Search results for "ALP"

Towards highly accurate ab initio thermochemistry of larger systems: benzene.

2011

The high accuracy extrapolated ab initio thermochemistry (HEAT) protocol is applied to compute the total atomization energy (TAE) and the heat of formation of benzene. Large-scale coupled-cluster calculations with more than 1500 basis functions and 42 correlated electrons as well as zero-point energies based on full cubic and (semi)diagonal quartic force fields obtained with the coupled-cluster singles and doubles with perturbative treatment of the triples method and atomic natural orbital (ANO) triple- and quadruple-zeta basis sets are presented. The performance of modifications to the HEAT scheme and the scaling properties of its contributions with respect to the system size are investiga…

Unravelling the kinetics and molecular mechanism of the degenerate Cope rearrangement of bullvalene

2020

The kinetics and molecular mechanism of the gas phase degenerate Cope rearrangement (DCR) of bullvalene have been investigated by applying quantum mechanical calculations. Highly accurate energies (CBS-QB3 and CBS-APNO) and RRKM calculations were employed to study the kinetics and ‘fall-off’ behavior. It was found that the DCR of bullvalene (C3v) occurs through a bishomoaromatic transition structure (C2v) with an energy barrier of ∼49 kJ mol−1. The calculated activation energy and enthalpy were in good agreement with the available values in the literature, but lower than those of common Cope rearrangement; this result is related to the high stabilization energy due to the interaction of the…

Organocatalytic enantioselective Strecker reaction with seven-membered cyclic imines

2018

[EN] A highly enantioselective Strecker reaction with dibenzo[b,f][1,4]oxazepines has been described using a dihydroquinine-derived thiourea as organocatalyst. The reaction affords chiral 10,11-dihydrodibenzo[b,f][1,4] oxazepine 11-carbonitrile derivatives in excellent yields (up to 99%) and excellent enantioselectivities (up to 98%) under mild reaction conditions.

2020

Teraryl-based alpha-helix mimetics have resulted in efficient inhibitors of protein-protein interactions (PPIs). Extending the concept to even longer oligoarene systems would allow for the mimicking of even larger interaction sites. We present a highly efficient synthetic modular access to quateraryl alpha-helix mimetics, in which, at first, two phenols undergo electrooxidative dehydrogenative cross-coupling. The resulting 4,4′-biphenol is then activated by conversion to nonaflates, which serve as leaving groups for iterative Pd-catalyzed Suzuki-cross-coupling reactions with suitably substituted pyridine boronic acids. This work, for the first time, demonstrates the synthetic efficiency of …

Environmental and biological factors are joint drivers of mercury biomagnification in subarctic lake food webs along a climate and productivity gradi…

2021

Subarctic lakes are getting warmer and more productive due to the joint effects of climate change and intensive land-use practices (e.g. forest clear-cutting and peatland ditching), processes that potentially increase leaching of peat- and soil-stored mercury into lake ecosystems. We sampled biotic communities from primary producers (algae) to top consumers (piscivorous fish), in 19 subarctic lakes situated on a latitudinal (69.0-66.5 degrees N), climatic (+3.2 degrees C temperature and +30% precipitation from north to south) and catchment land-use (pristine to intensive forestry areas) gradient. We first tested how the joint effects of climate and productivity influence mercury biomagnific…

Long-term stability of alpha particle damage in natural zircon

2005

Abstract We report the first discovery of radiation damage haloes generated by alpha particles in zircon. Proterozoic zircon crystals from a potassium-rich leucogranite from the Adirondack Mountains, New York State, have interior regions that are generally low in actinide elements (UO 2  + ThO 2  ≤ 0.02 wt.%) but show a remarkable pattern of heterogeneous metamictisation. The degree of radiation damage in these regions is not uniformly low, as would be expected if it corresponded to the observed actinide distribution patterns and age of the crystals. Rather, radiation damage is significantly increased in the outermost micro-areas of the low-actinide regions. The additional radiation damage …

Prediction of Soil Formation as a Function of Age Using the Percolation Theory Approach

2018

Recent modeling and comparison with field results showed that soil formation by chemical weathering, either from bedrock or unconsolidated material, is limited largely by solute transport. Chemical weathering rates are proportional to solute velocities. Nonreactive solute transport described by non-Gaussian transport theory appears compatible with soil formation rates. This change in understanding opens new possibilities for predicting soil production and depth across orders of magnitude of time scales. Percolation theory for modeling the evolution of soil depth and production was applied to new and published data for alpine and Mediterranean soils. The first goal was to check whether the e…

Occurrence of fossil organic matter in modern environments: optical, geochemical and isotopic evidence

2011

International audience; This study relates to the input and fate of fossil organic matter (FOM) in the modern environment, and focuses on two experimental watersheds overlying Jurassic marls: Le Laval and Le Brusquet (1 km(2) in area), located near Digne, Alpes-de-Haute-Provence, France. Considering that FOM delivery is mainly a result of different processes affecting sedimentary rocks [(bio)chemical and mechanical weathering], samples from different pools were collected: bedrocks, weathering profiles, soils and riverine particles. The samples were examined using complementary techniques: optical (palynofacies methods), geochemical (Rock-Eval 6 pyrolysis, C/N ratio), molecular (gas chromato…

Tectonics of the Northern Bresse region (France) during the Alpine cycle

2003

International audience; Combining fieldwork and surface data, we have reconstructed the Cenozoic structural and tectonic evolution of the Northern Bresse. Analysis of drainage network geometry allowed to detect three major fault zones trending NE-SW, E-W and NW-SE, and smooth folds with NNE trending axes, all corroborated with shallow well data in the graben and fieldwork on edges. Cenozoic paleostress succession was determined through fault slip and calcite twin inversions, taking into account data of relative chronology. A N-S major compression, attributed to the Pyrenean orogenesis, has activated strike-slip faults trending NNE along the western edge and NE-SW in the graben. After a tran…

Palaeoecological implications of Neanderthal occupation at Unit Xb of El Salt (Alcoi, eastern Spain) during MIS 3 using small mammals proxy

2018

Nearly 250 small mammal remains from Unit Xb of El Salt Middle Palaeolithic site have been studied in order to reconstruct the palaeoecological conditions during a phase of Neanderthal occupation in this locality at 52.3 ± 4.6 ka. A total of 7rodents (Microtus arvalis, M. agrestis, M. (Terricola) duodecimcostatus, Microtus (Iberomys) cabrerae, Arvicola sapidus, Eliomys quercinus and Apodemus sylvaticus), 4 insectivores (Erinaceus cf. europaeus, Crocidura sp., Sorex sp. and Talpidae indet.) and 1 lagomorph (Oryctolagus cf. cuniculus) have been identified. Applying the Mutual Ecogeographic Range and Habitat Weighting methods, Unit Xb may correspond to a relatively cold (−3.3 °C in comparison …