Ionic liquids with fluorine-containing anions as a new class of functional materials: features of the synthesis,physicochemical properties,and use

Russian Chemical Bulletin - The results obtained by the authors and literature data on the methods of preparation, properties, and the use of ionic liquids with fluorine-containing anions are...     

Approximation and Complexity II: Iterated Integration

We introduce two classes of real analytic functions W \subset U on an interval. Starting with rational functions to construct functions in W we allow the application of three types of operations: addition, integration, and multiplication by a polynomial with rational coefficients. In a similar way, to construct functions in U we allow integration, addition, and multiplication of functions already constructed in U and multiplication by rational numbers. Thus, U is a subring of the ring of Pfaffian functions [7]. Two lower bounds on the L _∈fty -norm are proved on a function f from W (or from U , respectively) in terms of the complexity of constructing f .     

Focused grid‐based resampling for protein docking and mapping

The fast Fourier transform (FFT) sampling algorithm has been used with success in application to protein‐protein docking and for protein mapping, the latter docking a variety of small organic molecules for the identification of binding hot spots on the target protein. Here we explore the local rather than global usage of the FFT sampling approach in docking applications. If the global FFT based search yields a near‐native cluster of docked structures for a protein complex, then focused resampling of the cluster generally leads to a substantial increase in the number of conformations close to the native structure. In protein mapping, focused resampling of the selected hot spot regions generally reveals further hot spots that, while not as strong as the primary hot spots, also contribute to ligand binding. The detection of additional ligand binding regions is shown by the improved overlap between hot spots and bound ligands. © 2016 Wiley Periodicals, Inc.     

From the microscopic to the mesoscopic properties of lyotropic reverse hexagonal liquid crystals

In the present study we aimed to explore a correlation between the microstructural properties of the lyotropic reverse hexagonal phase (HII) of the GMO/tricaprylin/phosphatidylcholine/water system and its mesoscopic structure. The mesoscopic organization of discontinuous and anisotropic domains was examined, in the native state, using environmental scanning electron microscopy. The topography of the HII mesophases was imaged directly in their hydrated state, as a function of aqueous-phase concentration and composition, when a proline amino acid was solubilized into the systems as a kosmotropic (water-structure maker) guest molecule. The domain structures of several dozen micrometers in size, visualized in the environmental scanning electron microscopy, were found to possess fractal characteristics, indicating a discontinuous and disordered alignment of the corresponding internal water rods on the mesoscale. On the microstructural level, SAXS measurements revealed that as water content (Cw) increases the characteristic lattice parameter of the mesophases increases as well. Using the water concentration as the mass measure of the mixtures, a scaling relationship between the lattice parameter and the concentration was found to obey a power law whereby the derived fractal dimension was the relevant exponent, confirming the causal link between the microscopic and mesoscopic organizations. The topography of the HII mesophase was found to be affected by the microstructural parameters and the composition of the samples. Thermal analysis experiments involving these systems further confirmed that the behavior of water underpins both microscopical and mesoscopic features of the systems. It was shown that both the swelling of the lattice parameter and the mesoscopic domains is correlated to the bulk water concentration in the water rods.     

Interactions between hydrophobic and ionic solutes in aqueous guanidinium chloride and urea solutions: lessons for protein denaturation mechanism

In order to clarify the mechanism of denaturant-induced unfolding of proteins we have calculated the interactions between hydrophobic and ionic species in aqueous guanidinium chloride and urea solutions using molecular dynamics simulations. Hydrophobic association is not significantly changed in urea or guanidinium chloride solutions. The strength of interaction between ion pairs is greatly diminished by the guanidinium ion. Although the changes in electrostatic interactions in urea are small, examination of structures, using appropriate pair functions, of urea and water around the solutes show strong hydrogen bonding between urea's carbonyl oxygen and the positively charged solute. Our results strongly suggest protein denaturation occurs by the direct interaction model according to which the most commonly used denaturants unfold proteins by altering electrostatic interactions either by solvating the charged residues or by engaging in hydrogen bonds with the protein backbone. To further validate the direct interaction model we show that, in urea and guanidinium chloride solutions, unfolding of an unusually stable helix (H1) from mouse PrPC (residues 144-153) occurs by hydrogen bonding of denaturants to charged side chains and backbone carbonyl groups.     

