Thermoelectric behavior of Ruddlesden-Popper series iridates

The goal of this work is studying the evolution of thermoelectric transport across the members of the Ruddlesden-Popper series iridates Srn+1IrnO3n+1, where a metal-insulator transition driven by bandwidth change occurs, from the strongly insulating Sr2IrO4 to the metallic non Fermi liquid behavior of SrIrO3. Sr2IrO4 (n=1), Sr3Ir2O7 (n=2) and SrIrO3 (n=inf.) polycrystals are synthesized at high pressure and characterized by structural, magnetic, electric and thermoelectric transport analyses. We find a complex thermoelectric phenomenology in the three compounds. Thermal diffusion of charge carriers accounts for the Seebeck behavior of Sr2IrO4, whereas additional drag mechanisms come into play in determining the Seebeck temperature dependence of Sr3Ir2O7 and SrIrO3. These findings reveal close relationship between magnetic, electronic and thermoelectric properties, strong coupling of charge carriers with phonons and spin fluctuations as well as relevance of multiband description in these compounds.Comment: main paper + supplementary informatio

Ferroelectric order driven Eu3+ photoluminescence in BaZrxTi1−xO3 perovskite

The ability to tune and enhance the properties of luminescent materials is essential for enlarging their application potential. Recently, the modulation of the photoluminescence emission of lanthanide-doped ferroelectric perovskites by applying an electric field has been reported. Herein, we show that the ferroelectric order and, more generally the polar order, has a direct effect on the photoluminescence of Eu3+ in the model BaZrxTi1-xO3 perovskite even in the absence of an external field. The dipole arrangement evolves with increasing xfrom long-range ferroelectric order to short-range order typical of relaxors until the non-polar paraelectric BaZrO3 is achieved. The cooperative polar interactions existing in the lattice (x < 1) promote the off-center displacement of the Eu3+ ion determining a change of the lanthanide site symmetry and, consequently, an abrupt variation of the photoluminescence emission with temperature. Each type of polar order is characterized by a distinct photoluminescence behaviour

The emergence of memory in liquid crystals

The nematic phase of liquid crystals (LC), used in most LC display applications, is a fluid state formed by orientationally ordered molecules. The direction of their alignment, and hence the overall optical response of the material, is easily modified by the application of an electric field and elastically relaxes back to a well-defined off-state when the field is removed. It has been recently shown that hybrid materials formed by nematic LCs incorporated in complex micro-structured porous matrices are often capable of indefinitely retaining the alignment direction imposed by an electric field. Such multistability is ultimately due to the interactions of the porous material with the lines of topological defects that develop within the confined nematic. Controlling the defect lines and their interactions is crucial to the design of materials whose optical properties are electrically driven but spontaneously preserved

Dynamics of Structural Elements of GB1 &#946;-Hairpin Revealed by Tryptophan-Cysteine Contact Formation Experiments

Quenching of the triplet state of tryptophan by close contact with cysteine provides a tool for measuring the rate of intramolecular contact formation, one of the most elementary events in the folding process, in peptides and proteins using only natural probes. Here we present a study performed on a stabilized mutant of the second \u3b2-hairpin of the GB1 domain, where we combine steady-state fluorescence, laser-induced temperature-jump, and contact formation measurements to unveil the role of elementary structural components on hairpin dynamics and overall stability. In particular, our methodology provides access to the conformational dynamics of both the folded and unfolded state of the hairpin under native conditions, revealing the presence of extremely slow dynamics on the microsecond time scale in the unfolded state and coexistence of structures with partial pairing of the tails in the folded state. Comparing model peptides that mimic the turn sequence, we found that both ion pairing and hydrogen bonding due to the threonine side chain contribute to the propensity of turn formation but not to the much slower dynamics of the hydrophobic core formation. Interestingly, the dynamics of the turn region in isolation are significantly faster than the dynamics measured for the unfolded state of the complete hairpin, suggesting that non-native hydrophobic contacts slow down the reconfiguration dynamics of the unfolded state. Overall, the information extracted from these experiments provides kinetic limits on interconversions among conformational populations, hence enabling a simplified multistate free-energy landscape for the GB1 hairpin to be drawn

