Control of calcium oxalate crystal growth by face-specific adsorption of an osteopontin phosphopeptide

Mineral-associated proteins have been proposed to regulate many aspects of biomineralization, including the location, type, orientation, shape, and texture of crystals. To understand how proteins achieve this exquisite level of control, we are studying the interaction between the phosphoprotein osteopontin (OPN) and the biomineral calcium oxalate monohydrate (COM). In the present study, we have synthesized peptides corresponding to amino acids 220-235 of rat bone OPN (pSHEpSTEQSDAIDpSAEK), one of several highly phosphorylated, aspartic-, and glutamic acid-rich sequences found in the protein. To investigate the role of phosphorylation in interaction with crystals, peptides containing no (P0), one (P1), or all three (P3) phosphates were prepared. Using a novel combination of confocal microscopy and scanning electron microscopy, we show that these peptides adsorb preferentially to {100} faces of COM and inhibit growth of these faces in a phosphorylation-dependent manner. To characterize the mechanism of adsorption of OPN peptides to COM, we have performed the first atomic-scale molecular-dynamics simulation of a protein-crystal interaction. P3 adsorbs to the {100} face much more rapidly than P1, which in turn adsorbs more rapidly than P0. In all cases, aspartic and glutamic acid, not phosphoserine, are the amino acids in closest contact with the crystal surface. These studies have identified a COM face-specific adsorption motif in OPN and delineated separate roles for carboxylate and phosphate groups in inhibition of crystal growth by mineral-associated phosphoproteins. We propose that the formation of close-range, stable, and face-specific interactions is a key factor in the ability of phosphoproteins to regulate biomineralization processes.     

Spectroscopic analysis of the riboflavin—serum albumins interaction on silver nanoparticles

Metallic nanoparticles (NPs) supported on oxides thin films are commonly used as model catalysts for studies of heterogeneous catalysis. Several 4d and 5d metal NPs (for example, Pd, Pt and Au) grown on alumina, ceria and titania have shown strong metal support interaction (SMSI), for instance the encapsulation of the NPs by the oxide. The SMSI plays an important role in catalysis and is very dependent on the support oxide used. The present work investigates the growth mechanism and atomic structure of Rh NPs supported on epitaxial magnetite Fe₃O₄(111) ultrathin films prepared on Pd(111) using the Molecular Beam Epitaxy (MBE) technique. The iron oxide and the Rh NPs were characterized using X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction and photoelectron diffraction (PED). The combined XPS and PED results indicate that Rh NPs are metallic, cover approximately 20 % of the iron oxide surface and show height distribution ranging 3–5 ML (monolayers) with essentially a bulk fcc structure.     

An agent-based model for the bibliometric h-index

We model a virtual scientific community in which authors publish and cite articles. Citations are attributed according to a preferential attachment mechanism. From the numerical simulations, the h-index can be computed. This bottom-up approach reproduces well real bibliometric data. We consider two versions of our model. (1) The single-scientist is controlled by two parameters which can be tuned to reproduce the value of the h-index of many real scientists. Moreover, this model shows how the h-index grows with the number of citations, for a fixed number of articles. We also define an average h-index that can be used to compare the scientific productivity of institutions of different sizes. (2) The multi-scientist model considers a population of scientists and allows us to study the impact of removing citations from the low h-index researchers on the community. Simulations on real bibilometric data, as well as the predictions of the model, show that the h-index eco-system can be strongly affected by such a filtering.     

On the Fluorescence of Luminol in a Silver Nanoparticles Complex

The photophysical properties of luminol in a silver nanoparticles complex have been studied by steady-state and time resolved fluorescence spectroscopy. The effect of the serum albumin on the luminol fluorescence in the silver nanoparticles has been also investigated. It was found that the fluorescence quantum yield value of luminol in a silver nanoparticles complex is ??=?0.00407. The decrease of the average fluorescence lifetime value of the luminol in the silver nanoparticles complex was found to be low, <τ>?=?1.712 ns. The luminol does not bind to the serum albumins in the presence of silver nanoparticles. The formation of a new species of luminol on silver nanoparticles is discussed. The results have influence regarding the use of luminol as an assay for bio-analytical applications.     

EIS microfluidic chips for flow immunoassay and ultrasensitive cholera toxin detection

A flow-injection impedimetric immunosensor for the sensitive, direct and label-free detection of cholera toxin is reported. A limit of detection smaller than 10 pM was achieved, a value thousands of times lower than the lethal dose. The developed chips fulfil the requirement of low cost and quick reply of the assay and are expected to enable field screening, prompt diagnosis and medical intervention without the need of specialized personnel and expensive equipment, a perspective of special relevance for use in developing countries. Since the chip layout includes two sensing areas each one with a 2 × 2 sensor array, our biochips can allow statistical or (alternatively) multiplex analysis of biorecognition events between antibodies immobilized on each working electrode and different antigens flowing into the chamber.     

