Curtin-Hammett versus non-Curtin-Hammett frameworks is optimizing the enantioselective binolam/titanium(IV)-catalyzed cyanobenzoylation of aldehydes: Part 2

Extensive experimental and computational studies have been carried out on the enantioselective titanium(IV)-catalyzed cyanobenzoylation of aldehydes using 1:n Binolam:Ti(OiPr)4 mixtures as precatalysts, with the purpose of identifying the key mechanistic aspects governing enantioselectivity. HCN and isopropyl benzoate were detected in the reacting mixtures. This, as well as the reaction’s response to the presence of an exogenous base, and the failure to react in the presence of Binol:Ti(OiPr)4 mixtures, led us to propose not a direct cyanobenzoylation but an indirect process involving enantioselective hydrocyanation followed by O-benzoylation. Computational work provided positive evidence for the intervention of both indirect and direct cyanobenzoylation routes, the former being faster. However, the standard Curtin–Hammett-based optimization search ended with unsatisfactory results. Experimental and computational DFT studies (B3LYP/6-31G*) led us to conclude that: (1) the overall cyanobenzoylation of aldehydes catalyzed by 1:n Binolam:Ti(OiPr)4 mixtures involves an enantioselective hydrocyanation followed by an stereochemically inert O-benzoylation; (2) the initial complexes prevailing in a 1:1 Binolam:Ti(OiPr)4 mixture are the solvated mononuclear monomer 5·2(iPrOH) and solvated dinuclear dimer 9·2(iPrOH), whereas 9·2(iPrOH) is the major component in a 1:2 or higher 1:n mixture; (3) since the slowest step is that of benzoylation of ligated iPrOH which yields the actual catalysts 5–9, the catalytic system fits into a non-Curtin–Hammett framework, the final products deriving from a kinetic quench of the competing routes; and (4) accordingly, catalysis by 1:1 Binolam:Ti(OiPr)4 mixtures should involve cyanobenzoylations promoted by mononuclear 5, contaminated with those promoted by some dinuclear open dimer 9, whereas cyanobenzoylations catalyzed by a 1:2 and higher 1:n mixtures should be the result of catalysis promoted by the large amounts of dinuclear open dimer 9.

Guión de la excursión a la Cordillera Ibérica de la asignatura de Geología Histórica y Regional

Esta guía surge como documento complementario al campamento de prácticas de campo de la asignatura de Geología Histórica y Regional del Grado de Geología de la Universidad de Alicante. El objetivo principal de este campamento es el conocimiento de los materiales sedimentarios del Paleozoico, Triásico y Jurásico de la Cordillera Ibérica.

Brachiopod assemblages from the Early-Middle Jurassic transition in the Eastern Subbetic (SE Spain): Systematic and palaeobiogeographic implications and palaeoenvironmental significance

New data on brachiopod assemblages recorded in the Eastern Subbetic area (Alicante, SE Spain) and attributed to the Early Bajocian (Humphriesianum Zone and/or immediately older) are provided. Eleven species have been distinguished and reported for the first time in the Subbetic domain of the Betic Cordillera. The description of the morphological evidences on each analysed taxa, especially in relation to their internal morphology, brings new implications in the systematics of the Middle Jurassic brachiopods. The analysis of faunistic affinity between the recorded assemblages and those from other palaeogeographic domains, shows that the Subbetic brachiopod fauna has a clear Mediterranean affinity, as proved by the different species belonging to the genera Striirhynchia, Septocrurella, Mondegia?, Karadagithyris, Linguithyris, Papodina?, Viallithyris?, and Zugmayeria?. It is also evidenced that the Early-Middle Jurassic transition in the Eastern Subbetic accounted, in qualitative terms, a remarkable interval of faunistic renewal in the brachiopod assemblages, strongly influenced by a complex tectonic and stratigraphic framework controlled by a period of intense extensional tectonics, globally framed in the evolution of the Atlantic Ocean.

Biostratigraphy and paleobiogeographic affinities of the Jurassic brachiopod assemblages from Sierra Espuña (Maláguide Complex, Internal Betic Zones, Spain)

The assemblages of Early Jurassic brachiopods (Pliensbachian - Toarcian) from Sierra Espuña (Murcia Province, SE Spain) are described. This is the only area in the Internal Zones of the Betic Cordillera, corresponding to the margins of the Alborán Terrane, where Jurassic brachiopods are known to occur. In the tectonic Unit of Morrón de Totana (more southward located) assemblage MT1 of Late Pliensbachian age has been characterized. This assemblage has been subdivided into three successive sub-assemblages: MT1a (Algovianum Zone), MT1b (Emaciatum Zone, Solare Subzone) and MT1c (Emaciatum Zone, Elisa Subzone). Northward, in the Perona tectonic Unit two distinct assemblages, P1 (Latest Sinemurian - Early Pliensbachian) and P2 (Early Toarcian, Serpentinum Zone) have been recognized. Differences between the assemblages from the two tectonic units are evident after the paleobiogeographical analysis. In the Morrón de Totana Unit, taxa with Mediterranean affinities occur. MT1 assemblage is very similar to assemblages previously known in the Eastern Subbetic as well as in other areas of the Mediterranean Province. In the Perona Unit the Mediterranean affinity of the assemblages is not so evident. P1 Assemblage consists of widely distributed taxa, lacking in the most characteristic elements of the Mediterranean Province which, however, are present in neighbouring Betic areas. P2 Assemblage belongs to the Spanish Province that develops in Western Tethys after the Early Toarcian Mass Extinction Event. The occurrence in this assemblage of Prionorhynchia aff. msougari Rousselle, until now only found in North Africa, indicates a closer connection of the Perona Unit with the African paleomargin of the Tethys than with the South Iberian paleomargin. The paleobiogeographical data suggest a more southern and marginal (close to epicontinental areas) position of the Perona Unit than the Morrón de Totana Unit.

