The structure and dynamics of hydrated and hydroxylated magnesium oxide nanoparticles

An understanding of the structure of water on metal oxide nanoparticles is important due to its involvement in a number of surface processes, such as in the modification of transport near surfaces and the resulting impact on crystal growth and dissolution. However, as direct experimental measurements probing the metal oxide-water interface of nanoparticles are not easily performed, we use atomistic simulations using experimentally derived potential parameters to determine the structure and dynamics of the interface between magnesium oxide nanoparticles and water. We use a simple strategy to generate mineral nanoparticles, which can be applied to any shape, size, or composition. Molecular dynamics simulations were then used to examine the structure of water around the nanoparticles, and highly ordered layers of water were found at the interface. The structure of water is strongly influenced by the crystal structure and morphology of the mineral and the extent of hydroxylation of the surface. Comparison of the structure and dynamics of water around the nanoparticles with their two-dimensional flat surface counterparts revealed that the size, shape, and surface composition also affects properties such as water residence times and coordination number.     

Wild quotient singularities of surfaces

Let $(B,\mathcal{M }_B)$ be a noetherian regular local ring of dimension $2$ with residue field $B/\mathcal{M }_B$ of characteristic $p>0$ . Assume that $B$ is endowed with an action of a finite cyclic group $H$ whose order is divisible by $p$ . Associated with a resolution of singularities of $\mathrm{Spec}B^H$ is a resolution graph $G$ and an intersection matrix $N$ . We prove in this article three structural properties of wild quotient singularities, which suggest that in general, one should expect when $H= \mathbb{Z }/p\mathbb{Z }$ that the graph $G$ is a tree, that the Smith group $\mathbb{Z }^n/\mathrm{Im}(N)$ is killed by $p$ , and that the fundamental cycle $Z$ has self-intersection $|Z^2|\le p$ . We undertake a combinatorial study of intersection matrices $N$ with a view towards the explicit determination of the invariants $\mathbb{Z }^n/\mathrm{Im}(N)$ and $Z$ . We also exhibit explicitly the resolution graphs of an infinite set of wild $\mathbb{Z }/2\mathbb{Z }$ -singularities, using some results on elliptic curves with potentially good ordinary reduction which could be of independent interest.     

Competitive Process of Binding Between the Anionic Surfactants Sodium Dodecyl Sulfate and Sodium Cholate in Bovine Serum Albumin

Summary: In this study sodium cholate (NaC) was used as a representative bile salt for the competitive binding between NaC and sodium dodecyl sulfate (SDS) in bovine serum albumin (BSA), in 0.02 M tris-HCl buffer solution at pH 7.50 and 25 °C. The NaC and SDS associations with BSA were monitored at low surfactant concentrations where only this specific binding process can develop. The applied method to monitor the binding was based on the analysis of the effect of SDS and NaC concentrations and their mixtures upon the fluorescence intensity of the BSA tryptophan residues. This consists of the measurement of the surfactant monomer partitioning between the dispersion medium and the microaggregates on the protein molecule where the binding is indicated by the quenching of the fluorescence chromophores. Experimentally, varying the protein concentration, the surfactant concentration needed to reach a given I_o/I ratio (I_o and I are the intensities with and without protein, respectively) was measured. The analyses, based on the average number of surfactant molecules bound on the protein, indicated that the SDS is a more efficient quencher than the bile salt. The need for 4–6 NaC bound molecules to give the same protein quenching efficiency by a single molecule of SDS was estimated. We concluded that the differences in the competitive binding on the protein are exclusively related to the quenching efficiency in the formation of the nonfluorescent fluorophore-quencher complex via a physical contact and static quenching process.     

Free-base porphyrin polymer for bifunctional electrochemical water splitting

Water splitting is considered a promising approach for renewable and sustainable energy conversion. The development of water splitting electrocatalysts that have low-cost, long-lifetime, and high-performance is an important area of research for the sustainable generation of hydrogen and oxygen gas. Here, we report a metal-free porphyrin-based two-dimensional crystalline covalent organic polymer obtained from the condensation of terephthaloyl chloride and 5,10,15,20-tetrakis(4-aminophenyl) porphyrin which is stabilized by an extensive hydrogen bonding network. This material exhibits bifunctional electrocatalytic performance towards water splitting with onset overpotentials, η, of 36 mV and 110 mV for HER (in 0.5 M H₂SO₄) and OER (in 1.0 M KOH), respectively. The as-synthesized material is also able to perform water splitting in neutral phosphate buffer saline solution, with 294 mV for HER and 520 mV for OER, respectively. Characterized by electrochemical impedance spectroscopy (EIS) and chronoamperometry, the as-synthesized material also shows enhanced conductivity and stability compared to its molecular counterpart. Inserting a non-redox active zinc metal center in the porphyrin unit leads to a decrease in electrochemical activity towards both HER and OER, suggesting the four-nitrogen porphyrin core is the active site. The high performance of this metal-free material towards water splitting provides a sustainable alternative to the use of scarce and expensive metal electrocatalysts in energy conversion for industrial applications.

