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81.
Diggle SP Matthijs S Wright VJ Fletcher MP Chhabra SR Lamont IL Kong X Hider RC Cornelis P Cámara M Williams P 《Chemistry & biology》2007,14(1):87-96
Pseudomonas aeruginosa produces 2-heptyl-3-hydroxy-4(1H)-quinolone (PQS), a quorum-sensing (QS) signal that regulates numerous virulence genes including those involved in iron scavenging. Biophysical analysis revealed that 2-alkyl-3-hydroxy-4-quinolones form complexes with iron(III) at physiological pH. The overall stability constant of 2-methyl-3-hydroxy-4-quinolone iron(III) complex was log beta(3) = 36.2 with a pFe(3+) value of 16.6 at pH 7.4. PQS was found to operate via at least three distinct signaling pathways, and its precursor, 2-heptyl-4-quinolone (HHQ), which does not form an iron complex, was discovered to function as an autoinducer molecule per se. When PQS was supplied to a P. aeruginosa mutant unable to make pyoverdine or pyochelin, PQS associated with the cell envelope and inhibited bacterial growth, a finding that reveals a secondary function for PQS in iron entrapment to facilitate siderophore-mediated iron delivery. 相似文献
82.
Houriez C Ferré N Flament JP Masella M Siri D 《The journal of physical chemistry. A》2007,111(45):11673-11682
The electronic and structural properties of dihydronitroxide/water clusters are investigated and compared to the properties of formaldehyde/water clusters. Exploring the stationary points of their potential energy surfaces (structurally, vibrationally, and energetically) and characterizing their hydrogen bonds (by both atoms in molecules and natural bond orbitals methods) clearly reveal the strong similarity between these two kind of molecular systems. The main difference involves the nature of the hydrogen bond taking place between the X-H bond and the oxygen atom of a water molecule. All the properties of the hydrogen bonds occurring in both kind of clusters can be easily interpreted in terms of competition between intermolecular and intramolecular hyperconjugative interactions. 相似文献
83.
Caroline Delehedde Marcel Culcasi Emilie Ricquebourg Mathieu Cassien Didier Siri Bruno Blaive Sylvia Pietri Sophie Thtiot-Laurent 《Molecules (Basel, Switzerland)》2022,27(14)
In order to discover new 31P NMR markers for probing subtle pH changes (<0.2 pH unit) in biological environments, fifteen new conformationally constrained or sterically hindered α-aminophosphonates derived from diethyl(2-methylpyrrolidin-2-yl)phosphonate were synthesized and tested for their pH reporting and cytotoxic properties in vitro. All compounds showed near-neutral pKas (ranging 6.28–6.97), chemical shifts not overlapping those of phosphorus metabolites, and spectroscopic sensitivities (i.e., chemical shifts variation Δδab between the acidic and basic forms) ranging from 9.2–10.7 ppm, being fourfold larger than conventional endogenous markers such as inorganic phosphate. X-ray crystallographic studies combined with predictive empirical relationships and ab initio calculations addressed the inductive and stereochemical effects of substituents linked to the protonated amine function. Satisfactory correlations were established between pKas and both the 2D structure and pyramidalization at phosphorus, showing that steric crowding around the phosphorus is crucial for modulating Δδab. Finally, the hit 31P NMR pH probe 1b bearing an unsubstituted 1,3,2-dioxaphosphorinane ring, which is moderately lipophilic, nontoxic on A549 and NHLF cells, and showing pKa = 6.45 with Δδab = 10.64 ppm, allowed the first clear-cut evidence of trans-sarcolemmal pH gradients in normoxic Dictyostelium discoideum cells with an accuracy of <0.05 pH units. 相似文献
84.
85.
