Melting of crystallites in a solid porous matrix and the application limits of the Gibbs-Thomson equation.

A thermodynamic model is proposed to describe the melting of lamellar crystallite in a solid medium. This model includes a modification of the Gibbs-Thomson equation to make it applicable to the above-mentioned crystallites. The need for such modification is supported experimentally by studying the impact of the surroundings on the melting point of the crystallites. In particular, the application of the model to nanocrystals in open-porous systems makes it possible to determine the analytical relations for the melting point, the heat of melting, and the inverse effective size of the pores. The fitting of the experimental data with these functional relations then allows for the calculation of the nanocrystalline density, pressure in the nanocrystal, and difference in the surface tension coefficients at the nanocrystal-matrix interface and melt-matrix interface, as well as the difference in the surface entropies per unit area at the nanocrystal-matrix and melt-matrix interfaces.

Some universality in subcritical behavior of real substances and model fluids.

On the basis of the latest advances in Mayer's cluster-based approach, the reduced forms of the well-known virial expansions are derived in terms of scaled reducible and irreducible cluster integrals. This transformation minimizes the dependence on temperature and the effect of parameters specific for each thermodynamic system, thus making the resulting reduced expansions indeed universal on the quantitative level. In particular, the scaling of isotherms and saturation curves for various systems (the Lennard-Jones model, different lattice gases, and real substances with simple nonpolar molecules as well as complex polar ones) confirms the approximate universality of the proposed reduced variables for temperature, pressure, and density at subcritical gaseous states up to the saturation point. In addition, the temperature dependence of the correspondingly scaled second virial coefficients also appears similar for various systems.

Construction of subcritical isotherms for model and real gases on the basis of Mayer's cluster expansion.

Existing rigorous statistical approaches still cannot quantitatively describe condensation phenomena in real fluids and even model systems with some simplified interaction potential. Here, we present a method to evaluate the unlimited subcritical set of Mayer's reducible cluster integrals (the power coefficients of virial expansions) by using the information on several virial coefficients and empirical value of saturation activity. As to the requirements on the initial number of known virial coefficients, the calculations for the Lennard-Jones model indicate that only the second virial coefficient is sufficient to reproduce gas isotherms (including the flat phase-transition region) with high accuracy at low temperatures. This remarkable feature allows the simplification of the method for real fluids with an unknown interaction potential: In particular, the calculated isotherms of several real substances (including water) are in good agreement with experiments. Additionally, the obtained results indicate the existence of some important universality which needs serious future exploration.

Divergence of activity expansions: Is it actually a problem?

For realistic interaction models, which include both molecular attraction and repulsion (e.g., Lennard-Jones, modified Lennard-Jones, Morse, and square-well potentials), the asymptotic behavior of the virial expansions for pressure and density in powers of activity has been studied taking power terms of high orders into account on the basis of the known finite-order irreducible integrals as well as the recent approximations of infinite irreducible series. Even in the divergence region (at subcritical temperatures), this behavior stays thermodynamically adequate (in contrast to the behavior of the virial equation of state with the same set of irreducible integrals) and corresponds to the beginning of the first-order phase transition: the divergence yields the jump (discontinuity) in density at constant pressure and chemical potential. In general, it provides a statistical explanation of the condensation phenomenon, but for liquid or solid states, the physically proper description (which can turn the infinite discontinuity into a finite jump of density) still needs further study of high-order cluster integrals and, especially, their real dependence on the system volume (density).

Virial and high-density expansions for the Lee-Yang lattice gas.

On the basis of the recently established "hole-particle" symmetry of the lattice-gas Hamiltonian, the high-density equation of state has been derived in a form of pressure and density expansions in powers of activity. This equation is proposed as an alternative and complementary to the previously obtained pressure expansion in powers of density. For the well-known Lee-Yang lattice-gas model (a two-dimensional square lattice with a square-well interaction potential), the power coefficients (i.e., cluster and irreducible cluster integrals) up to the seventh order have been evaluated as accurate functions of temperature. The convergence of the expansions in powers of both density and activity to the exact Lee-Yang solution is investigated.

Radiation influence on the temperature-dependent parameters of fluids.

