Topology optimization of composite hyperelastic material using SPIMFO-method

Meccanica - Fiber reinforced materials are used in assorted engineering application and for this reason, new additive manufacturing technologies have been developed for this type of materials. With...     

Detailed experimental and kinetic modeling study of 3-carene pyrolysis

3-Carene is an important potential biofuel with properties similar to the jet-propellant JP-10. Its thermal decomposition and combustion behavior is to date unknown, which is essential to assess its quality as a fuel. A combined experimental and kinetic modeling study has been conducted to understand the initial decomposition of 3-carene. The pyrolysis of 3-carene was investigated in a jet-stirred quartz reactor at atmospheric pressure, at temperatures varying from 650 to 1050 K, covering the complete conversion range. The decomposition of 3-carene was observed to start around 800 K, and it is almost complete at 970 K. Online gas chromatography shows that primarily aromatics are generated which suggests that 3-carene is not a good fuel candidate. The potential energy surface for the initial decomposition pathways determined by KinBot shows that a hydrogen elimination reaction dominates, giving primarily cara-2,4-diene. Next to this molecular pathway, radical pathways lead to aromatics via ring opening. The kinetic model was automatically generated with Genesys and consists of 2565 species and 9331 reactions. New quantum chemical calculations at the CBS-QB3 level of theory were needed to calculate rate coefficients and thermodynamic properties relevant for the primary decomposition of 3-carene. Both the conversion of 3-carene and the yields of the primary products (ie, benzene and hydrogen gas) are well predicted with this kinetic model. Rate of production analyses shows that the dominant pathways to convert 3-carene are hydrogen elimination reaction and radical chemistry.     

Code2vect: An efficient heterogenous data classifier and nonlinear regression technique

The aim of this paper is to present a new classification and regression algorithm based on Artificial Intelligence. The main feature of this algorithm, which will be called Code2Vect, is the nature of the data to treat: qualitative or quantitative and continuous or discrete. Contrary to other artificial intelligence techniques based on the “Big-Data,” this new approach will enable working with a reduced amount of data, within the so-called “Smart Data” paradigm. Moreover, the main purpose of this algorithm is to enable the representation of high-dimensional data and more specifically grouping and visualizing this data according to a given target. For that purpose, the data will be projected into a vectorial space equipped with an appropriate metric, able to group data according to their affinity (with respect to a given output of interest). Furthermore, another application of this algorithm lies on its prediction capability. As it occurs with most common data-mining techniques such as regression trees, by giving an input the output will be inferred, in this case considering the nature of the data formerly described. In order to illustrate its potentialities, two different applications will be addressed, one concerning the representation of high-dimensional and categorical data and another featuring the prediction capabilities of the algorithm.     

New palladium (II) complexes containing phosphine‐nitrogen ligands and their use as catalysts in aminocarbonylation reaction

Aminocarbonylation of aryl halides, homogeneously catalysed by palladium, is an efficient method that can be employed for obtaining amides for pharmaceutical and synthetic applications. In this work, palladium (II) complexes containing P^N ligands were studied as catalysts in the aminocarbonylation of iodobenzene in the presence of diethylamine. Two types of systems were used: a palladium (II) complex formed in situ; and one prepared prior to the catalytic reaction. In general, the palladium complexes studied achieved high conversions in an average reaction time of less than 2 hr, which is less than that for the standard system (Pd (II)/PPh₃) used. The pre‐synthesized complexes were faster than their in situ counterparts, as the latter require an induction time to form the Pd/P^N species. The structure and electronic properties of the ligand P^N can influence both the activity and the selectivity of the reaction, stabilizing the acyl‐palladium intermediates formed in a better manner.     

Organocatalytic Enantioselective Pictet–Spengler Reaction of α-Ketoesters: Development and Application to the Total Synthesis of (+)-Alstratine A

We report herein an asymmetric Pictet–Spengler reaction of α-ketoesters. In the presence of a catalytic amount of simple alanine-derived squaramide and p-nitrobenzoic acid, reaction of tryptamines with methyl 2-oxoalkanoates afforded the corresponding 1-alkyl-1-methoxycarbonyl tetrahydro-β-carbolines (THBCs) in high yields and ee values. A primary kinetic isotope effect (KIE=4.5) using C2-deteurium-labelled tryptamine indicates that rearomatization through deprotonation of the pentahydro-β-carbolinium ion could be the rate- and enantioselectivity-determining step. A concise enantioselective total synthesis of (+)-alstratine A, a hexacyclic cagelike monoterpene indole alkaloid, featuring this reaction as a key step, was subsequently accomplished. Remeasurement of the [a]_D value of the natural product indicates that natural alstratine A is dextrorotatory rather than levorotatory as it was initially reported in the isolation paper.     

