Pulsed-field gradient nuclear magnetic resonance study of transport properties of fluid catalytic cracking catalysts

Pulsed-field gradient nuclear magnetic resonance (PFG NMR) has been applied to study molecular diffusion in industrial fluid catalytic cracking (FCC) catalysts and in USY zeolite for a broad range of molecular displacements and temperatures. The results of this study have been used to elucidate the relevance of molecular transport on various displacements for the rate of molecular exchange between catalyst particles and their surroundings. It turned out that this rate, which may determine the overall rate and selectivity of FCC process, is primarily related to the diffusion mode associated with displacements larger than the size of zeolite crystals located in the particles but smaller than the size of the particles. This conclusion has been confirmed by comparative studies of the catalytic performance of different FCC catalysts.     

Parkin-deficient mice are not more sensitive to 6-hydroxydopamine or methamphetamine neurotoxicity

Background  

Autosomal recessive juvenile parkinsonism (AR-JP) is caused by mutations in the parkin gene which encodes an E3 ubiquitin-protein ligase. Parkin is thought to be critical for protecting dopaminergic neurons from toxic insults by targeting misfolded or oxidatively damaged proteins for proteasomal degradation. Surprisingly, mice with targeted deletions of parkin do not recapitulate robust behavioral or pathological signs of parkinsonism. Since Parkin is thought to protect against neurotoxic insults, we hypothesized that the reason Parkin-deficient mice do not develop parkinsonism is because they are not exposed to appropriate environmental triggers. To test this possibility, we challenged Parkin-deficient mice with neurotoxic regimens of either methamphetamine (METH) or 6-hydroxydopamine (6-OHDA). Because Parkin function has been linked to many of the pathways involved in METH and 6-OHDA toxicity, we predicted that Parkin-deficient mice would be more sensitive to the neurotoxic effects of these agents.     

The puzzle of contrast inversion in DNA STM imaging

DNA has been at the center of an imaging effort since the invention of the scanning tunneling microscope (STM). In some of the STM imaging reports the molecules appeared with negative contrast, i.e., "submerged" under the metal background and darker. We demonstrate the phenomenon of contrast inversion in DNA STM imaging by controlled and spontaneous contrast inversions and by the dependence of the DNA apparent height with respect to the surface on the imaging bias voltage. Using these characterizations, we formulate a model explaining the above phenomenon by resonant tunneling through virtual states in the vacuum between the STM tip and the DNA molecule.     

Bundle Gerbes for Chern-Simons and Wess-Zumino-Witten Theories

We develop the theory of Chern-Simons bundle 2-gerbes and multiplicative bundle gerbes associated to any principal G-bundle with connection and a class in H⁴(BG, ℤ) for a compact semi-simple Lie group G. The Chern-Simons bundle 2-gerbe realises differential geometrically the Cheeger-Simons invariant. We apply these notions to refine the Dijkgraaf-Witten correspondence between three dimensional Chern-Simons functionals and Wess-Zumino-Witten models associated to the group G. We do this by introducing a lifting to the level of bundle gerbes of the natural map from H⁴(BG, ℤ) to H³(G, ℤ). The notion of a multiplicative bundle gerbe accounts geometrically for the subtleties in this correspondence for non-simply connected Lie groups. The implications for Wess-Zumino-Witten models are also discussed.The authors acknowledge the support of the Australian Research Council. ALC thanks MPI für Mathematik in Bonn and ESI in Vienna and BLW thanks CMA of Australian National University for their hospitality during part of the writing of this paper.     

Comparative analysis of the conformational profile of substance P using simulated annealing and molecular dynamics

The present study describes an extensive conformational search of substance P using two different computational methods. On the one hand, the peptide was studied using the iterative simulated annealing, and on the other, molecular dynamics simulations at 300 and 400 K. With the former method, the peptide was studied in vacuo with a dielectric constant of 80, whereas using the latter study the peptide was studied in a box of TIP3P water molecules. Analysis of the results obtained using both methodologies was carried out using an in-house methodology using a cluster analysis method based on information theory. Comparison of the two sampling methodologies and the different environment used in the calculations is also analyzed. Finally, the conformational motifs that are characteristic of substance P in a hydrophilic environment are presented and compared with the experimental results available in the literature.     

Chern Character in Twisted K-Theory: Equivariant and Holomorphic Cases

 It was argued in [25, 5] that in the presence of a nontrivial B-field, D-brane charges in type IIB string theories are classified by twisted K-theory. In [4], it was proved that twisted K-theory is canonically isomorphic to bundle gerbe K-theory, whose elements are ordinary Hilbert bundles on a principal projective unitary bundle, with an action of the bundle gerbe determined by the principal projective unitary bundle. The principal projective unitary bundle is in turn determined by the twist. This paper studies in detail the Chern-Weil representative of the Chern character of bundle gerbe K-theory that was introduced in [4], extending the construction to the equivariant and the holomorphic cases. Included is a discussion of interesting examples. Received: 10 January 2002 / Accepted: 9 December 2002 Published online: 25 February 2003 RID="⋆" ID="⋆" The authors acknowledge the support of the Australian Research Council Communicated by R.H. Dijkgraaf     

Electronic and steric effects in thermal denitrosation of N-nitrosoamides

N-Alkyl-N-nitrosoamides undergo competitive reactions whose rates are dependent upon the interplay of a number of factors. There already exists a significant body of work delineating the effects of pH on the partitioning of the nitrosoamides along their deaminative (-N(2)) and denitrosative (-"NO(+)") pathways. In this paper, the issue of pH dependence is discussed with particular attention to nitrosoamide decompositions in nonaqueous media. The role of the acidity of the medium in the partitioning of the nitrosoamide between deamination and denitrosation and in the choice of deaminative pathways is revisited. In nonaqueous media under near-neutral conditions, the partitioning's pH dependence is evidently accompanied by a sensitivity to structural features in the nitrosoamide. Thus, diminution of steric crowding around the N-nitroso moiety as well as the presence of strongly electron-withdrawing acyl units (i.e., those derived from strong acids, e.g., tosyl and trifyl) increase the relative yield of amides by encouraging the denitrosative pathway. A mechanism for thermal denitrosation of nitrosoamides under near-neutral conditions is proposed in which rapid protonation at the acyl O rather than slow protonation at the amidic N is the first step in the reaction profile. A rate-limiting, bimolecular reaction between the O-conjugate acid and adventitious nucleophiles at the nitrosyl group then occurs followed by rapid tautomerization to amide.     

Tetrahedral onsager crosses for solubility improvement and crystallization bypass

Pure organic molecules exhibiting a suitable concave rigid shape are expected to give porous glasses in the solid state. Such a feature opens new opportunities to avoid crystallization and to improve molecular solubility in relation to the high internal energy of these solid phases. To quantitatively explore the latter strategy, a series of rigid tetrahedral conjugated molecules nC and the corresponding models nR have been synthesized. Related to the present purpose, several properties have been investigated using UV absorption, steady-state fluorescence emission, differential scanning calorimetry, (1)H NMR translational self-diffusion, magic angle spinning (13)C NMR, and multiple-beam interferometry experiments. The present tetrahedral crosses are up to 8 orders of magnitude more soluble than the corresponding model compounds after normalization to the same molecular length. In addition, they give concentrated monomeric solutions that can be used to cover surfaces with homogeneous films whose thickness goes down to the nanometer range. Such attractive features make cross-like molecular architectures promising for many applications.