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91.
Babankova D Civis S Juha L Bittner M Cihelka J Pfeifer M Skala J Bartnik A Fiedorowicz H Mikolajczyk J Ryć L Sedivcova T 《The journal of physical chemistry. A》2006,110(44):12113-12120
Large-scale plasma was created in molecular gases (CO, CO2, N2, H2O) and their mixtures by high-power laser-induced dielectric breakdown (LIDB). Compositions of the mixtures used are those suggested for the early earth's atmosphere of neutral and/or mildly reducing character. Time-integrated optical spectra emitted from the laser spark have been measured and analyzed. The spectra of the plasma generated in the CO-containing mixtures are dominated by emission of both C2 and CN radicals. A vibrational temperature of approximately 10(4) K was determined according to an intensity distribution in a vibronic structure of the CN (B2Sigma(+)u-X2Sigma(+)g) violet band. For comparison, the NH3-CH4-H2-H2O mixture has been irradiated as a model of the strongly reducing version of the early earth's atmosphere. In this mixture, excited CN seems to be significantly less abundant than C2. The LIDB experiments were in the molecular gases carried out not only in the static cell but also using a large, double stream pulse jet (gas puff target) placed in the vacuum interaction chamber. The obtained soft X-ray emission spectra indicate the presence of highly charged atomic ions in the hot core of high-power laser sparks. 相似文献
92.
We give a complete classification of algebraic curves in ℂ2 which are homeomorphic with ℂ* and which satisfy a certain natural condition about codimensions of its singularities. In
the proof we use the method developed in [BZI]. It relies on estimation of certain invariants of the curve, the so-called
numbers of double points hidden at singularities and at infinity. The sum of these invariants is given by the Poincaré-Hopf
formula applied to a suitable vector field. 相似文献
93.
The classical functional delta method (FDM) provides a convenient tool for deriving the asymptotic distribution of statistical functionals from the weak convergence of the respective empirical processes. However, for many interesting functionals depending on the tails of the underlying distribution this FDM cannot be applied since the method typically relies on Hadamard differentiability w.r.t. the uniform sup-norm. In this article, we present a version of the FDM which is suitable also for nonuniform sup-norms, with the outcome that the range of application of the FDM enlarges essentially. On one hand, our FDM, which we shall call the modified FDM, works for functionals that are “differentiable” in a weaker sense than Hadamard differentiability. On the other hand, it requires weak convergence of the empirical process w.r.t. a nonuniform sup-norm. The latter is not problematic since there exist strong respective results on weighted empirical processes obtained by Shorack and Wellner (1986) [25], Shao and Yu (1996) [23], Wu (2008) [32], and others. We illustrate the gain of the modified FDM by deriving the asymptotic distribution of plug-in estimates of popular risk measures that cannot be treated with the classical FDM. 相似文献
94.
Positron binding by the HCN molecule was studied within a modified adiabatic approximation. This approach, in which the positron is treated as a light pseudonucleus with fractional charge, leads to the binding energy of 0.65?mHartree. Using effective positron mass which reproduces the Quantum Monte Carlo binding energy gives an estimation of the two-photon annihilation rate of e +HCN, equal to 0.091?ns?1. 相似文献
95.
96.
JPC – Journal of Planar Chromatography – Modern TLC - As it was presented in our previous works, applying external magnetic field during chromatogram development results in changes of... 相似文献
97.
Gaggelli E Janicka-Klos A Jankowska E Kozlowski H Migliorini C Molteni E Valensin D Valensin G Wieczerzak E 《The journal of physical chemistry. B》2008,112(1):100-109
Alzheimer's disease is a fatal neurodegenerative disorder involving the abnormal accumulation and deposition of peptides (amyloid-beta, Abeta) derived from the amyloid precursor protein. Here, we present the structure and the Zn2+ binding sites of human and rat Abeta(1-28) fragments in water/sodium dodecyl sulfate (SDS) micelles by using 1H NMR spectroscopy. The chemical shift variations measured after Zn2+ addition at T>310 K allowed us to assign the binding donor atoms in both rat and human zinc complexes. The Asp-1 amine, His-6 Ndelta, Glu-11 COO-, and His-13 Nepsilon of rat Abeta28 all enter the metal coordination sphere, while His-6 Ndelta, His-13, His-14 Nepsilon, Asp-1 amine, and/or Glu-11 COO- are all bound to Zn2+ in the case of human Abeta28. Finally, a comparison between the rat and human binding abilities was discussed. 相似文献
98.
