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11.
The pentafluorobenzenethiyl radical is an efficient hydrogen abstractor from an activated methylene or methine group and bis(pentafluorophenyl) disulfide is an efficient electron acceptor from the resulting radical intermediate. Thus benzyl-OTBS ether was easily converted into the corresponding pinacol, and 2-phenyl-1,3-dioxanes are converted into the monobenzoates of diols.  相似文献   
12.
Lattice strains around a platelet oxygen precipitate in Si wafer is studied by energy filtering convergent-beam electron diffraction (CBED) and calculations based on the finite element method (FEM). Local lattice strains are measured from CBD patterns obtained with a probe size less than 2 nm in a specimen thicker than 450 nm. Strains measured are compressive along a direction normal to a plate of the precipitation and tensile along a direction parallel to the plate. Two-dimensional stress fields near the precipitate are obtained with FEM computer analyses by fitting the measured strains. It appears that shear stresses are concentrated at the end of the precipitate edge and the maximum shear stress at an interface between the precipitate and the Si-matrix is 1.9 GPa. It is demonstrated that a combination of the energy filtering CBED and FEM is very useful for the study of local strains near interfaces in semiconductor devices, in particular for the study of stress fields that are too steep for application of the conventional CBED technique.  相似文献   
13.
The Japan Society for Analytical Chemistry has developed some new plastic certified reference materials (CRMs) for the analysis of mercury in polyester disks using XRF analysis. These CRMs (named as JSAC 0621-0625) were prepared by casting polyesters including a toluene solution of organometallic compounds as a standard. Concentrations of the five levels of mercury ranged from 0 to 250 mg/kg. Homogeneity tests of prepared disks had shown excellent results. Interlaboratory comparison study for the certification was performed by 15 laboratory participants. The z-scores in robust statistical method was applied for the evaluation of outliers. The certified values were assigned after discarding outliers. The uncertainties of certified values were determined as the confidence levels of 95%.  相似文献   
14.
Woodceramics, a carbon/carbon composite of plant-originated carbon reinforced by glassy carbon from phenolic resin, was prepared from apple pomace at carbonizing temperatures of 1073 K (AWC800) and 1473 K (AWC1200), and characterized by thermoanalytical methods and X-ray diffraction (XRD). Simultaneous differential scanning calorimetry (DSC) and thermogravimetric (TG) showed complicated overlapping reactions similar to those of coal. The initial temperature of pyrolysis was obtained by fitting logistic functions to observed TG data. The results suggested that AWC1200 contained more volatile matter than AWC800. In an inert atmosphere, complicated devolatilization takes place. In an oxidizing atmosphere, thermal change occurs roughly in four steps: desorption of physically adsorbed matter; pyrolysis into aliphatic and aromatic fragments; ignition; combustion of char. The oxidation resistance of AWC1200 was superior to AWC800.  相似文献   
15.
In the title compound, [Ca(C6H5O4)2(C6H6O4)2]·4H2O, which is a kojic acid–Ca2+ complex, the Ca atom is on a twofold axis and is octacoordinated by O atoms from four pyrone ligand mol­ecules. The hydroxyl and ketone O atoms of each ligand form a five‐membered chelate ring with the Ca atom. The crystal structure is stabilized by partial stacking and O—H?O hydrogen bonds.  相似文献   
16.
Simplification and evaluation of a gold-deposited SPR optical fiber sensor.   总被引:1,自引:0,他引:1  
The structure of the sensing element of a gold-deposited optical fiber sensor was simplified and quantitative analyses of various alcohols with the sensor showed improvement of the performance. The sensor uses surface plasmon resonance (SPR) at the interface of a sample solution and a thin (10 - 70 nm) gold film deposited on half of the exposed core of the optical fiber. The sensor with a film thickness of 45 nm can detect a small change of 5.6 x 10(-5) refractive index (RI) units in the refractivity. The response time is less than 0.5 min and the relative standard deviation for measurements is less than or equal to 1%. A straight line with a correlation coefficient of 0.9995 was obtained below 10%, v/v in the calibration curve for methanol solutions of benzyl alcohol. The minimum of the response curve due to the maximum excitation of SPR in the refractivity range from 1.33 to 1.44 RI units shifts to a lower refractivity as the film becomes thicker. The response curves of the sensors were calculated from SPR theoretical equations while considering of the distribution in the thickness of the deposited gold films. The improvement in the performance of the sensor is discussed.  相似文献   
17.