Pharmacological and Therapeutic Properties of Punica granatum Phytochemicals: Possible Roles in Breast Cancer

Background: Pomgranate (Punica granatum) represents a high source of polyphenols with great bioavailability. The role of this fruit in the prevention and treatment of various malignant pathologies has been long time cited in both scientific and non-scientific literature, making thus important to identify its involvement in the pathophysiological processes. The treatment for breast cancer had focused on the inhibition of the mechanisms that governs the estrogen activity. These mechanisms are covered either by the antagonism of the estrogen receptor (ER) or by the inhibition of the estrogen synthesis. Our interest in identifying a bioactive compound rich in polyphenols, which induces both the antagonism of the estrogen receptor, and the inhibition of the estrogen synthesis, revealed us the pomegranate fruit and its derivatives: peel and seeds. Pomegranates’ chemical composition include many biological active substances such as flavonols, flavanols, anthocyanins, proanthocyanidins, ellagitannins and gallotannins. Materials and Methods: We performed a review of the scientific literature by using the following keywords: “pomegranate”, “breast cancer”, “Punica granatum”, “pomegranate polyphenols”. Our search was performed in the PubMed and Google Scholar databases, and it included only original research written in English from the last 20 years. None of the articles were excluded due to affiliation. A total number of 28 original papers, which mentioned the beneficial activity of pomegranate against breast cancer, were selected. Both clinical and preclinical studies were considered for this review. Results: Recent discoveries pointed out that polyphenols from Punica granatum possess strong anti-cancer activity, exhibited by a variety of mechanisms, such as anti-estrogenic, anti-proliferative, anti-angiogenetic, anti-inflammatory, and anti-metastatic. Pomegranate extracts induced cell cycle arrest in the G0/G1 phase, and induced cytotoxicity in a dose- and time-dependent manner. Moreover, several polyphenols extracted from pomegranate inhibited the invasion potential, migration and viability of breast cancer cells. The effects of pomegranate juice on serum estrogens and other sexual hormones levels were also investigated on two human cohorts. Conclusions: Punica granatum represents a promising area in oncology. The large availability and low cost, associated with the lack of side effects, made from this natural product a great strategy for the management of breast cancer. There are several mechanistic studies in mouse models and in breast cancer cell lines, suggesting the possible pathways through which polyphenols from pomegranate extracts act, but larger and better-controlled studies are necessary in the future. Only two small clinical trials were conducted on humans until now, but their results are contradictory and should be considered preliminary.     

Scaling Platinum-Catalyzed Hydrogen Dissociation on Corrugated Surfaces

We determine absolute reactivities for dissociation at low coordinated Pt sites. Two curved Pt(111) single-crystal surfaces allow us to probe either straight or highly kinked step edges with molecules impinging at a low impact energy. A model extracts the average reactivity of inner and outer kink atoms, which is compared to the reactivity of straight A- and B-type steps. Local surface coordination numbers do not adequately capture reactivity trends for H₂ dissociation. We utilize the increase of reactivity with step density to determine the area over which a step causes increased dissociation. This step-type specific reactive area extends beyond the step edge onto the (111) terrace. It defines the reaction cross-section for H₂ dissociation at the step, bypassing assumptions about contributions of individual types of surface atoms. Our results stress the non-local nature of H₂ interaction with a surface and provide insight into reactivity differences for nearly identical step sites.     

Non-linear oscillations of a Hamiltonian system in the case of 3:1 resonance

The motion of an autonomous Hamiltonian system with two degrees of freedom near its equilibrium position is considered. It is assumed that, in a certain region of the equilibrium position, the Hamiltonian is an analytic and sign-definite function, while the frequencies of linear oscillations satisfy a 3:1 ratio. A detailed analysis of the truncated system, corresponding to the normalized Hamiltonian is given, in which terms of higher than the fourth order are dropped. It is shown that the truncated system can be integrated in terms of Jacobi elliptic functions, and its solutions describe either periodic motions or motions that are asymptotic to periodic motions, or conventionally periodic motions. It is established, using the KAM-theory methods, that the majority of conventionally periodic motions are also preserved in the complete system. Moreover, in a fairly small neighbourhood of the equilibrium position, the trajectories of the complete system, which are not conventionally periodic, form a set of exponentially small measure. The results of the investigation are used in the problem of the motion of a dynamically symmetrical satellite in the region of its cylindrical precession.     

Standard model light-by-light scattering in SANC: Analytic and numeric evaluation

The implementation of the Standard Model process γγ → γγ through a fermion and boson loop into the framework of SANC system and additional precomputation modules used for calculation of massive box diagrams are described. The computation of this process takes into account nonzero mass of loop particles. The covariant and helicity amplitudes for this process, some particular cases of D ₀ and C ₀ Passarino-Veltman functions, and also numerical results of corresponding SANC module evaluation are presented. Whenever possible, the results are compared with those existing in the literature.     

SANC: the process γγ → <Emphasis Type="Italic">ΖΖ</Emphasis>

The implementation of the process γγ → ΖΖ at the one-loop level within SANC system multichannel approach is considered. The derived one-loop scalar form factors can be used for any cross channel after an appropriate permutation of their arguments–Mandelstam variables s, t, u. To check of the correctness of the results we observe the independence of the scalar form factors on the gauge parameters and the validity of Ward identity (external photon transversality). We present the complete analytical results for the covariant and tensor structures and helicity amplitudes for this process. We make an extensive comparison of our analytical and numerical results with those existing in the literature.