Medial temporal lobe functional connectivity predicts stimulation-induced theta power.

Focal electrical stimulation of the brain incites a cascade of neural activity that propagates from the stimulated region to both nearby and remote areas, offering the potential to control the activity of brain networks. Understanding how exogenous electrical signals perturb such networks in humans is key to its clinical translation. To investigate this, we applied electrical stimulation to subregions of the medial temporal lobe in 26 neurosurgical patients fitted with indwelling electrodes. Networks of low-frequency (5-13 Hz) spectral coherence predicted stimulation-evoked increases in theta (5-8 Hz) power, particularly when stimulation was applied in or adjacent to white matter. Stimulation tended to decrease power in the high-frequency broadband (HFB; 50-200 Hz) range, and these modulations were correlated with HFB-based networks in a subset of subjects. Our results demonstrate that functional connectivity is predictive of causal changes in the brain, capturing evoked activity across brain regions and frequency bands.

Widespread theta synchrony and high-frequency desynchronization underlies enhanced cognition.

The idea that synchronous neural activity underlies cognition has driven an extensive body of research in human and animal neuroscience. Yet, insufficient data on intracranial electrical connectivity has precluded a direct test of this hypothesis in a whole-brain setting. Through the lens of memory encoding and retrieval processes, we construct whole-brain connectivity maps of fast gamma (30-100 Hz) and slow theta (3-8 Hz) spectral neural activity, based on data from 294 neurosurgical patients fitted with indwelling electrodes. Here we report that gamma networks desynchronize and theta networks synchronize during encoding and retrieval. Furthermore, for nearly all brain regions we studied, gamma power rises as that region desynchronizes with gamma activity elsewhere in the brain, establishing gamma as a largely asynchronous phenomenon. The abundant phenomenon of theta synchrony is positively correlated with a brain region's gamma power, suggesting a predominant low-frequency mechanism for inter-regional communication.

Localized or diffuse: the link between prefrontal cortex volume and cognitive reappraisal.

Despite functional brain imaging research pointing to the role of prefrontal cortex in cognitive reappraisal, the structural correlates of habitual engagement of reappraisal are unclear. Functional imaging studies of reappraisal have shown broad engagement of bilateral middle frontal cortex (MFC) and left superior frontal cortex (SFC), and specific engagement of the right SFC. However, volumetric studies have not identified clear associations between reappraisal and these regions. This discrepancy between functional and structural studies suggests that broad functional engagement associated with reappraisal might not be detectable at a structural level using highly localized volumetric measures. This study addressed the discrepant structural findings by assessing the relation between reappraisal and grey matter volume, using methods that allow both region-level broad/diffuse assessments (surface-based morphometry), and voxel-level specific/localized (voxel-based morphometry) measures. Results were consistent with diffuse positive volumetric associations with reappraisal in the right MFC and left SFC, and a localized positive volumetric association in the right SFC, thus resolving the discrepancy between functional and structural studies. This study provides novel evidence supporting the idea that functional engagement related to transient manipulations of reappraisal can be linked to structural associations related to habitual engagement of similar operations, within the same brain regions.

Thermodynamics, interfacial pressure isotherms and dilational rheology of mixed protein-surfactant adsorption layers.

Proteins and their mixtures with surfactants are widely used in many applications. The knowledge of their solution bulk behavior and its impact on the properties of interfacial layers made great progress in the recent years. Different mechanisms apply to the formation process of protein/surfactant complexes for ionic and non-ionic surfactants, which are governed mainly by electrostatic and hydrophobic interactions. The surface activity of these complexes is often remarkably different from that of the individual protein and has to be considered in respective theoretical models. At very low protein concentration, small amounts of added surfactants can change the surface activity of proteins remarkably, even though no strongly interfacial active complexes are observed. Also small added amounts of non-ionic surfactants change the surface activity of proteins in the range of small bulk concentrations or surface coverages. The modeling of the equilibrium adsorption behavior of proteins and their mixtures with surfactants has reached a rather high level. These models are suitable also to describe the high frequency limits of the dilational viscoelasticity of the interfacial layers. Depending on the nature of the protein/surfactant interactions and the changes in the interfacial layer composition rather complex dilational viscoelasticities can be observed and described by the available models. The differences in the interfacial behavior, often observed in literature for studies using different experimental methods, are at least partially explained by a depletion of proteins, surfactants and their complexes in the range of low concentrations. A correction of these depletion effects typically provides good agreement between the data obtained with different methods, such as drop and bubble profile tensiometry.

