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31.
The 1205 classical isomers of fullerene C58, as well as one quasi-fullerene C58 isomer with a heptagonal ring (labeled as Cs:hept) have been investigated by the quantum chemical methods PM3, HCTH/3-21G, and B3LYP/6-31G(d). Isomer C3v:0001, which has the lowest number of adjacent pentagons, is predicted to be the most stable isomer, but the quasi-fullerene isomer Cs:hept is only 2.50 kcal mol-1 higher in energy. Systematic investigations of the electronic properties of C3v:0001 and Cs:hept find that the C3v:0001 isomer has high vertical electron affinity (3.19 eV). The nucleus-independent chemical shifts (NICS) value at the center of Cs:hept (-5.1 ppm) is more negative than that of C60 (-2.8 ppm). The NICS value at the center of the heptagonal ring in Cs:hept (-2.5 ppm) indicates weakly aromatic character. In contrast, the C58(6-) and C58(8-) ions of the C3v:0001 and Cs:hept geometries possess large aromatic character, with NICS values between -14.0 and -26.2 ppm. To clarify the thermodynamic stabilities of C58 isomers at different temperatures, the entropy contributions are taken into account on the basis of the Gibbs energy at the B3LYP/6-31G(d) level. The C3v:0001 isomer prevails in a wide range of temperatures, and the Cs:hept isomer is also an important component around 2800 K. The IR spectra of C58 isomers are simulated to facilitate experimental identification of different isomers. In addition, the electronic spectra and the second-order hyperpolarizabilities are predicted by ZINDO and the sum-over-states model. The static second-order hyperpolarizability of the C3v:0001 isomer is 96.5 % larger than that of C60, and its second-order hyperpolarizabilities at external field frequencies are at least nine times larger than those of C60. 相似文献
32.
Chunfu Zhang Yongxian Wang Haibin Tian Duanzhi Yin 《Journal of Radioanalytical and Nuclear Chemistry》2002,253(2):313-316
A method for 103Pd molecular plating onto the surface of the copper rod is reported. The optimal composition of the plating bath was: palladium chloride 2 g/l, ammonium hydroxide (28%) 150 ml/l, sodium hypophosphite 12 g/l, and ammonium chloride 37 g/l. The whole procedure of 103Pd molecular plating will last 50 minutes at 40 °C. This article provides valuable experience for the preparation of 103Pd seeds. 相似文献
33.
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35.
The addition of carboxylic acids to terminal alkynes is efficiently catalyzed by the early transition-metal complex Re(CO)5Br in toluene or n-heptane at 110 degrees C in an air atmosphere, affording the anti-Markovnikov adducts in good yields with high selectivity. In most cases, the reactions afford unusual Z-adduct predominantly. When n-heptane was used as solvent, Re(CO)5Br can be partly recovered from the reaction mixture. 相似文献
36.
Separation and determination of podophyllum lignans by micellar electrokinetic chromatography 总被引:2,自引:0,他引:2
A micellar electrokinetic chromatography method was established for the quantitative analysis of seven podophyllum lignans in Podophyllum emodi Wall. var. chinesis sprague. The optimum buffer system was 10 mM NaH2PO4-5 mM borate-100 mM sodium dodecylsulfate-30% isopropanol (pH 7.20). Voltage was 18 kV and detection at 214 nm. The second derivative chromatogram was used to determine a low-content component and those not fully separated from adjacent ones. The RSD values of migration times and peak areas were <2.2 and <5.5%, respectively. The effects of several CE parameters on the resolutions were studied systematically. 相似文献
37.
Gallic acid was separated from a n-butanol extract of the fruit of Cornus officinalis Sieb. et Zucc by high-speed countercurrent chromatography in two steps using two solvent systems composed of ethyl-acetate-ethanol n-butanol-water (5:1.8:6, v/v/v) and ethyl acetate-ethanol-water (5:0.5:6, v/v/v) successively. From 1 g of n-butanol extract the method produced 60 mg of gallic acid at a purity of 97%. 相似文献
38.
A new highly sensitive and selective chromogenic reagent, 2-(2,5-disulfonic-4-methoxyphenylazo)-7-(2-hydroxyl-5-carboxylphenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic
acid (1), was synthesized and applied to the spectrophotometric determination of trace thorium. In 5 mL of a 6 M perchloric acid
medium, which greatly increases the selectivity, thorium reacts with 1 to form a 1: 2 green complex, having a sensitive absorption peak at 670 nm. Under optimal conditions, Beer’s law is obeyed
over the range from 0 to 0.8 μg/mL Th(IV) and the apparent molar absorptivity is 2.09 × 105 L/mol cm. It is found that, uranium(VI), Ti(IV), heavy rare earths, and most of other common metal ions do not interfere.
The method has been tested on the determination of thorium in food samples with satisfactory results.
The text was submitted by the authors in English. 相似文献
39.
This paper is the study of the fluorescence enhancement of Eu3+-1-ethyl-6-fluoro-4-oxo-7-(1-piperazinyl)-1,8-naphthyridin-3-carbonic acid (enoxacin, EFLX) system by surfactants. It was
found that sodium dodecylbenzenesulfonate (SDBS) exhibits great enhancement on the fluorescence of the Eu-EFLX system. The
molar ratio is 1:2:1 for Eu:EFLX: SDBS. Under the optimum conditions, the fluorescence intensity is a linear function of europium
in the range of 1.0 × 10−8 ∼ 5.0 × 10−6 mol/L, the detection limit is 1.0 × 10−9 mol/L. The application of the Eu-EFLX-SDBS system for the determination of trace europium in rare earth samples gave satisfactory
results.
Received October 19, 2000. Revision August 10, 2001. 相似文献
40.
H. Kurreck S. Aguirre H. Dieks J. Gtschmann J. v. Gersdorff H. Newman H. Schubert M. Speck T. Stabingis J. Sobek P. Tian A. Wiehe 《Radiation Physics and Chemistry》1995,45(6):853-865
Porphyrin quinones (P-Qs), covalently linked via different aliphatic bridges, have been synthesized and studies in their (porphyrin) cationic and (semiquinone) anionic radical states by EPR, ENDOR and TRIPLE resonance techniques. Electron transfer (ET) from the porphyrin donor to the quinone acceptor could be observed by time-resolved picosecond fluorescence spectroscopy (singlet ET) and by time-resolved EPR spectroscopy (triplet ET) in isotropic fluid solution and in anisotropic media (liquid crystals and reversed micelles). Steady-state in situ photoexcitation of P-Qs in CTAB cationic reversed micelles yielded the corresponding semiquinone radical anions. In TRITON X-100 reversed micelles both the radical cation of the porphyrin and the radical anion of the semiquinone could be detected, which occured in complete emission. In covalently linked porphyrin flavins ET from the photoexcited porphyrin fragment to the flavin and, in addition, energy transfer from the photoexcited flavin to the porphyrin could be observed. 相似文献