Delphinidin–Aluminum(III) Complexes in Aqueous and Non-Aqueous Media: Spectroscopic Characterization and Theoretical Study

Summary. The study of delphinidin complexation with trivalent aluminum in acidic aqueous buffered (pH 3.0 and 3.8) and methanolic solutions was performed utilizing electronic absorption spectroscopy and quantum chemical calculations. In its structure delphinidin possesses several chelating sites in competition towards aluminum(III). Molar ratio plots denoted the formation of only one aluminum(III):delphinidin complex of stoichiometry of 1:1 in both investigated media. Semiempirical calculations, performed at the restricted HF AM1 level, enabled the determination of the structural features of free delphinidin and structural modifications caused by chelation of aluminum(III). Considering the pigment molecular structure and the results of the theoretical calculations it is possible to equally implicate C3′–C4′ and C4′–C5′ hydroxyl groups as those with the predominant chelating power.     

Screening an In-House Isoquinoline Alkaloids Library for New Blockers of Voltage-Gated Na+ Channels Using Voltage Sensor Fluorescent Probes: Hits and Biases

Voltage-gated Na⁺ (Na_V) channels are significant therapeutic targets for the treatment of cardiac and neurological disorders, thus promoting the search for novel Na_V channel ligands. With the objective of discovering new blockers of Na_V channel ligands, we screened an In-House vegetal alkaloid library using fluorescence cell-based assays. We screened 62 isoquinoline alkaloids (IA) for their ability to decrease the FRET signal of voltage sensor probes (VSP), which were induced by the activation of Na_V channels with batrachotoxin (BTX) in GH3b6 cells. This led to the selection of five IA: liriodenine, oxostephanine, thalmiculine, protopine, and bebeerine, inhibiting the BTX-induced VSP signal with micromolar IC₅₀. These five alkaloids were then assayed using the Na⁺ fluorescent probe ANG-2 and the patch-clamp technique. Only oxostephanine and liriodenine were able to inhibit the BTX-induced ANG-2 signal in HEK293-hNa_V1.3 cells. Indeed, liriodenine and oxostephanine decreased the effects of BTX on Na⁺ currents elicited by the hNa_V1.3 channel, suggesting that conformation change induced by BTX binding could induce a bias in fluorescent assays. However, among the five IA selected in the VSP assay, only bebeerine exhibited strong inhibitory effects against Na⁺ currents elicited by the hNav1.2 and hNav1.6 channels, with IC₅₀ values below 10 µM. So far, bebeerine is the first BBIQ to have been reported to block Na_V channels, with promising therapeutical applications.     

Generating functional for mesonic ChPT with virtual photons in a general covariant gauge

The European Physical Journal A - The divergent part of the one-loop effective action in Chiral Perturbation Theory with virtual photons has been evaluated in an arbitrary covariant gauge. The...     

Moduli of symplectic instanton vector bundles of higher rank on projective space ℙ<Superscript>3</Superscript>

Symplectic instanton vector bundles on the projective space ℙ³ constitute a natural generalization of mathematical instantons of rank-2. We study the moduli space I _n;r of rank-2r symplectic instanton vector bundles on ℙ³ with r ≥ 2 and second Chern class n ≥ r, n ≡ r (mod 2). We introduce the notion of tame symplectic instantons by excluding a kind of pathological monads and show that the locus I _n;r ^* of tame symplectic instantons is irreducible and has the expected dimension, equal to 4n(r + 1) −r(2r + 1).     

