Recovery of Anthocyanins and Monosaccharides from Grape Marc Extract by Nanofiltration Membranes

Wastewaters and by-products generated in the winemaking process are important and inexpensive sources of value-added compounds that can be potentially reused for the development of new products of commercial interest (i.e., functional foods). This research was undertaken in order to evaluate the potential of nanofiltration (NF) membranes in the recovery of anthocyanins and monosaccharides from a clarified Carménère grape marc obtained through a combination of ultrasound-assisted extraction and microfiltration. Three different flat-sheet nanofiltration (NF) membranes, covering the range of molecular weight cut-off (MWCO) from 150 to 800 Da, were evaluated for their productivity as well as for their rejection towards anthocyanins (malvidin-3-O-glucoside, malvidin 3-(acetyl)-glucoside, and malvidin 3-(coumaroyl)-glucoside) and sugars (glucose and fructose) in selected operating conditions. The selected membranes showed differences in their performance in terms of permeate flux and rejection of target compounds. The NFX membrane, with the lowest MWCO (150–300 Da), showed a lower flux decay in comparison to the other investigated membranes. All the membranes showed rejection higher than 99.42% for the quantified anthocyanins. Regarding sugars rejection, the NFX membrane showed the highest rejection for glucose and fructose (100 and 92.60%, respectively), whereas the NFW membrane (MWCO 300–500 Da) was the one with the lowest rejection for these compounds (80.57 and 71.62%, respectively). As a general trend, the tested membranes did not show a preferential rejection of anthocyanins over sugars. Therefore, all tested membranes were suitable for concentration purposes.     

Interactive model-based search with reactive resource allocation

We revisit the interactive model-based approach to global optimization proposed in Wang and Garcia (J Glob Optim 61(3):479–495, 2015) in which parallel threads independently execute a model-based search method and periodically interact through a simple acceptance-rejection rule aimed at preventing duplication of search efforts. In that paper it was assumed that each thread successfully identifies a locally optimal solution every time the acceptance-rejection rule is implemented. Under this stylized model of computational time, the rate of convergence to a globally optimal solution was shown to increase exponentially in the number of threads. In practice however, the computational time required to identify a locally optimal solution varies greatly. Therefore, when the acceptance-rejection rule is implemented, several threads may fail to identify a locally optimal solution. This situation calls for reallocation of computational resources in order to speed up the identification of local optima when one or more threads repeatedly fail to do so. In this paper we consider an implementation of the interactive model-based approach that accounts for real time, that is, it takes into account the possibility that several threads may fail to identify a locally optimal solution whenever the acceptance-rejection rule is implemented. We propose a modified acceptance-rejection rule that alternates between enforcing diverse search (in order to prevent duplication) and reallocation of computational effort (in order to speed up the identification of local optima). We show that the rate of convergence in real-time increases with the number of threads. This result formalizes the idea that in parallel computing, exploitation and exploration can be complementary provided relatively simple rules for interaction are implemented. We report the results from extensive numerical experiments which are illustrate the theoretical analysis of performance.     

Metal free coupling of heteroaryl N-tosylhydrazones and thiols: Efficient synthesis of sulfides

A metal free coupling of heteroaromatic N-tosylhydrazones with thiols is presented. A convenient synthetic route to synthesize heteroaryl N-tosylhydrazones is also showed. Valuable thioethers with pyrroles, pyridines, thieno[2,3-b]pyridines, imidazo[1,2-a]pyridines, and 6H-thieno[2,3-b]pyrroles derivatives were synthesized in good yields. This coupling reaction can be carried out in a one-pot fashion and scaled up to the gram scale by using heteroaryl aldehydes, without the need to isolate the N-tosylhydrazone.     

Trihapto Ligation of a Borirene to a Single Metal Atom: A Heterocyclic Analogue of the η3‐Cyclopropenyl Ligand

The first example of a complex containing an η³‐coordinated borirene ligand bound to a single metal atom was prepared by photolytic transfer of an arylborylene ligand to diphenylacetylene and loss of three CO ligands from the precursor. The η³‐borirene complex possesses a chromium(0) atom which is also bound to one phenyl group in an η⁶ fashion. The complex was isolated in 15 % yield along with the corresponding metal‐free borirene, which was isolated in 62 % yield. The bonding between the chromium center and the borirene ring was studied computationally by DFT methods.     

Synthesis of [N,P] ligands based on pyrrole. Application to the total synthesis of arnottin I

This paper describes the synthesis of a new class of [N,P] ligands based on pyrrole with a dimethylamino group as hard donor and a phosphine moiety as soft base. We have also modified the phosphine fragment to change the electronic and steric properties of these ligands. Palladium complex 3a proved to be very efficient in Heck cross-coupling reactions and in intramolecular aryl–aryl couplings of esters and amides. We have demonstrated the applicability and efficiency of this novel catalyst in the total synthesis of the natural product arnottin I.     

Exclusive π Encapsulation of Light Alkali Metal Cations by a Neutral Molecule

Cation–π interactions are one of the most important classes of noncovalent bonding, and are seen throughout biology, chemistry, and materials science. However, in almost every documented case, these interactions play only a supporting role to much stronger covalent or dative bonds, thus making examples of exclusive cation–π bonding exceedingly rare. In this study, a neutral diboryne molecule is found to encapsulate the light alkali metal cations Li⁺ and Na⁺ in the absence of a net charge, covalent bonds, or lone‐pair donor groups. The resulting encapsulation complexes are, to our knowledge, the first structurally authenticated species in which a neutral molecule binds the light alkali metals exclusively through cation–π interactions.     

Gravitoelectromagnetic inflation from a 5D vacuum state: A new formalism

We propose a novel formalism for inflation from a 5D vacuum state which could explain both, seeds of matter and magnetic fields in the early universe.