El conocimiento de los electrones determina la interacción molecular

Página web divulgativa.Peer Reviewe

Critical phenomena in higher dimensional spaces: The hexagonal-to-orthorhombic phase transition in aperiodic n-nonadecane/urea

PACS number(s): 61.44.Fw, 64.60.−i, 61.05.cf.-- et al.Upon cooling, the aperiodic inclusion compound n-nonadecane/urea presents a hexagonal-to-orthorhombic group-subgroup phase transition at Tcl that increases the structure's superspace dimensionality from four to five. This paper reports on pretransitional phenomena in such a high-dimensional space, generalizing the critical results previously reported at a lower dimensionality. Very high-resolution diffraction data reveal anomalously large correlation lengths along the aperiodic direction, with all correlation lengths diverging at Tcl. This could be explained by low-frequency phason excitations that soften at Tcl at the critical wave vector, in accordance with an increase in the critical diffuse scattering intensity. © 2013 American Physical Society.Peer Reviewe

Google Scholar Metrics evolution: an analysis according to languages

The final publication is available at Springer via http://dx.doi.org/10.1007/s11192-013-1164-8In November 2012 the Google Scholar Metrics (GSM) journal rankings were updated, making it possible to compare bibliometric indicators in the ten languages indexed—and their stability—with the April 2012 version. The h-index and h-5 median of 1,000 journals were analysed, comparing their averages, maximum and minimum values and the correlation coefficient within rankings. The bibliometric figures grew significantly. In just seven and a half months the h-index of the journals increased by 15 % and the median h-index by 17 %. This growth was observed for all the bibliometric indicators analysed and for practically every journal. However, we found significant differences in growth rates depending on the language in which the journal is published. Moreover, the journal rankings seem to be stable between April and November, reinforcing the credibility of the data held by Google Scholar and the reliability of the GSM journal rankings, despite the uncontrolled growth of Google Scholar. Based on the findings of this study we suggest, firstly, that Google should upgrade its rankings at least semi-annually and, secondly, that the results should be displayed in each ranking proportionally to the number of journals indexed by language.Orduña Malea, E.; Delgado López-Cózar, E. (2014). Google Scholar Metrics evolution: an analysis according to languages. Scientometrics. 98(3):2353-2367. doi:10.1007/s11192-013-1164-8S23532367983Aguillo, & Isidro, F. (2012). Is Google Scholar useful for bibliometrics? A webometric analysis. Scientometrics, 91(2), 343–351.Brewington, B. E., & Cybenko, G. (2000). How dynamic is the Web? Computer Networks, 33(1–6), 257–276.Chen, X. (2010). Google Scholar’s dramatic coverage improvement five years after debut. Serials Review, 36(4), 221–226.Cho, Y. & Garcia-Molina, H. (2000). The evolution of the web and implications for an incremental crawler. Proceedings of the 26th International Conference on very large data bases, 200–209.Costas, R., & Bordons, M. (2007). The h-index: advantages, limitations and its relation with other bibliometric indicators at the micro level. Journal of Informetrics, 1(3), 193–203.de Winter, J. C. F., Zadpoor, A. A., & Dodou, D. (2013). The expansion of Google Scholar versus Web of Science: a longitudinal study. Scientometrics. doi: 10.1007/s11192-013-1089-2 .Delgado López-Cózar, E., & Cabezas-Clavijo, A. (2012). Google Scholar Metrics: an unreliable tool for assessing scientific journals. El profesional de la información, 21(4), 419–427.Delgado López-Cózar, E., & Cabezas-Clavijo, A. (2013). Ranking journals: could Google Scholar metrics be an alternative to journal citation reports and Scimago journal ranks. Learned publishing, 26(2), 101–114.Fetterly, D., Manasse, M., Najork, M. & Wiener, J. (2003). A large scale study of the evolution of web pages. Proceedings of the Twelfth International Conference on World Wide Web, 669–678.Harzing, A.-W. (2013). A preliminary test of Google Scholar as a source for citation data: a longitudinal study of Nobel prize winners. Scientometrics, 94(3), 1057–1075.Jacsó, P. (2012). Google Scholar Metrics for Publications—The software and content feature of a new open access bibliometric service. Online Information Review, 36(4), 604–619.Koehler, W. (2002). Web page change and persistence-4-year longitudinal web study. Journal of the American Society for Information Science and Technology, 53(2), 162–171.Koehler, W (2004). A longitudinal study of Web pages continued a consideration of document persistence. Information Research, 9(2). http://informationr.net/ir/9-2/paper174.html . Accessed 1 Sep 2013.Kousha, K., & Thelwall, M. (2007). Google Scholar Citations and Google Web/URL citations: a multidiscipline exploratory analysis. Journal of the American Society for Information Science and Technology, 58(7), 1055–1065.Leydesdorff, L. (2012). World shares of publications of the USA, EU-27, and China compared and predicted using the new Web of Science interface versus Scopus. El profesional de la información, 21(1), 43–49.Neuhaus, C., Neuhaus, E., Asher, A., & Wrede, C. (2006). The depth and breadth of Google Scholar: An empirical study. Libraries and the Academy, 6(2), 127–141.Orduña-Malea, E., Serrano-Cobos, J., & Lloret-Romero, N. (2009). Las universidades públicas españolas en Google Scholar: presencia y evolución de su publicación académica web. El profesional de la información, 18(5), 493–500.Orduña-Malea, E., Serrano-Cobos, J., Ontalba-Ruipérez, J.-A., & Lloret-Romero, N. (2010). Presencia y visibilidad web de las universidades públicas españolas. Revista española de documentación científica, 33(2), 246–278.Ortega, J. L., Aguillo, I. F., & Prieto, J. A. (2006). Longitudinal study of contents and elements in the scientific Web environment. Journal of Information Science, 32(4), 344–351.Payne, N., & Thelwall, M. (2007). A longitudinal study of academic webs: growth and stabilization. Scientometrics, 71(3), 523–539

