FT-Raman spectroscopic study of calcium-rich and magnesium-rich carbonate minerals

Calcium and magnesium carbonates are important minerals found in sedimentary environments. Although sandstones are the most common rock colonized by endolith organisms, the production of calcium and magnesium carbonates is important in survival strategies of organisms and as a source for the removal of oxalate ions. Extremophile organisms in some situations may convert or destroy carbonates of calcium and magnesium, which gives important information about the conditions under which these organisms can survive. The identification on the surface of Mars of 'White Rock' formations, in Juventae Chasma or Sabaea Terra, as possibly carbonate rocks makes the study of these minerals a prerequisite of remote Martian exploration. Here, we show the protocol for the identification by Raman spectroscopy of different calcium and magnesium carbonates and we present a database of relevance in the search for life, extinct or extant, on Mars; this will be useful for the assessment of data obtained from remote, miniaturized Raman spectrometers now proposed for Mars exploration.     

Thermoanalytical investigation of tin and cerium salt mixtures

Summary Oxide materials belonging to the Sn-Ce-O system are very interesting due to their use as solid electrolytes in fuel cells, catalysts, sensors and photoanodes in solar cells. The aim of the present work is to investigate the thermal behaviour of some tin and cerium salt mixtures. Mixtures with different representative Sn:Ce atomic ratio were prepared by classical ceramic method using SnC₂O₄, Ce(SO₄)₂·4H₂O and (NH₄)₂Ce(NO₃)₆ as starting compounds. The samples were investigated by means of TG/DTA methods in flowing and static air atmosphere. SnO₂ and/or CeO₂ were identified by X-ray diffraction and IR spectroscopy in the final decomposition products, depending on the initial composition of the both series. A different crystallinity degree of the solid products was observed depending on the Ce precursor.     

Group 11 complexes with the bis(3,5-dimethylpyrazol-1-yl)methane ligand. How secondary bonds can influence the coordination environment of Ag(I): the role of coordinated water in [Ag2(mu-L)2(OH2)2](OTf)2

The complexation properties of the ligand bis(3,5-dimethylpyrazol-1-yl)methane (L) towards group 11 metals have been studied. The reaction in a 1 : 1 molar ratio with [Cu(NCMe)4]PF6 or Ag(OTf) complexes gives the mononuclear [CuL(NCMe)]PF6 (1), with crystallographic mirror symmetry, or dinuclear [Ag2(mu-L)2](OTf)2 (2) (OTf = trifluoromethanesulfonate) in which the ligand bridges both silver centres, an unprecedented mode of coordination for this type of ligands. Compound 2 crystallizes with two water molecules and forms a supramolecular structure through classical hydrogen bonding. The reaction in a 2 : 1 ratio affords in both cases the four-coordinated derivatives [ML2]X (M = Cu, X = PF6 (3); Ag, X = OTf 4). The treatment of [Ag(OTf)(PPh3)] with the ligand L gives [AgL(PPh3)]OTf (5). The gold(I) derivative [Au2(C6F5)2(mu-L)] (6) has also been obtained by reaction of L with two equivalents of [Au(C6F5)(tht)]. These complexes present a luminescent behaviour at low temperature; the emissions being mainly intraligand but enhanced after coordination of the metal. Compounds 1-4 have been characterized by X-ray crystallography. DFT studies showed that, in the silver complex 2, coordination of H2O to Ag in the binuclear complex is favoured by formation of a hydrogen-bonding network, involving the triflato anion, and releasing enough energy to allow distortion of the Ag2 framework.     

Diastereoselective synthesis of (+/-)-(3-aminocyclopentane)alkylphosphinic acids, conformationally restricted analogues of GABA

A divergent synthesis of both diastereoisomers of (+/-)-(3-aminocyclopentane)alkylphosphinic acid is described. Both diastereoisomers are obtained in 5 steps from the key (+/-)-(3-hydroxycyclopent-1-ene)alkylphosphinate esters which are prepared via a palladium catalysed C-P bond forming reaction.     

Mathematical help-seeking: observing how undergraduate students use the Internet to cope with a mathematical task

ZDM – Mathematics Education - We report on a study focused on identifying how undergraduate students make use of the Internet as a source of help to solve their mathematical queries. In...     

A genetic algorithm for a global optimization problem arising in the detection of gravitational waves

The detection of gravitational waves is a long-awaited event in modern physics and, to achieve this challenging goal, detectors with high sensitivity are being used or are under development. In order to extract gravitational signals emitted by coalescing binary systems of compact objects (neutron stars and/or black holes), from noisy data obtained by interferometric detectors, the matched filter technique is generally used. Its computational kernel is a box-constrained global optimization problem with many local solutions and a highly nonlinear and expensive objective function, whose derivatives are not available. To tackle this problem, we designed a real-coded genetic algorithm that exploits characteristic features of the problem itself; special attention was devoted to the choice of the initial population and of the recombination operator. Computational experiments showed that our algorithm is able to compute a reasonably accurate solution of the optimization problem, requiring a much smaller number of function evaluations than the grid search, which is generally used to solve this problem. Furthermore, the genetic algorithm largely outperforms other global optimization algorithms on significant instances of the problem.     

Synthesis of Polysubstituted Iodoarenes Enabled by Iterative Iodine‐Directed para and ortho C−H Functionalization

Among halogenated aromatics, iodoarenes are unique in their ability to produce the bench‐stable halogen(III) form. Earlier, such iodine(III) centers were shown to enable C?H functionalization ortho to iodine via halogen‐centered rearrangement. The broader implications of this phenomenon are explored by testing the extent of an unusual iodane‐directed para C?H benzylation, as well as by developing an efficient C?H coupling with sulfonyl‐substituted allylic silanes. Through the combination of the one‐shot nature of the coupling event and the iodine retention, multisubstituted arenes can be prepared by sequentially engaging up to three aromatic C?H sites. This type of iodine‐based iterative synthesis will serve as a tool for the formation of value‐added aromatic cores.     

A conserved karyotype of Sternopygus macrurus (Sternopygidae, Gymnotiformes) in the Amazon region: differences from other hydrographic basins suggest cryptic speciation

We studied the karyotypes of 35 Sternopygus macrurus fishes of four localities from rivers of the Eastern Amazon basin. In these four places the karyotypes have 2n = 46 chromosomes, NF = 92, where 30 are metacentric (M) and 16 submetacentric (SM). The constitutive heterochromatin (CH) is found in the centromeric region of most chromosomes and in the pericentromeric region of pairs 5, 17 and 19. Pair 1 has a large and not common heterochromatic block in the short arm, useful as a marker for this species if not found in other Sternopygus taxa. The NOR is located in the distal region of the short arm of pair 1, showing a size heteromorphism in some specimens. The CMA₃ and DAPI fluorochrome bandings and the fluorescent in situ hybridization (FISH), using pantelomeric human probes techniques are described for the first time for this species. DAPI has banding coincident with the C-banded regions, which suggests that the CH is AT base-pair-rich. CMA₃ banding is coincident with the NOR, meaning that this region is GC base-pair-rich. The FISH showed that the probes hybridized only with the telomeric regions, without any sign of interstitial telomeric regions. The karyotype of the samples from different places in the Amazon basin is quite conserved, probably because of the gene flow among the populations. The karyotype differences among the Sternopygus macrurus from the Amazon basin and the São Francisco and Paraná rivers suggest that these taxa may be different species.