Vapour–liquid phase equilibria of simple fluids confined in patterned slit pores

We present the influence of surface heterogeneity on the vapour–liquid phase behaviour of square-well fluids in slit pores using grand-canonical transition-matrix Monte Carlo simulations along with the histogram-reweighting method. Properties such as phase coexistence envelopes, critical properties and local density profiles of the confined SW fluid are reported for chemically and physically patterned slit surfaces. It is observed that in the chemically patterned pores, fluid–fluid and surface attraction parameters along with the width of attractive and inert stripes play fundamentally different roles in the phase coexistence and critical properties. On the other hand, pillar gap and height significantly affect the vapour–liquid equilibria in the physically patterned slit pores. We also present the effect of chemically and physically patterned slit surfaces on the spreading pressure.     

A comparative study of critical temperature estimation of atomic fluid and chain molecules using fourth-order Binder cumulant and simplified scaling laws

Grand-canonical transition-matrix Monte Carlo simulation with histogram reweighting and finite-size scaling technique are used to calculate fourth-order Binder cumulant of order parameter along the vapour–liquid coexistence line to calculate the critical temperature of bulk and confined square-well fluid in slit pore of two pore sizes. Further, this approach is utilised to estimate the critical temperatures of relatively more complex fluids such as n-alkanes confined in graphite and mica slit pores of different slit widths. The estimated critical temperatures are compared with the critical temperature obtained for the same systems using simplified form of the scaling law. This investigation reveals that critical temperatures of simple and complex fluids in bulk state and under confinement, estimated using the scaling law, are within reasonable accuracy with that obtained using more accurate and rigorous approach of fourth-order Binder's cumulant.     

Effects of Porosity and Mixed Convection on MHD Two Phase Fluid Flow in an Inclined Channel

The present study deals with the flow and heat transfer analysis of two immiscible fluids in an inclined channel embedded in a porous medium. The channel is divided in two phases such that a third grade fluid occupies the phase I and a viscous fluid occupies the phase II. Both viscous and third grade fluids are electrically conducting. A constant magnetic field is imposed perpendicular to the channel walls. The mathematical model is developed by using Darcy''s and modified Darcy''s laws for viscous and third grade fluids respectively. The transformed ordinary differential equations are solved numerically using a shooting method. The obtained results are presented graphically and influence of emerging parameters is discussed in detail.     

Pressure effects in confined nanophases

In this article, we review how pressure effects in pores affect both the physics of the confined fluid and the properties of the host porous material. Molecular simulations in which high-pressure effects were observed are first discussed; we will see how the strong dependence on bulk phase pressure of the freezing temperature of a fluid confined in nanopores can be explained by important variations of the pressure within the pore. We then discuss recent works in which direct calculations of the pressure tensor of fluids confined in pores provide evidence for large pressure enhancements. Finally, practical applications of these pressure effects in which gas adsorption in microporous solids (pore size < 2 nm) was found to enhance their mechanical properties by increasing the elastic modulus by a factor 4 are discussed.     

The role of particle softness in determining the value of Poisson's ratio for soft sphere solids

The influence of particle softness on the Poisson's ratio of model solids has been investigated. We have used the repulsive inverse power potential (～r ^? n for particle separations, r) between the particles, which is conveniently characterised by one adjustable parameter, ? = 1/n. For large ?, the interaction is soft whereas in the ? → 0 limit the particles approach hard spheres. The pressure and elastic constants of the solid phase have been calculated at various densities with constant temperature molecular dynamics (MD) simulation for a range of the softness parameter in the range, n>12. Density-softness surfaces of these quantities were determined which revealed hitherto unrecorded trends in the behaviour of the elastic moduli and Poisson's ratio. It was found that the pressure and some elastic properties, e.g. the C₁₂ elastic constant and the bulk modulus, manifest a maximum value or ‘ridge’ on this surface. The height of the maximum increases with density and interaction steepness (small ?). The Poisson's ratio varies essentially linearly with softness and is relatively insensitive to density. However, at higher densities and for larger steepness a considerable lowering of the Poisson's ratio is observed. In order to identify possible mechanisms for reducing the value of Poisson's ratio, ν, the fluctuation and Born-Green contributions were analysed. Changes in the Poisson's ratio are mainly determined by the fluctuation contribution which can cause a considerable decrease as well as increase of its value.     

