Undoped a‐C thin films were deposited with varying power density from 10 to 25 W/cm2 using unbalanced closed‐field magnetron sputtering (CFUBMS). The effect of power density on the physical and electrochemical properties was investigated by experimental characterization methods and atomistic simulations. XPS indicated that the films were composed mostly of sp2‐bonded carbon (55–58 at.%) with a small amount of oxygen (8–9 at.%) in the surface region. The films appeared completely amorphous in XRD. The ID/IG ratio obtained by Raman spectroscopy indicated an increase from 1.76 to 2.34 with power density. The experimental and simulated data suggested a possible ordering and/or clustering of the sp2 phase with power density as the cause of the improved electrical properties of the a‐C films. The electrochemical properties of a‐C were between those of glassy carbon and tetrahedral amorphous carbon with potential windows ranging from 2.77 to 2.93 V and double‐layer capacitance values around 0.90 μF cm?2. Electron transfer for Ru(NH3)63+/2+ and FcMeOH+1/0 was reversible whereas that for IrCl62?/3? was quasi‐reversible. Peak potential separation of dopamine and oxidation potential of ascorbic acid decreased with power density, correlating with the structural and electrical changes of the films. The a‐C thin films deposited by CFUBMS are inherently conductive and their physical properties can be adjusted by varying the deposition parameters to a wide range of electrochemical applications. 相似文献
Concentration profiles of nitrogen in vacuum-annealed p- and n-type single-crystal (1 0 0) InP implanted with 1 × 1016 30 keV15N+ ions cm–2 have been studied by Secondary Ion Mass Spectrometry (SIMS) and Nuclear Resonance Broadening (NRB) techniques. Damage induced by the nitrogen implantation was studied by Rutherford Backscattering Spectrometry (RBS) and channeling. Annealing the samples led to loss and redistribution of nitrogen in the temperature range from 575 to 675 °C. At temperatures from 575 to 600 °C, rapid migration of nitrogen towards the sample surface was observed. The n-type InP material had a very dominant tendency for surface nitrogen build-up, whereas the p-type material had a markedly smaller surface peak in the nitrogen distribution. The surface peak in n-type material is due to sulphur acting partly as a diffusion barrier. SIMS analyses showed sulphur build-up on the surface in the course of annealing. At temperatures from 600 to 675 °C, the nitrogen profiles of n- and p-type InP were similar. A small loss of nitrogen was observed at 625–675 °C. Two different recovery stages were observed at 575–600°C and at 625–650 °C. The corresponding activation energies for nitrogen loss are 2.9 and 3.0 eV, respectively. 相似文献
The NCTM “Curriculum and Evaluation Standards for School Mathematics” (1989) reflect the current movement to introduce probability and statistics in the precollege curriculum. These standards include topics and principles for instruction in probability and statistics which are included in the Quantitative Literacy Project (QLP) curriculum materials. This paper presents results of a survey which explored the successes of the QLP materials in terms of student reactions to instruction in probability and statistics. A student survey of 917 students of teachers trained in QLP workshops assessed how students regarded the instructional materials in general, how well they liked learning topics in probability and statistics, and how well they believed that they had learned the content. Results indicated that students have mostly positive attitudes towards learning statistics. However, fewer students felt it was useful to learn about these topics. An increase in positive attitudes with grade level suggests the topics may be received more favorably and, therefore, may more appropriately be used in higher grades. 相似文献
A colorimetric protein phosphatase inhibition assay (PPI assay), a commercial enzyme-linked immunosorbent assay (ELISA) test and different HPLC methods using UV detection were compared for the detection of cyanobacterial hepatotoxins, microcystins (MCYST) and nodularin. The suitability of the methods to detect different toxin variants was evaluated by using pure toxins and laboratory cultures as well as water and bloom samples of toxic cyanobacteria. The emphasis of the study was on the analysis of polar demethyl microcystin variants that are common in nature but for which there exist no commercial standards. The IC50 values of MCYST-LR for the PPI assay and the ELISA test were 2.2-2.5 and 0.26-0.38 μg l−1, respectively. The most important factors that decreased toxin recovery in sample