Dinuclear pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture

A series of dinuclear pyridine-4-thiolate (4-Spy)-bridged rhodium and iridium compounds [M(μ-4-Spy)(diolef)]2 [diolef = 1,5-cyclooctadiene (cod), M = Rh (1), Ir (2); diolef = 2,5-norbornadiene (nbd), M = Rh (3)] were prepared by the reaction of Li(4-Spy) with the appropriate compound [M(μ-Cl)(diolef)]2 (M = Rh, Ir). The dinuclear compound [Rh(μ-4-Spy)(CO)(PPh3)]2 (4) was obtained by the reaction of [Rh(acac)(CO)(PPh3)] (acac = acetylacetonate) with 4-pySH. Compounds 1-4 were assessed as metalloligands in self-assembly reactions with the cis-blocked acceptors [M(cod)(NCCH3)2](BF 4) [M = Rh (a), Ir (b)] and [M(H2O)2(dppp)] (OTf)2 [M = Pd (c), Pt (d); dppp = 1,3-bis(diphenylphosphino)propane] . The homometallic hexanuclear metallomacrocycles [{M2(μ-4-Spy) 2(cod)2}2{M(cod)}2](BF 4)2 (M = Rh [(1a)2], Ir [(2b)2]) and the heterometallic hexanuclear metallomacrocycles [{Rh2(μ-4-Spy) 2(cod)2}2{Ir(cod)}2](BF 4)2 [(1b)2], [{Rh2(μ-4-Spy) 2(cod)2}2{M′(dppp)}2](OTf) 4 (M′ = Pd [(1c)2], Pt [(1d)2]), and [{Ir2(μ-4-Spy)2(cod)2}2{M′ (dppp)}2](OTf)4 (M′ = Pd [(2c)2], Pt [(2d)2]) were obtained. NMR spectroscopy in combination with electrospray ionization mass spectrometry was used to elucidate the nature of the metalloligands and their respective supramolecular assemblies. Most of the synthesized species were found to be nonrigid in solution, and their fluxional behavior was studied by variable-temperature 1H NMR spectroscopy. An X-ray diffraction study of the assemblies (1a)2 and (1d)2 revealed the formation of rectangular (9.6 Å × 6.6 Å) hexanuclear metallomacrocycles with alternating dinuclear (Rh2) and mononuclear (Rh or Pt) corners. The hexanuclear core is supported by four pyridine-4-thiolate linkers, which are bonded through the thiolate moieties to the dinuclear rhodium units, exhibiting a bent-anti arrangement, and through the peripheral pyridinic nitrogen atoms to the mononuclear corners.Financial support for this work was provided by the Ministerio de Economía y Competitividad (MINECO/FEDER) of Spain (Projects CTQ2010-15221 and CTQ2012-31335), Diputación General de Aragón (Group E07), and Fondo Social Europeo.Peer Reviewe

Topology and excited state multiplicity as controlling factors in the carbazole-photosensitized CPD formation and repair

