Ozone-induced dissociation of conjugated lipids reveals significant reaction rate enhancements and characteristic odd-electron product ions

Ozone-induced dissociation (OzID) is an alternative ion activation method that relies on the gas phase ion-molecule reaction between a mass-selected target ion and ozone in an ion trap mass spectrometer. Herein, we evaluated the performance of OzID for both the structural elucidation and selective detection of conjugated carbon-carbon double bond motifs within lipids. The relative reactivity trends for \[M + X](+) ions (where X = Li, Na, K) formed via electrospray ionization (ESI) of conjugated versus nonconjugated fatty acid methyl esters (FAMEs) were examined using two different OzID-enabled linear ion-trap mass spectrometers. Compared with nonconjugated analogues, FAMEs derived from conjugated linoleic acids were found to react up to 200 times faster and to yield characteristic radical cations. The significantly enhanced reactivity of conjugated isomers means that OzID product ions can be observed without invoking a reaction delay in the experimental sequence (i.e., trapping of ions in the presence of ozone is not required). This possibility has been exploited to undertake neutral-loss scans on a triple quadrupole mass spectrometer targeting characteristic OzID transitions. Such analyses reveal the presence of conjugated double bonds in lipids extracted from selected foodstuffs. Finally, by benchmarking of the absolute ozone concentration inside the ion trap, second order rate constants for the gas phase reactions between unsaturated organic ions and ozone were obtained. These results demonstrate a significant influence of the adducting metal on reaction rate constants in the fashion Li > Na > K.

Investigation of two-proton emission from excited states of the odd-Z nucleus P-28 by complete-kinematics measurements

An experiment to study exotic two-proton emission from excited levels of the odd-Z nucleus P-28 was performed at the National Laboratory of Heavy Ion Research-Radioactive Ion Beam Line (HIRFL-RIBLL) facility. The projectile P-28 at the energy of 46.5 MeV/u was bombarding a Au-197 target to populate the excited states via Coulomb excitation. Complete-kinematics measurements were realized by the array of silicon strip detectors and the CsI + PIN telescope. Two-proton events were selected and the relativistic-kinematics reconstruction was carried out. The spectrum of relative momentum and opening angle between two protons was deduced from Monte Carlo simulations. Experimental results show that two-proton emission from P-28 excited states less than 17.0 MeV is mainly two-body sequential emission or three-body simultaneous decay in phase space. The present simulations cannot distinguish these two decay modes. No obvious diproton emission was found.

Multi-phonon gamma-vibrational bands in odd-mass nuclei studied by triaxial projected shell model approach

Inspired by the recent experimental data [J.-G. Wang, et al., Phys. Lett. B 675 (2009) 420], we extend the triaxial projected shell model approach to study the gamma-band structure in odd-mass nuclei. As a first application of the new development, the gamma-vibrational structure of Nb-103 is investigated. It is demonstrated that the model describes the ground-state band and multi-phonon gamma-vibrations quite satisfactorily, supporting the interpretation of the data as one of the few experimentally-known examples of simultaneous occurrence of one- and two-gamma-phonon vibrational bands. This generalizes the well-known concept of the surface gamma-oscillation in deformed nuclei built on the ground-state in even-even systems to gamma-bands based on quasiparticle configurations in odd-mass systems. (c) 2010 Elsevier BM. All rights reserved.

High-spin states of odd-odd nuclei in the A similar to 170 mass region

Efforts have been made in our group to study the band structure of odd-odd nuclei in the A similar to 170 mass region. We aimed at providing new data of high-spin states and searching for the low-spin signature inversion in the 2-qp bands built on the pi h(9/2) circle times nu i(13/2) and pi i(13/2)circle times nu i(13/2) configurations. In this talk, main results of our work will be summarized, and some systematic features of signature inversion discussed. The spin and parity assignments for the pi i(13/2) circle times nu i(13/2) band in (184)An could be regarded as firm providing a good example for systematic and theoretical investigations.

Correlation of Kauzman temperature with odd-even effect in n-alkanes

A unique correlation has been established between Kauzmann temperature (Tk1) and the odd–even effect in n‐alkanes. The derived new parameter, i.e., Tm/Tk1 obtained from entropy conservation at Tk1, when plotted against chain length, provides a much sharper odd–even contrast than entropy of fusion plot reported earlier. © 1996 American Institute of Physics.

Odd-even oscillations of SHG efficiencies in twin NLO chromophores

Twin NLO chromophores having two azobenzene units linked by a flexible polymethylene spacer of varying lengths are shown to exhibit odd-even oscillations in their second harmonic generation (SHG) efficiencies, when measured in the powder form. These twin systems were designed to also exhibit liquid cystallinity, and indeed most of them do exhibit a nematic mesophase. The anticipated odd-even oscillations, in both their isotropization transition temperatures (Ti) and isotropization entropies (Delta Si), were also observed. The odd-even oscillation of the SHG efficiencies has been ascribed to a more effective cancellation of mesogenic dipoles in the even twins as compared to their odd counterparts, due to a preferred centrosymmetric packing in the former case. Based on the behaviour of these twin chromophoric molecules, it may be anticipated that such odd-even oscillations will also be observed in the analogous main chain NLO polymers.

