Improvement of the Derjaguin-Broekhoff-de Boer theory for the capillary condensation/evaporation of nitrogen in spherical cavities and its application for the pore size analysis of silicas with ordered cagelike mesopores

In a previous work, we proposed an improvement of the Derjaguin-Broekhoff-de Boer (DBdB) theory for capillary condensation/evaporation in open-ended cylindrical mesopores. In this paper, we report a further extension of this approach to the capillary condensation/evaporation of nitrogen in siliceous spherical cavities. The main idea of this improvement is to employ the Gibbs-Tolman-Koenig-Buff equation to predict the variation of the surface tension in spherical mesopores. In addition, the statistical film thickness (the so-called t-curve), which is evaluated accurately on the basis of adsorption isotherms measured for MCM-41 materials, is used instead of the originally proposed t-curve to take into account the excess chemical potential due to the surface forces. It is shown that the aforementioned modifications of the original DBdB theory that was refined by Ravikovitch and Neimark have significant implications for the pore size analysis of cagelike mesoporous silicas. To verify the proposed improvement of the DBdB pore size analysis (IDBdB), two series of FDU-1 samples, which are well-defined cagelike mesoporous materials (composed of siliceous spherical cavities interconnected by short necks), were used for the evaluation of the pore size distributions (PSDs). The correlation between the spinodal condensation point in the spherical pores predicted by the nonlocal density functional theory (NDFT) developed by Ravikovitch and Neimark and that predicted by the IDBdB theory is very good in the whole range of mesopores. This feature is mirrored to the realistic PSD characterized by the bimodal structure of pores computed from the IDBdB theory. As in the case of open-ended cylindrical pores, the improvement of the classical DBdB theory preserves its simplicity and simultaneously ensures a significant improvement of the pore size analysis, which is confirmed by the independent estimation of the average pore size by the NDFT and the powder X-ray diffraction method.     

Synthesis and Diels-Alder reaction of a sapphyrin derivative

Sapphyrins participate in Diels-Alder reactions with pentacene affording novel barrelene-fused sapphyrins. The new compounds were synthesized using traditional heating and microwave irradiation conditions. The experiments carried out under microwave irradiation proved cleaner, affording only the monoadduct and in higher yields.     

Estimating the pore size distribution of activated carbons from adsorption data of different adsorbates by various methods

Experimental adsorption isotherms of four adsorbates (N2, Ar, C6H6, and CCl4) as well as adsorption enthalpy (C6H6 and CCl4) measured on two strictly microporous carbons are used to evaluate the porosity of adsorbents (i.e., pore size distributions (PSDs) and average pore diameter ( Lav )). The influence of the diameter of adsorbates ( dA) as well as of the temperature ( T ) is analyzed in order to explain the differences or similarities between the above-mentioned quantities for all systems. Proposed previously, the general relationships between the parameters of the Dubinin-Astakhov (DA) isotherm equation (the characteristic energy of adsorption ( E0 ) and the exponent of this equation ( n )) and the average slit-width of carbon micropores are investigated. Moreover, the thermodynamic verification of the Horvath-Kawazoe (HK) theory and the ND model is presented based on data of the adsorption and enthalpy of adsorption of benzene and carbon tetrachloride on two carbons. Finally, the pore diameters calculated from calorimetry data using the Everett and Powl method and those calculated applying the recently developed equations are compared. In our opinion the change of apparent PSD should be monitored by performing a series of isotherm measurements from high (equal and higher than room temperature) to low temperatures (ca. 77.5 K) as was presented in the current study. Moreover, the analysis of the experimental data leads to the conclusion that the entropy of C6H6 and CCl4 can approach to the values characteristic of quasi-solid (a partially ordered structure). Therefore, this behavior of the adsorbate should be taken into consideration in the theoretical assumptions of model and its thermodynamic verification.     

