Magnetism and transport studies in off-stoichiometric metallic perovskite compounds GdPd3Bx (x=0.25, 0.50 and 0.75)

We report the magnetic and transport properties of the off-stoichiometric metallic perovskite like compounds GdPd₃B_x (x=0.25, 0.50 and 0.75). Our results show that doping with boron in the lattice of parent binary-compound GdPd₃ leads to lattice expansion. Which in turn manifests in contrasting magnetic and transport behaviors of the doped compounds in comparison with the undoped GdPd₃. An attempt has been made to compare and correlate the results of magnetic and transport measurements of GdPd₃B_x with that of stoichiometric compositions GdPd₃B_xC_1−x. The comparative study of GdPd₃B_x and GdPd₃B_xC_1−x confirms that there is a strong correlations between the structural, magnetic and transport properties of these compounds.     

Thiamin biosynthesis in eukaryotes: characterization of the enzyme-bound product of thiazole synthase from Saccharomyces cerevisiae and its implications in thiazole biosynthesis

The biosynthesis of thiamin pyrophosphate in eukaryotes is different from the prokaryotic biosynthesis and is poorly understood to date. Only one thiazole biosynthetic gene has been identified (Thi4 in Saccharomyces cerevisiae). Here we report the identification and characterization of a Thi4-bound metabolite that consists of the ADP adduct of 5-(2-hydroxyethyl)-4-methylthiazole-2-carboxylic acid. The unexpected structure of this compound yields the first insights into the mechanism of thiamin thiazole biosynthesis in eukaryotes.     

A functional model for the cysteinate-ligated non-heme iron enzyme superoxide reductase (SOR)

Superoxide reductases (SORs) are cysteine-ligated, non-heme iron enzymes that reduce toxic superoxide radicals (O2-). The functional role of the trans cysteinate, as well as the mechanism by which SOR reduces O2-, is unknown. Herein is described a rare example of a functional metalloenzyme analogue, which catalytically reduces superoxide in a proton-dependent mechanism, via a trans thiolate-ligated iron-peroxo intermediate, the first example of its type. Acetic-acid-promoted H2O2 release, followed by Cp2Co reduction, regenerates the active Fe(II) catalyst. The thiolate ligand and its trans positioning relative to the substrate are shown to contribute significantly to the catalyst's function, by lowering the redox potential, changing the spin state, and dramatically lowering the nuFe-O stretching frequency well-below that of any other reported iron-peroxo, while leaving nuO-O high, so as to favor superoxide reduction and Fe-O, as opposed to O-O, bond cleavage. Thus we provide critical insight into the relationship between the SOR structure and its function, as well as important benchmark parameters for characterizing highly unstable thiolate-ligated iron-peroxo intermediates.     

A topological nullstellensatz for tensor-triangulated categories

Let $\mathrm{Spec}(\mathbb{T})$ be the spectrum of a tensor-triangulated category $(\mathbb{T},?,\mathbf{1})$. We show that there is a homeomorphism between the spectral space of radical thick tensor ideals in $(\mathbb{T},?,\mathbf{1})$ and the collection of open subsets of $\mathrm{Spec}(\mathbb{T})$ in inverse topology. In fact, we prove a more general result in terms of supports on $(\mathbb{T},?,\mathbf{1})$ and work by combining methods from commutative algebra, topology and tensor triangular geometry.     

Artificial Neural Network (ANN) design for Hg–Se interactions and their effect on reduction of Hg uptake by radish plant

The tendency of selenium to interact with heavy metals in presence of naturally occurring species has been exploited for the development of green bioremediation of toxic metals from soil using Artificial Neural Network (ANN) modeling. The cross validation of the data for the reduction in uptake of Hg(II) ions in the plant R. sativus grown in soil and sand culture in presence of selenium has been used for ANN modeling. ANN model based on the combination of back propagation and principal component analysis was able to predict the reduction in Hg uptake with a sigmoid axon transfer function. The data of fifty laboratory experimental sets were used for structuring single layer ANN model. Series of experiments resulted into the performance evaluation based on considering 20% data for testing and 20% data for cross validation at 1,500 Epoch with 0.70 momentums The Levenberg–Marquardt algorithm (LMA) was found as the best of BP algorithms with a minimum mean squared error at the eighth place of the decimal for training (MSE) and cross validation.     

