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991.
Influence of surface melting effects and availability of reagent ions on LDI‐MS efficiency after UV laser irradiation of Pd nanostructures
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Yuliya E. Silina Marcus Koch Dietrich A. Volmer 《Journal of mass spectrometry : JMS》2015,50(3):578-585
In this study, the influence of surface morphology, reagent ions and surface restructuring effects on atmospheric pressure laser desorption/ionization (LDI) for small molecules after laser irradiation of palladium self‐assembled nanoparticular (Pd‐NP) structures has been systematically studied. The dominant role of surface morphology during the LDI process, which was previously shown for silicon‐based substrates, has not been investigated for metal‐based substrates before. In our experiments, we demonstrated that both the presence of reagent ions and surface reorganization effects – in particular, melting – during laser irradiation was required for LDI activity of the substrate. The synthesized Pd nanostructures with diameters ranging from 60 to 180 nm started to melt at similar temperatures, viz. 890–898 K. These materials exhibited different LDI efficiencies, however, with Pd‐NP materials being the most effective surface in our experiments. Pd nanostructures of diameters >400–800 nm started to melt at higher temperatures, >1000 K, making such targets more resistant to laser irradiation, with subsequent loss of LDI activity. Our data demonstrated that both melting of the surface structures and the presence of reagent ions were essential for efficient LDI of the investigated low molecular weight compounds. This dependence of LDI on melting points was exploited further to improve the performance of Pd‐NP‐based sampling targets. For example, adding sodium hypophosphite as reducing agent to Pd electrolyte solutions during synthesis lowered the melting points of the Pd‐NP materials and subsequently gave reduced laser fluence requirements for LDI. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
992.
Let G and H be Lie groups with Lie algebras
and
. Let G be connected. We prove that a Lie algebra homomorphism
is exact if and only if it is completely positive. The main resource is a corresponding theorem about representations on
Hilbert spaces.
This article summarizes the main results of [1].
Received: 6 December 2005 相似文献
993.
We calculate the solvation free energy of proteins in the tube model of Banavar and Maritan [Rev. Mod. Phys. 75, 23 (2003)10.1103/RevModPhys.75.23] using morphological thermodynamics which is based on Hadwiger's theorem of integral geometry. Thereby we extend recent results by Snir and Kamien [Science 307, 1067 (2005)10.1126/science.1106243] to hard-sphere solvents at finite packing fractions and obtain new conclusions. Depending on the solvent properties, parameter regions are identified where the beta sheet, the optimal helix, or neither is favored. 相似文献
994.
We consider a nonspherical colloidal particle immersed in a fluid close to its critical point. The temperature dependence of the corresponding order parameter profile is calculated explicitly. We perform a systematic expansion of the order parameter profile in powers of the local curvatures of the surface of the colloidal particle. This curvature expansion reduces to the short distance expansion of the order parameter profile in the case that the solvent is at the critical composition. 相似文献
995.
996.
997.
The effect of partial substitution, up to x = 0.4, of La by trivalent Eu on the phase stability, thermal expansion, and transport properties of La2Mo2O9 are investigated using temperature-controlled X-ray powder diffraction, differential thermal analysis, and complex impedance spectroscopy. At low europium content (x < or = 0.1), the alpha-beta phase transition is observed at a temperature dependent on the sample shaping (powder, pellet, etc.). At high europium content (x > or = 0.25), the samples remain cubic (beta phase), regardless of the shaping. In the intermediate range of europium content (x = 0.15, 0.2), the phase stability is highly sensitive to the thermal history and the sample shaping, with a double-reversed beta-alpha-beta transition suppressed by the shaping/sintering process. The influence of the amount of europium on the transport mechanisms and parameters is studied in both low- (Arrhenius) and high-temperature (Vogel-Tammann-Fulcher = VTF) regimes. If the effect of substitution is rather mild and monotonous within each transport regime and crystallographic phase, an abrupt change in the Arrhenius parameters between the alpha- and beta-type phases is observed. 相似文献
998.
