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731.
Futera Z Koval T Leszczynski J Gu J Mitoraj M Srebro M Burda JV 《The journal of physical chemistry. A》2011,115(5):784-794
This study focuses on the first step of interaction between DNA and the paddle-wheel dirhodium complex. The ammonia molecule was used to model the oligonucleotide sequence. The reaction was considered in neutral and acidic conditions, in gas phase, and in solvent, using the COSMO model. Molecular structures of the complexes were optimized in both models at the B3PW91/6-31G(d) level. The B3LYP functional and aug-cc-pvdz basis set were employed for single-point energy determination and electron distribution analyses. It was shown that in neutral solution the replacement of axial aqua ligand is mildly exoergic. The reaction is characterized by a relatively low activation barrier (10-12 kcal/mol), and, according to Eyring transition state theory, it proceeds very quickly. The breaking of the Rh-O(ac) bond in neutral solution is mildly endoergic (less than 1 kcal/mol) with an activation barrier of about 21 kcal/mol. However, this process can occur much more spontaneously (ΔG of -14 kcal/mol) when the dirhodium complex is protonated at the acetyl oxygen in remote position. 相似文献
732.
Magdalena Staszewska Monika Dzieciuch Joanna Lewandowska Mariusz Kepczynski Szczepan Zapotoczny Marcin Oszajca Anna Łatkiewicz Maria Nowakowska 《Journal of Sol-Gel Science and Technology》2011,59(2):276-282
In this article, we report on the formation of well-defined highly emissive silica-covered porphyrin microstructures in base-catalyzed
sol–gel processes. The microstructures were obtained by self-assembly of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (mTHPP)
at room temperature. Tetraethoxysilane (TEOS) was used as a silica precursor. The hybrid mTHPP- silica particles were characterized
by means of reflectance UV–Vis and microscopy techniques including atomic force microscopy, scanning electron microscopy (SEM)
and confocal fluorescence microscopy (CM). The SEM and TEM observations revealed that depending on the porphyrin concentration
used in the synthesis, the shape of the hybrid mTHPP-silica particles has changed from ribbon-like (c
mTHPP = 2.09 mM) to rhombus-like structures (c
mTHPP = 4.35 mM). The ribbons were straight-edged, uniform in width (1.2–1.8 μm) and height (350–400 nm), and variable in length
(40–100 μm). The rhombs were 1–3.7 μm in height, 7–25 μm in length, and 3.5–15 μm in width, and the ratio of length to width
was uniform and equal to ca. 1.8–2. UV–Vis absorption spectra indicated that the J-aggregates and H-aggregates formed in the
systems with lower and higher porphyrin content, respectively. Formation of different type of porphyrin aggregates in both
systems resulted in different emission spectra, as it was shown with CM. 相似文献
733.
In this work, the possibility of application of free base porphyrin as a lipophilic pH chromoionophore for the preparation of optical cation-selective sensors was investigated. The properties of polymeric membranes, containing porphyrins of different structures, namely tetraphenylporphyrin (TPP) and octaethylporphyrin (OEP), were compared. Changes in equilibrium between protonated and deprotonated form of porphyrin, resulting from variations in ACh concentration, were evaluated. The influence of various factors (kind and quantity of anionic additive and porphyrin in the membrane phase, pH of sample solution) on initial equilibrium was studied. The best membrane composition was chosen as: TPP 3 wt.%, KTFPB 175 mol.% relative to ionophore, PVC:o-NPOE (1 : 4) and measuring buffer solution: 0.05 M MES, pH 4.5. Selectivity, response stability, reversibility and repeatability tests were carried out for chosen sensor. Developed sensor allowed for the determination of a model analyte, acetylcholine, at the concentration range of 10(-5) to 10(-2) M, both in stationary and flow-injection system. Sensor response was reversible and repeatable in the mentioned concentration range. 相似文献
734.
Mariusz Jancelewicz Zbigniew Fojud Wiktor Waszkowiak Stefan Jurga 《European Polymer Journal》2011,(1):48-51
Spin–lattice relaxation time constants, T1, were studied for low-molecular-weight linear and grafted polydimethylsiloxane over a wide temperature and frequency range. Quantitative evaluations of proton T1 measurements indicated two relaxation processes: anisotropic rotation of methyl groups around the Si–C bond (low temperature process) and motions of the PDMS side-chains connected with the glass transition (high temperature process). Additional analyses of the T1 relaxation dispersion profiles revealed specific local segment fluctuation times, which are characteristic of the coherent motions in the grafted polymer chains. 相似文献
735.
Mariusz Grech 《Journal of Graph Theory》2011,66(4):303-318
In this article, we improve known results, and, with one exceptional case, prove that when k≥3, the direct product of the automorphism groups of graphs whose edges are colored using k colors, is itself the automorphism group of a graph whose edges are colored using k colors. We have handled the case k = 2 in an earlier article. We prove similar results for directed edge‐colored graphs. © 2010 Wiley Periodicals, Inc. J Graph Theory 66:303‐318, 2011 相似文献
736.
