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111.
112.
AbstractThe reactions of methyl radicals with MII-(ntp)(H2O)2 complexes were studied. The formation of an unstable intermediate (ntp)(H2O)MIII-CH3 is observed. This reaction is an equilibrium process, i.e. the MIII-C bond decomposes via homolysis. The (ntp)(H2O)MIII-CH3 complexes isomerize to a more stable form. The results compared to those obtained in analogous reactions of the MII-(nta)(H2O)2 complexes were shown to be similar with one exception – for the nta complexes no isomerization process is observed. 相似文献
113.
Jing Zhao Yanan Zhu Xuehong Song Yuanyuan Xiao Guowei Su Xinyue Liu Zhangjie Wang Yongmei Xu Jian Liu David Eliezer Trudy F. Ramlall Guy Lippens James Gibson Fuming Zhang Robert J. Linhardt Lianchun Wang Chunyu Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(5):1834-1843
Prion-like transcellular spreading of tau in Alzheimer's Disease (AD) is mediated by tau binding to cell surface heparan sulfate (HS). However, the structural determinants for tau–HS interaction are not well understood. Microarray and SPR assays of structurally defined HS oligosaccharides show that a rare 3-O-sulfation (3-O-S) of HS significantly enhances tau binding. In Hs3st1−/− (HS 3-O-sulfotransferase-1 knockout) cells, reduced 3-O-S levels of HS diminished both cell surface binding and internalization of tau. In a cell culture, the addition of a 3-O-S HS 12-mer reduced both tau cell surface binding and cellular uptake. NMR titrations mapped 3-O-S binding sites to the microtubule binding repeat 2 (R2) and proline-rich region 2 (PRR2) of tau. Tau is only the seventh protein currently known to recognize HS 3-O-sulfation. Our work demonstrates that this rare 3-O-sulfation enhances tau–HS binding and likely the transcellular spread of tau, providing a novel target for disease-modifying treatment of AD and other tauopathies. 相似文献
114.
Steffen H. Symoens Syam Ukkandath Aravindakshan Florence H. Vermeire Kevin De Ras Marko R. Djokic Guy B. Marin Marie-Françoise Reyniers Kevin M. Van Geem 《国际化学动力学杂志》2019,51(11):872-885
Automatically generated kinetic networks are ideally validated against a large set of accurate, reproducible, and easy-to-model experimental data. However, although this might seem simple, it proves to be quite challenging. QUANTIS, a publicly available Python package, is specifically developed to evaluate both the precision and accuracy of experimental data and to ensure a uniform, quick processing, and storage strategy that enables automated comparison of developed kinetic models. The precision is investigated with two clustering techniques, PCA and t-SNE, whereas the accuracy is probed with checks for the conservation laws. First, the developed tool processes, evaluates, and stores experimental yield data automatically. All data belonging to a given experiment, both unprocessed and processed, are stored in the form of an HDF5 container. The demonstration of QUANTIS on three different pyrolysis cases showed that it can help in identifying and overcoming instabilities in experimental datasets, reduce mass and molar balance closure discrepancies, and, by evaluating the visualized correlation matrices, increase understanding in the underlying reaction pathways. Inclusion of all experimental data in the HDF5 file makes it possible to automate simulating the experiment with CHEMKIN. Because of the employed InChI string identifiers for molecules, it is possible to automate the comparison experiment/simulation. QUANTIS and the concepts demonstrated therein is a potentially useful tool for data quality assessment, kinetic model validation, and refinement. 相似文献
115.
Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties
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Sara Lefevre Dawei Zhang Estelle Godart Marion Jean Dr. Nicolas Vanthuyne Jean‐Christophe Mulatier Dr. Jean‐Pierre Dutasta Dr. Laure Guy Prof. Alexandre Martinez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(6):2068-2074
A convenient and efficient gram‐scale synthesis for enantiopure hemicryptophane–tren (tren=tris(2‐aminoethyl)amine) derivatives has been developed. The four‐step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway. The assignments of the absolute configurations have been performed by electronic circular dichroism and the enantiopurity was determined by NMR spectroscopy in the presence of enantiopure camphor sulfonic acid. To highlight the interest of such compounds, the recognition of norephedrine neurotransmitter was investigated and showed a remarkable enantioselectivity towards the C3 symmetrical hosts. Finally, this highly modular synthetic pathway was used to provide eight enantiopure hemicryptophanes with different sizes, shapes, and functionalities. These results underline the high potential of this approach, which could lead to many applications in chiral recognition or asymmetric supramolecular catalysis. 相似文献
116.
We investigate the expressivity of many-valued modal logics based on an algebraic structure with a complete linearly ordered lattice reduct. Necessary and sufficient algebraic conditions for admitting a suitable Hennessy–Milner property are established for classes of image-finite and (appropriately defined) modally saturated models. Full characterizations are obtained for many-valued modal logics based on complete BL-chains that are finite or have the real unit interval [0, 1] as a lattice reduct, including ?ukasiewicz, Gödel, and product modal logics. 相似文献
117.
Back Cover: Large‐Scale Synthesis of Helicene‐Like Molecules for the Design of Enantiopure Thin Films with Strong Chiroptical Activity (Chem. Eur. J. 10/2016)
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118.
Detrimental Ni(0) transfer in Kumada catalyst transfer polycondensation of benzo[2,1‐b:3,4‐b']dithiophene
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Anjan Bedi Julien De Winter Pascal Gerbaux Guy Koeckelberghs 《Journal of polymer science. Part A, Polymer chemistry》2016,54(12):1706-1712
This article deals with the Kumada Catalyst Transfer Polycondensation (KCTP) of 4,7‐dioctylbenzo[2,1‐b:3,4‐b']dithiophene ( BDP‐Oct ) using Ni(II) catalyst or In/cat combination. A combination of MALDI MS, GPC, and 31P NMR spectroscopy is used to reveal the failure of the KCTP of this particular monomer. Intermolecular transfer reactions to monomer appeared to prevent the formation of polymer. This result is remarkable, since isomeric benzo[1,2‐b:4,5‐b']dithiophene polymerizes in a controlled way. The presence of a “non‐aromatic double bond” in annulated monomers is discussed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1706–1712 相似文献
119.
Large‐Scale Synthesis of Helicene‐Like Molecules for the Design of Enantiopure Thin Films with Strong Chiroptical Activity
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Dr. Amina Bensalah‐Ledoux Delphine Pitrat Thibault Reynaldo Dr. Monika Srebro‐Hooper Barry Moore II Prof. Jochen Autschbach Dr. Jeanne Crassous Prof. Stéphan Guy Dr. Laure Guy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3333-3346
Helicenes are fascinating molecules owing to their unusual properties and applications in many fields from catalysis to organic electronics. Herein, we report a straightforward pathway for the synthesis of helicene‐like molecules on a gram scale in an enantiopure form. Thin‐film materials with good propagating optical properties and very high chiroptical responses have been grown by using pulsed laser ablation without altering the structure or the enantiopurity of the molecules. Moreover, electronic and vibrational circular dichroism spectroscopies coupled with theoretical calculations enabled some dependences of the chiroptical properties with the structure to be highlighted, for example, effects of rigidification, aromatization, or the state of matter (liquid versus solid). 相似文献
120.