Interstitial fluid flow in the osteon with spatial gradients of mechanical properties: a finite element study

Bone remodelling is the process that maintains bone structure and strength through adaptation of bone tissue mechanical properties to applied loads. Bone can be modelled as a porous deformable material whose pores are filled with cells, organic material and interstitial fluid. Fluid flow is believed to play a role in the mechanotransduction of signals for bone remodelling. In this work, an osteon, the elementary unit of cortical bone, is idealized as a hollow cylinder made of a deformable porous matrix saturated with an interstitial fluid. We use Biot’s poroelasticity theory to model the mechanical behaviour of bone tissue taking into account transverse isotropic mechanical properties. A finite element poroelastic model is developed in the COMSOL Multiphysics software. Elasticity equations and Darcy’s law are implemented in this software; they are coupled through the introduction of an interaction term to obtain poroelasticity equations. Using numerical simulations, the investigation of the effect of spatial gradients of permeability or Poisson’s ratio is performed. Results are discussed for their implication on fluid flow in osteons: (i) a permeability gradient affects more the fluid pressure than the velocity profile; (ii) focusing on the fluid flow, the key element of loading is the strain rate; (iii) a Poisson’s ratio gradient affects both fluid pressure and fluid velocity. The influence of textural and mechanical properties of bone on mechanotransduction signals for bone remodelling is also discussed.     

Local response in nanopores

In this work the transient time correlation function (TTCF) algorithm is applied to study highly confined molecular fluids. We focus on linear polymer chains of various lengths trapped in a slab pore which is a few nanometres thick and made of atomistic walls, and the behaviour and response of the polymer melt subject to shear flow are considered. The shearing is produced by shifting the walls in opposite directions, and the temperature inside the channel is controlled by a thermostat applied to the wall atoms alone, so as to mimic the dissipation of heat as it occurs in real devices. It is shown how the TTCF algorithm can be applied to extract the fluid's dynamical and structural properties as they evolve from equilibrium and until a steady state has been established. We note that this procedure is applicable to fluids of any complexity and down to extremely low fields, comparable to those present in experimental devices. It is also shown that this technique can be used to probe local properties at specific locations across the channel. This feature is of particular significance because liquid properties inside nanoconfined geometries are mostly determined by the interactions at the interface and specifically by the structural reordering which affects the first few atomic/molecular layers close to the wall surface, e.g. slip.     

A density functional theory for Yukawa chain fluids in a nanoslit

A weighted density functional theory is developed for Yukawa chain fluids confined in a nanoslit. The excess free-energy functional is separated into repulsive and attractive contributions. A simple Heaviside function is used as the weighting function to calculate the weighted density in both contributions. The excess free-energy functional of repulsive interaction is calculated by the equation of state developed by Liu et al., while the contribution to excess free-energy functional by attractive interaction is calculated using the statistical associating fluids theory for chain molecules with attractive potentials of variable range. For pure fluids, the predicted density profiles near the nanoslit wall are in good agreement with simulations. The effect of cut-off introduced in the weighting function for the attractive part is examined; in addition, the surface excess and partition coefficient are calculated. The density profiles are also predicted for mixtures of two Yukawa chain fluids with different chain lengths, hard-core diameters, fluid–fluid and wall–fluid interactions. This work reveals that it is important to decompose the excess free-energy functional into repulsive and attractive contributions, and a simple weighting function can be used for both contributions.     

