A series of Pd and Pt chloride complexes with pyridine (py), 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen), of general formulae trans-/cis-[M(py)2Cl2], [M(py)4]Cl2, trans-/cis-[M(py)2Cl4], [M(bpy)Cl2], [M(bpy)Cl4], [M(phen)Cl2], [M(phen)Cl4], where M = Pd, Pt, was studied by 1H, 195Pt, and 15N NMR. The 90-140 ppm low-frequency 15N coordination shifts are discussed in terms of such structural features of the complexes as the type of platinide metal, oxidation state, coordination sphere geometry and the type of ligand. The results of quantum-chemical NMR calculations were compared with the experimental 15N coordination shifts, well reproducing their magnitude and correlation with the molecular structure.

Au(III), Co(III) and Rh(III) chloride complexes with pyridine (py), 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen) of the general formulae [M1LCl3], trans-[M2L4Cl2]+, mer-[M2L3Cl3], [M1(LL)Cl2]+, cis-[M2(LL)2Cl2]+, where M1=Au; M2=Co, Rh; L=py; LL=bpy, phen, were studied by 1H--13C HMBC and 1H--15N HMQC/HSQC. The 1H, 13C and 15N coordination shifts (the latter from ca-78 to ca-107 ppm) are discussed in relation to the type of metal, electron configuration, coordination sphere geometry and the type of ligand. The 13C and 15N chemical shifts were also calculated by quantum-chemical NMR methods, which reproduced well the experimental tendencies concerning the coordination sphere geometry and the ligand type.

Here we present evidence that in water/acetonitrile solvent detailed structural and dynamic information can be obtained for important proteins that are naturally present as oligomers under native conditions. An NMR-derived human insulin monomer structure in H2O/CD3CN, 65/35 vol%, pH 3.6 is presented and compared with the available X-ray structure of a monomer that forms part of a hexamer (Acta Crystallogr. 2003 Sec. D59, 474) and with NMR structures in water and organic cosolvent. Detailed analysis using PFGSE NMR, temperature-dependent NMR, dilution experiments and CSI proves that the structure is monomeric in the concentration and temperature ranges 0.1-3 mM and 10-30 degrees C, respectively. The presence of long-range interstrand NOEs, as found in the crystal structure of the monomer, provides the evidence for conservation of the tertiary structure. Starting from structures calculated by the program CYANA, two different molecular dynamics simulated annealing refinement protocols were applied, either using the program AMBER in vacuum (AMBER_VC), or including a generalized Born solvent model (AMBER_GB).

(1)H, (13)C, (15)N and (195)Pt NMR studies of gold(III) and platinum(II) chloride organometallics with N(1),C(2')-chelated, deprotonated 2-phenylpyridine (2ppy*) of the formulae [Au(2ppy*)Cl(2)], trans(N,N)-[Pt(2ppy*)(2ppy)Cl] and trans(S,N)-[Pt(2ppy*)(DMSO-d(6))Cl] (formed in situ upon dissolving [Pt(2ppy*)(micro-Cl)](2) in DMSO-d(6)) were performed. All signals were unambiguously assigned by HMBC/HSQC methods and the respective (1)H, (13)C and (15)N coordination shifts (i.e. differences between chemical shifts of the same atom in the complex and ligand molecules: Delta(1H)(coord) = delta(1H)(complex) - delta(1H)(ligand), Delta(13C)(coord) = delta(13C)(complex) - delta(13C)(ligand), Delta(15N)(coord) = delta(15N)(complex) - delta(15N)(ligand)), as well as (195)Pt chemical shifts and (1)H-(195)Pt coupling constants discussed in relation to the known molecular structures. Characteristic deshielding of nitrogen-adjacent H(6) protons and metallated C(2') atoms as well as significant shielding of coordinated N(1) nitrogens is discussed in respect to a large set of literature NMR data available for related cyclometallated compounds.

In the title compound, [ZnCl2(C4H4N2)2], the tetrahedral coordination sphere of ZnII is formed by two Cl ions and two pyridazine ligands. The rings of the two pyridazine ligands in the coordination sphere are almost perpendicular to each other. Each pyridazine is involved in one C—H⋯Cl interaction but only one chloride participates in these contacts.

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A dumbbell double-stranded DNA decamer tethered with a hexaethylene glycol linker moiety (DDSDPEG), with a nick in the centre of one strand, has been synthesised. The standard NMR methods, E.COSY, TOCSY, NOESY and HMQC, were used to measure (1)H, (31)P and T:(1) spectral parameters. Molecular modelling using rMD-simulated annealing was used to compute the structure. Scalar couplings and dipolar contacts show that the molecule adopts a right-handed B-DNA helix in 38 mM phosphate buffer at pH 7. Its high melting temperature confirms the good base stacking and stability of the duplex. This is partly attributed to the presence of the PEG(6) linker at both ends of the duplex that restricts the dynamics of the stem pentamers and thus stabilises the oligonucleotide. The inspection of the global parameters shows that the linker does not distort the B-DNA geometry. The computed structure suggests that the presence of the nick is not disturbing the overall tertiary structure, base pair geometry or duplex base pairing to a substantial extent. The nick has, however, a noticeable impact on the local geometry at the nick site, indicated clearly by NMR analysis and reflected in the conformational parameters of the computed structure. The (1)H spectra also show much sharper resonances in the presence of K(+) indicating that conformational heterogeneity of DDSDPEG is reduced in the presence of potassium as compared to sodium or caesium ions. At the same time the (1)H resonances have longer T:(1) times. This parameter is suggested as a sensitive gauge of stabilisation.

Heparins can be contaminated with oversulfated chondroitin sulfate, OSCS, the impurity being linked to adverse clinical events that certain lots of heparins have had on humans. Here, we propose labeling of the N-acetyl peaks in (1)H NMR spectra of heparins with the parameter D(t), describing the translational diffusion coefficient available from DOSY NMR. We show how DOSY can be applied as a routine method for screening the lots of heparins for obtaining the impurity profile when using (1)H NMR.