NMR Titration Experiments (nmr + titration_experiment)

Distribution by Scientific Domains

Selected Abstracts

Peptide Recognition: Encapsulation and ,-Helical Folding of a Nine-Residue Peptide within a Hydrophobic Dimeric Capsule of a Bowl-Shaped Host

Shohei Tashiro
Abstract A dimeric capsule of coordination bowl 1 encapsulated a nine-residue peptide (Trp-Ala-Glu-Ala-Ala-Ala-Glu-Ala-Trp; 2) within the large hydrophobic cavity in water, and stabilized the ,-helical conformation of bound 2. An NMR titration experiment revealed that monomeric bowl 1 recognized two Trp residues at the both terminals of 2 through 1/2=1:1 to 2:1 complexation. The 1:1 and 2:1 species exist in equilibrium even in the presence of excess 1. It was found that the formation of the 2:1 complex, in which two bowls of 1 wrapped the whole of 2, became dominant by the addition of NaNO3 due to the fact that the enhanced ion strength increased the hydrophobic interaction between Trp residues and the cavity of 1. The ,-helical conformation of 2 within the dimeric capsule of 1 was elucidated from detailed NOESY analysis. [source]

A solid-state 23Na NMR study of monovalent cation binding to double-stranded DNA at low relative humidity

Alan Wong
Abstract We report a solid-state 23Na NMR study of monovalent cation (Li+, Na+, K+, Rb+, Cs+ and NH4+) binding to double-stranded calf thymus DNA (CT DNA) at low relative humidity, ca 0,10%. Results from 23Na31P rotational echo double resonance (REDOR) NMR experiments firmly establish that, at low relative humidity, monovalent cations are directly bound to the phosphate group of CT DNA and are partially dehydrated. On the basis of solid-state 23Na NMR titration experiments, we obtain quantitative thermodynamic parameters concerning the cation-binding affinity for the phosphate group of CT DNA. The free energy difference (,G ) between M+ and Na+ ions is as follows: Li+ (,1.0 kcal mol,1), K+ (7.2 kcal mol,1), NH4+ (1.0 kcal mol,1), Rb+ (4.5 kcal mol,1) and Cs+ (1.5 kcal mol,1). These results suggest that, at low relative humidity, the binding affinity of monovalent cations for the phosphate group of CT DNA follows the order: Li+ > Na+ > NH4+ > Cs+ > Rb+ > K+. This sequence is drastically different from that observed for CT DNA in solution. This discrepancy is attributed to the different modes of cation binding in dry and wet states of DNA. In the wet state of DNA, cations are fully hydrated. Our results suggest that the free energy balance between direct cation,phosphate contact and dehydration interactions is important. The reported experimental results on relative ion-binding affinity for the DNA backbone may be used for testing theoretical treatment of cation-phosphate interactions in DNA. Copyright 2008 John Wiley & Sons, Ltd. [source]

Stabilization of G-Quadruplex DNA with Platinum(II) Schiff Base Complexes: Luminescent Probe and Down-Regulation of c- myc Oncogene Expression

Peng Wu Dr.
Abstract The interactions of a series of platinum(II) Schiff base complexes with c- myc G-quadruplex DNA were studied. Complex [PtL1a] (1,a; H2L1a=N,N,-bis(salicylidene)-4,5-methoxy-1,2-phenylenediamine) can moderately inhibit c- myc gene promoter activity in a cell-free system through stabilizing the G-quadruplex structure and can inhibit c- myc oncogene expression in cultured cells. The interaction between 1,a and G-quadruplex DNA has been examined by 1H NMR spectroscopy. By using computer-aided structure-based drug design for hit-to-lead optimization, an in silico G-quadruplex DNA model has been constructed for docking-based virtual screening to develop new platinum(II) Schiff base complexes with improved inhibitory activities. Complex [PtL3] (3; H2L3=N,N,-bis{4-[1-(2-propylpiperidine)oxy]salicylidene}-4,5-methoxy-1,2-phenylenediamine) has been identified with a top score in the virtual screening. This complex was subsequently prepared and experimentally tested in vitro for its ability to stabilize or induce the formation of the c -myc G-quadruplex. The inhibitory activity of 3 (IC50=4.4,,M) is tenfold more than that of 1,a. The interaction between 1,a or 3 with c- myc G-quadruplex DNA has been examined by absorption titration, emission titration, molecular modeling, and NMR titration experiments, thus revealing that both 1,a and 3 bind c- myc G-quadruplex DNA through an external end-stacking mode at the 3' terminal face of the G-quadruplex. Such binding of G-quadruplex DNA with 3 is accompanied by up to an eightfold increase in the intensity of photoluminescence at ,max=652,nm. Complex 3 also effectively down-regulated the expression of c- myc in human hepatocarcinoma cells. [source]

Ag+ selection by aza-18-crown-6 ethers N -Substituted on heterocyclic aromatics ,,

Kiyoshi Matsumoto
Substitution on the nitrogen atom, where necessary by high-pressure SNAr reactions, of aza-18-crown-6 ethers linked to heterocyclic aromatics has extended the number of potential host compounds for Ag+. The complexation of Ag+ by the new compounds has been evaluated by liquid membrane ion transport and ion extraction experiments. The nature of the binding sites of these new host compounds for Ag+ has been assessed, in DMF/D2O (4/1), by 13C nmr titration experiments with AgClO4. [source]