Fe(AsO4): a new iron(III) arsenate synthesized from thermal treatment of (NH4)[Fe(AsO4)F

The new orthorhombic Fe(AsO4) phase has been synthesized by thermal treatment at 525 degrees C of a new (NH4)[Fe(AsO4)F] compound, with a [Fe(AsO4)F]- skeleton showing channels where the ammonium cations are located. The crystal structure of Fe(AsO4) has been solved from single-crystal data. The structure is formed by layers of edge-sharing dimeric octahedra, and interconnected by chains of alternating FeO6 octahedra and AsO4 tetrahedra.     

Sublethal effects of ultraviolet A radiation on Enterobacter cloacae

We report the sublethal effects of ultraviolet A (UVA) on Enterobacter cloacae in comparison with those produced in Escherichia coli. UVA-induced sublethal effects were investigated in either bacterial membrane and at tRNA level. Limited dependence on oxygen concentration for photoinduced inhibition of biochemical membrane functions and low levels of oxidative damage during the irradiation period were found in En. cloacae. On the other hand, ultraviolet spectroscopy and reversed-phase HPLC analysis of hydrolysed tRNA showed that radio induced damage to tRNA is similar in En. cloacae and E. coli. Nevertheless, growth delay induced by UVA in En. cloacae was shorter than that found in E. coli submitted to the same experimental conditions. A limited post-irradiation ppGpp accumulation and the absence of any influence of the membrane damage on the growth delay extent seem to be responsible for the shortness of this effect in En. cloacae. Most of the differences between En. cloacae and E. coli could be attributed to an increased ability of En. cloacae to overcome oxidative stress during UVA exposure.     

On solving the multi-period single-sourcing problem under uncertainty

We present a framework for solving the strategic problem of assigning retailers to facilities in a multi-period single-sourcing product environment under uncertainty in the demand from the retailers and the cost of production, inventory holding, backlogging and distribution of the product. By considering a splitting variable mathematical representation of the Deterministic Equivalent Model, we specialize the so-called Branch-and-Fix Coordination algorithmic framework. It exploits the structure of the model and, specifically, the non-anticipativity constraints for the assignment variables. The algorithm uses the Twin Node Family (TNF) concept. Our procedure is specifically designed for coordinating the selection of the branching TNF and the branching S3 set, such that the non-anticipativity constraints are satisfied. Some computational experience is reported. D. Romero Morales: The work of this author was supported in part by the National Science Foundation under Grant No. DMI-0355533 The work of the first three authors has been partially supported by the grants TIC2003-05982-C05-05 and SEC2002-00112 from MCyT, Spain     

AFM characterization of bovine enamel and dentine after acid-etching

Teeth are constituted mainly of hydroxyapatite molecules (Ca₁₀(PO₄)₆(OH)₂), grouped in different microstructural arrangements, depending on the dental layer considered (enamel or dentine). In the present work, these dental microstructural arrangements were characterized by atomic force microscopy. Enamel and dentine samples were cut from freshly extracted bovine incisor teeth. After metallographic polishing, the dental surfaces were etched with lactic acid (113.8 mmol/L, pH 3.3). Three etching times were tested: 1, 3 and 5 min. Atomic force micrographs showed that 1 min of etching time was effective to remove the smear layer, polishing debris and scratches, and display the characteristics of interest for both enamel and dentine. Although the bovine dental enamel rod cross-section presented keyhole-like shape, its measured dimensions (8.8 μm of major axis and 3.7 μm of minor axis) exhibited an insignificant discrepancy from human prisms diameters. Bovine dentinal tubules displayed larger mean diameters (4.0 μm) and a lower density (～17,100 tubules/mm²) than human dentine, suggesting that the use of bovine dentine as a substitute for human dentine in resin adhesion investigations should be reconsidered. Apatite nanoparticles presented a mean radius (22–23 nm) considerably smaller than that of human teeth.     

Mirror‐Image Organometallic Osmium Arene Iminopyridine Halido Complexes Exhibit Similar Potent Anticancer Activity

Four chiral Os^II arene anticancer complexes have been isolated by fractional crystallization. The two iodido complexes, (S_Os,S_C)‐[Os(η⁶‐p‐cym)(ImpyMe)I]PF₆ (complex 2 , (S)‐ImpyMe: N‐(2‐pyridylmethylene)‐(S)‐1‐phenylethylamine) and (R_Os,R_C)‐[Os(η⁶‐p‐cym)(ImpyMe)I]PF₆ (complex 4 , (R)‐ImpyMe: N‐(2‐pyridylmethylene)‐(R)‐1‐phenylethylamine), showed higher anticancer activity (lower IC₅₀ values) towards A2780 human ovarian cancer cells than cisplatin and were more active than the two chlorido derivatives, (S_Os,S_C)‐[Os(η⁶‐p‐cym)(ImpyMe)Cl]PF₆, 1 , and (R_Os,R_C)‐[Os(η⁶‐p‐cym)(ImpyMe)Cl]PF₆, 3 . The two iodido complexes were evaluated in the National Cancer Institute 60‐cell‐line screen, by using the COMPARE algorithm. This showed that the two potent iodido complexes, 2 (NSC: D‐758116/1) and 4 (NSC: D‐758118/1), share surprisingly similar cancer cell selectivity patterns with the anti‐microtubule drug, vinblastine sulfate. However, no direct effect on tubulin polymerization was found for 2 and 4 , an observation that appears to indicate a novel mechanism of action. In addition, complexes 2 and 4 demonstrated potential as transfer‐hydrogenation catalysts for imine reduction.     

