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251.
Ellis PD Sears JA Yang P Dupuis M Boron TT Pecoraro VL Stich TA Britt RD Lipton AS 《Journal of the American Chemical Society》2010,132(47):16727-16729
We have examined the antiferromagneticly coupled bis(μ-oxo)dimanganese(IV) complex [Mn(2)O(2)(salpn)(2)] (1) with (55)Mn solid-state NMR at cryogenic temperatures and first-principle theory. The extracted values of the (55)Mn quadrupole coupling constant, C(Q), and its asymmetry parameter, η(Q), for 1 are 24.7 MHz and 0.43, respectively. Further, there was a large anisotropic contribution to the shielding of each Mn(4+), i.e. a Δσ of 3375 ppm. Utilizing broken symmetry density functional theory, the predicted values of the electric field gradient (EFG) or equivalently the C(Q) and η(Q) at ZORA, PBE QZ4P all electron level of theory are 23.4 MHz and 0.68, respectively, in good agreement with experimental observations. 相似文献
252.
We generalise the work of Segre (Ann Mat Pura Appl 4(70):1–201, 1965), Cameron et al. (J Algebra 55(2):257–280, 1978), and Vanhove (J Algebr Comb 34(3):357–373, 2011) by showing that nontrivial m-ovoids of the dual polar spaces \(\mathsf {DQ}(2d, q)\), \(\mathsf {DW}(2d-1,q)\) and \(\mathsf {DH}(2d-1,q^2)\) (\(d\geqslant 3\)) are hemisystems. We also provide a more general result that holds for regular near polygons. 相似文献
253.
254.
Martin J. B. Appel Michael J. Klass Ralph P. Russo 《Journal of Theoretical Probability》1999,12(1):27-47
Let U
1, U
2,... be a sequence of i.i.d. random mappings taking values in a space S and let h be a symmetric function on S×S with global maximum
Let {x
n} be any nondecreasing real sequence converging to
Then p=P(H
n>x
n, infinitely often) is either zero or one, where H
n=max{h(U
i, U
j), 1 ijn}. This paper provides a nonrandom series criterion which is necessary and sufficient to determine the value of p. In addition, various sufficient conditions are presented which may be easier to apply. A number of metric space applications are given. 相似文献
255.
Seyler Isabelle Appel Martine Devissaguet Jean-Philippe Legrand Philippe Barratt Gillian 《Journal of nanoparticle research》1999,1(1):91-97
Different colloidal formulations: nanocapsules (NC), emulsion and micelles, containing the lipophilic immunomodulator muramyltripeptide cholesterol (MTP-Chol) induce nitric oxide synthase activity in the RAW 264.7 cell line. The use of cytochalasin B, an inhibitor of cell movements, showed that phagocytosis was an important mechanism as far as NC and the emulsion were concerned. However, when the cells were separated from particles containing the immunomodulator by a membrane of 100nm pore size, significant activity could still be obtained, provided that serum was included in the medium. To determine whether low-density lipoprotein (LDL) might act as an intermediate carrier for MTP-Chol, the transfer of the immunomodulator from NC to LDL was studied by an ultrafiltration/centrifugation method followed by HPLC analysis. Although MTP-Chol could be transferred to LDL, when purified human LDL was added to serum-free medium, activation by MTP-Chol NC was reduced, rather than increased. This suggests that intact LDL carrying MTP-Chol is not taken up to a great extent by these macrophages. 相似文献
256.
257.
Alves GA Amato S Anjos JC Appel JA Astorga J Bernard T Bracker SB Cremaldi LM Darling CL Dixon RL Errede D Gay C Green DR Jedicke R Karchin PE Kwan S Lueking LJ de Mello Neto JR Metheny J Milburn RH de Miranda JM da Motta Filho H Napier A Passmore D Rafatian A dos Reis AC Ross WR Santoro AF Sheaff M Souza MH Spalding WJ Stoughton C Streetman ME Summers DJ Takach SF Wallace A Wu Z 《Physical review letters》1994,72(6):812-815
258.
The synthesis of the 2,4,6-tri-tert-butylphenyl(halogenmethylene)phosphanes 4a—d from the tri-tert-butylphenylphosphane 1 and trihalogenomethanes 2a—d is described. Tri-tert-butylphenyl(difluoromethylene)phosphane 8a and the analogous (diiodomethylene)-phosphane 8d are obtained by dehalogenation of the chloro(trifluoromethyl)phosphane 7 and dehydrohalogenation of the triiodomethylphosphane 10 . The first different halogeno-substituted (bromochloromethylene)phosphane 8e leads after metallation with lithiumbis (trimethylsilyl)phosphide 13 and elimination of lithiumchloride to the phosphaalkyne 16 . Direct addition of chlorotrimethylsilane to the metallated 8e yields the 2,4,6-tri-tert-butylphenyl(chloro(trimethylsilyl)-methylene)phosphane 17 . 相似文献
259.
Donald S. Bethune Costantino S. Yannoni Mark Hoinkis Mattanjah de Vries Jesse R. Salem Mark S. Crowder Robert D. Johnson 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1993,26(1):153-158
Fullerenes containing metal atoms and clusters can be formed by the arc-vaporization method. The electronic structure of these metallofullerenes can be probed using magnetic resonance techniques. Electron paramagnetic resonance (EPR) spectra of LaC82, YC82, ScC82 and Sc3C82 have been obtained. Metallofullerenes containing a single metal atom (MC82 with M = La, Y, or Sc), have small hyperfine couplings and g-values close to 2, implying that they can be described as + 3 metal cations within — 3 fullerene radical anion cages. In the La and Y cases, additional EPR active MC82 species have been found. The EPR spectrum of Sc3C82 shows that the metal atoms are equivalent, suggesting that they may form a triangular molecule. No EPR spectrum is found for Y2C82 or for Sc2C2n species (with 2n = 82,84,86), suggesting that they are diamagnetic. Sc NMR spectra of a solution containing Sc2C2n species have been obtained which confirm the diamagnetism of the discandium metallofullerenes. 相似文献
260.
Kroll JH Donahue NM Cee VJ Demerjian KL Anderson JG 《Journal of the American Chemical Society》2002,124(29):8518-8519
Gas-phase ozone-alkene reactions are known to produce the hydroxyl radical (OH) in high yields. Most mechanistic studies to date have focused on the role of syn carbonyl oxides; however, OH production from ethene ozonolysis indicates a second, poorly understood OH-forming channel, which may contribute to OH production in the ozonolysis of substituted alkenes as well. Using laser-induced fluorescence, we have measured OH and OD yields from the ozonolysis of two partially deuterated alkenes, cis- and trans-3-hexene-3,4-d2. OD is formed from both alkenes, indicating a pathway of hydroxyl-radical formation involving vinylic hydrogens, accounting for one-third of total OH formation from cis-3-hexene. The lack of a significant kinetic isotope effect suggests this pathway is the "hot acid" channel, arising from rearrangement of anti carbonyl oxides. Measured yields also allow for the estimation of syn:anti carbonyl oxide ratios, approximately 50:50 for trans-3-hexene and approximately 20:80 for cis-3-hexene, qualitatively consistent with our understanding of ozonide decomposition pathways. 相似文献