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991.
Moein B. Sayed 《Journal of Solid State Electrochemistry》2003,7(4):223-231
Variable strength H-bonding affects the mobility and so electric conduction of protons differently. Also, variable extent
mesomerism modifies electric conduction with varying dielectric features. Both these molecular modifiers are properly cited
using azophenol derivatives as model compounds for discussion of their consequences in the varying features of electric conduction.
The electric permittivity shows low-frequency dispersion characteristic of ionic conduction over mobile charge carries; the
mobility shifts at a critical temperature T
c, being structure dependent. The frequency-dependent Z′′-Z′ layout changes with temperature from linear at low temperatures to semicircular above T
c within a frame of temperature-sensitive dipole-ionic mediated conduction. The a.c. conductivity, σac, increases with frequency and temperature and becomes frequency insensitive, like d.c. conductivity, σdc, above the T
c because of the escalating contribution from the d.c. conduction. The mesomeric structure seems to prompt a dipole-based electric
conduction of high relaxation energy over the strongly associated phenolic protons that may be thermally activated above the
T
c into a much lower relaxation energy protonic conduction of up to two orders higher conductivity. The protonic conduction
emerges at a T
c that falls with a drop in the relaxation energy following a similar order of increasing proton mobility and mesomerism in
the azophenol derivatives: azocatechol>azoquinol>azoresorcinol. On the molecular level, variable temperature infrared spectroscopy
reveals higher proton mobility and mesomerism for the azocatechol derivative that demonstrates its higher protonic conductivity
at lower T
c and relaxation energy, compared to the azoquinol and azoresorcinol derivatives. This is well verified in the light of conflicting
intramolecular H-bonding that assists the proton mobility in azocatechol whereas it associates the protons in azoresorcinol
more than in azoquinol.
Electronic Publication 相似文献
992.
Microwave-assisted extraction of zearalenone from wheat and corn 总被引:9,自引:0,他引:9
Pallaroni L von Holst C Eskilsson S Björklund E 《Analytical and bioanalytical chemistry》2002,374(1):161-166
A microwave-assisted extraction (MAE) method has been developed for determination of zearalenone in wheat and corn by LC-MS with an atmospheric pressure chemical ionization interface (APCI). Matrix effects were minimized by use of matrix-matched standard curves for quantification of the analyte. The limit of quantification (LOQ) of the method was 30 ng g(-1) in wheat and 20 ng g(-1) in corn. The rapid LC-MS method enabled analysis of the extracts without clean-up, thereby reducing analyte losses, the time required for the analytical procedure, and costs. A factorial design approach was used to examine the effect on extraction efficiency of the main extraction conditions - time, temperature, and solvent. On the basis of results from statistical assessment extraction was performed with 1:1 (v/v) methanol-acetonitrile at 80 degrees C for 5 min. When these extraction conditions were applied to a wheat sample from a recently conducted international proficiency test, 92% (103 ng g(-1)) of the assigned zearalenone concentration (112 ng g(-1)) in the test material was obtained. This result was within the uncertainty (u) range of the assigned value of the test material (u=+/-15.8 ng g(-1), alpha=0.05) thereby demonstrating the accuracy of the method was sufficient. The precision of the whole method was also confirmed to be adequate, because the observed relative standard deviation (RSD) of 12% (n=10) also fulfils the quality criteria recommended by European guidelines for in-house method validation. 相似文献
993.
994.
The perfect matching vector and forcing and the Kekulé-vector of cata-benzenoids are defined. Two theorems are given which
set the sufficient and necessary conditions for HKZ-vector (Harary et al. J Math Chem 6:295, 1991) and Kekulé-vector in cata-benzenoids.
Additional two theorems are obtained which give sharp bounds for the modules of HKZ- and Kekulé vectors.
Dedicated to Professor Tadeusz Marek Krygowski on the happy occasion of his 70th birthday. 相似文献
995.
Samuel Melaku Rita Cornelis Frank Vanhaecke Richard Dams Luc Moens 《Mikrochimica acta》2005,150(3-4):225-231
A simple, sensitive and inexpensive method for the speciation of Cr(VI) and Cr(III) in river and industrial wastewater was developed, optimized and validated. Samples were collected, filtered and then chromium species were determined in the filtrate. In the filtrate, total Cr was determined directly by Graphite Furnace Atomic Absorption Spectrometry (GFAAS). A portion of the filtered sample was buffered to pH 6.4, extracted with Amberlite LA-2/MIBK and finally Cr(VI) was determined in the organic extract and Cr(III) in the aqueous phase using GFAAS. The method was evaluated by analysis of the certified reference material, CRM 544, and good accuracy was obtained. The limit of detection for Cr(VI) and Cr(tot)/Cr(III) was found to be 0.30 and 0.08 µg L−1, respectively, and a precision expressed as relative standard deviation of better than 11% was achieved for nine replicates. A number of water samples from the Tinishu Akaki River, Ethiopia, and wastewater samples from a chemical plant in Germany, were analysed. In addition to the GFAAS method, Cr(tot) was also determined using ICP-MS (in CRM 544, lyophilized water, and Tinishu Akaki River water samples) and Cr(tot) and Cr(VI) using UV-VIS spectrophotometry (in CRM 544 and industrial wastewater samples). Good agreement between the different methods was found. 相似文献
996.
