optical display devices. Further, these samples showed efficient photocatalytic activity for the degradation of rhodamine B (RhB) dye under visible light irradiation. These photocatalysts are useful for the removal of toxic and non-biodegradable organic pollutants in water.