Long-lived states to sustain hyperpolarized magnetization.

Major breakthroughs have recently been reported that can help overcome two inherent drawbacks of NMR: the lack of sensitivity and the limited memory of longitudinal magnetization. Dynamic nuclear polarization (DNP) couples nuclear spins to the large reservoir of electrons, thus making it possible to detect dilute endogenous substances in magnetic resonance spectroscopy (MRS) and magnetic resonance imaging (MRI). We have designed a method to preserve enhanced ("hyperpolarized") magnetization by conversion into long-lived states (LLS). It is shown that these enhanced long-lived states can be generated for proton spins, which afford sensitive detection. Even in complex molecules such as peptides, long-lived proton states can be sustained effectively over time intervals on the order of tens of seconds, thus allowing hyperpolarized substrates to reach target areas and affording access to slow metabolic pathways. The natural abundance carbon-13 polarization has been enhanced ex situ by almost four orders of magnitude in the dipeptide Ala-Gly. The sample was transferred by the dissolution process to a high-resolution magnet where the carbon-13 polarization was converted into a long-lived state associated with a pair of protons. In Ala-Gly, the lifetime T(LLS) associated with the two nonequivalent H(alpha) glycine protons, sustained by suitable radio-frequency irradiation, was found to be seven times longer than their spin-lattice relaxation time constant (T(LLS)/T(1) = 7). At desired intervals, small fractions of the populations of long-lived states were converted into observable magnetization. This opens the way to observing slow chemical reactions and slow transport phenomena such as diffusion by enhanced magnetic resonance.

Nanowires network for biomolecular detection using contactless impedance tomoscopy technique.

Here we present the detection of ultralow concentrations of biomolecules in a device made from a polycarbonate membrane containing a network of gold nanowires and using a "contactless" impedance tomoscopy technique. The sensor comprises a thin dielectric layer with two parallel band electrodes on the one side and a microchannel containing gold nanowires onto which the adsorption of antibodies occurs. Upon applying a high-frequency ac voltage between the two electrodes, the adsorption process occurring at the surface of the gold nanowires can be followed through contactless impedance measurements. The configuration allows the real-time detection of biomolecules with a bulk concentration in the picomolar range.

Orbital domain state and finite size scaling in ferromagnetic insulating manganites.

55Mn and 139La NMR measurements on a high quality single crystal of ferromagnetic (FM) La0.80Ca0.20MnO3 demonstrate the formation of localized Mn(3+,4+) states below 70 K, accompanied by a strong cooling-rate dependent increase of certain FM neutron Bragg peaks. (55,139)(1/T(1)) spin-lattice and (139)(1/T(2)) spin-spin relaxation rates are strongly enhanced on approaching this temperature from below, signaling a genuine phase transition at T(tr) approximately 70 K. The disappearance of the FM metallic signal by applying a weak external magnetic field, the different NMR radio-frequency enhancement of the FM metallic and insulating states, and the observed finite size scaling of T(tr) with Ca (hole) doping, as observed in powder La(1-x)CaxMnO3 samples, are suggestive of freezing into an inhomogeneous FM insulating and orbitally ordered state embodying "metallic" hole-rich walls.

NMR studies of simple molecules on metal surfaces.

In recent years, improvements in the sensitivity of nuclear magnetic resonance have made it possible to detect progressively smaller numbers of nuclei. Experiments and studies previously thought to be impractical can now be undertaken, for example, the study of phenomena at surfaces. Nuclear magnetic resonance has been applied to study simple molecules (carbon monoxide, acetylene, and ethylene) adsorbed on metal surfaces (ruthenium, rhodium, palladium, osmium, iridium, and platinum). The metals, in the form of clusters 10 to 50 angstroms in diameter, supported on alumina, are typical of real catalysts. The experiments provide information about the bonding of the molecules to the metal, the structures the molecules assume after adsorption, the motion of molecules on the surface, the breakup of molecules induced by heating, and the products of such breakup.