Asymmetric Synthesis of Spirooxindoles via Nucleophilic Epoxidation Promoted by Bifunctional Organocatalysts

Taking into account the postulated reaction mechanism for the organocatalytic epoxidation of electron-poor olefins developed by our laboratory, we have investigated the key factors able to positively influence the H-bond network installed inside the substrate/catalyst/oxidizing agent. With this aim, we have: (i) tested a few catalysts displaying various effects that noticeably differ in terms of steric hindrance and electron demand; (ii) employed α-alkylidene oxindoles decorated with different substituents on the aromatic ring (11a-g), the exocylic double bond (11h-l), and the amide moiety (11m-v). The observed results suggest that the modification of the electron-withdrawing group (EWG) weakly conditions the overall outcomes, and conversely a strong influence is unambiguously ascribable to either theN-protected orN-unprotected lactam framework. Specifically, when the NH free substrates (11m-u) are employed, an inversion of the stereochemical control is observed, while the introduction of a Boc protecting group affords the desired product12vin excellent enantioselectivity (97:3er)

PRGdb: a bioinformatics platform for plant resistance gene analysis

PRGdb is a web accessible open-source (http://www.prgdb.org) database that represents the first bioinformatic resource providing a comprehensive overview of resistance genes (R-genes) in plants. PRGdb holds more than 16 000 known and putative R-genes belonging to 192 plant species challenged by 115 different pathogens and linked with useful biological information. The complete database includes a set of 73 manually curated reference R-genes, 6308 putative R-genes collected from NCBI and 10463 computationally predicted putative R-genes. Thanks to a user-friendly interface, data can be examined using different query tools. A home-made prediction pipeline called Disease Resistance Analysis and Gene Orthology (DRAGO), based on reference R-gene sequence data, was developed to search for plant resistance genes in public datasets such as Unigene and Genbank. New putative R-gene classes containing unknown domain combinations were discovered and characterized. The development of the PRG platform represents an important starting point to conduct various experimental tasks. The inferred cross-link between genomic and phenotypic information allows access to a large body of information to find answers to several biological questions. The database structure also permits easy integration with other data types and opens up prospects for future implementations

Asymmetric Organocatalytic Aziridination: Recent Advances

Aziridines, the nitrogen counterparts of epoxides, are among the most challenging and intriguing heterocycles in organic chemistry since they not only represent the endpoints of several total syntheses as common scaffolds in natural products but also act as crucial precursors of complex molecules. The present review provides a brief overview of aziridine derivatives as well as the authors’ choice of published papers that highlight recent enhancements concerning asymmetric organocatalytic strategies involved in aziridination reactions

Exploiting Scaling Laws for Designing Polymeric Bottle Brushes: a Theoretical Coarse-Graining for Homopolymeric Branched Polymers

Bottle brushes are polymeric macromolecules made of a linear polymeric backbone grafted with side chains. The choice of the grafting density sg, of the length ns of the grafted side chains and their chemical nature, fully determines the properties of each macromolecule, such as its elasticity and its folding behaviour. Typically experimental bottle brushes are systems made of tens of thousands of monomeric units, rendering a computational approach extremely expensive, especially in the case of bottle brushes solutions. A proper coarse graining description of these macromolecules, thus appears essential. We here present a theoretical approach able to develop a general, transferable and analytical multi-scale coarse graining of homopolymeric bottle brush polymers under good solvent condition. Starting from scaling theories, each macromolecule is mapped onto a chain of tethered star polymers, whose effective potential is known from scaling predictions, computational and experimental validations and can be expressed as a function of the number of arms f , and on the length na of each arm. Stars are then tethered to one another and the effective potentials between them is shown to only depend on the key parameters of the original bottle brush polymer (sg, ns). The generalised form of the effective potential is then used to reproduce properties of the macromolecules obtained both with scaling theories and with simulations. The general form of the effective potentials derived in the current study, allows to describe theoretically and computationally properties of homopolymeric bottle brush polymers for all grafting densities and all lengths of both backbone and grafted arms, opening the path for a manifold of applications

