WorldWideScience

Sample records for macroscopic hydrophobic interaction

  1. Hydrophobic interactions and chemical reactivity

    NARCIS (Netherlands)

    Otto, Sijbren; Engberts, Jan B.F.N.

    2003-01-01

    This perspective describes how kinetic studies of organic reactions can be used to increase our understanding of hydrophobic interactions. In turn, our understanding of hydrophobic interactions can be used as a tool to influence chemical reactions.

  2. Hydrophobic interactions and chemical reactivity

    NARCIS (Netherlands)

    Otto, Sijbren; Engberts, Jan B.F.N.

    2003-01-01

    This perspective describes how kinetic studies of organic reactions can be used to increase our understanding of hydrophobic interactions. In turn, our understanding of hydrophobic interactions can be used as a tool to influence chemical reactions.

  3. A Heuristic Molecular Model of Hydrophobic Interactions

    CERN Document Server

    Hummer, G; García, A E; Pohorille, A; Pratt, L R

    1995-01-01

    Hydrophobic interactions provide driving forces for protein folding, membrane formation, and oil-water separation. Motivated by information theory, the poorly understood nonpolar solute interactions in water are investigated. A simple heuristic model of hydrophobic effects in terms of density fluctuations is developed. This model accounts quantitatively for the central hydrophobic phenomena of cavity formation and association of inert gas solutes; it therefore clarifies the underlying physics of hydrophobic effects and permits important applications to conformational equilibria of nonpolar solutes and hydrophobic residues in biopolymers.

  4. A Heuristic Molecular Model of Hydrophobic Interactions

    OpenAIRE

    Hummer, G; Garde, S; Garcia, A.E.; Pohorille, A; Pratt, L.R.

    1995-01-01

    Hydrophobic interactions provide driving forces for protein folding, membrane formation, and oil-water separation. Motivated by information theory, the poorly understood nonpolar solute interactions in water are investigated. A simple heuristic model of hydrophobic effects in terms of density fluctuations is developed. This model accounts quantitatively for the central hydrophobic phenomena of cavity formation and association of inert gas solutes; it therefore clarifies the underlying physics...

  5. How specific halide adsorption varies hydrophobic interactions.

    Science.gov (United States)

    Stock, Philipp; Müller, Melanie; Utzig, Thomas; Valtiner, Markus

    2016-03-11

    Hydrophobic interactions (HI) are driven by the water structure around hydrophobes in aqueous electrolytes. How water structures at hydrophobic interfaces and how this influences the HI was subject to numerous studies. However, the effect of specific ion adsorption on HI and hydrophobic interfaces remains largely unexplored or controversial. Here, the authors utilized atomic force microscopy force spectroscopy at well-defined nanoscopic hydrophobic interfaces to experimentally address how specific ion adsorption of halide ions as well as NH4 (+), Cs(+), and Na(+) cations alters interaction forces across hydrophobic interfaces. Our data demonstrate that iodide adsorption at hydrophobic interfaces profoundly varies the hydrophobic interaction potential. A long-range and strong hydration repulsion at distances D > 3 nm, is followed by an instability which could be explained by a subsequent rapid ejection of adsorbed iodides from approaching hydrophobic interfaces. In addition, the authors find only a weakly pronounced influence of bromide, and as expected no influence of chloride. Also, all tested cations do not have any significant influence on HI. Complementary, x-ray photoelectron spectroscopy and quartz-crystal-microbalance with dissipation monitoring showed a clear adsorption of large halide ions (Br(-)/I(-)) onto hydrophobic self-assembled monolayers (SAMs). Interestingly, iodide can even lead to a full disintegration of SAMs due to specific and strong interactions of iodide with gold. Our data suggest that hydrophobic surfaces are not intrinsically charged negatively by hydroxide adsorption, as it was generally believed. Hydrophobic surfaces rather interact strongly with negatively charged large halide ions, leading to a surface charging and significant variation of interaction forces.

  6. Developing a general interaction potential for hydrophobic and hydrophilic interactions.

    Science.gov (United States)

    Donaldson, Stephen H; Røyne, Anja; Kristiansen, Kai; Rapp, Michael V; Das, Saurabh; Gebbie, Matthew A; Lee, Dong Woog; Stock, Philipp; Valtiner, Markus; Israelachvili, Jacob

    2015-02-24

    We review direct force measurements on a broad class of hydrophobic and hydrophilic surfaces. These measurements have enabled the development of a general interaction potential per unit area, W(D) = -2γ(i)Hy exp(-D/D(H)) in terms of a nondimensional Hydra parameter, Hy, that applies to both hydrophobic and hydrophilic interactions between extended surfaces. This potential allows one to quantitatively account for additional attractions and repulsions not included in the well-known combination of electrostatic double layer and van der Waals theories, the so-called Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The interaction energy is exponentially decaying with decay length D(H) ≈ 0.3-2 nm for both hydrophobic and hydrophilic interactions, with the exact value of D(H) depending on the precise system and conditions. The pre-exponential factor depends on the interfacial tension, γ(i), of the interacting surfaces and Hy. For Hy > 0, the interaction potential describes interactions between partially hydrophobic surfaces, with the maximum hydrophobic interaction (i.e., two fully hydrophobic surfaces) corresponding to Hy = 1. Hydrophobic interactions between hydrophobic monolayer surfaces measured with the surface forces apparatus (SFA) are shown to be well described by the proposed interaction potential. The potential becomes repulsive for Hy < 0, corresponding to partially hydrophilic (hydrated) interfaces. Hydrated surfaces such as mica, silica, and lipid bilayers are discussed and reviewed in the context of the values of Hy appropriate for each system.

