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We use tools of the equilibrium statistical mechanics of disordered systems to study analytically the statistical properties of an ecosystem composed of N species interacting via random mutual interactions, as well as via deterministic self-interactions of order p>/=2. We show that the main effect of increasing the order of the interactions among the species is to make the system less competitive, in the sense that the fraction of extinct species is greatly reduced. In addition, we find that for p>2 there is a threshold value which gives a lower bound to the concentration of the surviving species, preventing then the existence of rare species and, consequently, increasing the robustness of the ecosystem to external perturbations. 相似文献
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Yassin A. Jeilani Beatriz H. Cardelino Victor M. Ibeanusi 《Journal of mass spectrometry : JMS》2010,45(6):678-685
We report the first positive chemical ionization (PCI) fragmentation mechanisms of phthalates using triple‐quadrupole mass spectrometry and ab initio computational studies using density functional theories (DFT). Methane PCI spectra showed abundant [M + H]+, together with [M + C2H5]+ and [M + C3H5]+. Fragmentation of [M + H]+, [M + C2H5]+ and [M + C3H5]+ involved characteristic ions at m/z 149, 177 and 189, assigned as protonated phthalic anhydride and an adduct of phthalic anhydride with C2H5+ and C3H5+, respectively. Fragmentation of these ions provided more structural information from the PCI spectra. A multi‐pathway fragmentation was proposed for these ions leading to the protonated phthalic anhydride. DFT methods were used to calculate relative free energies and to determine structures of intermediate ions for these pathways. The first step of the fragmentation of [M + C2H5]+ and [M + C3H5]+ is the elimination of [R? H] from an ester group. The second ester group undergoes either a McLafferty rearrangement route or a neutral loss elimination of ROH. DFT calculations (B3LYP, B3PW91 and BPW91) using 6‐311G(d,p) basis sets showed that McLafferty rearrangement of dibutyl, di(‐n‐octyl) and di(2‐ethyl‐n‐hexyl) phthalates is an energetically more favorable pathway than loss of an alcohol moiety. Prominent ions in these pathways were confirmed with deuterium labeled phthalates. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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Allison M Fox Mike Anderson Corinne Reid Tim Smith Dorothy VM Bishop 《BMC neuroscience》2010,11(1):1-15
Background
We examined development of auditory temporal integration and inhibition by assessing electrophysiological responses to tone pairs separated by interstimulus intervals (ISIs) of 25, 50, 100, 200, 400, and 800 ms in 28 children aged 7 to 9 years, and 15 adults.Results
In adults a distinct neural response was elicited to tones presented at ISIs of 25 ms or longer, whereas in children this was only seen in response to tones presented at ISIs above 100 ms. In adults, late N1 amplitude was larger for the second tone of the tone pair when separated by ISIs as short as 100 ms, consistent with the perceptual integration of successive stimuli within the temporal window of integration. In contrast, children showed enhanced negativity only when tone pairs were separated by ISIs of 200 ms. In children, the amplitude of the P1 component was attenuated at ISIs below 200 ms, consistent with a refractory process.Conclusions
These results indicate that adults integrate sequential auditory information into smaller temporal segments than children. These results suggest that there are marked maturational changes from childhood to adulthood in the perceptual processes underpinning the grouping of incoming auditory sensory information, and that electrophysiological measures provide a sensitive, non-invasive method allowing further examination of these changes. 相似文献4.
Jeilani YA Cardelino BH Ibeanusi VM 《Journal of the American Society for Mass Spectrometry》2011,22(11):1999-2010
This is the first ab initio study of the energetics of the fragmentation mechanisms of phthalate, by mass spectrometry, leading
to protonated phthalic anhydride (m/z 149). Phthalates fragment by two major pathways; namely, the McLafferty + 1 rearrangement and the loss of alkoxy. Both pathways
involve a carbonyl oxygen attack to the ortho-carbonyl carbon leading to structures with tetrahedral carbon intermediates that eventually give m/z 149. These pathways were studied by collision induced dissociation (CID) using triple quadrupole mass spectrometry. The proposed
McLafferty + 1 pathway proceeds through a distonic M•+, leading to the loss of an allylic-stabilized alkene radical. The McLafferty rearrangement step proceeds through a six-membered
ring transition state with a small activation energy ranging 0.4–6.2 kcal/mol; the transfer of a second H from the distonic
ion of the rearrangement step proceeds through a radical cation molecule complex. Based on quantum chemical modeling of the
cation molecule complexes, two kinds of cation molecule complexes were identified as radical cation molecule complex and hyperconjugated
cation molecule complex. This distinction is based on the cation and simplifies future modeling of similar complexes. Optimization
of important fragments in these pathways showed cyclized and hydrogen-bonded structures to be favored. An exception was the
optimized structure of the protonated phthalic anhydride (m/z 149) that showed a structure with an open anhydride ring. 相似文献
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The fragmentation mechanisms of progesterone have been studied by triple quadrupole tandem mass spectrometry (MSMS) and density functional theory (DFT). Mechanisms leading to major product ions are proposed. The data suggest that progesterone fragments preferentially via hydrogen and other rearrangements lead to neutral losses. These fragmentations are quite complex and are preceded by σ-bond cleavages in most cases. Four major pathways for progesterone fragmentation are proposed involving: (1) cleavage of ring B at C9-C10, (2) cleavage of C6-C7 bond in ring B through m/z 191, (3) two types of cleavages of ring D, and (4) ketene elimination in ring A. Pathways (1)-(3) proceed via charge-remote fragmentations while pathway (4) proceeds via charge-site initiated mechanism. The geometry of product ions in these pathways were optimized using DFT at the B3LYP/6-311G(d,p) level of theory from which the free energies of the pathways were calculated. The effect that the choice of basis sets and density functionals has on the results was tested by performing additional calculations using B3LYP/6-31G(d) and B3PW91/6-311G(d,p). 相似文献
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