Pressure-dependent Changes Research Articles

Calcium Sensitive Fluorescent Dyes Fluo-4 and Fura Red under Pressure: Behaviour of Fluorescence and Buffer Properties under Hydrostatic Pressures up to 200 MPa.

The fluorescent Ca2+ sensitive dyes Fura Red (ratiometric) and Fluo-4 (non-ratiometric) are widely utilized for the optical assessment of Ca2+ fluctuations in vitro as well as in situ. The fluorescent behavior of these dyes is strongly depends on temperature, pH, ionic strength and pressure. It is crucial to understand the response of these dyes to pressure when applying calcium imaging technologies in the field of high pressure bioscience. Therefore, we use an optically accessible pressure vessel to pressurize physiological Ca2+-buffered solutions at different fixed concentrations of free Ca2+ (1 nM to 25.6 μM) and a specified dye concentration (12 μM) to pressures of 200 MPa, and record dye fluorescence intensity. Our results show that Fluo-4 fluorescence intensity is reduced by 31% per 100 MPa, the intensity of Fura Red is reduced by 10% per 100 MPa. The mean reaction volume for the dissociation of calcium from the dye molecules is determined to -17.8 ml mol-1 for Fluo-4 and -21.3 ml mol-1 for Fura Red. Additionally, a model is presented that is used to correct for pressure-dependent changes in pH and binding affinity of Ca2+ to EGTA, as well as to determine the influence of these changes on dye fluorescence.

Binaural blood flow control by astrocytes: listening to synapses and the vasculature.

Astrocytes are the most common glial cells in the brain with fine processes and endfeet that intimately contact both neuronal synapses and the cerebral vasculature. They play an important role in mediating neurovascular coupling (NVC) via several astrocytic Ca2+ -dependent signalling pathways such as K+ release through BK channels, and the production and release of arachidonic acid metabolites. They are also involved in maintaining the resting tone of the cerebral vessels by releasing ATP and COX-1 derivatives. Evidence also supports a role for astrocytes in maintaining blood pressure-dependent change in cerebrovascular tone, and perhaps also in blood vessel-to-neuron signalling as posited by the 'hemo-neural hypothesis'. Thus, astrocytes are emerging as new stars in preserving the intricate balance between the high energy demand of active neurons and the supply of oxygen and nutrients from the blood by maintaining both resting blood flow and activity-evoked changes therein. Following neuropathology, astrocytes become reactive and many of their key signalling mechanisms are altered, including those involved in NVC. Furthermore, as they can respond to changes in vascular pressure, cardiovascular diseases might exert previously unknown effects on the central nervous system by altering astrocyte function. This review discusses the role of astrocytes in neurovascular signalling in both physiology and pathology, and the impact of these findings on understanding BOLD-fMRI signals.

Pressure induced elastic softening in framework aluminosilicate- albite (NaAlSi3O8).

Albite (NaAlSi3O8) is an aluminosilicate mineral. Its crystal structure consists of 3-D framework of Al and Si tetrahedral units. We have used Density Functional Theory to investigate the high-pressure behavior of the crystal structure and how it affects the elasticity of albite. Our results indicate elastic softening between 6–8 GPa. This is observed in all the individual elastic stiffness components. Our analysis indicates that the softening is due to the response of the three-dimensional tetrahedral framework, in particular by the pressure dependent changes in the tetrahedral tilts. At pressure <6 GPa, the PAW-GGA can be described by a Birch-Murnaghan equation of state with = 687.4 Å3, = 51.7 GPa, and = 4.7. The shear modulus and its pressure derivative are = 33.7 GPa, and = 2.9. At 1 bar, the azimuthal compressional and shear wave anisotropy = 42.8%, and = 50.1%. We also investigate the densification of albite to a mixture of jadeite and quartz. The transformation is likely to cause a discontinuity in density, compressional, and shear wave velocity across the crust and mantle. This could partially account for the Mohorovicic discontinuity in thickened continental crustal regions.

