Design, construction, and validation of a 1-mm triple-resonance high-temperature-superconducting probe for NMR

We report a 600-MHz 1-mm triple-resonance high-temperature-superconducting (HTS) probe for nuclear magnetic resonance spectroscopy. The probe has a real sample volume of about 7.5 microl, an active volume of 6.3 microl, and appears to have the highest mass sensitivity at any field strength. The probe is constructed with four sets of HTS coils that are tuned to 1H, 2H, 13C, and 15N, and there is a z-axis gradient. The coils are cooled with a conventional Bruker CryoPlatform to about 20 K, and the sample chamber can be regulated above or below room temperature over a moderate range using a Bruker variable temperature unit. The absolute S/N for 0.1% ethylbenzene is approximately 1/3 that of a conventional 5mm probe with just 1/70 of the sample volume. We demonstrate the utility of this probe for small molecules and proteins with 2D spectra of just 1.7 microg of ibuprofen and 400 microM 15N-labeled ubiquitin.     

Bifurcation and Lorentz-factor scaling of relativistic magnetized plasma expansion

We report the long-term results of 2 1/2-dimensional particle-in-cell simulations of the relativistic expansion of strongly magnetized electron-positron plasmas. When the simulation is carried to >150 light-crossing time of the initial plasma, the plasma pulse exhibits a number of remarkable properties. These include the repeated bifurcation of the pulse profile, development of a power-law momentum distribution with low-energy cutoff, and a simple scaling law for the peak Lorentz factor.     

An eight-coil high-frequency probehead design for high-throughput nuclear magnetic resonance spectroscopy

In order to increase the throughput of high-resolution nuclear magnetic resonance spectroscopy a multiple-coil probe, which enables the simultaneous analysis of eight different samples, was designed. The probe, consisting of eight identical solenoidal coils, was constructed for operation at 600 MHz. By using four receivers and radiofrequency switches, spectra from eight different chemical solutions were acquired in the time normally required for one. Two-dimensional COSY, gradient COSY, and TOCSY data have been acquired. Intercoil electrical isolation was between 25 and 45 dB, with signal cross-talk between approximately 1 and 5% measured by NMR. The spectral linewidths for the eight coils were between 3 and 6Hz for a single optimized shim setting.     

Particle energization in an expanding magnetized relativistic plasma

Using a 21 / 2-dimensional particle-in-cell (PIC) code to simulate the relativistic expansion of a magnetized collisionless plasma into a vacuum, we report a new mechanism in which the magnetic energy is efficiently converted into the directed kinetic energy of a small fraction of surface particles. We study this mechanism for both electron-positron and electron-ion (m(i)/m(e)=100, m(e) is the electron rest mass) plasmas. For the electron-positron case, the pairs can be accelerated to ultrarelativistic energies. For electron-ion plasmas, most of the energy gain goes to the ions.     

Exfoliation and Noncovalent Functionalization of Graphene Surface with Poly-N-Vinyl-2-Pyrrolidone by In Situ Polymerization

Heteroatom functionalization on a graphene surface can endow the physical and structural properties of graphene. Here, a one-step in situ polymerization method was used for the noncovalent functionalization of a graphene surface with poly-N-vinyl-2-pyrrolidone (PNVP) and the exfoliation of graphite into graphene sheets. The obtained graphene/poly-N-vinyl pyrrolidone (GPNVP) composite was thoroughly characterized. The surface morphology of GPNVP was observed using field emission scanning electron microscopy and high-resolution transmission electron microscopy. Raman spectroscopy and X-ray diffraction studies were carried out to check for the exfoliation of graphite into graphene sheets. Thermogravimetric analysis was performed to calculate the amount of PNVP on the graphene surface in the GPNVP composite. The successful formation of the GPNVP composite and functionalization of the graphene surface was confirmed by various studies. The cyclic voltammetry measurement at different scan rates (5–500 mV/s) and electrochemical impedance spectroscopy study of the GPNVP composite were performed in the typical three-electrode system. The GPNVP composite has excellent rate capability with the capacitive property. This study demonstrates the one-pot preparation of exfoliation and functionalization of a graphene surface with the heterocyclic polymer PNVP; the resulting GPNVP composite will be an ideal candidate for various electrochemical applications.     

Origin of 13C complexation shifts in the adduct formation of 2-butyl phenyl ethers with a dirhodium tetracarboxylate complex

Complexation of the oxygen atom in 2-butyl phenyl ethers to a rhodium atom of the dirhodium tetracarboxylate Rh(II) 2[(R)-(+)-MTPA]4(Rh*, MTPA-H = methoxytrifluoromethylphenylacetic acid identical with Mosher's acid) deshields an sp3-hybridized 13C nucleus directly bonded to the ether oxygen; apparently, the inductive effect of the oxygen is enhanced when it is complexed to the rhodium atom. On the other hand, deshielding complexation shifts of aromatic ipso-carbons (alpha-positioned) are minute but ortho- and para-carbon signals are influenced by the resonance effect of oxygen. This effect can be modulated by further substituents at the benzene ring. In turn, this modulation of the resonance correlates linearly ith the magnitude of the inductive effect exerted on the aliphatic alpha-carbon atoms. Diastereomeric dispersion effects at 13C signals can be observed for most compounds, indicating that enantiodifferentiation is possible in this class of ethers.     

Description of the evolution of inhomogeneities on a dark matter halo with the Vlasov equation

We use a direct numerical integration of the Vlasov equation in spherical symmetry with a background gravitational potential to determine the evolution of a collection of particles in different models of a galactic halo in order to test its stability against perturbations. Such collection is assumed to represent a dark matter inhomogeneity which is represented by a distribution function defined in phase-space. Non-trivial stationary states are obtained and determined by the virialization of the system. We describe some features of these stationary states by means of the properties of the final distribution function and final density profile. We compare our results using the different halo models and find that the NFW halo model is the most stable of them, in the sense that an inhomogeneity in this halo model requires a shorter time to virialize.     

Chemometric Classification of Colombian Cacao Crops: Effects of Different Genotypes and Origins in Different Years of Harvest on Levels of Flavonoid and Methylxanthine Metabolites in Raw Cacao Beans

The aim of this study was to evaluate the levels of chemical markers in raw cacao beans in two clones (introduced and regional) in Colombia over several years. Multivariate statistical methods were used to analyze the flavanol monomers (epicatechin and catechin), flavanol oligomers (procyanidins) and methylxanthine alkaloids (caffeine and theobromine) of cocoa samples. The results identified genotype as the main factor contributing to cacao chemistry, although significant differences were not observed between universal and regional clones in PCA. The univariate analysis allowed us to establish that EET-96 had the highest contents of both flavanol monomers (13.12 ± 2.30 mg/g) and procyanidins (7.56 ± 4.59 mg/g). In addition, the geographic origin, the harvest conditions of each region and the year of harvest may contribute to major discrepancies between results. Turbo cocoa samples are notable for their higher flavanol monomer content, Chigorodó cocoa samples for the presence of both types of polyphenol (monomer and procyanidin contents) and the Northeast cocoa samples for the higher methylxanthine content. We hope that knowledge of the heterogeneity of the metabolites of interest in each clone will contribute to the generation of added value in the cocoa production chain and its sustainability.