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1.
Chris H. Hill Agnete H. Viuff Samantha J. Spratley Stéphane Salamone Stig H. Christensen Randy J. Read Nigel W. Moriarty Henrik H. Jensen Janet E. Deane 《Chemical science》2015,6(5):3075-3086
Krabbe disease is a devastating neurodegenerative disorder characterized by rapid demyelination of nerve fibers. This disease is caused by defects in the lysosomal enzyme β-galactocerebrosidase (GALC), which hydrolyzes the terminal galactose from glycosphingolipids. These lipids are essential components of eukaryotic cell membranes: substrates of GALC include galactocerebroside, the primary lipid component of myelin, and psychosine, a cytotoxic metabolite. Mutations of GALC that cause misfolding of the protein may be responsive to pharmacological chaperone therapy (PCT), whereby small molecules are used to stabilize these mutant proteins, thus correcting trafficking defects and increasing residual catabolic activity in cells. Here we describe a new approach for the synthesis of galacto-configured azasugars and the characterization of their interaction with GALC using biophysical, biochemical and crystallographic methods. We identify that the global stabilization of GALC conferred by azasugar derivatives, measured by fluorescence-based thermal shift assays, is directly related to their binding affinity, measured by enzyme inhibition. X-ray crystal structures of these molecules bound in the GALC active site reveal which residues participate in stabilizing interactions, show how potency is achieved and illustrate the penalties of aza/iminosugar ring distortion. The structure–activity relationships described here identify the key physical properties required of pharmacological chaperones for Krabbe disease and highlight the potential of azasugars as stabilizing agents for future enzyme replacement therapies. This work lays the foundation for new drug-based treatments of Krabbe disease. 相似文献
2.
Henrik Kalisch 《Comptes Rendus Mathematique》2005,341(7):457-460
In this Note, it is shown that a Fourier Galerkin approximation of the Korteweg–de Vries equation with periodic boundary conditions converges exponentially fast if the initial data can be continued analytically to a strip about the real axis. To cite this article: H. Kalisch, C. R. Acad. Sci. Paris, Ser. I 341 (2005). 相似文献
3.
4.
Christophe Roussel Loc Dayon Henrik Jensen Hubert H. Girault 《Journal of Electroanalytical Chemistry》2004,570(2):187-199
A series of electrogenerated selective electrophiles based on substituted benzoquinones has been characterized as tags for l-cysteine and cysteine residues in proteins. The electrophiles are generated electrochemically from the corresponding hydroquinones. It is shown from mass spectrometry analysis that the electrogenerated benzoquinone can tag the biomolecules. The rate constants pertaining to the addition of l-cysteine onto the electrogenerated benzoquinones have been determined using electrochemical techniques. The substitution patterns have been unraveled leading to the assessment of site-specific rate constants. It is shown that the rate constants are primarily dependent on the electronic nature of the substituents as expressed by the Hammett substitution constant. The apparent tagging yields observed for l-cysteine in nanospray mass spectrometry experiments do not correspond to the yields expected from the electrochemical study, as the ionisation efficiencies are highly dependent on the tag. Finally, the on-line tagging has been tested using β-lactoglobulin A and myoglobin. Based on these results, it is concluded that the tagging reaction is selective towards cysteine when it takes place in the nanospray interface. The results show that the methodology presented can be used for a rapid characterization and identification of reactive sites in biomolecules. 相似文献
5.
In this paper we prove the equivalence of various algebraically or geometrically defined assembly maps used in formulating the main conjectures in K- and L-theory, and C*-theory.Partially supported by NSERC grant A4000 and NSF grant DMS 9104026. The authors also wish to thank the SFB für Geometrie und Analysis, Münster, and the Max Planck Institut für Mathematik, Bonn, for their hospitality and support.Received: 7 May 2001 相似文献
6.
What features characterize complex system dynamics? Power laws and scale invariance of fluctuations are often taken as the hallmarks of complexity, drawing on analogies with equilibrium critical phenomena. Here we argue that slow, directed dynamics, during which the system's properties change significantly, is fundamental. The underlying dynamics is related to a slow, decelerating but spasmodic release of an intrinsic strain or tension. Time series of a number of appropriate observables can be analyzed to confirm this effect. The strain arises from local frustration. As the strain is released through “quakes,” some system variable undergoes record statistics with accompanying log‐Poisson statistics for the quake event times. We demonstrate these phenomena via two very different systems: a model of magnetic relaxation in type II superconductors and the Tangled Nature model of evolutionary ecology and show how quantitative indications of aging can be found. © 2004 Wiley Periodicals, Inc. Complexity 10: 49–56, 2004 相似文献
7.
We show that reductions of KP hierarchies related to the loop algebra of SLn with homogeneous gradation give solutions of the Darboux-Egoroff system of PDE's. Using explicit dressing matrices of the Riemann-Hilbert problem generalized to include a set of commuting additional symmetries, we construct solutions of the Witten– Dijkgraaf–E. Verlinde–H. Verlinde equations. 相似文献
8.
The mechanism of ozone formation has been studied using 16O and 18O2. High-resolution microwave spectroscopy was used to measure the amounts of the isotopomeric ozone species formed. The study is hampered by the very rapid exchange process between the reactants, that tends to scramble the isotopes and hence give a 2:1 statistical ratio between the two possible isotopomers. We have found a strategy to come around this difficulty and conclude that the mechanism is a simple end-on-addition. 相似文献
9.
1-(3-Alkyl-2,3-dideoxy-alpha,beta-D-erythro-pentofuranosyl)uracils and 1-(3-alkyl-2,3-dideoxy-alpha,beta-D-threo-pentofuranosyl)uracils have been prepared from (E)-4,5-di-O-acetyl-2,3-dideoxy-aldehydo-D-glycero-pent-2-enose by a Michael addition reaction of the appropriate organocopper reagent followed in subsequent order by glycosidation of the resulting 3-alkyl-4,5-diacetoxypentanal with methanolic hydrogen chloride, protection with p-methoxybenzoyl chloride, and trimethylsilyl triflate catalyzed coupling with 2,4-di-O-(trimethylsilyl)uracil. The nucleosides were deprotected by treatment with 33% methylamine in absolute ethanol and separated by reversed-phase HPLC. 相似文献
10.
Henrik Stetkær 《Journal of Functional Analysis》2007,252(1):1-33
We extend results on square integrable representations of a locally compact group to subrepresentations of a representations induced from a character of a closed subgroup. We do so working in the framework of quotient representations of ∗-algebras. 相似文献