Tailoring of Polarizing Agents in the bTurea Series for Cross‐Effect Dynamic Nuclear Polarization in Aqueous Media 下载免费PDF全文
Claire Sauvée Dr. Gilles Casano Dr. Sébastien Abel Prof. Antal Rockenbauer Dr. Dimitry Akhmetzyanov Dr. Hakim Karoui Prof. Didier Siri Dr. Fabien Aussenac Dr. Werner Maas Dr. Ralph T. Weber Prof. Thomas Prisner Dr. Mélanie Rosay Prof. Paul Tordo Dr. Olivier Ouari 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5598-5606
A series of 18 nitroxide biradicals derived from bTurea has been prepared, and their enhancement factors ? (1H) in cross‐effect dynamic nuclear polarization (CE DNP) NMR experiments at 9.4 and 14.1 T and 100 K in a DNP‐optimized glycerol/water matrix (“DNP juice”) have been studied. We observe that ? (1H) is strongly correlated with the substituents on the polarizing agents, and its trend is discussed in terms of different molecular parameters: solubility, average e–e distance, relative orientation of the nitroxide moieties, and electron spin relaxation times. We show that too short an e–e distance or too long a T1e can dramatically limit ? (1H). Our study also shows that the molecular structure of AMUPol is not optimal and its ? (1H) could be further improved through stronger interaction with the glassy matrix and a better orientation of the TEMPO moieties. A new AMUPol derivative introduced here provides a better ? (1H) than AMUPol itself (by a factor of ca. 1.2). 相似文献
86.
The C-ON bond homolysis in alkoxyamine 2a can be chemically triggered by the protonation of the 4-pyridylalkyl fragment. The resulting 15-fold increase in k(d) (Chem. Commun. 2011, 47, 4291-4293) was investigated experimentally and theoretically by quaternization of the pyridyl moiety using methylating (MeOTs), acylating (AcCl), and benzylating (PhCH(2)Br) agents as well as by oxidation of the pyridyl moiety into N-oxide and by the formation of a dative bond with BH(3) as a Lewis acid. 相似文献
87.
Gilles Olive Dianne D. Ellis Didier Siri Franois Le Moigne Martin Lutz Anthony L. Spek Paul Tordo Jean‐Pierre Reboul 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(6):720-722
The title compound, C4H11NO6P2, reveals a two‐dimensional network of P—O—H?O=P and N—H?O=P hydrogen‐bond interactions, forming molecular slabs parallel with the (010) plane. One O—H?O interaction is distinct within these sets: whilst forming the shortest intermolecular hydrogen bond, it possesses a short P—O(H) bond of 1.5291 (10) Å. Weak C—H?O contacts link individual stacks to produce a three‐dimensional array. The compound is zwitterionic: one H atom from a P—O—H group has transferred to the pyrrolidine ring N atom. 相似文献
88.
Gerardo F. Santori Mónica L. Casella Guillermo J. Siri Hugo R. Adúriz Osmar A. Ferrettia 《Reaction Kinetics and Catalysis Letters》2002,75(2):225-230
The present work reports the effect of metal particle size on the selectivity to crotyl alcohol (SUOL) in the liquid phase hydrogenation of crotonaldehyde over SiO2 and a-Al2O3-supported Pt and Pt-Sn catalysts. It was demonstrated that, for the monometallic catalysts, a higher particle size led to a higher SUOL, while for the bimetallic catalysts, this effect was not so important. 相似文献
89.
90.
Dr. Zhongrui Chen Dr. Rose Haddoub Jérôme Mahé Dr. Gabriel Marchand Prof. Denis Jacquemin Dr. Judicaelle Andeme Edzang Dr. Gabriel Canard Dr. Daniel Ferry Dr. Olivier Grauby Alain Ranguis Dr. Olivier Siri 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(49):17820-17832
Pre‐ and postintroduction of substituents with respect to the macrocyclization step leads to previously unknown N‐substituted azacalixphyrins. The stepwise synthetic approach has been studied in detail to highlight the key role of the N‐substituents of the precursors and/or intermediates in terms of reactivity. Based on a combined experimental and theoretical investigation, the relationship between the properties of the macrocycles and their degree of substitution is rationalized. Depending on the nature of the N‐substituents, the formation of supramolecular ribbon‐like structures could also be observed, as demonstrated by combined TEM, SEM, AFM, and FTIR experiments. 相似文献