Fragmentations of some bifunctional phenylether compounds by intermediate ion/neutral complexes

The fragmentations of three bifunctional phenylether compounds including 2-(2, 6-dichloro)phenoxyl propionitrile, N-hydroxyl-4-butoxyl phenylacetyl amine(bufexamc) and 2-(1-methylethoxyl) phenol methylcarbamate (Propoxur) under electron impact ionization were reported, Metastable ion(MI) and collision-induced dissociation(CID) at a low energy have been used to study the fragmentation pathways from molecular ions. Apart from the simple bond cleavages, and the unimolecular dissociations via ion/neutral complex intermediate as a competitive mechanism were demonstrated, Moreover, the intramolecular hydrogen transfer and double hydrogen transfers in the fragmentations of these compounds were discussed in detail.

CHEMICAL-IONIZATION MASS-SPECTROMETRY OF SOME NITRO-CONTAINING BIFUNCTIONAL AROMATIC-COMPOUNDS - LOCATION OF PROTONATION SITE

It is found that the nitro substituent of some aromatic bifunctional compounds shows unusual reactivity towards protonation. In the chemical ionization mass spectra of nitrobenzoic acids and their esters and amides, and of nitrophenols and their ethers, protonations on the carboxyl, ester, amide, hydroxyl or alkoxyl groups are highly suppressed by that on the nitro group. As a result, fragmentations based on protonation on these groups unexpectedly become negligible. Ortho effects were observed for all the ortho isomers where the initial protonation on the nitro group is followed by an intramolecular proton transfer reaction, which leads to the expected 'normal' fragmentations. Protonation on the nitro substituent is much more favourable in energy than on any of the other substituents. The interaction of the two substituents through the conjugating benzene ring is found to be responsible for this 'unfair' competitive protonation. The electron-attracting nitro group strongly destabilizes the MH+ ions formed through protonation on the other substituent; although the COR (R = OH, OMe, OEt, NH2) groups are also electron-withdrawing, their effects are weaker than that of NO2; thus protonation on the latter group produces more-stable MH+ ions. On the other hand, an electron-releasing group OR (R = H, Me, Et) stabilizes the nitro-protonated species; the stronger the electron-donating effect of this group the more stable the nitro-protonated ions.

