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31.
32.
S. Trippett 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):89-98
Abstract In order to dicuss mechanism in organophosphorus chemistry a number of assumptions have to be made. Among them are: (a) that substitutions at tetrahedral phosphorus proceed via five-coordinate intermediates; (b) these intermediates are trigonal bipyramidal; (c) they are formed by apical attack and decompose by apical loss; and (d) if sufficiently long-lived, they may undergo permutational isomerization, that is the ligands may alter their relative dispositions round the phosphorus, before going on to products or back to reactants. Assuming that the course of a given substitution is dictated primarily by thermodynamic considerations, in order to understand the course of that substitution one needs to know how to assess the relative stabilities of the four isomeric tbps (trigonal bipyramids) that can be formed initially and of the others that could be formed by subsequent isomerization, the barriers to those isomerizations, and the relative rates of the various product-forming steps. We have concentrated on the first of these factors and this lecture describes our attempts to provide the necessary data. The energy difference between two isomeric tbps can be analyzed in terms of changes in the relative apicophilicities1 of the groups occupying apical positions, changes in ring-strain as small rings move between apical-equatorial and diequatorial positions, and changes in steric strain. I shall consider each of these in turn. Ligand subset symmetry may also have to be taken into account.1,2 相似文献
33.
The in situ synthesis and subsequent reactions of macrocylic imine 2 are reported. The imine was trapped with cyanotrimethylsilane to give α-amino nitrile aza-[13]-macrodiolides in a 1:1 ratio of diastereomers. A crystal structure of the syn α-cyano nitrile diastereomer, 7a, provided insights into the lack of selectivity in reactions of 2 relative to macrocyclic alkene 1. Reactions to functionalize the syn diastereomer 7a are also reported. 相似文献
34.
The aging process induces progressive and irreversible changes in the structural and functional organization of animals. The objective of this study was to evaluate the effects of aging on the structure and composition of the extracellular matrix of the arytenoid cartilage found in the larynx of male bullfrogs (Lithobates catesbeianus) kept in captivity for commercial purposes. Animals at 7, 180 and 1080 days post-metamorphosis (n = 10/age) were euthanized and the cartilage was removed and processed for structural and biochemical analysis. For the structural analyses, cartilage sections were stained with picrosirius, toluidine blue, Weigert’s resorcin-fuchsin and Von Kossa stain. The sections were also submitted to immunohistochemistry for detection of collagen types I and II. Other samples were processed for the ultrastructural and cytochemical analysis of proteoglycans. Histological sections were used to chondrocyte count. The number of positive stainings for proteoglycans was quantified by ultrastructural analysis. For quantification and analysis of glycosaminoglycans were used the dimethyl methylene blue and agarose gel electrophoresis methods. The chloramine T method was used for hydroxyproline quantification. At 7 days, basophilia was observed in the pericellular and territorial matrix, which decreased in the latter over the period studied. Collagen fibers were arranged perpendicular to the major axis of the cartilaginous plate and were thicker in older animals. Few calcification areas were observed at the periphery of the cartilage specimens in 1080-day-old animals. Type II collagen was present throughout the stroma at the different ages. Elastic fibers were found in the stroma and perichondrium and increased with age in the two regions. Proteoglycan staining significantly increased from 7 to 180 days and reduced at 1080 days. The amount of total glycosaminoglycans was higher in 180-day-old animals compared to the other ages, with marked presence of chondroitin- and dermatan-sulfate especially in this age. The content of hydroxyproline, which infers the total collagen concentration, was higher in 1080-day-old animals compared to the other ages. The results demonstrated the elastic nature of the arytenoid cartilage of L. catesbeianus and the occurrence of age-related changes in the structural organization and composition of the extracellular matrix. These changes may contribute to alter the function of the larynx in the animal during aging. 相似文献
35.
《Comptes Rendus Physique》2015,16(10):986-993
Deciphering the mechanisms at play in the formation and evolution of the large-scale structure of the universe is part of the scientific goals of many projects of observational cosmology. In particular, large-scale structure observations can be used to infer mode-coupling effects, whether they come from the physics of the early universe or from its late time evolution. Specificities of such couplings are presented, noting that in principle they can be directly detected through bispectra of the cosmic microwave background temperature anisotropies or density in the local universe. The existence of such couplings have however more far-reaching consequences for the growth of the structure. Those are sketched as well as their possible observational impacts. 相似文献
36.
