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91.
Jane S. Murray Pat Lane Anian Nieder Thomas M. Klapötke Peter Politzer 《Theoretical chemistry accounts》2010,127(4):345-354
Si-pentaerythritol tetranitrate (PETN), Si[CH2ONO2]4, is a silicon analog of the widely used explosive PETN, C[CH2ONO2]4. Si-PETN is extremely sensitive to impact, much more so than PETN. This was attributed by Liu et al. to Si-PETN having a
much lower activation barrier to decomposition, via a facile rearrangement that is not as readily available to PETN, and which
releases considerable energy that can promote further steps. We have investigated computationally why the barrier to the rearrangement
is so much lower for Si-PETN than for PETN, using 5, (H3C)3C–CH2ONO2, and 6, (H3C)3Si–CH2ONO2, as models for PETN and Si-PETN. Reaction force analysis shows that most of the difference between the rearrangement barriers
for 5 and 6 comes about in the initial (reactant) stages of the processes, in which 6 benefits from a 1,3 electrostatic interaction involving a positive σ–hole on the silicon and the negative linking oxygen.
The analogous interaction is weaker in 5, since the central carbon does not have positive σ–holes; furthermore, this carbon is less able than silicon to temporarily
expand its coordination sphere. A similar explanation involving a positive silicon σ–hole and a linking oxygen is proposed
for Si-PETN. The greater exothermicity of the rearrangement of 6 (and also Si-PETN) can be rationalized, following Liu et al., in terms of the formation of the strong Si–O bond. 相似文献
92.
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94.
Julian J. Adams David E. Berry Jane Browning Dirk Burth Owen J. Curnow 《Journal of organometallic chemistry》1999,580(2):6418
The preparation, isolation and characterisation of 1,3-bis(diphenylphosphino)indene (1) from indene and chlorodiphenylphosphine is described. The reaction of 1 with selenium gives the diselenide adduct 1,3-bis(diphenylselenophosphino)indene (2) which was characterised crystallographically. Deprotonation of 1 and treatment with ferrous chloride gives the unstable tetraphosphine complex bis(1,3-bis(diphenylphosphino)indenyl)iron(II) (3). Complex 3 decomposes to the diphosphine complex bis(1-diphenylphosphinoindenyl)iron(II) (4) via replacement of one diphenylphosphine substituent per indenyl ligand by a hydrogen atom. Complex 4 was also prepared by treatment of two equivalents of 1-diphenylphosphinoindenide with ferrous chloride. The heterobimetallic complex tetracarbonyl(bis(1-diphenylphosphinoindenyl)iron(II))molybdenum(0) (5) was also prepared and crystal structures of both the meso (5a) and C2-symmetric racemic (5b) isomers are reported. 相似文献
95.
96.
We have coupled CIEF with an LIF detector that is based on a post‐column sheath flow cuvette. We employed Chromeo P503 as a fluorogenic reagent to label proteins before analysis. This reagent reacts with the ε‐amine of lysine residues, preserving the cationic nature of the residue; labeled proteins generate extremely sharp peaks in CIEF. A set of four standard proteins generated a linear relationship between migration time and pI. A protein homogenate prepared from a Barrett's esophagus cell line resolved over 100 components in a 40 min separation. Detection limits for Chromeo P503‐labeled β‐lactoglobulin were 5 amol injected into the capillary. Fluorescent impurities present in the ampholytes generated a large background signal that degraded the detection limit by four orders of magnitude compared with other forms of capillary electrophoresis with this detector. 相似文献
97.
98.
Jane McDougall Lisbeth Schaubroeck 《Journal of Mathematical Analysis and Applications》2008,340(1):721-738
A JS surface is a minimal graph over a polygonal domain that becomes infinite in magnitude at the domain boundary. Jenkins and Serrin characterized the existence of these minimal graphs in terms of the signs of the boundary values and the side-lengths of the polygon. For a convex polygon, there can be essentially only one JS surface, but a non-convex domain may admit several distinct JS surfaces. We consider two families of JS surfaces corresponding to different boundary values, namely JS0 and JS1, over domains in the form of regular stars. We give parameterizations for these surfaces as lifts of harmonic maps, and observe that all previously constructed JS surfaces have been of type JS0. We give an example of a JS1 surface that is a new complete embedded minimal surface generalizing Scherk's doubly periodic surface, and show also that the JS0 surface over a regular convex 2n-gon is the limit of JS1 surfaces over non-convex stars. Finally we consider the construction of other JS surfaces over stars that belong neither to JS0 nor to JS1. 相似文献
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100.
Ching-Hua Kuo Chia-Wen Lee I-Lin Tsai Y. Jane Tseng Jaw-Jou Kang Fu-Chuo Peng 《Talanta》2010,80(5):1672-161
Aristolochic acids (AAs) are a mixture of structural-related compounds, in which aristolochic acid I (AA I) and aristolochic acid II (AA II) are reported to be correlated with Aristolochic acid nephropathy (AAN). In this work, a rapid and sensitive ultra-high-pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed to determine AA I and AA II in herbal products and biological fluids. By using gradient elution with a mobile phase composed of a mixture of 10 mM ammonium formate buffer (pH 3.0) and acetonitrile, AAs could be determined within 10 min. Under optimum UHPLC-MS/MS conditions, the limit of detections was 0.14 and 0.26 ng mL−1 for AA I and AA II, respectively. Run-to-run repeatability and intermediate precision of peak area for AA I and AA II were less than 5.74% relative standard deviation (RSD). Accuracy was tested by spiking 10, 100 and 1000 ng mL−1 in rat serum and the recoveries were within 76.5-92.9%. Matrix effects were within 78.8-127.7%. The developed method was successfully applied to determine AA I and AA II in several herbal products and to investigate their pharmacokinetic behavior in female Wister rats. The result shows that the developed UHPLC-MS/MS method is efficient, sensitive, and accurate for the determination of AA I and AA II in herbal products and biological samples. 相似文献