Based on the fundamental Bogolyubov chain of equations, a model relating the structural and thermophysical properties of the nonequilibrium liquid systems under irradiation in stationary state is introduced. The obtained results suggest that the thermophysical properties of the liquid systems under irradiation are defined by the "effective temperature" that can be calculated from the perturbed momentum distribution functions of the systems. It is shown that the structural changes in the liquid systems under irradiation are caused by the changes in the coefficients of the Maxwell distribution function due to the momentum exchange between the active particles and the particles forming the liquid. To confirm the theoretical predictions, a qualitative comparison of the model with the existing experimental data on irradiation influence on the surface tension coefficients of liquids is performed.

Impact of high-frequency ultrasound on nanocomposite microcapsules: in silico and in situ visualization.

The impact of high-frequency (1.2 MHz) ultrasound with a power density of 0.33 W cm(-2) on microcapsule nanocomposite shells with embedded zinc oxide nanoparticles was investigated by exploring modeling simulations and direct visualization. For the first time the sonication effect has been monitored in situ on individual microcapsules upon exposure of their aqueous suspension to ultrasound. The stress distribution on the microcapsule shell for the impact of ultrasound with high (1.2 MHz) and low (20 kHz) frequency at two fixed intensities (0.33 and 30 W cm(-2)) has been modeled. As shown in silico and experimentally the nanocomposite microcapsules were destroyed more effectively by the action of high-frequency (1.2 MHz) ultrasound in comparison to the low frequency (20 kHz) one with the same power density.

Mechanistic interpretation of the varying selectivity of Cesium-137 and potassium uptake by radish (Raphanus sativus L.) under field conditions near Chernobyl.

The selectivity of cation uptake by radish (Raphanus sativus L.) growing in the field near Chernobyl varies during the growth season. It is hypothesised that this is a consequence of variation in (137)Cs (Csss) and potassium (Kss) concentrations in the soil solution or the amount of dissolved potassium available to the plants. In the experiments reported here, it was observed that (1) Csss and Kss were positively correlated, (2) the selectivity for uptake of (137)Cs versus potassium (r) increased exponentially with decreasing Csss and Kss, and (3) the (137)Cs concentration, but not the potassium concentration, in plant material, increased abruptly upon the simultaneous reduction of Kss and Csss below about 10 µg ml(-1) and 6.7 Bq l(-1), respectively. It is thought that potassium enters root cells from the soil solution through constitutively-expressed, inward rectifying K(+) channels (KIRC) and K(+)/H(+)-symporters, whose abundance increases when plants become potassium-deficient. Cesium is thought to enter root cells through non-specific cation channels (NSCC) and, in plants lacking sufficient potassium, through K(+)/H(+)-symporters. It is argued that the increase in r, together with the abrupt increase (137)Cs concentration in plant tissues, when Kss and Csss decrease simultaneously cannot be attributed to competition between Cs(+) and K(+) for transport though KIRC, NSCC or K(+)/H(+)-symporters and that the most plausible explanation of these phenomena is an increase in the abundance of K(+)/H(+)-symporters in plants exhibiting incipient potassium deficiency.

Structural self-organization of C60 and cisplatin in physiological solution.

The specific features of structural self-organization of C60 fullerene and antitumor drug cisplatin (Cis) in physiological solution (0.9% NaCl) have been investigated by means of small-angle neutron scattering, scanning electron and atomic force microscopies, as well as isothermal titration calorimetry, dynamic light scattering and UV-Vis spectroscopy. The formation of C60 + Cis complexes, has been reported, unveiling the mechanism of medico-biological synergy observed during administration of the mixture of these drugs.

Effect of iron oxide loading on magnetoferritin structure in solution as revealed by SAXS and SANS.

Synthetic biological macromolecule of magnetoferritin containing an iron oxide core inside a protein shell (apoferritin) is prepared with different content of iron. Its structure in aqueous solution is analysed by small-angle synchrotron X-ray (SAXS) and neutron (SANS) scattering. The loading factor (LF) defined as the average number of iron atoms per protein is varied up to LF=800. With an increase of the LF, the scattering curves exhibit a relative increase in the total scattered intensity, a partial smearing and a shift of the match point in the SANS contrast variation data. The analysis shows an increase in the polydispersity of the proteins and a corresponding effective increase in the relative content of magnetic material against the protein moiety of the shell with the LF growth. At LFs above ∼150, the apoferritin shell undergoes structural changes, which is strongly indicative of the fact that the shell stability is affected by iron oxide presence.

[Interaction of DNA nucleotide bases with anticancer drug ThioTEPA: molecular docking and quantum-mechanical analysis].

