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排序方式: 共有147条查询结果,搜索用时 31 毫秒
41.
派热克斯玻璃的Hugoniot实验数据显示了在20GPa以下存在相变,我们认为这是一种固态-固态的一级相变,根据Gibbs相平衡条件并应用了相变前的低压物态方程,计算了这种固态-固态相变的熵增。计算表明熵增为负值,即相变为放热过程。在此基础上给出了相变区的物态方程,其中冷压为平台,内能计入了相变熵的影响。由相变区的物态方程得到的理论的与实验的Hugoniot曲线基本一致。 相似文献
42.
43.
Mixed liquids for single-drop microextraction of organochlorine pesticides in vegetables 总被引:2,自引:0,他引:2
A new approach for the extraction of nine kinds of organochlorine pesticides (OCPs) from vegetable samples coupling single-drop microextraction with gas chromatography-mass spectrometry was presented. Experimental parameters, such as organic solvent, exposure time, agitation and organic drop volume were controlled and optimized. An effective extraction was achieved by suspending a 1.00microL mixed drop of p-xylene and acetone (8:2, v/v) to the tip of a microsyringe immersed in a 2mL donor aqueous solution and stirred at 400rpm. The approach was applied to the determination of OCPs in vegetable samples with a linearity range of 0.05-20ng mL(-1) for alpha-, beta-, gamma-, delta-hexachlorobenzene (BHC) and dicofol, 0.5-20ng mL(-1) for dieldrin and 2,2-bis(4-chlorophenyl)-1,1-dichloroethane (DDD) or 0.5-50ng mL(-1) for 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (DDE) and 2-(2-chlorophenyl)-2 (4-chlorophenyl)-1,1,1-trichloroethane (p,p'-DDT). Correspondingly, the determination limit at an S/N of 3 ranged from 0.05ng mL(-1) for alpha-, beta-, gamma-, delta-BHC to 0.2ng mL(-1) for dicofol, dieldrin or p,p'-DDT. The relative recoveries were from 63.3 to 100%, with repeatability ranging from 8.74 to 18.9% (relative standard deviation, R.S.D.). The single-drop microextraction was proved to be a fast and simple approach for the pre-concentration of organochlorine pesticides in vegetable samples. 相似文献
44.
Time-resolved optical spectroscopy was used to examine chemical decomposition of RDX crystals shocked along the [111] orientation to peak stresses between 7 and 20 GPa. Shock-induced emission, produced by decomposition intermediates, was observed over a broad spectral range from 350 to 850 nm. A threshold in the emission response of RDX was found at about 10 GPa peak stress. Below this threshold, the emission spectrum remained unchanged during shock compression. Above 10 GPa, the emission spectrum changed with a long wavelength component dominating the spectrum. The long wavelength emission is attributed to the formation of NO2 radicals. Above the 10 GPa threshold, the spectrally integrated intensity increased significantly, suggesting the acceleration of chemical decomposition. This acceleration is attributed to bimolecular reactions between unreacted RDX and free radicals. These results provide a significant experimental foundation for further development of a decomposition mechanism for shocked RDX (following paper in this issue). 相似文献
45.
Quantum chemical calculations on single molecules were performed to provide insight into the decomposition mechanism of shocked RDX. These calculations complement time-resolved spectroscopy measurements on shock wave compressed RDX crystals (previous paper, this issue). It is proposed that unimolecular decomposition is the primary pathway for RDX decomposition in its early stages and at stresses lower than approximately 10 GPa. This decomposition leads to the generation of broadband emission from 350 to 850 nm. Chemiluminescence from (2)B1 and (2)B2 excited states of NO2 radicals is associated with a major portion of the experimentally observed emission spectrum (>400 nm). The remaining portion (<400 nm) of the emission spectrum primarily results from excited HONO intermediates. It is proposed that for stresses higher than 10 GPa, bimolecular reactions between radical decomposition products and unreacted RDX molecules become the dominant pathway. This radical assisted homolysis pathway is cyclic and leads to the acceleration of decomposition, with increased production of low energy NO2 radicals. These radicals produce emission that is stronger in the long wavelength portion of the spectrum. Finally, a comprehensive chemical decomposition mechanism is put forward that is consistent with the experimental observations of shock-induced emission in RDX crystals. 相似文献
46.
