Effective potentials induced by mixtures of patchy and hard co-solutes.

The addition of co-solutes to colloidal suspensions is often employed to induce tunable depletion interactions. In this work, we investigate effective colloidal interactions arising from binary co-solute mixtures of hard spheres and patchy particles. By changing the relative concentration of the two species, we show that the resulting effective potential V continuously changes from the one obtained for a single-component hard sphere co-solute to that mediated by the single-component patchy particle co-solute.

Polarizable and non-polarizable force fields: Protein folding, unfolding, and misfolding.

Molecular dynamics simulations are an invaluable tool to characterize the dynamic motions of proteins in atomistic detail. However, the accuracy of models derived from simulations inevitably relies on the quality of the underlying force field. Here, we present an evaluation of current non-polarizable and polarizable force fields (AMBER ff14SB, CHARMM 36m, GROMOS 54A7, and Drude 2013) based on the long-standing biophysical challenge of protein folding.

Charge Anisotropy of Nitrogen: Where Chemical Intuition Fails.

For more than half a century computer simulations were developed and employed to study ensemble properties of a wide variety of atomic and molecular systems with tremendous success. Nowadays, a selection of force-fields is available that describe the interactions in such systems. A key feature of force-fields is an adequate description of the electrostatic potential (ESP).

Dynamics Rationalize Proteolytic Susceptibility of the Major Birch Pollen Allergen Bet v 1.

Proteolytic susceptibility during endolysosomal degradation is decisive for allergic sensitization. In the major birch pollen allergen Bet v 1 most protease cleavage sites are located within its secondary structure elements, which are inherently inaccessible to proteases. The allergen thus must unfold locally, exposing the cleavage sites to become susceptible to proteolysis.

Glass polymorphism and liquid-liquid phase transition in aqueous solutions: experiments and computer simulations.

One of the most intriguing anomalies of water is its ability to exist as distinct amorphous ice forms (glass polymorphism or polyamorphism). This resonates well with the possible first-order liquid-liquid phase transition (LLPT) in the supercooled state, where ice is the stable phase. In this Perspective, we review experiments and computer simulations that search for LLPT and polyamorphism in aqueous solutions containing salts and alcohols.

Glass polymorphism in TIP4P/2005 water: A description based on the potential energy landscape formalism.

The potential energy landscape (PEL) formalism is a statistical mechanical approach to describe supercooled liquids and glasses. Here, we use the PEL formalism to study the pressure-induced transformations between low-density amorphous ice (LDA) and high-density amorphous ice (HDA) using computer simulations of the TIP4P/2005 molecular model of water. We find that the properties of the PEL sampled by the system during the LDA-HDA transformation exhibit anomalous behavior.

q-Independent Slow Dynamics in Atomic and Molecular Systems.

Investigating million-atom systems for very long simulation times, we demonstrate that the collective density-density correlation time (τ_{α}) in simulated supercooled water and silica becomes wave-vector independent (q^{0}) when the probing wavelength is several times larger than the interparticle distance. The q independence of the collective density-density correlation functions, a feature clearly observed in light-scattering studies of some soft-matter systems, is thus a genuine feature of many (but not all) slow-dynamics systems, either atomic, molecular, or colloidal. Indeed, we show that when the dynamics of the density fluctuations includes particle-type diffusion, as in the case of the Lennard-Jones binary-mixture model, the q^{0} regime does not set in and the relaxation time continues to scale as τ_{α}∼q^{-2} even at small q.

Size dependence of dynamic fluctuations in liquid and supercooled water.

We study the evolution of dynamic fluctuations averaged over different space lengths and time scales to characterize spatially and temporally heterogeneous behavior of TIP4P/2005 water in liquid and supercooled states. Analyzing a 250 000 molecules simulated system, we provide evidence of the existence, upon supercooling, of a significant enhancement of spatially localized dynamic fluctuations stemming from regions of correlated mobile molecules. We show that both the magnitude of the departure from the value expected for the system-size dependence of an uncorrelated system and the system size at which such a trivial regime is finally recovered clearly increase upon supercooling.

The Adam-Gibbs relation and the TIP4P/2005 model of water.

We report a numerical test of the Adam-Gibbs relation for the TIP4P/2005 model of water. The configurational entropy is here evaluated as the logarithm of the number of different basins in the potential energy landscape sampled in equilibrium conditions. Despite the non-monotonic behaviour which characterise the density dependence of the diffusion coefficient, the Adam-Gibbs relation is satisfied within the numerical precision in a wide range of densities and temperatures.