Mechanical properties of the porcine growth plate and its three zones from unconfined compression tests

The aim of the study was to determine intrinsic mechanical properties of the complete growth plate and its reserve, proliferative and hypertrophic zones. Growth plate disk samples from newborn swine's ulnae were tested using stress relaxation tests under unconfined compression. The Transversely Isotropic Biphasic Model (TIBPE) derived by [Cohen, B., Lai, W. M., Mow, V. C., 1998. A transversely isotropic biphasic model for unconfined compression of growth plate and chondroepiphysis. Journal of Biomechanical Engineering, 120, pp. 491–496] was used to extract intrinsic mechanical properties using a four-parameter optimization procedure. Significant differences were found for the transverse permeability k₁, the Poisson's ratio in the transverse plane ν₂₁, the out-of-plane Poisson's ratio ν₃₁ and the out-of-plane Young's modulus E₃ between the reserve zone and the proliferative zone as well as between the reserve zone and the hypertrophic zone. The same trends were obtained for the Young's modulus in the transverse plane E₁, but significant differences were also found between the reserve zone and the complete growth plate. The proliferative and hypertrophic zones are half as stiff as the reserve zone along the compression axis and about three times less stiff than the reserve zone in the transverse plane. These two zones are also three times as permeable as the reserve zone in the radial direction. The mechanical behavior of the newborn porcine distal ulna growth plate is non-uniform along its thickness. The reserve zone, with its greater zonal component at that development stage, has noteworthy effects on the complete growth plate intrinsic mechanical properties. This study provides, for the very first time, an investigation of the intrinsic mechanical properties of the reserve, proliferative and hypertrophic zones of the growth plate.     

Orientation-Based Control of Microfluidics

Most microfluidic chips utilize off-chip hardware (syringe pumps, computer-controlled solenoid valves, pressure regulators, etc.) to control fluid flow on-chip. This expensive, bulky, and power-consuming hardware severely limits the utility of microfluidic instruments in resource-limited or point-of-care contexts, where the cost, size, and power consumption of the instrument must be limited. In this work, we present a technique for on-chip fluid control that requires no off-chip hardware. We accomplish this by using inert compounds to change the density of one fluid in the chip. If one fluid is made 2% more dense than a second fluid, when the fluids flow together under laminar flow the interface between the fluids quickly reorients to be orthogonal to Earth’s gravitational force. If the channel containing the fluids then splits into two channels, the amount of each fluid flowing into each channel is precisely determined by the angle of the channels relative to gravity. Thus, any fluid can be routed in any direction and mixed in any desired ratio on-chip simply by holding the chip at a certain angle. This approach allows for sophisticated control of on-chip fluids with no off-chip control hardware, significantly reducing the cost of microfluidic instruments in point-of-care or resource-limited settings.     

A biphasic and transversely isotropic mechanical model for tendon: application to mouse tail fascicles in uniaxial tension

A transversely isotropic biphasic mixture model was applied to tendon in uniaxial tension. Parametric analyses were performed and the sensitivity in predicting material parameters was evaluated. Our results provide quantitative evidence for fluid flow as a mechanism that contributes to tendon viscoelasticity. Transversely isotropic material properties were calculated for mouse tail tendon fascicles. The average transverse modulus (E(1)) was 0.046 MPa, the fiber-aligned Poisson's ratio (v(31)) was 2.73, and the transverse Poisson's ratio [(v(21)) was 0.96; these properties were not strain-dependent. The fiber-aligned modulus (E(s)) was strain-dependent and was 20.7 MPa in the toe region and 86.1 MPa in the linear region. These solid matrix properties were consistent with previously published tendon tissue and fascicle data. The fascicle permeability was strain-dependent and was 5.5 x 10(-18)m(4)/Ns in the toe region and 0.32 x 10(-18)m(4)/Ns in the linear region, similar to previously reported meniscus permeability in tension. The similar permeabilities of both fascicle and tissue-level samples suggest that fluid flow from individual fascicles, not the packing of multiple fascicles together, may be the primary barrier to fluid flow in tendon and thus the primary mechanism for viscoelasticity.     

