Search results for "Protonation"
showing 10 items of 583 documents
Protonation and rearrangement of the tricyclo[4.2.2.22,5]dodeca-3,7,9,11-tetraene scaffold
2006
The biplanemers 2a,b contain enol ether substructures, which permit facile protonations of the π electron system. The subsequent ether cleavage is characterized by rearrangements of the polycyclic scaffold of the carbenium ions or the electroneutral primary products. Apart from the expected products 3a and 5a, a series of unexpected ketones and diketones (4a′, 9b, 10b, 11b, and 12b) were obtained.
Determination of Amino Acids by Micellar High-Performance Liquid Chromatography and Pre-column Derivatization withO-Phthalaldehyde and N-Acetyl-L-cys…
1995
Abstract Micellar liquid chromatography of proteic primary amino acids with pre-column derivatization with o-phthalaldehyde (OPA) and N-acetyl-L-cysteine was studied, using mobile phases containing a short-chain alcohol. The modification of pH gave a large variation of the retention as a result of the protonation of the carboxylate group of amino acids. Maximum resolution and adequate retentions were achieved with a 0.05 M sodium dodecyl sulphate/3% propanol mobile phase at pH 3. The reproducibility was lower than 1.0% at a 1 × 10−4 M concentration level and between 0.6 and 2.2% for 1 × 10−6 M. The determination of glycine, lysine, methionine and threonine in pharmaceutical formulations gav…
Coordination of copper(II) ions by α,β-dehydro-dipeptides. Potentiometric and spectroscopic study
1991
Abstract Potentiometric and spectroscopic data have shown that the double bond within dehydro-peptides considerably affects their behaviour as ligands relative to their saturated parents, with proton and copper(II) ions.
Coupling of the guanosine glycosidic bond conformation and the ribonucleotide cleavage reaction: implications for barnase catalysis.
2007
To examine the possible relationship of guanine-dependent GpA conformations with ribonucleotide cleavage, two potential of mean force (PMF) calculations were performed in aqueous solution. In the first calculation, the guanosine glycosidic (Gχ) angle was used as the reaction coordinate, and computations were performed on two GpA ionic species: protonated (neutral) or deprotonated (negatively charged) guanosine ribose O2 ′. Similar energetic profiles featuring two minima corresponding to the anti and syn Gχ regions were obtained for both ionic forms. For both forms the anti conformation was more stable than the syn, and barriers of ∼4 kcal/mol were obtained for the anti → syn transition. Str…
NMR Matrix Technique for Detecting Self Diffusion in Polymers
1979
A technique is discussed where monodisperse small spheres or cylindrical fibers of a polymer are embedded in a matrix of the corresponding fully deuterated polymer. On annealing the sample at a temperature above the glass transition the protonated macromolecules diffuse into the deuterated matrix and vice versa. Since the NMR spectrum depends upon the intermolecular proton proton dipolar coupling, the decrease of this coupling can be used to monitor the diffusion process. For particle diameters d ∼ 10−4 cm and annealing times t ∼ 105 s, extremely small diffusion constants D < d2/t are attainable. The NMR analysis of prospective diffusion experiments with polystyrene is discussed in some det…
ChemInform Abstract: Highly Enantioselective Protonation of the 3,4-Dihydro-2-methylnaphthalen-1(2H)-one Li-Enolate by TADDOLs.
2001
A series of nine TADDOLs (=α,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanols) 1a – 1i, have been tested as proton sources for the enantioselective protonation of the Li-enolate of 2-methyl-1-tetralone (=3,4-dihydro-2-methylnaphthalen-1(2H)-one). The enolate was generated directly from the ketone (with LiN(i-Pr)2 (LDA)/MeLi) or from the enol acetate (with 2 MeLi) or from the silyl enol ether (with MeLi) in CH2Cl2 or Et2O as the solvent (Scheme). The Li-enolate (associated with LiBr/LDA, or LiBr alone) was combined with 1.5 – 3.0 equiv. of the TADDOL at −78° by addition of the latter or by inverse addition. 2-Methyl-1-tetralone of (S)-configuration is formed (≤80% yield) with up to 99.5% sele…
Cu2+ Coordination Properties of a 2-Pyridine Heptaamine Tripod: Characterization and Binding Mechanism
2009
The synthesis, protonation, and Cu(2+) coordination chemistry of a tripodal heptaamine ligand (L(1)) functionalized with 2-pyridine fragments at the ends of its three branches are reported. L(1) presents six relatively high protonation constants followed by much more reduced constant that as indicated by the UV-vis and NMR data, occur on the pyridine fragments. p[H]-metric, ESI/MS(+), EPR and UV-vis data show that L(1) is able to form mono-, di-, and trinuclear Cu(2+) complexes. Slippage movements and molecular reorganizations have been observed to occur as a function of p[H] in the 1:1 Cu(2+) complexes. The kinetic studies showed that the complex formation is fast and proceeds through a di…
Star-Shaped Compounds Having 1,3,5-Triazine Cores
2003
The 1,3,5-triazine derivatives 1−4 having styryl or higher oligo(phenylenevinylene) chains in the 2-, 4-, and 6-positions represent star-shaped push-pull compounds. Alkoxy or dimethylamino groups on the peripheral benzene rings, which act as electron donors, and the central 1,3,5-triazine ring, which acts as an electron acceptor, cause intramolecular charge transfer (ICT) to occur in the absorption S0⇄S1. Protonation of the 1,3,5-triazine core enhances the effect, as demonstrated by a bathochromic shift; a secondary protonation on the dimethylamino groups, however, leads to the breakdown of the ICT. Thus, the yellow compound 1d first becomes violet and then colorless upon the addition of tr…
Effect of Protonated Organic Cations and Anion−π Interactions on the Magnetic Behavior of Hexabromorhenate(IV) Salts
2015
Two novel Re-IV compounds of formula (Hbpym)(2)[(ReBr6)-Br-IV]center dot 4H(2)O (1) and (H(4)biim)[(ReBr6)-Br-IV]center dot 4H(2)O (2) [Hbpym(+) = 2,2'-bipyrimidinium cation and H(4)biim(2+) = 2,2'-biimidazolium dication] have been prepared and magnetostructurally characterized. 1 and 2 exhibit distinct crystal packing, and the presence of weak intermolecular contacts, such as Re-Br...B-rRe (1 and 2), Re-Br center dot center dot center dot(H2O)center dot center dot center dot BrRe (1 and 2), and Re-Br center dot center dot center dot pi center dot center dot center dot Br-Re (2), lead to different magnetic behaviors. While 1 is antiferromagnetic, 2 is a ferromagnetic compound and indeed the…
Star-Shaped Push-Pull Compounds Having 1,3,5-Triazine Cores
2006
The 1,3,5-triazines 9–11 having OPV chains in the 2-, 4- and 6-position represent star-shaped compounds which exhibit strong push-pull effects. Their long-wavelength absorption S0 S1 is characterized by an intramolecular charge transfer (ICT) from the dialkylamino group as electron donor D via the conjugated chain to the 1,3,5-triazine core as electron acceptor A. Protonation of the dialkylamino group removes the donor capability, whereas protonation of the 1,3,5-triazine ring enhances the acceptor strength. Thus, the prevailing protonation site has a crucial influence on the push-pull effect and the ICT. The transition energies ΔE (S0 S1) pass through a minimum for the second generation 10…