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81.
Tatsuya Oshima Masahiro Goto Shintaro Furusaki 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(1-2):77-86
A series of calixarene carboxylic acid derivatives were synthesized for the extraction of amino acids. A calix[6]arene carboxylic acid derivative showed the highest extractability to the target tryptophan ester. The main driving forcefor the complexation was the interaction between the ammonium cation of the aminoacid and the oxygen atoms of the host molecule. Stripping of amino acids was alsoaccomplished by contacting the organic solution with a fresh acidic solution. Basedon slope and Job method analyses, it was confirmed that the calix[6]arene formsa 1 : 1 complex with the amino acid ester. The structure of the complex between the calix[6]arene and the amino acid was investigated by 1H-NMR and CD spectra. The calix[6]arene includes a guest molecule in the cavity, and the inclusion induces the asymmetrization of the host molecule. This host compound functions as a novel recognition tool for amino acids. 相似文献
82.
Single nucleotide polymorphisms (SNPs) of cancer repression gene p53 were analyzed electrochemically with ferrocenyl naphthalene diimide (1) as a hybridization indicator. The SNPs studied were the transition to A from G in the codon for amino acid at positions 175, 248 or 273 and the transversion to C from G in the codon for the amino acid at position 72. Thus, 20-meric oligonucleotides carrying the SNP site were used both as a sample and a probe with the latter immobilized on an electrode. Even one base difference on the p53 gene resulted in a significant difference in the current response of 1 and the magnitude of the response correlated with the amount of the DNA hybrid on the electrode. Moreover, when PCR products of exon 4, on which the P72/R72 SNP resides, of the p53 gene were analyzed by this method, the heterozygote and homozygotes were discriminated with modest precision. 相似文献
83.
Koji Oshita Mitsuko Oshima Yunhua Gao Kyue-Hyung Lee Shoji Motomizu 《Analytica chimica acta》2003,480(2):239-249
A chitosan resin derivatized with serine moiety (serine-type chitosan) was newly developed by using the cross-linked chitosan as a base material. The adsorption behavior of trace amounts of metal ions on the serine-type chitosan resin was systematically examined by packing it in a mini-column, passing a metal solution through it and measuring metal ions in the effluent by ICP-MS. The resin could adsorb a number of metal cations at pH from neutral to alkaline region, and several oxoanionic metals at acidic pH region by an anion exchange mechanism. Uranium and Cu could be adsorbed selectively at pH from acidic to alkaline region by a chelating mechanism; U could be adsorbed quantitatively even at pH 3–4. Uranium adsorbed on the resin was easily eluted with 1 M nitric acid: the preconcentration (5-, 10-, 50- and 100-fold) of U was possible. The column treatment method was used prior to the ICP-MS measurement of U in natural river, sea and tap waters; R.S.D. were 2.63, 1.13 and 1.37%, respectively. Uranium in tap water could be determined by 10-fold preconcentration: analytical result was 1.46±0.02 ppt. The resin also was applied to the recovery of U in sea water: the recovery tests for artificial and natural sea water were 97.1 and 93.0%, respectively. 相似文献
84.
An efficient and reliable multiresidue method for determining pesticide residues in a large number of vegetable samples was studied. First, the important target compounds for monitoring, 52 nitrogen- and/or phosphorus-containing pesticides, were selected. The sample was extracted with acetonitrile, and the separated acetonitrile layer was cleaned up by a salting-out step. The acetonitrile extract was purified by gel permeation chromatography that divided the pesticide eluate into 2 fractions; the pesticide fractions were respectively purified by a 2-step minicolumn cleanup in which the second pesticide fraction was loaded on a silica-gel minicolumn. After a Florisil minicolumn was inserted on the silica-gel minicolumn, the first pesticide fraction was loaded on the tandem minicolumn, which was eluted with acetone-petroleum ether (3 + 7). The combined eluate was subjected to dual-column gas chromatography (GC) with nitrogen-phosphorus and flame photometric detection. By application of the optimum cleanup conditions to the 52 pesticides selected, good resolution and low breakdown levels of the pesticides during GC were maintained. Recoveries of the 52 pesticides from fortified cabbage, lettuce, spring onion, and spinach ranged from 72 to 108% with relative standard deviations of 2-17%, except for the recoveries of methamidophos and chlorothalonil. The detection limits of the pesticides were satisfactory (0.001-0.009 mg/kg) for monitoring pesticide residues in vegetables. 相似文献
85.