Convergence behavior of the density-matrix renormalization group algorithm for optimized orbital orderings

The density-matrix renormalization group algorithm has emerged as a promising new method in ab initio quantum chemistry. However, many problems still need to be solved before this method can be applied routinely. At the start of such a calculation, the orbitals originating from a preceding quantum chemical calculation must be placed in a specific order on a one-dimensional lattice. This ordering affects the convergence of the density-matrix renormalization group iterations significantly. In this paper, we present two approaches to obtain optimized orderings of the orbitals. First, we use a genetic algorithm to optimize the ordering with respect to a low total electronic energy obtained at a predefined stage of the density-matrix renormalization group algorithm with a given number of total states kept. In addition to that, we derive orderings from the one- and two-electron integrals of our test system. This test molecule is the chromium dimer, which is known to possess a complicated electronic structure. For this molecule, we have carried out calculations for the various orbital orderings obtained. The convergence behavior of the density-matrix renormalization group iterations is discussed in detail.     

A quantum-chemical study of dinitrogen reduction at mononuclear iron-sulfur complexes with hints to the mechanism of nitrogenase

The mechanism of biological dinitrogen reduction is still unsolved, and the structure of the biological reaction center, the FeMo cofactor with its seven iron atoms bridged by sulfur atoms, is too complicated for direct attack by current sophisticated quantum chemical methods. Therefore, iron-sulfur complexes with biologically compatible ligands are utilized as models for studying particular features of the reduction process: coordination energetics, thermodynamic stability of intermediates, relative stability of isomers of N2H2, end-on versus side-on binding of N2, and the role of states of different multiplicity at a single iron center. From the thermodynamical point of view, the crucial steps are dinitrogen binding and reduction to diazene, while especially the reduction of hydrazine to ammonia is not affected by the transition metal complex, because the complex-free reduction reaction is equally favored. Moreover, the abstraction of coordinated ammonia can be easily achieved and the complex is recovered for the next reduction cycle. Our results are discussed in the light of studies on various model systems in order to identify common features and to arrive at conclusions which are of importance for the biological mechanism.     

Synthesis of new isoxazoles derivatives attached to sugar moieties

This work reports the synthesis of isoxazoles linked to sugar derivatives in different positions of furanosidic rings, by intramolecular oxidative cyclization of α,β‐unsaturated oximes with iodine, potassium iodide and sodium hydrogen carbonate. These oximes were obtained from aldehyde‐sugar derivatives.     

Application of Discrete Wavelet Transform in the Analysis of Nonlinear Chemical System

Oscillations of species concentration are phenomena accompanying several types of electrochemical and purely chemical processes. Importance of analyzing of such processes results from both scientific and practical reasons. In the paper the authors deal with investigation of time dependent spectra of various stages of Belousov-Zhabotinsky type chemical oscillations. As the analytical tool the discrete wavelet transform is proposed.     

De novo design of a redox-active minimal rubredoxin mimic

Metal-binding sites in metalloproteins frequently occur at the interfaces of elements of secondary structure, which has enabled the retrostructural analysis of natural proteins and the de novo design of helical bundles that bind metal ion cofactors. However, the design of metalloproteins containing beta-structure is less well developed, despite the frequent occurrence of beta-conformations in natural metalloproteins. Here, we describe the design and construction of a beta-protein, RM1, that forms a stable, redox-active 4-Cys thiolate Fe(II/III) site analogous to the active site of rubredoxin. The protein folds into a beta-structure in the presence and absence of metal ions and binds Fe(II/III) to form a redox-active site that is stable to repeated cycles of oxidation and reduction, even in an aerobic environment.     

Optimal investment with two-factor uncertainty

This paper presents a real options model to value the option to invest in a project contingent on two stochastic factors. A general sensitivity analysis is conducted highlighting the importance of the variance and correlation between the two variables. A higher correlation is shown to increase always the values of the trigger, the active project and the option. The impact of uncertainty is more complex and depends on the assumption about which variables adjust and the correlation between the variables and the market.