  7. Recent experimental advances on hydrophobic interactions at solid/water and fluid/water interfaces.

    Science.gov (United States)

    Zeng, Hongbo; Shi, Chen; Huang, Jun; Li, Lin; Liu, Guangyi; Zhong, Hong

    2015-03-15

    Hydrophobic effects play important roles in a wide range of natural phenomena and engineering processes such as coalescence of oil droplets in water, air flotation of mineral particles, and folding and assembly of proteins and biomembranes. In this work, the authors highlight recent experimental attempts to reveal the physical origin of hydrophobic effects by directly quantifying the hydrophobic interaction on both solid/water and fluid/water interfaces using state-of-art nanomechanical techniques such as surface forces apparatus and atomic force microscopy (AFM). For solid hydrophobic surfaces of different hydrophobicity, the range of hydrophobic interaction was reported to vary from ∼10 to >100 nm. With various characterization techniques, the very long-ranged attraction (>100 nm) has been demonstrated to be mainly attributed to nonhydrophobic interaction mechanisms such as pre-existing nanobubbles and molecular rearrangement. By ruling out these factors, intrinsic hydrophobic interaction was measured to follow an exponential law with decay length of 1-2 nm with effective range less than 20 nm. On the other hand, hydrophobic interaction measured at fluid interfaces using AFM droplet/bubble probe technique was found to decay with a much shorter length of ∼0.3 nm. This discrepancy of measured decay lengths is proposed to be attributed to inherent physical distinction between solid and fluid interfaces, which impacts the structure of interface-adjacent water molecules. Direct measurement of hydrophobic interaction on a broader range of interfaces and characterization of interfacial water molecular structure using spectroscopic techniques are anticipated to help unravel the origin of this rigidity-related mismatch of hydrophobic interaction and hold promise to uncover the physical nature of hydrophobic effects. With improved understanding of hydrophobic interaction, intrinsic interaction mechanisms of many biological and chemical pathways can be better

  8. Hydrophobic Interactions Involved in Attachment of a Baculovirus to Hydrophobic Surfaces

    OpenAIRE

    Small, Deirdre A.; Moore, Norman F.; Entwistle, Philip F.

    1986-01-01

    The hydrophobic interactions of Trichoplusia ni nuclear polyhedrosis virus were characterized by hydrophobic interaction chromatography. The determination of the hydrophobic force and some of the factors that influence its size is discussed in relation to the attachment to leaf surfaces of polyhedra during their use as biological control agents against insect pests.

  9. Hydrophobic Interactions Modulate Self-Assembly of Nanoparticles

    OpenAIRE

    Sánchez-Iglesias, Ana; Grzelczak, Marek; Altantzis, Thomas; Goris, Bart; Pérez-Juste, Jorge; Bals, Sara; Van Tendeloo, Gustaaf; Donaldson, Stephen H.; Chmelka, Bradley F.; Israelachvili, Jacob N.; Liz-Marzán, Luis M.

    2012-01-01

    Abstract: Hydrophobic interactions constitute one of the most important types of nonspecific interactions in biological systems, which emerge when water molecules rearrange as two hydrophobic species come close to each other. The prediction of hydrophobic interactions at the level of nanoparticles (Brownian objects) remains challenging because of uncontrolled diffusive motion of the particles. We describe here a general methodology for solvent-induced, reversible self-assembly of gold nanopar...

  10. Statistical analyses of hydrophobic interactions: A mini-review

    CERN Document Server

    Pratt, L R; Rempe, Susan B

    2016-01-01

    This review focuses on the striking recent progress in solving for hydrophobic interactions between small inert molecules. We discuss several new understandings. Firstly, the _inverse _temperature phenomenology of hydrophobic interactions, _i.e., strengthening of hydrophobic bonds with increasing temperature, is decisively exhibited by hydrophobic interactions between atomic-scale hard sphere solutes in water. Secondly, inclusion of attractive interactions associated with atomic-size hydrophobic reference cases leads to substantial, non-trivial corrections to reference results for purely repulsive solutes. Hydrophobic bonds are _weakened by adding solute dispersion forces to treatment of reference cases. The classic statistical mechanical theory for those corrections is not accurate in this application, but molecular quasi-chemical theory shows promise. Finally, because of the masking roles of excluded volume and attractive interactions, comparisons that do not discriminate the different possibilities face an...

  11. Macroscopic and microscopic self-organization by nonlocal anisotropic interactions

    CERN Document Server

    Cristiani, Emiliano; Tosin, Andrea

    2009-01-01

    This paper is concerned with mathematical modeling of intelligent systems, such as human crowds and animal groups. In particular, the focus is on the emergence of different self-organized patterns from non-locality and anisotropy of the interactions among individuals. A mathematical technique by time-evolving measures is introduced to deal with both macroscopic and microscopic scales within a unified modeling framework. Then self-organization issues are investigated and numerically reproduced at the proper scale, according to the kind of agents under consideration.

  12. Hydrophobic interactions increase attachment of gum Arabic- and PVP-coated Ag nanoparticles to hydrophobic surfaces.

    Science.gov (United States)

    Song, Jee Eun; Phenrat, Tanapon; Marinakos, Stella; Xiao, Yao; Liu, Jie; Wiesner, Mark R; Tilton, Robert D; Lowry, Gregory V

    2011-07-15

    A fundamental understanding of attachment of surface-coated nanoparticles (NPs) is essential to predict the distribution and potential risks of NPs in the environment. Column deposition studies were used to examine the effect of surface-coating hydrophobicity on NP attachment to collector surfaces in mixtures with varying ratios of octadecylichlorosilane (OTS)-coated (hydrophobic) glass beads and clean silica (hydrophilic) glass beads. Silver nanoparticles (AgNPs) coated with organic coatings of varying hydrophobicity, including citrate, polyvinylpyrrolidone (PVP), and gum arabic (GA), were used. The attachment efficiencies of GA and PVP AgNPs increased by 2- and 4-fold, respectively, for OTS-coated glass beads compared to clean glass beads. Citrate AgNPs showed no substantial change in attachment efficiency for hydrophobic compared to hydrophilic surfaces. The attachment efficiency of PVP-, GA-, and citrate-coated AgNPs to hydrophobic collector surfaces correlated with the relative hydrophobicity of the coatings. The differences in the observed attachment efficiencies among AgNPs could not be explained by classical DLVO, suggesting that hydrophobic interactions between AgNPs and OTS-coated glass beads were responsible for the increase in attachment of surface-coated AgNPs with greater hydrophobicity. This study indicates that the overall attachment efficiency of AgNPs will be influenced by the hydrophobicity of the NP coating and the fraction of hydrophobic surfaces in the environment.

  13. Modulation of hydrophobic interactions by proximally immobilized ions.

    Science.gov (United States)

    Ma, C Derek; Wang, Chenxuan; Acevedo-Vélez, Claribel; Gellman, Samuel H; Abbott, Nicholas L

    2015-01-15

    The structure of water near non-polar molecular fragments or surfaces mediates the hydrophobic interactions that underlie a broad range of interfacial, colloidal and biophysical phenomena. Substantial progress over the past decade has improved our understanding of hydrophobic interactions in simple model systems, but most biologically and technologically relevant structures contain non-polar domains in close proximity to polar and charged functional groups. Theories and simulations exploring such nanometre-scale chemical heterogeneity find it can have an important effect, but the influence of this heterogeneity on hydrophobic interactions has not been tested experimentally. Here we report chemical force microscopy measurements on alkyl-functionalized surfaces that reveal a dramatic change in the surfaces' hydrophobic interaction strengths on co-immobilization of amine or guanidine groups. Protonation of amine groups doubles the strength of hydrophobic interactions, and guanidinium groups eliminate measurable hydrophobic interactions in all pH ranges investigated. We see these divergent effects of proximally immobilized cations also in single-molecule measurements on conformationally stable β-peptides with non-polar subunits located one nanometre from either amine- or guanidine-bearing subunits. Our results demonstrate the importance of nanometre-scale chemical heterogeneity, with hydrophobicity not an intrinsic property of any given non-polar domain but strongly modulated by functional groups located as far away as one nanometre. The judicious placing of charged groups near hydrophobic domains thus provides a strategy for tuning hydrophobic driving forces to optimize molecular recognition or self-assembly processes.

