Search results for "Proton"
showing 10 items of 5886 documents
Open-chain polyamine ligands bearing an anthracene unit - Chemosensors for logic operations at the molecular level
2001
In this work the absorption and the fluorescence emission properties as well as the protonation sequence of three open chain polyamine ligands of different dimensions bearing an anthracene unit were studied. The protonation and stability constants with Ni2+, Cu2+, Zn2+, and Cd2+ have been determined in 0.15 mol·dm−3 NaCl at 298.1 ± 0.1 K. The values of both protonation and stability constants follow the expected trends according to the number of nitrogen donors, sequence of chelate rings and hydrophilic−hydrophobic balance. Chelation enhancement of the fluorescence emission (CHEF) was observed for some complexes of these ligands with Zn2+ and Cd2+. In contrast the analog complexes containin…
A step forward in the development of superoxide dismutase mimetic nanozymes: the effect of the charge of the surface on antioxidant activity
2019
Two binucleating hezaaza macrocycles containing a pyridinol spacer have been prepared and characterised. Protonation studies indicate the deprotonation of the phenol group at relatively low pH values with the concomitant occurrence of a keto-enolic equilibrium. These ligands readily form binuclear Cu2+ and Zn2+ complexes as denoted by potentiometric and spectroscopic studies. The binding of the metals yields to the ready deprotonation of the phenol with the stabilisation of the keto form that results in complexes of greater stabilities than the analogous ones containing pyridine as spacer instead of pyridine. Mixed Cu2+–Zn2+-complexes were also detected in aqueous solutions containing equim…
Azonia spiro polyaza macrocycles containing biphenyl subunits as anion and cation receptors
2011
Abstract The reaction of N-Boc triprotected cyclam with bis(chloromethyl)biphenyl followed by the corresponding deprotection of the nitrogen atoms allows the preparation of receptor 3 containing an azonia spiro subunit. This receptor shows slightly increased basicity than cyclam, in particular for the formation of the appropriate triply charged species as a consequence of the reduced capacity of the structure present in 3 to stabilize the species with lower protonation degrees through the formation of intramolecular hydrogen bonds. The properties of 3 as a receptor for Cu2+ and Zn2+ and the anions derived from PO 4 3 − ( Pi ) , P 2 O 7 4 − ( PPi ) , P 3 O 10 5 − ( TPP ) and ATP have been st…
Metal ions modulate thermal aggregation of betalactoglobulin: a join chemical and physical characterization
2014
Abstract Molecular basis of the role played by Cu 2 + and Zn 2 + ions during the thermal aggregation processes of beta-lactoglobulin (BLG) was studied by using a joint application of different techniques. In particular, Raman spectroscopy was very useful in identifying the different effects caused by the two metals at molecular level (i.e. changes in His protonation state, disulfides bridge conformation, and micro-environment of aromatic residues), evidencing the primary importance of the protein charge distribution during the aggregation process. Both metal ions are able to act on this factor and favor the protein aggregation, but Zn 2 + is able to alter the natural conformational state of…
An Off-On-Off Fluorescent Sensor for pH Windows Based on the 13aneN4-Zn 2+ System
2016
International audience; The new ligand L was prepared and features a 13-membered tetraaza macrocyclic ring with a 1,8-naphthalimide fluorophore appended to a C atom of its backbone. The protonation constants of L as well as its complexation constants with Zn2+ ions were determined in 1:1 water/methanol solutions by potentiometric titrations. Fluorimetric pH titrations were performed with L alone and L in the presence of Zn2+ ions (1:1), and the species distributions (%) versus pH were compared. A window-shaped fluorescence trend was observed with pH for the L/Zn2+ system, which behaves as an off-on-off pH sensor. The on window is centred in the 6.5-7.5 pH range, in correspondence with the f…
Synthesis, Characterization, and Cu(2+) Coordination Studies of a 3-Hydroxy-4-pyridinone Aza Scorpiand Derivative.
2016
The synthesis, acid-base behavior, and Cu(2+) coordination chemistry of a new ligand (L1) consisting of an azamacrocyclic core appended with a lateral chain containing a 3-hydroxy-2-methyl-4(1H)-pyridinone group have been studied by potentiometry, cyclic voltammetry, and NMR and UV-vis spectroscopy. UV-vis and NMR studies showed that phenolate group was protonated at the highest pH values [log K = 9.72(1)]. Potentiometric studies point out the formation of Cu(2+) complexes of 1:2, 2:2, 4:3, 1:1, and 2:1 Cu(2+)/L1 stoichiometries. UV-vis analysis and electrochemical studies evidence the implication of the pyridinone moieties in the metal coordination of the 1:2 Cu(2+)/L1 complexes. L1 shows …
A measurement of the neutron to 199Hg magnetic moment ratio
2014
The neutron gyromagnetic ratio has been measured relative to that of the 199Hg atom with an uncertainty of 0.8 ppm. We employed an apparatus where ultracold neutrons and mercury atoms are stored in the same volume and report the result γn/γHg=3.8424574(30).
Atomistic Insights into Nitrogen-Cycle Electrochemistry: A Combined DFT and Kinetic Monte Carlo Analysis of NO Electrochemical Reduction on Pt(100)
2017
Electrocatalytic denitrification is a promising technology for the removal of NOx species in groundwater. However, a lack of understanding of the molecular pathways that control the overpotential and product distribution have limited the development of practical electrocatalysts, and additional atomic-level insights are needed to advance this field. Adsorbed NO has been identified as a key intermediate in the NOx electroreduction network, and the elementary steps by which it decomposes to NH4+, N2, NH3OH+, or N2O remain a subject of debate. Herein, we report a combined density functional theory (DFT) and kinetic Monte Carlo (kMC) study of this reaction on Pt(100), a catalytic surface that i…
Nano-sized I12L6 Molecular Capsules Based on the [N⋅⋅⋅I+⋅⋅⋅N] Halogen Bond
2017
Summary Self-assembly of pre-organized subunits with a concave overall shape is an effective strategy for the synthesis of supramolecular capsules. We report the synthesis of a cavitand-based hexameric capsule held together solely by 12 robust [N⋅⋅⋅I + ⋅⋅⋅N] halogen bonds and its characterization in solution and in the gas phase via 1 H NMR spectroscopy, diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY), and electrospray ionization mass spectrometry. The [N⋅⋅⋅I + ⋅⋅⋅N] halogen-bonded hexameric capsule was efficiently synthesized from the isolobal metallosupramolecular Ag + capsule by application of the [N⋅⋅⋅Ag + ⋅⋅⋅N] → [N⋅⋅⋅I + ⋅⋅⋅N] cation-exchange reaction.
Electronic and Steric Effects: How Do They Work in Ionic Liquids? The Case of Benzoic Acid Dissociation
2010
The need to have a measure of the strength of some substituted benzoic acids in ionic liquid solution led us to use the protonation equilibrium of sodium p-nitrophenolate as a probe reaction, which was studied by means of spectrophotometric titration at 298 K. In order to evaluate the importance of electronic effect of the substituents present on the aromatic ring, both electron-withdrawing and -donor substituents were taken into account. Furthermore, to have a measure of the importance of the steric effect of the substituents both para- and ortho-substituted benzoic acids were analyzed. The probe reaction was studied in two ionic liquids differing for the ability of the cation to give hydr…