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Cumulant functions are introduced to describe the statistical state of a radiation field. These functions are simply related
to the optical coherence functions but have some interesting features. It is shown that if the cumulant functions of all orders
greater than some numberN
0 vanish then they also vanish for all orders greater than 2. Thermal field is the only field having this property. This property
holds whether the field is described by a classical stochastic process or by a quantum density operator. Further the particular
operator ordering used in defining these cumulant functions for the quantized field affects only the second order cumulant
function. To describe the statistical state of a vector field such as partially polarized or unpolarized radiation, one would
need to introduce cumulant tensors. 相似文献
2.
MA Freitas CL Hendrickson AG Marshall 《Rapid communications in mass spectrometry : RCM》1999,13(15):1639-1642
We present a novel approach for the determination of activation energy for the unimolecular dissociation of a large (>50 atoms) ion, based on measurement of the unimolecular dissociation rate constant as a function of continuous-wave CO(2) laser intensity. Following a short ( approximately 1 s) induction period, CO(2) laser irradiation produces an essentially blackbody internal energy distribution, whose 'temperature' varies inversely with laser intensity. The only currently available method for measuring such activation energies is blackbody infrared radiative dissociation (BIRD). Compared with BIRD, FRAGMENT: (a) eliminates the need to heat the surrounding ion trap and vacuum chamber to each of several temperatures (each requiring hours for temperature equilibration); (b) offers a three-fold wider range of effective blackbody temperature; and (c) extends the range of applications to include initially cold ions (e.g., gas-phase H/D exchange). Our FRAGMENT-determined activation energy for dissociation of protonated bradykinin, 1.2 +/- 0.1 eV, agrees within experimental error to the value, 1.3 +/- 0.1 eV, previously reported by Williams et al. from BIRD experiments. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
3.
This article provides a detailed analysis of the behavior of suprema and moduli of continuity for a large class of random fields which generalize Gaussian processes, sub-Gaussian processes, and random fields that are in the nth chaos of a Wiener process. An upper bound of Dudley type on the tail of the random field's supremum is derived using a generic chaining argument; it implies similar results for the expected supremum, and for the field's modulus of continuity. We also utilize a sharp and convenient condition using iterated Malliavin derivatives, to arrive at similar conclusions for suprema, via a different proof, which does not require full knowledge of the covariance structure. 相似文献
4.
Matthew R. Mehlenbacher Rahma Elsiesy Rabina Lakha Rhiza Lyne E. Villones Marina Orman Christina L. Vizcarra Gabriele Meloni Dean E. Wilcox Rachel N. Austin 《Chemical science》2022,13(18):5289
Metallothioneins (MTs) are a ubiquitous class of small metal-binding proteins involved in metal homeostasis and detoxification. While known for their high affinity for d10 metal ions, there is a surprising dearth of thermodynamic data on metals binding to MTs. In this study, Zn2+ and Cu+ binding to mammalian metallothionein-3 (MT-3) were quantified at pH 7.4 by isothermal titration calorimetry (ITC). Zn2+ binding was measured by chelation titrations of Zn7MT-3, while Cu+ binding was measured by Zn2+ displacement from Zn7MT-3 with competition from glutathione (GSH). Titrations in multiple buffers enabled a detailed analysis that yielded condition-independent values for the association constant (K) and the change in enthalpy (ΔH) and entropy (ΔS) for these metal ions binding to MT-3. Zn2+ was also chelated from the individual α and β domains of MT-3 to quantify the thermodynamics of inter-domain interactions in metal binding. Comparative titrations of Zn7MT-2 with Cu+ revealed that both MT isoforms have similar Cu+ affinities and binding thermodynamics, indicating that ΔH and ΔS are determined primarily by the conserved Cys residues. Inductively coupled plasma mass spectrometry (ICP-MS) analysis and low temperature luminescence measurements of Cu-replete samples showed that both proteins form two Cu4+–thiolate clusters when Cu+ displaces Zn2+ under physiological conditions. Comparison of the Zn2+ and Cu+ binding thermodynamics reveal that enthalpically-favoured Cu+, which forms Cu4+–thiolate clusters, displaces the entropically-favoured Zn2+. These results provide a detailed thermodynamic analysis of d10 metal binding to these thiolate-rich proteins and quantitative support for, as well as molecular insight into, the role that MT-3 plays in the neuronal chemistry of copper.Metallothioneins (MTs) are a ubiquitous class of small metal-binding proteins involved in metal homeostasis and detoxification. 相似文献
5.
Characterization and surface properties of amino-acid-modified carbonate-containing hydroxyapatite particles 总被引:2,自引:0,他引:2
Jack KS Vizcarra TG Trau M 《Langmuir : the ACS journal of surfaces and colloids》2007,23(24):12233-12242
The surface properties (nature, strength, and stability of interaction of functional groups) and bulk morphologies of a series of amino-acid-functionalized carbonate-containing hydroxyapatite (CHA) particles were investigated. It was found that the amino acids were both occluded in and presented on the surface of the CHA particles. Furthermore, their presence enhanced particle colloidal stability by retardation of Ostwald ripening and in some cases increasing the magnitude of the zeta-potential. Measurements of adsorption isotherms and zeta-potential titrations have shown that the amino-acid-surface interactions are weak and reversible at pH 9 and consistent with a model in which the carboxyl terminus interacts with calcium ions in the CHA lattice. Complexities in adsorption behavior are discussed in terms of different adsorption mechanisms that may be prevalent at different pHs. 相似文献
6.
铌酸锶钡薄膜的微结构与电光性能的研究 总被引:3,自引:1,他引:2
本文叙述了使用溶胶凝胶法在MgO(0 0 1)的衬底上制备铌酸锶钡薄膜的过程 ,膜层厚度可达 5 μm。通过X射线衍射、摇摆曲线、扫描、拉曼散射光谱等方法研究了薄膜的微结构性能 ,实验发现 ,铌酸锶钡薄膜具有了较好的 (0 0 1)方向的优先取向性能 ,并且随着薄膜厚度的增加 ,其晶体取向性也会随之不断改进。熔石英的透明衬底上生长的SBN薄膜具有较大的电致双折射效应 ,其有效电光系数能够高达 6 6 2× 10 -11m/V。 相似文献
7.
Vizcarra CL Zhang N Marshall SA Wingreen NS Zeng C Mayo SL 《Journal of computational chemistry》2008,29(7):1153-1162
Our goal is to develop accurate electrostatic models that can be implemented in current computational protein design protocols. To this end, we improve upon a previously reported pairwise decomposable, finite difference Poisson-Boltzmann (FDPB) model for protein design (Marshall et al., Protein Sci 2005, 14, 1293). The improvement involves placing generic sidechains at positions with unknown amino acid identity and explicitly capturing two-body perturbations to the dielectric environment. We compare the original and improved FDPB methods to standard FDPB calculations in which the dielectric environment is completely determined by protein atoms. The generic sidechain approach yields a two to threefold increase in accuracy per residue or residue pair over the original pairwise FDPB implementation, with no additional computational cost. Distance dependent dielectric and solvent-exclusion models were also compared with standard FDPB energies. The accuracy of the new pairwise FDPB method is shown to be superior to these models, even after reparameterization of the solvent-exclusion model. 相似文献
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