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891.
The Fourier transform infrared spectrum of monoisotopic SC80Se has been investigated in the ν2, ν3, 2ν2, 2ν3, and ν1 regions with a resolution between 3 and 4 × 10−3 cm−1. In addition, the millimeter-wave spectrum has been studied in the region 150 to 320 GHz, and ground and ν2 = 1 excited state transitions have been measured. Ground state constants, B0 = 2043.285 4(4) MHz and D0 = 146.53(5) Hz, have been determined from a merge of millimeter-wave data and ground state combination differences spanning J values up to 77 and 143, respectively. The band centers ν2 = 352.341 075(9) cm−1 and ν3 = 505.480 06(5)cm−1 have been determined. The rovibrational parameters of numerous overtone and combination levels (ν1νl22ν3) = 0200, 0220, 0310, 0330, 0400, 0420, 0002, and 0003 have been obtained from polynomial analyses whose standard deviations ranged from 0.7 to 3.5 × 10−4 cm−1. The 1000 level, νeff 1435.840 cm−1, is anharmonically perturbed by the 0400 level, with an avoided crossing at J = 55, and W12222 = 0.963 09(1) cm−1. Transitions to both the upper (E+) and lower (E−) sublevels of the dyad were observed for 1 ≤ J′ ≤ 117 and 4 ≤ J′ ≤ 171, respectively, and the deperturbed wavenumbers ν1 = 1435.542 76(2) and 4ν02 = 1432.725 00(3) cm−1 were derived. Furthermore, a local crossing of the E− and 0420 levels involving l-type resonance was observed at J = 91. 相似文献
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J. Telser H. -I. Lee E. T. Smith H. Huang P. Brereton M. W. W. Adams R. C. Conover M. K. Johnson B. M. Hoffman 《Applied magnetic resonance》1998,14(2-3):305-321
The hyperthermophilic archaeonPyrococcus furiosus contains a four-Fe ferredoxin (Pf- Fd) that differs from most other 4Fe-Fd’s in that its [Fe4S4] cluster is anchored to protein by only three cysteinyl residues.Pf- Fd also is of interest because in its reduced form, [Fe4S4]+, the cluster exhibits bothS = 1/2 andS = 3/2 spin states. Addition of excess cyanide ion converts the cluster exclusively to anS = 1/2 state (g1 = 2.09, g2 = 1.95, g3 = 1.92), however dialysis restores the EPR signal of native reduced protein indicating that the cluster is not irreversibly altered by cyanide. Both the native protein and protein in the presence of excess cyanide ion (Pf- Fd 4Fe-CN) were investigated here using the techniques of electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy. In particular,Pf- Fd 4Fe-CN was investigated using13CN? and C15N? ligands.13C and15N ENDOR indicated that a single cyanide ion bound directly, with the cluster showing an unusually small contact interaction (aiso(13C)~ ?3 MHz, aiso(15N) ~ 0). This is in contrast to cyanide bound to monomeric low-spin Fe(III)-containing proteins such as transferrin and myoglobin, for which the13C hyperfine coupling has a large isotropic component (aiso(13C) ≈ ?30 MHz). This small contact interaction is not due to low spin density of Fe, as57Fe ENDOR of the singly and triply labeledPf- Fd 4FeCN isotopologs, [57FeFe3S4]+ and [Fe57Fe3S4]+, show hyperfine coupling characteristic for [Fe4S4]+ clusters, particularly for the Fe to which cyanide binds. Thus, the low spin density on13C is not due to low spin density on the Fe ion to which it binds. Further theoretical work is needed to explain the contrast between the strong electronic effect of cyanide ion binding with the low spin density on the ligand. 相似文献
895.
Polyethers, which are produced by alcoholysis of oxiranes, are often used as solvents in chemical plants. The spectra of the products can be influenced by the choice of the catalyst (acid or base). The results of the base-catalyzed ethanolysis of 1,2-epoxybutane are displayed. The reaction was investigated calorimetrically by varying the molar ratio between ethanol and 1,2-epoxybutane, the starting temperature and the concentration of the catalyst sodium hydroxide. Additionally, the influence of the used alcohol will be shown in one example. To determine the activation parameters, the experiments were evaluated by the nonlinear software package TA-kin v3.3. 相似文献
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The primary objective of this investigation was to document fluctuations of levels of ions in airborne particles and in rain water with the help of ion chromatography. The environmental emission situation in the investigated geographic area is characterized by a widespread use of domestic coal-burning furnaces. The use of a parallel impactor for particulate sampling permits the results to be interpreted additionally in terms of particle size. The anions and cations were extracted from the filters in the sampling devices into ethanol-water mixtures by sonication. Rain water samples were analysed after a simple dilution step. The data obtained on ionic fluctuations are compared with similar data sets published by other laboratories. 相似文献
899.
Both homogeneous and asymmetric polyethersulfone (PES) membranes were prepared by solvent casting. The sorption and permeation behavior of CO2, O2, and N2 using these two kinds of cast PES membranes and commercially available homogeneous PES film was investigated to extract the pressure dependence of gas permeability and the permselectivity for CO2 relative to N2, and to confirm the validity of the working assumption that a skin layer in an asymmetric membrane can be essentially replaced by a thick homogeneous dense membrane. The pressure dependence of the mean permeability coefficient to CO2 in homogeneous membranes obeys the dual-mode mobility model. The ideal separation factor for CO2 relative to N2 at an upstream pressure of 0.5 MPa attains ca. 40, while the permeability to CO2 is about 2.7 Barrer at the same upstream pressure. The same separation factor in asymmetric membranes amounts to 35. The diffusion behavior for the skin layer in an asymmetric membrane with a thin skin layer can be simulated approximately by that in a homogeneous dense membrane. © 1993 John Wiley & Sons, Inc. 相似文献
900.