Varying Hydration Levels Research Articles

Limitations of effective medium models for tissue phantoms in the THz frequency range

The absorption of terahertz (THz) radiation by water molecules facilitates its application to several biomedical applications such as cancer detection. Therefore, it is critical for the THz technologies to be characterised with water content in a sample. In this paper, we analyse gelatine phantoms in the THz frequency range, with continuously varying hydration levels as they dry over time. Water molecules in close proximity to the protein molecule, termed ‘bound water’, feature properties different from the ‘free water’ molecules at larger distances. We find that a common model for predicting electromagnetic properties of phantoms and tissue samples, which assumes that only the free water varies with hydration while the bound water remains constant, does not agree well with measured results. To gain insight into this behaviour, we simultaneously measured the phantom in Raman spectroscopy, which shows a continuously varying concentration of bound water with hydration level. It follows from this investigation, that the permittivity contributions of neither the biomolecules nor water are expected to be linear with water density. This means that the often used, simple effective medium model will not be accurate for many biological tissues or phantoms.

Photografted Zwitterionic Hydrogel Coating Durability for Reduced Foreign Body Response to Cochlear Implants.

The durability of photografted zwitterionic hydrogel coatings on cochlear implant biomaterials was examined to determine the viability of these antifouling surfaces during insertion and long-term implant usage. Tribometry was used to determine the effect of zwitterionic coatings on the lubricity of surfaces with varying hydration levels, applied normal force, and time frame. Additionally, flexural resistance was investigated using mandrel bending. Ex vivo durability was assessed by determining the coefficient of friction between tissues and treated surfaces. Furthermore, cochlear implantation force was measured using cadaveric human cochleae. Hydrated zwitterionic hydrogel coatings reduced frictional resistance approximately 20-fold compared to uncoated PDMS, which led to significantly lower mean force experienced by coated cochlear implants during insertion compared to uncoated systems. Under flexural force, zwitterionic films resisted failure for up to 60 min of desiccation. The large increase in lubricity was maintained for 20 h under continual force while hydrated. For loosely cross-linked systems, films remained stable and lubricious even after rehydration following complete drying. All coatings remained hydrated and functional under frictional force for at least 30 min in ambient conditions allowing drying, with lower cross-link densities showing the greatest longevity. Moreover, photografted zwitterionic hydrogel samples showed no evidence of degradation and nearly identical lubricity before and after implantation. This work demonstrates that photografted zwitterionic hydrogel coatings are sufficiently durable to maintain viability before, during, and after implantation. Mechanical properties, including greatly increased lubricity, are preserved after complete drying and rehydration for various applied forces. Additionally, this significantly enhanced lubricity translates to significantly decreased force during insertion of implants which should result in less trauma and scarring.

Changes in the basic structure and strength deterioration of clay minerals with different hydration degrees

AbstractTo investigate the influence of clay mineral microstructures on mechanical properties across varying hydration levels, this study employed molecular dynamics simulations to conduct uniaxial tensile strength tests in three orthogonal directions (x, y, z) using illite, montmorillonite and kaolinite. The moisture content was varied from 0% to 10% in 1% increments and from 0% to 50% in 10% increments. The observations highlight the role of water molecules in disrupting the inherent microscopic atomic structure of clay minerals, leading to diminished stability and a decline in tensile strength. As moisture content increased, there was a pronounced increase in the layer spacing of all three clay minerals, indicative of their hydration expansion behaviour. Concurrently, discernible reductions in both the tensile strength and Young's modulus of the clay minerals were observed.

Unraveling the Molecular Mechanisms of Trehalose-Mediated Protection and Stabilization of Escherichia coli Lipid Membrane during Desiccation.

Trehalose, a disaccharide renowned for its ability to stabilize biomolecular architectures under strenuous conditions, finds extensive use in the cryopreservation of probiotics. A profound comprehension of its molecular-level interactions is of great significance. It is notable that current research in the realm of lipid-sugar interactions primarily employs single-component lipid bilayers, which are far from being representative of real cell membranes. Our investigation, however, utilizes molecular dynamics simulations to delve into the specifics of a realistic Escherichia coli membrane that encompasses a diverse array of lipid types, comprising fourteen distinct species, subject to varying hydration levels. The results of our study showcase that the reduction of hydration levels induces lipid ordering and the formation of gel phases, yet trehalose, by forming hydrogen bonds with lipid headgroups, serves to uphold fluidity and supplant the role of water. Moreover, our findings evince that augmented trehalose concentrations lead to a slowdown in lipid motion and contribute to the maintenance of fluidity by way of endowing a viscous matrix. It is noteworthy that our conclusions lend support to the notion that water replacement and vitrification, despite their seemingly disparate nature, need not be considered mutually exclusive in a real bacterial membrane.