Generalizing minimal supergravity

In Grand Unified Theories (GUTs), the Standard Model (SM) gauge couplings need not be unified at the GUT scale due to the high-dimensional operators. Considering gravity mediated supersymmetry breaking, we study for the first time the generic gauge coupling relations at the GUT scale, and the general gaugino mass relations which are valid from the GUT scale to the electroweak scale at one loop. We define the index k   for these relations, which can be calculated in GUTs and can be determined at the Large Hadron Collider and the future International Linear Collider. Thus, we give a concrete definition of the GUT scale in these theories, and suggest a new way to test general GUTs at future experiments. We also discuss five special scenarios with interesting possibilities. With our generic formulae, we present all the GUT-scale gauge coupling relations and all the gaugino mass relations in the SU(5)$\mathit{SU}(5)$ and SO(10)$\mathit{SO}(10)$ models, and calculate the corresponding indices k. Especially, the index k   is 5/3 in the traditional SU(5)$\mathit{SU}(5)$ and SO(10)$\mathit{SO}(10)$ models that have been studied extensively so far. Furthermore, we discuss the field theory realization of the U(1)$U(1)$ flux effects on the SM gauge kinetic functions in F-theory GUTs, and calculate their indices k as well.     

Carboxylate clays: A model study for polypropylene/clay nanocomposites

Sodium-montmorillonite was intercalated by carboxylate salts to prepare carboxylate clays. The intercalation of sodium acetate doubles the clay basal spacing and no degradation of the carboxylate clay is noticed in the extrusion temperature range. These carboxylate clays were used to synthesize polypropylene-graft-maleic anhydride (PP-g-MA)/clay nanocomposites. Nanocomposites were also produced by a one-pot process using in situ prepared carboxylate clay. The carboxylate salts within the clay layers partially neutralize the maleic anhydride groups of the PP-g-MA matrix, in situ during the melt compounding. The ionic groups of the partially neutralized polymer offer favourable interactions with the clay, hence reinforcing the interfacial bond between the polymer and the clay and improving the composite properties. The use of carboxylate clay clearly improves the clay dispersion into the PP-g-MA matrix and improves the nanocomposite’s thermal and rheological properties.     

A fluorescence toolbox: A review of investigation of electrophoretic separations,process, and interfaces

This review focuses on fluorescence spectroscopy techniques for the investigation of electrophoretic separations. Fluorescence has been used as a sensitive detector for capillary, gel, and microchip electrophoresis for decades. However, advanced fluorescence methods can be used to study transport, interfacial phenomena, intermolecular and affinity interactions, and other processes that occur during separation. This so‐called spectroscopic toolkit can be implemented to understand fundamental behavior in electrophoresis and electrokinetic chromatography. Techniques such as fluorescence recovery after photobleaching, fluorescence correlation spectroscopy, and fluorescence anisotropy are discussed in relation to electrophoretic separations. Newer methods such as super‐resolution microscope are also introduced.     

Mechanistic pathways for the reaction of quercetin with hydroperoxy radical

The extensive theoretical study of the interaction of one of the most abundant and reactive flavonols, quercetin, with hydroperoxy radical (HOO·), using the M052X/6-31 + Gd, p level of theory, was performed. Results indicating that quercetin is not a planar molecule are in accord with the X-ray analysis. The applied method successfully reproduces the bond dissociation enthalpy, and reveals that the reaction of quercetin with the hydroperoxy radical is governed by a hydrogen atom transfer mechanism. It is confirmed that the 3′OH and 4′OH are the most reactive sites, and that the reaction in the 3′OH position is faster than that in the 4′OH position.     

A cryosolution infrared study of the complexes of fluoroform with ammonia and pyridine: Evidence for a C-H...N pseudo blue-shifting hydrogen bond

Mid-infrared spectra of mixed solutions in liquid xenon containing fluoroform and either ammonia or pyridine have been investigated at temperatures between 173 and 213 K. For both Lewis bases, a new band is found in the CH stretching region at a frequency approximately 5 cm(-1) higher than that of monomer fluoroform, which is assigned to a complex between fluoroform and the Lewis base. A detailed analysis of the nu1/2nu(4) Fermi resonance in the proton donor shows that the blue shifts observed for the complexes are not caused by a strengthening of the CH bond during the complexation, but are due to the changes in the Fermi resonance interactions. Information on the nu1/2nu(4) Fermi resonance was also obtained for the complexes of fluoroform with dimethyl ether and trimethyl amine.