Tuneable Current Rectification Through a Designer Graphene Nanoribbon.

Unimolecular current rectifiers are fundamental building blocks in organic electronics. Rectifying behavior has been identified in numerous organic systems due to electron-hole asymmetries of orbital levels interfaced by a metal electrode. As a consequence, the rectifying ratio (RR) determining the diode efficiency remains fixed for a chosen molecule-metal interface.

Addressing Electron Spins Embedded in Metallic Graphene Nanoribbons.

Spin-hosting graphene nanostructures are promising metal-free systems for elementary quantum spintronic devices. Conventionally, spins are protected from quenching by electronic band gaps, which also hinder electronic access to their quantum state. Here, we present a narrow graphene nanoribbon substitutionally doped with boron heteroatoms that combines a metallic character with the presence of localized spin 1/2 states in its interior.

Visualization and identification of single meteoritic organic molecules by atomic force microscopy.

Using high-resolution atomic force microscopy (AFM) with CO-functionalized tips, we atomically resolved individual molecules from Murchison meteorite samples. We analyzed powdered Murchison meteorite material directly, as well as processed extracts that we prepared to facilitate characterization by AFM. From the untreated Murchison sample, we resolved very few molecules, as the sample contained mostly small molecules that could not be identified by AFM.

Selectivity in single-molecule reactions by tip-induced redox chemistry.

Controlling selectivity of reactions is an ongoing quest in chemistry. In this work, we demonstrate reversible and selective bond formation and dissociation promoted by tip-induced reduction-oxidation reactions on a surface. Molecular rearrangements leading to different constitutional isomers are selected by the polarity and magnitude of applied voltage pulses from the tip of a combined scanning tunneling and atomic force microscope.

Toward 2-Thiophyne: Ketocarbene versus Hetaryne Intermediates from 2-(Trimethylsilyl)thiophen-3-yl Triflate.

The reaction of 2-(trimethylsilyl)thiophen-3-yl triflate with CsF in the presence of 2,3,4,5-tetraphenylcyclopentadienone affords 4,5,6,7-tetraphenylbenzo[]thiophene, as it would be expected from the hypothesized generation and trapping of 2-thiophyne. However, a detailed experimental and computational study discards the intermediacy of this elusive 5-membered hetaryne. Instead, a complex mechanism involving the generation of an intermediate ketocarbene, which adds to the cyclopentadienone to give an isolable tricyclic intermediate, followed by thermal rearrangements, is proposed.

Microscopic Visualization of Porous Nanographenes Synthesized through a Combination of Solution and On-Surface Chemistry.

On-surface synthesis has recently been regarded as a promising approach for the generation of new molecular structures. It has been particularly successful in the synthesis of graphene nanoribbons, nanographenes and intrinsically reactive and instable, yet attractive species. It is based on the combination of solution chemistry aimed at preparation of appropriate molecular precursors for further ultra-high vacuum surface assisted transformations.

Magnetism of Topological Boundary States Induced by Boron Substitution in Graphene Nanoribbons.

Graphene nanoribbons (GNRs), low-dimensional platforms for carbon-based electronics, show the promising perspective to also incorporate spin polarization in their conjugated electron system. However, magnetism in GNRs is generally associated with localized states around zigzag edges, difficult to fabricate and with high reactivity. Here we demonstrate that magnetism can also be induced away from physical GNR zigzag edges through atomically precise engineering topological defects in its interior.

2,6,10-Triphenylenotriyne: a star-shaped trisaryne.

During the last two decades aryne and bisaryne equivalents have been increasingly used as privileged building blocks for the synthesis of polycyclic aromatic hydrocarbons (PAHs). Here we report the synthesis and reactivity of an efficient precursor of the 2,6,10-triphenylenotriyne synthon, which constitutes the best example to date of a trisaryne equivalent on a benzofused polyaromatic core.

Geographic patterns of stress in insular lizards reveal anthropogenic and climatic signatures.

Anthropization of insular ecosystems may have negative impacts on native populations of lizards, which provide core ecosystem services on islands. We aimed to identify environmental factors to explain the interlocal variation in faecal glucocorticoids, parasite intensity, and body condition in populations of insular lizards. A cross-sectional design during the summer of 2017 and 2018 was used to sample 611 adult lizards, Gallotia galloti.

Synthesis and reactivity of a trigonal porous nanographene on a gold surface.

The synthesis of porous nanographenes is a challenging task for solution chemistry, and thus, on-surface synthesis provides an alternative approach. Here, we report the synthesis of a triporous nanographene with 102 sp carbon atoms by combining solution and surface chemistry. The carbon skeleton was obtained by Pd-catalyzed cyclotrimerization of arynes in solution, while planarization of the molecule was achieved through two hierarchically organized on-surface cyclodehydrogenation reactions, intra- and inter-blade.

Catalytic Asymmetric Fluorination of Copper Carbene Complexes: Preparative Advances and a Mechanistic Rationale.

The Cu-catalyzed reaction of substituted α-diazoesters with fluoride gives α-fluoroesters with ee values of up to 95 %, provided that chiral indane-derived bis(oxazoline) ligands are used that carry bulky benzyl substituents at the bridge and moderately bulky isopropyl groups on their core. The apparently homogeneous solution of CsF in C F /hexafluoroisopropanol (HFIP) is the best reaction medium, but CsF in the biphasic mixture CH Cl /HFIP also provides good results. DFT studies suggest that fluoride initially attacks the Cu- rather than the C-atom of the transient donor/acceptor carbene intermediate.