Decodificando mediante microfósiles la Crisis de Salinidad del Mediterráneo como recurso didáctico en Ciencias de la Tierra

El estudio de las disciplinas científicas resulta más atractivo si se acompaña de actividades de carácter práctico. En este trabajo se propone un taller cuya finalidad es introducir al alumnado en el estudio de los microfósiles y de las reconstrucciones paleoambientales aplicándolo a uno de los eventos más significativos ocurridos en el área Mediterránea, que conllevó la desecación y posterior reinundación de toda la cuenca hace aproximadamente unos cinco millones de años. El taller consta de tres sesiones: una teórica, de introducción de los contenidos necesarios para el desarrollo de la actividad, una práctica, de obtención de datos, y una final, de interpretación de los cambios ambientales y presentación de los resultados en forma de artículo científico y posterior debate en el aula. Todos los datos necesarios para el desarrollo de la actividad se proporcionan en el presente artículo. Además, se proponen una serie de recursos bibliográficos y audiovisuales de fácil acceso para la introducción de los conceptos teóricos.

Self-sensing properties of alkali activated blast furnace slag (BFS) composites reinforced with carbon fibers

In recent years, several researchers have shown the good performance of alkali activated slag cement and concretes. Besides their good mechanical properties and durability, this type of cement is a good alternative to Portland cements if sustainability is considered. Moreover, multifunctional cement composites have been developed in the last decades for their functional applications (self-sensing, EMI shielding, self-heating, etc.). In this study, the strain and damage sensing possible application of carbon fiber reinforced alkali activated slag pastes has been evaluated. Cement pastes with 0, 0.29 and 0.58 vol % carbon fiber addition were prepared. Both carbon fiber dosages showed sensing properties. For strain sensing, function gage factors of up to 661 were calculated for compressive cycles. Furthermore, all composites with carbon fibers suffered a sudden increase in their resistivity when internal damages began, prior to any external signal of damage. Hence, this material may be suitable as strain or damage sensor.

Multifunctional cement composites strain and damage sensors applied on reinforced concrete (RC) structural elements

In this research, strain-sensing and damage-sensing functional properties of cement composites have been studied on a conventional reinforced concrete (RC) beam. Carbon nanofiber (CNFCC) and fiber (CFCC) cement composites were used as sensors on a 4 m long RC beam. Different casting conditions (in situ or attached), service location (under tension or compression) and electrical contacts (embedded or superficial) were compared. Both CNFCC and CFCC were suitable as strain sensors in reversible (elastic) sensing condition testing. CNFCC showed higher sensitivities (gage factor up to 191.8), while CFCC only reached gage factors values of 178.9 (tension) or 49.5 (compression). Furthermore, damage-sensing tests were run, increasing the applied load progressively up to the RC beam failure. In these conditions, CNFCC sensors were also strain sensitive, but no damage sensing mechanism was detected for the strain levels achieved during the tests. Hence, these cement composites could act as strain sensors, even for severe damaged structures near to their collapse.

Strain and damage sensing properties on multifunctional cement composites with CNF admixture

Both strain and damage sensing properties on carbon nanofiber cement composites (CNFCC) are reported in the present paper. Strain sensing tests were first made on the material’s elastic range. The applied loading levels have been previously calculated from mechanical strength tests. The effect of several variables on the strain-sensing function was studied, e.g. cement pastes curing age, current density, loading rate or maximum stress applied. All these parameters were discussed using the gage factor as reference. After this first set of elastic experiments, the same specimens were gradually loaded until material’s failure. At the same time both strain and resistivity were measured. The former was controlled using strain gages, and the latter using a multimeter on a four probe setup. The aim of these tests was to prove the sensitivity of these CNF composites to sense their own damage, i.e. check the possibility of fabricating structural damage sensors with CNFCC’s. All samples with different CNF dosages showed good strain-sensing capacities for curing periods of 28 days. Furthermore, a 2%CNF reinforced cement paste has been sensitive to its own structural damage.

Pràctiques de Micropaleontologia I

Cuaderno de prácticas de Micropaleontología que abarca las siguientes prácticas: Webs de interés en Micropaleontología, recogida de muestras en campo, levigados, frotis, lámina delgada y observación de muestras: lupa binocular y microscopio.