First-principles simulation on pressure-dependent local structure change of AsS melt

The local structure of AsS melt has been investigated by the first-principles method. At ambient pressure, As4S4 molecules remain in liquid AsS similar to that of crystal As4S4(II). Structural analyses based on the first and second coordination shell indicate that the local structure of AsS melt undergo two sudden change processes with increasing pressure from 0.0 to 6.9GPa: the first is from 1.5 to 2.9GPa that the AsS melt transforms from molecular into polymeric liquid, the second is from 4.3 to 5.6GPa where the coordination number of the first shell for As and S change apparently. Our calculated results and conclusion for the structural change of AsS melt under compression are very different from those of previous report (Phys. Rev. B 84, 224202). Corresponding to the local structure change, the dynamical properties, such as diffusion coefficients and velocity-velocity autocorrelation function, also show apparent transformation in theses pressure intervals. On the basis of the calculated results, we concluded that the local structure changes of AsS melt should be consistent with its liquid-liquid phase transition under compression.

OCT Study of Mechanical Properties Associated with Trabecular Meshwork and Collector Channel Motion in Human Eyes.

We report the use of a high-resolution optical coherence tomography (OCT) imaging platform to identify and quantify pressure-dependent aqueous outflow system (AOS) tissue relationships and to infer mechanical stiffness through examination of tissue properties in ex vivo human eyes. Five enucleated human eyes are included in this study, with each eye prepared with four equal-sized quadrants, each encompassing 90 degrees of the limbal circumference. In radial limbal segments perfusion pressure within Schlemm’s canal (SC) is controlled by means of a perfusion cannula inserted into the canal lumen, while the other end of the cannula leads to a reservoir at a height that can control the pressure in the cannula. The OCT system images the sample with a spatial resolution of about 5 μm from the trabecular meshwork (TM) surface. Geometric parameters are quantified from the 2D OCT images acquired from the sample subjected to controlled changes in perfusion pressures; parameters include area and height of the lumen of SC, collector channel entrances (CCE) and intrascleral collector channels (ISCC). We show that 3D OCT imaging permits the identification of 3-D relationships of the SC, CCE and ISCC lumen dimensions. Collagen flaps or leaflets are found at CCE that are attached or hinged at only one end, whilst the flaps are connected to the TM by cylindrical structures spanning SC. Increasing static SC pressures resulted in SC lumen enlargement with corresponding enlargement of the CCE and ISCC lumen. Pressure-dependent SC lumen area and height changes are significant at the 0.01 levels for ANOVA, and at the 0.05 for both polynomial curves and Tukey paired comparisons. Dynamic measurements demonstrate a synchronous increase in SC, CCE and ISCC lumen height in response to pressure changes from 0 to 10, 30 or 50 mm Hg, respectively, and the response time is within the 50-millisecond range. From the measured SC volume and corresponding IOP values, we demonstrate that an elastance curve can be developed to infer the mechanical stiffness of the TM by means of quantifying pressure-dependent SC volume changes over a 2 mm radial region of SC. Our study finds pressure-dependent motion of the TM that corresponds to collagen leaflet configuration motion at CCE; the synchronous tissue motion also corresponds with synchrony of SC and CCE lumen dimension changes.

Structural transformations in sodium silicate liquids under pressure: A molecular dynamics study

We present the results of force-field molecular dynamics simulations of the static and dynamic properties of sodium silicate liquids. We studied the relationship between the structure and properties with varying SiO2 content and pressure. We found that the silicate liquids have at least three types of characteristic structures before the coordination number of Si changes with increasing pressure; these structures are, ionic, network, and coesitic structured liquids. In the ionic liquid like structure, simple diffusion of large silicate anions is dominant in the liquid and their motion is impeded by compression. In contrast, in the network liquid, a small portion of the network of corner-shared SiO4 tetrahedra diffuses via bond exchange and flow globally. Bond exchange is activated by pressure in the entangled network liquid because of distortion of the corner-shared SiO4 tetrahedra network and the tetrahedra themselves. The SiO2 rich liquids soften as a result from of these distortions. The derivative of bulk moduli of the sodium silicate liquids increases significantly at a certain pressure because of changes in densification mechanism. The changes in those densification mechanisms are coherent with the changes in pressure dependence of transport coefficient.