Origin of Life Scenarios: between Fantastic Luck and Marvelous Fine-Tuning

The unequivocal sign of creativity in science is the emergence of previously unrecognized links between facts, concepts, strategies and goals. Observations and speculations become real discoveries as they partake in a network of conceptual implications, thus becoming significant to knowledge. The anticipation of acquiring new beneficial knowledge has always motivated the work of scientists and spurred unconventional thinking, often leading to scientific discoveries that have affected our perception of reality, nature and life. The desire of new revolutionary, paradigm-breaking understanding pushes science toward topics relevant for our metaphysical or even religious perspective on reality: the boundaries of the cosmos, consciousness, the constituents of matter, the destiny of the universe and so on. In this article we offer a short description of the state of the art in the origin of life research and describe examples of creative thinking in this field. We will also discuss the far reaching implications of the direction underlying the most recent research efforts and visions. The occasion for this discussion is given by the recent finding involving the authors, of a new mechanism of molecular self-association: namely, the self-assembly of extremely short fragments of DNA or RNA into large scale ordered structures which could help explaining the prebiotic formation of polymers

A bit stickier, a bit slower, a lot stiffer: Specific vs. nonspecific binding of gal4 to dna

Transcription factors regulate gene activity by binding specific regions of genomic DNA thanks to a subtle interplay of specific and nonspecific interactions that is challenging to quantify. Here, we exploit Reflective Phantom Interface (RPI), a label-free biosensor based on optical reflectivity, to investigate the binding of the N-terminal domain of Gal4, a well-known gene regulator, to double-stranded DNA fragments containing or not its consensus sequence. The analysis of RPI-binding curves provides interaction strength and kinetics and their dependence on temperature and ionic strength. We found that the binding of Gal4 to its cognate site is stronger, as expected, but also markedly slower. We performed a combined analysis of specific and nonspecific binding— equilibrium and kinetics—by means of a simple model based on nested potential wells and found that the free energy gap between specific and nonspecific binding is of the order of one kcal/mol only. We investigated the origin of such a small value by performing all-atom molecular dynamics simulations of Gal4–DNA interactions. We found a strong enthalpy–entropy compensation, by which the binding of Gal4 to its cognate sequence entails a DNA bending and a striking conformational freezing, which could be instrumental in the biological function of Gal4

Towards a Universal Method for the Stable and Clean Functionalization of Inert Perfluoropolymer Nanoparticles : Exploiting Photopolymerizable Amphiphilic Diacetylenes

Highly fluorinated materials are being widely investigated due to a number of peculiar properties, which are potentially useful for various applications, including use as lubricants, anti-adhesive films, and substitutes for biological fluids for biomedical utilization. However, at present such potential is still poorly exploited. One of the major drawbacks that hampers the rapid development of nanoscale fluoro-hybrid devices is the remarkable inertness of perfluoropolymeric materials that lack reactive functionalities, as they do not offer any functional groups that can be employed to covalently anchor organic molecules on their surface. In this paper, a convenient method for the stable biofunctionalization of strongly unreactive perfluoropolymer nanoparticles (PnPs) is reported. PnPs are easily coated with newly synthesized asymmetric diacetylenic monomer compounds (ADMs), thanks to PnP's high propensity to interact with hydrophobic moieties. Once monomerically adsorbed onto PnPs, such suitably designed ADMs enable the formation of a robust polymeric shell around the perfluoroelastomer core via a clean UV-promoted localized photopolymerization. Given the peculiar optical characteristics of PnPs, the coating of the particles can be monitored step by step using light scattering, which also allows estimation of the fraction of reacted monomers by competitive adsorption with smaller particles. The potential of this method for the biofunctionalization of PnPs is demonstrated with representative proteins and carbohydrates. Among them, the extension to avidin-biotin technology may broaden the scope and applicability of this strategy to potentially a large number of molecules of biomedical interest. Making the unreactive reactive: A smart method for the biofunctionalization of strongly inert perfluoropolymer nanoparticles (PnPs) is presented, using a stable coating with novel diacetylenic compounds followed by clean UV photopolymerization to generate reactive functionalities on the PnP surface. This method further allows fine tuning of the amount of conjugated biomolecules, which can be sensitively and straightforwardly quantified

Field-induced anti-nematic ordering in assemblies of anisotropically polarizable particles

We have investigated the effects of dipolar interactions in a lattice system of anisotropically polarizable particles in the presence of an external field both by Monte Carlo computer simulations and through a mean-field analysis. In a specific range of low temperature, large external field and large particle density, a novel staggered nematic structure is found, in which two intercalated sublattices have different nematic order parameters. First- and second-order phase transition lines, connected at a tricritical point, enclose the anti-nematic phase in the temperature-density plane