Conformational analysis of 2,2-difluoroethylamine hydrochloride: double gauche effect

The gauche effect in fluorinated alkylammonium salts is well known and attributed either to an intramolecular hydrogen bond or to an electrostatic attraction between the positively charged nitrogen and the vicinal electronegative fluorine atom. This work reports the effect of adding a fluorine atom in 2-fluoroethylamine hydrochloride on the conformational isomerism of the resulting 2,2-difluoroethylamine chloride (2). The analysis was carried out using NMR coupling constants in D2O solution, in order to mimic the equilibrium conditions in a physiological medium, in the gas phase and in implicit water through theoretical calculations. Despite the presence of sigma(CH)->sigma(*)(CF) and sigma(CH)->sigma(*)(CN) interactions, which usually rule the hyperconjugative gauche effect in 1,2-disubstituted ethanes, the most important forces leading to the double gauche effect (+NH3 in the gauche relationship with both fluorine atoms) in 2 are the Lewis-type ones. Particularly, electrostatic interactions are operative even in water solution, where they should be significantly attenuated, whereas hyperconjugation and hydrogen bond have secondary importance10877882CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE MINAS GERAIS - FAPEMIGFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPsem informaçãosem informação2012/03933-5; 2011/11098-6; 2011/01170-

Metastability in Spin-Polarized Fermi Gases

We study the role of particle transport and evaporation on the phase separation of an ultracold, spin-polarized atomic Fermi gas. We show that the previously observed deformation of the superfluid paired core is a result of evaporative depolarization of the superfluid due to a combination of enhanced evaporation at the center of the trap and the inhibition of spin transport at the normal-superfluid phase boundary. These factors contribute to a nonequilibrium jump in the chemical potentials at the phase boundary. Once formed, the deformed state is highly metastable, persisting for times of up to 2 s.Comment: 4 pages, 6 figure

Ultra-cold Polarized Fermi Gases

Recent experiments with ultra-cold atoms have demonstrated the possibility of realizing experimentally fermionic superfluids with imbalanced spin populations. We discuss how these developments have shed a new light on a half- century old open problem in condensed matter physics, and raised new interrogations of their own.Comment: 27 pages; 8 figures; Published in Report in Rep. Prog. Phys. 73 112401 (2010

Ground states and dynamics of population-imbalanced Fermi condensates in one dimension

By using the numerically exact density-matrix renormalization group (DMRG) approach, we investigate the ground states of harmonically trapped one-dimensional (1D) fermions with population imbalance and find that the Larkin-Ovchinnikov (LO) state, which is a condensed state of fermion pairs with nonzero center-of-mass momentum, is realized for a wide range of parameters. The phase diagram comprising the two phases of i) an LO state at the trap center and a balanced condensate at the periphery and ii) an LO state at the trap center and a pure majority component at the periphery, is obtained. The reduced two-body density matrix indicates that most of the minority atoms contribute to the LO-type quasi-condensate. With the time-dependent DMRG, we also investigate the real-time dynamics of a system of 1D fermions in response to a spin-flip excitation.Comment: 20 pages, 15 figures, accepted for publication in New Journal of Physic

The genetics of the Lp Antigen

Several genetic models were considered to explain the distribution of qualitatively positive and negative children in 204 Caucasian families. A model which best describes the inheritance of the Lp antigenic expression involves a major genetic locus which distinguishes two overlapping continuously distributed modes of quantitative activity.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/66139/1/j.1469-1809.1974.tb01992.x.pd

Mycobacteria Attenuate Nociceptive Responses by Formyl Peptide Receptor Triggered Opioid Peptide Release from Neutrophils

In inflammation, pain is regulated by a balance of pro- and analgesic mediators. Analgesic mediators include opioid peptides which are secreted by neutrophils at the site of inflammation, leading to activation of opioid receptors on peripheral sensory neurons. In humans, local opioids and opioid peptides significantly downregulate postoperative as well as arthritic pain. In rats, inflammatory pain is induced by intraplantar injection of heat inactivated Mycobacterium butyricum, a component of complete Freund's adjuvant. We hypothesized that mycobacterially derived formyl peptide receptor (FPR) and/or toll like receptor (TLR) agonists could activate neutrophils, leading to opioid peptide release and inhibition of inflammatory pain. In complete Freund's adjuvant-induced inflammation, thermal and mechanical nociceptive thresholds of the paw were quantified (Hargreaves and Randall-Selitto methods, respectively). Withdrawal time to heat was decreased following systemic neutrophil depletion as well as local injection of opioid receptor antagonists or anti-opioid peptide (i.e. Met-enkephalin, β-endorphin) antibodies indicating an increase in pain. In vitro, opioid peptide release from human and rat neutrophils was measured by radioimmunoassay. Met-enkephalin release was triggered by Mycobacterium butyricum and formyl peptides but not by TLR-2 or TLR-4 agonists. Mycobacterium butyricum induced a rise in intracellular calcium as determined by FURA loading and calcium imaging. Opioid peptide release was blocked by intracellular calcium chelation as well as phosphoinositol-3-kinase inhibition. The FPR antagonists Boc-FLFLF and cyclosporine H reduced opioid peptide release in vitro and increased inflammatory pain in vivo while TLR 2/4 did not appear to be involved. In summary, mycobacteria activate FPR on neutrophils, resulting in tonic secretion of opioid peptides from neutrophils and in a decrease in inflammatory pain. Future therapeutic strategies may aim at selective FPR agonists to boost endogenous analgesia