How Do Urea and Trimethylamine N-Oxide Influence the Dehydration-Induced Phase Transition of a Lipid Membrane?

Living organisms are often exposed to extreme dehydration, which is detrimental to the structure and function of the cell membrane. The lipid membrane undergoes fluid-to-gel phase transition due to dehydration and thus loses fluidity and functionality. To protect the fluid phase of the bilayer these organisms adopt several strategies. Enhanced production of small polar organic solutes (also called osmolytes) is one such strategy. Urea and trimethylamine N-oxide (TMAO) are two osmolytes found in different organisms combating osmotic stress. Previous experiments have found that both these osmolytes have strong effects on lipid membrane under different hydration conditions. Urea prevents the dehydration-induced phase transition of the lipid membrane by directly interacting with the lipids, while TMAO does not inhibit the phase transition. To provide atomistic insights, we have carried out all-atom molecular dynamics (MD) simulation of a lipid membrane under varying hydration levels and studied the effect of these osmolytes on different structural and dynamic properties of the membrane. This study suggests that urea significantly inhibits the dehydration-induced fluid-to-gel phase transition by strongly interacting with the lipid membrane via hydrogen bonds, which balances the reduced lipid hydration due to the decreasing water content. In contrast, TMAO is excluded from the membrane surface due to unfavorable interaction with the lipids. This induces further dehydration of the lipids which reinforces the fluid-to-gel phase transition. We have also studied the counteractive role of TMAO on the effect of urea on lipid membrane when both the osmolytes are present. TMAO draws some urea molecules out of the membrane and thereby reduces the effect of urea on the lipid membrane at lower hydration levels. This is similar to the counteraction of urea's deleterious effects on protein by TMAO. All these observations are consistent with the experimental results and thus provide deep molecular insights into the role of these osmolytes in protecting the fluid phase of the membrane, the key survival strategy against osmotic-stress-induced dehydration.

Investigations into the role of water concentration on mechanical behavior and nanomechanics of Bombyx mori silk fibroin using molecular dynamics simulations

Bombyx mori silk fibroin (B. mori SF) is emerging as a promising biomaterial for its application in biomedical field such as hard and soft tissue engineered grafts considering it is a load-bearing polymer with biocompatible and biodegradable characteristics. B. mori SF being a biopolymer is made up of amino acids (residues) comprising crystalline and amorphous domains at nanoscale. In general, mechanical behavior of a biomaterial is actively governed by its chemical environment. Extent of water present in silk can significantly affect its mechanical behavior and alter structural functions at the molecular level. Hence, it is essential to understand the mechanical behavior and molecular deformation mechanics of B. mori SF at the building block level under varying hydration conditions. In current investigation, tensile mechanical behavior of two characteristic computational models of B. mori SF, along the fiber axis, under varying hydration levels (0 to 70 wt%) has been studied using molecular dynamics simulations. Elastic modulus values in the range of 7 to 11 GPa and 8 to 13 GPa were obtained for the two models for varying hydration levels. Analyses reveal that the hydrophobic effect has a dominating role at lower hydration levels resulting in an enhanced interaction between protein chains. This results in mechanical strengthening of B. mori SF nanostructure. However, at higher hydration levels, the osmotic pressure plays a dominating role, resulting into screening of interatomic interaction between protein chains thus giving a weakening effect. Overall, this work contributes toward developing an understanding of mechanistic interactions between different protein phases (amorphous and crystalline regions) and water in hydrated B. mori SF nanostructure, which is useful for explorations in silk-based biomaterials.

