Moreno Marcellini

Dimensionality crossover in the induced magnetization of Pd layers

The magnetic ordering of a series of samples consisting of ultrathin Fe layers embedded in Pd was investigated using the magneto-optical Kerr effect. The samples consisted of a single Fe layer with nominal thickness 0.2≤d(Fe)≤1.6 monolayers sandwiched between two 20 monolayer Pd layers. A dimensionality crossover from two dimensions to three dimensions occurs as d(Fe) is increased from 0.4 to 1.0 monolayers. First-principles calculations were performed in order to determine the magnetic profile, and we used a spin-wave quantum well model for obtaining a qualitative description of the dimensionality crossover. The results clearly prove the existence of a dimensionality crossover in the induced magnetization, opening new routes for addressing the influence of extension on order.

Changes in electronic structure of copper films in aqueous solutions

The possibilities for using x-ray absorption spectroscopy (XAS) and resonant inelastic x-ray scattering (RIXS) to probe the Cu oxidation state and changes in the electronic structure during interaction between copper and ground-water solutions were examined. Surface modifications induced by chemical reactions of oxidized 100 A Cu films with Cl−, SO42− and HCO3− ions in aqueous solutions with various concentrations were studied in situ using liquid cells. Copper corrosion processes in ground water were monitored for up to nine days. By comparing Cu 2p–3d, 4s transitions for a number of reference substances previously measured, changes in electronic structure of the Cu films were analysed. The XAS and RIXS spectral shape at the Cu edge, the chemical shift of the main line for Cu2+, and the energy positions of the observed satellites served as a tool for monitoring the changes during the reaction. It was found that the pH value and the Cl− concentration in solutions strongly affect the speed of the corrosion reaction.

Deciphering Solution Scattering Data with Experimentally Guided Molecular Dynamics Simulations

Time-resolved X-ray solution scattering is an increasingly popular method to measure conformational changes in proteins. Extracting structural information from the resulting difference X-ray scattering data is a daunting task. We present a method in which the limited but precious information encoded in such scattering curves is combined with the chemical knowledge of molecular force fields. The molecule of interest is then refined toward experimental data using molecular dynamics simulation. Therefore, the energy landscape is biased toward conformations that agree with experimental data. We describe and verify the method, and we provide an implementation in GROMACS.

Dimensionality and confinement effects in δ-doped Pd(Fe) layers

We address the dimensionality aspects of the magnetic ordering in δ-doped Pd(Fe) structures. The key property we investigate, via magneto-optic Kerr measurements, is the magnetization induced by iron in palladium, over a wide temperature range 5 K < T < 300 K. The dimensional crossover we observe cannot be rationalized on the basis of structural considerations alone, since we find the dimensionality of the low temperature and of the critical region can differ. We discuss the crossover in terms of the temperature dependence of the magnon modes, giving rise to lower dimensionality at low temperatures.

Oscillatory exchange coupling in the two-dimensional limit

The dimensionality aspects of the order–disorder transition in single and double magnetic layers is addressed. A single Fe film of three monolayers, embedded in V(001) layers, was determined to be two-dimensional and XY-like. Two Fe layers, separated by 14.4 monolayers of V(001), were determined to belong to the same universality class as the single Fe film. The interlayer exchange coupling was altered in situ by introducing hydrogen in the V layers. An oscillation of the ordering temperature was observed, consistent with an oscillatory interlayer exchange coupling. The two-dimensional nature of the bilayer was confirmed by the ratio of the interlayer and intralayer couplings (). The results therefore support the existence of an oscillatory exchange coupling in the quasi-two-dimensional limit.

Time-Lapse, in Situ Imaging of Ice Crystal Growth Using Confocal Microscopy

Ice crystals nucleate and grow when a water solution is cooled below its freezing point. The growth velocities and morphologies of the ice crystals depend on many parameters, such as the temperature of ice growth, the melting temperature, and the interactions of solutes with the growing crystals. Three types of morphologies may appear: dendritic, cellular (or fingerlike), or the faceted equilibrium form. Understanding and controlling which type of morphology is formed is essential in several domains, from biology to geophysics and materials science. Obtaining, in situ, three dimensional observations without introducing artifacts due to the experimental technique is nevertheless challenging. Here we show how we can use laser scanning confocal microscopy to follow in real-time the growth of smoothed and faceted ice crystals in zirconium acetate solutions. Both qualitative and quantitative observations can be made. In particular, we can precisely measure the lateral growth velocity of the crystals, a measure otherwise difficult to obtain. Such observations should help us understand the influence of the parameters that control the growth of ice crystals in various systems.