Watson MD Jäckel F Severin N Rabe JP Müllen K 《Journal of the American Chemical Society》2004,126(5):1402-1407
Cyclophanes with the largest-to-date polycyclic aromatic hydrocarbon (hexa-peri-hexabenzocoronene, HBC) to be entrained in such a structural motif are reported. The two disks are covalently captured by intermolecular ring-closing olefin metathesis of dienes in good yield. DSC, optical microscopy, and WAXD show the new cyclophanes to self-assemble to thermotropic columnar liquid crystal mesophases similar to monomeric analogues. Solution spectroscopic studies reveal that the two disks within a single unit lie face-to-face, with a small average lateral offset. Self-assembly into two-dimensional crystals at a solid-liquid interface was visualized by STM, and the electrical properties of single molecules were assessed by scanning tunneling spectroscopy revealing a diode-like behavior which is similar to that previously reported for single HBC disks, laying the groundwork for future electrical interrogations of dynamic molecular complexes. 相似文献
997.
Collison D Goodgame DM Hitchman MA Lippert B Mabbs FE McInnes EJ 《Inorganic chemistry》2002,41(11):2826-2833
Multifrequency continuous wave EPR spectra (4-34 GHz) on a powder of the title compound are consistent with a spin-triplet state. This arises from interaction between centrosymmetrically related pairs of copper(II) ions in the solid. The spectra at all frequencies have been simulated with a single set of spin-Hamiltonian parameters. The results show that there is noncoincidence between the principal axes of the g-matrices on each copper center and those of the zero-field splitting (D) tensor. This noncoincidence is a single rotation of 33 degrees +/- 2 degrees. The parameters from the powder spectra have been verified by a subsequent single-crystal EPR study which yielded the spin-Hamiltonian parameters g(XX) = 2.074, g(YY) = 2.093, g(ZZ) = 2.385, D(XX) = +/-0.0228 cm(-1), D(YY) = +/-0.0211 cm(-1), D(ZZ) = -/+0.0439 cm(-1) with Euler angles of alpha = 179 degrees, chi = 33.4 degrees, and gamma = 328 degrees. Analysis of the zero-field splitting tensor in terms of exchange indicates that the interaction between the pairs of copper(II) ions is almost entirely dipolar in origin. This study shows that multifrequency EPR spectroscopy on powders, coupled with spectrum simulation, can detect and measure noncoincidence between the principal axes of the g-matrix and zero-field splitting tensor, and does not necessarily require the presence of metal hyperfine interactions. 相似文献
998.
The synthesis of 4-(methylthio)-1H-imidazo[4,5-c]pyridine 2′-deoxy-β-D -ribonucleosides 2 and 9 and the conversion of the N1-isomer 2 into the 2′,3′-didehydro-2′,3′-dideoxyribonucleoside 3a or (via 7 ) 3-deaza-2′-deoxyadenosine ( 1 ) is described. Phosphonate building blocks of 1 were employed in solid-phase synthesis of self-complementary base-modified oligonucleotides. Their properties were studied with regard to duplex stability and hydrolysis by the restriction enzyme Eco RI. 相似文献
999.
Alfred Fischer Michael W. Morgan Colin Eaborn 《Journal of organometallic chemistry》1977,136(3):323-332
Rates of cleavage of some picoyl- and (quinolylmethyl)-trimethylsilanes (RSiMe3, where R = PyCH2 or QnCH2SiMe3) have been measured in “90%” aqueous methanolic sodium methoxide at 50°C. Relative reactivities are: 2-PyCH2, 1.0; 3-PyCH2, 0.030; 4-PyCH2, 8.9; 2-QnCH2, 41; 3-QnCH2, 0.161; 4-QnCH2, 37. The rates correlate well with those for base-catalysed hydrogen-exchange in the parent carbon acids RH. Approximate pKa's (based on the scale of ion-pair acidities in CsNHC6H11H2NC6H11, with pKa of 9-phenylfluorene = 18.6) for the carbon acids, RH, can be derived as follows: 2-PyCH3, 29.5; 3-PyCH3, 34; 4-PyCH3, 27; 2-QnCH3, 25; 3-QnCH3, 32; 4-QnCH3, 25.Rates of cleavage of pyridyl- and quinolyl-trimethylsilanes (PySiMe3 and QnSiMe3) by sodium hydroxide in 4 : 1 v/v Me2SO/H2O at 50°C have also been measured; and the relative reactivities are: 2-Py, 1.0; 3-Py, 2.9; 4-Py, 8.4; 2-Qn, 15.9; 3-Qn, 12.7; 4-Qn, 184. The sequence of reactivity differes from that for base-catalysed hydrogen-exchange at the relevant positions of pyridine and quinoline, indicating that the reactivities are not determined in both cases (if in either) solely by the stabilities of the corresponding carbanions. 相似文献
1000.
Syed Laik Ali 《Analytical and bioanalytical chemistry》1973,262(4):278-282
The different aspects of Vitamin D3 determination and the data reported in the literature are discussed. The spectrophotometric determination of Vitamin D3 in cod-liver oil is carried out after the alkaline saponification, extraction of unsaponified parts, precipitation of accompanying sterols and the column- and thin-layer chromatographic purification and separation of vitamin D3 on 40 cm plates from other vitamins. The dyestuff α-naphtholbenzein is suited well as standard substance for the better location and identification of vitamin D3 zone on the thin-layer plate. The results obtained from the chemical method were checked through the simultaneous biological determination. 相似文献