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Mechanical stress can directly activate chemical reactions by reducing the reaction energy barrier. A possible mechanism of such mechanochemical activation is structural deformation of the reactant species. However, the effect of deformation on the reaction energetics is unclear, especially, for shear stress-driven reactions. Here, we investigated shear stress-driven oligomerization reactions of cyclohexene on silica using a combination of reactive molecular dynamics simulations and ball-on-flat tribometer experiments. Both simulations and experiments captured an exponential increase in reaction yield with shear stress. Elemental analysis of ball-on-flat reaction products revealed the presence of oxygen in the polymers, a trend corroborated by the simulations, highlighting the critical role of surface oxygen atoms in oligomerization reactions. Structural analysis of the reacting molecules in simulations indicated the reactants were deformed just before a reaction occurred. Quantitative evidence of shear-induced deformation was established by comparing bond lengths in cyclohexene molecules in equilibrium and prior to reactions. Nudged elastic band calculations showed that the deformation had a small effect on the transition state energy but notably increased the reactant state energy, ultimately leading to a reduction in the energy barrier. Finally, a quantitative relationship was developed between molecular deformation and energy barrier reduction by mechanical stress.

 

Tribochemistry, which is another name for mechanochemistry driven by shear, deals with complex and dynamic interfacial processes that can lead to surface wear or formation of beneficial tribofilms. For better mechanistic understanding of these processes, we investigated the reactivity of tribopolymerization of organic molecules with different internal ring strain (methylcyclopentane, cyclohexane, and cyclohexene) on a stainless steel (SS) surface in inert (N2), oxidizing (O2), and reducing (H2) environments at room temperature. On the clean stainless steel surface, precursor molecules were found to physisorb with a broad range of molecular orientations. In inert and reducing environments, the strain-free cyclohexane showed the lowest tribochemical activity among the three molecules tested. Compared to the N2 environment, the tribochemical activity in H2 was suppressed. In the O2 environment, only cyclohexene produced tribofilms and methylcyclopentane while cyclohexane did not. When tribofilms were analyzed with Raman spectroscopy, the spectral features of diamond-like carbon (DLC) or amorphous carbon (a-C) were observed due to photochemical degradation of triboproducts. Based on infrared spectroscopy, tribofilms were found to be organic polymers containing oxygenated groups. Whenever polymeric tribrofilms were produced, wear volume was suppressed by orders of magnitudes but not completely to zero. These results support previously suggested mechanisms which involve surface oxygen as a reactant species in the tribopolymerization process. 

Dipyridyl molecular junctions often show intriguing conductance switching behaviors with mechanical modulations, but the mechanisms are still not completely revealed. By applying the ab initio -based adiabatic simulation method, the configuration evolution and electron transport properties of dipyridyl molecular junctions in stretching and compressing processes are systematically investigated. The numerical results reveal that the dipyridyl molecular junctions tend to form specific contact configurations during formation processes. In small electrode gaps, the pyridyls almost vertically adsorb on the second Au layers of the tip electrodes by pushing the top Au atoms aside. These specific contact configurations result in stronger molecule–electrode couplings and larger electronic incident cross-sectional areas, which consequently lead to large breaking forces and high conductance. On further elongating the molecular junctions, the pyridyls shift to the top Au atoms of the tip electrodes. The additional scattering of the top Au atoms dramatically decreases the conductance and switches the molecular junctions to the lower conductive states. Perfect cyclical conductance switches are obtained as observed in the experiments by repeatedly stretching and compressing the molecular junctions. The O atom in the side-group tends to hinder the pyridyl from adsorbing on the second Au layer and further inhibits the conductance switch of the dipyridyl molecular junction. 