The calixarene-fullerene interaction,which causes only a slight change in the absorptionspectra, has been substantiated by calorimetricmeasurements: the H° values arecomparable with those obtained from the associationconstants estimated by a spectroscopic method. Furthermore, we determined the association constantbetween homooxacalix[3]arene and [60]fullerenederivatives with a porphyrin moiety by fluorescencespectra.  相似文献   
18.
The INDO calculations were performed on the three azines: pyridazine, pyrimidine, and pyrazine. The cannonical molecular orbitais obtained by these calculations were then transformed into the localized molecular orbitals. With the use of the localized molecular orbitals, the variation in the lone-pair orbital energies of these molecules were pursued in the light of the through-space and/or the through-bond interactions between the specified localized molecular orbitals in a molecule selectively. The interactions were expressed by the summation of several terms: through-space, through-bond, through-virtuals and coupling terms.  相似文献   
19.
The reactions of heparin with 2,4,6-trinitrobenzenesulfonic acid (TNBS) were studied spectrometrically. Seven different commercial heparins were used in this study. The amino groups react with TNBS to form equimolar amounts of trinitrophenylated (TNP) amino groups and bisulfite ions. The TNP-amino groups further react with bisulfite ions to form the monosubstituted anionic sigma complex. The absorption spectrum with two maxima at approximately 350 nm and approximately 420 nm, characteristic of either the TNP-amino groups or the complex, was analyzed for the reaction of TNBS with heparin. It was shown that the reactivities of TNBS with amino groups from α-amino acid and hexosamine residues are greatly different. By combining the results of the reaction kinetics and the reaction of heparin with Sanger's reagent, the number of the α-amino groups and the free amino groups in hexosamine residues were determined. These data have been performed with a range of heparins from different commercial sources, of different activities and physical characteristics. No correlation was found between the free amino contents of these heparins and biological potency. © 1993 John Wiley & Sons, Inc.  相似文献   
20.
A ruthenium-catalyzed intermolecular, anti-Markovnikov hydroamination of vinylarenes with secondary aliphatic and benzylic amines is reported. The combination of Ru(cod)(2-methylallyl)2, 1,5-bis(diphenylphosphino)pentane, and triflic acid was the most effective catalyst of those tested. Control reactions conducted without ligand or acid did not form the amine. The reaction of morpholine, piperidine, 4-phenylpiperazine, 4-BOC-piperazine, 4-piperidone ethylene ketal, and tetrahydroisoquinoline with styrene in the presence of 5 mol % of this catalyst formed the corresponding beta-phenethylamine products in 64-96% yield, with 99% regioselectivity, and without enamine side products. Acyclic amines such as n-hexylmethylamine and N-benzylmethylamine reacted with styrene in 63 and 50% yields, respectively. Alkyl-, methoxy-, and trifluoromethyl-substituted styrenes reacted with morpholine in the presence of this catalyst or a related one containing 1,1'-bis(diisopropylphosphino)ferrocene as ligand to give the products in 51-91%. Further, the hydroamination of alpha-methyl styrene was observed for the first time with a homogeneous transition metal catalyst. Preliminary mechanistic studies showed that the reaction occurred by direct, irreversible, anti-Markovnikov hydroamination and that the mechanism of the ruthenium-catalyzed hydroamination is likely to be distinct from that of the recently reported rhodium-catalyzed reaction.  相似文献   
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