A comprehensive spectroscopic study of synthetic Fe2+, Fe3+, Mg2+ and Al3+ copiapite by Raman,XRD, LIBS,MIR and vis–NIR

The identification of iron sulfates on Mars by the Mars Exploration Rovers (MERs) and the Mars Reconnaissance Orbiter emphasized the importance of studying iron sulfates in laboratory simulation experiments. The copiapite group of minerals was suggested as one of the potential iron sulfates occurring on the surface and subsurface on Mars, so it is meaningful to study their spectroscopic features, especially the spectral changes caused by cation substitutions. Four copiapite samples with cation substitutions (Fe³⁺, Al³⁺, Fe²⁺, Mg²⁺) were synthesized in our laboratory. Their identities were confirmed by powder X‐ray diffraction (XRD). Spectroscopic characterizations by Raman, mid‐IR, vis‐NIR and laser‐induced‐breakdown spectroscopy (LIBS) were conducted on those synthetic copiapite samples, as these technologies are being (and will be) used in current (and future) missions to Mars. We have found a systematic ν₁peak shift in the Raman spectra of the copiapite samples with cation substitutions, a consistent atomic ratio detection by LIBS, a set of systematic XRD line shifts representing structural change caused by the cation substitutions and a weakening of selection rules in mid‐IR spectra caused by the low site symmetry of (SO₄)²⁻ in the copiapite structures. The near‐infrared (NIR) spectra of the trivalent copiapite species show two strong diagnostic water features near 1.4 and 1.9 µm, with two additional bands near 2.0 µm. In the vis‐NIR spectra, the position of an electronic band shifts from 0.85 µm for ferricopiapite to 0.866 µm for copiapite, and this shift suggests the appearance of a Fe²⁺ electronic transition band near 0.9 µm. Copyright © 2010 John Wiley & Sons, Ltd.     

Cosmological models in the scalar-tetradic theory B

We present two methods for solving the cosmological equations of the scalar-tetradic theory B [19] when a Friedmann-Robertson-Walker (FRW) geometry is assumed. Among the many solutions found there are several physically meaningful ones including inflationary universe solutions.     

A sparse counterpart of Reichel and Gragg’s package QRUP

We describe how to maintain the triangular factor of a sparse QR factorization when columns are added and deleted and Q cannot be stored for sparsity reasons. The updating procedures could be thought of as a sparse counterpart of Reichel and Gragg’s package QRUP. They allow us to solve a sequence of sparse linear least squares subproblems in which each matrix B_k is an independent subset of the columns of a fixed matrix A, and B_k+1 is obtained by adding or deleting one column. Like Coleman and Hulbert [T. Coleman, L. Hulbert, A direct active set algorithm for large sparse quadratic programs with simple bounds, Math. Program. 45 (1989) 373-406], we adapt the sparse direct methodology of Björck and Oreborn of the late 1980s, but without forming A^TA, which may be only positive semidefinite. Our Matlab 5 implementation works with a suitable row and column numbering within a static triangular sparsity pattern that is computed in advance by symbolic factorization of A^TA and preserved with placeholders.     

Gleason parts in uniform Fréchet algebras

We prove that Gleason parts in uniform distinguished Fréchet algebras are open and closed in the weak topology.     

Effects of brain polarization on reaction times and pinch force in chronic stroke

Background  

Previous studies showed that anodal transcranial DC stimulation (tDCS) applied to the primary motor cortex of the affected hemisphere (M1_{affected hemisphere}) after subcortical stroke transiently improves performance of complex tasks that mimic activities of daily living (ADL). It is not known if relatively simpler motor tasks are similarly affected. Here we tested the effects of tDCS on pinch force (PF) and simple reaction time (RT) tasks in patients with chronic stroke in a double-blind cross-over Sham-controlled experimental design.     

Binary-black-hole encounters, gravitational bursts, and maximum final spin

The spin of the final black hole in the coalescence of nonspinning black holes is determined by the "residual" orbital angular momentum of the binary. This residual momentum consists of the orbital angular momentum that the binary is not able to shed in the process of merging. We study the angular momentum radiated, the spin of the final black hole, and the gravitational bursts in a sequence of equal mass encounters. The initial orbital configurations range from those producing an almost direct infall to others leading to numerous orbits before infall, with multiple bursts of radiation. Our sequence consists of orbits with fixed impact parameter. What varies is the initial linear momentum of the black holes. For this sequence, the final black hole of mass M_{h} gets a maximum spin parameter a/M_{h} approximately 0.823, with this maximum occurring for initial orbital angular momentum L/M_{h};{2} approximately 1.176.     

[2]Rotaxane End-Capping Synthesis by Click Michael-Type Addition to the Vinyl Sulfonyl Group

We report the application of the click Michael-type addition reaction to vinyl sulfone or vinyl sulfonate groups in the synthesis of rotaxanes through the threading-and-capping method. This methodology has proven to be efficient and versatile as it allowed the preparation of rotaxanes using template approaches based on different noncovalent interactions (i.e., donor-acceptor π–π interactions or hydrogen bonding) in yields of generally 60–80 % and up to 91 % aided by the mild conditions required (room temperature or 0 °C and a mild base such as Et₃N or 4-(N,N-dimethylamino)pyridine (DMAP)). Furthermore, the use of vinyl sulfonate moieties, which are suitable motifs for coupling-and-decoupling (CAD) chemistry, implies another advantage because it allows the controlled chemical disassembly of the rotaxanes into their components through nucleophilic substitution of the sulfonates resulting from the capping step with a thiol under mild conditions (Cs₂CO₃ and room temperature).     

A Germylene Supported by Two 2-Pyrrolylphosphane Groups as Precursor to PGeP Pincer Square-Planar Group 10 Metal(II) and T-Shaped Gold(I) Complexes

An efficient synthesis of 2-di-tert-butylphosphanylmethylpyrrole (HpyrmPtBu₂), by treating 2-dimethylaminomethylpyrrole (HpyrmNMe₂) with tBu₂PH at 135 °C in the absence of any solvent, has allowed the preparation of the new PGeP germylene Ge(pyrmPtBu₂)₂ ( 1 ), by treating [GeCl₂(dioxane)] with LipyrmPtBu₂, in which the Ge atom is stabilized by intramolecular interactions with one (solid state) or both (solution) of its phosphane groups. Reactions of germylene 1 with Group 10 metal dichlorido complexes containing easily displaceable ligands have led to [MCl{κ³P,Ge,P-GeCl(pyrmPtBu₂)₂}] [M=Ni ( 2 ), Pd ( 3 ), Pt ( 4 )], which have an unflawed square-planar metal environment. Treatment of germylene 1 with [AuCl(tht)] (tht=tetrahydrothiophene) rendered [Au{κ³P,Ge,P-GeCl(pyrmPtBu₂)₂}] ( 5 ), which is a rare case of a T-shaped gold(I) complex. The hydrolysis of 5 gave the linear gold(I) derivative [Au(κP-HpyrmPtBu₂)₂]Cl ( 6 ). Complexes 2 – 5 contain a PGeP pincer chloridogermyl ligand that arises from the insertion of the Ge atom of germylene 1 into a M−Cl bond of the corresponding metal reagent. The bonding in these molecules has been studied by DFT/NBO/QTAIM calculations. These results demonstrate that the great flexibility of germylene 1 makes it a better precursor to PGeP pincer complexes than the previously known germylenes of this type.