Dynamics of drops ­ Formation, growth, oscillation, detachment, and coalescence.

Single drops or bubbles are frequently used for the characterization of liquid-fluid interfaces. Their advantage is the small volume and the various protocols of their formation. Thus, several important methods are based on single drops and bubbles, such as capillary pressure and profile analysis tensiometry. However, these methods are often applied under dynamic conditions, although their principles are defined under equilibrium conditions. Thus, specific attention has to be paid when these methods are used beyond certain limits. In many cases, computational fluid dynamics (CFD) simulations have allowed researchers, to extend these limits and to gain important information on the interfacial dynamics. Examples discussed here are the capillary pressure tensiometry used for short time and profile analysis tensiometry for long time dynamic interfacial tension measurements, the oscillating drop methods for measuring dilational visco-elasticity. For measuring the coalescence of two drops the liquid dynamics of the subsequently formed liquid bridges have to be considered. In this paper, a thorough review of important experimental and computational findings, related to the dynamics of drops, including its formation, growth, oscillation, detachment, and coalescence is presented. Emphasis is however on some selected important developments. In addition, the paper tries to predict the main directions of advancement in interfacial research for the near future.

Transition from spherical to irregular dispersed phase in water/oil emulsions.

Bulk properties of transparent and dilute water in paraffin oil emulsions stabilized with sodium dodecyl sulfate (SDS) are analyzed by optical scanning tomography. Each scanning shot of the considered emulsions has a precision of 1 µm. The influence of aluminum oxide nanoparticles in the structure of the water droplets is investigated. Depending on concentrations of SDS and nanoparticles, a transition occurs in their shape that changes from spherical to polymorphous. This transition is controlled by the SDS/alumina nanoparticles mixing ratio and is described using an identification procedure of the topology of the gray level contours extracted from each images. The transition occurs for a critical mixing ratio of Rcrit ≈ 0.05 which does not significantly depend on temperature and electrolyte concentration. This structural change seems to be a general feature when emulsifying dispersions and most probably involves both interfacial and bulk phenomena.

Polyelectrolyte/surfactant mixtures in the bulk and at water/oil interfaces.

Stabilization of emulsions by mixed polyelectrolyte/surfactant systems is a prominent example for the application in modern technologies. The formation of complexes between the polymers and the surfactants depends on the type of surfactant (ionic, non-ionic) and the mixing ratio. The surface activity (hydrophilic-lipophilic balance) of the resulting complexes is an important quantity for its efficiency in stabilizing emulsions. The interfacial adsorption properties observed at liquid/oil interfaces are more or less equivalent to those observed at the aqueous solution/air interface, however, the corresponding interfacial dilational and shear rheology parameters differ quite significantly. The interfacial properties are directly linked to bulk properties, which support the picture for the complex formation of polyelectrolyte/surfactant mixtures, which is the result of electrostatic and hydrophobic interactions. For long alkyl chain surfactants the interfacial behavior is strongly influenced by hydrophobic interactions while the complex formation with short chain surfactants is mainly governed by electrostatic interactions.

Viscoelasticity moduli of aqueous C14EO8 solutions as studied by drop and bubble profile methods.

The drop and bubble profile methods are used to study the viscoelasticity modulus of C14EO8 aqueous solutions within a wide concentration range. To determine the equilibrium concentration of the surfactant in the drop bulk, the correction is introduced for the surfactant losses caused by its adsorption on the drop surface. It is shown that with this correction the frequency dependencies of the viscoelasticity modulus measured by either of the two experimental techniques are almost the same. The theoretical model is used, which describes the surfactant dilational rheology assuming the diffusion-governed adsorption. The experimental data for C14EO8 solutions is described by the reorientation model that assumes the two states of surfactant molecules with different molar areas in the surface layer and the intrinsic compressibility of the molecules.