  14. Inverse colloidal crystal membranes for hydrophobic interaction membrane chromatography.

    Science.gov (United States)

    Vu, Anh T; Wang, Xinying; Wickramasinghe, S Ranil; Yu, Bing; Yuan, Hua; Cong, Hailin; Luo, Yongli; Tang, Jianguo

    2015-08-01

    Hydrophobic interaction membrane chromatography has gained interest due to its excellent performance in the purification of humanized monoclonal antibodies. The membrane material used in hydrophobic interaction membrane chromatography has typically been commercially available polyvinylidene fluoride. In this contribution, newly developed inverse colloidal crystal membranes that have uniform pores, high porosity and, therefore, high surface area for protein binding are used as hydrophobic interaction membrane chromatography membranes for humanized monoclonal antibody immunoglobulin G purification. The capacity of the inverse colloidal crystal membranes developed here is up to ten times greater than commercially available polyvinylidene fluoride membranes with a similar pore size. This work highlights the importance of developing uniform pore size high porosity membranes in order to maximize the capacity of hydrophobic interaction membrane chromatography. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. On the thermodynamics and kinetics of hydrophobic interactions at interfaces.

    Science.gov (United States)

    Vembanur, Srivathsan; Patel, Amish J; Sarupria, Sapna; Garde, Shekhar

    2013-09-05

    We have studied how primitive hydrophobic interactions between two or more small nonpolar solutes are affected by the presence of surfaces. We show that the desolvation barriers present in the potential of mean force between the solutes in bulk water are significantly reduced near an extended hydrophobic surface. Correspondingly, the kinetics of hydrophobic contact formation and breakage are faster near a hydrophobic surface than near a hydrophilic surface or in the bulk. We propose that the reduction in the desolvation barrier is a consequence of the fact that water near extended hydrophobic surfaces is akin to that at a liquid-vapor interface and is easily displaced. We support this proposal with three independent observations. First, when small hydrophobic solutes are brought near a hydrophobic surface, they induce local dewetting, thereby facilitating the reduction of desolvation barriers. Second, our results and those of Patel et al. (Proc. Natl. Acad. Sci. U.S.A. 2011, 108, 17678-17683) show that, whereas the association of small solutes in bulk water is driven by entropy, that near hydrophobic surfaces is driven by enthalpy, suggesting that the physics of interface deformation is important. Third, moving water away from its vapor-liquid coexistence, by applying hydrostatic pressure, leads to recovery of bulklike signatures (e.g., the presence of a desolvation barrier and an entropic driving force) in the association of solutes. These observations for simple solutes also translate to end-to-end contact formation in a model peptide with hydrophobic end groups, for which lowering of the desolvation barrier and acceleration of contact formation are observed near a hydrophobic surface. Our results suggest that extended hydrophobic surfaces, such as air-water or hydrocarbon-water surfaces, could serve as excellent platforms for catalyzing hydrophobically driven assembly.

  16. Exploratory numerical experiments with a macroscopic theory of interfacial interactions

    Science.gov (United States)

    Giordano, D.; Solano-López, P.; Donoso, J. M.

    2017-09-01

    Phenomenological theories of interfacial interactions are founded on the core idea to model macroscopically the thin layer that forms between media in contact as a two-dimensional continuum (surface phase or interface) characterised by physical properties per unit area; the temporal evolution of the latter is governed by surface balance equations whose set acts as bridging channel in between the governing equations of the volume phases. These theories have targeted terrestrial applications since long time and their exploitation has inspired our research programme to build up, on the same core idea, a macroscopic theory of gas-surface interactions targeting the complex phenomenology of hypersonic reentry flows as alternative to standard methods in aerothermodynamics based on accommodation coefficients. The objective of this paper is the description of methods employed and results achieved in the exploratory study that kicked off our research programme, that is, the unsteady heat transfer between two solids in contact in planar and cylindrical configurations with and without interface. It is a simple numerical-demonstrator test case designed to facilitate quick numerical calculations but, at the same time, to bring forth already sufficiently meaningful aspects relevant to thermal protection due to the formation of the interface. The paper begins with a brief introduction on the subject matter and a review of relevant literature within an aerothermodynamics perspective. Then the case is considered in which the interface is absent. The importance of tension (force per unit area) continuity as boundary condition on the same footing of heat-flux continuity is recognised and the role of the former in governing the establishment of the temperature-difference distribution over the separation surface is explicitly shown. Evidence is given that the standard temperature-continuity boundary condition is just a particular case. Subsequently the case in which the interface is

  17. Vector description of electric and hydrophobic interactions in protein homodimers.

    Science.gov (United States)

    Mozo-Villarías, Angel; Cedano, Juan; Querol, Enrique

    2016-05-01

    This article describes the formation of homodimers from their constituting monomers, based on the rules set by a simple model of electric and hydrophobic interactions. These interactions are described in terms of the electric dipole moment (D) and hydrophobic moment vectors (H) of proteins. The distribution of angles formed by the two dipole moments of monomers constituting dimers were analysed, as well as the distribution of angles formed by the two hydrophobic moments. When these distributions were fitted to Gaussian curves, it was found that for biological dimers, the D vectors tend mostly to adopt a perpendicular arrangement with respect to each other, in which the constituting dipoles have the least interaction. A minor population tends towards an antiparallel arrangement implying maximum electric attraction. Also in biological dimers, the H vectors of most monomers tend to interact in such a way that the total hydrophobic moment of the dimer increases with respect to those of the monomers. This shows that hydrophobic moments have a tendency to align. In dimers originating in the crystallisation process, the distribution of angles formed by both hydrophobic and electric dipole moments appeared rather featureless, probably because of unspecific interactions in the crystallisation processes. The model does not describe direct interactions between H and D vectors although the distribution of angles formed by both vectors in dimers was analysed. It was found that in most cases these angles tended to be either small (both moments aligned parallel to each other) or large (antiparallel disposition).

