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131.
Intermediates formed during reduction of Fe(2)(mu-PPh(2))(2)(CO)(6) (1) in the presence of protons have been identified by spectroelectrochemical, continuous-flow, and interrupted-flow techniques. The mechanism for electrocatalytic proton reduction suggested by these observations yields digital simulation of the voltammetry in close agreement with measurements conducted in THF over a range of acid concentrations. The mechanism for electrocatalytic proton reduction involves initial formation of the dianion, 1(2-), which is doubly protonated prior to further reduction and dihydrogen elimination. The IR spectra of the singly and doubly protonated forms of 1(2-) indicate structures corresponding to [FeH(CO)(3)(mu-PPh(2))(2)Fe(CO)(3)](-) (1H-) and FeH(CO)(3)(mu-PPh(2))(2)FeH(CO)(3) (1H(2)). The thiolato and dithiolato analogues of 1 exhibit electrocatalytic proton reduction associated with the two-electron reduction step, and this implies that the corresponding two-electron reduced doubly protonated species is unstable with respect to dihydrogen elimination. The stability of 1H(2) is most likely to be due to the weak interactions between the iron centers of the flattened [2Fe2P] core. Whereas 1H(2) is stable in the absence of a reducing potential, 1H- rearranges rapidly to a product previously described as [Fe(2)(mu-PPh(2))(mu-CO)(PHPh(2))(CO)(5)](-) (1H-(W)). Another protonation product of 1(2-), previously formulated as [Fe(2)(mu-PPh(2))(2)(mu-CO)H(CO)(5)](-), has been reformulated as [Fe(2)(mu-PPh(2))(mu-CO)(CO)(6)](-) (2) on the basis of a range of spectroscopic measurements. Solution EXAFS measurements of 1, 1(2-), 1H-(W), and 2 are reported, and these yield model-independent Fe-Fe distances of 2.61 (1), 3.58 (1(2-)), 2.58 (1H-(W)), and 2.59 A (2). The presence of an Fe-Fe bond for both 1H-(W) and 2 is a key aspect of the proposed structures, and this strongly supports the deductions based on spectroscopic evidence. The fits of the solution EXAFS to different structural models give statistics in agreement with the proposed structures. 相似文献
132.
133.
The toxicity of certain elements is known to be related to their organic substituents and/or oxidation states. As such, total elemental determinations do not always yield sufficient information for accurate risk assessments and therefore speciation or fractionation data are required. In order to obtain fractionation data for trace levels of arsenic and selenium, a novel sequential pneumatic nebulisation (PN)/hydride generation (HG) inductively coupled plasma mass spectrometry (ICP-MS) method was developed. The method offers the advantage of sample introduction via either PN or HG by simply rotating a 4-way switching valve while the system is in operation. In PN mode, the liquid sample is aspirated into ICP, allowing for the determination of the total amount of each element, whilst in HG mode only the arsenic and selenium species that form volatile hydrides are determined. Conveniently, in the case of arsenic, this allows for differentiation between the four most toxic arsenic species (arsenate, arsenite, monomethylarsonic acid and dimethylarsinic acid), which form volatile hydrides, and the virtually non-toxic forms (arsenobetaine, arsenosugars, etc.), which do not. This allows for the rapid estimation of the amounts of toxic and non-toxic arsenic species present in a sample. For arsenic, the technique gave detection limits of 36 ng l−1 in PN mode and 1 ng l−1 in HG mode. For selenium, detection limits of 150 ng l−1 were achieved in PN mode and 220 ng l−1 in HG mode. The technique also gave good long- and short-term stabilities of under 6% RSD for both elements. A variety of samples, including water and urine standard reference materials, were analysed in both modes, and the precision and accuracy of the results for total arsenic and selenium levels were assessed. Using the technique in both modes also allowed for the fractionation of As and Se species into their volatile hydride-forming and non-hydride-forming species. This was particularly informative, with respect to As species present, in the case of a kelp powder extract. Digested tobacco samples were only analysed for their total As levels, in which case results obtained via both sample introduction modes showed good agreement. 相似文献
134.
Kalovidouris SA Blixt O Nelson A Vidal S Turnbull WB Paulson JC Stoddart JF 《The Journal of organic chemistry》2003,68(22):8485-8493
Four glycodendrons and a glycocluster were synthesized from carbohydrate building blocks to form paucivalent (di- to tetravalent) structures of controlled scaffold architectures. Enzymatic sialylation of the functionalized cluster and dendrons, terminated in lactose residues, generated a library of paucivalent synthetic sialosides displaying sialic acids with different dispositions. These newly constructed bioactive sialic acid-based structures were differentially recognized by sialoadhesin, a mammalian macrophage sialic acid binding protein. The binding of the sialosides to sialoadhesin was evaluated by an enzyme-linked immunosorbant assay to investigate the complementarity of scaffold structure and binding to sialoadhesin. Modulating the interaction between sialoadhesin and its sialic acid ligands has important implications in immunobiology. 相似文献
135.
Godard C Duckett SB Polas S Tooze R Whitwood AC 《Journal of the American Chemical Society》2005,127(14):4994-4995
para-Hydrogen-induced polarization methods are shown to enable the in situ detection of linear and branched monophosphine-containing intermediates during hydroformylation when Co(eta3-C3H5)(CO)2(PCy3) is the catalyst precursor. The NMR signal characteristics of the alkyl arms of these species provide direct evidence for the rapid interconversion of linear and branched cobalt alkyls prior to the CO insertion step. The observation of additional para-hydrogen-enhanced signals for the corresponding linear and branched aldehydes enables the reactions selectivity to be rapidly monitored as a function of H2 and CO pressure or reaction temperature. 相似文献
136.