Antioxidant, xanthine oxidase and lipoxygenase inhibitory activities and phenolics of Bauhinia rufescens Lam. (Caesalpiniaceae)

An aqueous acetone extract of the stem with the leaves of Bauhinia rufescens and its fractions were analysed for their antioxidant and enzyme-inhibitory activities, as well as their phytochemical composition. For measurement of the antioxidant activities, the 2,2-diphenyl-1-picrylhydrazyl, 2,2'-azinobis(3-ethylbenzoline-6-sulphonate) and the ferric-reducing methods were used. The results indicated that the aqueous acetone, its ethyl acetate and n-butanol fractions possessed considerable antioxidant activity. Further, the xanthine oxidase and lipoxygenase inhibitory assays showed that the n-butanol fraction possessed compounds that can inhibit both these enzymes. In the phytochemical analysis, the ethyl acetate and the n-butanol fractions of the aqueous acetone extract were screened by HPLC-MS for their phenolic content. The results indicated the presence of hyperoside, isoquercitrin, rutin quercetin, quercitrin, p-coumaric and ferulic acids in the non-hydrolysed fractions. In the hydrolysed fractions, kaempferol, p-coumaric and ferulic acids were identified.     

ToF‐SIMS characterisation of methane‐ and hydrogen‐plasma‐modified graphite using principal component analysis

Time of flight secondary ion mass spectrometry (ToF‐SIMS) has been used to determine the extent of surface modification of highly ordered pyrolytic graphite (HOPG) samples that were exposed to radio‐frequency methane and hydrogen plasmas. The ToF‐SIMS measurements were examined with the multivariate method of principal component analysis (PCA), to maximise the amount of spectral information retained in the analysis. This revealed that the plasma (methane or hydrogen plasma) modified HOPG exhibited greater hydrogen content than the pristine HOPG. The hydrogen content trends observed from the ToF‐SIMS studies were also observed in elastic recoil detection analysis measurements. The application of the ToF‐SIMS PCA method also showed that small hydrocarbon fragments were sputtered from the hydrogen‐plasma‐treated sample, characteristic of the formation of a plasma‐damaged surface, whereas the methane‐plasma‐treated surface sputtered larger hydrocarbon fragments, which implies the growth of a polymer‐like coating. Scanning tunnelling microscopy measurements of the modified surfaces showed surface features that are attributable to either etching or film growth after exposure to the hydrogen or methane plasma. Copyright © 2009 John Wiley & Sons, Ltd.     

Toward sustainable energy: photocatalysis of Cr-doped TiO<Subscript>2</Subscript>: 2. effect of defect disorder

The present chain of five papers considers the concept of solar-to-chemical energy conversion using TiO₂-based semiconductors. The series reports the effect of chromium on the key performance-related properties of polycrystalline TiO₂ (rutile), including electronic structure, photocatalytic activity, intrinsic defect disorder, electrochemical coupling and surface versus bulk properties. In this work, we show that the effect of chromium on photocatalytic performance of TiO₂ depends on its elemental content and the related defect disorder that is determined by oxygen activity in the oxide lattice. At high oxygen activity, chromium leads to enhanced photocatalytic performance only for dilute solid solutions (up to 0.04–0.043 at.% Cr). Higher chromium content results in a decrease of photocatalytic activity below that for pure TiO₂, despite the observed substantial decrease of the band gap. The photocatalytic performance of Cr-doped TiO₂ annealed in reducing conditions is low within the entire studied range of compositions. The obtained results led to derivation of a theoretical model representing the mechanism of the light-induced reactivity of TiO₂ with water and the related charge transfer. The photocatalytic performance is considered in terms of a competitive effect of several key performance-related properties. The performance is predominantly influenced by the concentration of titanium vacancies acting as reactive surface sites related to anodic charge transfer.

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电感耦合等离子体原子发射光谱(ICP-AES)法测定铅锭中11种杂质元素

研究了用酸分解试样后不需分离基体直接用电感耦合等离子体原子发射光谱(ICP-AES)法测定铅锭中银、铜、铋、砷、锑、锡、锌、铁、镉、镍、铊11种杂质元素的方法。优化了样品前处理条件及仪器检测条件。方法的检出限为0.0012～0.0168μg/mL,回收率为89%～110%,RSD为2.3%～5.0%。方法简便快速,检出限低,精密度和准确度能满足铅锭中杂质元素的检测要求,具有较强的实用性和可操作性,可用于铅锭中杂质元素的测定。     

q-Torsion freeness of symmetric powers

Letq be an integer ≥1, we study theq-torsion freeness of the symmetric powers of a module of projective dimension ≥2, by using the approximation complex of the module.