Revisiting Kekulene: Synthesis and Single-Molecule Imaging.

Four decades after the first (and only) reported synthesis of kekulene, this emblematic cycloarene has been obtained again through an improved route involving the construction of a key synthetic intermediate, 5,6,8,9-tetrahydrobenzo[]tetraphene, by means of a double Diels-Alder reaction between styrene and a versatile benzodiyne synthon. Ultra-high-resolution AFM imaging of single molecules of kekulene and computational calculations provide additional support for a molecular structure with a significant degree of bond localization in accordance with the resonance structure predicted by the Clar model.

Synthesis of Nanographenes, Starphenes, and Sterically Congested Polyarenes by Aryne Cyclotrimerization.

In recent years, synthetic transformations based on aryne chemistry have become particularly popular, mostly due to the spread of methods to generate these highly reactive intermediates in a controlled manner under mild reaction conditions. In fact, aryne cycloadditions such as the Diels-Alder reaction are nowadays widely used for the efficient preparation of polycyclic aromatic compounds. In 1998, our group discovered that arynes can undergo transition metal-catalyzed reactions, a finding that opened new perspectives in aryne chemistry.

1,7-Naphthodiyne: a new platform for the synthesis of novel, sterically congested PAHs.

The synthesis of an efficient precursor of the novel 1,7-naphthodiyne synthon is reported. Preliminary experiments demonstrate the usefulness of this platform for the synthesis of sterically congested polyarenes, such as helicenes and angularly fused acene derivatives. Furthermore, a novel intramolecular aryne trapping reaction is described.

In vitro invasion efficiency and intracellular proliferation rate comprise virulence-related phenotypic traits of Neospora caninum.

In this study, we examined the in vitro invasion and proliferation capacities of the Nc-Liv and ten Spanish Neospora caninum isolates (Nc-Spain 1 H - Nc-Spain 10). The invasion rate was determined as the number of tachyzoites that completed their internalisation into MARC-145 cells at 2, 4, and 6 h post-inoculation (pi). The proliferation rate was evaluated by determining the doubling time during the exponential proliferation period.

Influence of Neospora caninum intra-specific variability in the outcome of infection in a pregnant BALB/c mouse model.

Previous assays in pregnant animals have demonstrated the effect of different host factors and timing of infection on the outcome of neosporosis during pregnancy. However, the influence of Neospora caninum isolate itself has been poorly investigated. Here, we compared the effects on clinical outcome and vertical transmission observed in a pregnant mouse model following infection with 10 different N.

Pathogenic characterization in mice of Neospora caninum isolates obtained from asymptomatic calves.

In this study, we characterized 8 new isolates obtained from healthy but congenitally infected calves using a BALB/c mouse model. Neospora caninum-infected mice survived without exhibiting any clinical signs of disease. Nevertheless, differences among isolates in parasite organ distribution, parasite burden and the severity of histopathological lesions were determined.

Effects of re-infection with Neospora caninum in bulls on parasite detection in semen and blood and immunological responses.

Three bulls with experimentally induced primary infection with Neospora caninum were re-infected intravenously with 10(8) live N. caninum tachyzoites of the NC-1 isolate at 300 days post-infection to investigate the presence of N. caninum in semen and blood, and the associated immune responses.

Experimental neosporosis in bulls: parasite detection in semen and blood and specific antibody and interferon-gamma responses.

Aim: To investigate the presence of Neospora caninum in semen and blood, and the development of specific antibody and interferon-gamma (IFN-gamma) responses in experimentally infected bulls.

Methods: Eight bulls were intravenously infected with 10(8) live N. caninum tachyzoites of NC-1 isolate.

Intrauterine Neospora caninum inoculation of heifers and cows using contaminated semen with different numbers of tachyzoites.

Objective: To investigate the potential of different Neospora caninum tachyzoite doses to infect heifers (experiment 1) and cows (experiment 2) when administered in utero by artificial insemination via contaminated semen.

Methods: In experiment 1, five groups of 5, 7, 8, 9, and 5 cyclic heifers were hormonally synchronized and artificially inseminated with semen containing 0 (A, controls), 10(2) (B), 5 x 10(3) (C), 5 x 10(4) (D), and 5 x 10(5) (E) live N. caninum NC-1 isolate-tachyzoites, respectively.

Detection of Neospora caninum in the semen and blood of naturally infected bulls.

A prospective study was designed to investigate the presence of Neospora caninum in semen and blood of eight bulls seropositive to N. caninum using nested-PCR procedures. Positive semen and blood samples were bioassayed in a BALB/c nu/nu mouse model.

Neospora caninum infection in breeder bulls: seroprevalence and comparison of serological methods used for diagnosis.

Aims: To investigate the seroprevalence of Neospora caninum infection in breeder bulls. In addition, the level of agreement of serological methods used was evaluated.

Methods: A total of 285 bulls of different ages and breeds raised for reproductive purposes in Spain were sampled for serum antibody activity to N.