  18. Nonclassical interactions portrait in a macroscopic pedestrian flow model

    Science.gov (United States)

    Rosini, Massimiliano D.

    In this paper we describe the main characteristics of the macroscopic model for pedestrian flows introduced in [R.M. Colombo, M.D. Rosini, Pedestrian flows and non-classical shocks, Math. Methods Appl. Sci. 28 (13) (2005) 1553-1567] and recently sperimentally verified in [D. Helbing, A. Johansson, H.Z. Al-Abideen, Dynamics of crowd disasters: An empirical study, Phys. Rev. E (Statistical, Nonlinear, and Soft Matter Physics) 75 (4) (2007) 046109]. After a detailed study of all the possible wave interactions, we prove the existence of a weighted total variation that does not increase after any interaction. This is the main ingredient used in [R.M. Colombo, M.D. Rosini, Existence of nonclassical Cauchy problem modeling pedestrian flows, technical report, Brescia Department of Mathematics, 2008] to tackle the Cauchy problem through wave front tracking, see [A. Bressan, Hyperbolic Systems of Conservation Laws. The One-Dimensional Cauchy Problem, Oxford Lecture Ser. Math. Appl., vol. 20, Oxford Univ. Press, Oxford, 2000, The one-dimensional Cauchy problem; A. Bressan, The front tracking method for systems of conservation laws, in: C.M. Dafermos, E. Feireisl (Eds.), Handbook of Differential Equations; Evolutionary Equations, vol. 1, Elsevier, 2004, pp. 87-168; R.M. Colombo, Wave front tracking in systems of conservation laws, Appl. Math. 49 (6) (2004) 501-537]. From the mathematical point of view, this model is one of the few examples of conservation laws in which nonclassical solutions have a physical motivation, see [P.G. Lefloch, Hyperbolic Systems of Conservation Laws, Lectures Math. ETH Zürich, Birkhäuser, Basel, 2002, The theory of classical and nonclassical shock waves], and an existence result is available.

  19. A Model for Macroscopic Quantum Tunneling of Bose-Einstein Condensate with Attractive Interaction

    Institute of Scientific and Technical Information of China (English)

    YAN Ke-Zhu; TAN Wei-Han

    2000-01-01

    Based on the numerical wave function solutions of neutral atoms with attractive interaction in a harmonic trap, we propose an exactly solvable model for macroscopic quantum tunneling of a Bose condensate with attractive interaction. We calculate the rate of macroscopic quantum tunneling from a metastable condensate state to the collapse state and analyze the stability of the attractive Bose-Einstein condensation.

  20. The quantum interaction of macroscopic objects and gravitons

    Science.gov (United States)

    Piran, Tsvi

    2016-09-01

    Copious production of gravitational radiation requires a compact source that moves relativistically. Such sources are rare and are found only in extreme cases such as the formation of a black hole in either via a gravitational collapse or via a merger. Noncompact, nonrelativistic objects emit gravitational radiation, however, this emission is extremely weak due to very large value of the Planck energy. The quantum nature of gravitons, namely the fact that a single graviton carries energy of order ℏω implies that macroscopic objects whose kinetic energy is less than the Planck energy emit gravitons quantum mechanically, emitting a single graviton at a time. This is a unique situation in which a macroscopic object behaves quantum mechanically. While it is impossible to check experimentally this quantum gravitational effect, it might be possible to carry out analogous electromagnetic experiments that will shed light on this macroscopic quantum mechanical behavior.

  1. Use and application of hydrophobic interaction chromatography for protein purification.

    Science.gov (United States)

    McCue, Justin T

    2014-01-01

    The objective of this section is to provide the reader with guidelines and background on the use and experimental application of Hydrophobic Interaction chromatography (HIC) for the purification of proteins. The section will give step by step instructions on how to use HIC in the laboratory to purify proteins. General guidelines and relevant background information is also provided.

  2. The dynamics of hydrophobic interaction : A microwave dielectric study

    NARCIS (Netherlands)

    Hallenga, Klaas

    1972-01-01

    To investigate the relation between the structure of liquid water and hydrophobic interaction the dielectric relaxation of water in dilute aqueous solutions has been studied. After an introduction of the problem in which the dynamic aspects of water structure are emphasized, a theoretical analysis o

  3. Interaction of Fluorocarbon Containing Hydrophobically Modified Polyelectrolyte with Nonionic Surfactants

    Institute of Scientific and Technical Information of China (English)

    GUO,Jin-Feng(郭金峰); ZHUANG,Dong-Qing(庄东青); ZHOU,Hui(周晖); ZHANG,Yun-Xiang(章云祥)

    2002-01-01

    The interaction of fluorocarbon containing hydrophobically modified polyelectrolyte (FMPAANa) with two kinds of nonionic surfactants (hydrogenated and fluorinated) in a semidilute (0.5 wt% ) aqueous solution had been studied by rheological measurements. Association behavior was found in both systems. The hydrophobic interaction of FMPAANa with fluorinated surfactant (FC171) is much stronger than that with hydrogenated surfactant (NP7.5) at low surfactant concentrations. The interaction is strengthened by surfactants being added for the density of active junctions increased. Whereas distinct phenomena for FC171 and NP7. 5 start to be found as the surfactants added over their respective certain concentration. The interaction of polyelectrolyte with fluorinated surfactant increases dramatical ly while that with hydrogenated surfactant decreases.

  4. Compositional fingerprint of soy sauces via hydrophobic surface interaction.

    Science.gov (United States)

    Jakobi, Victoria; Salmen, Paul; Paulus, Michael; Tolan, Metin; Rosenhahn, Axel

    2017-03-01

    In this work, the interaction of soy sauces with hydrophobic surfaces has been analyzed. Hydrophobic self-assembled monolayers on gold or silicon dioxide were used to harvest conditioning layers from soy sauce products with varying amounts of additives. The data was compared to adsorption of soy protein and glutamic acid as common ingredients. Spectral ellipsometry revealed that all tested sauces led to the formation of thin overlayers on hydrophobic surfaces. Products with less additives yielded adlayers in the same thickness range as pure soy protein. In contrast, sauces with more ingredients create distinctly thicker films. Using water contact angle goniometry, it is shown that all adlayers render the substrate more hydrophilic. Infrared spectroscopy provided a deeper insight into the adlayer chemistry and revealed that the adlayer composition is dominated by protein rich components. X-ray reflectivity on selected films provided further insight into the density profiles within the adlayers on the molecular scale.

