Review of Clinical Effects and Presumed Mechanism of Action of the French Oak Wood Extract Robuvit.

Since ancient times, oak wood polyphenols are consumed concomitantly with beverages that are stored and aged in oak wood barrels. Among these polyphenols are roburins, which belong to the class of ellagitannins and only occur in oak. To date, water-extracted standardized French Quercus robur wood extract, commercially known as Robuvit®, has been investigated in 1172 subjects in over 20 published clinical trials. The results of the clinical studies are consistent with reported effects of urolithins regarding increased mitophagy, pointing to enhanced energy capacity. The Robuvit metabolite urolithin A, B, and C levels and the number of urolithin producers were found to be increased after intake of the extract. Mitophagy is a process, which assigns energy inefficient mitochondria to disassembly, followed by reconstruction to new and more efficient replacements. This effect of Robuvit was observed in different study groups. Supplementation of Robuvit is ascribed to aid chronically fatigued or burnt-out individuals to regain higher energy and activity levels. Robuvit has been further shown to improve conditions such as renal insufficiency, liver insufficiency, mild heart failure, posttraumatic stress disorder and fatigue after surgery and facilitate recovery from mild health impairments such as flu or hangover. There are also indications that Robuvit helps improve erectile function and general loss of vigor in elderly men. Ex vivo gene expression experiments using metabolites collected from Robuvit consumers point to increased ribosomal biogenesis in endothelial, neuronal, and keratinocyte cells. Higher ribosome density accelerates the peptide production to meet protein demand, making Robuvit a potential enhancer of physical endurance and performance. A study with recreational athletes, supplemented with Robuvit daily, reported significantly increased performance in triathlon.

How are small endohedral silicon clusters stabilized?

Clusters in the (Be, B, C)@Si(n)((0,1,2+)) (n = 6-10) series, isoelectronic to Si(n)(2-), present multiple symmetric structures, including rings, cages and open structures, which the doping atom stabilizes using contrasting bonding mechanisms. The most striking feature of these clusters is the absence of electron transfer (for Be) or even the inversion (for B and C) in comparison to classic endohedral metallofullerenes (e.g. from the outer frameworks towards the enclosed atom). The relatively small cavity of the highly symmetric Si(8) cubic cage benefits more strongly from the encapsulation of a boron atom than from the insertion of a too large beryllium atom. Overall, the maximization of multicenter-type bonding, as visualized by the Localized Orbital Locator (LOL), is the key to the stabilization of the small Si(n) cages. Boron offers the best balance between size, electronegativity and delocalized bonding pattern when compared to beryllium and carbon.

Identifying clusters as low-lying mimina--efficiency of stochastic and genetic algorithms using inexpensive electronic structure levels.

Molecular candidates possessing unconventional chemical bonding paradigms (e.g., boron wheels, molecular stars, and multicenter bonding) have attracted a great deal of attention by the computational community. The viability of such systems is necessarily assessed through the identification of the lowest lying energy forms of a given chemical composition on the potential energy surface (PES). Although dozens of search algorithms have been developed, only a few are general and simple enough to become standard everyday procedures for this purpose. The simple random search and genetic algorithm (GA) are among these: but how do these approaches perform on typical isomeric searches? The performance of three specific variants for the ab initio exploration of the PES of prototype planar tetracoordinated and hypercoordinated carbon-containing systems C(2) Al(4) and CB(6) (2-) are compared. The advantages of preoptimizing with a low-cost semiempirical method (e.g., PM6) together with the most cost-efficient GA-based variant are discussed, and the trends verified by the isomer search of the larger Si(5) Li(7) (+) clusters.

Efficiency of random search procedures along the silicon cluster series: Si(n) (n=5-10, 15, and 20).

The efficiency of the simplest isomeric search procedure consisting in random generation of sets of atomic coordinates followed by density functional theory geometry optimization is tested on the silicon cluster series (Si(5-10, 15, 20)). Criteria such as yield, isomer distributions and recurrences are used to clearly establish the performance of the approach with respect to increasing cluster size. The elimination of unphysical candidate structures and the use of distinct box shapes and theoretical levels are also investigated. For the smaller Si(n) (n=5-10) clusters, the generation of random coordinates within a spherical box is found to offer a reasonable alternative to more complex algorithms by allowing straightforward identification of every known low-lying local minima. The simple stochastic search of larger clusters (i.e. Si(15) and Si(20)) is however complicated by the exponentially increasing number of both low- and high-lying minima leading to rather arbitrary and non-comprehensive results.

