Communication: Identification of the molecule-metal bonding geometries of molecular nanowires

Molecular nanowires in which a single molecule bonds chemically to two metal electrodes and forms a stable electrically conducting bridge between them have been studied intensively for more than a decade. However, the experimental determination of the bonding geometry between the molecule and electrodes has remained elusive. Here we demonstrate by means of ab initio calculations that inelastic tunneling spectroscopy (IETS) can determine these geometries. We identify the bonding geometries at the gold-sulfur interfaces of propanedithiolate molecules bridging gold electrodes that give rise to the specific IETS signatures that were observed in recent experiments.     

Asymmetric aldol addition of α-azido ketones to ethyl pyruvate mediated by a cinchona-based bifunctional urea catalyst

The first asymmetric synthesis of ethyl 4-aryl-3-azido-2-hydroxy-2-methyl-4-oxobutanoates via a cinchona organocatalyst induced aldol addition of α-azido ketones to ethyl pyruvate has been developed. The coupling reaction under optimized conditions was carried out to furnish tetrafunctionalized synthons with enantioselectivities of up to 91:9 and enriched diastereoselectivities of up to 95:5 (syn:anti).     

Oxidation of Aryl Alkyl Ketones To α-Acyloxy, α-(Camphorsulfonyloxy), or α-Hydroxy Derivatives Using Manganese(III) Acetate in Combination with Carboxylic Acids or (1S)-(+)-10-Camphorsulfonic Acid

The α-oxidation of aryl alkyl ketones using manganese(III) acetate in the presence of various carboxylic acids and (1S)-(+)-10-camphorsulfonic acid provided a convenient synthesis of α-acyloxy, α-(10-camphorsulfonyloxy), and α-hydroxy derivatives in good yield.     

5-HT1A Serotonergic, α-Adrenergic and Opioidergic Receptors Mediate the Analgesic Efficacy of Vortioxetine in Mice

Vortioxetine is a multimodal antidepressant drug that affects several brain neurochemicals and has the potential to induce various pharmacological effects on the central nervous system. Therefore, we investigated the centrally mediated analgesic efficacy of this drug and the mechanisms underlying this effect. Analgesic activity of vortioxetine (5, 10 and 20 mg/kg, p.o.) was examined by tail-clip, tail-immersion and hot-plate tests. Motor performance of animals was evaluated using Rota-rod device. Time course measurements (30–180 min) showed that vortioxetine (10 and 20 mg/kg) administrations significantly increased the response latency, percent maximum possible effect and area under the curve values in all of the nociceptive tests. These data pointed out the analgesic effect of vortioxetine on central pathways carrying acute thermal and mechanical nociceptive stimuli. Vortioxetine did not alter the motor coordination of mice indicating that the analgesic activity of this drug was specific. In mechanistic studies, pre-treatments with p-chlorophenylalanine (serotonin-synthesis inhibitor), NAN-190 (serotonin 5-HT_1A receptor antagonist), α-methyl-para-tyrosine (catecholamine-synthesis inhibitor), phentolamine (non-selective α-adrenoceptor blocker), and naloxone (non-selective opioid receptor blocker) antagonised the vortioxetine-induced analgesia. Obtained findings indicated that vortioxetine-induced analgesia is mediated by 5-HT_1A serotonergic, α-adrenergic and opioidergic receptors, and contributions of central serotonergic and catecholaminergic neurotransmissions are critical for this effect.     

Synthesis of a bipyridine-derived achiral thiourea trifluoromethanesulfonic acid salt and its application as an additive in organocatalytic asymmetric reactions

The host–guest complex of a proline–thiourea bipyridine trifluoromethanesulfonic acid salt can catalyze organocatalytic asymmetric reactions such as aldol, Michael, and Mannich in polar protic medium with high stereoselectivities. The privileged bipyridine backbone and the thiourea motif are essential to the activity and enantioselectivity through hydrogen bonding interactions.     

Novel Enantioselective Synthesis of Both Enantiomers of Furan‐2‐yl Amines and Amino Acids

A new enantioselective synthesis of furan‐2‐yl amines and amino acids is described, in which the key step is the oxazaborolidine‐catalyzed enantioselective reduction of O‐benzyl (E)‐ and (Z)‐furan‐2‐yl ketone oximes to the corresponding chiral amines. The chirality of the furan‐2‐yl amines is fully controlled by the appropriate choice of the geometrical isomer of the O‐benzyl oxime. Oxidation of the furan ring furnished amino acids in high yields.     

Investigation of mass attenuation coefficients of water, concrete and bakelite at different energies using the FLUKA Monte Carlo code

The mass attenuation coefficients of water, bakelite and concrete sample defined in the simulation package were obtained using the FLUKA Monte Carlo code at 59.5, 80.9, 140.5, 356.5, 661.6, 1173.2 and 1332.5 keV photon energies. The results for the mass attenuation coefficients obtained by simulation have been compared with experimental and the theoretical ones and good agreement has been observed. The results indicate that this process can be followed to determine the data on the attenuation of gamma-rays with the several energies in other materials. Also, the deposited energy by 661.6 keV photons at several thicknesses of each media was determined as being an important data for radiation shielding studies.     

Butylene linked palladium N-heterocyclic carbene complexes: Synthesis and catalytic properties

New bis(NHC)-Pd complexes were synthesized and characterized by elemental analysis, ¹H NMR, ¹³C NMR, and IR spectroscopy. The reaction of Pd(OAc)₂ and bis(benzimidazolium) salts in DMSO gave the monomeric palladium complex in which the N-heterocyclic carbene was bound to the metal centre. The crystal and molecular structure of the cis-dibromo{1,1′-di[2,3,4,5,6-pentamethylbenzyl]-3,3′-butylenedibenzimidazol-2,2′-diylidene}-palladium(II) complex was determined by single-crystal X-ray diffraction. The activity of the Pd(II) complexes in the direct arylation of benzothiazole with arylbromides was investigated. A preliminary catalytic study showed that these bis(NHC)-Pd complexes were highly active in the direct arylation of benzothiazole with arylbromides.     

Role of copper species in the oxidative dimerization of arylboronic acids: synthesis of symmetrical biaryls

Certain Cu(I) and Cu(II) salts are able to mediate the dimerization of arylboronic acids in DMF. They provide the corresponding symmetrical biaryls in moderate to very good yields. It is possible to run the reaction catalytically under an oxygen atmosphere without a significant loss of yields.