Aseries of pyrrolo[2,1-c] [1,4]benzodiazepine-3,11-dione derivatives was designed and synthesized, and their neuroprotective activity against SH-SY5Y cell injury induced by N-methyl-D-aspartic acid(NMDA) was evaluated. All the compounds showed significant neuroprotective effects, especially B16, which showed excellent performance and better activity than the positive control ifenprodil(B16:56.2%±0.6%; ifenprodil:41.0%±2.7%). Further investigation indicated that B16 could attenuate the Ca2+ influx induced by NMDA in SH-SY5Y cells and Western blotting also showed that B16 could attenuate the NR2B upregulation in SH-SY5Y cells induced by NMDA. The molecular docking results showed that compound B16 fitted in the binding pocket of NR2B-NMDAR well and could interact with binding sites of compounds 1 and 2 simultaneously. The ADME/Tox prediction results suggested that compound B16 had good blood-brain barrier(BBB) permeability and the zero alert of Pan Assay Interference Structures(PAINS) indicated that B16 could not elicit false-positive activities. These results strongly suggest that B16 is a promising and effective candidate neuroprotective compound, and that NR2B-NMDAR is a potential target of B16. 相似文献
47.
Xu M Ye J Yang D Xu X Yeo TT Ng WH Lim CC 《Analytical and bioanalytical chemistry》2007,389(7-8):2153-2159
Ex-vivo and in-vitro nuclear magnetic resonance (NMR) spectroscopy techniques have been used for studying chemical metabolites
in surgically resected specimens of human neoplasms, and may provide complementary information to in-vivo whole-body magnetic-resonance
spectroscopy (MRS). We describe an ex-vivo NMR in water method for measurement of water-soluble metabolites in unprocessed
normal rat brain tissue and human intracranial neoplasms. The NMR spectra obtained using the method described here were comparable
to those obtained using high-resolution magic-angle spinning (HRMAS) NMR methods, with good correlation in metabolite concentrations
relative to creatine (r
2 = 0.7635). Improved spectral resolution and baseline were noted compared to HRMAS, but macromolecule resonances were not
detected. Ex-vivo NMR of unprocessed tissue in water is rapid and technically simple to perform, and has the potential to
be used for direct assessment of intracranial neoplasms. 相似文献
48.
49.
Experimental and numerical investigations of tip injection on tip clearance flow in an axial turbine cascade 总被引:4,自引:0,他引:4
This investigation presents detailed experimental measurements of an active tip-clearance control method based on tip injection in a high-turning axial turbine cascade. Besides that, numerical investigations are also conducted to study phenomena which are not easily measured in the experiments. It aims to study the influence of tip injection on tip clearance flow, with emphasis on the effects of injection locations. Detailed flow field measurements were made downstream of the cascade using a three-hole probe. Static pressure distributions were also measured on the blade surface at 50% and 97.5% span, respectively. The results suggest that tip injection can weaken tip clearance flow, reducing the tip clearance mass flow and its associated losses. Meanwhile, the heat transfer condition on the blade tip surface can be also improved significantly. It also can be found that injection chordwise location plays an important role in the redistribution of secondary flow within the cascade passage. When the same number of injection holes and injection mass flow are applied, holes located in the aft part of blade can perform much better than that in the front part. 相似文献
50.
With the help of a divalent-metal ion, 10-23 DNAzyme cleaves RNA. Chemical modification of its catalytic loop to make a more efficient enzyme has been a challenge. Our strategy started from its five 2'-deoxyadenosine residues (A5, A9, A11, A12, and A15) in the loop based on the capability of the N7 atom to form hydrogen bonds in tertiary structures. 8-Aza-7-deaza-2'-deoxyadenosine and its analogs with 7-substituents (3-aminopropyl, 3-hydroxylpropyl, or phenethyl) were each used to replace five dA residues, respectively, and their effect on cleavage rate were evaluated under single-turnover conditions. The results indicated that the N7 atom of five dA residues were necessary for catalytic activity, and the N8 atom and 7-substituents were detrimental to the catalytic behavior of 10-23 DNAzyme, except that all these modifications at A9 were favourable for the activity. Especially, DZ-3-9 with 7-(3-aminopropyl)-8-aza-7-deaza-2'-deoxyadenosine (3) at A9 position gave a 12- fold increase of k(obs), compared to the corresponding parent 10-23 DNAzyme. DZ-3-9 was supposed to catalyze the cleavage reaction with the same mechanism as 10-23 DNAzyme based on their very similar pH-dependent and divalent metal ions-dependent cleavage patterns. Introduction of functional groups at A9 position was demonstrated to be a successful and feasible approach for more efficient 10-23 DNAzyme analogs. 相似文献