Search results for "Orbit"
showing 10 items of 1104 documents
EPR, ENDOR and TRIPLE Resonance and MO Studies on Ubiquinones (Q-n): Comparison of Radical Anions and Cations of Coenzymes Q-10 and Q-6 with the Mode…
1997
Radical anions and cations of the biologically important coenzymes Q-6 and Q-10, which have 6 and 10 unsaturated isoprene units in their side chains, respectively, have been generated in various solvents, and the results compared with those obtained for Q-0, a ubiquinone with no isoprene units, and for decylubiquinone Q-2 which has a saturated side chain. Hyperfine splitting constants (hfsc) of methyl and methoxy protons of the substituents in the quinone ring, and beta and gamma protons of the side chain were measured by EPR and ENDOR spectroscopy for both the radical anions and cations of Q-0, Q-6 and Q-10, and for the radical anion of Q-2. The relative signs of the hfsc were determined b…
A quantum-chemical study of the structure, vibrations and SiH bond properties of disilylamine, NH(SiH3)2.
2002
Quantum-chemical calculations at HF, MP2 and B3LYP levels with 6-31G* and 6-311G** basis sets are reported for disilylamine, NH(SiH3)2. The equilibrium structure is found to vary with both level and basis set, all but one of the structures exhibiting a small lack of planarity of the HNSi2 system. The barrier to inversion, however, is found to be very low, at most 38 cm(-1). Vibration frequencies and intensities are calculated. The frequencies are scaled, where possible, either using updated infrared data or with the aid of factors transferred from N(CH3)(SiH3)2. Unobserved frequencies due to the v(s)NSi2, deltaNSi2 and delta(perpendicular)NH modes are predicted near 610, 210 and 360 cm(-1),…
Effect of protonation and deprotonation on the gas phase reactivity of fluorinated 1,2,4-triazines
2008
Positive and negative electrospray mass spectrometry (MS), in-time and in-space MS n experiments, high-resolution and accurate mass measurements obtained with an Orbitrap, together with density functional theory calculations have been used to study the gas-phase ion chemistry of a series of fluorinated 1,2,4-triazines. As a result of low-energy collision-induced dissociations, occurring in an ion trap and in a triple quadrupole, their protonated and deprotonated molecules show interesting features depending on the nature and structure of the precursor ions. The occurrence of elimination/hydration reactions produced by positive ions in the ion trap is noteworthy. Decompositions of deprotonat…
The first unpaired electron placed inside a C3-symmetry P-chirogenic cluster
2010
The Pd(3)(dppm*)(3)(CO)(n+) enantiomers (n = 2 (2), 1 (3)) were prepared either from (R,R)- or (S,S)-P-chirogenic bis(phenyl-m-xylylphosphino)methane (dppm*; 1) and Pd(OAc)(2) in the presence of CF(3)CO(2)H, CO and water (n = 2), and then by reductive electrolysis (n = 1). The stable enantiomeric [Pd(3)((S,S)-dppm*)(3)(CO)](+)˙ (3), is the first C(3)-symmetry radical-cation M-M bonded cluster, therefore the odd electron is delocalized onto the Pd(3) frame within this symmetry. The novel chiral species have been characterized by circular dichroism (CD) of both enantiomers of the Pd(3)(dppm*)(3)(CO)(2+) clusters (2) and by EPR spectroscopy for the Pd(3)((S,S)-dppm*)(3)(CO)(+)˙ paramagnetic co…
Density functional theory fragment descriptors to quantify the reactivity of a molecular family: Application to amino acids
2007
By using the exact density functional theory, one demonstrates that the value of the local electronic softness of a molecular fragment is directly related to the polarization charge (Coulomb hole) induced by a test electron removed (or added) from (at) the fragment. Our finding generalizes to a chemical group a formal relation between these molecular descriptors recently obtained for an atom in a molecule using an approximate atomistic model [P. Senet and M. Yang, J. Chem. Sci. 117, 411 (2005)]. In addition, a practical ab initio computational scheme of the Coulomb hole and related local descriptors of reactivity of a molecular family having in common a similar fragment is presented. As a b…
Toward an Understanding of the Catalytic Role of Hydrogen-Bond Donor Solvents in the Hetero-Diels−Alder Reaction between Acetone and Butadiene Deriva…
2006
A detailed theoretical investigation of the catalytic role of hydrogen-bond- (HB-) donor molecules (water, methanol, chloroform, dichloromethane, and chloromethane) in the hetero-Diels-Alder reaction between acetone and N,N-dimethyl-1-amino-3-methoxy-1,3-butadiene is presented. This work extends a previous study (Domingo, L. R.; Andres, J. J. Org. Chem. 2003, 68, 8662) in which the importance of weak HB-donor solvents to catalyze more effectively than solvents with a higher dielectric constant but no HB-donor capability was analyzed. Now, based on density functional theory (DFT) at B3LYP/6-31+G(d) level calculations, different techniques for analyzing the nature of HB interaction, namely, n…
Orbital varices: a tricky diagnosis in MRI
1995
Orbital varix (OV) is a rare condition causing intermittent positional exophthalmos. Because of low venous pressure, OVs tend to collapse, being frequently undetectable in routine CT or MRI examinations. We describe one case of giant intraorbital varix studied with CT and MRI techniques.
Validation of a multi-residue UHPLC-HRMS method for antibiotics screening in milk, fresh cheese, and whey
2022
Abstract The aim of this study was to develop a UHPLC–HRMS methodology as a suitable tool for the screening of antibiotics in milk, fresh cheese, and whey. Compounds were analysed using an Orbitrap Exactive™ analyser working at a resolving power of 50,000 FWHM in full scan, both in positive and negative electrospray ionization mode, and a high mass accuracy (
Trait empathy modulates music-related functional connectivity
2021
It has been well established through behavioural studies that empathy significantly influences music perception. Such individual differences typically manifest as variability in whole brain functional connectivity patterns. To date, nobody has examined the modulatory effect of empathy on functional connectivity patterns during continuous music listening. In the present study, we seek to investigate the global and local connectivity patterns of 36 participants whose fMRI scanning was done by employing the naturalistic paradigm wherein they listened to a continuous piece of music. We used graph-based measures of functional connectivity to identify how cognitive and affective components of emp…
Swings between rotation and accretion power in a binary millisecond pulsar
2013
It is thought that neutron stars in low-mass binary systems can accrete matter and angular momentum from the companion star and be spun-up to millisecond rotational periods1, 2, 3. During the accretion stage, the system is called a low-mass X-ray binary, and bright X-ray emission is observed. When the rate of mass transfer decreases in the later evolutionary stages, these binaries host a radio millisecond pulsar4, 5 whose emission is powered by the neutron star’s rotating magnetic field6. This evolutionary model is supported by the detection of millisecond X-ray pulsations from several accreting neutron stars7, 8 and also by the evidence for a past accretion disc in a rotation-powered milli…