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161.
Determination of estrogens and their conjugates in water using solid-phase extraction followed by liquid chromatography-tandem mass spectrometry 总被引:2,自引:0,他引:2
Isobe T Shiraishi H Yasuda M Shinoda A Suzuki H Morita M 《Journal of chromatography. A》2003,984(2):195-202
An analytical procedure for the determination of steroid estrogens and their conjugates was developed and applied to aqueous environmental samples. The analytes of 15 compounds were solid-phase extracted and fractionated into two fractions: one containing unconjugated (free) steroids and the other containing conjugates (sulfates and glucuronides). Identification and quantification were carried out using liquid chromatography coupled with tandem mass spectrometry. The recoveries for each compound ranged from 57 to 116% and reproducibilities represented as RSD ranged from 2.9 to 17%. Some of the sulfates and free compounds were detected in environmental samples, whereas most of the conjugates were below the detection limits. 相似文献
162.
Akiko Tsuchida Makoto Suda Masatoshi Ohta Takeshi Yamauchi Norio Tsubokawa 《Journal of polymer science. Part A, Polymer chemistry》2006,44(9):2972-2979
The effects of radicals on silica surface, which were formed by γ‐ray irradiation, on the polymerization of vinyl monomers were investigated. It was found that the polymerization of styrene was remarkably retarded in the presence of γ‐ray‐irradiated silica above 60 °C, at which thermal polymerization of styrene is readily initiated. During the polymerization, a part of polystyrene formed was grafted onto the silica surface but percentage of grafting was very small. On the other hand, no retardation of the polymerization of styrene was observed in the presence of γ‐ray‐irradiated silica below 50 °C; the polymerization tends to accelerate and polystyrene was grafted onto the silica surface. Poly(vinyl acetate) and poly(methyl methacrylate) (MMA) were also grafted onto the surface during the polymerization in the presence of γ‐ray‐irradiated silica. The grafting of polymers onto the silica surface was confirmed by thermal decomposition GC‐MS. It was considered that at lower temperature, the grafting based on the propagation of polystyrene from surface radical (“grafting from” mechanism) preferentially proceeded. On the contrary, at higher temperature, the coupling reaction of propagating polymer radicals with surface radicals (“grafting onto” mechanism) proceeded to give relatively higher molecular weight polymer‐grafted silica. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2972–2979, 2006 相似文献
163.
Ito S Ando M Nomura A Morita N Kabuto C Mukai H Ohta K Kawakami J Yoshizawa A Tajiri A 《The Journal of organic chemistry》2005,70(10):3939-3949
[structure: see text] This paper describes the cyclotrimerization reaction of di(2-azulenyl)acetylenes (2a,b) catalyzed by Co2(CO)8 to produce hexa(2-azulenyl)benzene derivatives (1a,b). The cyclooligomerization of 2a and 2b utilizing CpCo(CO)2 as a catalyst produced (eta5-cyclopentadienyl)[tetra(2-azulenyl)cyclobutadiene]cobalt complexes (3a,b). The redox behavior of hexakis(6-octyl-2-azulenyl)benzene (1b), bis(6-octyl-2-azulenyl)acetylene (2b), and the cobalt complexes 3a and 3b along with 6-octyl-2-phenylazulene (19) was examined by cyclic voltammetry (CV). The reduction of compound 1b exhibited multiple-electron transfers in one step upon CV with a reduction potential similar to that of compound 19. However, the CVs of compounds 2b, 3a, and 3b were characterized by stepwise waves because of the reduction of each azulene ring. The mesomorphic behaviors of 1b, 2b, and 19 were also studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction (XRD) techniques. A new series of azulene derivatives, 1b, 2b, and 19, substituted by a long alkyl chain at the 6-position shows mesomorphism with crystalline polymorphs. Compound 1b showed a large temperature range of hexagonal columnar mesophases (Col(ho)) from 115.5 to 199.9 degrees C. Compound 2b has rectangular columnar (Col(ro)), smectic E (S(E)), and nematic (N) mesophases. Compound 19 exhibited an S(E) mesophase. 相似文献
164.
Kazuo Sasazawa Yuko Yamada Akiko Fujisawa Toshikazu Saitoh Katsuya Ueno Kazuya Oharu Hideo Sawada 《Colloid and polymer science》2005,283(7):812-816
Self-assembled fluorinated molecular aggregates formed by fluoroalkyl end-capped N-(1,1-dimethyl-3-oxobutyl)acrylamide oligomers, N,N-dimethylacrylamide oligomers, and acrylic acid oligomers in methanol could selectively recognize fluoresceins as guest molecules to form a new class of fluorinated aggregates-fluorescein nanocomposites. These fluorinated fluorescein nanocomposites that are obtained exhibit an extraordinarily enhanced light absorption (max ca. 440 nm) compared to that (maxs 452, 480 nm) of the parent fluorescein in the absence of fluorinated aggregates. 相似文献
165.
