Cleavage of protected amino acids and peptides from the new o-nitrogenzoyl polyethylene glycol support by catalytic hydrogenolysis

Catalytic hydrogenolysis as a cleavage method for removal of protected amino acids and peptides from the 3-nitro-4-bromonethylbenzoyl polyethylene glycol support used in liquid-phase peptide synthesis is demonstrated.     

Magnetic density of states at low energy in geometrically frustrated systems

Using muon-spin-relaxation measurements we show that the pyrochlore compound Gd(2)Ti(2)O(7), in its magnetically ordered phase below approximately 1 K, displays persistent spin dynamics down to temperatures as low as 20 mK. The characteristics of the induced muon relaxation can be accounted for by a scattering process involving two magnetic excitations, with a density of states characterized by an upturn at low energy and a small gap depending linearly on the temperature. We propose that such a density of states is a generic feature of geometrically frustrated magnetic materials.     

Magnetic properties of Yb Mo O and Gd Mo O from rare earth Mössbauer measurements

Using ¹⁷⁰Yb and ¹⁵⁵Gd M?ssbauer measurements down to ∼ 0.03 K, we have examined the semiconducting pyrochlore Yb₂Mo₂O₇ where the Mo intra-sublattice interaction is anti-ferromagnetic and the metallic pyrochlore Gd₂Mo₂O₇ where this interaction is ferromagnetic. Additional information was obtained from susceptibility, magnetisation and ¹⁷²Yb perturbed angular correlation measurements. The microscopic measurements evidence lattice disorder which is important in Yb₂Mo₂O₇ and modest in Gd₂Mo₂O₇. Magnetic irreversibilities occur at 17 K in Yb₂Mo₂O₇ and at 75 K in Gd₂Mo₂O₇ and below these temperatures the rare earths carry magnetic moments which are induced through couplings with the Mo sublattice. In Gd₂Mo₂O₇, we observe the steady state Gd hyperfine populations at 0.027 K are out of thermal equilibrium, indicating that Gd and Mo spin fluctuations persist at very low temperatures. Frustration is thus operative in this essentially isotropic pyrochlore where the dominant Mo intra-sublattice interaction is ferromagnetic. Received 13 January 2003 Published online 4 June 2003 RID="a" ID="a"e-mail: hodges@drecam.saclay.cea.fr     

A practical approach to the preparative purification of peptides using analytical instrumentation with analytical and semipreparative columns

Summary We have examined the effect of particle size of silica-based reversed-phase packings and column packing techniques on the reversed-phase analytical separation of a peptide mixture. A C₁₈ packing of 15–20 μm average particle size produced satisfactory peptide resolution, allowing a relatively inexpensive scale up to the preparative purification of peptides. A shallow gradient (0.1% acetonitrile/min) elution procedure was developed for the preparative purification of closely related decapeptides (differing by one methyl group) on analytical (250×4.1 mm I.D.) and semipreparative (250×10 mm I.D.) columns. Up to 30 mg and 225 mg of the two-peptide mixture was efficiently resolved, with high yields of homogeneous peptides, on analytical and semipreparative columns, respectively, containing the 15–20 μm packing. We have also demonstrated the potential of our purification procedure for resolving more complex multicomponent mixtures by efficiently separating a total of 22 mg of three closely-related peptides on analytical columns containing 7 μm or 15–20 μm particle size reversed-phase packings. The use of the inexpensive 15–20 μm packing, coupled with the ability to pack efficient columns with analytical HPLC instrumentation, offers great cost saving potential.     

Imaging mesoscopic nuclear spin noise with a diamond magnetometer

Magnetic resonance imaging can characterize and discriminate among tissues using their diverse physical and biochemical properties. Unfortunately, submicrometer screening of biological specimens is presently not possible, mainly due to lack of detection sensitivity. Here we analyze the use of a nitrogen-vacancy center in diamond as a magnetic sensor for nanoscale nuclear spin imaging and spectroscopy. We examine the ability of such a sensor to probe the fluctuations of the "classical" dipolar field due to a large number of neighboring nuclear spins in a densely protonated sample. We identify detection protocols that appropriately take into account the quantum character of the sensor and find a signal-to-noise ratio compatible with realistic experimental parameters. Through various example calculations we illustrate different kinds of image contrast. In particular, we show how to exploit the comparatively long nuclear spin correlation times to reconstruct a local, high-resolution sample spectrum.     

Directed immobilization of reduced antibody fragments onto a novel SAM on gold for myoglobin impedance immunosensing

The successful construction of an immunosensor depends on having an effective procedure for immobilising the bio-recognition element to the transducer surface. In the present study, an amino-terminated 4-aminothiophenol (ATP) self-assembled monolayer (SAM) was modified with heterobifunctional crosslinker sulfosuccinimidyl 4-[N-maleimidomethyl] cyclohexane-1-carboxylate to couple reduced anti-myoglobin half-antibody fragments. The disulphide groups present in the hinge region of IgG molecules were selectively cleaved by 2-mercaptoethylamine to produce reduced half-antibody fragments with free sulphydryl groups. The maleimide terminated 4-ATP SAM modified surface was coupled to these reduced antibody fragments to produce highly oriented immobilization of the half-antibody via its Fc domain and to allow free access to the Fv bindings sites. This represents an improvement by comparison with biotin/avidin mediated IgG attachment which is essentially randomly oriented. Functional immunosensors were able to detect myoglobin in both phosphate buffered saline and whole serum over the range of concentrations from 10(-13)M to 10(-6)M, and order of magnitude better than avidin/biotin linked immunosensors. In addition, atomic force microscopy (AFM) was carried out to elucidate the nanotopology of the immunosensor surface at different stages of fabrication; the images demonstrate that half antibodies bind as described and show structural changes on subsequent antigen binding.     

Die Reaktion aliphatischer Iminoäther mit Hydrazin

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