The focus in protein folding has been very much on the backbone and sidechains. However, hydration waters make comparable contributions to structure energy of proteins. coupling between fast dynamics is considered play an important role folding. Fundamental questions include, how far out into solvent does influence biomolecule reach, water affected, are properties influenced by separation molecules solution? We show here that Terahertz spectroscopy directly probes such solvation around...

Solvation of molecules in water is at the heart a myriad molecular phenomena and crucial importance to understanding such diverse issues as chemical reactivity or biomolecular function. Complementing well-established approaches, it has been shown that laser spectroscopy THz frequency domain offers new insights into hydration from small solutes proteins. Upon introducing spatially-resolved analyses absorption cross section by simulations, sensitivity traced back characteristic...

The dynamics of water surrounding a solute is fundamental importance in chemistry and biology. properties molecules near the surface bio-molecule have been subject numerous, sometimes controversial experimental theoretical studies, with some suggesting existence rather rigid structures around carbohydrates proteins [Pal, S. K., Peon, J., Bagchi, B. & Zewail A. H. (2002) J. Phys. Chem. B 106, 12376–12395]. Hydrogen bond rearrangement occurs on picosecond time scale, so relevant...

Abstract Hydration water is the natural matrix of biological macromolecules and essential for their activity in cells. The coupling between protein dynamics has been intensively studied, yet it remains controversial. Here we combine perdeuteration, neutron scattering molecular simulations to explore nature hydration motions at temperatures 200 300 K, across so-called dynamical transition, intrinsically disordered human tau globular maltose binding protein. Quasi-elastic broadening fitted...

We present new terahertz (THz) spectroscopic measurements of solvated sugars and compare the effect two disaccharides (trehalose lactose) one monosaccharide (glucose) with respect to solute-induced changes in sub-picosecond network dynamics hydration water. found that solute affects fast collective motions solvent, even beyond first solvation layer. For all three carbohydrates, we find an increase 2−4% THz absorption coefficient water comparison bulk Concentration-dependent between 2.1 2.8...

The details of ion hydration still raise fundamental questions relevant to a large variety problems in chemistry and biology. concept water "structure breaking" making" by ions aqueous solutions has been invoked explain the Hofmeister series introduced over 100 years ago, which provides basis for interpretation experimental observations, particular stabilization/destabilization biomolecules. Recent studies, using state-of-the-art experiments molecular dynamics simulations, either challenge...

Abstract Biomolecules evolve and function in densely crowded highly heterogeneous cellular environments. Such conditions are often mimicked the test tube by addition of artificial macromolecular crowding agents. Still, it is unclear if such cosolutes indeed reflect physicochemical properties environment as in‐cell effect has not yet been quantified. We have developed a sensor based on FRET‐labeled polymer to probe inside single living cells. Surprisingly, we find that excluded‐volume...

Using molecular dynamics simulations, we analyze collective vibrations in the hydration water of a small globular protein. We develop tools that allow spatial resolution correlated protein and motion, use them to reveal extend up 10 \AA{} from surface at far-infrared/THz frequencies are sensitive chemical properties surface. Our results provide first detailed description long-range effects on highlight differences between single particle dynamics, which relevant interpreting experimental...

Solvation free energy changes induced by protein folding and function are comparable to the corresponding overall changes. Yet structure, dynamics, energetics of itself have received more attention because they easier probe. Here we use terahertz (far-infrared) spectroscopy directly probe effect mutations solvent pH on shell−protein interaction. We study absorption spectra 80 residue viral protein, a five helix bundle, in 2.1−2.8 THz region. find that wild type at 7 has much pronounced...

In this article we report the detection and characterization of adsorbed interfacial water within cages metal-organic framework MOF-5 (Zn(4)O(BDC)(3)) by terahertz time-domain spectroscopy (THz TDS) in frequency range from 5 to 46 cm(-1). The experimental spectra suggest a coupling intermolecular motions molecules collective vibrations network at 4 wt% hydration. This finding is supported results MD simulations. When increasing content 8 observed non reversible decomposition MOF-5.

