Search results for "molecular conformation"
showing 10 items of 376 documents
Rare Example of μ-Nitrito-1κ2O,O′:2κO Coordinating Mode in Copper(II) Nitrite Complexes with Monoanionic Tridentate Schiff Base Ligands: Structure, M…
2008
Three new copper(II) complexes, [CuL(1)(NO(2))](n) (1), [CuL(2)(NO(2))] (2), and [CuL(3)(NO(2))] (3), with three similar tridentate Schiff base ligands [HL(1) = 6-amino-3-methyl-1-phenyl-4-azahept-2-en-1-one, HL(2) = 6-amino-3-methyl-1-phenyl-4-azahex-2-en-1-one, and HL(3) = 6-diethylamino-3-methyl-1-phenyl-4-azahex-2-en-1-one] have been synthesized and characterized structurally and magnetically. In all three complexes, the tridentate Schiff base ligand and one oxygen atom of the nitrite ion constitute the equatorial plane around Cu(II), whereas the second oxygen atom of the nitrite ligand coordinates to one of the axial positions. In 1, this axially coordinated oxygen atom of the nitrite …
Conformational investigation of ?,?-dehydropeptides.N-acetyl-(E)-dehydrophenylalanineN?-methylamide: conformational properties from infrared and theo…
2005
N-Acetyl-(E)-dehydrophenylalanine N'-methylamide [Ac-(E)-DeltaPhe-NHMe], one of a few representative (E)-alpha,beta-dehydroamino acids, was studied by FTIR in dichloromethane and acetonitrile. To support spectroscopic interpretations and to gain some deeper insight into the Ac-(E)-DeltaPhe-NHMe molecule, the Ramachandran potential energy surface was calculated by the B3LYP/6-31G*//HF/3-21G method and the conformers localized were fully optimized at the B3LYP/6-31 + G** level. The spectra and calculations were compared with those of the related molecules Ac-DeltaAla-NHMe and Ac-(Z)-DeltaPhe-NHMe. The title compound assumes two conformational states in equilibrium in dichloromethane solution …
The Molecular and Crystal Structure of tert-Butyl N.ALPHA.-tert-Butoxycarbonyl-L-(S-trityl)cysteinate and the Conformation-Stabilizing Function of We…
2001
The title compound, C31H37NO4S [systematic name: (R)-tert-butyl-2-[(tert-butoxycarbonyl)amino]-3-(tritylsulfanyl)propanoate] is an L-cysteine derivative with three functions: NH2, COOH and SH, blocked by protecting groups tert-butoxycarbonyl, tert-butyl and trityl, respectively. The main chain of the molecule adopts the extended, nearly all-trans C5 conformation with the intramolecular N-H...O=C hydrogen bond. The urethane group is not involved in any intermolecular hydrogen bonding. Only weak intermolecular hydrogen bonds and hydrophobic contacts are observed in the crystal structure. These are C-H...O hydrogen bonds and CH/pi interactions with donor...acceptor distances, C...O ca. 3.5 A a…
The first unpaired electron placed inside a C3-symmetry P-chirogenic cluster
2010
The Pd(3)(dppm*)(3)(CO)(n+) enantiomers (n = 2 (2), 1 (3)) were prepared either from (R,R)- or (S,S)-P-chirogenic bis(phenyl-m-xylylphosphino)methane (dppm*; 1) and Pd(OAc)(2) in the presence of CF(3)CO(2)H, CO and water (n = 2), and then by reductive electrolysis (n = 1). The stable enantiomeric [Pd(3)((S,S)-dppm*)(3)(CO)](+)˙ (3), is the first C(3)-symmetry radical-cation M-M bonded cluster, therefore the odd electron is delocalized onto the Pd(3) frame within this symmetry. The novel chiral species have been characterized by circular dichroism (CD) of both enantiomers of the Pd(3)(dppm*)(3)(CO)(2+) clusters (2) and by EPR spectroscopy for the Pd(3)((S,S)-dppm*)(3)(CO)(+)˙ paramagnetic co…
Synthesis, in vitro activity, and three-dimensional quantitative structure-activity relationship of novel hydrazine inhibitors of human vascular adhe…
2010
Vascular adhesion protein-1 (VAP-1) belongs to the semicarbazide-sensitive amine oxidases (SSAOs) that convert amines into aldehydes. SSAOs are distinct from the mammalian monoamine oxidases (MAOs), but their substrate specificities are partly overlapping. VAP-1 has been proposed as a target for anti-inflammatory drug therapy because of its role in leukocyte adhesion to endothelium. Here, we describe the synthesis and in vitro activities of novel series of VAP-1 selective inhibitors. In addition, the molecular dynamics simulations performed for VAP-1 reveal that the movements of Met211, Ser496, and especially Leu469 can enlarge the ligand-binding pocket, allowing larger ligands than those s…
Synthetically persistent, self assembled [V(IV)2V(V)4] polyoxovanadates: facile synthesis, structure and magnetic analysis.
