Protein-matrix coupling/uncoupling in "dry" systems of photosynthetic reaction center embedded in trehalose/sucrose: the origin of trehalose peculiarity

Trehalose is a nonreducing disaccharide of glucose found in organisms, which can survive adverse conditions such as extreme drought and high temperatures. Furthermore, isolated structures, as enzymes or liposomes, embedded in trehalose are preserved against stressing conditions [see, e.g., Crowe, L. M. Comp. Biochem. Physiol. A 2002, 131, 505-513]. Among other hypotheses, such protective effect has been suggested to stem, in the case of proteins, from the formation of a water-mediated, hydrogen bond network, which anchors the protein surface to the water-sugar matrix, thus coupling the internal degrees of freedom of the biomolecule to those of the surroundings [Giuffrida, S.; et al. J. Phys. Chem. B 2003, 107, 13211-13217]. Analogous protective effect is also accomplished by other saccharides, although with a lower efficiency. Here, we studied the recombination kinetics of the primary, light-induced charge separated state (P(+)Q(A)(-)) and the thermal stability of the photosynthetic reaction center (RC) of Rhodobacter sphaeroides in trehalose-water and in sucrose-water matrixes of decreasing water content. Our data show that, in sucrose, at variance with trehalose, the system undergoes a "nanophase separation" when the water/sugar mole fraction is lower than the threshold level approximately 0.8. We rationalize this result assuming that the hydrogen bond network, which anchors the RC surface to its surrounding, is formed in trehalose but not in sucrose. We suggest that both the couplings, in the case of trehalose, and the nanophase separation, in the case of sucrose, start at low water content when the components of the system enter in competition for the residual water.     

Through-space interactions between parallel-offset arenes at the van der Waals distance: 1,8-diarylbiphenylene syntheses, structure and QM computations

A model for studying polar-pi interactions between arenes spaced at van der Waals distances is developed on the basis of peri-diarylbiphenylenes. A set of 1,8-diarylbiphenylenes is synthesized comprising two Hammett series, one with reference to mesityl ring interactions and the other with reference to pentafluorophenyl ring interactions. X-Ray crystal structures of several derivatives are determined. Barriers to rotation of the probe aryl ring are derived from dynamic NMR data and show a trend for the mesityl reference series (DeltaG(not equal) vs. sigma(0)). The model is also used as a test for comparison of modern density functional methods, including B3LYP, M06-2X and BMK functionals; dispersive effects are seen to be an important factor in the proper theoretical treatment of arene interactions.     

Recurrence analysis on Julia sets of semigroups of complex polynomials

We introduce a recurrence function in order to analyze the dynamics of semigroups of complex polynomials. We show that under a regularity hypothesis, the recurrence function is continuous in the complex plane. This is a new notion even for the case of a semigroup with just one generator.     

Generic entanglement and standard form for N-mode pure Gaussian states

We investigate the correlation structure of pure N-mode Gaussian resources which can be experimentally generated by means of squeezers and beam splitters, whose entanglement properties are generic. We show that those states are specified (up to local unitaries) by N(N-1)/2 parameters, corresponding to the two-point correlations between any pair of modes. Our construction yields a practical scheme to engineer such generic-entangled N-mode pure Gaussian states by linear optics. We discuss our findings in the framework of Gaussian matrix product states of harmonic lattices, raising connections with entanglement frustration and the entropic area law.     

Handling the particle size and distribution of Fe3O4 nanoparticles through ball milling

A series of samples consisting of spinel Fe₃O₄ nanoparticles with controlled particle sizes and increasing concentration has been obtained through ‘mild’ ball milling (BM) experiments by using an organic carrier liquid. We have succeeded in producing quite narrow particle size distributions with mean values d7–10 nm by an appropriate choice of the milling time for each concentration. The method proved to be practical to tailor the final particle size without formation of undesirable phases. All samples showed superparamagnetic behavior at room temperature, with transition to a blocked state at T_B10–20 K. The mean value and distribution width of the size distributions for the three samples studied were obtained from M(H) cycles recorded at T>T_B showing good agreement with X-ray diffraction and electron microscopy results. The effect of increasing interparticle interactions was to shift T_B upwards, as inferred from magnetization measurements. Mössbauer spectra at low temperatures showed no evidence of enhanced spin disorder.     

Monogamy inequality for distributed gaussian entanglement

We show that for all n-mode Gaussian states of continuous variable systems, the entanglement shared among n parties exhibits the fundamental monogamy property. The monogamy inequality is proven by introducing the Gaussian tangle, an entanglement monotone under Gaussian local operations and classical communication, which is defined in terms of the squared negativity in complete analogy with the case of n-qubit systems. Our results elucidate the structure of quantum correlations in many-body harmonic lattice systems.     

Strong monogamy of bipartite and genuine multipartite entanglement: the Gaussian case

We demonstrate the existence of general constraints on distributed quantum correlations, which impose a trade-off on bipartite and multipartite entanglement at once. For all N-mode Gaussian states under permutation invariance, we establish exactly a monogamy inequality, stronger than the traditional one, that by recursion defines a proper measure of genuine N-partite entanglement. Strong monogamy holds as well for subsystems of arbitrary size, and the emerging multipartite entanglement measure is found to be scale invariant. We unveil its operational connection with the optimal fidelity of continuous variable teleportation networks.     

Influence of temperature on the colloidal stability of the F-DPPC and DPPC liposomes induced by lanthanum ions

The influence of La(3+) on the colloidal stability of liposomes made up by two zwitterionic phospholipids, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1-palmitoyl-2-[16-fluoropalmitoyl-phosphatidylcholine (F-DPPC), in aqueous media has been investigated by dynamic light scattering and electrophoretic mobility. The critical aggregation concentration (c.a.c.) of La(3+) for F-DPPC and DPPC liposomes were experimentally obtained, and the results were compared with theoretical predictions using the Derjaguin-Landau-Verwey-Overbeek theory. In order to evaluate the influence of the state of the bilayer on the stability of liposomes, all experiments were performed at temperatures below and above the chain-melting phase-transition temperature of lipids (transition temperature of lipids). Changes in the size of both types of liposomes and high values of polydispersity in the presence of La(3+) showed that these ions induce aggregation of liposomes at 25 °C and at 60 °C. At 25 °C, when the bilayer of F-DPPC liposomes is interdigited, DPPC liposomes are more resistant to aggregation than the liposomes formed with F-DPPC. However, this difference disappears at 60 °C, when both bilayers have the same conformation. The experimental results also indicate that the c.a.c. is higher at 60 °C than at 25 °C for both types of liposomes. In fact, it has been observed by dynamic light scattering measurements that aggregation of liposomes at 25 °C can be prevented by increasing the solution temperature for La(3+) concentrations near to the c.a.c. Moreover, the behavior of these liposomes in the presence of the ion was studied at temperatures above and below the transition temperature of the phospholipids.     

Ferromagnetic alloys: A Cluster-Bethe-lattice approach

We apply the Cluster-Bethe-lattice method to calculate the local density of one-magnon states for a binary substitutional ferromagnetic alloy. Short range order effects for the alloy are included. Simple clusters of one atom and one atom plus its nearest neighbors are studied. We show that, for the latter type of cluster, there are localized excitations the energies of which fall outside the continuum of excitations.