Development and validation of a high‐performance liquid chromatography method for the simultaneous determination of aspirin and folic acid from nano‐particulate systems

Attention has shifted from the treatment of colorectal cancer (CRC) to chemoprevention using aspirin and folic acid as agents capable of preventing the onset of colon cancer. However, no sensitive analytical method exists to simultaneously quantify the two drugs when released from polymer‐based nanoparticles. Thus, a rapid, highly sensitive method of high‐performance liquid chromatography analysis to simultaneously detect low quantities of aspirin (hydrolyzed to salicylic acid, the active moiety) and folic acid released from biodegradable polylactide‐co‐glycolide (PLGA) copolymer nanoparticles was developed. Analysis was done on a reversed‐phase C₁₈ column using a photodiode array detector at wavelengths of 233 nm (salicylic acid) and 277 nm (folic acid). The mobile phase consisted of acetonitrile–0.1% trifluoroacetic acid mixture programmed for a 30 min gradient elution analysis. In the range of 0.1–100 μg/mL, the assay showed good linearity for salicylic acid (R² = 0.9996) and folic acid (R² = 0.9998). The method demonstrated good reproducibility, intra‐ and inter‐day precision and accuracy (99.67, 100.1%) and low values of detection (0.03, 0.01 μg/mL) and quantitation (0.1 and 0.05 μg/mL) for salicylic acid and folic acid, respectively. The suitability of the method was demonstrated by simultaneously determining salicylic acid and folic acid released from PLGA nanoparticles. Copyright © 2009 John Wiley & Sons, Ltd.     

5-Hydroxy-pyrrolone based building blocks as maleimide alternatives for protein bioconjugation and single-site multi-functionalization

Recent dramatic expansion in potential uses of protein conjugates has fueled the development of a wide range of protein modification methods; however, the desirable single-site multi-functionalization of proteins has remained a particularly intransigent challenge. Herein, we present the application of 5-hydroxy-1,5-dihydro-2H-pyrrol-2-ones (5HP2Os) as advantageous alternatives to widely used maleimides for the chemo- and site-selective labeling of cysteine residues within proteins. A variety of 5HP2O building blocks have been synthesized using a one-pot photooxidation reaction starting from simple and readily accessible furans and using visible light and oxygen. These novel reagents display excellent cysteine selectivity and also yield thiol conjugates with superior stability. 5HP2O building blocks offer a unique opportunity to introduce multiple new functionalities into a protein at a single site and in a single step, thus, significantly enhancing the resultant conjugate''s properties.

Recent expansion in potential uses of protein conjugates has fueled the development of a range of protein modification methods; however, the desirable single-site multi-functionalization of proteins has remained a particularly intransigent challenge.     

Stress relaxation in a perfect nanocrystal by coherent ejection of lattice layers

We show that a small crystal trapped within a potential well and in contact with its own fluid responds to large compressive stresses by a novel mechanism--the transfer of complete lattice layers across the solid-fluid interface. Further, when the solid is impacted by a momentum impulse set up in the fluid, a coherently ejected lattice layer carries away a definite quantity of energy and momentum, resulting in a sharp peak in the calculated phonon absorption spectrum. Apart from its relevance to studies of stability and failure of small sized solids, such coherent nanospallation may be used to make atomic wires or monolayer films.     

Return to return point memory

We describe a new class of systems exhibiting return point memory (RPM), different from those discussed before in the context of ferromagnets. We show numerically that one-dimensional random Ising antiferromagnets have exact RPM when evolving from a large field, but not when started at finite field, unlike the ferromagnetic case. This implies that the standard approach to understanding ferromagnetic RPM will fail for this case. We also demonstrate RPM with a set of variables that keeps track of spin flips at each site. Conventional RPM for the spins is a projection of this result, suggesting that spin flip variables might be a more fundamental representation of the dynamics. We also present a mapping that embeds the antiferromagnetic chain in a two-dimensional ferromagnet, and prove RPM for spin-exchange dynamics in the interior of the chain with this mapping.     

Self‐Assembly of Ambidentate Pyridyl‐Carboxylate Ligands with Octahedral Ruthenium Metal Centers: Self‐Selection for a Single‐Linkage Isomer and Anticancer‐Potency Studies

The synthesis of six new [2+2] metallarectangles through the coordination‐driven self‐assembly of octahedral Ru^II‐based acceptors with ambidentate pyridyl‐carboxylate donors is described. These molecular rectangles are fully characterized by ¹H NMR spectroscopy, high‐resolution electrospray mass spectrometry, and single‐crystal X‐ray diffraction. In each case, despite the possible formation of multiple isomers, based on the relative orientation of the pyridyl and carboxylate groups (head‐to‐head versus head‐to‐tail), evidence for the formation of a single preferred ensemble (head‐to‐tail) was found in the ¹H NMR spectra. Furthermore, the cytotoxicities of all of the rectangles were established against A549 (lung), AGS (gastric), HCT‐15 (colon), and SK hep 1 (liver) human cancer cell lines. The cytotoxicities of rectangles that contained the 5,8‐dihydroxy‐1,4‐naphthaquinonato bridging moiety between the Ru centers ( 9 – 11 ) were particularly high against AGS cancer cells, with IC₅₀ values that were comparable to that of reference drug cisplatin.