Search results for " bonding"
showing 10 items of 934 documents
Infrared Difference Spectroscopy of Proteins: From Bands to Bonds
2020
Infrared difference spectroscopy probes vibrational changes of proteins upon their perturbation. Compared with other spectroscopic methods, it stands out by its sensitivity to the protonation state, H-bonding, and the conformation of different groups in proteins, including the peptide backbone, amino acid side chains, internal water molecules, or cofactors. In particular, the detection of protonation and H-bonding changes in a time-resolved manner, not easily obtained by other techniques, is one of the most successful applications of IR difference spectroscopy. The present review deals with the use of perturbations designed to specifically change the protein between two (or more) functional…
Isolated glyoxylic acid-water 1:1 complexes in low temperature argon matrices
2015
Abstract The 1:1 hydrogen bonded complexes between glyoxylic acid (GA) and water are studied in low temperature argon matrices. Four different complex structures were found in deposited matrices. The lowest energy conformer (T1) of GA was found to form complex, where the water molecule was attached to the opposite side of the intramolecular hydrogen bond in the molecule (T1B). Interestingly, this complex was estimated to be +8.0 kJ mol −1 higher in energy than the most stable structure (T1A), where the water is inserted into the internal hydrogen bond, and also found in solid argon but in smaller abundance. For the second-lowest energy conformer of GA (T2), the two lowest-energy complex str…
Rhenium(I) and platinum(II) complexes with diimine ligands bearing acidic phenol substituents: hydrogen-bonding, acid-base chemistry and optical prop…
2010
Tricarbonylchloro-rhenium(i) (1-4) and catecholato-platinum(ii) complexes (6, 7) of diimine ligands bearing phenol and O-protected phenol substituents have been prepared and fully characterised including single crystal structure analyses of 1, 4 and 7. The redox behaviour of the catecholato platinum(ii) complexes 6 and 7 has been probed by cyclic voltammetry, preparative oxidation and EPR spectroscopy (6˙(+), 7˙(+)). Reversible deprotonation of the hydroxy substituted complexes 1, 3 and 6 to 1(-), 3(-) and 6(-) resulted in significant changes in their electronic spectra. The luminescence properties of the diamagnetic complexes have been investigated using emission spectroscopy. DFT and TD-D…
Extent of the influence of phosphate buffer and ionic liquids on the reduction of the silanol effect in a C18 stationary phase
2017
The presence of anionic free silanols in the silica-based stationary phases gives rise to broad and asymmetrical peaks when cationic basic compounds are chromatographed using hydro-organic mobile phases. The addition to the mobile phase of a reagent with ionic character prevents the access of analytes to the free silanols, improving the peak shape. The silanol activity can be affected by the buffer concentration and mobile phase pH, factors that are not always considered sufficiently in the literature. In this work, the chromatographic behaviour of three basic β-adrenoceptor antagonists (acebutolol, nadolol and timolol), using mobile phases containing acetonitrile, was examined at different…
Electron correlation in metal clusters, quantum dots and quantum rings
2009
This short review presents a few case studies of finite electron systems for which strong correlations play a dominant role. In simple metal clusters, the valence electrons determine stability and shape of the clusters. The ionic skeleton of alkali metals is soft, and cluster geometries are often solely determined by electron correlations. In quantum dots and rings, the electrons may be confined by an external electrostatic potential, formed by a gated heterostructure. In the low density limit, the electrons may form so-called Wigner molecules, for which the many-body quantum spectra reveal the classical vibration modes. High rotational states increase the tendency for the electrons to loca…
Validity of the electroneutrality and goldman constant-field assumptions in describing the diffusion potential for ternary electrolyte systems in sim…
1986
Abstract Three numerical algorithms capable of simulating transport processes through simple, porous membranes in the steady state have been employed in order to study the change in the diffusion potential with the membrane thickness and the ionic concentrations for the ternary systems NaClHClH20 and CaCI2NaC1H 2 O. The first simulation procedure uses Poisson's equation, the two others replace this equation by the electroneutrality and Goldman constant-field approximations respectively. From the results presented here, conditions for the applicability of the electroneutrality and constantfield assumption to ternary electrolyte systems are given.
ChemInform Abstract: UEBER ARSEN-HALTIGE HETEROCYCLEN 3. MITT. KRISTALLSTRUKTUR VON 2,6-DIMETHYL-4,4-DIPHENYL-1,4-OXOARSENANIUMBROMID-MONOHYDRAT
1975
Abstract The crystal structure of the title compound has been determined from single crystal X-ray data and refined to a conventional R factor of 0.046. The coordination of the As atom is tetrahedral with a mean As—C distance of 1.92 A. The six-membered heterocycle has chair conformation with two equatorial methyl and one equatorial and one axial phenyl substituent. The transannular 1,4-As⋯O distance is 3.11 A, interactions are discussed. The connection of the structure is more van der Waals than ionic type. Some unspecific gaps are statistically occupied by one molecule of crystal water.
Interaction of the Dioxouranium(VI) Ion with Aspartate and Glutamate in NaCl(aq) at Different Ionic Strengths
2005
The formation of complexes species of the dioxouranium(VI) ion with aspartic and glutamic acids was studied in the pH range of 3 to 6 at 25 °C by potentiometric measurements (H+−glass electrode). R...
Molecular recognition of naphthalene diimide ligands by telomeric quadruplex-DNA: the importance of the protonation state and mediated hydrogen bonds.
2016
In depth Monte Carlo conformational scans in combination with molecular dynamics (MD) simulations and electronic structure calculations were applied in order to study the molecular recognition process between tetrasubstituted naphthalene diimide (ND) guests and G-quadruplex (G4) DNA receptors. ND guests are a promising class of telomere stabilizers due to which they are used in novel anticancer therapeutics. Though several ND guests have been studied experimentally in the past, the protonation state under physiological conditions is still unclear. Based on chemical intuition, in the case of N-methyl-piperazine substitution, different protonation states are possible and might play a crucial …
Straightforward Regio- and Diastereoselective Synthesis, Molecular Structure, Intermolecular Interactions and Mechanistic Study of Spirooxindole-Engr…
2021
Straightforward regio- and diastereoselective synthesis of bi-spirooxindole-engrafted rhodanine analogs 5a–d were achieved by one-pot multicomponent [3 + 2] cycloaddition (32CA) reaction of stabilized azomethine ylide (AYs 3a–d) generated in situ by condensation of L-thioproline and 6-chloro-isatin with (E)-2-(5-(4-chlorobenzylidene)-2,4-dioxothiazolidin-3-yl)-N-(2-morpholinoethyl)acetamide. The bi-spirooxindole-engrafted rhodanine analogs were constructed with excellent diastereo- and regioselectivity along with high chemical yield. X-ray crystallographic investigations for hybrid 5a revealed the presence of four contiguous stereocenters related to C11, C12, C19 and C22 of the spiro struct…