Water splitting is considered a promising approach for renewable and sustainable energy conversion.     

Two-dimensional gas of disks: Thermal conductivity

The phenomenon of heat conduction in a two-dimensional gas ofN hard disks is studied in the hydrostatic regime by means of nonequilibrium molecular dynamics (N ranging from 100 to 8000). For systems withN1500 the temperature and density profiles observed are in excellent agreement with the continuous theory, but the conductivityk differs from the one derived from Enskog's theory in a systematic way. This difference seems to slowly decrease with increasing density.     

Metabolic signature of breast cancer cell line MCF-7: profiling of modified nucleosides via LC-IT MS coupling

Background  

Cancer, like other diseases accompanied by strong metabolic disorders, shows characteristic effects on cell turnover rate, activity of modifying enzymes and DNA/RNA modifications, resulting also in elevated amounts of excreted modified nucleosides. For a better understanding of the impaired RNA metabolism in breast cancer cells, we screened these metabolites in the cell culture supernatants of the breast cancer cell line MCF-7 and compared it to the human mammary epithelial cells MCF-10A. The nucleosides were isolated and analyzed via 2D-chromatographic techniques: In the first dimension by cis-diol specific boronate affinity extraction and subsequently by reversed phase chromatography coupled to an ion trap mass spectrometer.     

Structural and magnetic evidence concerning spin crossover in formamidinate compounds with ru2 5+ cores

The magnetic and structural properties of two Ru2(DArF)4Cl compounds, where DArF is the anion of a diaryl formamidine, are presented here. The compounds with Ar = p-anisyl and m-anisyl both show temperature dependence of chiT (chi = molar magnetic susceptibility), but for different reasons. For the para compound, there is a Boltzmann distribution between a pi*3 ground state and a delta*pi*2 upper state, and this is confirmed by a temperature dependence of the Ru-Ru bond length: 2.4471(5) A at 23 K and 2.3968(5) A at 300 K. For the meta compound, a delta*pi*2 configuration persists over the range of 23-300 K as shown by an invariant Ru-Ru bond length, but the chiT drops with decreasing temperature owing to zero-field splitting of a 4B2u ground state.     

Palladium-catalyzed sequential alkylation-alkenylation reactions: application towards the synthesis of polyfunctionalized fused aromatic rings

The synthesis of polyfunctionalized fused aromatic carbo- and heterocycles from aryl iodides and bromoenoates via a tandem palladium-catalyzed aromatic substitution intramolecular Heck sequence is reported. Using Pd(OAc)₂ and tri-2-furylphosphine (TFP) in the presence of norbornene and Cs₂CO₃ in CH₃CN at 85 °C gave a variety of functionalized bi- and tricyclic fused aromatic rings in good yield.     

A force-field study of the conformational characteristics of the iduronate ring

Methods of molecular mechanics were applied to investigate the conformation of the (methyl 2-O-sulfate-4-methyl-α-L-idopyranose) uronic acid (DMIS), in order to correlate the peculiar vicinal proton coupling constants observed in polysaccharides containing the iduronate ring to the conformational characteristics of this sugar ring. We found three conformers with comparable energies, namely the two chair forms ¹C₄ and ⁴C₁ and the skew-boat form ²S₀(L); the latter is separated from each chair form by a barrier of about 9 kcal/mol. Along the pseudorotational path three additional minima (³S₁, ¹S₃, and ¹S₅) were found, yet at least 4 kcal/mol higher than ²S₀. The results obtained for the relative energies of the three conformers and the conformation of the side groups were affected by the inclusion of the electrostatic term and, in particular, by the charge assigned to the ionic groups of DMIS. However, the conformational properties of the idopyranosidic ring in DMIS (and in related compounds) should still be interpreted in terms of equilibrium among these three conformers only.