Lipase and Water in a Deep Eutectic Solvent: Molecular Dynamics and Experimental Studies of the Effects of Water-In-Deep Eutectic Solvents on Lipase Stability

Given the accumulated evidence on the effects of water-in-deep eutectic solvents (DESs) on the solvent nanostructure and the yield of lipase reactions, here we have used molecular dynamics (MD) simulations to delineate the structure and dynamics of thermoalkalophilic lipases in choline chloride/urea-based DES (reline) with varying hydration levels. Results indicated that pure reline almost froze the lipase backbone, while hydrated reline that showed a less ordered nanostructure than the pure form introduced some fluctuations to lipase structures, particularly to the lid domain. Although none of the solvents led to unfolding, solvation by 8 M urea or water when accompanied with elevated temperature caused the most significant loss of secondary structure. Experimental results indicated that lipase incubation in slightly hydrated reline [5% (v/v)] led to the highest level of residual activity, implying interfacial activation. Overall, we report that slightly hydrated reline activates thermoalkalophilic lipases, consistent with the particular MD observation showing enhanced mobility of the lid domain. These insights provided by this study contribute to designing efficient lipase applications in DES-based reaction media, giving cues for customizing water-in-DESs for optimal enzyme stability and activity.

The plant dehydrin Lti30 stabilizes lipid lamellar structures in varying hydration conditions

A major challenge to plant growth and survival are changes in temperature and diminishing water supply. During acute temperature and water stress, plants often express stress proteins, such as dehydrins, which are intrinsically disordered hydrophilic proteins. In this article, we investigated how the dehydrin Lti30 from Arabidopsis thaliana stabilizes membrane systems that are exposed to large changes in hydration. We also compared the effects of Lti30 on membranes with those of the simple osmolytes urea and trimethylamine N-oxide. Using X-ray diffraction and solid-state NMR, we studied lipid-protein self-assembly at varying hydration levels. We made the following observations: 1) the association of Lti30 with anionic membranes relies on electrostatic attraction, and the protein is located in the bilayer interfacial membrane region; 2) Lti30 can stabilize the lamellar multilayer structure, making it insensitive to variations in water content; 3) in lipid systems with a composition similar to those present in some seeds and plants, dehydrin can prevent the formation of nonlamellar phases upon drying, which may be crucial for maintaining membrane integrity; and 4) Lti30 stabilizes bilayer structures both at high and low water contents, whereas the small osmolyte molecules mainly prevent dehydration-induced transitions. These results corroborate the idea that dehydrins are part of a sensitive and multifaceted regulatory mechanism that protects plant cells against stress.

Molecular Modeling of Structure and Dynamics of Nafion Protonation States.

We present the results of the atomistic molecular dynamics modeling of different protonation states of Nafion at varying hydration levels. Previous experiments have shown that the degree of deprotonation (DDP) of the sulfonic acid groups in a Nafion membrane varies significantly upon hydration. Our goal is to provide insights into the effects of variable protonation states and water content on the internal structure and vehicular transport inside the Nafion membrane. The Nafion side chain lengths showed a weak increasing trend with increasing DDP at all hydration levels, exposing more of the sulfonic acid groups to the hydrophilic/water phase. The water-phase characteristic size/diameter decreased with increasing DDP, but, interestingly, the average number of water molecules per cluster increased. The probability of water–hydronium hydrogen bond formation decreased with increasing DDP, despite an increase in the total number of such hydrogen bonds. The water diffusion was largely unaffected by the state of deprotonation. In contrast to that, the hydronium ion diffusion slowed down with increasing DDP in the overall membrane. The hydronium ion residence times around the sulfonic acid group increased with increasing DDP. Our simulations show a strong connection between the morphology of the water domains and protonation states of Nafion. Such a connection can also be expected in polyelectrolyte membranes similar to Nafion.

Polarity of Hydrated Phosphatidylcholine Headgroups.