Rheology of poly(methyl methacrylate) Langmuir monolayers: percolation transition to a soft glasslike system.

An experimental study of the equilibrium properties and of the surface rheology of Langmuir monolayers of poly(methyl methacrylate) (PMMA) at the air/water interface has been carried out as a function of polymer concentration (Γ) and molecular weight (M(w)). Dilational and shear complex elasticity moduli covering a frequency range from 10(-3) to 0.2 Hz have been discussed. It was found that the air∕water interface behaves as a poor solvent for PMMA monolayers, thus suggesting that the polymer coils take collapsed soft-disks (pancakes) shape at the interface. The equilibrium and dynamic results suggest a fluid-to-soft-glass transition as the polymer concentration increases above a critical packing fraction at constant temperature. This two-dimensional transition is in agreement with results previously discussed for the dilational rheology of poly(4-hydroxystyrene) [F. Monroy, F. Ortega, R. G. Rubio, H. Ritacco, and D. Langevin, J. Chem. Phys. 95, 056103 (2005)]. Furthermore, the Γ-dependence of the relaxation dynamics of the monolayers suggests that the gel state may be considered as a fragile soft glass.

Degree of crosslinking of collagen at interfaces: adhesion and shear rheological indicators.

Work of adhesion (ΔW) and surface rheology at solid/air and solution/air interface have been used as indicators to study the stabilization of collagen by different crosslinking agents like basic chromium sulfate (BCS), tannic acid, catechin and formaldehyde. The results show that an increase in rate of ΔW would promote adsorption while a decrease leads to hindered adsorption. Shear rheological studies on collagen demonstrate an increase in both shear viscosity and elasticity with time while for collagen with polyphenols like catechin and tannic acid there is an unusual breakdown of these values. A correlation between the rheological properties and the work of adhesion suggests that the time frame in which the viscoelastic behavior is initiated for collagen with different crosslinking agents determines the final macroscopic property of the protein. The study attempts to quantify the degree of crosslinking of collagen through the dynamics and strength of the water molecules in the assembly of hydrated protein and the crosslinking agents.

Capillary pressure studies under low gravity conditions.

For the understanding of short-time adsorption phenomena and high-frequency relaxations at liquid interfaces particular experimental techniques are needed. The most suitable method for respective studies is the capillary pressure tensiometry. However, under gravity conditions there are rather strong limitations, in particular due to convections and interfacial deformations. This manuscript provides an overview of the state of the art of experimental tools developed for short-time and high-frequency investigations of liquid drops and bubbles under microgravity. Besides the brief description of instruments, the underlying theoretical basis will be presented and limits of the applied methods under ground and microgravity conditions will be discussed. The results on the role of surfactants under highly dynamic conditions will be demonstrated by some selected examples studied in two space shuttle missions on Discovery in 1998 and Columbia in 2003.

Thermodynamics, adsorption kinetics and rheology of mixed protein-surfactant interfacial layers.

