Silver: a novel growth catalyst for Ge nanoislands on Si(113)

The impact of silver pre‐adsorption on germanium growth on Si(113) was investigated using in‐situ low‐energy electron microscopy (LEEM) as well as low‐energy electron diffraction (LEED). The adsorption of silver leads to the formation of a regular pattern of nanofacets along the [1 0] direction. The periodicity of this pattern in [33 ] direction was determined to (44 ± 4) nm. From LEED series at different energies the facets were identified to be of (111) and (115) orientation. While the (111) facets show a (√3 × √3)‐R30° reconstruction, the (115) facets exhibit a (2 × n) superstructure. The subsequent growth of Ge results in the formation of nanoislands that are aligned along the facets. These Ge islands have an anisotropic shape with typical sizes of about 100 nm in [33 ] direction and 400 nm in [1 0] direction. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

New results on the melting thermodynamics of a circular DNA chain

We investigate the impact of supercoil period and nonzero supercoil formation energy on the thermal denaturation of a circular DNA. Our analysis is based on a recently proposed generalization of the Poland-Scheraga model that allows the DNA melting to be studied for plasmids with circular topology, where denaturation is accompanied by formation of supercoils. We find that the previously obtained first-order melting transition persists under the generalization discussed. The dependence of the size of the order-parameter jump at the transition point and the associated melting temperature are obtained analytically.     

Refratometric study of ternary mixtures formed by water,glucose and acetonitrile at temperatures ranging from 293 K to 333 K

The study of thermodynamic properties of solutions provides important information on existing molecular interactions between the components present in a solution. These studies are critical for testing, validation and development of theories and mathematical models. The refractometric study of a solution is a simple assessment that can contribute to the understanding of these interactions. In this context, the behaviour of the binary water and glucose mixture was studied as well as ternary mixtures of water, glucose and acetonitrile at five different temperatures in the range 293–333 K by the determination of the refractive index of the solution. Due to the weakening of the molecular interactions with the increasing of the temperature, a decreasing dependence of refractive index with temperature was observed. The addition of acetonitrile provides an increase in the refractive index indicating the formation of clusters in the solution.     

N‐dimensional switch function for energy conservation in multiprocess reaction dynamics

The MReaDy program was designed for studying Multiprocess Reactive Dynamic systems, that is, complex chemical systems involving different and concurrent reactions. It builds a global potential energy surface integrating a variety of potential energy surfaces, each one of them representing an elementary reaction expected to play a role in the chemical process. For each elementary reaction, energy continuity problems may happen in the transition between potential energy surfaces due to differences in the functional form for each of the fragments, especially if built by different authors. A N‐dimensional switch function is introduced in MReaDy in order to overcome such a problem. As an example, results of a collision trajectory calculation for H₂ + OH → H₃O are presented, showing smooth transition in the potential energy, leading to conservation in the total energy. Calculations for a hydrogen combustion system from 1000 K up to 4000 K shows a variation of 0.012% when compared to the total energy of the system. © 2016 Wiley Periodicals, Inc.     

New insights on the origins of the stereocontrol of the staudinger reaction: [2 + 2] cycloaddition between ketenes and N-silylimines

Density-functional theory studies on the [2 + 2] reaction between N-silylimines and ketenes to form the corresponding 2-azetidinones (beta-lactams) help to clarify several aspects on the mechanism of the Staudinger reaction. This reaction has been studied experimentally by Panunzio et al. It is shown that the formation of the 2-azetidinone ring takes place via two consecutive reactions. The first reaction consists of the nucleophilic addition of the iminic nitrogen to the sp-hybridized carbon atom of the ketene, with simultaneous migration of the silyl group from the imine to the oxygen atom of the ketene. This leads to silyl enol intermediates, in good agreement with the experimental results. Formation of the N-silylated beta-lactam takes place via a domino reaction consisting of a conrotatory thermal electrocyclization followed by a new silatropic rearrangement. It is also found that isomerization of the starting N-silylimine has a lower activation barrier than that associated with the formation of the C-N bond, which explains the stereochemical outcome experimentally observed. Further considerations on the asymmetric torquoelectronic effects involved in this reaction are also reported.     

2,4‐Dibromo‐3‐methoxy‐6‐nitrobenz­aldeyde: effect of substituents on ring geometry

In the title compound, C₈H₅Br₂NO₄, the endocyclic angles of the ring deviate significantly from the ideal value of 120°. The substituents deviate from the plane of the ring, with large twist angles for the aldehyde, nitro and methoxy groups. The geometry of the mol­ecule in the crystal is compared with that of the isolated mol­ecule, as given by a self‐consistent field molecular‐orbital Hartree–Fock calculation. Only weak hydrogen bonds of the C—H?Br and C—H?O types are present in the crystal structure.     

Adiabatic corrections to density functional theory energies and wave functions

The adiabatic finite-nuclear-mass-correction (FNMC) to the electronic energies and wave functions of atoms and molecules is formulated for density-functional theory and implemented in the deMon code. The approach is tested for a series of local and gradient corrected density functionals, using MP2 results and diagonal-Born-Oppenheimer corrections from the literature for comparison. In the evaluation of absolute energy corrections of nonorganic molecules the LDA PZ81 functional works surprisingly better than the others. For organic molecules the GGA BLYP functional has the best performance. FNMC with GGA functionals, mainly BLYP, show a good performance in the evaluation of relative corrections, except for nonorganic molecules containing H atoms. The PW86 functional stands out with the best evaluation of the barrier of linearity of H2O and the isotopic dipole moment of HDO. In general, DFT functionals display an accuracy superior than the common belief and because the corrections are based on a change of the electronic kinetic energy they are here ranked in a new appropriate way. The approach is applied to obtain the adiabatic correction for full atomization of alcanes C(n)H(2n+2), n = 4-10. The barrier of 1 mHartree is approached for adiabatic corrections, justifying its insertion into DFT.     

