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31.
López Fontán JL Costa J Ruso JM Prieto G Sarmiento F 《The European physical journal. E, Soft matter》2004,15(2):133-140
The application of a statistical method, the local polynomial regression method, (LPRM), based on a nonparametric estimation of the regression function to determine the critical micelle concentration (cmc) is presented. The method is extremely flexible because it does not impose any parametric model on the subjacent structure of the data but rather allows the data to speak for themselves. Good concordance of cmc values with those obtained by other methods was found for systems in which the variation of a measured physical property with concentration showed an abrupt change. When this variation was slow, discrepancies between the values obtained by LPRM and others methods were found.Received: 2 October 2003, Published online: 25 March 2004PACS:
02.50.-r Probability theory, stochastic processes, and statistics - 82.70.-y Disperse systems; complex fluids 相似文献
32.
Giampiero Mei Almerinda Di Venere Eleonora Nicolai Nicola Rosato Alessandro Finazzi Agro' 《Journal of fluorescence》2003,13(1):33-39
Tryptophan fluorescence is extremely useful to monitor structural conformational transitions in proteins. Denaturant-induced unfolding of azurin and ascorbate oxidase has been studied by dynamic fluorescence measurements in the frequency domain and the results have been interpreted in terms of continuous distribution of lifetimes. The data add new information on the unfolding mechanism that was previously analyzed by steady-state emission spectroscopy. In particular, the existence of multiple, parallel unfolding pathways may be envisaged and correlated, in both cases, to the two protein structures. The effect of metal depletion has been also characterized by fluorescence lifetime measurements. In the case of azurin, a monomeric protein, the data demonstrate that copper removal yields a totally different unfolding pathways with respect to the holo protein, indicating that metal ion plays a fundamental structural role in the wild type, native protein. In the case of ascorbate oxidase a dimer of 140 kDa, only minor effects have been detected by copper removal. However, the analysis of the fluorescence decay in presence of different amounts of guanidinium hydrochloride gives new important insights on the unfolding intermediates. In particular the data support the hypothesis of a partial exposure of an outer layer of dimer at intermediate denaturant concentration. This ability of dynamic fluorescence to pinpoint the presence of structural micro-heterogeneity in the unfolding pathways of proteins demonstrates the greater power of this technique compared to the most commonly used steady-state measurements. 相似文献
33.
We construct maximally supersymmetric gauged N = 16 supergravity in three dimensions, thereby obtaining an entirely new class of anti--de Sitter supergravities. These models apparently cannot be derived from any known higher-dimensional theory and point to the existence of a new type of supergravity beyond D = 11. One of their noteworthy features is a non-Abelian generalization of the duality between scalar and vector fields in three dimensions. Among the possible gauge groups, SO(8) x SO(8) is distinguished as the maximal compact gauge group, but there are also more exotic possibilities such as F(4(-20)) x G2. 相似文献
34.
35.
We study random skew 3D partitions weighted by q
vol
and, specifically, the q → 1 asymptotics of local correlations near various points of the limit shape. We obtain sine-kernel asymptotics for correlations in the bulk of the disordered region, Airy kernel asymptotics near a general point of the frozen boundary, and a Pearcey kernel asymptotics near a cusp of the frozen boundary. 相似文献
36.
Meier R Maigut J Kallies B Lehnert N Paulat F Heinemann FW Zahn G Feth MP Krautscheid H van Eldik R 《Chemical communications (Cambridge, England)》2007,(38):3960-3962
The equilibrium between the twist-boat (tb) and half-chair (hc) conformers of the central diamine chelate ring of [Fe(III)(tmdta)]- in solids and aqueous solution has been studied by Raman spectroscopy, supported by calculated Raman spectra using Density Functional Theory. 相似文献
37.
Türkoglu G Heinemann FW Burzlaff N 《Dalton transactions (Cambridge, England : 2003)》2011,40(17):4678-4686
The new N,N,O ligand 2,2-bis(3,5-dimethylpyrazol-1-yl)propionic acid (2,2-Hbdmpzp) (2) and its transition metal complexes [Mn(2,2-bdmpzp)(CO)(3)] (3), [Re(2,2-bdmpzp)(CO)(3)] (4), [Cu(2,2-bdmpzp)(2)] (5), and [Ru(2,2-bdmpzp)Cl(L)(PPh(3))] [L = PPh(3) (6), N(2) (7), CO (8a/b), SO(2) (9a/b)] have been synthesized, characterized and compared to analogous complexes bearing a bis(3,5-dimethylpyrazol-1-yl)acetic acid. It was found that the additional methyl group has a remarkable influence on the stability and reactivity of transition metal complexes. 相似文献
38.
Nickel(0)‐Catalyzed Enantioselective Annulations of Alkynes and Arylenoates Enabled by a Chiral NHC Ligand: Efficient Access to Cyclopentenones 下载免费PDF全文
Joachim S. E. Ahlin Dr. Pavel A. Donets Prof. Dr. Nicolai Cramer 《Angewandte Chemie (International ed. in English)》2014,53(48):13229-13233
Cyclopentenones are versatile structural motifs of natural products as well as reactive synthetic intermediates. The nickel‐catalyzed reductive [3+2] cycloaddition of α,β‐unsaturated aromatic esters and alkynes constitutes an efficient method for their synthesis. Here, nickel(0) catalysts comprising a chiral bulky C1‐symmetric N‐heterocyclic carbene ligand were shown to enable an efficient asymmetric synthesis of cyclopentenones from mesityl enoates and internal alkynes under mild conditions. The bulky NHC ligand provided the cyclopentenone products in very high enantioselectivity and led to a regioselective incorporation of unsymmetrically substituted alkynes. 相似文献
39.
Daniel Francisco Palacios Juan A. Alfonso Haydn Barros John J. LaBrecque Karla Prez Marian R. Lossada 《Radiation measurements》2008,43(1):77-84
A semi-empirical method to determine radionuclide concentrations in large environmental samples without the use of reference material and avoiding the typical complexity of Monte-Carlo codes is proposed. The calculation of full-energy peak efficiencies was carried out from a relative efficiency curve (obtained from the gamma spectra data), and the geometric (simulated by Monte-Carlo), absorption, sample and intrinsic efficiencies for energies between 130 and 3000 keV. The absorption and sample efficiencies were determined from the mass absorption coefficients, whereas the intrinsic efficiency was approximated by an empirical function. The deviations between calculated and experimental efficiencies for a reference material in most cases are less than 10%. Radionuclide activities in marine sediment samples calculated by the proposed method and by the experimental comparative method were not significantly different. This new method can be used for routine environmental monitoring when uncertainties up to 10% are acceptable. 相似文献
40.