Synthesis and properties of new Mo(II) complexes with N-heterocyclic and ferrocenyl ligands

New Mo(II) complexes with 2,2'-dipyridylamine (L1), [Mo(CH(3)CN)(eta(3)-C(3)H(5))(CO)(2)(L1)]OTf (C1a) and [{MoBr(eta(3)-C(3)H(5))(CO)(2)(L1)}(2)(4,4'-bipy)](PF(6))(2) (C1b), with {[bis(2-pyridyl)amino]carbonyl}ferrocene (L2), [MoBr(eta(3)-C(3)H(5))(CO)(2)(L2)] (C2), and with the new ligand N,N-bis(ferrocenecarbonyl)-2-aminopyridine (L3), [MoBr(eta(3)-C(3)H(5))(CO)(2)(L3)] (C3), were prepared and characterized by FTIR and (1)H and (13)C NMR spectroscopy. C1a, C1b, L3, and C2 were also structurally characterized by single crystal X-ray diffraction. The Mo(II) coordination sphere in all complexes features the facial arrangement of allyl and carbonyl ligands, with the axial isomer present in C1a and C2, and the equatorial in the binuclear C1b. In both C1a and C1b complexes, the L1 ligand is bonded to Mo(II) through the nitrogen atoms and the NH group is involved in hydrogen bonds. The X-ray single crystal structure of C2 shows that L2 is coordinated in a kappa(2)-N,N-bidentate chelating fashion. Complex C3 was characterized as [MoBr(eta(3)-C(3)H(5))(CO)(2)(L3)] with L3 acting as a kappa(2)-N,O-bidentate ligand, based on the spectroscopic data, complemented by DFT calculations. The electrochemical behavior of the monoferrocenyl and diferrocenyl ligands L2 and L3 has been studied together with that of their Mo(II) complexes C2 and C3. As much as possible, the nature of the different redox changes has been confirmed by spectrophotometric measurements. The nature of the frontier orbitals, namely the localization of the HOMO in Mo for both in C2 and C3, was determined by DFT studies.

Spectral gap for Glauber type dynamics for a special class of potentials

We consider an equilibrium birth and death type process for a particle system in infinite volume, the latter is described by the space of all locally finite point configurations on Rd. These Glauber type dynamics are Markov processes constructed for pre-given reversible measures. A representation for the ``carré du champ'' and ``second carré du champ'' for the associate infinitesimal generators L are calculated in infinite volume and for a large class of functions in a generalized sense. The corresponding coercivity identity is derived and explicit sufficient conditions for the appearance and bounds for the size of the spectral gap of L are given. These techniques are applied to Glauber dynamics associated to Gibbs measure and conditions are derived extending all previous known results and, in particular, potentials with negative parts can now be treated. The high temperature regime is extended essentially and potentials with non-trivial negative part can be included. Furthermore, a special class of potentials is defined for which the size of the spectral gap is as least as large as for the free system and, surprisingly, the spectral gap is independent of the activity. This type of potentials should not show any phase transition for a given temperature at any activity.

Asymptotic behavior at infinity of solutions of multidimensional second kind integral equations

We consider second kind integral equations of the form x(s) - (abbreviated x - K x = y ), in which Ω is some unbounded subset of Rn. Let Xp denote the weighted space of functions x continuous on Ω and satisfying x (s) = O(|s|-p ),s → ∞We show that if the kernel k(s,t) decays like |s — t|-q as |s — t| → ∞ for some sufficiently large q (and some other mild conditions on k are satisfied), then K ∈ B(XP) (the set of bounded linear operators on Xp), for 0 ≤ p ≤ q. If also (I - K)-1 ∈ B(X0) then (I - K)-1 ∈ B(XP) for 0 < p < q, and (I- K)-1∈ B(Xq) if further conditions on k hold. Thus, if k(s, t) = O(|s — t|-q). |s — t| → ∞, and y(s)=O(|s|-p), s → ∞, the asymptotic behaviour of the solution x may be estimated as x (s) = O(|s|-r), |s| → ∞, r := min(p, q). The case when k(s,t) = к(s — t), so that the equation is of Wiener-Hopf type, receives especial attention. Conditions, in terms of the symbol of I — K, for I — K to be invertible or Fredholm on Xp are established for certain cases (Ω a half-space or cone). A boundary integral equation, which models three-dimensional acoustic propaga-tion above flat ground, absorbing apart from an infinite rigid strip, illustrates the practical application and sharpness of the above results. This integral equation mod-els, in particular, road traffic noise propagation along an infinite road surface sur-rounded by absorbing ground. We prove that the sound propagating along the rigid road surface eventually decays with distance at the same rate as sound propagating above the absorbing ground.

Identification and expression analyses of Cytosolic Glutamine Synthetase genes in barley (Hordeum vulgare L.)