Preparative treatment with NaOH to selectively concentrate iron oxides of a Chilean volcanic soil?material to produce effective heterogeneous Fenton catalyst

A Chilean volcanic Ultisol material was first size-fractionated so as to obtain the fraction with mean particle sizes ??<?53 ??m. This sample was then sequentially treated three or five times with 5 mol L^???1 NaOH, in an attempt to evaluate the effectiveness of the selective chemical dissolution to concentrate iron oxides, as a preparation procedure before using the materials as heterogeneous Fenton catalysts. The effects of those treatments on the iron oxides mineralogy were monitored with Mössbauer spectroscopy. The NaOH-treated samples were tested as catalysts towards the H₂O₂ decomposition. Three or five sequential NaOH treatments were found to be comparably effective, by concentrating nearly the same proportion of iron oxides in the remaining solid phase (25.1 ± 0.4 and 23.3 ± 0.2 mass%, respectively). 298 K-Mössbauer patterns were similar for both samples, with a central (super)paramagnetic Fe^3?+? doublet and a broad sextet, assignable to several closely coexisting magnetically ordered forms of iron oxides. Despite of this nearly similar effect of the two treatments, the Ultisol material treated three times with NaOH presents higher heterogeneous catalytic efficiency and is more suitable to decompose H₂O₂ than that with five treatments.     

A compact rational Krylov method for large‐scale rational eigenvalue problems

In this work, we propose a new method, termed as R‐CORK, for the numerical solution of large‐scale rational eigenvalue problems, which is based on a linearization and on a compact decomposition of the rational Krylov subspaces corresponding to this linearization. R‐CORK is an extension of the compact rational Krylov method (CORK) introduced very recently in the literature to solve a family of nonlinear eigenvalue problems that can be expressed and linearized in certain particular ways and which include arbitrary polynomial eigenvalue problems, but not arbitrary rational eigenvalue problems. The R‐CORK method exploits the structure of the linearized problem by representing the Krylov vectors in a compact form in order to reduce the cost of storage, resulting in a method with two levels of orthogonalization. The first level of orthogonalization works with vectors of the same size as the original problem, and the second level works with vectors of size much smaller than the original problem. Since vectors of the size of the linearization are never stored or orthogonalized, R‐CORK is more efficient from the point of view of memory and orthogonalization than the classical rational Krylov method applied directly to the linearization. Taking into account that the R‐CORK method is based on a classical rational Krylov method, to implement implicit restarting is also possible, and we show how to do it in a memory‐efficient way. Finally, some numerical examples are included in order to show that the R‐CORK method performs satisfactorily in practice.     

Diazido Mixed‐Amine Platinum(IV) Anticancer Complexes Activatable by Visible‐Light Form Novel DNA Adducts

Platinum diam(m)ine complexes, such as cisplatin, are successful anticancer drugs, but suffer from problems of resistance and side‐effects. Photoactivatable Pt^IV prodrugs offer the potential of targeted drug release and new mechanisms of action. We report the synthesis, X‐ray crystallographic and spectroscopic properties of photoactivatable diazido complexes trans,trans,trans‐[Pt(N₃)₂(OH)₂(MA)(Py)] ( 1 ; MA=methylamine, Py=pyridine) and trans,trans,trans‐[Pt(N₃)₂(OH)₂(MA)(Tz)] ( 2 ; Tz=thiazole), and interpret their photophysical properties by TD‐DFT modelling. The orientation of the azido groups is highly dependent on H bonding and crystal packing, as shown by polymorphs 1 p and 1 q . Complexes 1 and 2 are stable in the dark towards hydrolysis and glutathione reduction, but undergo rapid photoreduction with UVA or blue light with minimal amine photodissociation. They are over an order of magnitude more potent towards HaCaT keratinocytes, A2780 ovarian, and OE19 oesophageal carcinoma cells than cisplatin and show particular potency towards cisplatin‐resistant human ovarian cancer cells (A2780cis). Analysis of binding to calf‐thymus (CT), plasmids, oligonucleotide DNA and individual nucleotides reveals that photoactivated 1 and 2 form both mono‐ and bifunctional DNA lesions, with preference for G and C, similar to transplatin, but with significantly larger unwinding angles and a higher percentage of interstrand cross‐links, with evidence for DNA strand cross‐linking further supported by a comet assay. DNA lesions of 1 and 2 on a 50 bp duplex were not recognised by HMGB1 protein, in contrast to cisplatin‐type lesions. The photo‐induced platination reactions of DNA by 1 and 2 show similarities with the products of the dark reactions of the Pt^II compounds trans‐[PtCl₂(MA)(Py)] ( 5 ) and trans‐[PtCl₂(MA)(Tz)] ( 6 ). Following photoactivation, complex 2 reacted most rapidly with CT DNA, followed by 1 , whereas the dark reactions of 5 and 6 with DNA were comparatively slow. Complexes 1 and 2 can therefore give rapid potent photocytotoxicity and novel DNA lesions in cancer cells, with no activity in the absence of irradiation.