Extract from the Marine Seaweed Padina pavonica Protects Mitochondrial Biomembranes from Damage by Amyloidogenic Peptides

The identification of compounds which protect the double-membrane of mitochondrial organelles from disruption by toxic confomers of amyloid proteins may offer a therapeutic strategy to combat human neurodegenerative diseases. Here, we exploited an extract from the marine brown seaweed Padina pavonica (PPE) as a vital source of natural bioactive compounds to protect mitochondrial membranes against insult by oligomeric aggregates of the amyloidogenic proteins amyloid-β (Aβ), α-synuclein (α-syn) and tau, which are currently considered to be major targets for drug discovery in Alzheimer’s disease (AD) and Parkinson’s disease (PD). We show that PPE manifested a significant inhibitory effect against swelling of isolated mitochondria exposed to the amyloid oligomers, and attenuated the release of cytochrome c from the mitochondria. Using cardiolipin-enriched synthetic lipid membranes, we also show that dye leakage from fluorophore-loaded vesicles and formation of channel-like pores in planar bilayer membranes are largely prevented by incubating the oligomeric aggregates with PPE. Lastly, we demonstrate that PPE curtails the ability of Aβ42 and α-syn monomers to self-assemble into larger β-aggregate structures, as well as potently disrupts their respective amyloid fibrils. In conclusion, the mito-protective and anti-aggregator biological activities of Padina pavonica extract may be of therapeutic value in neurodegenerative proteinopathies, such as AD and PD.     

Terminal Ligand and Packing Effects on Slow Relaxation in an Isostructural Set of [Dy(H2dapp)X2]+ Single Molecule Magnets**

We report three structurally related single ion Dy compounds using the pentadentate ligand 2,6-bis((E)-1-(2-(pyridin-2-yl)-hydrazineylidene)ethyl)pyridine (H₂dapp) [Dy(H₂dapp)(NO₃)₂]NO₃ ( 1 ), [Dy(H₂dapp)(OAc)₂]Cl ( 2 ) and [Dy(H₂dapp)(NO₃)₂]Cl_0.92(NO₃)_0.08 ( 3 ). The (H₂dapp) occupies a helical twisted pentagonal equatorial arrangement with two anionic ligands in the axial positions. Further influence on the electronic and magnetic structure is provided by a closely associated counterion interacting with the central N−H group of the (H₂dapp). The slow relaxation of the magnetisation shows that the anionic acetates give the greatest slowing down of the magnetisation reversal. Further influence on the relaxation properties of compounds 1 and 2 is the presence of short nitrate-nitrate intermolecular ligand contact opening further lattice relaxation pathways.     

Nickel‐Catalyzed Enantioselective C?C Bond Formation through C?O Cleavage in Aryl Esters

We report the first enantioselective C C bond formation through C O bond cleavage using aryl ester counterparts. This method is characterized by its wide substrate scope and results in the formation of quaternary stereogenic centers with high yields and asymmetric induction.     

Symmetry calculation for molecules and transition states

The symmetry of molecules and transition states of elementary reactions is an essential property with important implications for computational chemistry. The automated identification of symmetry by computers is a very useful tool for many applications, but often relies on the availability of three‐dimensional coordinates of the atoms in the molecule and hence becomes less useful when these coordinates are a priori unavailable. This article presents a new algorithm that identifies symmetry of molecules and transition states based on an augmented graph representation of the corresponding structures, in which both topology and the presence of stereocenters are accounted for. The automorphism group order of the graph associated with the molecule or transition state is used as a starting point. A novel concept of label‐stereoisomers, that is, stereoisomers that arise after labeling homomorph substituents in the original molecule so that they become distinguishable, is introduced and used to obtain the symmetry number. The algorithm is characterized by its generic nature and avoids the use of heuristic rules that would limit the applicability. The calculated symmetry numbers are in agreement with expected values for a large and diverse set of structures, ranging from asymmetric, small molecules such as fluorochlorobromomethane to highly symmetric structures found in drug discovery assays. The new algorithm opens up new possibilities for the fast screening of the degree of symmetry of large sets of molecules. © 2014 Wiley Periodicals, Inc.