The use of acridine orange base (AOB) as molecular probe to characterize nonaqueous AOT reverse micelles

The behavior of acridine orange base (AOB) in nonaqueous reverse micelles composed of n-heptane/AOT/polar solvent has been performed. Ethylene glycol (EG), propylene glycol (PG), glycerol (GY), formamide (FA), dimethylformamide (DMF), and dimethylacetamide (DMA) were employed as water substitutes. The studies were performed by static and time-resolved emission spectroscopy. Thus, the distribution of AOB between the two pseudophases of the aggregates was quantified by measuring the partition constants from emission spectra at different surfactant concentration. Similar values to those obtained by means of absorption spectroscopy were obtained. This match is indicating that AOB is not experiencing partition during the lifetime of the excited state. Partitioning to the micelles is strongly favored in micelles containing hydrogen-bond donor (HBD) solvents rather than non-HBD solvents. Variations of fluorescence lifetimes with AOT concentration confirm these results. By the solvatochromic behavior of AOB in the different systems it is shown that the microenvironment at the interface is distinct from that of the bulk polar solvent, indicating that the probe senses no "free" solvent. The steady state anisotropy (r) was measured for EG/AOT/n-heptane and DMF/AOT/n-heptane systems as representatives for HBD and non-HBD polar solvents, respectively. The value of r is higher in the micelles containing EG than that obtained with DMF, and increases with AOT concentration. This is explained as due to highly structured polar solvents in the inner core. EG is interacting with the polar heads of AOT through hydrogen-bond interaction, while DMF can only interact with the Na+ counterions. This is confirmed by the time-resolved emission spectra (TRES) of the probe in the micellar systems, in comparison with the bulk solvents.     

New gold(III) chlorophenyl terpyridine complex: Biomolecular interactions and anticancer activity against human oral squamous cell carcinoma

In this work we synthesized new monofunctional gold(III) complex [Au(Cl-Ph-tpy)Cl]Cl₂ (Cl-Ph-tpy = 4′-[4-chlorophenyl]-2,2′:6′, 2″-terpyridine). This complex was characterized by UV–Vis, NMR, IR, and ESI-MS spectrometry. The kinetic study of the substitution reactions of the Au-Cl-Ph-tpy complex with biomolecules showed that the rate constants depend on the nature of the entering nucleophile. Based on the calculated values of entropy (∆H^≠ > 0) and enthalpy (∆S^≠ < 0) the proposed substitution mechanism is associative. Additionally, the relative stability and thermodynamic properties of Au-Cl-Ph-tpy complex were compared with the analogue Au-tpy complex by the B3LYP/def2-svp method. DNA/BSA binding studies showed that Au-Cl-Ph-tpy complex interacts with CT DNA through the intercalation and moderately quenches the fluorescence of tryptophan residues in serum albumin (BSA). Molecular docking confirmed results obtained by spectroscopic experiments and suggested site I (subdomain IIA) for binding of Au complex to BSA. We demonstrated that the Au chlorophenyl terpyridine complex possessed significant in vitro cytotoxic activity against human oral squamous carcinoma cells (CAL-27), induced apoptosis, inhibited proliferation of CAL-27 cells, and induced cell cycle disturbance. Treatment of CAL-27 cells with the Au complex enhanced expression of cyclin-dependent kinase inhibitors p21 and p27, resulting in cell cycle arrest in the G1 phase, reduced the percentage of CAL-27 cells in S phase and decreased expression of Ki-67. Additionally, Au complex reduced expression of phosphorylated STAT3 and downstream regulated molecules associated with cancer stemness, NANOG, and Sox2 protein.     

Molecular Hybridization Strategy on the Design,Synthesis, and Structural Characterization of Ferrocene-N-acyl Hydrazones as Immunomodulatory Agents

Immunomodulatory agents are widely used for the treatment of immune-mediated diseases, but the range of side effects of the available drugs makes necessary the search for new immunomodulatory drugs. Here, we investigated the immunomodulatory activity of new ferrocenyl-N-acyl hydrazones derivatives (SintMed(141–156). The evaluated N-acyl hydrazones did not show cytotoxicity at the tested concentrations, presenting CC₅₀ values greater than 50 µM. In addition, all ferrocenyl-N-acyl hydrazones modulated nitrite production in immortalized macrophages, showing inhibition values between 14.4% and 74.2%. By presenting a better activity profile, the ferrocenyl-N-acyl hydrazones SintMed149 and SintMed150 also had their cytotoxicity and anti-inflammatory effect evaluated in cultures of peritoneal macrophages. The molecules were not cytotoxic at any of the concentrations tested in peritoneal macrophages and were able to significantly reduce (p < 0.05) the production of nitrite, TNF-α, and IL-1β. Interestingly, both molecules significantly reduced the production of IL-2 and IFN-γ in cultured splenocytes activated with concanavalin A. Moreover, SintMed150 did not show signs of acute toxicity in animals treated with 50 or 100 mg/kg. Finally, we observed that ferrocenyl-N-acyl hydrazone SintMed150 at 100 mg/kg reduced the migration of neutrophils (44.6%) in an acute peritonitis model and increased animal survival by 20% in an LPS-induced endotoxic shock model. These findings suggest that such compounds have therapeutic potential to be used to treat diseases of inflammatory origin.