79/81Br nuclear quadrupole resonance spectroscopic characterization of halogen bonds in supramolecular assemblies.

Despite the applicability of solid-state NMR to study the halogen bond, the direct NMR detection of 79/81Br covalently bonded to carbon remains impractical due to extremely large spectral widths, even at ultra-high magnetic fields. In contrast, nuclear quadrupole resonance (NQR) offers comparatively sharp resonances. Here, we demonstrate the abilities of 79/81Br NQR to characterize the electronic changes in the C-Br···N halogen bonding motifs found in supramolecular assemblies constructed from 1,4-dibromotetrafluorobenzene and nitrogen-containing heterocycles. An increase in the bromine quadrupolar coupling constant is observed, which correlates linearly with the halogen bond distance (dBr···N). Notably, 79/81Br NQR is able to distinguish between two symmetry-independent halogen bonds in the same crystal structure. This approach offers a rapid and reliable indication for the occurrence of a halogen bond, with experimental times limited only by the observation of 79/81Br NQR resonances.

Superfluorinated and NIR-luminescent gold nanoclusters.

A novel class of superfluorinated and NIR-luminescent gold nanoclusters were obtained starting from a branched thiol, bearing 27 equivalent 19F atoms per molecule. These unprecedented clusters combine in a unique nanosystem both NIR photoluminescence and 19F NMR properties, thus representing a promising multimodal platform for bioimaging applications.

Role of the reaction intermediates in determining PHIP (parahydrogen induced polarization) effect in the hydrogenation of acetylene dicarboxylic acid with the complex [Rh (dppb)]+ (dppb: 1,4-bis(diphenylphosphino)butane).

This study deals with the parahydrogenation of the symmetric substrate acetylene dicarboxylic acid catalyzed by a Rh(I) complex bearing the chelating diphosphine dppb (1,4-bis(diphenylphosphino)butane). The two magnetically equivalent protons of the product yield a hyperpolarized emission signal in the (1)H-NMR spectrum. Their polarization intensity varies upon changing the reaction solvent from methanol to acetone. A detailed analysis of the hydrogenation pathway is carried out by means of density functional theory calculations to assess the structure of hydrogenation intermediates and their stability in the two solvents. The observed polarization effects have been accounted on the basis of the obtained structures. Insights into the lifetime of a short-lived reaction intermediate are also obtained.

Solid-state and unilateral NMR study of deterioration of a Dead Sea Scroll fragment.

Unilateral and solid-state nuclear magnetic resonance (NMR) analyses were performed on a parchment fragment of the Dead Sea Scroll (DSS). The analyzed sample belongs to the collection of non-inscribed and nontreated fragments of known archaeological provenance from the John Rylands University Library in Manchester. Therefore, it can be considered as original DSS material free from any contamination related to the post-discovery period. Considering the paramount significance of the DSS, noninvasive approaches and portable in situ nondestructive methods are of fundamental importance for the determination of composition, structure, and chemical-physical properties of the materials under study. NMR studies reveal low amounts of water content associated with very short proton relaxation times, T(1), indicating a high level of deterioration of collagen molecules within scroll fragments. In addition, (13)C cross-polarization magic-angle-spinning (CPMAS) NMR spectroscopy shows characteristic peaks of lipids whose presence we attribute to the production technology that did not involve liming. Extraction with chloroform led to the reduction of both lipid and protein signals in the (13)C CPMAS spectrum indicating probable involvement of lipids in parchment degradation processes. NMR absorption and relaxation measurements provide nondestructive, discriminative, and sensitive tools for studying the deterioration effects on the organization and properties of water and collagen within ancient manuscripts.

Didanosine polymorphism in a supercritical antisolvent process.

Solid-state properties of active ingredients are crucial in pharmaceutical development owing to their significant clinical and economical implications. In the present work we investigated the solid-state properties and the solubility in water of didanosine, DDI, re-crystallized from a dimethylsulfoxide solution using supercritical CO(2) as an antisolvent (SAS process) for comparison with the commercially available drug product. We also applied modern solid-state NMR (SS NMR) techniques, namely 2D (1)H DQ CRAMPS (Combined Rotation And Multiple Pulse Spectroscopy) and (1)H-(13)C on- and off-resonance CP (cross polarization) FSLG-HETCOR experiments, known for providing reliable information about (1)H-(1)H and (1)H-(13)C intra- and intermolecular proximities, in order to address polymorphism issues arising from the crystallization of a new form in the supercritical process. A new polymorph of didanosine was obtained from the supercritical antisolvent process and characterized by means of 1D and 2D multinuclear ((1)H, (13)C, (15)N) SS NMR. The particle size of the new crystal phase was reduced by varying the antisolvent density through a pressure increase. The structural differences between the commercial product and the SAS re-crystallized DDI are highlighted by X-ray diffractometry and well described by solid-state NMR. The carbon C6 (13)C chemical shift suggests that both commercial and re-crystallized didanosine samples are in the enol form. The analysis of homo- and heteronuclear proximities obtained by means of 2D NMR experiments shows that commercial and SAS re-crystallized DDI possess very similar molecular conformation and hydrogen bond network, but different packing. The new polymorph proved to be a metastable form at ambient conditions, showing higher solubility in water and lower stability to mechanical stress.

