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41.
Multiconfiguration (MC ) SCF calculations are reported for CO2 for bond angles between 60° and 180°. The ground state configuration is found to be …?5a4b∣b∣a for small bending angles and …?6a3b∣b∣a for large bending angles, the change in ground state character occurring at a bond angle of about 100°. The force constant for bending obtained from the MC –SCF function is about 8.0% lower than the corresponding SCF value, and in considerably better agreement with experiment. 相似文献
42.
Leon P. Jenner Mickael V. Cherrier Patricia Amara Luis M. Rubio Yvain Nicolet 《Chemical science》2021,12(14):5269
The nitrogenase MoFe protein contains two different FeS centers, the P-cluster and the iron–molybdenum cofactor (FeMo-co). The former is a [Fe8S7] center responsible for conveying electrons to the latter, a [MoFe7S9C-(R)-homocitrate] species, where N2 reduction takes place. NifB is arguably the key enzyme in FeMo-co assembly as it catalyzes the fusion of two [Fe4S4] clusters and the insertion of carbide and sulfide ions to build NifB-co, a [Fe8S9C] precursor to FeMo-co. Recently, two crystal structures of NifB proteins were reported, one containing two out of three [Fe4S4] clusters coordinated by the protein which is likely to correspond to an early stage of the reaction mechanism. The other one was fully complemented with the three [Fe4S4] clusters (RS, K1 and K2), but was obtained at lower resolution and a satisfactory model was not obtained. Here we report improved processing of this crystallographic data. At odds with what was previously reported, this structure contains a unique [Fe8S8] cluster, likely to be a NifB-co precursor resulting from the fusion of K1- and K2-clusters. Strikingly, this new [Fe8S8] cluster has both a structure and coordination sphere geometry reminiscent of the fully reduced P-cluster (PN-state) with an additional μ2-bridging sulfide ion pointing toward the RS cluster. Comparison of available NifB structures further unveils the plasticity of this protein and suggests how ligand reorganization would accommodate cluster loading and fusion in the time-course of NifB-co synthesis.The K-cluster of NifB as a key intermediate in the synthesis of the nitrogenase active site supports [Fe4S4] cluster fusion occurs before carbide and sulfide insertion and displays ligand spatial arrangement reminiscent to that of the P-cluster. 相似文献
43.
Rb2I(OH): A Hydroxide Iodide in the System RbOH/RbI The pseudobinary system RbOH/RbI was investigated by X-ray methods. The crystal structure of Rb2I(OH) was solved by single crystal data: Rb2I(OH): Pnma, Z = 4, a = 7.748(1) Å, b = 5.654(2) Å,c = 13.254(2) Å Z(Fo) with (Fo)2 ? 3σ = (Fo)2 = 449, Z (parameter) = 25, R/Rw = 0.021/0.023 Rb2I(OH) crystallizes in a new type of structure, built up by a three dimensional network of [Rb2(OH)+] containing the iodide ions. 相似文献
44.
Backinowsky LV Abronina PI Shashkov AS Grachev AA Kochetkov NK Nepogodiev SA Stoddart JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(19):4412-4423
Glycosylation of sugar trityl ethers with sugar 1,2-O-(1-cyano)ethylidene derivatives (the trityl-cyanoethylidene condensation) has been applied to the synthesis of highly branched (dendritic) mannooligosaccharides incorporating a Manalpha1-->3(Manalpha1-->6)Man structural motif. The convergent synthetic strategy used to assemble these oligosaccharides was based on the use of glycosyl acceptors and/or a glycosyl donor already bearing this structural motif. The former were represented by mono- and ditrityl ethers of ManalphaOMe, Manalpha1-->3ManalphaOMe, and Manalpha1-->3(Manalpha1-->6)ManalphaX, where X=OMe or SEt. The pivotal glycosyl donor was the peracetylated 1,2-O-(1-cyano)ethylidene-3,6-di-O-(alpha-D-mannopyranosyl)-beta-D-mannopyranose (1), prepared by orthogonal Helferich glycosylation of the known 1,2-O-(1-cyano)ethylidene-beta-D-mannopyranose with tetra-O-acetyl-alpha-D-mannopyranosyl bromide followed by O-acetylation. Glycosylation of acetates of methyl 6-O-trityl-alpha-D-mannopyranoside and methyl 3,6-di-O-trityl-alpha-D-mannopyranoside with one equivalent of the donor 1 gave rise to the isomeric tetrasaccharide derivatives, Manalpha1-->3(Manalpha1-->6)Manalpha1-->6ManalphaOMe and Manalpha1-->3(Manalpha1-->6)Manalpha1-->3ManalphaOMe, respectively. The latter derivative was further mannosylated at the remaining 6-O-trityl acceptor site to give the protected pentasaccharide Manalpha1-->3(Manalpha1-->6)Manalpha1-->3(Manalpha1-->6)ManalphaOMe. The isomeric pentasaccharide, Manalpha1-->3(Manalpha1-->6)Manalpha1-->6(Manalpha1-->3)ManalphaOMe, was prepared by reaction of 1 with the 6-O-trityl derivative of (Manalpha1-->3)ManalphaOMe. In a similar fashion, 6'- and 6"-O-trityl derivatives of the branched trisaccharide Manalpha1-->3(Manalpha1-->6)ManalphaOMe served as precursors for two isomeric mannohexaosides. The 3,6-di-O-trityl ether of ManalphaOMe and the 6',6"-di-O-trityl ether of Manalpha1-->3(Manalpha1-->6)ManalphaX (X=OMe or SEt) were efficiently bis-glycosylated with the donor 1 to give the corresponding protected mannoheptaoside and mannononaoside. The yields of these glycosylations with the donor 1 ranged from 50 to 66 %. Final deprotection of all the oligosaccharides was straightforward and afforded the target products in high yields. Both the acylated and deprotected products were characterized, and the intersaccharide connectivities were elucidated by extensive one- and two-dimensional NMR spectroscopy. The described blockwise convergent approach allows assembly of a variety of 3,6-branched mannooligosaccharides. 相似文献
45.