The headgroup (H) stratum (sometimes called the polar region) of membrane bilayers is a relevant yet poorly understood solvation phase for small molecules and macromolecules interacting with the membranes. Solvation of compounds in bilayer strata is characterized experimentally by wide- and small-angle X-ray scattering, neutron diffraction, and various NMR techniques. The quantification is tedious and only available for a limited set of small molecules. Our recently published model of liposome partitioning of small molecules shows that solvation of compounds in the H-stratum of fluid phosphatidylcholine (PC) bilayers correlates well with their solvation in hydrated diacetyl phosphatidylcholine (DAcPC), and solvation in the core (C) depends in a similar way on that in n-hexadecane. These two correlations became a basis for a model describing the location of compounds in the H- and C-strata and at the connecting interface as a nonlinear function of the fragment solvation characteristics of the compounds. In this study, refractivity of hydrated DAcPC phases with varying water contents was measured and polarity was determined using the steady-state fluorescence of indole and Nile Red. The results were compared with the published data obtained by other techniques for PC bilayers in liposomes or on solid supports. The demonstrated qualitative agreement, as well as the polarity and refractivity dependencies on the DAcPC concentration, supports the suitability of hydrated DAcPC as the H-stratum surrogate. Interestingly, depending on hydrations typical for the H-strata of fluid PC bilayers, the dielectric constant could decrease significantly from 31.0 to 7.3 for 16 and 8 water molecules per headgroup, respectively. Although additional experiments are needed for confirmation, this observation could help set proper dielectric constant magnitudes in continuum-based computational models of accumulation and crossing of the PC bilayers with varying hydration levels thanks to the temperature or the structure of fatty acid chains.

Nanostructure and Dynamics of Humidified Nafion/Graphene-Oxide Composites via Molecular Dynamics Simulations

In this work, we elucidated the nanostructure and dynamics of Nafion-doped graphene-oxide (GO) systems from molecular dynamics simulations at varying hydration levels and temperature. It was found that the presence of GO resulted in the formation of Nafion layers along a direction normal to the GO surface. Chain conformations in the Nafion layers close to the GO interface were characterized by a backbone preferably oriented parallel to the GO plane, whereas the size of the formed nanochannels was found to be commensurate to the average dimensions of the Nafion side chains. The mechanism of water cluster growth was found to change drastically upon introduction of Nafion chains, although addition of GO in the membranes did not impart further measurable changes at the examined temperatures. Hydronium ions were found to adsorb partly onto the GO surface, whereas the pertinent adsorption/desorption rate increased significantly with hydration. Translational dynamics of water molecules was much slower close to t...

Changes in Some Antinutritional Components and In Vitro Multienzymes Protein Digestibility during Hydrothermal Processing of Cassia hirsutta.

The seed of Cassia hirsutta was subjected to aqueous soaking and four hydrothermal processing techniques (atmospheric boiling, atmospheric steaming, pressure boiling, and pressure steaming). Soaking of the seed to varying hydration levels before hydrothermal treatments induced the reduction in the concentration of the antinutritional components. The lowest concentration of each of the antinutritional components was observed at 100% hydration level. The effects of hydrothermal techniques on the antinutritional components and protein digestibility were investigated. All the hydrothermal techniques caused significant reduction (P<0.05) in the antinutritional components. Boiling at elevated pressure resulted in greater reduction of antinutrients. The hydrothermal techniques caused total elimination of trypsin inhibitor activity. Reduction in the concentration of the antinutritional components after hydrothermal processing led to the increase in in vitro protein digestibility. The highest in vitro protein digestibility of 86.82% was observed after the legume seed was boiled at elevated pressure. Adoption of this underutilised legume will strengthen dietary diversity, improve feeding patterns, and prevent protein energy malnutrition especially in developing countries since the seed is a good source of nutritionally important nutrients.

Alleviation of Hard-to-cook Phenomenon in Legumes: Effects of Hydrothermal Processing Techniques on Two Species of Vigna subterranean

The hard-to-cook nature of Vigna subterranean constitutes an hindrance to its utilisation. Two species of a hard-to-cook legume Vigna subterranean were subjected to hydrothermal processing after soaking. This study is aimed at investigating the effects of soaking followed by hydrothermal processing on the cooking times. The seeds of two species of Vigna subterranean (the cream coloured specie and the mottled coloured specie,) were processed by four different hydrothermal techniques before and after aqueous soaking to varying hydration levels. Soaking of the seeds to varying hydration levels before processing by hydrothermal techniques induced decrease in the cooking times. Highest percentage reduction of 66.24% was recorded when the seed of the cream coloured variety was boiled at elevated pressure.

Collagen Fibrils: Nature's Highly Tunable Nonlinear Springs.