Onidas D Gustavsson T Lazzarotto E Markovitsi D 《Physical chemistry chemical physics : PCCP》2007,9(37):5143-5148
Polymeric and oligomeric DNA helices, poly(dAdT).poly(dAdT) and (dAdT)(10).(dAdT)(10), composed of 200-400 and 20 adenine-thymine base pairs, respectively, are studied by fluorescence upconversion. Fluorescence decays, anisotropy decays and time-resolved spectra, obtained for this alternating base sequence, are compared with those determined previously for the homopolymeric sequence (dA)(n).(dT)(n). It is shown that identical fluorescence decays may correspond to quite different anisotropy decays and vice versa, both varying with the emission wavelength, the base sequence and the duplex size. Our observations cannot be explained in terms of monomer and excimer emission exclusively, as concluded in the past on the basis of steady-state measurements. Excitons also contribute to the fluorescence. These are rapidly trapped by excimers, characterized by long-lived weak emission. 相似文献
999.
Zimmermann M Frøystein NA Fischbach A Sirsch P Dietrich HM Törnroos KW Herdtweck E Anwander R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(31):8784-8800
The complexes [Ln(AlMe4)3] (Ln=Y, La, Ce, Pr, Nd, Sm, Ho, Lu) have been synthesized by an amide elimination route and the structures of [Lu{(micro-Me)2AlMe2}3], [Sm{(micro-Me)2AlMe2}3], [Pr{(micro-Me)2AlMe2}3], and [La{(micro-Me)2AlMe2}2{(micro-Me)3AlMe}] determined by X-ray crystallography. These structures reveal a distinct Ln3+ cation size-dependency. A comprehensive insight into the intrinsic properties and solution coordination phenomena of [Ln(AlMe4)3] complexes has been gained from extended dynamic 1H and 13C NMR spectroscopic studies, as well as 1D 89Y, 2D 1H/89Y, and 27Al NMR spectroscopic investigations. [Ce(AlMe4)3] and [Pr(AlMe4)3] have been used as alkyl precursors for the synthesis of heterobimetallic alkylated rare-earth metal complexes. Both carboxylate and siloxide ligands can be introduced by methane elimination reactions that give the heterobimetallic complexes [Ln{(O2CAriPr)2(micro-AlMe2)}2(AlMe4)(C6H14)n] and [Ln{OSi(OtBu)3}(AlMe3)(AlMe4)2], respectively. [Pr{OSi(OtBu)3}(AlMe3)(AlMe4)2] has been characterized by X-ray structure analysis. All of the cerium and praseodymium complexes are used as precatalysts in the stereospecific polymerization of isoprene (1-3 equivalents of Et2AlCl as co-catalyst) and compared to the corresponding neodymium-based initiators reported previously. The superior catalytic performance of the homoleptic complexes leads to quantitative yields of high-cis-1,4-polyisoprene (>98%) in almost all of the polymerization experiments. In the case of the binary catalyst mixtures derived from carboxylate or siloxide precatalysts quantitative formation of polyisoprene is only observed for nLn:nCl=1:2. The influence of the metal size is illustrated for the heterobimetallic lanthanum, cerium, praseodymium, neodymium, and gadolinium carboxylate complexes, and the highest activities are observed for praseodymium as a metal center in the presence of one equivalent of Et2AlCl. 相似文献
1000.
Ornelas C Boisselier E Martinez V Pianet I Ruiz Aranzaes J Astruc D 《Chemical communications (Cambridge, England)》2007,(47):5093-5095
A new water-soluble polyanionic dendrimer containing 81 benzoate termini (diameter: 11+/-1 nm from DOSY NMR spectroscopy) has been synthesized; it interacts with acetylcholine cations in water-soluble assemblies in which each carboxylate terminus reversibly forms contact ion pairs and aggregates at the tether termini, as shown by 1H NMR spectroscopy. 相似文献