Glutamine synthetase (GS) is a key enzyme in nitrogen (N) assimilation, particularly during seed development. Three cytosolic GS isoforms (HvGS1) were identified in barley (Hordeum vulgare L. cv Golden Promise). Quantitation of gene expression, localization and response to N supply revealed that each gene plays a non-redundant role in different tissues and during development. Localization of HvGS1_1 in vascular cells of different tissues, combined with its abundance in the stem and its response to changes in N supply, indicate that it is important in N transport and remobilization. HvGS1_1 is located on chromosome 6H at 72.54 cM, close to the marker HVM074 which is associated with a major quantitative trait locus (QTL) for grain protein content (GPC). HvGS1_1 may be a potential candidate gene to manipulate barley GPC. HvGS1_2 mRNA was localized to the leaf mesophyll cells, in the cortex and pericycle of roots, and was the dominant HvGS1 isoform in these tissues. HvGS1_2 expression increased in leaves with an increasing supply of N, suggesting its role in the primary assimilation of N. HvGS1_3 was specifically and predominantly localized in the grain, being highly expressed throughout grain development. HvGS1_3 expression increased specifically in the roots of plants grown on high NH+4, suggesting that it has a primary role in grain N assimilation and also in the protection against ammonium toxicity in roots. The expression of HvGS1 genes is directly correlated with protein and enzymatic activity, indicating that transcriptional regulation is of prime importance in the control of GS activity in barley.

TNF-alpha mediated transport of NF-kappaB to the nucleus is independent of the cytoskeleton-based transport system in non-neuronal cells

In unstimulated cells, proteins of the nuclear factor kappaB (NF-kappaB) transcription factor family are sequestered in the cytoplasm through interactions with IkappaB inhibitor proteins. Tumor necrosis factor alpha (TNF-alpha) activates the degradation of IkappaB-alpha and the nuclear import of cytoplasmic NF-kappaB. Nuclear localization of numerous cellular proteins is mediated by the ability of the cytoskeleton, usually microtubules, to direct their perinuclear accumulation. In a former study we have shown that activated NF-kappaB rapidly moves from distal processes in neurons towards the nucleus. The fast transport rate suggests the involvement of motor proteins in the transport of NF-kappaB. Here we address the question how NF-kappaB arrives at the nuclear membrane before import in non-neuronal cells, i.e., by diffusion alone or with the help of active transport mechanisms. Using confocal microscopy imaging and analysis of nuclear protein extracts, we show that NF-kappaB movement through the cytoplasm to the nucleus is independent of the cytoskeleton, in the three cell lines investigated here. Additionally we demonstrate that NF-kappaB p65 is not associated with the dynein/dynactin molecular motor complex. We propose that cells utilize two distinct mechanisms of NF-kappaB transport: (1) signaling via diffusion over short distances in non-neuronal cells and (2) transport via motor proteins that move along the cytoskeleton in neuronal processes where the distances between sites of NF-kappaB activation and nucleus can be vast.

Transreal limits and elementary functions

We extend all elementary functions from the real to the transreal domain so that they are defined on division by zero. Our method applies to a much wider class of functions so may be of general interest.

Expression of the receptor tyrosine kinase ephb2 on dendritic cells is modulated by toll-like receptor ligation but is not required for t cell activation

The Eph receptor tyrosine kinases interact with their ephrin ligands on adjacent cells to facilitate contact-dependent cell communication. Ephrin B ligands are expressed on T cells and have been suggested to act as co-stimulatory molecules during T cell activation. There are no detailed reports of the expression and modulation of EphB receptors on dendritic cells, the main antigen presenting cells that interact with T cells. Here we show that mouse splenic dendritic cells (DC) and bone-marrow derived DCs (BMDC) express EphB2, a member of the EphB family. EphB2 expression is modulated by ligation of TLR4 and TLR9 and also by interaction with ephrin B ligands. Co-localization of EphB2 with MHC-II is also consistent with a potential role in T cell activation. However, BMDCs derived from EphB2 deficient mice were able to present antigen in the context of MHC-II and produce T cell activating cytokines to the same extent as intact DCs. Collectively our data suggest that EphB2 may contribute to DC responses, but that EphB2 is not required for T cell activation. This result may have arisen because DCs express other members of the EphB receptor family, EphB3, EphB4 and EphB6, all of which can interact with ephrin B ligands, or because EphB2 may be playing a role in another aspect of DC biology such as migration.

The multidimensional character of accounting numbers

This paper takes as its motivation debates surrounding the multiplicity of functions of accounting information. We are in particular interested in the existential function of accounting numbers and argue that numerical signs having discursive possibilities may acquire new meanings through reframing. Drawing on Goffman’s (1974) frame analysis and Vollmer’s (2007) work on three-dimensional character of numerical signs, we explore the ways in which numbers can go through instantaneous transformations and tell a new kind of story. In our analysis, we look at the main historical developments and current controversies surrounding accounting practice with a specific focus on scandals involving numerical signs as moments where our understandings and the discursive function of previously inoffensive signs shifts through a collective involvement. We map the purpose and usefulness of Vollmer’s three-dimensional framework in the analysis of selected financial accounting practices and scandals as examples of instances where numbers are reframed to suddenly perform a different existential function in context of their calculative and symptomatic dimensions.