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971.
Tobias Kluge Martin Wieser Werner Aeschbach-Hertig 《Isotopes in environmental and health studies》2013,49(3):299-311
3H–3He measurements constitute a well-established method for the determination of the residence time of young groundwater. However, this method has rarely been applied to karstified aquifers and in particular to drip water in caves, despite the importance of the information which may be obtained. Besides the determination of transfer times of climate signals from the atmosphere through the epikarst to speleothems as climate archives, 3H–3He together with Ne, Ar, Kr, Xe data may also help to give new insights into the local hydrogeology, e.g. the possible existence of a perched aquifer above a cave. In order to check the applicability of 3H–3He dating to cave drips, we collected drip water samples from three adjacent caves in northwestern Germany during several campaigns. The noble gas data were evaluated by inverse modelling to obtain recharge temperature and excess air, supporting the calculation of the tritiogenic 3He and hence the 3H–3He age. Although atmospheric noble gases were often found to be close to equilibrium with the cave atmosphere, several drip water samples yielded an elevated 3He/4He ratio, providing evidence for the accumulation of 3He from the decay of 3H. No significant contribution of radiogenic 4He was found, corresponding to the low residence times mostly in the range of one to three years. Despite complications during sampling, conditions of a perched aquifer could be confirmed by replicate samples at one drip site. Here, the excess air indicator ΔNe was about 10 %, comparable to typical values found in aquifers in mid-latitudes. The mean 3H–3He age of 2.1 years at this site presumably refers to the residence time in the perched aquifer and is lower than the entire transit time of 3.4 years estimated from the tritium data. 相似文献
972.
Thaler T Guo LN Steib AK Raducan M Karaghiosoff K Mayer P Knochel P 《Organic letters》2011,13(12):3182-3185
Sulfoxide-alkene hybrids are introduced as a new class of chiral heterodentate ligands for the Hayashi-Miyaura reaction. The synthesis of these ligands was achieved without the use of protecting groups. A chiral resolution was performed via simple column-chromatographic separation of the diastereomeric ligands. Both diastereomers proved to be excellent ligands in Rh-catalyzed 1,4-addition reactions, furnishing chiral products with high enantioselectivities and, remarkably, opposite stereoconfigurations. 相似文献
973.
En route to a comprehensive set of hydroxylactone building blocks (4R,5R)-, (4R,5S)-, (4S,5R)-, and (4S,5S)-5a, Sharpless asymmetric dihydroxylations of allylic chlorides (E)- and (Z)-9 were performed. They delivered the four stereoisomers of diol 10 with up to 92% ee and absolute configurations, which were proven to be in accordance with the Sharpless mnemonic. 相似文献
974.
El-Rafei A Engelhorn T Wärntges S Dörfler A Hornegger J Michelson G 《Magnetic resonance imaging》2011,29(8):1076-1087
Glaucoma is an optic neuropathy affecting the entire visual system. The understanding of the glaucoma mechanism and causes remains unresolved. Diffusion tensor imaging (DTI) has been used to analyze the optic nerve and optic radiation showing global fiber abnormalities associated with glaucoma. Nevertheless, the complex structure of the optic radiation and the limitations of DTI make the localization of the glaucoma effect a difficult task. The aim of this work is to establish a framework for the determination of the local changes of the optic radiation due to glaucoma using DTI. The proposed system utilizes a semiautomated algorithm to produce an efficient identification of the optic radiation. Segmented optic radiations are transformed to a unified space using shape-based nonrigid registration. Using the deformation fields that resulted from the registration, the maps of the diffusion tensor-derived parameters are transformed to the unified space. This allows for statistical voxel-wise analysis to produce significant abnormality maps. The proposed system is applied to a group of 13 glaucoma patients and a normal control group of 10 subjects. The groups are age matched to eliminate the age effect on the analysis. Diffusion-related parameters (axial, radial and mean diffusivities) and an anisotropy index (fractional anisotropy) are studied. The anisotropy analysis indicates that the majority of the significant voxels show decreased fractional anisotropy in the glaucoma patients compared with the control group. In addition, the significant regions are mainly distributed in the middle (in reference to anterior–posterior orientation) of the optic radiation. Glaucoma subjects have increased radial diffusivity and mean diffusivity significant voxels with a main concentration in the proximal part of the right optic radiation. The proposed analysis provides a framework to capture the significant local changes of the optic radiation due to glaucoma. The preliminary analysis suggests that the glaucomatous optic radiation may suffer from localized white matter degeneration. The framework facilitates further studies and understanding of the pathophysiology of glaucoma. 相似文献
975.
We report on a large‐scale synthesis of F‐PNA trimer 10 and PNA trimer 11 . The key improvement is the facile two‐step synthesis of (2,4‐difluoro‐5‐methylphenyl)acetic acid ( 2 ). Water solubility of the corresponding F‐PNA oligomer 10 was achieved by synthesizing solubility enhancer 5a , which is twofold positively charged and only consists of inherent structural elements of PNA. Protected and unpaired PNA n‐mers exist in a mixture of 2n conformers undergoing slow exchange and leading to complicated NMR spectra. Structure analysis was improved by recording 1H‐ and 13C‐NMR spectra at elevated temperatures above the coalescence point. Fully protected backbone derivatives show sharp resonances where expected, and spectra of protected PNAs are remarkably simplified, thereby allowing an interpretation for the first time. Both trimers 10 and 11 are considered as building blocks for a self‐replicating system based on PNA. 相似文献
976.
Winter P Swatschek J Willot M Radtke L Olbrisch T Schäfer A Christmann M 《Chemical communications (Cambridge, England)》2011,47(44):12200-12202
Merging J?rgensen's and MacMillan's organocatalytic aldehyde chlorinations enables the synthesis of chiral vinylcyclopropanes and (-)-cis-aerangis lactone via terpene-derived 1,2-epoxides. 相似文献
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