Thermal variation of organic fluid properties and impact on thermal remediation feasibility

Preliminary evaluations of the feasibility of thermal remediation techniques such as hot water flooding and steam flushing can be conducted with a knowledge of the influence of temperature on organic fluid properties such as interfacial tension, density, viscosity, solubility, vapor pressure, and Henry's constant. Relationships quantifying the effect of these fluid properties on organic removal and empirical equations for predicting the thermal variation of fluid properties are reviewed. Methods for measuring these properties are reviewed and applied to the characterization of perchloroethylene and a transformer oil. The importance of various removal mechanisms associated with thermal remediation is evaluated for these two fluids. Perchloroethylene solubilities increased by approximately 60% as temperature increased from 30°C to 90°C, suggesting that increased solubilization at higher temperatures would not be a significant removal mechanism. Viscosity and density reductions for both NAPLs were small, indicating that hydraulic displacement of NAPL would not be greatly enhanced with hot water or steam flushing. Interfacial tension decreases were not great enough to cause concem about downward remobilization of pools and residual zones of NAPLs. Capillary numbers for hot water flooding decreased for both NAPL, suggesting that hot water flooding would not enhance hydraulic removal of entrapped NAPL.     

Progress in packed column supercritical fluid chromatography: materials and methods

This article summarizes recent developments in packed column supercritical fluid chromatography. Silica-based chemically bonded sorbents, similar to those used for HPLC, are widely used with solvent-modified fluids containing additives to suppress undesirable solute-sorbent interactions that lead to poor peak shapes. Composition programming is the most useful approach to gradient elution separations since solvent-modified fluids have low compressibility. Packed column SFC is most useful for the separation of mixtures usually separated by normal-phase HPLC. Compared to normal-phase HPLC it offers faster separations, higher efficiencies, faster column re-equilibration, and a wider range of experimental variables for optimization. Packed column SFC is being increasingly selected for the analytical and preparative separation of racemic mixtures using enantiomer-selective sorbents.     

The Ultrastructure of Chaenea teres and an Analysis of the Phylogeny of the Haptorid Ciliates

Chaenea teres has typical haptorid ultrastructure. The somatic monokinetid has two transverse microtubular ribbons, an overlapping postciliary microtubular ribbon, and a laterally directed kinetodesmal fiber. The evered cytopharynx forms a dome at the apical end of the cell. The base of the dome is surrounded by oral dikinetids. The left, anterior kinetosome of the oral pair is not ciliated and has a transverse microtubular ribbon, a nematodesmata and a single postciliary microtubule. The right, posterior kinetosome is ciliated and has only postciliary microtubules. The kinetosomes at the anterior ends of the somatic kinetics are close together and their transverse microtubules and nematodesmata contribute to the support of the cytopharynx. The transverse microtubules of these oralized somatic kinetosomes, together with those from the oral dikinetids, line the cytopharynx. Accessory or bulge microtubules arise perpendicular to the transverse microtubules. A dorsal brush of three kineties of clavate cilia is found on the cell surface just posterior to the oral region. Mucocysts and a single type of toxicyst are present. The toxicysts are confined to the oral region. There are multiple ovoid macronuclei that stain weakly. Micronuclei were not observed. Cladistic analysis indicates the Chaenea may be most closely related to Fuscheria and Acropisthium. The cladistic analysis also suggests that existing taxonomies of the subclass Haptoria need to be revised. We propose some modifications to Foissner & Foissner's classification that include transferring Helicoprorodon, Actinobolina, the buetschiliids, and the balantidiids to the order Haptorida and recognizing the close relationship between pleurostomes and spathidiids.     

On the ability of isolated frog skin to manufacture Ringer's fluid

Fresh, empty, isolated sacs of leg skin from R. pipiens manufacture a salt solution reasonably balanced with respect to ions and approximating a somewhat dilute Ringer''s fluid. Concentrations of ions bear little relationship to concentrations in the external medium even down to 12 mM. An effective regulatory mechanism is indicated whereby the amount of salt transported is adjusted to the amount of water or vice versa, the rate of movement of either salt or water being largely independent of osmotic or ionic gradients (outer fluid to manufactured inner fluid). Concentrations of the inner fluids appear to be regulated to conform to a fairly constant concentration within the skin. Some evidence is presented that a major factor in regulating concentration of the inner fluid is triggered by an initial dilution of the inner fluid, followed by stimulation of salt uptake.     