Using modern methods of molecular docking, quantum chemistry and quantum theory of atoms in molecules the interaction of anticancer drug ThioTEPA with isolated nucleotide bases and deoxyribonucleosidemonophosphates of DNA has been studied. Physical properties and some trends of binding have been established for the complexes of "nucleotide base + ThioTEPA" and "deoxyribonucleosidemonophosphate + ThioTEPA" types. It has been shown that strong hydrogen bonds of NH...N type are the key factor responsible for high selectivity of binding of ThioTEPA to the guanine-containing units of the DNA.

On the origin of C60 fullerene solubility in aqueous solution.

In this work, we report that the surface hydroxylation of C60 molecules is the most likely mechanism for pristine C60 fullerenes/C60 fullerene aggregate stabilization in water, being independent of the method of C60 fullerene aqueous solution preparation.

[The heavy ion irradiation influence on the thermodynamic parameters of liquids in human body].

In this manuscript a theoretical model describing the influence of the heavy ion radiotherapy on the liquid matter in the human body is suggested. Based on the fundamental equations of Bogoliubov chain the effective temperatures in the case of constant particles fluent are found in the context of single component model. An existence of such temperatures allows the use of equilibrium thermodynamics formalism to nonequilibrium stationary state. The obtained results provide the possibility of predicting the liquid matter structural changes in the biological systems in the area influenced by the heavy ion beams.

Sedimentation stability and aging of aqueous dispersions of Laponite in the presence of cetyltrimethylammonium bromide.

This work discusses the sedimentation stability and aging of aqueous suspensions of Laponite in the presence of cetyltrimethylammonium bromide (CTAB). The concentration of Laponite was fixed at a constant level C(l)=2%wt, which corresponds to the threshold between equilibrium gel IG(1) and glass IG(2) states. The concentration of CTAB C(s) was within 0-0.3 %wt. In the presence of CTAB, the Laponite aqueous suspensions were unstable against sedimentation and separated into the upper and bottom layers (U and B layers, respectively). The dynamic light-scattering technique has revealed that addition of CTAB even at a rather small concentration, C(s)=0.0164 %wt (0.03 cation exchange capacity), induced noticeable changes in the aging dynamics of the U layer. It was explained by equilibration of CTAB molecules that were initially nonuniformly distributed between different Laponite particles. Accelerated stability analysis by means of analytical centrifugation with rotor speed ω=500-4000 rpm revealed three sedimentation regimes: continuous (I, C(s)<0.14 %wt), zonelike (II, 0.140.2%wt). It was demonstrated that the B layer was "soft" in the zonelike regime. The increase of ω resulted in its supplementary compressing and collapse of "soft" sediment above certain critical centrifugal acceleration. The physical nature of the observed behavior, accounting for enhancement of hydrophobic interactions between Laponite particles, is discussed.

Dispersion of electron-phonon resonances in one-layer graphene and its demonstration in micro-Raman scattering.

In the present work, we used Raman spectroscopy as sensitive tool for characterization of dispersion of electron-phonon resonances in one-layer graphene. We analyzed Stokes and anti-Stokes components of the Raman spectra to investigate the temperature dependence of the graphene G-band on the power of exciting radiation. Appearance and drastic intensity increase of zone-edge D-like modes caused by introduction of structural defects and/or deformations in the graphene layer were observed in the Raman spectra at high powers of excitation. We investigated phonon dispersion of one-layer graphene for iTO phonon branch at K point along K-M direction, which is involved in double-resonance Raman scattering. Raman dispersion slope of D-band is in good agreement with results of theoretical calculations based on the Green's functions approach based on the screened electron-electron interaction. Deviation of the experimental iTO phonon frequency from the linear dependence on excitation energy was observed at excitation E(exc) = 3.81 eV. Self-consistent classification of phonon states according to the symmetry for all dispersion branches of one-layer graphene was carried out.

Low- and high-frequency intermediate modes with step-like dispersion in resonance Raman scattering of carbon nanotubes.

Resonance Raman spectra of mixture of single-wall carbon nanotubes were investigated in details. The diameter distribution of the investigated nanotubes was estimated from the experimental frequencies of radial breathing modes. Two series of two-phonon lines revealing step-like behavior with excitation energy as well as non-dispersive single-phonon lines were registered in the intermediate frequency range 200-1200 cm(-1). Observed Raman lines were analyzed and their assignment to particular phonons was carried out. Step-like dispersive high intermediate-frequency modes in the range of 720-1000 cm(-1) are attributed to resonance two-phonon processes with combinations of optical and acoustical modes Low intermediate-frequency modes in the range of 300-650 cm(-1), also revealing step-like behavior, are attributed to resonance two-phonon processes with combinations of flexural optical and acoustical modes.