Graphene Membranes for Atmospheric Pressure Photoelectron Spectroscopy.

Atmospheric pressure X-ray photoelectron spectroscopy (XPS) is demonstrated using single-layer graphene membranes as photoelectron-transparent barriers that sustain pressure differences in excess of 6 orders of magnitude. The graphene serves as a support for catalyst nanoparticles under atmospheric pressure reaction conditions (up to 1.5 bar), where XPS allows the oxidation state of Cu nanoparticles and gas phase species to be simultaneously probed. We thereby observe that the Cu(2+) oxidation state is stable in O2 (1 bar) but is spontaneously reduced under vacuum. We further demonstrate the detection of various gas-phase species (Ar, CO, CO2, N2, O2) in the pressure range 10-1500 mbar including species with low photoionization cross sections (He, H2). Pressure-dependent changes in the apparent binding energies of gas-phase species are observed, attributable to changes in work function of the metal-coated grids supporting the graphene. We expect atmospheric pressure XPS based on this graphene membrane approach to be a valuable tool for studying nanoparticle catalysis.

Structural Effects of High Hydrostatic Pressure on Human Low Density Lipoprotein Revealed by Small Angle X-ray and Neutron Scattering

Low-density lipoprotein (LDL) is the principal cholesterol transporter in the human blood circulation. The quasi-spherical LDL particles (∼20 nm) are made up of a complex combination of various lipids and a large single amphipathic protein moiety, named apolipoprotein B-100. LDL has a hydrophobic core and an amphiphilic shell. Each particle has a specific phase transition temperature (Tm) corresponding to the melting of the core lipids from an ordered liquid crystalline to a disordered fluid phase.The structural impact of high hydrostatic pressure (HHP) was studied with different types of LDL (native, oxidized and triglyceride rich) with SANS (PSI, Switzerland) and SAXS (Elettra, Italy). The HHP ranged from 50 to 3000 bar. Temperature points were chosen below, on and above Tm.The pair distance distribution functions p(r) of the SAS curves revealed pressure dependent changes of the particle structure seen in the low q-region (∼0.25 nm−1), also reflected by a decrease of Radii of Gyration (Rg) with increasing pressure.Especially the p(r) functions from the SAXS data do not only show an overall particle change but also a highly pressure sensitive inner organization. A triple-peak feature indicating the lamellar lipid organization below Tm was induced by raising the pressure up to 3000 bar. These pressure sensitive lipid layers were observed by scattering intensity changes in SAXS curves at q=1.7 nm−1.The shape alterations could be evidenced by fitting an ellipsoidal model to the SANS curves resulting in a decrease of the ellipsoidal radii under pressure. A new LDL model considering the cross-sectional electron density profile is developed and applied to the SAS data to get a more detailed insight into pressure dependent behavior.

Evidence for a new phase of dense hydrogen above 325 gigapascals.

Almost 80 years ago it was predicted that, under sufficient compression, the H-H bond in molecular hydrogen (H2) would break, forming a new, atomic, metallic, solid state of hydrogen. Reaching this predicted state experimentally has been one of the principal goals in high-pressure research for the past 30 years. Here, using in situ high-pressure Raman spectroscopy, we present evidence that at pressures greater than 325 gigapascals at 300 kelvin, H2 and hydrogen deuteride (HD) transform to a new phase--phase V. This new phase of hydrogen is characterized by substantial weakening of the vibrational Raman activity, a change in pressure dependence of the fundamental vibrational frequency and partial loss of the low-frequency excitations. We map out the domain in pressure-temperature space of the suggested phase V in H2 and HD up to 388 gigapascals at 300 kelvin, and up to 465 kelvin at 350 gigapascals; we do not observe phase V in deuterium (D2). However, we show that the transformation to phase IV' in D2 occurs above 310 gigapascals and 300 kelvin. These values represent the largest known isotropic shift in pressure, and hence the largest possible pressure difference between the H2 and D2 phases, which implies that the appearance of phase V of D2 must occur at a pressure of above 380 gigapascals. These experimental data provide a glimpse of the physical properties of dense hydrogen above 325 gigapascals and constrain the pressure and temperature conditions at which the new phase exists. We speculate that phase V may be the precursor to the non-molecular (atomic and metallic) state of hydrogen that was predicted 80 years ago.

