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Malte Drescher 《Chemie in Unserer Zeit》2012,46(3):150-157
During the last two decades electron paramagnetic resonance (EPR) witnessed a tremendous methodological and instrumental development, in particular in the areas of pulsed EPR and double resonance techniques. Often in combination with site‐directed spin‐labeling these techniques are applied within different subdisciplines in chemistry and in particular in biostructure research. Applications on the intrinsically disordered protein Alpha‐Synuclein associated with Parkinson's disease are used to illustrate the potential of modern EPR spectroscopy. 相似文献
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Venkatraman Ramanujam Cyril Charlier Ad Bax 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(43):15453-15456
In aqueous solution, many biochemical reaction pathways involve reaction of an aldehyde with an amine, which progresses through generally unstable, hydrated and dehydrated, Schiff base intermediates that often are unobservable by conventional NMR. There are 4 states in the relevant equilibrium: 1) gem‐diol, 2) aldehyde, 3) hemiaminal, and 4) Schiff base. For the reaction between protein amino groups and DOPAL, a highly toxic metabolite of dopamine, the 1H resonances of both the hemiaminal and the dehydrated Schiff base can be observed by CEST NMR, even when their populations fall below 0.1 %. CEST NMR reveals the quantitative exchange kinetics between reactants and Schiff base intermediates, explaining why the Schiff base NMR signals are rarely observed. The reactivity of DOPAL with Nα‐amino groups is greater than with lysine N?‐amines and, in the presence of O2, both types of Schiff base DOPAL–peptide intermediates rapidly react with free DOPAL to irreversibly form dicatechol pyrrole adducts. 相似文献
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α‐Synuclein (α‐S) protein is expressed in presynaptic terminals in the central nervous system. The aggregation of α‐S is implicated in the pathogenesis of Parkinson’s disease (PD). In this report, the interaction of α‐S with clioquinol (CQ) was investigated in the presence of Cu(II) ions using electrochemistry, as well as Thioflavin T‐based fluorescence and Congo Red‐based UV‐Vis studies. In the presence of CQ, the α‐S aggregation rate was observed to decrease. The preliminary results showed promise in the future development of CQ derivatives as novel small molecule therapeutic agents with potential efficacy targeting α‐S in PD therapy. 相似文献
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The aggregation of alpha-synuclein in the dopaminergic neurons of the substantia nigra is a critical step in the Parkinson's disease (PD). The etiology of the disease is unknown but recent epidemiological and experimental studies have renewed interest in the hypothesis that environmental factors, especially herbicides and metals, have a role on the pathogenesis of PD. For the first time, the association constants of alpha-synuclein with five herbicides have been calculated using a capillary electrophoresis (CE) method. In addition, the effect of a number of metals on this binding has been investigated. It appears that the herbicides preferentially bind to a partially folded intermediate conformation of alpha-synuclein induced by manganese, aluminium, cadmium, copper and zinc. Then, metal increases the synuclein-herbicide association. However, this study shows contrasting actions with the antibiotic rifampicin and magnesium addition leading to a decrease of the alpha-synuclein-herbicide interaction even if other metals are present in the bulk solvent. Considering epidemiological studies, all these results suggest an underlying molecular basis for PD and related body diseases. 相似文献
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