Photosensitized thyminethymine (ThyThy) formation and repair can be mediated by carbazole (Cbz). The former occurs from the Cbz triplet excited state via energy transfer, while the latter takes place from the singlet excited state via electron transfer. Here, fundamental insight is provided into the role of the topology and excited state multiplicity, as factors governing the balance between both processes. This has been achieved upon designing and synthesizing different isomers of trifunctional systems containing one Cbz and two Thy units covalently linked to the rigid skeleton of the natural deoxycholic acid. The results shown here prove that the Cbz photosensitized dimerization is not counterbalanced by repair when the latter, instead of operating through-space, has to proceed through-bond. © 2022 The Authors. Published by American Chemical Society

Towards a Precision Cosmology from Starburst Galaxies at z>2

This work investigates the use of a well-known empirical correlation between the velocity dispersion, metallicity, and luminosity in H beta of nearby HII galaxies to measure the distances to HII-like starburst galaxies at high redshifts. This correlation is applied to a sample of 15 starburst galaxies with redshifts between z=2.17 and z=3.39 to constrain Omega_m, using data available from the literature. A best-fit value of Omega_m = 0.21 +0.30 -0.12 in a Lambda-dominated universe and of Omega_m = 0.11 +0.37 -0.19 in an open universe is obtained. A detailed analysis of systematic errors, their causes, and their effects on the values derived for the distance moduli and Omega_m is carried out. A discussion of how future work will improve constraints on Omega_m by reducing the errors is also presented.Comment: 7 pages, 3 figures, accepted for publication in MNRA

Tratamiento de tumores óseos benignos mediante legrado y relleno con metilmetacrilato

Se expone la experiencia en ocho lesiones óseas tumorales y paratumorales benignas tratadas mediante legrado de la cavidad y posterior relleno mediante metilmetacrilato con contraste baritado. El seguimiento de los casos entre año y medio y once años permite que nos afirmemos en la bondad de los resultados en cuanto a función articular resistencia de la extremidad y control del tumor. Comentamos las estadísticas publicadas en las que destacan los casos de tumor de células gigantes (66 por 100) y los excelentes resultados funcionales; las recidivas recaen en tumores de células gigantes de tipo agresivo. Revisamos los fenómenos inducidos en el foco por la alta temperatura de la cementación y se comparan con los que se observan en la criocirugía. Destacamos la resistencia del cartílago adyacente al foco cementado y la aparición posterior de fenómenos artrósicos

Activation of H-H, HO-H, C(sp2)-H, C(sp3)-H, and RO-H bonds by transition-metal frustrated lewis pairs based onon M/N (M = Rh, Ir) couples

Reaction of the dimers (Cp*MCl)2(µ-Cl)2] (Cp* = 5-C5Me5) with Ph2PCH2CH2NC(NH(p-Tolyl))2 (H2L) in the presence of NaSbF6 affords the chlorido complexes Cp*MCl(¿2N, P-H2L)]SbF6] (M = Rh, 1; Ir, 2). Upon treatment with aqueous NaOH, solutions of 1 and 2 yield the corresponding complexes Cp*M(¿3N, N', P-HL)]SbF6] (M = Rh, 3; Ir, 4) in which the ligand HL presents a fac ¿3N, N', P coordination mode. Treatment of THF solutions of complexes 3 and 4 with hydrogen gas, at room temperature, results in the formation of the metal hydrido-complexes Cp*MH(¿2N, P-H2L)]SbF6] (M = Rh, 5; Ir, 6) in which the N(p-Tolyl) group has been protonated. Complexes 3 and 4 react with deuterated water in a reversible fashion resulting in the gradual deuteration of the Cp* group. Heating at 383 K THF/H2O solutions of the complexes 3 and 4 affords the orthometalated complexes Cp*M(¿3C, N, P-H2L-H)]SbF6] M = Rh, 7; Ir, 8, H2L-H = Ph2PCH2CH2NC(NH(p-Tolyl))(NH(4-C6H3Me))], respectively. At 333 K, complexes 3 and 4 react in THF with methanol, primary alcohols, or 2-propanol giving the metal-hydrido complexes 5 and 6, respectively. The reaction involves the acceptorless dehydrogenation of the alcohols at a relatively low temperature, without the assistance of an external base. The new complexes have been characterized by the usual analytical and spectroscopic methods including the X-ray diffraction determination of the crystal structures of complexes 1-5, 7, and 8. Notably, the chlorido complexes 1 and 2 crystallize both as enantiopure conglomerates and as racemates. Reaction mechanisms are proposed based on stoichiometric reactions, nuclear magnetic resonance studies, and X-ray crystallography as well as density functional theory calculations. © 2022 The Authors. Published by American Chemical Society