The Capacitance of Nickel Pattern Electrodes on Zirconia Electrolyte

Micro-structured thin-film electrodes were employed to investigate the capacitive behavior of nickel on yttria-stabilized zirconia (YSZ) electrolytes by means of electrochemical impedance spectroscopy. Electrodes with different shapes and electrode areas clearly showed a linear relationship between capacitance and the electrode area. Electrostatic double layer models, however, could not explain the observed area specific capacitance value of ca. 3 F/m². This fact, the characteristic voltage dependence with a hysteresis, and the effect of H2S on the electrode capacitance indicate substantial contributions of a chemical capacitance. Possible types of chemical capacitance in the system Ni(H2/H2O)/YSZ are discussed and an oxygen partial pressure dependent mechanism change is suggested.

Mechanistic study of pressure and temperature dependent structural changes in reactive formation of silicon carbonate

The structure changes of silicon carbonate with pressure and temperature are explored based on systematic ab initio molecular dynamics simulations.

Direct Pen Writing of Adhesive Particle-Free Ultrahigh Silver Salt-Loaded Composite Ink for Stretchable Circuits.

In this article, we describe a writable particle-free ink for fast fabrication of highly conductive stretchable circuits. The composite ink mainly consists of soluble silver salt and adhesive rubber. Low toxic ketone was employed as the main solvent. Attributed to ultrahigh solubility of silver salt in short-chain ketone and salt-assisted dissolution of rubber, the ink can be prepared into particle-free transparent solution. As-prepared ink has a good chemical stability and can be directly filled into ballpoint pens and use to write on different substrates to form well adhesive silver salt-based composite written traces as needed. As a result of high silver salt loading, the trace can be converted into highly conductive silver nanoparticle-based composites after in situ reduction. Because of the introduction of adhesive elastomeric rubber, the as-formed conductive composite written trace can not only maintain good adhesion to various substrates but also show good conductivity under various deformations. The conductivity of written traces can be enhanced by repeated writing-reduction cycles. Different patterns can be fabricated by either direct handwriting or hand-copying. As proof-of-concept demonstrations, a typical handwriting heart-like circuit was fabricated to show its capability to work under different deformations, and a pressure-sensitive switch was also manufactured to present pressure-dependent change of resistance.

A possible explanation of pressure dependence of critical temperature Tc of alkali doped C60 superconductors

The pressure dependent changes in transition temperature (Tc) of alkali doped C 60 superconductor has been studied theoretically considering the combination of phonon mediated mechanism and high energy electronic interaction mechanism. The latter mechanism involves bond polarization in interaction with conduction electrons. The expression for Tc, isotope effect coefficient (α) and (dTc/dP)P has been obtained to explain the observed experimental results of alkali doped C 60. A good agreement has been found in experimental (Tc) and (dTc/dP)P = 0 values and calculated values.

Driving Forces in Pressure-Induced Protein Transitions.

