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141.
142.
A method is described for the determination of total arsenic by hydride generation-atomic absorption spectrophotometry using a mixed acid as a pretreatment. Hydride generation is done by the flow-injection method. The authors investigated in detail the temperature and time of decomposition using inorganic, organic arsenic and environmental standard samples, pretreated with nitric-perchloric-sulfuric mixed acid. By using a mixed acid as a pretreatment agent at 220 degrees C, the decomposition time could be shortened and the blank value of arsenic from the reagents used was reduced. The mixed acid of nitric-perchloric-sulfuric was also found to be effective as a pretreatment agent for organic arsenic compounds in which a dimethylated compound, sodium cacodylate or biological samples, is known to be one of the indecomposables. The present approach was proved to be satisfactory as a pretreatment for the quantitative analysis of trace amounts of total arsenic in liquid or solid environmental samples, such as geothermal water, sediments and biological samples. 相似文献
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146.
Hiroshi Onizuka Masaki Kato Tetsuo Shimura Wataru Sakamoto Toshinobu Yogo 《Journal of Sol-Gel Science and Technology》2008,46(1):107-115
Proton conductive inorganic–organic hybrid membranes were synthesized from dimethylethoxyvinylsilane (DMEVS), vinylphosphonic
acid (VPA) and 3-glycidoxypropyltrimethoxysilane (GPTMS) through copolymerization followed by sol–gel process. The ratio of
phosphorus to silicon in the copolymer almost corresponded to the charged molar ratio of VPA to DMEVS when the ratio of VPA
to DMEVS was below 1/2. Self-standing, homogeneous, highly transparent membranes were synthesized from DMEVS–VPA copolymer
and GPTMS via sol–gel condensation. Differential thermal analysis-thermogravimetry analyses indicated that these membranes
were thermally stable up to 200 °C. The results of Fourier transform infrared and 13C NMR revealed that phosphonic acid groups of VPA were chemically bound to organosiloxane network. The copolymerization and
condensation of (DMEVS–VPA)/GPTMS were confirmed by 31P and 29Si NMR spectra. The proton conductivity of the hybrid membranes increased with phosphonic acid content. The membrane of (DMEVS–VPA)/GPTMS
showed a remarkable conductivity of 6.3 × 10−2 S cm−1 at 130 °C and 100% relative humidity. 相似文献
147.
The synthesis of various trifluoromethylated amino compounds was studied using trifluoroacetaldehyde, an industrial bulk material, as a starting compound. One general application of trifluoroacetaldehyde is the preparation of trifluoroethylamino derivatives via reductive amination reaction. This synthesis includes the formation of the corresponding N,O-acetal intermediates followed by their reduction using NaBH4 or 2-picoline borane complex, affording the target trifluoroethylamino compounds in moderate to good yields (47-87%).Another general application of trifluoroacetaldehyde is the synthesis of chiral α-substituted trifluoroethylamino compounds. In this synthesis, trifluoroacetaldehyde was first converted into the chiral trifluoromethyl tert-butyl sulfinimine, which was subjected to 1,2-nucleophilic addition reactions across its CN double bond. The addition of phenyllithium afforded α-(phenyl)trifluoroethylamino derivative in 83% yield and with 96% de. Allylation and Reformatsky reactions produced the corresponding α-substituted trifluoroethylamino derivatives in 82 and 58% yields and with 90 and 91% de, respectively. 相似文献
148.
Atsushi Mineshige Yoshiki OhnishiRyuta Sakamoto Yusuke DaikoMasafumi Kobune Tetsuo YazawaHideki Yoshioka Takayuki NakaoTomokazu Fukutsuka Yoshiharu Uchimoto 《Solid State Ionics》2011,192(1):195-199
Electronic as well as ionic conducting properties for oxyapatite-type solid electrolytes based on lanthanum silicate, La9.333 + xSi6O26 + 1.5x (LSO) were investigated in the oxygen-excess region (x > ca. 0.3). We have found that the oxygen excess-type LSO (OE-LSO), namely La10Si6O27 on weighted basis, exhibited high conductivity, and substitution of the Si-site of LSO with some dopants (Mn+) had a positive effect toward the conducting property. Furthermore, it was also found that addition of a very small amount of iron ions into the M-doped OE-LSO, La10(Si6-yMn+y)O27-(2-0.5n)y, improved its conductivity. On the other hand, replacement of the La-site with various ions for La10(Si6-yMn+y)O27-(2-0.5n)y did little to improve conductivity. The electronic transport numbers for Al-doped OE-LSO with Fe-addition, (1-α){La10(Si5.8Al0.2)O26.9}-α(FeOγ), evaluated with the Hebb-Wagner polarization method were very low: i.e., 1.1 × 10− 3 and 2.9 × 10− 3 under P(O2) = 1.1 × 104 Pa at 1073 K for α = 0.00 and 0.005, respectively. Conductivity for each sample was unchanged under humidified atmosphere at 1073 K sustained for over 50 h, revealing that both compositions were chemically stable. It was concluded that 0.995{La10(Si5.8Al0.2)O26.9}-0.005(FeOγ) is suitable for the fuel cell electrolytes because of its high and almost pure ionic conductivity, and its good chemical stability under humidified as well as reducing conditions. 相似文献
149.
For an affine algebra of nonexceptional type in the large rank we show the fermionic formula depends only on the attachment of the node 0 of the Dynkin diagram to the rest, and the fermionic formula of not type A can be expressed as a sum of that of type A with Littlewood–Richardson coefficients. Combining this result with Kirillov et al. (2002) [13] and Lecouvey et al. (2011) [18] we settle the X=M conjecture under the large rank hypothesis. 相似文献
150.
Ochiai M Suefuji T Miyamoto K Tada N Goto S Shiro M Sakamoto S Yamaguchi K 《Journal of the American Chemical Society》2003,125(3):769-773
Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda(3)-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph(2)IBF(4) and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction. (1)H NMR analyses and CSI-MS spectra showed that, in dichloromethane solution, Ph(2)IBF(4) exclusively forms the 1:1 complex with 18C6 (binding constant K(a), 1.02 x 10(3) M(-)(1)). The binding constants decrease with the increased solvent donor ability (Gutmann's DN). Changing the heteroatom ligand from BF(4) to the less nucleophilic PF(6) and AsF(6) increased the binding constant by about six times. Substitution of an electron-withdrawing group onto the para position of Ph(2)IBF(4) tends to increase in the complex stability. A linear Hammett relationship (rho = 0.59) between log K(a) and sigma(p)(+) values of substituents indicates that the diaryl-lambda(3)-iodanes with electropositive iodine(III) interact more efficiently with 18C6. Decreased binding magnitude was measured with 15C5, dibenzo-18C6, dibenzo-21C7, and dibenzo-30C10. 相似文献