Coarse graining and adsorption in bottlebrush--colloid mixtures

We study the adsorption properties in bottlebrushes/colloids binary mixtures, by combining scaling theories, theoretical predictions, Self-Consistent Field Computations (SCFC), and Molecular Dynamics simulations. In particular, we focus on adsorption in the case in which an attraction is set between the two species, by analysing the solution properties for a range of interactions and size ratio between colloids and bottlebrushes, in the case in which colloids are smaller than the macromolecules. We show that the onset for adsorption is dominated by the local properties of the adsorbing guest particle. This allows us to exploit the local similarity between a cylindrical bottlebrush and a spherical star polymer to predict the region of the parameter space in which adsorption takes place. By employing simple scaling arguments, we thus extend the analytical results on adsorption obtained for binary mixtures of star polymers/colloid nanoparticles. We then validate our predictions with Molecular Dynamic simulations. Moreover, by means of SCFC, we assess the adsorption-to-depletion transition of nanoparticles in polymeric bottlebrushes. Our results pave the road towards a smart rational design and coarse-graining of adsorbing/releasing systems, where an elongated shape might play an important role

Synthesis of Benzofuran-2-One Derivatives and Evaluation of Their Antioxidant Capacity by Comparing DPPH Assay and Cyclic Voltammetry

The present work aimed to synthesise promising antioxidant compounds as a valuable alternative to the currently expensive and easily degradable molecules that are employed as stabilizers in industrial preparation. Taking into account our experience concerning domino Friedel-Crafts/lactonization reactions, we successfully improved and extended the previously reported methodology toward the synthesis of 3,3-disubstituted-3H-benzofuran-2-one derivatives9-20starting from polyphenols1-6as substrates and either diethylketomalonate (7) or 3,3,3-trifluoromethyl pyruvate (8) as electrophilic counterpart. The antioxidant capacity of the most stable compounds (9-11and15-20) was evaluated by both DPPH assay and Cyclic Voltammetry analyses performed in alcoholic media (methanol) as well as in aprotic solvent (acetonitrile). By comparing the recorded experimental data, a remarkable activity can be attributed to few of the tested lactones

Thermoresponsive Block Copolymer Grafted on Core-Shell Nanoparticles

Since 1966, when the poly(2-oxazolines) (POx) were discovered, they have undoubtedly been recognized as a polymer class with high synthetic versatility and good biocompatibility, giving access to highly functional and adaptable materials. The poly(2-oxazolines) are prepared through cationic ring-opening polymerization (CROP), which allow for simple control of the reaction condition, mainly due to the absence of undesired termination and even chain transfer are suppressed. Furthermore, the large available number of monomers with different side chain modifications opens the path towards the fabrication of innovative smart materials with a manifold of applications. Taking into account such observations, we envisage the possibility of designing and synthesizing a block-copolymer featured by: (i) a polar side chain (Fragment A), able to trap organic and/or inorganic compounds (e.g. heavy metal in wastewater or active principles for drug delivery applications); (ii) a thermoresponsive scaffold (Fragment B), able to change the interaction with the media by tuning the temperature. Subsequently, we intend to graft these polymers onto iron oxide nanoparticles (high grafting density) or on organic cores. Pursuing this research, herein we report our results involving the synthesis of the two Fragments (A and B) and the consequent grafting system to the nanoparticles. Finally, we point out the test for heavy metal binding in combination with the thermoresponsive behaviour of our products

New Dihydroxytyrosyl Esters from Dicarboxylic Acids: Synthesis and Evaluation of the Antioxidant Activity In Vitro (ABTS) and in Cell-Cultures (DCF Assay)

New dihydroxytyrosyl esters 2a, 2c–2j of dicarboxylic acids were synthesized from methyl orthoformate protected hydroxytyrosol 3 and diacyl chlorides. New compounds were characterized (HRMS, FT-IR, 1H- and 13C-NMR), and tested for antioxidant activity both in vitro (ABTS) and on L6 myoblasts and THP1 leukemic monocytes cell culture by DCF assay. According to the ABTS assay, compounds 2a, 2c–2j showed a TEAC value of antioxidant capacity up to twice that of Trolox. Very high or complete ROS protections were obtained in the cell environment where lipophilicity and rigidity of dicarboxylic structure seem to facilitate the antioxidant effect. MTT assay and proliferation test were used for assessment of cell viability. These compounds can be envisaged as a new class of preservatives for food or cosmetic products