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...     

Silica-Supported MnII Sites as Efficient Catalysts for Carbonyl Hydroboration,Hydrosilylation, and Transesterification

Manganese, the third most abundant transition-metal element after iron and titanium, has recently been demonstrated to be an effective homogeneous catalyst in numerous reactions. Herein, the preparation of silica-supported Mn^II sites is reported using Surface Organometallic Chemistry (SOMC), combined with tailored thermolytic molecular precursors approach based on Mn₂[OSi(OtBu)₃]₄ and Mn{N(SiMe₃)₂}₂⋅THF. These supported Mn^II sites, free of organic ligands, efficiently catalyze numerous reactions: hydroboration and hydrosilylation of ketones and aldehydes as well as the transesterification of industrially relevant substrates.     

Origin of the Photoinduced Geometrical Change of Copper(I) Complexes from the Quantum Chemical Topology View

Copper(I) complexes (CICs) are of great interest due to their applications as redox mediators and molecular switches. CICs present drastic geometrical change in their excited states, which interferes with their luminescence properties. The photophysical process has been extensively studied by several time-resolved methods to gain an understanding of the dynamics and mechanism of the torsion, which has been explained in terms of a Jahn–Teller effect. Here, we propose an alternative explanation for the photoinduced structural change of CICs, based on electron density redistribution. After photoexcitation of a CIC (S₀→S₁), a metal-to-ligand charge transfer stabilizes the ligand and destabilizes the metal. A subsequent electron transfer, through an intersystem crossing process, followed by an internal conversion (S₁→T₂→T₁), intensifies the energetic differences between the metal and ligand within the complex. The energy profile of each state is the result of the balance between metal and ligand energy changes. The loss of electrons originates an increase in the attractive potential energy within the copper basin, which is not compensated by the associated reduction of the repulsive atomic potential. To counterbalance the atomic destabilization, the valence shell of the copper center is polarized (defined by ∇²ρ(r) and ∇²V_ne(r)) during the deactivation path. This polarization increases the magnitude of the intra-atomic nuclear–electron interactions within the copper atom and provokes the flattening of the structure to obtain the geometry with the maximum interaction between the charge depletions of the metal and the charge concentrations of the ligand.     

Chromium complexes based on thiophene–imine ligands for ethylene oligomerization

A new set of Cr(III) complexes, {L}CrCl₃(THF), based on thiophene–imine ( 2a , L = PhOC₆H₄(N═CH)‐2‐SC₄H₃; 2b , L = PhOC₂H₄(N═CH)‐2‐SC₄H₃; 2c , L = Ph(NH)C₂H₄(N═CH)‐2‐SC₄H₃; 2d , L = PhOC₆H₄(N═CH)‐2‐SC₄H₂‐5‐Ph; 2e , L = Ph(NH)C₂H₄(N═CH)‐2‐SC₄H₂‐5‐Ph) have been prepared and characterized using elemental analysis and infrared spectroscopy. Upon activation with methylaluminoxane, all the chromium complexes generated active systems affording a nonselective distribution of α‐olefins with turnover frequencies in the range 9500–93 500 (mol ethylene) (mol Cr)^?1 h^?1, and producing mostly oligomers (95.0–99.3 wt% of total products). Small amounts of polymer were produced in these oligomerization reactions (0.8–8.2 wt%). The catalytic activities were quite sensitive to the ligand environment. Moreover, the effects of oligomerization parameters (temperature, [Al]/[Cr] molar ratio, time) on the activity and on the product distribution were examined.     

The Plasticity of the Carbohydrate Recognition Domain Dictates the Exquisite Mechanism of Binding of Human Macrophage Galactose-Type Lectin

