63 research outputs found

    Why <i>trans</i>- or <i>cis</i>-Dimethyl Fumarate Addition to 2,5-Dimethylpyrrole Gives Exclusively <i>trans</i>-7-Azanorbornane

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    The addition mechanism of dimethyl fumarate into 2,5-dimethylpyrrole is explored using density functional theory (DFT) methods. Our calculations find that TpW­(NO)­(PMe<sub>3</sub>)­(η<sup>2</sup>-3<i>H</i>-2,5-di­methyl­pyrrole) prefers to undergo two TpW­(NO)­(PMe<sub>3</sub>) migrations, two 1,5-hydride migrations, and one reductive elimination to isomerize into TpW­(NO)­(PMe<sub>3</sub>)­(η<sup>2</sup>-1<i>H</i>-2,5-dimethylpyrrole), in which TpW­(NO)­(PMe<sub>3</sub>) plays a proton-transfer role. <i>trans</i>-Dimethyl fumarate and TpW­(NO)­(PMe<sub>3</sub>)­(η<sup>2</sup>-1<i>H</i>-2,5-dimethylpyrrole) tend to adopt a concerted cycloaddition manner to afford <i>trans</i>-7-azanorbornane with a free-energy barrier of 21.8 kcal/mol. <i>cis</i>-Dimethyl fumarate and TpW­(NO)­(PMe<sub>3</sub>)­(η<sup>2</sup>-1<i>H</i>-2,5-di­methyl­pyrrole) are the most likely to experience a concerted cycloaddition → ring opening → ring closing process to provide <i>trans</i>-7-azanorbornane in which the concerted cycloaddition and the ring-opening process are in dynamic equilibrium (with similar energy barriers of 21.5 and 21.9 kcal/mol, respectively). The presence of TpW­(NO)­(PMe<sub>3</sub>) not only promotes the cycloaddition of <i>trans</i>- or <i>cis</i>-dimethyl fumarate with 2,5-di­methyl­pyrrole by donating d-electrons of the W atom into the diene system of the Diels–Alder reaction, but also is favorable for the ring-opening process of the formed <i>cis</i>-7-azanorbornane. Furthermore, <i>trans</i>-azanorbornane is 7.4 kcal/mol more stable than <i>cis</i>-azanorbornane. Our calculations provide a new explanation of the addition of dimethyl fumarate with 2,5-dimethylpyrrole exclusively giving <i>trans</i>-7-azanorbornane

    Original data.

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    Natural disasters such as landslides often occur on soil slopes in seasonally frozen areas that undergo freeze‒thaw cycling. Ecological slope protection is an effective way to prevent such disasters. To explore the change in the mechanical properties of soil under the influence of both root reinforcement and freeze‒thaw cycles and its influence on slope stability, the Baijiabao landslide in the Three Gorges Reservoir area was taken as an example. The mechanical properties of soil under different confining pressures, vegetation coverages (VCs) and numbers of freeze‒thaw cycles were studied via mechanical tests, such as triaxial compression tests, wave velocity tests and FLAC3D simulations. The results show that the shear strength of a root–soil composite increases with increasing confining pressure and VC and decreases with increasing number of freeze‒thaw cycles. Bermuda grass roots and confining pressure jointly improve the durability of soil under freeze‒thaw conditions. However, with an increase in the number of freeze‒thaw cycles, the resistance of root reinforcement to freeze‒thaw action gradually decreases. The observed effect of freeze‒thaw cycles on soil degradation was divided into three stages: a significant decrease in strength, a slight decrease in strength and strength stability. Freeze‒thaw cycles and VC mainly affect the cohesion of the soil and have little effect on the internal friction angle. Compared with that of a bare soil slope, the safety factor of a slope covered with plants is larger, the maximum displacement of a landslide is smaller, and it is less affected by freezing and thawing. These findings can provide a reference for research on ecological slope protection technology.</div

    The vegetation coverage (VC) and root content.

    No full text
    Natural disasters such as landslides often occur on soil slopes in seasonally frozen areas that undergo freeze‒thaw cycling. Ecological slope protection is an effective way to prevent such disasters. To explore the change in the mechanical properties of soil under the influence of both root reinforcement and freeze‒thaw cycles and its influence on slope stability, the Baijiabao landslide in the Three Gorges Reservoir area was taken as an example. The mechanical properties of soil under different confining pressures, vegetation coverages (VCs) and numbers of freeze‒thaw cycles were studied via mechanical tests, such as triaxial compression tests, wave velocity tests and FLAC3D simulations. The results show that the shear strength of a root–soil composite increases with increasing confining pressure and VC and decreases with increasing number of freeze‒thaw cycles. Bermuda grass roots and confining pressure jointly improve the durability of soil under freeze‒thaw conditions. However, with an increase in the number of freeze‒thaw cycles, the resistance of root reinforcement to freeze‒thaw action gradually decreases. The observed effect of freeze‒thaw cycles on soil degradation was divided into three stages: a significant decrease in strength, a slight decrease in strength and strength stability. Freeze‒thaw cycles and VC mainly affect the cohesion of the soil and have little effect on the internal friction angle. Compared with that of a bare soil slope, the safety factor of a slope covered with plants is larger, the maximum displacement of a landslide is smaller, and it is less affected by freezing and thawing. These findings can provide a reference for research on ecological slope protection technology.</div

    Shear wave velocity test results.

    No full text
    Natural disasters such as landslides often occur on soil slopes in seasonally frozen areas that undergo freeze‒thaw cycling. Ecological slope protection is an effective way to prevent such disasters. To explore the change in the mechanical properties of soil under the influence of both root reinforcement and freeze‒thaw cycles and its influence on slope stability, the Baijiabao landslide in the Three Gorges Reservoir area was taken as an example. The mechanical properties of soil under different confining pressures, vegetation coverages (VCs) and numbers of freeze‒thaw cycles were studied via mechanical tests, such as triaxial compression tests, wave velocity tests and FLAC3D simulations. The results show that the shear strength of a root–soil composite increases with increasing confining pressure and VC and decreases with increasing number of freeze‒thaw cycles. Bermuda grass roots and confining pressure jointly improve the durability of soil under freeze‒thaw conditions. However, with an increase in the number of freeze‒thaw cycles, the resistance of root reinforcement to freeze‒thaw action gradually decreases. The observed effect of freeze‒thaw cycles on soil degradation was divided into three stages: a significant decrease in strength, a slight decrease in strength and strength stability. Freeze‒thaw cycles and VC mainly affect the cohesion of the soil and have little effect on the internal friction angle. Compared with that of a bare soil slope, the safety factor of a slope covered with plants is larger, the maximum displacement of a landslide is smaller, and it is less affected by freezing and thawing. These findings can provide a reference for research on ecological slope protection technology.</div

    Strength attenuation mechanism of the root–soil composite under freeze‒thaw action.

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    Strength attenuation mechanism of the root–soil composite under freeze‒thaw action.</p
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