  5. Macroscopic self-reorientation of interacting two-dimensional crystals.

    Science.gov (United States)

    Woods, C R; Withers, F; Zhu, M J; Cao, Y; Yu, G; Kozikov, A; Ben Shalom, M; Morozov, S V; van Wijk, M M; Fasolino, A; Katsnelson, M I; Watanabe, K; Taniguchi, T; Geim, A K; Mishchenko, A; Novoselov, K S

    2016-03-10

    Microelectromechanical systems, which can be moved or rotated with nanometre precision, already find applications in such fields as radio-frequency electronics, micro-attenuators, sensors and many others. Especially interesting are those which allow fine control over the motion on the atomic scale because of self-alignment mechanisms and forces acting on the atomic level. Such machines can produce well-controlled movements as a reaction to small changes of the external parameters. Here we demonstrate that, for the system of graphene on hexagonal boron nitride, the interplay between the van der Waals and elastic energies results in graphene mechanically self-rotating towards the hexagonal boron nitride crystallographic directions. Such rotation is macroscopic (for graphene flakes of tens of micrometres the tangential movement can be on hundreds of nanometres) and can be used for reproducible manufacturing of aligned van der Waals heterostructures.

  6. A comprehensive study to protein retention in hydrophobic interaction chromatography.

    Science.gov (United States)

    Baca, Martyna; De Vos, Jelle; Bruylants, Gilles; Bartik, Kristin; Liu, Xiaodong; Cook, Ken; Eeltink, Sebastiaan

    2016-10-01

    The effect of different kosmotropic/chaotropic salt systems on retention characteristics of intact proteins has been examined in hydrophobic interaction chromatography (HIC). The performance was assessed using different column chemistries, i.e., polyalkylamide, alkylamine incorporating hydrophobic moieties, and a butyl chemistry. Selectivity in HIC is mainly governed by the salt concentration and by the molal surface tension increment of the salt. Typically, a linear relationship between the natural logarithm of the retention factor and the salt concentration is obtained. Using a 250mm long column packed with 5μm polyalkylamide functionalized silica particles and applying a 30min linear salt gradient, a peak capacity of 78 was achieved, allowing the baseline separation of seven intact proteins. The hydrophobicity index appeared to be a good indicator to predict the elution order of intact proteins in HIC mode. Furthermore, the effect of adding additives in the mobile phase, such as calcium chloride (stabilizing the 3D conformation of α-lactalbumin) and isopropanol, on retention properties has been assessed. Results indicate that HIC retention is also governed by conformational in the proteins which affect the number of accessible hydrophobic moieties.

  7. Structures of multidomain proteins adsorbed on hydrophobic interaction chromatography surfaces.

    Science.gov (United States)

    Gospodarek, Adrian M; Sun, Weitong; O'Connell, John P; Fernandez, Erik J

    2014-12-05

    In hydrophobic interaction chromatography (HIC), interactions between buried hydrophobic residues and HIC surfaces can cause conformational changes that interfere with separations and cause yield losses. This paper extends our previous investigations of protein unfolding in HIC chromatography by identifying protein structures on HIC surfaces under denaturing conditions and relating them to solution behavior. The thermal unfolding of three model multidomain proteins on three HIC surfaces of differing hydrophobicities was investigated with hydrogen exchange mass spectrometry (HXMS). The data were analyzed to obtain unfolding rates and Gibbs free energies for unfolding of adsorbed proteins. The melting temperatures of the proteins were lowered, but by different amounts, on the different surfaces. In addition, the structures of the proteins on the chromatographic surfaces were similar to the partially unfolded structures produced in the absence of a surface by temperature as well as by chemical denaturants. Finally, it was found that patterns of residue exposure to solvent on different surfaces at different temperatures can be largely superimposed. These findings suggest that protein unfolding on various HIC surfaces might be quantitatively related to protein unfolding in solution and that details of surface unfolding behavior might be generalized.

  8. Protein interactions in hydrophobic charge induction chromatography (HCIC).

    Science.gov (United States)

    Ghose, Sanchayita; Hubbard, Brian; Cramer, Steven M

    2005-01-01

    A quantitative understanding of how proteins interact with hydrophobic charge induction chromatographic resins is provided. Selectivity on this mode of chromatography for monoclonal antibodies as compared to other model proteins is probed by means of a linear retention vs pH plot. The pH-dependent adsorption behavior on this mode of chromatography for a hydrophobic, charged solute is described by taking into account the equilibrium between a hydrophobic, charged solute and an ionizable, heterocyclic ligand. By analogy, an equation that is seen to adequately describe macromolecular retention under linear conditions over a range of pH is developed. A preparative, nonlinear isotherm that can capture both pH and salt concentration dependency for proteins is proposed by using an exponentially modified Langmuir isotherm model. This model is seen to successfully simulate adsorption isotherms for a variety of proteins over a range of pHs and mobile phase salt concentrations. Finally, the widely differing retention characteristics of two monoclonal antibodies are used to derive two different strategies for improving separations on this mode of chromatography. A better understanding of protein binding to this class of resins is seen as an important step to future exploitation of this mode of chromatography for industrial scale purification of proteins.

  9. Water-Mediated Interactions between Hydrophilic and Hydrophobic Surfaces.

    Science.gov (United States)

    Kanduč, Matej; Schlaich, Alexander; Schneck, Emanuel; Netz, Roland R

    2016-09-01

    All surfaces in water experience at short separations hydration repulsion or hydrophobic attraction, depending on the surface polarity. These interactions dominate the more long-ranged electrostatic and van der Waals interactions and are ubiquitous in biological and colloidal systems. Despite their importance in all scenarios where the surface separation is in the nanometer range, the origin of these hydration interactions is still unclear. Using atomistic solvent-explicit molecular dynamics simulations, we analyze the interaction free energies of charge-neutral model surfaces with different elastic and water-binding properties. The surface polarity is shown to be the most important parameter that not only determines the hydration properties and thereby the water contact angle of a single surface but also the surface-surface interaction and whether two surfaces attract or repel. Elastic properties of the surfaces are less important. On the basis of surface contact angles and surface-surface binding affinities, we construct a universal interaction diagram featuring three different interaction regimes-hydration repulsion, cavitation-induced attraction-and for intermediate surface polarities-dry adhesion. On the basis of scaling arguments and perturbation theory, we establish simple combination rules that predict the interaction behavior for combinations of dissimilar surfaces.

  10. Macroscopic Quantum Superposition States in a Model of Photon-Supersonic Phonon Interaction

    Institute of Scientific and Technical Information of China (English)

    CHAI Jin-Hua; WANG Yan-Bang; LU Yi-Qun

    2000-01-01

    A model of photon-hypersonic phonon interaction is proposed. The evolution of macroscopic quantum superpo sition states is analyzed, including the wave function and number distribution. It is shown that a superposition state of hypersonic phonon modes can be generated in the case of nondetuning and no losses.