Two-channel Kondo physics in odd impurity chains

We study odd-membered chains of spin-1/2 impurities, with each end connected to its own metallic lead. For antiferromagnetic exchange coupling, universal two-channel Kondo (2CK) physics is shown to arise at low energies. Two overscreening mechanisms are found to occur depending on coupling strength, with distinct signatures in physical properties. For strong interimpurity coupling, a residual chain spin-1/2 moment experiences a renormalized effective coupling to the leads, while in the weak-coupling regime, Kondo coupling is mediated via incipient single-channel Kondo singlet formation. We also investigate models in which the leads are tunnel-coupled to the impurity chain, permitting variable dot filling under applied gate voltages. Effective low-energy models for each regime of filling are derived, and for even fillings where the chain ground state is a spin singlet, an orbital 2CK effect is found to be operative. Provided mirror symmetry is preserved, 2CK physics is shown to be wholly robust to variable dot filling; in particular, the single-particle spectrum at the Fermi level, and hence the low-temperature zero-bias conductance, is always pinned to half-unitarity. We derive a Friedel-Luttinger sum rule and from it show that, in contrast to a Fermi liquid, the Luttinger integral is nonzero and determined solely by the ``excess'' dot charge as controlled by gate voltage. The relevance of the work to real quantum dot devices, where interlead charge-transfer processes fatal to 2CK physics are present, is also discussed. Physical arguments and numerical renormalization-group techniques are used to obtain a detailed understanding of these problems.

Odd-even effect in the elastic modulii of alpha,omega-Alkanedicarboxylic acids

Nanoindentation studies on alpha,omega-alkanedicarboxylic acids reveal that the elastic modulus, E, shows an odd-even alternation in exactly the same manner as the melting temperature, T-m. The results are consistent with the hypothesis that the strained molecular conformations in the odd diacids are the reasons for these alternations in T-m. The same packing features that lower T-m in the odd acids lead to easy accommodation of the deformation during nanoindentation and hence their low E.

On existence of periodic solutions for stable interval plants with odd, sector type nonlinearities

In several systems, the physical parameters of the system vary over time or operating points. A popular way of representing such plants with structured or parametric uncertainties is by means of interval polynomials. However, ensuring the stability of such systems is a robust control problem. Fortunately, Kharitonov's theorem enables the analysis of such interval plants and also provides tools for design of robust controllers in such cases. The present paper considers one such case, where the interval plant is connected with a timeinvariant, static, odd, sector type nonlinearity in its feedback path. This paper provides necessary conditions for the existence of self sustaining periodic oscillations in such interval plants, and indicates a possible design algorithm to avoid such periodic solutions or limit cycles. The describing function technique is used to approximate the nonlinearity and subsequently arrive at the results. Furthermore, the value set approach, along with Mikhailov conditions, are resorted to in providing graphical techniques for the derivation of the conditions and subsequent design algorithm of the controller.

Succinate esters: odd-even effects in melting points

Dialkyl succinates show a pattern of alternating behavior in their melting points, as the number of C atoms in the alkane side chain increases, unlike in the dialkyl oxalates Joseph et al. (2011). Acta Cryst. B67, 525-534]. Dialkyl succinates with odd numbers of C atoms in the alkyl side chain show higher melting points than the immediately adjacent analogues with even numbers. The crystal structures and their molecular packing have been analyzed for a series of dialkyl succinates with 1 - 4 C atoms in the alkyl side chain. The energy difference (Delta E) between the optimized and observed molecular conformations, density, Kitaigorodskii packing index (KPI) and C-H center dot center dot center dot O interactions are considered to rationalize this behavior. In contrast to the dialkyl oxalates where a larger number of moderately strong C-H center dot center dot center dot O interactions were characteristic of oxalates with elevated melting points, here the molecular packing and the density play a major role in raising the melting point. On moving from oxalate to succinate esters the introduction of the C2 spacer adds two activated H atoms to the asymmetric unit, resulting in the formation of stronger C-H center dot center dot center dot O hydrogen bonds in all succinates. As a result the crystallinity of long-chain alkyl substituted esters improves enormously in the presence of hydrogen bonds from activated donors.

Mitochondrial data support an odd-nosed colobine clade

To obtain a more complete understanding of the evolutionary history of the leaf-eating monkeys we have examined the mitochondrial genome sequence of two African and six Asian colobines. Although taxonomists have proposed grouping the "odd-nosed" colobines

Flexoelectric and elastic coefficients of odd and even homologous bimesogens.

It is known that bimesogenic liquid crystals exhibit a marked "odd-even" effect in the flexoelastic ratio (the effective flexoelectric coefficient to the average elastic coefficient), with the ratio being higher for the "odd-spaced" bimesogens (those with an odd number of alkyl groups in the spacer chain) than their neighboring even-spaced counterparts. To determine the contribution of each property to the flexoelastic ratio, we present experimental results on the flexoelectric and elastic coefficients of two homologous nonsymmetric bimesogens which possess odd and even alkyl spacers. Our results show that, although there are differences in the flexoelectric coefficients, there are substantially larger differences in the effective elastic coefficient. Specifically, the odd bimesogen is found to have both a low splay elastic coefficient and a very low bend elastic coefficient which, when combined, results in a significantly lower effective elastic coefficient and consequently a higher flexoelastic ratio.