Mariusz Marć Jacek Namieśnik 《International journal of environmental analytical chemistry》2013,93(2):151-167
This paper presents the results of atmospheric air quality research in Tczew (adjacent to the Vistula River) on the content of BTEX compounds. procedure applied during the sampling of the analytes from the air used the passive sampling technique (diffusive passive sampler, Radiello®). For determination of BTEX compounds in atmospheric air, two-stage thermal desorption technique combined with gas chromatography (TD-GC-FID) was applied.Research was conducted from March to December 2011. The annual average concentration of benzene, toluene, ethylbenzene and total xylenes determined in atmospheric air for the monitoring period were: 0.87 μg m–3, 2.9 μg m–3, 1.3 μg m–3 and 5.9 μg m–3, respectively. In order to pre-identify potential sources of emissions of BTEX compounds, statistical analysis was carried out. This determined interactions between specified concentration levels of BTEX compounds in atmospheric air for the monitored area. 相似文献
737.
Grzegorz Boczkaj Mariusz Jaszczołt Andrzej Przyjazny Marian Kamiński 《Analytical and bioanalytical chemistry》2013,405(18):6095-6103
The paper presents the results of investigations on new procedures of determination of selected cleaning additives in diesel fuel. Two procedures: one-step analysis using gas chromatography with flame ionization detection (GC-FID) or mass spectrometry (GC-MS) and a two-step procedure in which normal-phase high-performance liquid chromatography (NP-HPLC) was used for preliminary separation of the additives, were compared. The additive fraction was collected using either simple elution or eluent backflush. Final determinations were performed by GC-FID and GC-MS. The studies revealed that it was impossible to determine the investigated analytes by one-step procedures, i.e. by using solely HPLC or GC. On the other hand, the use of a two-step procedure ensures reproducible results of determinations, and the limits of quantitation are, depending on the method of fraction collection by HPLC, from 1.4–2.2 ppm (GC-MS in SIM mode) to 9.6–24.0 ppm (GC-FID). Precision and accuracy of the developed procedures are compared, and possible determination errors and shortcomings discussed. Figure
Overview of the developed method 相似文献
738.
It was proved by Urbański and Zdunik (Fund Math 220:23–69, 2013) that for every holomorphic endomorphism $f:{{\mathbb { P}}}^k\rightarrow {{\mathbb { P}}}^k$ of a complex projective space ${{\mathbb { P}}}^k,k\ge 1$ , there exists a positive number $\kappa _f>0$ such that if $J$ is the Julia set of $f$ (i.e. the support of the maximal entropy measure) and $\phi :J\rightarrow {\mathbb R}$ is a Hölder continuous function with $\sup (\phi )-\inf (\phi )<\kappa _f$ (pressure gap), then $\phi $ admits a unique equilibrium state $\mu _\phi $ on $J$ . In this paper we prove that the dynamical system ( $f,\mu _\phi $ ) enjoys exponential decay of correlations of Hölder continuous observables as well as the Central Limit Theorem and the Law of Iterated Logarithm for the class of these variables that, in addition, satisfy a natural co-boundary condition. We also show that the topological pressure function $t\mapsto P(t\phi )$ is real-analytic throughout the open set of all parameters $t$ for which the potentials $t\phi $ have pressure gaps. 相似文献
739.
Mariusz Żaba Piotr Garbaczewski Vladimir A. Stephanovich 《Central European Journal of Physics》2014,12(3):175-184
We discuss two independent methods of solution of a master equation whose biased jump transition rates account for long jumps of Lévy-stable type and admit a Boltzmannian (thermal) equilibrium to arise in the large time asymptotics of a probability density function ρ(x, t). Our main goal is to demonstrate a compatibility of a direct solution method (an explicit, albeit numerically assisted, integration of the master equation) with an indirect pathwise procedure, recently proposed in [Physica A 392, 3485, (2013)] as a valid tool for a dynamical analysis of non-Langevin jump-type processes. The path-wise method heavily relies on an accumulation of large sample path data, that are generated by means of a properly tailored Gillespie’s algorithm. Their statistical analysis in turn allows to infer the dynamics of ρ(x, t). However, no consistency check has been completed so far to demonstrate that both methods are fully compatible and indeed provide a solution of the same dynamical problem. Presently we remove this gap, with a focus on potential deficiencies (various cutoffs, including those upon the jump size) of approximations involved in simulation routines and solutions protocols. 相似文献
740.
Krzysztof Frączek Joanna Kułaga-Przymus Mariusz Lemańczyk 《Journal d'Analyse Mathématique》2014,122(1):163-227
By studying the weak closure of multidimensional off-diagonal self-joinings, we provide a sufficient condition for non-isomorphism of a flow with its inverse, hence the non-reversibility of a flow. This is applied to special flows over rigid automorphisms. In particular, we apply the criterion to special flows over irrational rotations, providing a large class of non-reversible flows, including some analytic reparametrizations of linear flows on $\mathbb{T}^2$ , so-called von Neumann flows and some special flows with piecewise polynomial roof functions. A topological counterpart is also developed with the full solution of the problem of the topological self-similarity of continuous special flows over irrational rotations. This yields examples of continuous special flows over irrational rotations without non-trivial topological self-similarities and having all non-zero real numbers as scales of measure-theoretic self-similarities. 相似文献