2011
Slow diffusion in a H-tube at room temperature of a methanolic solution of [VO(acac)(2)] (Hacac = acetylacetone) and 1,10-phenanthroline (phen) or 2,2'-bipyridine (bipy) into an aqueous solution of sodium pyrophosphate (Na(4)P(2)O(7)) resulted in the serendipitous formation of X-ray quality crystals of mixed-valent, hexameric oxovanadates of general formula [V(6)O(12)(OCH(3))(4)(L)(4)]·solv [L = 1,10-phenanthroline (phen) for 1· 2CH(3)OH · 4H(2)O (1a), and 2,2'-bipyridine (bipy) for 2· 4H(2)O (2a)]. These were characterized by single-crystal X-ray diffraction, IR, elemental and thermogravimetric analysis (TGA). A facile, rationalized synthetic route for the isolation of 1a and 2a could be e…
A DFT study of [3 + 2] cycloaddition reactions of an azomethine imine with N-vinyl pyrrole and N-vinyl tetrahydroindole
2016
The mechanism and selectivities of the [3+2] cycloaddition (32CA) reactions of azomethine imine (AI) 8 with two N-vinyl five-membered heterocycles (NVFH), 9a and 9b, have been theoretically studied using DFT methods at the MPWB1K/6-31G(d) computational level. The possible ortho/meta regio- and endo/exo stereoselective channels were explored and characterised. The low polar character of these 32CA reactions, which is the consequence of the high nucleophilic character of both reagents, as well as the non-effective reactivity of these NVFH as nucleophiles, accounts for the high calculated activation energies, 16.1 (9a) and 16.8 (9b) kcalmol-1 in chlorobenzene. Analysis of the relative electron…
A Molecular Electron Density Theory Study of the Reactivity of Azomethine Imine in [3+2] Cycloaddition Reactions
2017
The electronic structure and the participation of the simplest azomethine imine (AI) in [3+2] cycloaddition (32CA) reactions have been analysed within the Molecular Electron Density Theory (MEDT) using DFT calculations at the MPWB1K/6-311G(d) level. Electron localisation function (ELF) topological analysis reveals that AI has a pseudoradical structure, while the conceptual DFT reactivity indices characterise this TAC as a moderate electrophile and a good nucleophile. The non-polar 32CA reaction of AI with ethylene takes place through a one-step mechanism with low activation energy, 5.3 kcal/mol-1. A bonding evolution theory (BET) study indicates that this reaction takes place through a non-…
Energy transfers in monomers, dimers, and trimers of zinc(II) and palladium(II) porphyrins bridged by rigid Pt-containing conjugated organometallic s…
2009
A series of linear monomers (spacer-M(P)), dimers (M(P)-spacer-M'(P)), and trimers (M(P)-spacer-M'(P)-spacer-M(P)) of spacer/metalloporphyrin systems (M' = Zn, M = Zn, Pd, P = porphyrin, and spacer = trans-C(6)H(4)C[triple bond]CPtL(2)C[triple bond]CC(6)H(4)- (L = PEt(3))) including mixed metalloporphyrin compounds, were synthesized and characterized. The S(1) and T(1) energy transfers Pd(P)*--Zn(P) occur with rates of approximately 2 x 10(9) s(-1), S(1), and 0.15 x 10(3) (slow component) and 4.3 x 10(3) s(-1) (fast component), T(1). On the basis of a literature comparison with a related dyad, the Pt atom in the conjugated chain slows down the transfers. The excitation in the absorption ban…
Quenching of fluorescein-conjugated lipids by antibodies. Quantitative recognition and binding of lipid-bound haptens in biomembrane models, formatio…
1992
Three model biomembrane systems, monolayers, micelles, and vesicles, have been used to study the influence of chemical and physical variables of hapten presentation at membrane interfaces on antibody binding. Hapten recognition and binding were monitored for the anti-fluorescein monoclonal antibody 4–4-20 generated against the hapten, fluorescein, in these membrane models as a function of fluorescein-conjugated lipid architecture. Specific recognition and binding in this system are conveniently monitored by quenching of fluorescein emission upon penetration of fluorescein into the antibody's active site. Lipid structure was shown to play a large role in affecting antibody quenching. Interes…