Deconvoluting Protein (Un)folding Structural Ensembles Using X-Ray Scattering, Nuclear Magnetic Resonance Spectroscopy and Molecular Dynamics Simulation.

The folding and unfolding of protein domains is an apparently cooperative process, but transient intermediates have been detected in some cases. Such (un)folding intermediates are challenging to investigate structurally as they are typically not long-lived and their role in the (un)folding reaction has often been questioned. One of the most well studied (un)folding pathways is that of Drosophila melanogaster Engrailed homeodomain (EnHD): this 61-residue protein forms a three helix bundle in the native state and folds via a helical intermediate. Here we used molecular dynamics simulations to derive sample conformations of EnHD in the native, intermediate, and unfolded states and selected the relevant structural clusters by comparing to small/wide angle X-ray scattering data at four different temperatures. The results are corroborated using residual dipolar couplings determined by NMR spectroscopy. Our results agree well with the previously proposed (un)folding pathway. However, they also suggest that the fully unfolded state is present at a low fraction throughout the investigated temperature interval, and that the (un)folding intermediate is highly populated at the thermal midpoint in line with the view that this intermediate can be regarded to be the denatured state under physiological conditions. Further, the combination of ensemble structural techniques with MD allows for determination of structures and populations of multiple interconverting structures in solution.

Dynamics and ordering of weakly Brownian particles in directional drying

Drying of particle suspensions is an ubiquitous phenomenon with many natural and practical applications. In particular, in unidirectional drying, the evaporation of the solvent induces flows which accumulate particles at the liquid/air interface. The progressive buildup of a dense region of particles can be used, in particular, in the processing of advanced materials and architectures while the development of heterogeneities and defects in such systems is critical to their function. A lot of attention has thus been paid to correlating the flow and particle dynamics to the ordering of particles. However, dynamic observation at the particle scale and its correlation with local particle ordering are still missing. Here we show by measuring the particle velocities with high frame rate laser scanning confocal microscopy that the ordering of weakly Brownian particles during unidirectional drying in a Hele-Shaw cell opened on one side depends on the velocity of particles that impinge at the pinned liquid/solid interface. Under the ambient and experimental conditions presented in the following, the particle velocities accumulate in two branches. A higher degree of ordering is found for the branch of faster particle velocity which we explain by an increase in the pressure drop which drags the particles into a denser packing as the flow velocity increases. This counterintuitive behavior is the opposite to what is found with Brownian particles, which can reorganize by Brownian motion into denser packing during drying, as long as the flow velocity is not too high. These results show that different kinetic conditions can be used to obtain dense, defect-free regions of particles after drying. In particular, it suggests that rapid, directional drying could be used to control the crystallinity of particle deposits.

Water/ice phase transition: The role of zirconium acetate, a compound with ice-shaping properties

Few compounds feature ice-shaping properties. Zirconium acetate is one of the very few inorganic compounds reported so far to have ice-shaping properties similar to that of ice-shaping proteins, encountered in many organisms living at low temperature. When a zirconium acetate solution is frozen, oriented and perfectly hexagonal ice crystals can be formed and their growth follows the temperature gradient. To shed light on the water/ice phase transition while freezing zirconium acetate solution, we carried out differential scanning calorimetry measurements. From our results, we estimate how many water molecules do not freeze because of their interaction with Zr cations. We estimate the colligative properties of the Zr acetate on the apparent critical temperature. We further show that the phase transition is unaffected by the nature of the base which is used to adjust the pH. Our results provide thus new hints on the ice-shaping mechanism of zirconium acetate.

Polyproline as a Minimal Antifreeze Protein Mimic That Enhances the Cryopreservation of Cell Monolayers

Abstract Tissue engineering, gene therapy, drug screening, and emerging regenerative medicine therapies are fundamentally reliant on high‐quality adherent cell culture, but current methods to cryopreserve cells in this format can give low cell yields and require large volumes of solvent “antifreezes”. Herein, we report polyproline as a minimum (bio)synthetic mimic of antifreeze proteins that is accessible by solution, solid‐phase, and recombinant methods. We demonstrate that polyproline has ice recrystallisation inhibition activity linked to its amphipathic helix and that it enhances the DMSO cryopreservation of adherent cell lines. Polyproline may be a versatile additive in the emerging field of macromolecular cryoprotectants.