Octafluorocyclopentene (OFCP) engages linear, unprotected peptides in polysubstitution cascades that generate complex fluorinated polycycles. The reactions occur in a single flask at 0–25 °C and require no catalysts or heavy metals. OFCP can directly polycyclize linear sequences using native functionality, or fluorospiroheterocyclic intermediates can be intercepted with exogenous nucleophiles. The latter tactic generates molecular hybrids composed of peptides, sugars, lipids, and heterocyclic components. The platform can create stereoisomers of both single- and double-looped macrocycles. Calculations indicate that the latter can mimic diverse protein surface loops. Subsets of the molecules have low energy conformers that shield the polar surface area through intramolecular hydrogen bonding. A significant fraction of OFCP-derived macrocycles tested show moderate to high passive permeability in parallel artificial membrane permeability assays. 

In the Raman analysis of tribofilms produced from organic precursors, the D- and G-band features are often observed, which resemble the characteristic bands of diamond-like carbon (DLC), amorphous carbon (a-C), or graphitic materials. This study reports experimental evidence that the D- and G-bands features in the Raman spectra of tribofilms could be generated by photochemical degradation of triboproducts due to the focused irradiation of laser beam during the Raman analysis, indicating that they are not unique to the genuine structure of the tribofilm produced via friction. This finding suggests that other complementary and non-destructive characterization is required to determine whether DLC, a-C, or graphitic species are produced tribochemically by frictional shear. 

Risk patterns are crucial in biomedical research and have served as an important factor in precision health and disease prevention. Despite recent development in parallel and high-performance computing, existing risk pattern mining methods still struggle with problems caused by large-scale datasets, such as redundant candidate generation, inability to discover long significant patterns, and prolonged post pattern filtering. In this article, we propose a novel dynamic tree structure, Risk Hierarchical Pattern Tree (RHPTree), and a top-down search method, RHPSearch, which are capable of efficiently analyzing a large volume of data and overcoming the limitations of previous works. The dynamic nature of the RHPTree avoids costly tree reconstruction for the iterative search process and dataset updates. We also introduce two specialized search methods, the extended target search (RHPSearch-TS) and the parallel search approach (RHPSearch-SD), to further speed up the retrieval of certain items of interest. Experiments on both UCI machine learning datasets and sampled datasets of the Simons Foundation Autism Research Initiative (SFARI)—Simon’s Simplex Collection (SSC) datasets demonstrate that our method is not only faster but also more effective in identifying comprehensive long risk patterns than existing works. Moreover, the proposed new tree structure is generic and applicable to other pattern mining problems. 

We use Sentinel‐1 and ALOS‐2 Interferometric Synthetic Aperture Radar (InSAR), and Global Navigation Satellite System (GNSS) data to investigate the mechanisms of coseismic and postseismic deformation due to the 2021 M7.4 Maduo (China) earthquake. We present a refined coseismic slip model constrained by the rupture trace and precisely located aftershocks. The InSAR time series corrected for the atmospheric and decorrelation noise reveal postseismic line of sight displacements up to ∼0.1 m. The displacements are discontinuous along the fault trace, indicating shallow afterslip and velocity‐strengthening friction in the top 2–3 km of the upper crust. The magnitude of shallow afterslip is however insufficient to compensate for the coseismic slip deficit, implying substantial off‐fault yielding. The observed surface deformation does not exhibit obvious features that could be attributed to poroelastic effects. We developed a fully coupled model that accounts for both stress‐driven creep on a deep localized shear zone and viscoelastic relaxation in the bulk of the lower crust. The mid‐ to near‐field data can be reasonably well explained by deep afterslip and/or non‐Maxwellian visco‐elasticity. Our results suggest a power‐law stress exponent of ∼4–4.5 assuming a power‐law rheology, and transient and steady‐state viscosities of 10¹⁸and 10¹⁹ Pa s, respectively, assuming a bi‐viscous (Burgers) rheology. However, a good fit to the GNSS data cannot be achieved assuming the bulk viscoelastic relaxation alone, and requires a contribution of deep afterlip and/or a localized shear zone extending through much of the lower crust.