This study explores the thermodynamic and vibrational properties of water in three-dimensional environment solvated ions small molecules using molecular simulations. The spectrum intermolecular vibrations liquid solvents provides detailed information on shape local potential energy surface, which turn determines such as entropy. Here, we extract this a spatially resolved extension two-phase thermodynamics method to estimate hydration entropies based density states (3D-2PT). Combined with an...

Water dynamics in the hydration shell of peripheral membrane protein annexin B12 were studied using MD simulations and Overhauser DNP-enhanced NMR. We show that retardation water motions near phospholipid bilayers is extended by presence a membrane-bound protein, up to around 10 Å above protein. Near surface, electrostatic interactions with lipid head groups strongly slow down dynamics, whereas protein-induced weaker dominates only at distances beyond from surface. The results can be...

Hydration water on the surface of a protein is thought to mediate thermodynamics protein-ligand interactions. For hydration play role beyond modulating global solubility or stability, thermodynamic properties must reflect heterogeneous and thus spatially vary over surface. A potent read-out local variations in its equilibrium dynamics spanning picosecond nanosecond time scales. In this study, we employ Overhauser dynamic nuclear polarization (ODNP) probe at select sites Chemotaxis Y (CheY)...

In cells, proteins are embedded in a crowded environment that controls their properties via manifold avenues including weak protein–macromolecule interactions. A molecular level understanding of these quinary interactions and contribution to protein stability, function, localization the cell is central modern structural biology. Using mutational analysis quantify energetic contributions single amino acids stability ALS related superoxide dismutase I (SOD1) mammalian we show destabilize SOD1...

Water, being the universal solvent, acts as a competing agent in fundamental processes, such folding, aggregation or biomolecular recognition. A molecular understanding of hydrophobic hydration is central importance to subtle free energy differences, which dictate function. Ab initio and classical dynamics simulations yield two distinct water populations shell solvated tert-butanol noted "HB-wrap" "HB-hydration2bulk". The experimentally observed spectrum can be dissected into modes, centered...

Although hydrophobicity is a commonly used concept, its microscopic nature, particularly in the context of hydration, not well understood. Here, we present study hydrophobic and hydrophilic solutes using terahertz (THz) spectroscopy molecular dynamics (MD) simulations. We measured concentration dependent THz absorption (2.1–2.7 THz) several amino acids peptides aqueous solution. Experimentally, find correlation between change solvating water specific properties solute such as polarity...

Absorption of terahertz (THz) radiation by aqueous solutions large solutes reports on the polarization response their hydration shells. This is because dipolar relaxation solute dynamically frozen at these frequencies, and most solute-induced absorption changes, apart from expulsion water, are caused interfacial water. We propose a model expressing in terms single parameter, interface dipole moment induced water electromagnetic radiation. apply this concept to experimental THz hydrated...

In this molecular dynamics simulation study, we analyze the local structural and dynamic properties of water hydrating protein ubiquitin on a spatial grid with 1 Å resolution. This allows for insights into distribution number densities, orientations, translations, rotations as function distance from surface. Water molecule orientations follow heterogeneous preferred dipoles O-H bond vectors up to 10-15 distances protein, while variations density converge homogeneous bulk-like values within...

Significance α-Helical membrane proteins are assembled cotranslationally into cell membranes with the aid of heterotrimeric membrane-embedded translocon complex. The structures several translocons reveal that interior has an hourglass shape filled water. Because nascent peptide chains emerging from ribosome thought to pass through during secretion or insertion, is often referred as a protein-conducting channel. We show by all-atom molecular-dynamics simulations water molecules within do not...

Externally applied electric fields in liquid water can induce a plethora of effects with wide implications electrochemistry and hydrogen-based technologies. Although some effort has been made to elucidate the thermodynamics associated application aqueous systems, best our knowledge, field-induced on total local entropy bulk have never presented so far. Here, we report classical TIP4P/2005 ab initio molecular dynamics simulations measuring entropic contributions carried by diverse field...