The stannides RE2Au3Sn6 (RE = La, Ce, Pr, Nd, Sm) were synthesized from the elements by arc-melting. Small single crystals were grown by annealing samples in sealed tantalum tubes in an induction furnace with a special annealing sequence. The polycrystalline phases were characterized through their X-ray powder diffraction pattern. The structures of Ce2Au3Sn6, Pr2Au3Sn6, and Nd2Au3Sn6 were refined from single-crystal X-ray diffractometer data. The RE2Au3Sn6 stannides crystallize with the orthorhombic La2Zn3Ge6 type, space group Cmcm. The basic structural building units are Au1@Sn4 tetrahedra and Au2@Sn5 square pyramids. These units are condensed to layers and the structure can be described by a simple stacking of tetrahedral and pyramidal layers with the rare earth cations in between. Temperature dependent susceptibility studies indicate that all rare earth atoms are in the trivalent oxidation state, as their effective magnetic moments match the expected values of the free RE3+ ions. Pr2Au3Sn6 and Nd2Au3Sn6 exhibit antiferromagnetic ordering at TN = 6.3(1) and 6.7(1) K. Investigations of the electrical resistivity of La2Au3Sn6 and Ce2Au3Sn6 confirmed that these compounds are metallic, for La2Au3Sn6 a lower resistivity was observed, in line with the absence of screening unpaired electrons. 119Sn Mössbauer spectra for La2Au3Sn6, Ce2Au3Sn6, Pr2Au3Sn6 and Nd2Au3Sn6 show a complex superposition of three sub-spectra which can be differentiated through their distinctly different quadrupole splitting parameters. The isomer shifts (1.87 to 2.22 mm · s–1) indicate significant s electron density at the tin nuclei. 相似文献
37.
This work focuses on the effects of different ultrasound power densities on the microstructural changes and physicochemical properties of okara fibers, which are composed of carbohydrate-based polymers. Okara suspensions were treated with ultrasound at different power densities (0, 1, 2, 3, 4, and 5 W/mL) for 30 min, after which the ultrasound-treated okara were hydrolyzed by trypsin to obtain okara fibers. The ultrasound treatment of the okara fibers induced structural disorganization and changes, evidenced mainly in their morphological characteristics and their relative crystallinity degrees. Increasing the ultrasound power broke the okara fibers into flaky and stacked structures. When the ultrasound power density reached 4 W/mL, the parenchyma became compact and the hourglass structure fractured. The mean particle size of the okara fiber was reduced from 82.24 µm to 53.96 µm, and the homogeneity was enhanced significantly. The relative crystallinity of the okara fibers was reduced from 55.14% to 36.47%. The okara fiber surface charge decreased when the ultrasound power was increased. However, after ultrasound treatment at 4 W/mL (800 W), the okara fiber suspension exhibited the highest viscosity value and a higher swelling capacity, water-holding capacity, and oil-holding capacity. Therefore, the results indicated that the selection of processing conditions for okara fibers is critical and that okara fiber modification using a high ultrasound treatment might improve their use in potential applications. 相似文献
38.
Rui Liu Jing-fu Liu Xiao-xia Zhou Gui-bin Jiang Rui Liu 《Trends in analytical chemistry : TRAC》2011,30(9):1462-1476
Raman-based technologies have proved to be excellent tools for on-site and in-vivo analysis, due to the non-invasive nature of their detection, their capability of providing structure information, their high tolerance to aqueous samples, the ultra-sensitivity of surface-enhanced Raman scattering (SERS) and resonance Raman scattering (RRS), the high spatial resolution of tip-enhanced Raman scattering (TERS), and the ultrashort spectra-acquisition time for coherent anti-Stokes Raman scattering (CARS) and stimulated Raman scattering (SRS).In this review, we highlight the recent success of Raman-based technologies in various applications, including:
(1)
on-site surface analysis and chemical-reaction monitoring; (2)
on-site identification of cultural objects, archeological studies and planetary science; (3)
in-vivo analysis of cells and microorganisms; (4)
in-vivo diagnosis inside human and animal bodies; (5)
in-vivo fast Raman imaging and mapping; (6)
the study of SERS processes; and, (7)
assessment of nanomaterial safety.
39.
Cadmium-doped zinc oxide nanocrystals in the quantum confinement region have been firstly synthesized by a fast and facile sonochemical method.The alloyed structure of the nanocrystals is confirmed by X-ray diffraction,transmission electron microscopy,and infrared analysis.With the increase of cadmium to zinc molar ratio from 0 to 2.0,the crystallite sizes of the samples decrease from 5.1 nm to 2.6 nm,and the band gaps of the samples show a red shift then a blue shift,and a red shift again.The variations of band gaps of the samples can be interpreted by the crystallite size and the composition.It is found that both the non-thermal equilibrium environment established in the sonochemical reaction and the coordination ability of triethylene glycol solvent play crucial roles in the current preparation. 相似文献
40.
邢莹莹 《光谱学与光谱分析》2018,38(4):1036-1043
以硬玉岩中名义上无水硬玉矿物为研究对象,通过常温和变温红外光谱测量,确定硬玉矿物结构水表征及变温过程热变异行为。研究结果显示:由M-OH伸缩振动所致的红外吸收谱带集中于3 700~3 600,3 570~3 520,3 500~3 300及3 230~3 140 cm-1波数范围内,但在不同的硬玉岩中具有不同的红外吸收。变温过程中,该吸收谱带基本在500 ℃左右相对吸收强度出现较为明显的减弱,且结构水含量也逐渐下降,进一步表征硬玉矿物中的“水”是以结构水的形式进入晶格。但此M-OH伸缩振动所致的吸收谱带、结构水含量和指纹谱均在850 ℃附近出现较为明显的变化,预示该温度硬玉矿物的成分已出现变异。硬玉矿物中“水”的热变异行为为进一步了解水分子的赋存状态与结合方式及其成岩机制提供一定的佐证。 相似文献