Potential energy landscape of TIP4P/2005 water.

We report a numerical study of the statistical properties of the potential energy landscape of TIP4P/2005, one of the most accurate rigid water models. We show that, in the region where equilibrated configurations can be generated, a Gaussian landscape description is able to properly describe the model properties. We also find that the volume dependence of the landscape properties is consistent with the existence of a locus of density maxima in the phase diagram.

Experimental study of the polyamorphism of water. II. The isobaric transitions between HDA and VHDA at intermediate and high pressures.

Since the first report of very-high density amorphous ice (VHDA) in 2001 [T. Loerting et al., Phys.

Experimental study of the polyamorphism of water. I. The isobaric transitions from amorphous ices to LDA at 4 MPa.

The existence of more than one solid amorphous state of water is an extraordinary feature. Since polyamorphism might be connected to the liquid-liquid critical point hypothesis, it is particularly important to study the relations amongst the different amorphous ices. Here we study the polyamorphic transformations of several high pressure amorphous ices to low-density amorphous ice (LDA) at 4 MPa by isobaric heating utilising in situ volumetry and ex situ X-ray diffraction.

Supercooled and glassy water: Metastable liquid(s), amorphous solid(s), and a no-man's land.

We review the recent research on supercooled and glassy water, focusing on the possible origins of its complex behavior. We stress the central role played by the strong directionality of the water-water interaction and by the competition between local energy, local entropy, and local density. In this context we discuss the phenomenon of polyamorphism (i.

Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects.

Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping.

Condensation and Demixing in Solutions of DNA Nanostars and Their Mixtures.

We present a numerical/theoretical approach to efficiently evaluate the phase diagram of self-assembling DNA nanostars. Combining input information based on a realistic coarse-grained DNA potential with the Wertheim association theory, we derive a parameter-free thermodynamic description of these systems. We apply this method to investigate the phase behavior of single components and mixtures of DNA nanostars with different numbers of sticky arms, elucidating the role of the system functionality and of salt concentration.

The glass transition in high-density amorphous ice.

There has been a long controversy regarding the glass transition in low-density amorphous ice (LDA). The central question is whether or not it transforms to an ultraviscous liquid state above 136 K at ambient pressure prior to crystallization. Currently, the most widespread interpretation of the experimental findings is in terms of a transformation to a superstrong liquid above 136 K.

Temperature-induced amorphisation of hexagonal ice.

We systematically studied the competition between polymorphic transformations and amorphisation of hexagonal ice on isobaric heating from 77 K to 155-170 K at pressures between 0.50 and 1.00 GPa.

Water's second glass transition.

The glassy states of water are of common interest as the majority of H2O in space is in the glassy state and especially because a proper description of this phenomenon is considered to be the key to our understanding why liquid water shows exceptional properties, different from all other liquids. The occurrence of water's calorimetric glass transition of low-density amorphous ice at 136 K has been discussed controversially for many years because its calorimetric signature is very feeble. Here, we report that high-density amorphous ice at ambient pressure shows a distinct calorimetric glass transitions at 116 K and present evidence that this second glass transition involves liquid-like translational mobility of water molecules.

Limits of metastability in amorphous ices: the neutron scattering Debye-Waller factor.

Recently, it became clear that relaxation effects in amorphous ices play a very important role that has previously been overlooked. The thermodynamic history of amorphous samples strongly affects their transition behavior. In particular, well-relaxed samples show higher thermal stability, thereby providing a larger window to investigate their glass transitions.

Relaxation time of high-density amorphous ice.

Amorphous water plays a fundamental role in astrophysics, cryoelectron microscopy, hydration of matter, and our understanding of anomalous liquid water properties. Yet, the characteristics of the relaxation processes taking place in high-density amorphous ice (HDA) are unknown. We here reveal that the relaxation processes in HDA at 110-135 K at 0.

How many amorphous ices are there?

Many acronyms are used in the literature for describing different kinds of amorphous ice, mainly because many different preparation routes and many different sample histories need to be distinguished. We here introduce these amorphous ices and discuss the question of how many of these forms are of relevance in the context of polyamorphism. We employ the criterion of reversible transitions between amorphous "states" in finite intervals of pressure and temperature to discriminate between independent metastable amorphous "states" and between "substates" of the same amorphous "state".