Role of dispersion of vanadia on SBA-15 in the oxidative dehydrogenation of propane

A series of vanadia catalysts supported on the mesoporous silica SBA-15 are synthesized using an automated laboratory reactor. The catalysts contain from 0.6 up to 13.6V atoms/nm2 and are structurally characterized by various techniques (BET, XRD, SEM, TEM, Raman, IR, UV/Vis). Samples containing up to 3.1V/nm2 are structurally rather similar. They all contain a mixture of tetrahedral (VOx)n species, both monomeric and oligomeric. The ratio of monomeric and oligomeric species depends on the vanadia loading. At the highest loading of 13.6V/nm2, in addition to tetrahedral (VOx)n, also substantial amounts of three-dimensional, bulk-like V2O5 are present in the catalyst. The structural similarity of the low-loaded catalysts is reflected in their alike catalytical activity during the oxidative dehydrogenation (ODH) of propane between 380 and 480 °C. Propene, CO, and CO2 are formed as reaction products, while neither the formation of ethene nor acrolein or acrylic acid is observed in other than trace amounts. The activation energy for ODH of propane is not, vert, similar140 kJ/mol. The catalyst with the highest loading yields varying activation energies for different reaction conditions, which is probably related to rearrangements between bulk-like and dispersed, two-dimensional (VOx)n. Rather than the monomer to oligomer ratio, the ratio of two-dimensional to three-dimensional vanadia seems to be crucial for the catalytic properties of silica supported vanadia in the ODH of propane

Exactly solvable models in 2D semiclassical dilaton gravity and extremal black holes

Previously known exactly solvable models of 2D semiclassical dilaton gravity admit, in the general case, only non-extreme black holes. It is shown that there exist exceptional degenerate cases, that can be obtained by some limiting transitions from the general exact solution, which include, in particular, extremal and ultraextremal black holes. We also analyze properties of extreme black holes without demanding exact solvability and show that for such solutions quantum backreaction forbids the existence of ultraextreme black holes. The conditions,under which divergencies of quantum stresses in a free falling frame can disappear, are found. We derive the closed equation with respect to the metric as a function of the dilaton field that enables one, choosing the form of the metric, to restore corresponding Lagrangian. It is demonstrated that exactly solvable models, found earlier, can be extended to include an electric charge only in two cases: either the dilaton-gravitation coupling is proportional to the potential term, or the latter vanishes. The second case leads to the effective potential with a negative amplitude and we analyze, how this fact affects the structure of spacetime. We also discuss the role of quantum backreaction in the relationship between extremal horizons and the branch of solutions with a constant dilaton.Comment: 31 pages. In v.2 typo in Ref. [2] corrected, 4 references added. Accepted in Class. Quant. Gra

Generalized 2d dilaton gravity with matter fields

We extend the classical integrability of the CGHS model of 2d dilaton gravity [1] to a larger class of models, allowing the gravitational part of the action to depend more generally on the dilaton field and, simultaneously, adding fermion- and U(1)-gauge-fields to the scalar matter. On the other hand we provide the complete solution of the most general dilaton-dependent 2d gravity action coupled to chiral fermions. The latter analysis is generalized to a chiral fermion multiplet with a non-abelian gauge symmetry as well as to the (anti-)self-dual sector df = *df (df = -*df) of a scalar field f.Comment: 37 pages, Latex; typos and Eqs. (44,45) corrected; paragraph on p. 26, referring to a work of S. Solodukhin, reformulated; references adde

Significant Conditions on the Two-electron Reduced Density Matrix from the Constructive Solution of N-representability

We recently presented a constructive solution to the N-representability problem of the two-electron reduced density matrix (2-RDM)---a systematic approach to constructing complete conditions to ensure that the 2-RDM represents a realistic N-electron quantum system [D. A. Mazziotti, Phys. Rev. Lett. 108, 263002 (2012)]. In this paper we provide additional details and derive further N-representability conditions on the 2-RDM that follow from the constructive solution. The resulting conditions can be classified into a hierarchy of constraints, known as the (2,q)-positivity conditions where the q indicates their derivation from the nonnegativity of q-body operators. In addition to the known T1 and T2 conditions, we derive a new class of (2,3)-positivity conditions. We also derive 3 classes of (2,4)-positivity conditions, 6 classes of (2,5)-positivity conditions, and 24 classes of (2,6)-positivity conditions. The constraints obtained can be divided into two general types: (i) lifting conditions, that is conditions which arise from lifting lower (2,q)-positivity conditions to higher (2,q+1)-positivity conditions and (ii) pure conditions, that is conditions which cannot be derived from a simple lifting of the lower conditions. All of the lifting conditions and the pure (2,q)-positivity conditions for q>3 require tensor decompositions of the coefficients in the model Hamiltonians. Subsets of the new N-representability conditions can be employed with the previously known conditions to achieve polynomially scaling calculations of ground-state energies and 2-RDMs of many-electron quantum systems even in the presence of strong electron correlation

Dynamical N-body Equlibrium in Circular Dilaton Gravity

We obtain a new exact equilibrium solution to the N-body problem in a one-dimensional relativistic self-gravitating system. It corresponds to an expanding/contracting spacetime of a circle with N bodies at equal proper separations from one another around the circle. Our methods are straightforwardly generalizable to other dilatonic theories of gravity, and provide a new class of solutions to further the study of (relativistic) one-dimensional self-gravitating systems.Comment: 4 pages, latex, reference added, minor changes in wordin

Geometrodynamical Formulation of Two-Dimensional Dilaton Gravity

Two-dimensional matterless dilaton gravity with arbitrary dilatonic potential can be discussed in a unitary way, both in the Lagrangian and canonical frameworks, by introducing suitable field redefinitions. The new fields are directly related to the original spacetime geometry and in the canonical picture they generalize the well-known geometrodynamical variables used in the discussion of the Schwarzschild black hole. So the model can be quantized using the techniques developed for the latter case. The resulting quantum theory exhibits the Birkhoff theorem at the quantum level.Comment: 15 pages, LATE

Identifying a gene expression signature of cluster headache in blood.

Cluster headache is a relatively rare headache disorder, typically characterized by multiple daily, short-lasting attacks of excruciating, unilateral (peri-)orbital or temporal pain associated with autonomic symptoms and restlessness. To better understand the pathophysiology of cluster headache, we used RNA sequencing to identify differentially expressed genes and pathways in whole blood of patients with episodic (n = 19) or chronic (n = 20) cluster headache in comparison with headache-free controls (n = 20). Gene expression data were analysed by gene and by module of co-expressed genes with particular attention to previously implicated disease pathways including hypocretin dysregulation. Only moderate gene expression differences were identified and no associations were found with previously reported pathogenic mechanisms. At the level of functional gene sets, associations were observed for genes involved in several brain-related mechanisms such as GABA receptor function and voltage-gated channels. In addition, genes and modules of co-expressed genes showed a role for intracellular signalling cascades, mitochondria and inflammation. Although larger study samples may be required to identify the full range of involved pathways, these results indicate a role for mitochondria, intracellular signalling and inflammation in cluster headach