[The 5'-deoxyadenylic acid molecule conformational capacity: quantum-mechanical investigation using density functional theory (DFT)].

Exhaustive conformational analysis of the 5'-deoxyadenylic acid molecule, has been carried out by the quantum-mechanical density functional theory method at the MP2/6-311++G(d,p)//DFT B3LYP/6-31G(d,p) theory level. As many as 726 of its conformations have been revealed with the relative gas phase Gibbs energies under standard conditions from 0 to 12.1 kcal/mole. It has been shown, that the energetically most favorable conformation has north sugar puckering and synorientation of the nitrogenous base and is stabilized by intramolecular O(p1)H(p1)-N3 and O3'H-O(p) hydrogen bonds. Four conformations have been shown to have their geometry similar to that of AI-DNA and four - of BI-DNA. One conformer of the 5'-deoxyadenylic acid molecule is similar to its sodium salt hexahydrate structure in crystalline state resolved by the X-ray diffraction method and taken from literature. It is shown that effective charges of C4' and C5' atoms are the most sensitive to the molecule conformation ones. The role of the intramolecular OH-N hydrogen bonds in formation of the 5'-deoxyadenylic acid molecule structure has been demonstrated.

How flexible are DNA constituents? The quantum-mechanical study.

Relaxed force constants (RFCs) and vibrational root-mean-square deviations have been evaluated by the original calculation method for conformational parameters of the DNA structural units and their constituents: nucleic acid bases (uracile, thymine, cytosine, adenine and guanine) and their 'building blocks' (benzene, pyrimidine, imidazole and purine molecules), as well as the DNA backbone structural units: tetrahydrofuran, 1,2-dideoxyribose, methanol and orthophosphoric acid. It has been found that the RFCs for nomenclature torsions beta, gamma, epsilon; and sugar pseudorotation angle P in 1,2-dideoxyribose are sensible to the molecule conformation and their values are in the range of 1-25 kcal/(mole·rad²) obeying the inequality K(γ)> K(ε) > K(ρ) > K(ß). The RFCs values for endocyclic torsions of nucleic acid bases six-member rings lie within 15-45 kcal/(mole·rad²) in pyrimidines and within 20-60 kcal/(mole·rad²) in purines. It is shown that the quantum zero-point motion effectively neglects the amino group non-planarity in cytosine, adenine and partially in guanine.

[The simplest molecular model of 2'-deoxyribopolinucleotides sugar-phosphate backbone: quantum-chemical adequacy check].

The physical adequacy of the simplest molecular model "sugar residue (SR)--phosphate group (PG)--SR" of 2'-deoxyribopolinucleotides sugar-phosphate backbone is confirmed at DFT B3LYP/6-31++G(d,p) and DFT B3LYP/6-31G(d,p) of quantum-chemical methods. It is proved that complicacy of the model to the "SR-PG-SR-PG-SR" and higher levels does not noticeably change the numerical values of torsion angles. Also these angles depend negligibly on counterion nature (e.g. Na+ to Li+, K+ or Cs+ change) and transition from vacuum to continuum approximation with medium dielectrical values of 1.4, 24.9, and 78.4. It is shown that model loses its adequacy when PG is the end link.

[Conformational variety and physical properties of the 1,2-dideoxyribofuranose-5-phosphate, the model DNA monomer structural unit].

The results of exhaustive quantum-mechanical conformational analysis of 1,2-dideoxyribofuranose-5-phosphate molecule, the model DNA backbone structural unit, are presented. As many as 282 conformations with the relative Gibbs energies from 0 to 8.9 kcal/mole have been obtained at the MP2/cc-pVTZ // DFT B3LYP/cc-pVTZ theory level. Among them seven structures are similar to those of the DNA backbone in its AI, BI and ZII forms, while the B-DNA-like conformation has the lowest Gibbs energy (deltaG = 3.3 kcal/mole). It is shown that the relaxed force constants values for conformational parameters of all DNA-like conformations satisfy inequality K gamma > K alpha > K epsilon > K beta.