The molecular mechanisms underlying pressure-induced protein denaturation can be analyzed based on the pressure-dependent differences in the apparent volume occupied by amino acids inside the protein and when exposed to water in an unfolded conformation. This chapter presents a volumetric analysis of the peptide group and the 20 naturally occurring amino acid side chains in the interior of the native state, the micelle-like interior of the pressure-induced denatured state, and in the unfolded conformation modeled by low-molecular analogs of proteins. The transfer of a peptide group from the protein interior to water becomes increasingly favorable as pressure increases. This observation classifies solvation of peptide groups as a major driving force in pressure-induced protein denaturation. Polar side chains do not appear to exhibit significant pressure-dependent changes in their preference for the protein interior or solvent. The transfer of nonpolar side chains from the protein interior to water becomes more unfavorable as pressure increases. An inference can be drawn that a sizeable population of nonpolar side chains remains buried inside a solvent-inaccessible core of the pressure-induced denatured state. At elevated pressures this core, owing to the absence of structural constraints, may become packed almost as tightly as the interior of the native state. The presence and partial disappearance of large intraglobular voids is another driving force facilitating pressure-induced protein denaturation. Volumetric data presented here have implications for the kinetics of protein folding and shed light on the nature of the folding transition state ensembles.

Exploring the free energy and conformational landscape of tRNA at high temperature and pressure.

A combined temperature- and pressure-dependent study was employed to reveal the conformational and free-energy landscape of phenylalanine transfer RNA (tRNA(Phe) ), a known model for RNA function, to elucidate the features that are essential in determining its stability. These studies also help explore its structural properties under extreme environmental conditions, such as low/high temperatures and high pressures. To this end, fluorescence and FTIR spectroscopies, calorimetric and small-angle scattering measurements were carried out at different ion concentrations over a wide range of temperatures and pressures up to several hundred MPa. Compared with the pronounced temperature effect, the pressure-dependent structural changes of tRNA(Phe) are small. A maximum of only 15 % unpaired bases is observed upon pressurization up to 1 GPa. RNA unfolding differs not only from protein unfolding, but also from DNA melting. Its pressure stability seems to be similar to that of noncanonical DNA structures.

Ambient-Pressure Soft X-ray Absorption Spectroscopy of a Catalyst Surface in Action: Closing the Pressure Gap in the Selective n-Butane Oxidation over Vanadyl Pyrophosphate

In order to close the pressure gap in the investigation of catalyst surfaces under real operation conditions we have developed a variable-pressure soft X-ray (hν ≤1.5 keV) absorption cell coupled to a gas analysis system to study the pressure dependency of the electronic and catalytic properties of catalyst surfaces in reactive atmospheres at elevated temperatures. With this setup we investigated the vanadium L3-edge and catalytic performance of polycrystalline vanadyl pyrophosphate in the selective oxidation of n-butane to maleic anhydride between 10 and 1000 mbar at 400 °C. As a result, major gas phase and pressure dependent spectral changes are observed at energies attributed to V 2p-3dz2 excitations assigned to vanadium atoms square-pyramidally coordinated to oxygen atoms. This can be interpreted in terms of a shortened vanadyl bond (V═O) and an increased vanadium oxidation state with higher pressures. Since this is accompanied by an increasing catalytic activity and selectivity, it indicates that van...

In situ Investigations from Spinels under high pressure and high Temperatures

Spinels seem to be important constituents of the deep interior of the Earth while transition with spinel or pseudospinel structure strongly influence the dynamic of the mantle. On the other hand, spinels are widely used as artificial material. The spinels Magnetite, Franklinite, and Gahnite are investigated at the Hamburger Synchrotron Laboratory (HASYLAB) at Hamburg. The experiments were carried out using the high pressure multi anvil devices MAX80 (F2.1 Beamline) and MAX200x (W2 Beamline). The MAX80 is a single state apparatus located at a bending magnet, MAX200x is a double state system located at a wiggler. Energy-dispersive X-ray diffraction in combination with Rietveld refinement [1, 2] was used to determine the pressure and temperature induced volume change. Isothermal experiments were performed up to 15 GPa at ambient temperature. The temperature and pressure dependent volume change were derived from compression experiments using MAX80 apparatus up to 5 GPa at temperatures of 298, 500, 700, 900 and 1100 K. Bulk moduli at ambient temperatures using a Birch-Murnaghan equation of state result in KT=184(7) GPa with K'=4.5(2) for Magnetite, KT =178(6) with K'=4.6(4) for Franklinite, and KT =204(9) with K'=4.9(6) for Gahnite.

Relationship between nonlinear pressure-induced chemical shift changes and thermodynamic parameters.