Frustrated 3-Dimensional Quantum Spin Liquid in CuHpCl

Inelastic neutron scattering measurements are reported for the quantum antiferromagnetic material Cu_2(C_5H_12N_2)_2Cl_4 (CuHpCl). The magnetic excitation spectrum forms a band extending from 0.9 meV to 1.4 meV. The spectrum contains two modes that disperse throughout the a-c plane of the monoclinic unit cell with less dispersion along the unique b-axis. Simple arguments based on the measured dispersion relations and the crystal structure show that a spin ladder model is inappropriate for describing CuHpCl. Instead, it is proposed that hydrogen bond mediated exchange interactions between the bi-nuclear molecular units yield a three-dimensional interacting spin system with a recurrent triangular motif similar to the Shastry-Sutherland Model (SSM). Model independent analysis based on the first moment sum rule shows that at least four distinct spin pairs are strongly correlated and that two of these, including the dimer bond of the corresponding SSM, are magnetically frustrated. These results show that CuHpCl should be classified as a frustration induced three dimensional quantum spin liquid.Comment: 13 pages, 17 figures (Color) ReSubmitted to Phys. Rev. B 9/21/2001 resubmission has new content email comments to [email protected] or [email protected]

Solid 4He and the Supersolid Phase: from Theoretical Speculation to the Discovery of a New State of Matter? A Review of the Past and Present Status of Research

The possibility of a supersolid state of matter, i.e., a crystalline solid exhibiting superfluid properties, first appeared in theoretical studies about forty years ago. After a long period of little interest due to the lack of experimental evidence, it has attracted strong experimental and theoretical attention in the last few years since Kim and Chan (Penn State, USA) reported evidence for nonclassical rotational inertia effects, a typical signature of superfluidity, in samples of solid 4He. Since this "first observation", other experimental groups have observed such effects in the response to the rotation of samples of crystalline helium, and it has become clear that the response of the solid is extremely sensitive to growth conditions, annealing processes, and 3He impurities. A peak in the specific heat in the same range of temperatures has been reported as well as anomalies in the elastic behaviour of solid 4He with a strong resemblance to the phenomena revealed by torsional oscillator experiments. Very recently, the observation of unusual mass transport in hcp solid 4He has also been reported, suggesting superflow. From the theoretical point of view, powerful simulation methods have been used to study solid 4He, but the interpretation of the data is still rather difficult; dealing with the question of supersolidity means that one has to face not only the problem of the coexistence of quantum coherence phenomena and crystalline order, exploring the realm of spontaneous symmetry breaking and quantum field theory, but also the problem of the role of disorder, i.e., how defects, such as vacancies, impurities, dislocations, and grain boundaries, participate in the phase transition mechanism.Comment: Published on J. Phys. Soc. Jpn., Vol.77, No.11, p.11101

Mechanical properties of nanocrystalline metals, intermetalics and multiphase materials determined by tension, compression and disk-bend techniques

The mechanical behavior of nanocrystalline metallic, intermetallic, and multiphase materials was investigated using tension, compression, and disk-bend techniques. Nanocrystalline NiAl, Al-Al{sub 3}Zr, and Cu were synthesized by gas condensation and either resistive or electron beam heating followed by high temperature vacuum compaction. Disk- bend tests of nanocrystalline NiAl show evidence of improved ductility at room temperature in this normally extremely brittle material. In contrast, tension tests of multiphase nanocrystalline Al- Al{sub 3}Zr samples show significant increases in strength by substantial reductions in ductility with decreasing grain size. Compression tests of nanocrystalline copper result in substantially higher yield stress and total elongation values than those measured in tensile tests. Implications for operative deformation mechanisms in these materials are discussed

Spin-Imbalance in a One-Dimensional Fermi Gas

Superconductivity and magnetism generally do not coexist. Changing the relative number of up and down spin electrons disrupts the basic mechanism of superconductivity, where atoms of opposite momentum and spin form Cooper pairs. Nearly forty years ago Fulde and Ferrell and Larkin and Ovchinnikov proposed an exotic pairing mechanism (FFLO) where magnetism is accommodated by formation of pairs with finite momentum. Despite intense theoretical and experimental efforts, however, polarized superconductivity remains largely elusive. Here we report experimental measurements of density profiles of a two spin mixture of ultracold 6Li atoms trapped in an array of one dimensional (1D) tubes, a system analogous to electrons in 1D wires. At finite spin imbalance, the system phase separates with an inverted phase profile in comparison to the three-dimensional case. In 1D we find a partially polarized core surrounded by wings composed of either a completely paired BCS superfluid or a fully polarized Fermi gas, depending on the degree of polarization. Our observations are in quantitative agreement with theoretical calculations in which the partially polarized phase is found to be a 1D analogue of the FFLO state. This study demonstrates how ultracold atomic gases in 1D may be used to create non-trivial new phases of matter, and also paves the way for direct observation and further study of the FFLO phase.Comment: 30 pages, 7 figure