Efecto de la adición de nanofibras de carbono en las propiedades mecánicas y de durabilidad de materiales cementantes

En este artículo se han estudiado los cambios en las propiedades mecánicas de los morteros de cemento Portland debido a la adición de nanofibras de carbono (NFC). Se han determinado las resistencias a flexotracción y a compresión de los morteros en relación a la cantidad de NFC añadidas a la mezcla, al tiempo de curado y a la porosidad y densidad de los mismos. Además se han investigado los niveles de corrosión de barras de acero embebidas en pastas de cemento con NFC expuestos al ataque por carbonatación y por ingreso de cloruros. El aumento en el porcentaje de NFC añadido se traduce en un aumento la intensidad de corrosión registrada y una mejora de las propiedades mecánicas.

Uso potencial de ceniza de lodo de depuradora como sustitución de árido fino en bloques de hormigón prefabricados

El presente artículo se centra en la valorización de las cenizas de lodo de depuradora adicionadas en bloques de hormigón prefabricados, por tanto, en una matriz a base de cemento Portland con características particulares (consistencia seca). Se realiza una experiencia piloto mediante la fabricación de bloques en una planta industrial local, utilizando mezclas con porcentajes de sustitución de árido fino del 5, 10 y 15% por cenizas de lodo de depuradora, cuyos resultados se compararán con bloques de referencia (sin adición). Los ensayos aplicados son los preceptivos para su comercialización según normativa europea (marcado CE), lo que permitirá igualmente comprobar las características físicas y mecánicas de los hormigones. Los resultados obtenidos son prometedores: la utilización de este residuo permitiría su comercialización, mejora características de los bloques como la resistencia a compresión, y permitiría reducir un gran volumen de material utilizado habitualmente como materia prima y consumir un residuo destinado a vertedero.

Los microfósiles y la Crisis de Salinidad del Mediterráneo como recurso didáctico en Ciencias de la Tierra

El estudio de las disciplinas científicas resulta más atractivo si se acompaña de actividades de carácter práctico. En este trabajo se propone un taller cuya finalidad es introducir al alumnado en el trabajo científico que realizan los geólogos y paleontólogos a través de la información paleoambiental y bioestratigráfica que proporcionan los microfósiles y su aplicación a la Crisis de Salinidad del Messiniense. Este periodo es considerado como uno de los acontecimientos más relevantes de la historia geológica del Mediterráneo y se caracteriza por una acumulación masiva de evaporitas en el fondo de la cuenca, que se relaciona con la desecación y posterior reinundación del Mediterráneo hace aproximadamente cinco millones de años. El taller consta de tres sesiones: una teórica, de introducción de los contenidos necesarios para el desarrollo de la actividad, para la que se proponen una serie de recursos bibliográficos y audiovisuales de libre acceso en internet; una práctica, de obtención de datos; y una final, de interpretación de los cambios paleoambientales que conlleva la presentación de los resultados en forma de artículo científico y posterior debate en el aula. Todos los datos necesarios para el desarrollo de la actividad se proporcionan en el presente artículo, si bien esta propuesta de taller queda abierta a las posibles modificaciones y mejoras que el profesorado considere oportunas. Para vertebrar esta propuesta, en forma de ejemplo de aplicación, se ha incluido el taller en la programación de la asignatura Biología y Geología (4º ESO). La puesta a punto de este taller pone de manifiesto que resulta idóneo para el trabajo en grupo en el aula permitiendo que el alumnado se sienta partícipe de todas las fases que constituyen una investigación científica.

Mechanical Properties and Durability of CNT Cement Composites

In the present paper, changes in mechanical properties of Portland cement-based mortars due to the addition of carbon nanotubes (CNT) and corrosion of embedded steel rebars in CNT cement pastes are reported. Bending strength, compression strength, porosity and density of mortars were determined and related to the CNT dosages. CNT cement paste specimens were exposed to carbonation and chloride attacks, and results on steel corrosion rate tests were related to CNT dosages. The increase in CNT content implies no significant variations of mechanical properties but higher steel corrosion intensities were observed.

Self-heating function of carbon nanofiber cement pastes

The viability of carbon nanofiber (CNF) composites in cement matrices as a self-heating material is reported in this paper. This functional application would allow the use of CNF cement composites as a heating element in buildings, or for deicing pavements of civil engineering transport infrastructures, such as highways or airport runways. Cement pastes with the addition of different CNF dosages (from 0 to 5% by cement mass) have been prepared. Afterwards, tests were run at different fixed voltages (50, 100 and 150V), and the temperature of the specimens was registered. Also the possibility of using a casting method like shotcrete, instead of just pouring the fresh mix into the mild (with no system’s efficiency loss expected) was studied. Temperatures up to 138 °C were registered during shotcrete-5% CNF cement paste tests (showing initial 10 °C/min heating rates). However a minimum voltage was required in order to achieve a proper system functioning.