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When lubrication of rolling bearings with oil or grease is not possible, for example because the lubricant evaporates in vacuum, solid lubrication by multiwall carbon nanotubes (MWCNT) is a viable alternative. To understand the mechanisms underlying MWCNT lubrication of highly loaded contacts, we combine an experimental approach with large-scale molecular dynamics (MD) simulations. Tribometry is performed on ground iron plates coated with two different types of MWCNTs by electrophoretic deposition. Although structural differences in the MWCNT materials result in slightly different running-in behavior, most of the tests converge to a steady-state coefficient of friction of 0.18. The resulting wear tracks and tribolayers are subjected to structural and chemical characterization and suggest a tribo-induced phase transformation resulting in tribolayers that consist of MWCNT fragments, iron oxide, and iron carbide nanoparticles embedded in an amorphous carbon matrix. Covalent bonding of the tribolayer to the iron surface and low carbon transfer to the alumina counter body indicate sliding at the tribolayer/ball interface as the dominant mechanism underlying MWCNT solid lubrication. MD simulations of nascent a-C tribofilms lubricated by MWCNT bundles and stacks of crossed MWCNTs reveal two different sliding regimes: a low-load regime that leaves the MWCNTs intact and a high-load regime with partial collapse of the tube structure and formation of a-C regions. The critical load for this transition increases with the filling ratio of the MWCNT and the packing density of the stacks. The former determines the stability of the MWCNT, while the latter controls the local stresses at the MWCNT crossings. For both MWCNT materials, the high-load regime is predicted for the experimental loads. This is confirmed by a remarkable agreement between transmission electron microscopy (TEM) and atomistic simulation images. Based on the findings of this work, a multistep lubrication mechanism is formulated for MWCNT coatings rubbing against alumina on an iron substrate. [ABSTRACT FROM AUTHOR]

Azanone (nitroxyl, HNO) is a highly reactive compound whose biological role is still a matter of debate. One possible route for its formation is NO reduction by biological reductants. These reactions have been historically discarded due to the negative redox potential for the NO,H+/HNO couple. However, the NO to HNO conversion mediated by vitamins C, E, and aromatic alcohols has been recently shown to be feasible from a chemical standpoint. Based on these precedents, we decided to study the reaction of NO with thiols as potential sources of HNO. Using two complementary approaches, trapping by a Mn porphyrin and an HNO electrochemical sensor, we found that under anaerobic conditions aliphatic and aromatic thiols (as well as selenols) are able to convert NO to HNO, albeit at different rates. Further mechanistic analysis using ab initio methods shows that the reaction between NO and the thiol produces a free radical adduct RSNOH•, which reacts with a second NO molecule to produce HNO and a nitrosothiol. The nitrosothiol intermediate reacts further with RSH to produce a second molecule of HNO and RSSR, as previously reported. [ABSTRACT FROM AUTHOR]

The reduction of NO• to HNO/NO– under biologically compatible conditions has always been thought as unlikely, mostly because of the negative reduction potential: E°(NO•,H+/HNO) = −0.55 V vs NHE at physiological pH. Nonetheless, during the past decade, several works hinted at the possible NO-to-HNO conversion mediated by moderate biological reductants. Very recently, we have shown that the reaction of NO• with ascorbate and aromatic alcohols occurs through a proton-coupled nucleophilic attack (PCNA) of the alcohol to NO•, yielding an intermediate RO–N(H)O• species, which further decomposes to release HNO. For the present work, we decided to inspect whether other common biological aromatic alcohols obtained from foods, such as Vitamin E, or used as over-the-counter drugs, like aspirin, are able to undergo the reaction. The positive results suggest that the conversion of NO to HNO could occur far more commonly than previously expected. Taking these as the starting point, we set to review our and other groups’ previous reports on the possible NO-to-HNO conversion mediated by biological compounds including phenolic drugs and vitamins, as well as several thiol-bearing compounds. Analysis of revised data prompted us to ask ourselves the following key questions: What are the most likely physio/pathological conditions for NO•-to-HNO conversion to take place? Which effects usually attributed to NO• are indeed mediated by HNO? These inquiries are discussed in the context of 2 decades of NO and HNO research. [ABSTRACT FROM AUTHOR]

Owing to MXenes' tunable mechanical properties induced by their structural and chemical diversity, MXenes are believed to compete with state-of-the-art 2D nanomaterials such as graphene regarding their tribological performance. Their nanolaminate structure offers weak interlayer interactions and an easy-to-shear ability to render them excellent candidates for solid lubrication. However, the acting friction and wear mechanisms are yet to be explored. To elucidate these mechanisms, 100-nm-thick homogeneous multilayer Ti 3 C 2 T x coatings are deposited on technologically relevant stainless steel by electrospraying. Using ball-on-disk tribometry (Si 3 N 4 counterbody) with acting contact pressures of about 300 MPa, their long-term friction and wear performance under dry conditions are studied. MXene-coated specimens demonstrate a 6-fold friction reduction and an ultralow wear rate (4 × 10 -9 mm 3 N -1 m -1 ) over 100 000 sliding cycles, outperforming state-of-the-art 2D nanomaterials by at least 200% regarding their wear life. High-resolution characterization verified the formation of a beneficial tribolayer consisting of thermally/mechanically degraded MXenes and amorphous/nanocrystalline iron oxides. The transfer of this tribolayer to the counterbody transforms the initial steel/Si 3 N 4 contact to tribolayer/tribolayer contact with low shear resistance. MXene pileups at the wear track's reversal points continuously supply the tribological contact with fresh, lubricious nanosheets, thus enabling an ultra-wear-resistant and low-friction performance.

The reduction of NO(•) to HNO/NO(-) under biologically compatible conditions has always been thought as unlikely, mostly because of the negative reduction potential: E°(NO(•),H(+)/HNO) = -0.55 V vs NHE at physiological pH. Nonetheless, during the past decade, several works hinted at the possible NO-to-HNO conversion mediated by moderate biological reductants. Very recently, we have shown that the reaction of NO(•) with ascorbate and aromatic alcohols occurs through a proton-coupled nucleophilic attack (PCNA) of the alcohol to NO(•), yielding an intermediate RO-N(H)O(•) species, which further decomposes to release HNO. For the present work, we decided to inspect whether other common biological aromatic alcohols obtained from foods, such as Vitamin E, or used as over-the-counter drugs, like aspirin, are able to undergo the reaction. The positive results suggest that the conversion of NO to HNO could occur far more commonly than previously expected. Taking these as the starting point, we set to review our and other groups' previous reports on the possible NO-to-HNO conversion mediated by biological compounds including phenolic drugs and vitamins, as well as several thiol-bearing compounds. Analysis of revised data prompted us to ask ourselves the following key questions: What are the most likely physio/pathological conditions for NO(•)-to-HNO conversion to take place? Which effects usually attributed to NO(•) are indeed mediated by HNO? These inquiries are discussed in the context of 2 decades of NO and HNO research.