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31.
Peptides bind to class II major histocompatibility complex (MHC) proteins in an extended conformation. Pockets in the peptide binding site spaced to accommodate peptide side chains at the P1, P4, P6, and P9 positions have been previously characterized and help to explain the obtained peptide binding specificity. However, two peptides differing only at P10 have significantly different binding affinities for HLA-DR1. The structure of HLA-DR1 in complex with the tighter binding peptide shows that the peptide binds in the usual polyproline type II conformation, but with the P10 residue accommodated in a shallow pocket at the end of the binding groove. HLA-DR1 variants with polymorphic residues at these positions were produced and found to exhibit different side chain specificity at the P10 position. These results define a new specificity position in HLA-DR proteins. 相似文献
32.
Paramasivan Halasyamani Kevin R. Heier Michael J. Willis Charlotte L. Stern Kenneth R. Poeppelmeier 《无机化学与普通化学杂志》1996,622(3):479-485
Crystals of CuNb(pyz)2OF5 · (pyz)(H2O) ( 1 ) and [Cu(pyz)2.5]+ [NbF6]? · (pyz) ( 2 ) were grown (150°C and autogeneous pressures) from CuO, 1/2(Nb2O5), (HF)x · pyridine, and H2O in excess pyrazine. Light blue single crystals of ( 1 ) are orthorhombic, crystallizing in space group Cccm (No. 66), with a = 14.547(1) Å, b = 16.135(2) Å, c = 13.803(2) Å, and Z = 8. The structure of ( 1 ) contains corner shared [Cu(pyz)4/2F2/2]+, [Cu(pyz)4/2O2/2], and [NbF4O1/2F1/2]?0.5 octahedra. Orange crystals of ( 2 ) are monoclinic, crystallizing in space group C2/c (No. 15), with a = 11.792(8) Å, b = 17.123(3) Å, c = 17.051(5) Å, β = 90.04(4)°, and Z = 8. The structure of ( 2 ) contains puckered rings of corner shared [Cu(pyz)(pyz)3/2]+ tetrahedra and isolated [NbF6]? anions within the rings. 相似文献
33.
Dash AK Jensen TR Stern CL Marks TJ 《Journal of the American Chemical Society》2004,126(39):12528-12540
Single-site polymerization catalysts generated in situ via activation of Cp*MMe(3) (Cp* = C(5)Me(5); M = Ti, Zr), (CGC)MMe(2) (CGC = C(5)Me(4)SiMe(2)NBu(t)(); M = Ti, Zr), and Cp(2)ZrMe(2) with Ph(3)C(+)B(C(6)F(5))(4)(-) catalyze alkylation of aromatic molecules (benzene, toluene) with alpha-chloronorbornene at room temperature, to regioselectively afford the 1:1 addition products exo-1-chloro-2-arylnorbornane (aryl = C(6)H(5) (1a), C(6)H(4)CH(3) (1b)) in good yields. Analogous deuterium-labeled products exo-1-chloro-2-aryl-d(n)-norbornane-7-d(1) (aryl-d(n) = C(6)D(5) (1a-d(6)), C(6)D(4)CD(3) (1b-d(8))) are obtained via catalytic arylation of alpha-chloronorbornene in either benzene-d(6) or toluene-d(8). Isolated ion-pair complexes such as (CGC)ZrMe(toluene)(+)B(C(6)F(5))(4)(-) and Cp(2)ThMe(+)B(C(6)F(5))(4)(-) also catalyze the reaction of alpha-chloronorbornene in toluene-d(8) to give 1b-d(8) in good yields, respectively. Small quantities of the corresponding bis(1-chloronorbornyl)aromatics 2 are also obtained from preparative-scale reactions. These reactions exhibit turnover frequencies exceeding 120 h(-1) (for the Cp*TiMe(3)/Ph(3)C(+)B(C(6)F(5))(4)(-)-catalyzed system), and chlorine-free products are not observed. Compounds 1 and 2 were characterized by (1)H, (2)H, (13)C, and 2D NMR, GC-MS, and elemental analysis. The aryl group exo-stereochemistry in 1a and 1b is established using (1)H-(1)H COSY, (1)H-(13)C HMBC, and (1)H-(1)H NOESY NMR, and is further corroborated by X-ray analysis of the product 1,4-bis(exo-1-chloro-2-norbornyl)benzene (2a). Control experiments and reactivity studies on each component step suggest a mechanism involving participitation of the metal electrophiles in the catalytic cycle. 相似文献
34.