NMR chemical shift analysis is a powerful method to investigate local changes in the environment of the observed nuclear spin of a polypeptide that are induced by application of high hydrostatic pressure. Usually, in the fast exchange regime, the pressure dependence of chemical shifts is analyzed by a second order Taylor expansion providing the first- and second-order pressure coefficient B1 and B2. The coefficients then are interpreted in a qualitative manner. We show here that in a two-state model, the ratio of B2/B1 is related to thermodynamic parameters, namely the ratio of the difference of compressibility factors Δβ' and partial molar volumes ΔV. The analysis is applied to the random-coil model peptides Ac-Gly-Gly-Xxx-Ala-NH2, with Xxx being one of the 20 proteinogenic amino acids. The analysis gives an average Δβ'/ΔV ratio of 1.6 GPa(-1) provided the condition |ΔG(0)| ≪ 2RT holds for the difference of the Gibbs free energies (ΔG(0)) of the two states at the temperature (T0) and the pressure (p0). The amide proton and nitrogen B2/B1 of a given amino acid Xxx are strongly correlated, indicating that their pressure-dependent chemical shift changes are due to the same thermodynamic process. As a possible physical mechanism providing a two-state model, the hydrogen bonding of water with the corresponding amide protein was simulated for isoleucine in position Xxx. The obtained free energy could satisfy the relation |ΔG(0)| ≪ 2RT. The derived relation was applied to the β-amyloid peptide Aβ and the phosphocarrier protein HPr from S. carnosus. For the transition of state 1 to state 2' of Aβ, the derived relation of B2/B1 to Δβ'/ΔV can be confirmed experimentally. The HPr protein is characterized by substantially higher negative B2/B1 values than those found in the tetrapeptides with an average value of approximately -5.1 GPa(-1) (Δβ'/ΔV of 5.1 GPa(-1) provided |ΔG(0)| ≪ 2RT holds). Qualitatively, the B2/B1 ratio can be used to predict regions of the HPr protein involved in the interaction with enzyme I or HPr-kinase/phosphatase.

Pressure-Dependent Anharmonic Correlated Einstein Model Extended X-ray Absorption Fine Structure Debye–Waller Factors

A pressure-dependent anharmonic correlated Einstein model is derived for extended X-ray absorption fine structure (EXAFS) Debye–Waller factors (DWFs), which are presented in terms of cumulant expansion up to the third order. The model is based on quantum thermodynamic perturbation theory and includes anharmonic effects based on empirical potentials. Explicit analytical expressions of the pressure-dependent changes in the interatomic distance, anharmonic effective potential, thermodynamic parameters, first, second, and third EXAFS cumulants, and thermal expansion coefficient have been derived. This model avoids the use of extensive full lattice dynamical calculations, yet provides good and reasonable agreement of numerical results for Cu with experimental results of X-ray diffraction (XRD) analysis and pressure-dependent EXAFS. Significant pressure effects are shown by the decrease in the pressure-induced changes in the interatomic distance, EXAFS cumulants and thermal expansion coefficient, as well as by the increase in the pressure-induced changes in the interatomic effective potential, effective spring constant, correlated Einstein frequency, and temperature.

Dramatic softening of the negative thermal expansion material HfW2O8 upon heating through its WO4 orientational order-disorder phase transition

HfW2O8 undergoes a dramatic softening where the average bulk modulus (P = 52–414 MPa) drops from 69 GPa at 298 K to 48 GPa at 430 K as the temperature of the WO4 orientation order-disorder transition is approached. This is accompanied by increasingly negative thermal expansivity (−10 ppm·K−1 to −15 ppm·K−1) and reversible WO4 orientational disordering upon compression in α-HfW2O8. Additionally, α-HfW2O8 becomes elastically softer upon compression at constant temperature. The α→β phase transition temperature decreases by ∼30 K between 52 and 414 MPa. Above this phase transition, no further temperature-dependent softening or pressure-dependent changes in the coefficient of thermal expansion occurred.