Tribochemistry of graphene on iron and its possible role in lubrication of steel

Recent tribological experiments revealed that graphene is able to lubricate macroscale steel-on-steel sliding contacts very effectively both in dry and humid conditions. This effect has been attributed to a mechanical action of graphene related to its load-carrying capacity. Here we provide further insight into the functionality of graphene as lubricant by analysing its tribochemical action. By means of first principles calculations we show that graphene binds strongly to native iron surfaces highly reducing their surface energy. Thanks to a passivating effect, the metal surfaces coated by graphene become almost inert and present very low adhesion and shear strength when mated in a sliding contact. We generalize the result by establishing a connection between the tribological and the electronic properties of interfaces, which is relevant to understand the fundamental nature of frictional forces.Comment: 19 pages, 6 figure

Photochemical Organocatalytic Synthesis of Thioethers from Aryl Chlorides and Alcohols

Thioethers, often found in pharmaceuticals and natural compounds, typically involve metal cross-coupling reactions, high temperatures, and the use of disagreeable thiols for their synthesis. Here we present a straightforward, thiol-free organocatalytic protocol that uses mild conditions to stitch together inexpensive alcohols and aryl chlorides, yielding a diverse array of aryl alkyl thioethers. Central to this approach was the discovery that tetramethylthiourea can serve as a simple sulfur source upon intercepting photochemically generated aryl radicals. To form radicals, we used a readily available indole thiolate organocatalyst that, when excited with 405 nm light, gained a strongly reducing power, enabling the activation of typically unreactive aryl chlorides via single-electron transfer. Radical trapping by the thiourea, followed by an alcohol attack via a polar path, resulted in the formation of thioether products

Xsorb: a software for identifying the most stable adsorption configuration and energy of a molecule on a crystal surface

Molecular adsorption is the first important step of many surface-mediated chemical processes, from catalysis to tribology. This phenomenon is controlled by physical/chemical interactions, which can be accurately described by first principles calculations. In recent years, several computational tools have been developed to study molecular adsorption based on high throughput/automatized approaches. However, these tools can sometimes be over-sophisticated for non-expert users. In this work, we present Xsorb, a Python-based code that automatically generates adsorption configurations, guides the user in the identification the most relevant ones, which are then fully optimized. The code relies on well-established Python libraries, and on an open source package for density functional theory calculations. We show the program capabilities through an example consisting of a hydrocarbon molecule, 1-hexene, adsorbed over the (110) surface of iron. The presented computational tool will help users, even non-expert, to easily identify the most stable adsorption configuration of complex molecules on substrates and obtain accurate adsorption geometries and energies

Zinc dialkyldithiophosphates adsorption and dissociation on ferrous substrates: an ab initio study

Zinc dialkyldithiophosphates (ZDDPs) have been commonly used as anti-wear additives in the automotive industry for the past 80 years. The morphology, composition and structure of the ZDDPs phosphate-based tribofilm, which is essential for its lubricant functioning, have been widely studied experimentally. However, despite their widespread use, a general agreement on their primary functioning mechanism is still lacking. The morphology and composition of the ZDDPs phosphate-based tribofilm have been widely studied experimentally, but the formation process and the relevant driving forces are still largely debated. In particular, it is unclear whether the stress-induced molecular dissociation occurs in the bulk oil or on the substrate. In this work, we employ ab initio density-functional theory simulations to compare ZDDP fragmentation in vacuum and over a reactive substrate, considering the effects of surface oxidation on the dissociation path. Our results show that the molecular dissociation is highly endothermic in the absence of a supporting substrate, while in the presence of an iron substrate it becomes highly energetically favoured. Moreover, the presence of the substrate changes the reaction path. At the same time, surface oxidation reduces the molecule-substrate interaction. These findings provide valuable insights into the early stages of the formation of phosphate-based tribofilms

Role of Cinchona Alkaloids in the Enantio- and Diastereoselective Synthesis of Axially Chiral Compounds

Asymmetric synthesis using organic catalysts has evolved since it was first realized and defined. Nowadays, it can be considered a valid alternative to transition metal catalysis for synthesizing chiral molecules. According to the literature, the number of asymmetric organocatalytic processes associated with atropisomer synthesis has rapidly increased over the past 10 years because organocatalysis addresses the challenges posed by the most widespread strategies used for preparing axially chiral molecules with satisfactory results. These strategies, useful to prepare a wide range of C–C, C–heteroatom, and N–N atropisomers, vary from kinetic resolution to direct arylation, desymmetrization, and central-to-axial chirality conversion. In this field, our contribution focuses on determining novel methods for synthesizing atropisomers, during which, in most cases, the construction of one or more stereogenic centers other than the stereogenic axis occurred. To efficiently address this challenge, we exploited the ability of catalysts based on a cinchona alkaloid scaffold to realize enantioselective organic transformations. Desymmetrization of N-(2-tert-butylphenyl) maleimides was one of the first strategies that we pursued for preparing C–N atropisomers. The main principle is based on the presence of a rotationally hindered C–N single bond owing to the presence of a large tert-butyl group. Following the peculiar reactivity of this type of substrate as a powerful electrophile and dienophile, we realized several transformations. First, we investigated the vinylogous Michael addition of 3-substituted cyclohexenones, where a stereogenic axis and two contiguous stereocenters were concomitantly and remotely formed and stereocontrolled using a primary amine catalyst. Subsequently, we realized desymmetrization via an organocatalytic Diels–Alder reaction of activated unsaturated ketones that enabled highly atropselective transformation with efficient diastereoselectivity, thereby simultaneously controlling four stereogenic elements. Employing chiral organic bases allowed us to realize efficient desymmetrizations using carbon nucleophiles, such as 1,3-dicarbonyl compounds, cyanoacetates, and oxindoles. These reactions, performed with different types of catalysts, highlighted the versatility of organocatalysis as a powerful strategy for atropselective desymmetrization of pro-axially chiral maleimides. Hereafter, we studied the Friedel–Crafts alkylation of naphthols with indenones, a powerful method for enantioselective synthesis of conformationally restricted diastereoisomeric indanones. We realized the first axially chiral selective Knoevenagel condensation using cinchona alkaloid primary amine as the catalyst. This reaction provided a powerful method to access enantioenriched olefins containing the oxindole core. Subsequently, we initiated an intense program for the computational investigation of the reaction mechanism of our atropselective processes. An understanding of the catalytic activity for vinylogous atropselective desymmetrization as well as of the role played by the acidic cocatalyst used for the experimental work was achieved. Recently, we have garnered interest in the novel frontiers of atropselective synthesis. As observed in recent publications, there is considerable interest in the development of methods for preparing N–N atropisomers, an emerging topic in the field of atropselective synthesis. We focused on the synthesis of hydrazide atropisomers by developing a one-pot sequential catalysis protocol based on two sequential organocatalytic reactions that provided high stereocontrol of two contiguous stereogenic elements