Cover Image,Volume 116, Number 7, July 2019

Viral vectors such as adenovirus have successful applications in vaccines and gene therapy but the manufacture of the high-quality virus remains a challenge. It is desirable to use the adsorption-based chromatographic separations that so effectively underpin the therapeutic protein manufacture. However fundamental differences in the size and stability of this class of product mean it is necessary to revisit the design of sorbent's morphology and surface chemistry. In this study, the behaviour of a cellulose nanofiber ion-exchange sorbent derivatised with quaternary amine ligands at defined densities is characterised to address this. This material was selected as it has a large accessible surface area for viral particles and rapid process times. Initially, the impact of surface chemistry on infective product recovery using low (440 µmol/g), medium (750 µmol/g), and high (1029 µmol/g) ligand densities is studied. At higher densities product stability is reduced, this effect increased with prolonged adsorption durations of 24 min with just ~10% loss at low ligand density versus ~50% at high. This could be mitigated by using a high flow rate to reduce the cycle time to ~1 min. Next, the impact of ligand density on the separation's resolution was evaluated. Key to understanding virus quality is the virus particle: infectious virus particle ratio. It was found this parameter could be manipulated using ligand density and elution strategy. Together this provides a basis for viral vector separations that allows for their typically low titres and labile nature by using high liquid velocity to minimise both load and on-column times while separating key product and process-related impurities.     

Hemoglobin crystals in fluid specimens from confined body spaces

Hemoglobin crystals phagocytized by polymorphonuclear leukocytes were seen in cytologic preparations of a cerebrospinal fluid and two pleural fluids. In the last two cases, the crystals were seen within erythrocytes and also free in the background. Intraerythrocytic crystallization of hemoglobin is the result of polymerization of the hemoglobin molecules; it occurs in peripheral blood in certain hemoglobinopathies, being more pronounced in hemoglobin C disease. In our three cases, in which the crystallization occurred not in peripheral blood but in fluids of confined body spaces, there was no clinical evidence of hemoglobinopathy and blood hemoglobin electrophoresis performed in one of the cases revealed normal hemoglobin. Under laboratory conditions, we produced intraerythrocytic crystallization of hemoglobin in hemorrhagic pleural fluid specimens by subjecting them to agents that induced decreased oxygen concentration and osmotic dehydration of the cells. We suggest that similar processes operative in fluid accumulated in confined body spaces produce crystallization of the hemoglobin of extravasated red blood cells in the absence of hemoglobinopathy.     

Reversed phase high performance liquid chromatography of adrenocorticotropin 1-39 and its fragments in the native and oxidized forms

This paper reports HPLC separations of human ACTH 1-39 and its fragments (ACTH 1-10, 4-10, 11-24) making use of original gradient systems. Both H2O2 or chloramine T were demonstrated to oxidize the Met 4 present in ACTH 1-39, 1-10, and 4-10; the oxidized forms were HPLC separated from the corresponding native polypeptides, indicating that this method is suitable for the identification in biological fluid of ACTH, its fragment and their methionine-sulphoxide derivatives with possible relevance to the problem of ageing and inactivation of active polypeptide.     

Properties of Confined Square-well Fluids using the Gibbs Ensemble Simulation Technique

In this work we have used the extension of the Gibbs ensemble simulation technique to inhomogeneous fluids [Panagiotopoulos, A.Z. (1987) "Adsorption and capillary condensation of fluid in cylindrical pores by Monte Carlo simulation in the Gibbs ensemble", Mol. Phys. , 62 (3), 701-719], which has been applied to adsorption phenomena of confined fluids. Fluid molecules are described by spherical particles interacting via a square-well potential. The fluid is confined in two types of walls: symmetrical (two hard walls) and non-symmetrical (one square-well wall and one hard wall). In order to analyze the behavior of the confined fluid by varying the potential parameters, we evaluated the bulk and confined densities, the internal energies and the density profiles for different supercritical temperatures. A variety of adsorption profiles can be obtained by using this model. The simulation data reported here complements the available simulation data for this system and can be useful in the development of inhomogeneous fluid theories. Since the square-well parameters can be related to real molecules this system can also be used to understand real adsorption systems.