The human macrophage galactose-type lectin (MGL), expressed on macrophages and dendritic cells (DCs), modulates distinct immune cell responses by recognizing N-acetylgalactosamine (GalNAc) containing structures present on pathogens, self-glycoproteins, and tumor cells. Herein, NMR spectroscopy and molecular dynamics (MD) simulations were used to investigate the structural preferences of MGL against different GalNAc-containing structures derived from the blood group A antigen, the Forssman antigen, and the GM2 glycolipid. NMR spectroscopic analysis of the MGL carbohydrate recognition domain (MGL-CRD, C181-H316) in the absence and presence of methyl α-GalNAc (α-MeGalNAc), a simple monosaccharide, shows that the MGL-CRD is highly dynamic and its structure is strongly altered upon ligand binding. This plasticity of the MGL-CRD structure explains the ability of MGL to accommodate different GalNAc-containing molecules. However, key differences are observed in the recognition process depending on whether the GalNAc is part of the blood group A antigen, the Forssman antigen, or GM2-derived structures. These results are in accordance with molecular dynamics simulations that suggest the existence of a distinct MGL binding mechanism depending on the context of GalNAc moiety presentation. These results afford new perspectives for the rational design of GalNAc modifications that fine tune MGL immune responses in distinct biological contexts, especially in malignancy.     

Sensitive targeted multiple protein quantification based on elemental detection of Quantum Dots

A generic strategy based on the use of CdSe/ZnS Quantum Dots (QDs) as elemental labels for protein quantification, using immunoassays with elemental mass spectrometry (ICP-MS), detection is presented. In this strategy, streptavidin modified QDs (QDs-SA) are bioconjugated to a biotinylated secondary antibody (b-Ab₂). After a multi-technique characterization of the synthesized generic platform (QDs-SA-b-Ab₂) it was applied to the sequential quantification of five proteins (transferrin, complement C3, apolipoprotein A1, transthyretin and apolipoprotein A4) at different concentration levels in human serum samples. It is shown how this generic strategy does only require the appropriate unlabeled primary antibody for each protein to be detected. Therefore, it introduces a way out to the need for the cumbersome and specific bioconjugation of the QDs to the corresponding specific recognition antibody for every target analyte (protein). Results obtained were validated with those obtained using UV–vis spectrophotometry and commercial ELISA Kits.     

Columnar Liquid‐Crystalline Dinaphthoperylenetetracarboxdiimides

Although the double Friedel–Crafts acylation of arenes with ethyl chloroglyoxylate is hindered by the strongly deactivating effect of the first‐entering glyoxylic substituent, the double reaction is successful with the reactive arene perylene under long reaction times and with concomitant ester hydrolysis. The reaction is regiospecific, giving the 3,9‐regioisomer exclusively. This perylenylenediglyoxylic acid is condensed first with o‐bromophenylacetic acid and then with α‐branched alkylamines to yield the title compounds. Whilst the corresponding tetraalkyl esters only show monotropic mesophases, these diimides show enantiotropic columnar mesophases that can be maintained at room temperature if racemically branched alkyl chains of moderate size are used. A palladium‐induced C?C bond migration during the build‐up of the arene system leads to an isomeric side product of reduced symmetry that can be isolated by aggregation‐controlled chromatographic separation. The HOMO and LUMO energies of the title compounds are considerably higher than those of established perylenetetracarboxdiimides.     

“(Diphosphine)Nickel”‐Catalyzed Negishi Cross‐Coupling: An Experimental and Theoretical Study

The use of a strongly donating “(bis‐dialkylphosphine)Ni” fragment promotes the catalytic coupling of a large range of ArCl and ArZnCl derivatives under mild conditions. Stoichiometric mechanistic investigations and DFT calculations prove that a Ni⁰/Ni^II cycle is operative in this system.     

Dendronized Anionic Gold Nanoparticles: Synthesis,Characterization, and Antiviral Activity

Anionic carbosilane dendrons decorated with sulfonate functions and one thiol moiety at the focal point have been used to synthesize water‐soluble gold nanoparticles (AuNPs) through the direct reaction of dendrons, gold precursor, and reducing agent in water, and also through a place‐exchange reaction. These nanoparticles have been characterized by NMR spectroscopy, TEM, thermogravimetric analysis, X‐ray photoelectron spectroscopy (XPS), UV/Vis spectroscopy, elemental analysis, and zeta‐potential measurements. The interacting ability of the anionic sulfonate functions was investigated by EPR spectroscopy with copper(II) as a probe. Different structures and conformations of the AuNPs modulate the availability of sulfonate and thiol groups for complexation by copper(II). Toxicity assays of AuNPs showed that those produced through direct reaction were less toxic than those obtained by ligand exchange. Inhibition of HIV‐1 infection was higher in the case of dendronized AuNPs than in dendrons.