  11. Intramolecular hydrophobic interactions are critical mediators of STAT5 dimerization

    Science.gov (United States)

    Fahrenkamp, Dirk; Li, Jinyu; Ernst, Sabrina; Schmitz-van de Leur, Hildegard; Chatain, Nicolas; Küster, Andrea; Koschmieder, Steffen; Lüscher, Bernhard; Rossetti, Giulia; Müller-Newen, Gerhard

    2016-10-01

    STAT5 is an essential transcription factor in hematopoiesis, which is activated through tyrosine phosphorylation in response to cytokine stimulation. Constitutive activation of STAT5 is a hallmark of myeloid and lymphoblastic leukemia. Using homology modeling and molecular dynamics simulations, a model of the STAT5 phosphotyrosine-SH2 domain interface was generated providing first structural information on the activated STAT5 dimer including a sequence, for which no structural information is available for any of the STAT proteins. We identified a novel intramolecular interaction mediated through F706, adjacent to the phosphotyrosine motif, and a unique hydrophobic interface on the surface of the SH2 domain. Analysis of corresponding STAT5 mutants revealed that this interaction is dispensable for Epo receptor-mediated phosphorylation of STAT5 but essential for dimer formation and subsequent nuclear accumulation. Moreover, the herein presented model clarifies molecular mechanisms of recently discovered leukemic STAT5 mutants and will help to guide future drug development.

  12. Hydrophobic interactions and hydrogen bonds in \\beta-sheet formation

    CERN Document Server

    Narayanan, Chitra

    2013-01-01

    In this study, we investigate interactions of extended conformations of homodimeric peptides made of small (glycine or alanine) and large hydrophobic (valine or leucine) sidechains using all-atom molecular dynamics simulations to decipher driving forces for \\beta-sheet formation. We make use of a periodic boundary condition setup in which individual peptides are infinitely long and stretched. Dimers adopt \\beta-sheet conformations at short interpeptide distances (\\xi ~ 0.5 nm) and at intermediate distances (~ 0.8 nm), valine and leucine homodimers assume cross-\\beta-like conformations with side chains interpenetrating each other. These two states are identified as minima in the Potential of Mean Force (PMF). While the number of interpeptide hydrogen bonds increases with decreasing interpeptide distance, the total hydrogen bond number in the system does not change significantly, suggesting that formation of \\beta-sheet structures from extended conformations is not driven by hydrogen bonds. This is supported by...

  13. Interaction of engineered nanomaterials with hydrophobic organic pollutants

    Science.gov (United States)

    Sahle-Demessie, E.; Han, Changseok; Zhao, Amy; Hahn, Bill; Grecsek, Heidi

    2016-07-01

    As nanomaterials become an increasing part of everyday consumer products, it is imperative to monitor their potential release during production, use and disposal, and to assess their impact on the health of humans and the ecosystem. This necessitates research to better understand how the properties of engineered nanomaterials (ENMs) lead to their accumulation and redistribution in the environment, and to assess whether they could become novel pollutants or if they can affect the mobility and bioavailability of other toxins. This study focuses on understanding the influence of nanostructured-TiO2 and the interaction of multi-walled carbon nanotubes with organic pollutants in water. We studied the adsorption and water phase dispersion of model pollutants with relatively small water solubility (i.e., two- and three-ring polyaromatic hydrocarbons and insecticides) with respect to ENMs. The sorption of pollutants was measured based on water phase analysis, and by separating suspended particles from the water phase and analyzing dried samples using integrated thermal-chromatographic-mass spectroscopic (TGA/GC/MS) techniques. Solid phase analysis using a combination of TGA/GC/MS is a novel technique that can provide real-time quantitative analysis and which helps to understand the interaction of hydrophobic organic pollutants and ENMs. The adsorption of these contaminants to nanomaterials increased the concentration of the contaminants in the aqueous phase as compared to the ‘real’ partitioning due to the octanol-water partitioning. The study showed that ENMs can significantly influence the adsorption and dispersion of hydrophobic/low water soluble contaminants. The type of ENM, the exposure to light, and the water pH have a significant influence on the partitioning of pollutants.

  14. Comparison between Free and Immobilized Ion Effects on Hydrophobic Interactions: A Molecular Dynamics Study

    CERN Document Server

    Huang, Kai; Ma, C Derek; Abbott, Nicholas L; Szlufarska, Izabela

    2016-01-01

    Fundamental studies of the effect of specific ions on hydrophobic interactions are driven by the need to understand phenomena such as hydrophobically driven self-assembly or protein folding. Using beta-peptide-inspired nano-rods, we investigate the effects of both free ions (dissolved salts) and proximally immobilized ions on hydrophobic interactions. We find that the free ion effect is correlated with the water density fluctuation near a non-polar molecular surface, showing that such fluctuation can be an indicator of hydrophobic interactions in the case of solution additives. In the case of immobilized ion, our results demonstrate that hydrophobic interactions can be switched on and off by choosing different spatial arrangements of proximal ions on a nano-rod. For globally amphiphilic nano-rods, we find that the magnitude of the interaction can be further tuned using proximal ions with varying ionic sizes. In general, univalent proximal anions are found to weaken hydrophobic interactions. This is in contras...

  15. Effects of the protein denaturant guanidinium chloride on aqueous hydrophobic contact-pair interactions.

    Science.gov (United States)

    Macdonald, Ryan D; Khajehpour, Mazdak

    2015-01-01

    Guanidinium chloride (GdmCl) is one of the most common protein denaturants. Although GdmCl is well known in the field of protein folding, the mechanism by which it denatures proteins is not well understood. In fact, there are few studies looking at its effects on hydrophobic interactions. In this work the effect of GdmCl on hydrophobic interactions has been studied by observing how the denaturant influences model systems of phenyl and alkyl hydrophobic contact pairs. Contact pair formation is monitored through the use of fluorescence spectroscopy, i.e., measuring the intrinsic phenol fluorescence being quenched by carboxylate ions. Hydrophobic interactions are isolated from other interactions through a previously developed methodology. The results show that GdmCl does not significantly affect hydrophobic interactions between small moieties such as methyl groups and phenol; while on the other hand, the interaction of larger hydrophobes such as hexyl and heptyl groups with phenol is significantly destabilized.