Depending on the bulk composition, adsorption layers formed from mixed protein/surfactant solutions contain different amounts of protein. Clearly, increasing amounts of surfactant should decrease the amount of adsorbed proteins successively. However, due to the much larger adsorption energy, proteins are rather strongly bound to the interface and via competitive adsorption surfactants cannot easily displace proteins. A thermodynamic theory was developed recently which describes the composition of mixed protein/surfactant adsorption layers. This theory is based on models for the single compounds and allows a prognosis of the resulting mixed layers by using the characteristic parameters of the involved components. This thermodynamic theory serves also as the respective boundary condition for the dynamics of adsorption layers formed from mixed solutions and their dilational rheological behaviour. Based on experimental studies with milk proteins (beta-casein and beta-lactoglobulin) mixed with non-ionic (decyl and dodecyl dimethyl phosphine oxide) and ionic (sodium dodecyl sulphate and dodecyl trimethyl ammonium bromide) surfactants at the water/air and water/hexane interfaces, the potential of the theoretical tools is demonstrated. The displacement of pre-adsorbed proteins by subsequently added surfactant can be successfully studied by a special experimental technique based on a drop volume exchange. In this way the drop profile analysis can provide tensiometry and dilational rheology data (via drop oscillation experiments) for two adsorption routes--sequential adsorption of the single compounds in addition to the traditional simultaneous adsorption from a mixed solution. Complementary measurements of the surface shear rheology and the adsorption layer thickness via ellipsometry are added in order to support the proposed mechanisms drawn from tensiometry and dilational rheology, i.e. to show that the formation of mixed adsorption layer is based on a modification of the protein molecules via electrostatic (ionic) and/or hydrophobic interactions by the surfactant molecules and a competitive adsorption of the resulting complexes with the free, unbound surfactant. Under certain conditions, the properties of the sequentially formed layers differ from those formed simultaneously, which can be explained by the different locations of complex formation.

Molecular weight dependence of the shear rheology of poly(methyl methacrylate) Langmuir films: a comparison between two different rheometry techniques.

The surface shear rheology of Langmuir monolayers of poly(methyl methacrylate) (PMMA) has been studied as a function of polymer concentration (Gamma) and molecular weight (N). Two different rheology techniques were used, one based on free damped oscillations of a ring with a sharp edge and the other based on a forced oscillation of a biconical disk. Both instruments were used in the oscillatory mode at comparable oscillation frequency and amplitude, which gave access to the viscoelastic shear modulus (S). The two instruments, working in different viscosity ranges, provide complementary and mutually compatible data. The results obtained for four PMMA samples of molecular weight between 8x10(3) and 2.7x10(5) g.mol(-1) show powerlike behavior as S approximately Gamma10 and S approximately N4. These strong dependences suggest a structural scenario based on the 2D percolation of the polymer pancakes.

From spherical to polymorphous dispersed phase transition in water/oil emulsions.

Optical scanning tomography is used to characterize bulk properties of transparent water-in-paraffin oil emulsions stabilized with hexadecyl-trimethylammonium bromide (CTAB) and silica nanoparticles. A flow of 500 hundred images is used to analyze each scanning shot with a precision of about 1 microm. The role of silica particles in the shape of the water droplets is investigated. Depending on the concentration of CTAB and silica nanoparticles, a transition occurs in their geometry that changes from spherical to polymorphous. This transition is controlled by the ratio R=[CTAB]/[SiO2] and is described using an identification procedure of the topology of the gray level contours of the tomographic images. The transition occurs for Rcrit approximately 3x10(-2) and is shown to correspond to a pH of the dispersed phase of 8.5.

Dilation and shear rheology of mixed beta-casein/surfactant adsorption layers.

The present study deals with dilational and shear rheological properties of adsorption layers of the milk protein beta-casein (BCS) mixed with the nonionic dodecyl dimethyl phosphine oxide (C12DMPO) and the positively charged dodecyl trimethyl ammonium bromide (DoTAB), respectively. The drop profile analysis tensiometer PAT-1 was applied for the dilational rheological studies at low frequency harmonic relaxations. A special modification of the setup, consisting of a coaxial capillary combined with a double dosing system, provides exchange of the drop volume during experiments. This arrangement offers a unique protocol for studies of mixed surface layers, formed by sequential adsorption of the individual compounds. The dilational viscoelastic modulus and the dilational viscosity of the mixed layers, built-up in the two different ways, were investigated and compared. The features of the mixed surface layers drawn from the dilational rheology are qualitatively confirmed by the shear rheological parameters measured by torsion shear rheometry ISR-1. Recently derived theoretical models were used for a quantitative description of the equilibrium state and dilational rheology of the surface layers formed by the single components and their mixtures.

Interfacial shear rheology of protein-surfactant layers.