土石混合体细观结构力学及其边坡稳定性研究

Soil-rock mixture (S-RM) refers to one extremely uneven loose rock and soil materials system with certain stone content. Its formation has started since Quaternary and it is composed of block stone, fine grained soil and pore with certain project scale and high strength. S-RM has extensive distribution in nature, especially in southwest China where the geotectonic background is complicated, the fracture activity is developed and the geomorphological characteristics of high mountain and steep gorge area are protuberant. This kind of complicated geologic body has developed wider in these areas. S-RM has obvious difference with the general soil or rock (rock mass) in physical and mechanical properties because its two components-“soil” and “rock-block” has extreme differences in physical and mechanical properties. The proposition of S-RM and its deep research are needed in the modern engineering construction. It is also the necessity in the modern development of rock and soil mechanics. The dissertation starts from the meso-structural characteristics of soil-rock and takes a systematic research on its meso-structural mechanics, deformation and failure mechanism and the stability of S-RM slope. In summary, it achieves the following innovative results and conclusions. There are various views on the conception of S-RM and its classification system. Based on the large number of field tests, the dissertation makes the conception and classification of S-RM more systematic. It systematically proposed the conception of meso-structural mechanics of S-RM. Thus the dissertation has laid a foundation for its deep study. With the fast development of the computer technology and digital image processing theory, digital image processing technology has been successfully applied in many fields and provided reliable technology support for the quantitative description of the structural characteristics of S-RM. Based on the digital image processing technology, the dissertation systematically proposes and developed the quantitative analysis method and quantitative index for the meso-structure of S-RM. The results indicate that the meso-structure such as its internal soil-rock granularity composition, the soil-rock shape and the orientability has obvious self-organization in the macro statistical level. The dissertation makes a systematic research on the physical mechanical properties, deformation and failure mechanism of S-RM based on large field test. It proposes the field test for the underwater S-RM and deduces the 3D data analysis method of in-situ horizontal push-shear test. The result indicates that S-RM has significant phenomenon of shear dilatancy in the shearing process, and its dilatancy will be more obvious with the increased proportion of rock or the decreased confining pressure. The proportion of rock has great effect on the strength of S-RM and rock-block, especially the spatial position of particles with comparatively big size has great effect on the shape and spatial position of the sample shear zone. The dissertation makes some improvements in the single ring infiltration test equipment and its application on the permeability of S-RM. The results indicate that the increasing of rock-block would make it more difficult for the soil to fill in the vacuity between the rock-block and the proportion would increase which would result in the increased permeability coefficient. The dissertation builds the real meso-structural model of S-RM based on the digital image processing technology. By using geometric reconstruction technology, it transfers the structural mode represented by Binary image into CAD format, which makes it possible to introduce the present finite element analysis software to take research on numerical experimental investigation. It systematically realizes leaping research from the image，geometric mode, to meso-structural mechanics numerical experiment. By using this method, the dissertation takes large scale numerical direct-shear test on the section of S-RM. From the mesoscopic perspective, it reveals three extended modes about the shear failure plane of S-RM. Based on the real meso-structural model and by using the numerical simulation test, the character and mechanics of seepage failure of S-RM are studied. At the same time, it builds the real structural mode of the slope based on the analysis about the slope crosssection of S-RM. By using the strength reduction method, it takes the research on the stability of S-RM and gets great achievements. The three dimensional geometric reconstruction technology of rock block is proposed, which provides technical support for the reconstruction of the 3D meso-structural model of S-RM. For the first time, the dissertation builds the stochastic structure model of two-dimensional and three-dimensional polygons or polyhedron based on the stochastic simulation technique of monte carlo method. It breaks the traditional research which restricted to the random generation method of regular polygon and develops the relevant software system (R-SRM2D/3D) which has great effect on meso-structural mechanics of S-RM. Based on the R-SRM software system which randomly generates the meso-structural mode of S-RM according to the different meso-structural characteristics, the dissertation takes a series of research on numerical test of dual axis and real three-axis, systematically analyses the meso destroy system, the effects of meso-structural characteristics such as on the stone content, size composition and block directionality on the macro mechanical behavior and macro-permeability. Then it proposes the expression of the upper and lower limit for the macro-permeability coefficient of the inhomogeneous geomaterials, such as S-RM. By using the strength reduction FEM, the dissertation takes the research on the stability of the slope structural mode of the randomly formed S-RM. The results indicate that generally, the stability coefficient of S-RM slope increases with the increasing of stone content; on the condition of the same stone content, the stability coefficient of slope will be different with different size composition and the space position of large block at the internal slop has great effect on the stability. It suggests that meso-structural characteristics, especially the space position of large block should be considered when analyzing the stability of this kind of slope and strengthening design. Taking Xiazanri S-RM slope as an example, the dissertation proposes the fine modeling of complicated geologic body based on reverse engineering and the generation method of FLAC3D mode. It resolves the bottleneck problem about building the fine structural mode of three-dimensional geological body. By using FLAC3D, the dissertation takes research on the seepage field and the displacement field of Xiazanri S-RM slope in the process of reservoir water level rising and decreasing. By using strength reduction method, it analyses the three-dimension stability in the process of reservoir water level rising and decreasing. The results indicate that the slope stability firstly show downward trend in the process of reservoir water level rising and then rebound to increase; the sudden drawdown of reservoir water level has great effect on the slope stability and this effect will increase with the sudden drawdown amplitude rising. Based on the result of the rock block size analysis of S-RM, and using R-SRM2D the stochastic structure model of Xiazanri S-RM slope is built. By using strength reduction method, the stability of the stochastic structure model is analysis, the results shows that the stability factor increases significantly after considering the block.