The metalation of substituted N,N'-di-tert-butylethylenediamines by various aluminum hydride sources has been investigated. HN(t-Bu)CH(t-Bu)CH(2)N(H)(t-Bu) forms a dimeric lithium chelated adduct of LiAlH(4), [{[HN(t-Bu)CH(t-Bu)CH(2)N(H)(t-Bu)]Li(&mgr;-H)(2)AlH(2)}(2)], 4, which thermally decomposes to yield the tetrameric lithium diamidoaluminum hydride [{Li[N(t-Bu)CH(t-Bu)CH(2)N(t-Bu)]AlH(2)}(4)], 5. The same diamine reacts with AlH(3).NMe(3) or AlH(3) diethyl etherate to give the secondary amine stabilized amidoaluminum hydride species [{HN(t-Bu)CH(t-Bu)CH(2)N(t-Bu)}AlH(2)], 2. Similarly, the same aluminum hydride sources react with the diamine rac-HN(t-Bu)CH(Me)CH(Me)N(H)(t-Bu) to yield [{rac-HN(t-Bu)CH(Me)CH(Me)N(t-Bu)}AlH(2)], 3. Compounds 2 and 3 are stable with respect to elimination of hydrogen to form diamidoaluminum hydrides, but can be converted to the alane rich species, [H(2)Al{N(t-Bu)CH(t-Bu)CH(2)N(t-Bu)}AlH(2)],6, and [H(2)Al{rac-N(t-Bu)CH(Me)CH(Me)N(t-Bu)}AlH(2)], 7, by reaction with AlH(3).NMe(3) under special conditions. The varying reactivity of the three aluminum hydride sources in these reactions has enabled mechanistic information to be gathered, and the effect of the different steric requirements in the diamines on the stability of the complexes is discussed. Crystals of 3are monoclinic, space group P2(1)/n (No. 14), with a = 8.910(4), b = 14.809(1), and c = 12.239(6) ?, beta = 109.76(2) degrees, V = 1520(1) ?(3), and Z = 4. Crystals of 4 are orthorhombic, space group Pbca (No. 61), with a = 15.906(9), b = 24.651(7), and c = 9.933(7) ?, V = 3895(3) ?(3), and Z = 4. Crystals of 6 are monoclinic, space group P2(1)/c (No. 14), with a = 8.392(1), b = 17.513(2), and c = 12.959(1) ?, beta = 107.098(8) degrees, V = 1820.4(3) ?(3), and Z = 4. 相似文献
137.
Lindgren A Kosugi N Gisselbrecht M Kivimäki A Burmeister F Naves de Brito A Sorensen SL 《The Journal of chemical physics》2008,128(11):114311
Electron-ion-ion coincidence measurements of sulfur dioxide at discrete resonances near the O 1s ionization edge are reported. The spectra are analyzed using a model based upon molecular symmetry and on the geometry of the molecule. We find clear evidence for molecular alignment that can be ascribed to symmetry properties of the ground and core-excited states. Configuration interaction (CI) calculations indicate geometry changes in accord with the measured spectra. For the SO(2) molecule, however, we find that the localized core hole does not produce measurable evidence for valence localization, since the transition dipole moment is not parallel to a breaking sigma* O-S bond, in contrast to the case of ozone. The dissociation behavior based upon the CI calculations using symmetry-broken orbitals while fixing a localized core-hole site is found to be nearly equivalent to that using symmetry-adapted orbitals. This implies that the core-localization effect is not strong enough to localize the sigma* valence orbital. 相似文献
138.
Gisselbrecht M Lindgren A Burmeister F Tchaplyguine M Ohrwall G Lundin M de Brito AN Svensson S Björneholm O Sorensen SL 《The Journal of chemical physics》2008,128(4):044317
Photofragmentation of argon clusters of average size ranging from 10 up to 1000 atoms is studied using soft x-ray radiation below the 2p threshold and multicoincidence mass spectroscopy technique. For small clusters (=10), ionization induces fast fragmentation with neutral emission imparting a large amount of energy. While the primary dissociation takes place on a picosecond time scale, the fragments undergo slow degradation in the spectrometer on a microsecond time scale. For larger clusters ( >or=100) we believe that we observe the fragmentation pattern of multiply charged species on a time-scale which lasts a few hundred nanoseconds. The reason for these slower processes is the large number of neutral atoms which act as an efficient cooling bath where the excess energy ("heat") dissipates among all degrees of freedom. Further degradation of the photoionic cluster in spectrometer then takes place on the microsecond time scale, similar to small clusters. 相似文献
139.
We describe the detection of specific, conserved DNA sequences of herpes simplex virus (HSV) type 1 by means of a novel, high sensitivity acoustic biosensor. Repeated assays on planar and polymeric carboxylic acid- and biotin-presenting surface chemistries enabled statistical comparison of assay specificity and sensitivity and evaluation of assay Z-factor scores. Using a three minute hybridisation with NeutrAvidin capture for signal enhancement, it was possible to detect HSV viral nucleic acids at 5.2 x 10(-11) M concentration. 相似文献
140.
Bhadra S Appel JA Bartlett DF Denby BH Biel J Bintinger D Bharadwaj VK Blodgett DE Bracker SB Bronstein J Daum C Duncan AL Eisner AM Elliott JR Estabrooks P Hartner GF Kalbfleisch GR Kennett RG Kumar BR Losty MJ Lu A Luste GJ Mantsch PM Martin JF Morrison RJ Nash T Nauenberg U Pinfold J Robertson M Schmidke W Shahbazian KK Sheperd RA Sliwa K Sokoloff MD Spalding WJ Stacey J Stanfield KC Streetman M Summers DJ Willis SE Witherell MS Yellin SJ Zorn CJ 《Physical review letters》1985,55(25):2749-2751