Gaggelli E Grzonka Z Kozłowski H Migliorini C Molteni E Valensin D Valensin G 《Chemical communications (Cambridge, England)》2008,(3):341-343
The interaction between Cu(II) and the rat amyloid beta (1-28) fragment in micellar solutions at pH 7.5 was investigated by CD and NMR spectroscopy; the proton-copper distances were used in restrained molecular dynamics simulations to obtain a structural model of the Cu(II) complex. 相似文献
99.
Gralka E Valensin D Porciatti E Gajda C Gaggelli E Valensin G Kamysz W Nadolny R Guerrini R Bacco D Remelli M Kozlowski H 《Dalton transactions (Cambridge, England : 2003)》2008,(38):5207-5219
The prion protein (PrP) is a Cu(2+)-binding cell-surface glycoprotein. Using PrP peptide fragments, by means of potentiometric, spectroscopic and thermodynamic techniques, we have shown that Cu(2+) ions bind to the region comprising His-96, His-111 and the octarepeat domain within residues 60-91. Cu(2+) may bind in different modes, which strongly depend both on His position within the peptide sequence and on the adjacent residues. We have used a series of protected oligopeptides having His at the C- or the N-terminus, inducing different binding modes to amide nitrogens around the His residue, either towards the N- or C-terminus. His imidazole acts as an anchoring site for Cu(2+) and then binding to ionized amide nitrogens follows. When it is directed towards the C-terminus the formation of a less stable seven-membered chelate ring with a {N(im), N(-)} binding mode occurs. When coordination goes towards the N-terminus the thermodynamically more stable six-membered chelate ring is formed. NMR data suggest that both the coordination modes are possible for the model peptides; however, the thermodynamic measurements show that they only slightly differ in energy and the influence of the adjacent amino acid residues can address the coordination toward the C- or the N-terminus. 相似文献
100.
Mucha A Knobloch B Jezowska-Bojczuk M Kozłowski H Sigel RK 《Dalton transactions (Cambridge, England : 2003)》2008,(39):5368-5377
The interaction between metal ions and nucleotides is well characterized, as is their importance for metabolic processes, e.g. in the synthesis of nucleic acids. Hence, it is surprising to find that no detailed comparison is available of the metal ion-binding properties between nucleoside 5'-phosphates and 2'-deoxynucleoside 5'-phosphates. Therefore, we have measured here by potentiometric pH titrations the stabilities of several metal ion complexes formed with 2'-deoxyadenosine 5'-monophosphate (dAMP2-), 2'-deoxyadenosine 5'-diphosphate (dADP3-) and 2'-deoxyadenosine 5'-triphosphate (dATP4-). These results are compared with previous data measured under the same conditions and available in the literature for the adenosine 5'-phosphates, AMP(2-), ADP(3-) and ATP(4-), as well as guanosine 5'-monophosphate (GMP(2-)) and 2'-deoxyguanosine 5'-monophosphate (dGMP(2-)). Hence, in total four nucleotide pairs, GMP(2-)/dGMP(2-), AMP(2-)/dAMP(2-), ADP(3-)/dADP(3-) and ATP(4-)/dATP(4-) (= NP/dNP), could be compared for the four metal ions Mg2+, Ni2+, Cu2+ and Zn2+ (= M2+). The comparisons show that complex stability and extent of macrochelate formation between the phosphate-coordinated metal ion and N7 of the purine residue is very similar (or even identical) for the AMP(2-)/dAMP(2-) and ADP(3-)/dADP(3-) pairs. In the case of the complexes formed with ATP(4-)/dATP(4-) the 2'-deoxy complexes are somewhat more stable and show also a slightly enhanced tendency for macrochelate formation. This is different for guanine nucleotides: the stabilities of the M(dGMP) complexes are clearly higher, as are the formation degrees of their macrochelates, than is the case with the M(GMP) complexes. This enhanced complex stability and greater tendency to form macrochelates can be attributed to the enhanced basicity (DeltapKaca. 0.2) of N7 in the 2'-deoxy compound. These results allow general conclusions regarding nucleic acids to be made. 相似文献