Tissue hydration is well known to influence tissue mechanics and can be tuned via osmotic pressure. Collagen fibrils are nature's nanoscale building blocks to achieve biomechanical function in a broad range of biological tissues and across many species. Intrafibrillar covalent cross-links have long been thought to play a pivotal role in collagen fibril elasticity, but predominantly at large, far from physiological, strains. Performing nanotensile experiments of collagen fibrils at varying hydration levels by adjusting osmotic pressure in situ during atomic force microscopy experiments, we show the power the intrafibrillar noncovalent interactions have for defining collagen fibril tensile elasticity at low fibril strains. Nanomechanical tensile tests reveal that osmotic pressure increases collagen fibril stiffness up to 24-fold in transverse (nanoindentation) and up to 6-fold in the longitudinal direction (tension), compared to physiological saline in a reversible fashion. We attribute the stiffening to the density and strength of weak intermolecular forces tuned by hydration and hence collagen packing density. This reversible mechanism may be employed by cells to alter their mechanical microenvironment in a reversible manner. The mechanism could also be translated to tissue engineering approaches for customizing scaffold mechanics in spatially resolved fashion, and it may help explain local mechanical changes during development of diseases and inflammation.

Combining Water Percolation Analysis and Molecular Dynamics Simulations for Protein-Protein Binding Interface Prediction

We consider ab initio prediction of protein-protein binding interfaces of weakly-associating proteins in aqueous environment. Systems of interest are important in cellular signalling pathways and manifest Kd values in the micromolar range (weak binding). We use molecular dynamics simulations of individual proteins at varying hydration levels to determine percolation thresholds for water networks. By mapping average local water density around all residues at the percolation threshold, we are able to determine clusters of residues with low water density which we consider as potential binding regions. We have performed analysis on a series of 20 proteins and compare to existing automated protein-protein binding interface prediction servers.

Influence of Particle Size and Water Coverage on the Thermodynamic Properties of Water Confined on the Surface of SnO2 Cassiterite Nanoparticles

Inelastic neutron scattering (INS) data for SnO2 nanoparticles of three different sizes and varying hydration levels are presented. Data were recorded on five nanoparticle samples that had the following compositions: 2 nm SnO2·0.82H2O, 6 nm SnO2·0.055H2O, 6 nm SnO2·0.095H2O, 20 nm SnO2·0.072H2O, and 20 nm SnO2·0.092H2O. The isochoric heat capacity and vibrational entropy values at 298 K for the water confined on the surface of these nanoparticles were calculated from the vibrational density of states that were extracted from the INS data. This study has shown that the hydration level of the SnO2 nanoparticles influences the thermodynamic properties of the water layers and, most importantly, that there appears to be a critical size limit for SnO2 between 2 and 6 nm below which the particle size also affects these properties and above which it does not. These results have been compared with those for isostructural rutile-TiO2 nanoparticles [TiO2·0.22H2O and TiO2·0.37H2O], which indicated that water on the surface of TiO2 nanoparticles is more tightly bound and experiences a greater degree of restricted motion with respect to water on the surface of SnO2 nanoparticles. This is believed to be a consequence of the difference in chemical composition, and hence surface properties, of these metal oxide nanoparticles.

A solid-state NMR study of the fast and slow dynamics of collagen fibrils at varying hydration levels.

We report solid-state NMR investigations of the effect of temperature and hydration on the molecular mobility of collagen isolated from bovine achilles tendon. (13)C cross-polarization magic angle spinning (MAS) experiments were performed on samples at natural abundance, using NMR methods that detect motionally averaged dipolar interactions and chemical shift anisotropies and also slow reorientational processes. Fast motions with correlation times much shorter than 40 micro s scale dipolar couplings and chemical shift anisotropies of the carbon sites in collagen. These motionally averaged anisotropic interactions provide a measure of the amplitudes of the segmental motions expressed by a molecular order parameter. The data reveal that increasing hydration has a much stronger effect on the amplitude of the molecular processes than increasing temperature. In particular, the Cgamma carbons of the hydroxyproline residues exhibit a strong dependence of the amplitude of motion on the hydration level. This could be correlated with the effect of hydration on the hydrogen bonding structure in collagen, for which this residue is known to play a crucial role. The applicability of 1D MAS exchange experiments to investigate motions on the millisecond time-scale is discussed and first results are presented. Slow motions with correlation times of the order of milliseconds have also been detected for hydrated collagen.