treatment were the use of C18 cartridges and polypropylene containers. Good recoveries of toxins were obtained by using hydrophilic-lipophilic balanced (Oasis HLB, Waters) cartridges for concentrating the samples. The results obtained with the PPI assay, the ELISA test and HPLC correlated quantitatively well with the exception of [d-Asp3] microcystins. Concentrations of [d-Asp3]MCYST-RR measured with the PPI assay were only 5% of those obtained by the ELISA test and HPLC. Concentrations of hydrophobic microcystin variants were lower when analysed with ELISA than with the other methods. The World Health Organisation (WHO) has set a guideline value of 1 μg l−1 for the world-wide most common microcystin variant, MCYST-LR in drinking water. Since the quantitative ranges of the PPI assay and the ELISA test are within microcystin concentrations in natural waters, and both tests are easy to perform, they show potential for routine use in the screening and monitoring of microcystins from drinking water supplies and from recreational waters. 相似文献
The possibility to obtain unoccupied orbitals with correct energies in the new semi-empirical method HAM/3 implies new means to study frontier orbitals of chemical reactions. The transition state can often be identified as the state where the frontier orbitals are degenerate. The coplanar rectangular decomposition of cyclobutane into two ethylenes is chosen as a representative example. It is found that the activation energy is smaller than according to previous studies and thus not much different from the experimental value. It is pointed out that with a better parametrization of the HAM method it will be possible to study chemical reactions in detail and to calculate reliable activation energies. 相似文献
Reduction of 6/7-carboethoxy-3-phenyltrop-3-en-2-ones with H2/Pd/C and NaBH4 was studied in order to find a stereoselective route to the corresponding 3-phenyltropan-2-ones and 2α/2β-hydroxy-3-phenyltropanes. The 6/7-exo-carboethoxy-3-phenyltrop-3-en-2-ones were selectively reduced by Pd/C to 3β-phenyltropan-2-ones and 2α-hydroxy-3β-phenyltropanes. The corresponding 2β-hydroxy-3β-phenyl analogues were synthesized using NaBH4, with a yield of 40%. Reduction of 6-endo-carboethoxy-3-phenyltrop-3-en-2-one yielded several products. The corresponding 7-endo-substituted analogue was selectively reduced with both Pd/C and NaBH4 to 7-endo-carboethoxy-3β-phenyltropin-2-one. Analysis of stereochemically important 1H NMR spectroscopy parameters was performed for all the products and used for conformational analysis in solution. X-ray analysis was performed for selected compounds. 相似文献
A method to prepare NaOH sediment extracts for organic P compound analysis with electrospray ionization tandem mass spectrometry (ESI-MS-MS) was developed on natural samples. Ion exchange, rotary evaporation and mass cut-off filtering proved to be suitable for sample preparation. Samples were analyzed with ESI-MS-MS, and reproducibility and repeatability of the method was calculated. In addition, 31P-nuclear magnetic resonance spectroscopy (31P NMR) was used to measure recovery of different P compound groups such as orthophosphate (Ortho-P), orthophosphate monoesters (Monoester-P), orthophosphate diesters (Diester-P) and pyrophosphates (Pyro-P).
The developed sample preparation method resulted in an easy-to-spray liquid for the ESI-MS-MS instrumentation. The overall P recovery was 65% and 31P NMR showed that Diester-P, possibly in the form of DNA, was apparently lost through the filtering step most likely due to their size. Variances in the total intensities of the MS scans (relative standard deviation (R.S.D.) 35–54%) were for about 50% due to repeated MS runs. Covariances of the peaks in the MS spectra were calculated to be for about 30% due to the sample preparation procedure. Finally, with the ESI-MS-MS approach, 11 peaks in the mass spectra were found likely to represent phosphate containing compounds. 相似文献
Electrochemistry of hot electrons in fully aqueous solutions at tetrahedral amorphous carbon thin film electrodes is discussed. The generation of these highly reducing chemical species was confirmed by normal pulse voltammetry and several electrochemiluminescent systems. Electron transfer into pre-existing solvent cavities was observed at approximately −2.65 V vs. Ag/AgCl (sat.). Electrogenerated hot electrons were utilized as chemiluminescent mediators in heterogeneous sandwich immunoassay of Serum Amyloid A. The calibration curve was linear over four orders of magnitude and the detection limit was 85 ng L−1 that demonstrates the efficiency of hot electron generation at this electrode material. 相似文献