Search of self-organized criticality processes in magnetically confined plasmas: hints from the reversed field pinch configuration

In order to test the self-organized criticality (SOC) paradigm in transport processes, a novel technique has been applied for the first time to plasmas confined in reversed field pinch configuration. This technique consists of an analysis of the probability distribution function of the times between bursts in density fluctuations measured by microwave reflectometry and electrostatic probes. The same analysis has also been applied to intermittent events sorted out from the Gaussian background. In both cases, the experimental results disagree with the predictions for a SOC system.     

Neighbor Sum Distinguishing Index

We consider proper edge colorings of a graph G using colors of the set {1, . . . , k}. Such a coloring is called neighbor sum distinguishing if for any pair of adjacent vertices x and y the sum of colors taken on the edges incident to x is different from the sum of colors taken on the edges incident to y. The smallest value of k in such a coloring of G is denoted by ndi_Σ(G). In the paper we conjecture that for any connected graph G ≠ C ₅ of order n ≥ 3 we have ndi_Σ(G) ≤ Δ(G) + 2. We prove this conjecture for several classes of graphs. We also show that ndi_Σ(G) ≤ 7Δ(G)/2 for any graph G with Δ(G) ≥ 2 and ndi_Σ(G) ≤ 8 if G is cubic.     

Topological estimator of block entanglement for Heisenberg antiferromagnets

We introduce a computable estimator of block entanglement entropy for many-body spin systems admitting total singlet ground states. Building on a simple geometrical interpretation of entanglement entropy of the so-called valence bond states, this estimator is defined as the average number of common singlets to two subsystems of spins. We show that our estimator possesses the characteristic scaling properties of the block entanglement entropy in critical and noncritical one-dimensional Heisenberg systems. We invoke this new measure to examine entanglement scaling in the two-dimensional Heisenberg model on a square lattice revealing an "area law" for the gapped phase and a logarithmic correction to this law in the gapless phase.     

To be dinuclear or not: Z-DNA induction by nickel complexes

The left-handed Z-DNA has been identified as a gene regulating element. Therefore the generation of Z-DNA through metal complexes might be an innovative way for the regulation of gene expression. Use of the new dinuclear complex N,N,N',N'-tetrakis-[2-(3,5-dimethylpyrazol-1-yl)ethyl]-1,3-propylenediamine-bis(nickel(II) dinitrate) (2) reversibly induced Z-DNA formation. However, when a 1:1 ratio of metal/dinucleating ligand was used as a control, the midpoint of the B- to Z-DNA transition was at the same nickel concentration as in case of the dinuclear complex. The novel mononuclear analogue, N-methyl-N,N-bis-[2-(3,5-dimethylpyrazol-1-yl)ethyl]amine-nickel(II)-dinitrate (3) was inducing the Z-DNA at a similar ratio versus nucleotides as free nickel(II) itself. For the first time, proton and nickel binding constants for the bis-[2-(pyrazol-1-yl)ethyl]amine ligand system are reported and discussed. Both nickel complexes 2 and 3 were structurally characterized by single crystal analysis. Furthermore, the synthesis of the two new ligands, N,N,N',N'-tetrakis-[2-(3,5-dimethylpyrazol-1-yl)ethyl]-1,2-propylenediamine (4) and N-methyl-N,N-bis-[2-(3,5-dimethylpyrazol-1-yl)ethyl]amine (5) is described. The two major synthetic pathways leading to polypyrazoyl amines in general are critically discussed with respect to yield, reproducibility and handling of the intermediates.     

Catalytic itinerary in 1,3-1,4-β-glucanase unraveled by QM/MM metadynamics. Charge is not yet fully developed at the oxocarbenium ion-like transition state

Retaining glycoside hydrolases (GHs), key enzymes in the metabolism of polysaccharides and glycoconjugates and common biocatalysts used in chemoenzymatic oligosaccharide synthesis, operate via a double-displacement mechanism with the formation of a glycosyl-enzyme intermediate. However, the degree of oxocarbenium ion character of the reaction transition state and the precise conformational itinerary of the substrate during the reaction, pivotal in the design of efficient inhibitors, remain elusive for many GHs. By means of QM/MM metadynamics, we unravel the catalytic itinerary of 1,3-1,4-β-glucanase, one of the most active GHs, belonging to family 16. We show that, in the Michaelis complex, the enzyme environment restricts the conformational motion of the substrate to stabilize a (1,4)B/(1)S(3) conformation of the saccharide ring at the -1 subsite, confirming that this distortion preactivates the substrate for catalysis. The metadynamics simulation of the enzymatic reaction captures the complete conformational itinerary of the substrate during the glycosylation reaction ((1,4)B/(1)S(3) -(4)E/(4)H(3) - (4)C(1)) and shows that the transition state is not the point of maximum charge development at the anomeric carbon. The overall catalytic mechanism is of dissociative type, and proton transfer to the glycosidic oxygen is a late event, clarifying previous kinetic studies of this enzyme.     

Resting and active states of the ERK2:HePTP complex

The MAP kinase ERK2 (ERK2, extracellular signal-regulated kinase 2) is regulated by numerous phosphatases that tightly control its activity. For example, the hematopoietic tyrosine phosphatase (HePTP) negatively regulates T cell activation in lymphocytes via ERK2 dephosphorylation. However, only very limited structural information is available for these biologically important complexes. Here, we use small-angle X-ray scattering combined with EROS ensemble refinement to characterize the structures of the resting and active states of ERK2:HePTP complexes. Our data show that the resting state ERK2:HePTP complex adopts a highly extended, dynamic conformation that becomes compact and ordered in the active state complex. This work experimentally demonstrates that these complexes undergo significant dynamic structural changes in solution and provides the first structural insight into an active state MAPK complex.     

Photocatalytic properties of nanocrystalline TiO<Subscript>2</Subscript> thin films doped with Tb

In this work photocatalytic properties of TiO₂ thin films doped with different amount of Tb have been described. Thin films were prepared by high energy reactive magnetron sputtering process. Comparable photocatalytic activity has been found for all doped TiO₂ thin films, while different amounts of Tb dopant (0.4 and 2.6 at. %) results in either an anatase or rutile structure. It was found that the terbium dopant incorporated into TiO₂ was also responsible for the amount of hydroxyl groups and water particles adsorbed on the thin film surfaces and thus photocatalytic activity was few times higher in comparison with results collected for undoped TiO₂ thin films.     

Stereoselective synthesis of P-stereogenic aminophosphines: ring opening of bulky oxazaphospholidines

A highly diastereoselective and efficient synthesis of P-stereogenic bulky alkyl and aryl aminophosphines that relies on ring opening of tert-butyl-oxazaphospholidine 2 is described. Ring opening with several organometallic reagents takes place with inversion of configuration at the phosphorus center as it has been demonstrated by X-ray analysis of two ring-opened intermediates. The unprecedented reactivity observed is attributed to the presence of a free NH functionality that facilitates the attack of the organometallic reagent in an S(N)2@P-type process.