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61.
Eberhard Neumann Elvira Boldt Barbara Rauer Hendrik Wolf Hai Won Chang 《Macromolecular Symposia》1988,17(1):1-16
The nicotinic acetylcholine receptor (nAcChR) of the electric organ of Torpedo californica fish exhibits a pronounced hysteresis loop in the high affinity binding of the neurotransmitter acetylcholine (AcCh). When increasing amounts of AcCh are added (pulse mode) an extremely long-lived, metastable conformer distribution is obtained (lower hysteresis branch) between low affinity AcCh binding states (Rl) and high (Rh) and very high (Rvh) affinity states. Dialysis conditions always lead to the equilibrium binding curve (upper hysteresis branch; K̄A = 5 × 10−9M, 4°C; one A bound to the R-monomer of Mr ≈ 290 000). Cyclic, pulse mode addition and dilution of AcCh results in scanning loops within the main hysteresis. The kinetic analysis of the changes in free and bound AcCh during the open-system conditions of dialysis, that releases the metastability, shows that the AcCh (A) binding proceeds along an induced-fit pathway according to A+Rh ⇋ ARn ⇋ ARvh. The rate constant of the step ARh → ARvh is k2 = 6 × 10−3s−1 and that of the reverse step is k−2 = 3 × 10−4s−1. Direct binding of A to free Rvh can be excluded. Therefore, the state Rvh does not preexist, it is induced and only stable, as ARvh, by bound AcCh. The metastability can be described in terms of long-lived ARvh ·R1 hybrid dimers. Physiologically, the metastable hybrid may be viewed as a saving device: the functionally important, channel-active R1 conformer is, at low AcCh-concentrations [A] < 1μM, prevented to convert to the desensitized states Rh and ARvh. Furtheron, AcCh enhances the phosphorylation of phosphatidyl inositol and the auto-phosphorylation of the receptor. If the AcCh binding hysteresis causes a phosphorylation hysteresis the desensitized nAcChR may serve as a memory molecule of the transsynaptic information signalling of the neurotransmission. 相似文献
62.
Andy Buckley Hendrik Hoeth Heiko Lacker Holger Schulz Jan Eike von Seggern 《The European Physical Journal C - Particles and Fields》2010,65(1-2):331-357
In this article we describe Professor, a new program for tuning model parameters of Monte Carlo event generators to experimental data by parameterising the per-bin generator response to parameter variations and numerically optimising the parameterised behaviour. Simulated experimental analysis data is obtained using the Rivet analysis toolkit. This paper presents the Professor procedure and implementation, illustrated with the application of the method to tunes of the Pythia 6 event generator to data from the LEP/SLD and Tevatron experiments. These tunes are substantial improvements on existing standard choices, and are recommended as base tunes for LHC experiments, to be themselves systematically improved upon when early LHC data is available. 相似文献
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A series of N-(tosylmethyl)imino compounds [TosCH2N?C(L)A] has been prepared, and applied to a new, base-induced, one-operational synthesis of otherwise more difficultly accessible 2,3,4-trisubstituted pyrroles from electron deficient olefins. This regiospecific process probably is an 1,3-anionic cycloaddition, combined with the elimination of sulfinic acid and a leaving group L. The group A is retained as the 2-substituent of the resulting pyrroles. 相似文献
68.
In a previous work [Heinz, Castelijns, and Suter, J. Am. Chem. Soc. 115, 9500 (2003)], we developed an accurate force field and simulated the phase transitions in C18-mica (octadecyltrimethylammonium-mica) as well as the absence of such transitions in 2C18-mica (dioctadecyldimethylammonium-mica) between room temperature and 100 degrees C. Here we analyze (i) average z coordinates of the carbon atoms and interdigitation of the hydrocarbon bilayers, (ii) density profiles, and (iii) pressure profiles of the structures along all Cartesian axes. In C18-mica, the standard deviation in the z coordinate for the chain atoms is high and more than doubles in the disordered phase. The order-disorder transition is accompanied by a change in the orientation of the ammonium head group, as well as decreasing tensile and shear stress in the disordered phase. In 2C18-mica, the standard deviation in the z coordinate for the chain atoms is low and does not increase remarkably on heating. The backbones display a highly regular structure, which is slightly obscured by rotations in the C18 backbones and minor head group displacements at 100 degrees C. Close contacts between the bulky head groups with sidearms cause significant local pressure which is in part not relieved at 100 degrees C. An increase of the basal-plane spacing at higher temperature is found in both systems due to larger separation between the two hydrocarbon layers and an increased z spacing between adjacent chain atoms (=decreased tilt of the chains relative to the surface normal), and, in C18-mica only, a stronger upward orientation of the C18 chain at the ammonium head group. The likelihood for chain interdigitation between the two hydrocarbon layers is 24%-30% for C18-mica, and 65%-26% for 2C18-mica (for 20-100 degrees C). 相似文献
69.
Fernandez Ocaña M Neubert H Przyborowska A Parker R Bramley P Halket J Patel R 《The Analyst》2004,129(2):111-115
The epidemic of bovine spongiform encephalopathy (BSE) is thought to have resulted from feeding scrapie-infected sheep to cattle. This has led to a ban of feeding animals with "processed animal protein"(PAP). We report a novel approach for the mass spectrometric detection of PAP contamination in animal feedstuffs by detecting gelatine, a derivative of the major animal protein collagen. A method was developed to hydrolyse gelatine standards with hydrochloric acid, followed by detection of the derived hydrolytic peptides at m/z 828, 915, 957 and 1044 by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOF MS) and liquid chromatography electrospray ionisation mass spectrometry (LC-ESI-MS-MS). The marker peptides can be detected at concentrations of 100 ng ml(-1) gelatine in water with MALDI. The procedure was adapted to obtain a suitable peptide map of gelatine extracted from spiked feed. The ratio of signal area of the gelatine-derived peptide at m/z 1044 to the internal standard at m/z 556 is shown to relate to the total amount of gelatine present in the sample. 相似文献
70.
The interaction of C60 with single-wall carbon nanotubes (SWNTs) and graphite is studied experimentally by thermal desorption spectroscopy and theoretically by molecular-mechanics and molecular-dynamics calculations. The van der Waals parameters and force field for C60-graphene and C60-SWNT interactions are derived from the low-coverage C60 binding energy to the graphite surface. We use these to compare the efficiency of different mechanisms by which C60 can be encapsulated into SWNTs. 相似文献