Hyperpolarized agents for advanced MRI investigations.

The strong signal enhancement attainable by hyperpolarization methods has allowed the detection of heteronuclei in magnetic resonance imaging (MRI), allowing to obtain high quality images with very high signal to noise ratios in few seconds. The four methods to produce hyperpolarized molecules, i.e. the "brute force" approach, optical pumping of noble gases, parahydrogen induced polarization (PHIP) and dynamic nuclear polarization (DNP), are reported. The applications of hyperpolarized probes to MRI range from vascular imaging to interventional imaging and perfusion studies, up to the emerging and challenging field of molecular/metabolic imaging. In fact, the high signal intensities achievable by using hyperpolarized molecules make it possible to detect and image the metabolic products formed upon the administration of the hyperpolarized agent. The most striking examples are surveyed, including the use of hyperpolarized 13C-pyruvate in tumor diagnosis and stadiation, and in myocardium perfusion and activity studies, as well as the recently reported proposal of using 13C-bicarbonate as agent for pH-mapping in vivo.

63Cu-31P coupling constants and 63Cu quadrupole couplings from 31P CP/MAS spectra of copper (I)--phosphine complexes with aryldithiocarboxylates or benzoate.

Magic-angle spinning 31P NMR spectra of solid [CuS2C-Ph(PPh3)2] 1, [{CuS2C-pT}4(PPh3)2] 2, [{CuS2C-Ph}4(PPh3)2] 3. [CuS2C-Ph(dppm)]2 4 and [CuO2C-Ph(dppm)]2 5, (T = tolyl, dppm = bis(diphenylphosphino)methane) were obtained at 109.6 MH2. They consist of distorted quartets from non-equivalent phosphorus atoms and provide approximate values of the indirect spin-spin coupling constant J[63Cu,31P], that are indicative of the covalency of the dithiocarboxylate-copper bonding. The spacing distortions are related to a number of molecular and structural parameters and thereby allow an estimation of the copper quadrupole coupling constant e2qQ/h which, as expected, is smaller for tetra-coordinated (1, 2, 3 and 4) than for tri-coordinated (5) copper sites. The spectrum of 2 has been successfully simulated (including the isotope effects from the less abundant 65Cu isotope) using the full theory for calculation of the spin eigenfunctions of the quadrupolar nucleus.

Relationship between Solid State NMR Parameters and X-ray Structural Data in Tricadmium Phosphates.

31P and (113)Cd MAS NMR spectra of solid beta'-tricadmium phosphate (beta'-TCdP) show a number of highly resolved resonances that agree well with the number of independent crystallographic sites indicated by the results of X-ray diffraction studies. A correlation of the (31)P chemical shifts with the crystallographic sites for the six different PO(4)(3)(-) groups in the unit cell of beta'-TCdP has been obtained by a method based on the computation of bond strength at oxygen atoms in phosphate moieties. The assignment of the (113)Cd resonances has been carried out on the basis of the relationship between the asymmetry of the chemical shift tensor (evaluated by analysis of the spinning side bands intensities in the MAS spectrum) and a geometric parameter related to the distortion from the bipyramidal trigonal coordination at each cadmium center. Samples of tricadmium phosphate with different degrees of magnesium substitution for cadmium were investigated by (31)P MAS NMR, (113)Cd MAS NMR, and X-ray diffraction. The results of these investigations showed that the magnesiums distribute randomly in the cadmium sites, inducing a marked decrease in the order of the structure.

Solid-state 31P CP/MAS NMR vs. solution study of bis(tertiary phosphines).

Solid-state 31C CP/MAS results of several diphosphines are compared with solution phase data. Non-equivalence of the P atoms are observed in the solid state for the less flexible derivatives (including all chiral diphosphines studied), whereas the more flexible compounds with a linear alkyl chain such as the 1,2-ethane and the 1,4-butane derivatives give only rise to a single resonance. For the more strained bis(diphenylphosphino)methane contradictory data have been reported. Our experiments confirm the existence of an AB spin system, i.e., two different P atoms in solid state. Substantial chemical shift difference between P atoms have been observed in the solid state but not in solution of the chiral compounds. A possible explanation is suggested in terms of the concerted anisotropic effect of the phenyl rings attached to the phosphorus atom.