Motivated by Witten’s spinor proof of the positive mass theorem, we analyze asymptotically constant harmonic spinors on complete asymptotically flat nonspin manifolds with nonnegative scalar curvature. 相似文献
35.
A convenient laboratory scale preparation of cyanogen has been developed. This new method generates cyanogen from the pyrolysis of diacetyl-glyoxime which can be easily prepared from glyoxime. 相似文献
36.
Prof. Sergiy V. Rosokha Charlotte L. Stern Jeremy T. Ritzert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(27):8774-8788
The nature of halogen bonding is examined via experimental and computational characterizations of a series of associates between electrophilic bromocarbons R? Br (R? Br=CBr3F, CBr3NO2, CBr3COCBr3, CBr3CONH2, CBr3CN, etc.) and bromide anions. The [R? Br, Br?] complexes show intense absorption bands in the 200–350 nm range which follow the same Mulliken correlation as those observed for the charge‐transfer associates of bromide anions with common organic π‐acceptors. For a wide range of the associates, intermolecular R? Br???Br? separations decrease and intramolecular C? Br bond lengths increase proportionally to the Br?→R? Br charge transfer; and the energies of R? Br???Br? bonds are correlated with the linear combination of orbital (charge‐transfer) and electrostatic interactions. On the whole, spectral, structural and thermodynamic characteristics of the [R? Br, Br?] complexes indicate that besides electrostatics, the orbital (charge‐transfer) interactions play a vital role in the R? Br???Br? halogen bonding. This indicates that in addition to controlling the geometries of supramolecular assemblies, halogen bonding leads to electronic coupling between interacting species, and thus affects reactivity of halogenated molecules, as well as conducting and magnetic properties of their solid‐state materials. 相似文献
37.
J. Budagov V. Glagolev M. Lyablin G. Shirkov H. Mainaud Durand G. Stern 《Physics of Particles and Nuclei Letters》2014,11(3):286-293
The next generation of linear colliders is very demanding concerning the alignment tolerances of their components. For the CLIC project, the reference axis of the components will have to be pre-aligned within 10 μm at 1 sigma with respect to a straight line in a sliding window of 200 m. A solution based on stretched wires with wire positioning sensors has been proposed in order to fulfill the alignment requirements in the Conceptual Design Report of the project. This solution has some drawbacks and laser based alternative solutions are under study in order to validate the wire solution and possibly replace it. A new proposal is introduced in this paper, using a laser beam over 150 m as a straight alignment reference, with the objective of having an uncertainty in the determination of its straightness within 10 μm. Sensors coupled to the components to be aligned, would provide after calibration the horizontal and vertical offsets with respect to the laser beam, within a few micrometers, in their coordinate system. The method is based on the laser beam space stabilization effect when a beam propagates in atmospheric air inside a pipe with standing acoustic wave. The principal schemes of corresponding optoelectronics devices and temperature stabilization solutions are also proposed, making probable the extension of the laser fiducial line up to a 500 m length. 相似文献
38.
39.
Bin Du Adam Langlois Daniel Fortin Christine Stern Pierre D. Harvey 《Journal of Cluster Science》2012,23(3):737-751
The title cluster is luminescent at 77?K and exhibits an unsaturated site for binding anions when the counter ion is PF6 ?. A series of five non-luminescent metalloporphyrins exhibiting carboxylate anchoring groups were synthesized and characterized. These are the sodium salts of the 5-carboxyphenyl-tri-10,15,20-tolyl-, trans-di-5,10-carboxyphenyl-di-15,20-tolyl-, and tetra-5,10,15,20-carboxyphenyl(metallo)porphyrin (metallo?=?chloroiron(III), nickel(II)) anions. Evidence for supramolecular assemblies between the carboxylates and the cluster is provided by 31P NMR and UV?Cvis spectroscopy. The binding constant, K1n, extracted from the UV?Cvis data via Benesi-Hildebrand, Scott and Scatchard plots are approximately 21,000?±?5,000?M?1 for the nickel(II) species, in agreement with the previously reported zinc(II) ones (K11?=?20,000?±?2,000?M?1), but those for the chloroiron(III) are measured to be lower (12,500?±?3,500?M?1). This association is accompanied by a complete quenching of the luminescence of the cluster which can only be due to an efficient energy transfer to the d?Cd states of the chloroiron(III) and nickel(II) species but an electron transfer from the nickel(II)-containing chromophore to the cluster is also possible. This work demonstrates the profound effect that supramolecular interactions may have on the photophysical properties despite the long donor?Cacceptor separation. 相似文献
40.