Monitoring the removal of carbonate from alkali metal hydroxide (MOH, M = K, Na) solutions with calcium oxide (CaO) was studied using a newly developed method for the determination of trace amounts of total carbonate (TC) in alkaline solutions based on a flow injection (FI) technique coupled with a gas diffusion system. The optimized conditions of the FI system were as follows: the flow rate of each carrier, reaction solution (H2SO4) and receptor solution (Cresol Red, pH 8.9) was 0.25 ml min(-1), the sample size was 0.1 ml and the concentration of H2SO4 in the reaction solution was 0.09 M. The limit of detection of TC by the proposed method was 4 x 10(-7) M. The removal efficiency of carbonate was affected by the amount of CaO added, the shaking time of the solutions and the concentration of MOH. For 1 M NaOH and KOH solution, the removal efficiency of carbonate was about 99% and the concentration of residual carbonate was 4 x 10(-5) and 1.2 X 10(-4) M, respectively, when the amount of CaO added was 2 g l(-1) and the shaking time was 16 h. 相似文献
86.
Solvent extraction of trivalent group 13 metal cations such as aluminum, gallium and indium with tripod quadridentate phenolic ligand, tris(2-hydroxy-3,5-dimethylbenzyl)amine (H(3)tdmba), was investigated as fundamental study for their mutual separation. Gallium was extracted almost quantitatively as Ga(tdmba) (logK(ex)=-6.66+/-0.06 on using chloroform as extraction solvent), whereas aluminum and indium were hardly extracted due to steric hindrance on complexation of them with the ligand. The extracted Ga species was estimated as trigonal bipyramidal complex with one H(2)O molecule. Furthermore, extractability of Ga was increased by changing the ligand to more acidic tris(5-chloro-2-hydroxy-3-methylbenzyl)amine (H(3)tcmba) (logK(ex)=-6.18+/-0.18 on using dichloroethane as extraction solvent). 相似文献
87.
Analytical equations of two-step adsorption kinetics on surface have been derived. Moreover, computer simulations have been carried out to interpret various experimental adsorption kinetics previously reported. In the first case, molecules are further adsorbed from a solution onto a layer consisting of previously adsorbed molecules. This model was applied to the adsorption kinetics of hexadecyltrimethylammonium chloride (C16TAC) on a self-assembled monolayer (SAM) of 3-mercaptopropionic acid (T. Imae, H. Torii, J. Phys. Chem. B 104 (2000) 9218). The second case is that some of the initially adsorbed molecules are released from the adlayer with further time course. The adsorption of C16TAC on 1-dodecanethiol SAM (T. Imae, T. Takeshita, K. Yahagi, Stud. Surf. Sci. Catal. 132 (2001) 477) agrees with this mechanism. The strict mathematical developments presented in this work are demanded to specify the physical meaning of observed non-Langmuir adsorption kinetics, consisting of the two exponential terms. 相似文献
88.
A method for separation and determination of traces of 14 rare earth elements (REEs) in geological samples is described. Determination by inductively-coupled plasma atomic emission spectrometry follows oxalate coprecipitation of the REEs with calcium as carrier and cation- exchange column separation in nitric acid. The combination of the two separation techniques improved the low recoveries found for Sm, Eu, and Gd when only ion-exchange was used, especially for iron- and aluminum-rich samples. The method was applied to the analysis of geological standard materials NBS SRM 688 (basalt), NBS SRM 278 (obsidian), GSJ JB-1 (basalt), GSJ JA- 2 (andesite), and CCRMP SY-3 (syenite). The results were evaluated on the basis of chondrite- normalized rare earth element distribution patterns. 相似文献
89.
Ellipsometry, surface tensiometry, and contact-angle measurement have been used to study the transition between partial wetting and pseudo-partial wetting of surfactant solutions by alkanes. In the partial wetting regime, the air-water surface tension is the same with and without alkane. In the pseudo-partial wetting regime, the air-water surface tension is lowered by the presence of alkane, showing that oil is solubilised into the surfactant monolayer. A discontinuous change in the coefficient of ellipticity with increasing surfactant concentration provides unequivocal evidence for the first-order nature of the wetting transitions. Ellipsometry has been used to explore the generality of wetting transitions of alkanes (dodecane, hexadecane, and squalane) on surfactant solutions [dodecyltrimethylammonium bromide, tetredecyltrimethylammonium bromide, dibucaine hydrochloride, and Aerosol OT (AOT)]. Of the systems studied, only hexadecane on AOT solutions did not show a wetting transition. Excess alkane remains as a lens on the surface of the surfactant solutions at all concentrations, but the contact angle is a minimum at the wetting transition. A semiquantitative model for the variation of the contact angle with surfactant concentration is provided. 相似文献
90.
The reaction of cycloalkanones with silicon tetraisothiocyanate in the presence of (Me3SiO)2SO2?nBu3SnF or Zn(NCS)2 provides 1-cycloalkenyl isothiocyanates in good yields under mild conditions. 相似文献