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[en] The earliest Svecofennian magmatism in southern Finland has been dated at 1.90-1.88Ga. As an example of this, the Orijärvi (ca. 1.89Ga) and Enklinge (ca. 1.88Ga) volcanic centres comprise bimodal plutonic batholiths surrounded by volcanic rocks of comparable ages and chemical compositions. Here, we report geochemical and Sm-Nd isotope data from intrusive and extrusive samples, combined with zircon U-Pb and Lu-Hf isotopes for granodiorites from both study areas. The samples range from gabbros to granites and indicate a subduction-related continental margin setting. The zircons from the Orijärvi granodiorite define an age of 1892±4Ma whereas the Enklinge granodiorite yields an age of 1882±6Ma. Several inherited ages of 2.25-1.95Ga as well as younger ages of 1.86-1.80Ga were found in the Enklinge granodiorite. The initial εNd values from the mafic rocks from both locations fall in the range +1.1 to +2.9 whereas the felsic rocks exhibit initial εNd values of -0.4 to +1.2. The magmatic zircons from the Orijärvi and Enklinge granodiorites show average initial εHf values of -1.1 (at 1892Ma) and zero (at 1882Ma), respectively, each with a spread of about 7 ε-units. The initial εHf values for the inherited zircons from Enklinge range from +3.5 to +7.6 with increasing age. The Sm-Nd data indicate that the mafic rocks were derived from a “mildly depleted” mantle source while the felsic rocks show larger crustal contribution. Also, the variation in εHf values indicates minor mixing between mildly depleted mantle derived magmas and crustal sources. U-Pb ages and Hf isotopes for inherited zircons in the Enklinge granodiorite suggest the presence of juvenile Svecofennian “proto-crust” at depth.
[en] This paper presents experimental demonstrations of a self-repairing strain sensor waveguide created by self-writing in a photopolymerizable resin system. The sensor is fabricated between two multi-mode optical fibers via lightwaves in the ultraviolet (UV) wavelength range and operates as a sensor through interrogation of the power transmitted through the waveguide in the infrared (IR) wavelength range. After failure of the sensor occurs due to loading, the waveguide re-bridges the gap between the two optical fibers through the UV resin. The response of the original sensor and the self-repaired sensor to strain are measured and show similar behaviors
[en] We demonstrate the gas-phase catalytic production of methyl acrylates by oxygen-assisted coupling of methanol with the unsaturated alcohols allyl alcohol and methylallyl alcohol over nanoporous gold (npAu) at atmospheric pressure. Analogous investigations on O-activated Au(110) exhibit the same pattern of reactivity and are used to establish that the competition between methoxy and allyloxy (or methallyloxy) reaction intermediates for adsorption sites, mediated by the reactants themselves, determines the selectivity of reaction. These results clearly show that the C=C bond substantially increases the binding efficacy of the allyloxy (or methallyloxy), thus requiring extremely high methanol mole fractions (>0.99) in order to achieve comparable surface concentrations of methoxy and produce optimum yields of either methacrylate or methyl methacrylate. Allyloxy and methallyloxy were favored by factors of ~100 and ~450, respectively, vs methoxy. These values are more than 1 order of magnitude greater than those measured for competitive binding of ethoxy and 1-butoxy vs methoxy, demonstrating the strong effect of the carbon–carbon bond unsaturation. The 4.5-fold increase due to the addition of the methyl group in methylallyl alcohol vs allyl alcohol indicates the significant effect of the additional van der Waals interactions between the methyl group and the surface. Gas-phase acidity is also shown to be a good qualitative indicator for the relative binding strength of the alkoxides. This work then provides insight into the control of reaction selectivity for coupling reactions and demonstrates the value of fundamental studies on single crystals for establishing key principles governing reaction selectivity. Notably, these oxygen-assisted coupling reactions occur without oxidation of the C=C bond.
[en] It is important to achieve high selectivity for high volume chemical synthesis in order to lower energy consumption through reduction in waste. Here, we report the selective synthesis of methyl esters—methyl acetate and methyl butyrate—through catalytic O2-assisted cross-coupling of methanol with ethanol or 1-butanol using activated, support-free nanoporous gold (npAu). Both well-controlled studies on ingots in UHV and experiments under ambient pressure catalytic conditions on both ingots and microspherical hollow shell catalysts reveal guiding principles for controlling selectivity. Under UHV conditions, the ester products of the cross-coupling of methanol with both ethanol and 1-butanol evolve near room temperature in temperature-programmed reaction studies, indicating that the reactions occur facilely. Furthermore, under steady-state catalytic operation, high stable activity was observed for cross-coupling in flowing gaseous reactant mixtures at atmospheric pressure and 423 K with negligible combustion. Optimum selectivity for cross-coupling is obtained in methanol-rich mixtures due to a combination of two factors: (1) the relative coverage of the respective alkoxys and (2) the relative facility of their β-H elimination. The relative coverage of the alkoxys is governed by van der Waal’s interactions between the alkyl groups and the surface; here, we demonstrate the importance of these weak interactions in a steady-state catalytic process.
[en] Despite evidence for macrostructural alteration in epilepsy patients later in life, little is known about the underlying pathological or compensatory mechanisms at younger ages causing these alterations. The aim of this work was to investigate the impact of pediatric epilepsy on the central nervous system, including gray matter volume, cerebral blood flow, and water diffusion, compared with neurologically normal children. Inter-ictal magnetic resonance imaging data was obtained from 30 children with epilepsy ages 1–16 (73% F, 27% M). An atlas-based approach was used to determine values for volume, cerebral blood flow, and apparent diffusion coefficient in the cerebral cortex, hippocampus, thalamus, caudate, putamen, globus pallidus, amygdala, and nucleus accumbens. These values were then compared with previously published values from 100 neurologically normal children using a MANCOVA analysis. Most brain volumes of children with epilepsy followed a pattern similar to typically developing children, except for significantly larger putamen and amygdala. Cerebral blood flow was also comparable between the groups, except for the putamen, which demonstrated decreased blood flow in children with epilepsy. Diffusion (apparent diffusion coefficient) showed a trend towards higher values in children with epilepsy, with significantly elevated diffusion within the thalamus in children with epilepsy compared with neurologically normal children. Children with epilepsy show statistically significant differences in volume, diffusion, and cerebral blood flow within their thalamus, putamen, and amygdala, suggesting that epilepsy is associated with structural changes of the central nervous system influencing brain development and potentially leading to poorer neurocognitive outcomes.