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101.
Frache G Krier G Vernex-Loset L Muller JF Manuelli P 《Rapid communications in mass spectrometry : RCM》2007,21(16):2601-2607
Post-source decay (PSD) is a valuable tool for providing structural information from large molecules by time-of-flight mass spectrometry (TOFMS). We used PSD to obtain this type of data from small molecules in the laser desorption/ionization (LDI) study of diesel engine exhaust particles. As the original nitrogen laser (lambda = 337 nm, E = 3.5 eV/photon) of our TOF mass spectrometer does not yield sufficient energy to ionize polycyclic aromatic hydrocarbons (PAHs), a second laser with a shorter wavelength has been coupled to the instrument. The fourth harmonic of a Nd:YAG laser (lambda = 266 nm, 4.6 eV/photon) has been chosen to achieve two-photon single-step desorption/ionization of PAHs. The PSD fragmentation of functionalized, alkylated and sulfur PAHs is discussed. Diesel engine exhaust particles are also studied as an example of a real complex sample. This technique is presented herein as a way to identify small molecules in environmental samples. Information provided by LDI-PSD-TOFMS can be a way to distinguish pollutants with very close molecular weights even if the resolving power of a TOF mass spectrometer is not sufficient. 相似文献
102.
Peterka DS Kim JH Wang CC Poisson L Neumark DM 《The journal of physical chemistry. A》2007,111(31):7449-7459
The photoionization and photoelectron spectroscopy of pure He droplets were investigated at photon energies between 24.6 eV (the ionization energy of He) and 28.0 eV. Time-of-flight mass spectra and photoelectron images were obtained at a series of molecular beam source temperatures and pressures to assess the effect of droplet size on the photoionization dynamics. At source temperatures below 16 K, where there is significant production of clusters with more than 10(4) atoms, the photoelectron images are dominated by fast electrons produced via direct ionization, with a small contribution from very slow electrons with kinetic energies below 1 meV arising from an indirect mechanism. The fast photoelectrons from the droplets have as much as 0.5 eV more kinetic energy than those from atomic He at the same photon energy. This result is interpreted and simulated within the context of a "dimer model", in which one assumes vertical ionization from two nearest-neighbor He atoms to the attractive region of the He2+ potential energy curve. Possible mechanisms for the slow electrons, which were also seen at energies below IE(He), are discussed, including vibrational autoionizaton of Rydberg states comprising an electron weakly bound to the surface of a large HeN+ core. 相似文献
103.
Anne‐Marie Lamidey Lionel Fernon Laurent Pouysgu Charlotte Delattre Stphane Quideau Patrick Pardon 《Helvetica chimica acta》2002,85(8):2328-2334
The Echinacea‐derived immunostimulator and HIV‐1 integrase inhibitor (−)‐chicoric acid (=2,3‐bis{[3‐(3,4‐dihydroxyphenyl)‐1‐oxoprop‐2‐enyl]oxy}butanedioic acid; 1a ) was conveniently prepared via a silane‐promoted Pd‐mediated chemoselective hydrogenolysis of its perbenzylated derivative 12a , which was generated from an efficient and reliable carbodiimide‐mediated coupling reaction between the caffeic acid dibenzyl ether derivative 7 and commercially available (+)‐dibenzyl L ‐tartrate ( 9a ). The other naturally occurring dextrorotatory chicoric acid ( 1b ) can be similarly prepared. 相似文献
104.
Lionel?Bosco Teddy?Butscher Sylvain?R.?A.?MarqueEmail author 《Applied magnetic resonance》2017,48(4):379-406
Recently, we reported a significant solvent effect on the phosphorus hyperfine coupling constant a P in β-phosphorylated 6-membered ring nitroxides (?a P = 24 G in Org. Biomol. Chem. 2015). Thus, it led us to investigate the effect of solvent for several 6-membered ring nitroxides. Although smaller than mentioned above, a change of 5–7 G in a P with the polarity of solvent was still observed for these nitroxides. As for other β-phosphorylated nitroxides, a N increases with the polarity/polarizability π* and the Hydrogen Bond Donating α properties of the solvent whereas a P exhibits the reverse trends. The change of a P with the solvent depends a lot on a subtle interplay between the destabilizing steric hindrance due to the bulkiness of the substituents and the stabilizing hyperconjugation interactions SOMO → σ*C–P between the anti-bonding orbitals of the C–P bond and the SOMO. 相似文献
105.