Non-intuitive separation of vanilla compounds using rapid resolution high-performance liquid chromatography.

A method is presented for modeling the retention peak migration in rapid resolution high-performance liquid chromatography (HPLC) depending on experimental parameter values. It allows time reduction on the determination of the experimental conditions for optimal resolution (especially for untrained chromatographers). Separation for 18 species present in a conventional vanilla formulation was not possible in a single chromatogram, due to a systematic error in defining single peak migration with the usual assumptions. This was achieved by the means of two runs under different experimental conditions. Prediction of the peak inversion for quantitation purposes in a given mixture is now possible and can help to avoid misidentification on set-ups with UV-ELSD or other non-specific detectors.

Conformational changes and aggregation of alginic acid as determined by fluorescence correlation spectroscopy.

Insight into the conformations and aggregation of alginic acid was gained by measuring its diffusion coefficient at very dilute concentrations using fluorescence correlation spectroscopy. Both the pH and ionic strength (I) had an important influence on the diffusion coefficient of the polysaccharide. For pH, three effects were isolated: (i) below pH 4, the charge density decreased causing increased aggregation; (ii) between pH 4 and 8, a molecular expansion was observed with increasing pH, whereas (iii) above pH 8 some dissociation of the polymer was observed. Increasing I from 0.001 to 0.1 M resulted in a ca. 20% increase in the diffusion coefficient. By coupling these measurements to molar mass determinations obtained by size exclusion chromatography and monomer size estimations determined from ab initio calculations, it was possible to determine the radii of gyration via de Gennes renormalization theory. From diffusion coefficients and radii of gyration obtained as a function of ionic strength, persistence lengths (total, electrostatic, and intrinsic) were calculated from the Benoit-Doty relationship.

Mathematical discretization of size-exclusion chromatograms applied to commercial corn maltodextrins.

Discretization of a size-exclusion chromatography (SEC) chromatogram is shown here to be an important calculation for characterizing the distribution of a polydisperse polymer, especially when the polydispersity is large. Commercial poly-glucose maltodextrins are known to have such a polydispersity. A mathematical discretization method with Gaussian peaks centered on each individual degree of polymerization is proposed and is performed on the entire SEC chromatogram for three different grades of corn maltodextrins. Because SEC and high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) are based on different separation mechanisms, they can be considered orthogonal techniques, and HPAEC-PAD was therefore used to validate the SEC discretization procedure. Because this validation proved satisfactory for all commercially available oligomers, the discretization is extended to all of their SEC chromatograms. Comparing the number-average molar weight and the weight-average molar weight before and after the mathematical discretization verifies that such a mathematical treatment does not denaturate the chromatogram. This approach tentatively leads to a more exhaustive characterization of a broadly polydisperse sample, such as maltodextrins, than was previously available, as it (i) gets rid of the apparent, chemically irrelevant, continuous molar weight distribution obtained by raw SEC and (ii) addresses the current detection and quantitation limits of the HPAEC-PAD technique without any sample treatment.

Quantifying Pb and Cd complexation by alginates and the role of metal binding on macromolecular aggregation.

The Pb and Cd binding capacity of alginates were quantified by the determination of their complex stability constants and the concentration of complexing sites using H+, Pb2+, or Cd2+ selective electrodes in both static and dynamic titrations. Centrifugation filter devices (30 kDa filter cutoff), followed by inductively coupled plasma mass spectrometry (ICP-MS) measurements of lead or cadmium in the filtrates, were used to validate the results. The influence of ionic strength, pH, and the metal-to-alginate ratio was determined for a wide range of metal concentrations. Because of their polyelectrolytic properties, alginates may adopt different conformations depending on the physicochemistry of the medium, including the presence of metals. Therefore, molecular diffusion coefficients of the alginate were determined by fluorescence correlation spectroscopy under the same conditions of pH, ionic strength, and metal-to-alginate ratios that were used for the metal binding studies. The complexation and conformational properties of the alginate were related within the framework of the nonideal competitive adsorption isotherm (NICA) combined with a Donnan approach to account for both intrinsic and electrostatic contributions.