The shear rheology of adsorbed or spread layers at air/liquid and liquid/liquid phase boundaries is relevant in a wide range of technical applications such as mass transfer, monolayers, foaming, emulsification, oil recovery, or high speed coating. Interfacial shear rheological properties can provide important information about interactions and molecular structure in the interfacial layer. A variety of measuring techniques have been proposed in the literature to measure interfacial shear rheological properties and have been applied to pure protein or mixed protein adsorption layers at air/water or oil/water interfaces. Such systems play for example an important role as stabilizers in foams and emulsions. The aim of this contribution is to give a literature overview of interfacial shear rheological studies of pure protein and protein/surfactant mixtures at liquid interfaces measured with different techniques. Techniques which utilize the damping of waves, spectroscopic or AFM techniques and all micro-rheological techniques will not discuss here.

Lipases at interfaces: unique interfacial properties as globular proteins.

The adsorption behavior of two globular proteins, lipase from Rhizomucor miehei and beta-lactoglobulin, at inert oil/water and air/water interfaces was studied by the pendant drop technique. The kinetics and adsorption isotherms were interpreted for both proteins in different environments. It was found that the adopted mathematical models well describe the adsorption behavior of the proteins at the studied interfaces. One of the main findings is that unique interfacial properties were observed for lipase as compared to the reference beta-lactoglobulin. A folded drop with a "skinlike" film was formed for the two proteins after aging followed by compression. This behavior is normally associated with protein unfolding and covalent cross-linking at the interface. Despite this, the lipase activity was not suppressed. By highlighting the unique interfacial properties of lipases, we believe that the presented work contributes to a better understanding of lipase interfacial activation and the mechanisms regulating lipolysis. The results indicate that the understanding of the physical properties of lipases can lead to novel approaches to regulate their activity.

Contact angle determination of micro- and nanoparticles at fluid/fluid interfaces: the excluded area concept.

A novel and simple method for the determination of the contact angle of nano- and microparticles at the liquid/air interface is proposed. The principle is based on the consideration of differences between the pressure/area isotherms of a 2D single-component system of a surfactant and those of binary systems comprised of the same surfactant and the particles to be studied. The theoretical analysis of the contact-angle behavior in this system upon compression allows the prediction of direction of the particles' squeezing out of the surface layer and therefore the distinction between the particles with high contact angle (Theta(p) > 90 degrees) and low (Theta(p) < 90 degrees) hydrophobicity. The application of this method to microparticles of two different hydrophobicities demonstrates good agreement between the obtained contact angles and the corresponding degrees of hydrophobicity given by the particle provider.

Studies of the rate of water evaporation through adsorption layers using drop shape analysis tensiometry.

With modified measuring procedure and measuring cell design in the drop profile tensiometer PAT, it became possible to study the rate of water evaporation through adsorbed or spread surface layers. This method was employed to measure the rate of water evaporation from drops covered by adsorbed layers of some proteins and surfactants, in particular n-dodecanol. It was shown that the formation of dense (double or condensed) adsorbed layers of protein and the formation of 2D-condensed n-dodecanol layer decrease the water evaporation rate by 20-25% as compared with pure water. At the same time, the adsorbed layers of ordinary surfactants (sodium dodecyl sulfate and nonionic ethoxylated surfactant C(14)EO(8)) do not affect the water evaporation rate remarkably.

Rheological surface properties of C12DMPO solution as obtained from amplitude- and phase-frequency characteristics of an oscillating bubble system.

The experimental data on the surface rheological characteristics of dodecyl dimethyl phosphine oxide solutions obtained in a fully automatic oscillating bubble device under microgravity conditions in the frequency range 0.01-100 Hz are presented. The complex surface elasticity modulus is obtained form the amplitude- and phase-frequency characteristics of established pressure oscillations in a closed cell without calibration experiments by direct calculation of the necessary coefficients. The characteristics of the adsorption layers obtained from the elasticity modulus are in good agreement with adsorption isotherms and equations of state accounting for the intrinsic (2D) monolayer compressibility.