Xu J Mojet BL van Ommen JG Lefferts L 《The journal of physical chemistry. B》2005,109(39):18361-18368
The adsorption of oxygen and d2-propane (CH3CD2CH3) on a series of alkaline-earth-exchanged Y zeolite at room temperature was studied with in situ infrared spectroscopy. Surprisingly at room temperature, oxygen adsorption led to the formation of supercage M2+(O2) species. Further, at low propane coverage, propane was found to adsorb linearly on Mg2+ cations, but a ring-adsorption structure was observed for propane adsorbing on Ca2+, Sr2+, and Ba2+ cations. It is demonstrated that O2 and propane can simultaneously attach to one active center (M2+) to form a M2+(O2)(C3H8) species, which is proposed to be the precursor in thermal propane selective oxidation. Selectivity to acetone in the propane oxidation reaction decreases with increasing temperature and cation size due to the formation of 2-propanol and carboxylate ions. An extended reaction scheme for the selective oxidation of propane over alkaline earth exchanged Y zeolites is proposed. 相似文献
46.
C. Boekema A. B. Denison D. W. Cooke R. H. Heffner R. L. Hutson M. Leon M. E. Schillaci 《Hyperfine Interactions》1983,15(1-4):529-532
Muon Spin Rotation (SR) results for magnetite (Fe3O4) are analyzed and discussed. At room temperature, a SR signal is observed due to the presence of an internal magnetic field (Bint) at the muon site. External transverse field measurements show that Bint is parallel to the magnetic spin direction, the <111> direction in zero applied field. Calculations of the hyperfine field to pinpoint muon stopping sites in magnetite show that the local field contains supertransfer (covalent) and dipolar field contributions. The implanted muons appear to stop at sites structurally similar to those reported for hematite (-Fe3O4), where muon-oxygen bond formation was strongly indicated.Research partially supported by US Department of Energy 相似文献
47.
48.
Li2Br(NH2): The First Ternary Alkali Metal Amide Halide The pseudobinary system LiNH2/LiBr was investigated by X-ray methods. The crystal structure of the compound Li2Br(NH2) was solved by single crystal data: Li2Br(NH2): Pnma, Z = 8, a = 12.484(2) Å, b = 7.959(1) Å, c = 6.385(1) Å, Z(Fo) with (Fo)2 ≧ 3σ(Fo)2 = 348, Z (parameter) = 51, R/Rw = 0.019/0.021 Li2Br(NH2) crystallizes in a new type of structure. To one another isolated chains of [Li2Li4/2(NH2)22+] show the motif of closest rod packing. They are connected via bromide ions in a distorted cubic primitive arrangement. 相似文献
49.
The reagent 4-sulfophenyl isothiocyanate (SPITC) is an effective, stable, and inexpensive alternative to commercially available reagents used in the N-terminal sulfonation of peptides for enhanced postsource decay (PSD) in matrix-assisted laser desorption/ionization time-of-flight mass spectrometric (MALDI-TOFMS) analyses. However, suppression of ionization of sulfonated peptides due to sample and matrix contaminants such as sodium can be a problem when using prestructured MALDI target sample supports, such as the Bruker Daltonics AnchorChip. We show that use of the salt-tolerant matrix 2,4,6-trihydroxyacetophenone containing diammonium citrate (THAP/DAC) as an alternative to alpha-cyanohydroxycinnamic acid (HCCA) reduces the need for extensive washing of ZipTip-bound peptides or additional on-target sample clean-up steps. Use of the THAP/DAC matrix results in selective ionization of sulfonated peptides with greater peptide coverage, as well as detection of higher mass derivatized peptides, than was observed for HCCA or THAP alone. The THAP/DAC matrix is quite tolerant of sodium contamination, with SPITC-peptides detectable in preparations containing up to 50 mM NaCl. In addition, THAP/DAC matrix was found to promote efficient PSD fragmentation of sulfonated peptides. We demonstrated the utility of using the THAP/DAC MALDI matrix for peptide sequencing with DNA polymerase beta tryptic peptide mixture, as well as tryptic peptides derived from Xiphophorus maculatus brain extract proteins previously separated by two-dimensional polyacrylamide gel electrophoresis (2D-PAGE). 相似文献
50.