  16. Binding interaction between rice glutelin and amylose: Hydrophobic interaction and conformational changes.

    Science.gov (United States)

    Xu, Xingfeng; Liu, Wei; Zhong, Junzhen; Luo, Liping; Liu, Chengmei; Luo, Shunjing; Chen, Lin

    2015-11-01

    The interaction of rice glutelin (RG) with amylose was characterized by spectroscopic and molecular docking studies. The intrinsic fluorescence of RG increased upon the addition of amylose. The binding sites, binding constant and thermodynamic features indicated that binding process was spontaneous and the main driving force of the interaction was hydrophobic interaction. The surface hydrophobicity of RG decreased with increasing amount of amylose. Furthermore, synchronous fluorescence and circular dichroism (CD) spectra provided data concerning conformational and micro-environmental changes of RG. With the concentration of amylose increasing, the polarity around the tyrosine residues increased while the hydrophobicity decreased. Alteration of protein conformation was observed with increasing of α-helix and reducing of β-sheet. Finally, a visual representation of two binding sites located in the amorphous area of RG was presented by molecular modeling studies.

  17. Hydrophobically modified polyelectrolytes : synthesis, properties and interactions with surfactants

    NARCIS (Netherlands)

    Nieuwkerk, A.C.

    1998-01-01

    Hydrophobically modified polyelectrolytes can form micelle-like aggregates, so-called microdomains, in aqueous solution. The hydrophobic side chains constitute the apolar inner part of these microdomains and the hydrophilic groups on the polyelectrolyte backbone are at the surface of the

  18. CH-π Interaction Driven Macroscopic Property Transition on Smart Polymer Surface

    Science.gov (United States)

    Li, Minmin; Qing, Guangyan; Xiong, Yuting; Lai, Yuekun; Sun, Taolei

    2015-10-01

    Life systems have evolved to utilize weak noncovalent interactions, particularly CH-π interaction, to achieve various biofunctions, for example cellular communication, immune response, and protein folding. However, for artificial materials, it remains a great challenge to recognize such weak interaction, further transform it into tunable macroscopic properties and realize special functions. Here we integrate monosaccharide-based CH-π receptor capable of recognizing aromatic peptides into a smart polymer with three-component “Recognition-Mediating-Function” design, and report the CH-π interaction driven surface property switching on smart polymer film, including wettability, adhesion, viscoelasticity and stiffness. Detailed studies indicate that, the CH-π interaction induces the complexation between saccharide unit and aromatic peptide, which breaks the initial amphiphilic balance of the polymer network, resulting in contraction-swelling conformational transition for polymer chains and subsequent dramatic switching in surface properties. This work not only presents a new approach to control the surface property of materials, but also points to a broader research prospect on CH-π interaction at a macroscopic level.

  19. CH-π Interaction Driven Macroscopic Property Transition on Smart Polymer Surface.

    Science.gov (United States)

    Li, Minmin; Qing, Guangyan; Xiong, Yuting; Lai, Yuekun; Sun, Taolei

    2015-10-29

    Life systems have evolved to utilize weak noncovalent interactions, particularly CH-π interaction, to achieve various biofunctions, for example cellular communication, immune response, and protein folding. However, for artificial materials, it remains a great challenge to recognize such weak interaction, further transform it into tunable macroscopic properties and realize special functions. Here we integrate monosaccharide-based CH-π receptor capable of recognizing aromatic peptides into a smart polymer with three-component "Recognition-Mediating-Function" design, and report the CH-π interaction driven surface property switching on smart polymer film, including wettability, adhesion, viscoelasticity and stiffness. Detailed studies indicate that, the CH-π interaction induces the complexation between saccharide unit and aromatic peptide, which breaks the initial amphiphilic balance of the polymer network, resulting in contraction-swelling conformational transition for polymer chains and subsequent dramatic switching in surface properties. This work not only presents a new approach to control the surface property of materials, but also points to a broader research prospect on CH-π interaction at a macroscopic level.

  20. On the role of wave-particle interactions in the macroscopic dynamics of collisionless plasmas

    CERN Document Server

    Wilson, Lynn B; Osmane, Adnane; Malaspina, David M

    2015-01-01

    What is the relative importance of small-scale (i.e., electron to sub-electron scales), microphysical plasma processes to the acceleration of particles from thermal to suprathermal or even to cosmic-ray energies? Additionally, can these microphysical plasma processes influence or even dominate macroscopic (i.e., greater than ion scales) processes, thus affecting global dynamics? These are fundamental and unresolved questions in plasma and astrophysical research. Recent observations of large amplitude electromagnetic waves in the terrestrial radiation belts [i.e., Cattell et al., 2008; Kellogg et al., 2010; Wilson III et al., 2011] and in collisionless shock waves [i.e., Wilson III et al., 2014a,b] have raised questions regarding the macrophysical effect of these microscopic waves. The processes thought to dominate particle acceleration and the macroscopic dynamics in both regions have been brought into question with these recent observations. The relative importance of wave-particle interactions has recently ...

  1. Hydrophobic interactions of phenoxazine modulators with bovine serum albumin

    Indian Academy of Sciences (India)

    H N Kalpana; B C Channu; Chhabil Dass; P J Houghton; K N Thimmaiah

    2000-02-01

    The interaction of 10-(3’-N-morpholinopropyl)phenoxazine [MPP], 10-(4’-N-morpholinobutyl)phenoxazine [MBP], 10-(3’-N-morpholinopropyl)-2-chlorophenoxazine [MPCP], 10-(3’-N-piperidinopropyl)-2-chlorophenoxazine [PPCP] or 10-(3’-N-morpholinopropyl)-2-trifluoromethylphenoxazine [MPTP] with bovine serum albumin (BSA) has been studied by gel filtration and equilibrium dialysis methods. The binding of these modulators, based on dialysis experiments, has been characterized using the following parameters: percentage of bound drug (), the association constant (1), the apparent binding constant () and the free energy change ( °). The binding of phenoxazine derivatives to serum transporter protein, BSA, is correlated with their octanol-water partition coefficient, log10 ~ . In addition, effect of the displacing activities of hydroxyzine and acetylsalicylic acid on the binding of phenoxazine derivatives to albumin has been studied. Results of the displacement experiments show that phenoxazine benzene rings and tertiary amines attached to the side chain of the phenoxazine moiety are bound to a hydrophobic area on the albumin molecule.

