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21.
This work presents a systematic theoretical study on Cu(I) and Cu(II) cations in variable hydrogen sulfide-aqua-ammine ligand fields. These ligands model the biologically most common environment for Cu ions. Molecular structures of the complexes were optimized at the density functional theory (DFT) level. Subsequent thorough energy analyses revealed the following trends: (i) The ammine complexes are the most stable, followed by those containing the aqua and hydrogen sulfide ligands, which are characterized by similar stabilization energies. (ii) The most preferred Cu(I) coordination number is 2 in ammine or aqua ligand fields. A qualitatively different binding picture was obtained for complexes with H(2)S ligands where the 4-coordination is favored. (iii) The 4- and 5-coordinated structures belong to the most stable complexes for Cu(II), regardless of the ligand types. Vertical and adiabatic ionization potentials of Cu(I) complexes were calculated. Charge distribution (using the natural population analysis (NPA) method) and molecular orbital analyses were performed to elucidate the nature of bonding in the examined systems. The results provide in-depth insight into the Cu-binding properties and can be, among others, used for the calibration of bioinorganic force fields. 相似文献
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Tadej Dolenec Sbreveivana Lambasbrevea Matej Dolenec 《Isotopes in environmental and health studies》2013,49(1):77-85
Analyses of nitrogen stable isotopes in the marine sea grass Posidonia oceanica were used to investigate the influence of fish farming on the coastal ecosystem of Vrgada Island in the Murter Sea, Central Adriatic. The results show a statistically significant 15N enrichment (up to 4.7‰ at p?<?0.005) in P. oceanica leaf and shoot tissues from fish cage sites with respect to the unaffected offshore reference site of Lumbarda Reef Flat (Kornati Islands). Heavy nitrogen enrichment was also detected in other benthic organisms analysed during this study and is attributed to the absorption and assimilation of 15N-enriched fish farm derived nitrogen waste. 相似文献
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Let c(x 1,?…?,?x d ) be a multihomogeneous central polynomial for the n?×?n matrix algebra M n (K) over an infinite field K of positive characteristic p. We show that there exists a multihomogeneous polynomial c 0(x 1,?…?,?x d ) of the same degree and with coefficients in the prime field 𝔽 p which is central for the algebra M n (F) for any (possibly finite) field F of characteristic p. The proof is elementary and uses standard combinatorial techniques only. 相似文献
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Let R be a ring and let A be a subset of R. A map f : A→ R is commuting on A if [f(x),x]= 0 for all xεA where [x,y] = xy — yx. Suppose that R is a prime ring of characteristic ≠2 with extended centroid C. If L is a noncommutative Lie ideal of R and f:L→R an additive commuting map, then there is λε C and an additive map ∈: L→ C such that f(v) = λ(v)=λv+∈((v) for all vεL. 相似文献
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Indrek Jõgi Rasmus Talviste Sirli Raud Jüri Raud Toomas Plank Ladislav Moravský Matej Klas Štefan Matejčík 《等离子体物理论文集》2020,60(3):e201900127
The present study compares the operation of two cold atmospheric plasma jet (CAPJ) configurations: needle-to-cylinder electrode configuration (CAPJ I) and single high-voltage cylinder electrode around the quartz tube (CAPJ II). The CAPJs were operated in argon flowing through a quartz capillary with 0.5-mm inner diameter into the ambient air, and the plasma was generated by sinusoidal kHz frequency AC power supplies. The main emphasis of the study was on the mechanism of the initiation of ionization waves for these two configurations. For both CAPJs, there appeared several ionization waves during one half-period of the applied voltage waveform, and the number of ionization waves increased at higher voltage amplitudes. However, we discovered marked differences in the initiation of the ionization waves for two different CAPJ configuration. The applied voltage controlled the initiation of consecutive ionization waves, which propagated from the grounded electrode towards the tube orifice in CAPJ I. In the case of CAPJ II, certain time had to pass for the initiation of a new ionization wave, and subsequent ionization waves within the same half-period started at the tube orifice. In addition to the differences in the initiation of the ionization waves, we observed that the CAPJ I was ignited and sustained at lower voltages, while CAPJ II produced a longer plasma jet. The observed advantages and deficiencies of investigated CAPJ configurations point out their potential in different applications. 相似文献
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This paper discusses the role of process modeling in safety analysis. Process modeling is applied in the fault propagation behavior study of CSTR chemical production. For that purpose, HAZOP methodology and continuation analysis were used. The proposed hazard identification methodology involves analysis of steady-state multiplicity and safe operating conditions as well as those which can shift process units from one steady state to another. All presented case studies are also supported by system dynamic simulations, essential to detect oscillatory thermal instability. In this paper, N-oxide alkylpyridines production process was chosen to identify potential hazard and operational problems. Presented dynamic simulations represent an analysis of the system response to step changes in the key operating parameters. The effect of deviations of three key parameters on the reactor safe operation was investigated. The proposed numerical algorithms represent a mathematical engine of the simulation module within an automated model-based HAZOP analysis tool. 相似文献