We give holomorphic Chern-Simons-like action functionals on supertwistor space for self-dual supergravity theories in four
dimensions, dealing with supersymmetries, the cases where different parts of the R-symmetry are gauged, and with or without a cosmological constant. The gauge group is formally the group of holomorphic Poisson
transformations of supertwistor space where the form of the Poisson structure determines the amount of R-symmetry gauged and the value of the cosmological constant. We give a formulation in terms of a finite deformation of an
integrable -operator on a supertwistor space, i.e., on regions in . For , we also give a formulation that does not require the choice of a background. 相似文献
106.
Lionel Porcar Yun Liu Kunlun Hong Paul D. Butler E-Wen Huang Wei-Ren Chen 《Macromolecular Symposia》2009,279(1):65-71
Our previous study of the structure change of poly(amidoamine) starburst dendrimers (PAMAM) dendrimer of generation 5 (G5) have demonstrated that although the overall molecular size is practically unaffected by increasing DCl concentration, a configurational transformation, from a diffusive density profile to a more uniform density distribution, is clearly observed. In the current paper, the focus is placed on understanding the effect of counterion identity on the inter-molecular structure and the conformational properties by studying the effect due to DBr using small angle neutron scattering (SANS) and integral equation theory. While the overall molecular size is found to be essentially unaffected by the change in the pD of solutions, it is surprising that the intra-molecular configurational transformation is not observed when DBr is used. The overall effective charge of a dendrimer is nearly the same for α < 1, independent of the type of acids. However, when α > 1, the effect of counterion identity becomes significant, the effective charge carried by a charged G5 PAPAM protonated by DBr becomes smaller than that of solutions with DCl. As a consequence, a counterion identity dependence of counterion association is revealed: Under the same level of molecular protonation, the specific counterion association, which is defined as the ratio of bound chloride anions to positively charged amines per molecule, is larger for the G5 PAMAM dendrimer charged by DBr than the one by DCl. 相似文献
107.
Lionel Salmon Pierre Thury Michel Ephritikhine Bernardo Masci 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(1):m27-m29
The title compound, [UO2(C33H38N2O2)2](CF3SO3)2·2C5H5N, has been obtained by reaction of UIV trifluoromethanesulfonate with p‐tert‐butyltetrahomodioxacalix[4]arene in pyridine. The uranyl ion lies on an inversion centre and is bound to two O atoms from each diphenoxide ligand, which gives the usual square‐planar equatorial environment. The zwitterionic diphenoxide species results from nucleophilic attack by pyridine on the benzylic ether C atoms of the homooxacalixarene, assisted by initial U coordination to the ether groups, with subsequent metal oxidation giving the uranyl moiety. 相似文献
108.
The paper investigates the boundary controllability, as well as the internal controllability, of the complex Ginzburg–Landau equation. Zero-controllability results are derived from a new Carleman estimate and an analysis based upon the theory of sectorial operators. 相似文献
109.
In this paper we generalize the notion of cyclic code and construct codes as ideals in finite quotients of non-commutative
polynomial rings, so called skew polynomial rings of automorphism type. We propose a method to construct block codes of prescribed
rank and a method to construct block codes of prescribed distance. Since there is no unique factorization in skew polynomial
rings, there are much more ideals and therefore much more codes than in the commutative case. In particular we obtain a [40,
23, 10]4 code by imposing a distance and a [42,14,21]8 code by imposing a rank, which both improve by one the minimum distance of the previously best known linear codes of equal
length and dimension over those fields. There is a strong connection with linear difference operators and with linearized
polynomials (or q-polynomials) reviewed in the first section.
相似文献
110.
The rotor-router model is a deterministic analogue of random walk. It can be used to define a deterministic growth model analogous
to internal DLA. We prove that the asymptotic shape of this model is a Euclidean ball, in a sense which is stronger than our
earlier work (Levine and Peres, Indiana Univ Math J 57(1):431–450, 2008). For the shape consisting of sites, where ω
d
is the volume of the unit ball in , we show that the inradius of the set of occupied sites is at least r − O(logr), while the outradius is at most r + O(r
α
) for any α > 1 − 1/d. For a related model, the divisible sandpile, we show that the domain of occupied sites is a Euclidean ball with error in the radius a constant independent of the total
mass. For the classical abelian sandpile model in two dimensions, with n = πr
2 particles, we show that the inradius is at least , and the outradius is at most . This improves on bounds of Le Borgne and Rossin. Similar bounds apply in higher dimensions, improving on bounds of Fey and
Redig.
Yuval Peres is partially supported by NSF grant DMS-0605166. 相似文献