Synthesis of protein-silica hybrid hollow particles through the combination of protein catalysts and sonochemical treatment 总被引:1,自引:0,他引:1
Shiomi T Tsunoda T Kawai A Chiku H Mizukami F Sakaguchi K 《Chemical communications (Cambridge, England)》2005,(42):5325-5327
Hollow spherical particles with protein-silica hybrid shell structures have been synthesized through a combination of the catalytic activity of the protein and sonochemical treatment; the morphologies of the particles were controlled by varying the protein concentration. 相似文献
166.
We report a new sample target plate for MALDI-TOF mass spectrometry made of SiO2 with 30 nm Pt dots for which a highly reproducible and improved DNA analysis was achieved. 相似文献
167.
Yoshifumi Nishimura Akiko Y Hirakawa Masamichi Tsuboi 《Journal of Molecular Spectroscopy》1977,68(3):335-358
It has been shown that a Raman line of a nontotally symmetric vibration (b1g, b2g, or a2g) of a metalloporphyrin (D4h) can be caused, not only by a vibronic coupling between the first () and second () excited electronic states but also by a vibronic coupling within one of the electronic states (let us call the former the QS mechanism and the latter the QQ and/or SS mechanism). A simple formulation has been made for each of those different mechanisms, so that a numerical calculation can be made of the excitation profile of a Raman scattering for a given set of coupling constants and damping factors. Next, the result of an examination is given of the excitation profile of the Raman scatterings of some of the b1g, b2g, and a2g vibrations of nickel octaethylporphyrin and nickel octaethyltetrachloroporphryin. Most of the Raman lines of these nontotally symmetric vibrations show a resonance effect only in the Q-band () region but not in the Soret-band () region. On the basis of this fact, it has been suggested that those Raman lines are caused mainly by the QQ mechanism rather than the QS mechanism. The observed vibrational structure of an excitation profile also seems to support this suggestion. 相似文献
168.
A HPLC/GF AA procedure based on the use of C-18 columns is described for the quantitation of butyltin species in marine samples. When a mass spectrometer was used as detector (HPLC MS), evidence was obtained for the presence of other tin compounds in the samples. Extracts of samples were treated with CH3MgBr and examined by using GC MS; the presence of BunSnMe4?n (n = 3–1, Bu = butyl) and CynSnMe4?n (n = 3,2, Cy = cyclohexyl) was confirmed in the derivatized seawater, bivalve flesh, and bivalve shell samples. Quantitative data are given for butyl- and cyclohexyl-tin species in seawater and the surface microlayer, and oyster flesh. 相似文献
169.
Takeo OtsukaHengBo Cui Akiko Kobayashi Yohji MisakiHayao Kobayashi 《Journal of solid state chemistry》2002,168(2):444-449
Novel molecular metal salts comprising an organic donor 2,5-bis(1, 3-dithiol-2-ylidene)-1,3,4,6- tetrathiapentalene (BDT-TTP) and lanthanide nitrato complex anions [M(NO3)y]−(y−3) were synthesized as the composition (BDT-TTP)x[M(NO3)y]. Attempts on X-ray crystal structure analyses gave rise to a detection of two polymorphs. One of the polymorph, which had a composition of (BDT-TTP)5[M(NO3)5] for M= Nd, Sm, Eu and Gd, was analyzed in detail. Five crystallographically independent BDT-TTP molecules were stacked face-to-face to form a pentad, which was jointed one after another by crystallographic inversion centers into a one-dimensional column. The calculated overlap integrals of the highest occupied molecular orbitals revealed that not only intracolumnar orbital overlaps but also transverse intermolecular interactions were important in the electronic band formation. Consequently, the system has two-dimensional Fermi surfaces that explain the stable metallic states. Magnetic measurements on the four salts, with M= Nd, Sm, Eu and Gd, showed Curie paramagnetic moments on rare-earth ions which were superimposed on the Pauli paramagnetism of metallic π electrons. Especially, the magnetic susceptibility of the isolated Eu3+ ion was written using Curie term and extremely large Van Vleck term. 相似文献
170.
In this paper, we derive a portfolio optimization model by minimizing upper and lower bounds of loss probability. These bounds are obtained under a nonparametric assumption of underlying return distribution by modifying the so-called generalization error bounds for the support vector machine, which has been developed in the field of statistical learning. Based on the bounds, two fractional programs are derived for constructing portfolios, where the numerator of the ratio in the objective includes the value-at-risk (VaR) or conditional value-at-risk (CVaR) while the denominator is any norm of portfolio vector. Depending on the parameter values in the model, the derived formulations can result in a nonconvex constrained optimization, and an algorithm for dealing with such a case is proposed. Some computational experiments are conducted on real stock market data, demonstrating that the CVaR-based fractional programming model outperforms the empirical probability minimization. 相似文献