  2. Hydrophobic and hydrophilic interactions in aqueous mixtures of alcohols at a hydrophobic surface.

    Science.gov (United States)

    Ballal, Deepti; Chapman, Walter G

    2013-09-21

    Aqueous solutions of alcohols are interesting because of their anomalous behavior that is believed to be due to the molecular structuring of water and alcohol around each other in solution. The interfacial structuring and properties are significant for application in alcohol purification processes and biomolecular structure. Here we study aqueous mixtures of short alcohols (methanol, ethanol, 1-propanol, and 2-propanol) at a hydrophobic surface using interfacial statistical associating fluid theory which is a perturbation density functional theory. The addition of a small amount of alcohol decreases the interfacial tension of water drastically. This trend in interfacial tension can be explained by the structure of water and alcohol next to the surface. The hydrophobic group of an added alcohol preferentially goes to the surface preserving the structure of water in the bulk. For a given bulk alcohol concentration, water mixed with the different alcohols has different interfacial tensions with propanol having a lower interfacial tension than methanol and ethanol. 2-propanol is not as effective in decreasing the interfacial tension as 1-propanol because it partitions poorly to the surface due to its larger excluded volume. But for a given surface alcohol mole fraction, all the alcohol mixtures give similar values for interfacial tension. For separation of alcohol from water, methods that take advantage of the high surface mole fraction of alcohol have advantages compared to separation using the vapor in equilibrium with a water-alcohol liquid.

  3. Direct Numerical Test of the Statistical Mechanical Theory of Hydrophobic Interactions

    CERN Document Server

    Chaudhari, M I; Ashbaugh, H S; Pratt, L R

    2013-01-01

    This work tests the statistical mechanical theory of hydrophobic interactions, isolates consequences of excluded volume interactions, and obtains B2 for those purposes. Cavity methods that are particularly appropriate for study of hydrophobic interactions between atomic-size hard spheres in liquid water are developed and applied to test aspects of the Pratt-Chandler (PC) theory that have not been tested. Contact hydrophobic interactions between Ar-size hard-spheres in water are significantly more attractive than predicted by the PC theory. The corresponding results for the osmotic second virial coefficient are attractive (B2 <0), and more attractive with increasing temperature (Delta B2/Delta T < 0) in the temperature range 300K < T < 360K. This information has not been available previously, but is essential for development of the molecular-scale statistical mechanical theory of hydrophobic interactions, particularly for better definition of the role of attractive intermolecular interactions assoc...

  4. Applying flexible molecular docking to simulate protein retention behavior in hydrophobic interaction chromatography

    Institute of Scientific and Technical Information of China (English)

    ZHOU; Peng; TIAN; FeiFei; LI; ZhiLiang

    2007-01-01

    Interaction between proteins and stationary phase in hydrophobic interaction chromatography (HIC) is differentiated into two thermodynamic processes involving direct nonbonding/conformation interaction and surface hydrophobic effect of proteins, hence quantitatively giving rise to a binary linear relation between HIC retention time (RT) at concentrated salting liquid and ligand-protein binding free energy. Then, possible binding manners for 27 proteins of known crystal structures with hydrophobic ligands are simulated and analyzed via ICM flexible molecular docking and genetic algorithm, with results greatly consistent with experimental values. By investigation, it is confirmed local hydrophobic effects of proteins and nonbinding/conformation interaction between ligand and protein both notably influence HIC chromatogram retention behaviors, mainly focusing on exposed portions on the protein surface.

  5. Molecular theory for the effects of solute attractive forces on hydrophobic interactions

    CERN Document Server

    Chaudhari, M I; Asthagiri, D; Tan, L; Pratt, L R

    2015-01-01

    We consider the local molecular field (LMF) theory for the effects of solute attractive forces on hydrophobic interactions. The principal result of LMF theory is outlined, then tested by obtaining radial distribution functions (rdfs) for Ar atoms in water, with and without attractive interactions distinguished by the Weeks-Chandler-Andersen (WCA) separation. Change from purely repulsive atomic solute interactions to include realistic attractive interactions substantially \\emph{diminishes} the strength of hydrophobic bonds. Since attractions make a big contribution to hydrophobic interactions, Pratt-Chandler theory, which did not include attractions, should not be simply comparable to computer simulation results with general physical interactions, including attractions. The rdfs permit evaluation of osmotic second virial coefficients $B_2$. Those $B_2$ are consistent with the conclusion that incorporation of attractive interactions leads to more positive (repulsive) values. In all cases here, $B_2$ becomes mor...

  6. Neoclassical theory of electromagnetic interactions a single theory for macroscopic and microscopic scales

    CERN Document Server

    Babin, Anatoli

    2016-01-01

    In this monograph, the authors present their recently developed theory of electromagnetic interactions. This neoclassical approach extends the classical electromagnetic theory down to atomic scales and allows the explanation of various non-classical phenomena in the same framework. While the classical Maxwell–Lorentz electromagnetism theory succeeds in describing the physical reality at macroscopic scales, it struggles at atomic scales. Here, quantum mechanics traditionally takes over to describe non-classical phenomena such as the hydrogen spectrum and de Broglie waves. By means of modifying the classical theory, the approach presented here is able to consistently explain quantum-mechanical effects, and while similar to quantum mechanics in some respects, this neoclassical theory also differs markedly from it. In particular, the newly developed framework omits probabilistic interpretations of the wave function and features a new fundamental spatial scale which, at the size of the free electron, is much lar...

  7. Molecular aggregation in water : the interplay of hydrophobic and electrostatic interactions

    NARCIS (Netherlands)

    Buwalda, Rixt Tietje

    2001-01-01

    Hydrophobic interactions belong to the most important noncovalent interactions and play an important role in many (bio)chemical processes. A number of processes in aqueous solution like protein folding, surfactant aggregation or molecular recognition processes strongly rely on the interactions betwe

  8. Effects of the osmolyte TMAO (Trimethylamine-N-oxide) on aqueous hydrophobic contact-pair interactions.

    Science.gov (United States)

    Macdonald, Ryan D; Khajehpour, Mazdak

    2013-12-31

    Osmolytes are small, soluble organic molecules produced by living organisms for maintaining cell volume. These molecules have also been shown to have significant effects on the stability of proteins. Perhaps one of the most studied osmolytes is Trimethylamine-N-oxide (TMAO). Thermodynamic studies of the effects of TMAO on proteins have shown that this molecule is a strong stabilizer of the protein folded state, thus being able to counteract the effects of protein denaturants such as urea and guanidine hydrochloride. Most studies of TMAO effects on bio-molecular stability have until now been focused on how the osmolyte reduces the solubility of polypeptide backbones, while the effects of TMAO on hydrophobic interactions are still not well understood. In fact, there are few experimental data measuring the effect of TMAO on hydrophobic interactions. This work studies phenyl and alkyl contact pairs as model hydrophobic contact pairs. The formation of these contact pairs is monitored using fluorescence, i.e., through the quenching of phenol fluorescence by carboxylate ions; and a methodology is developed to isolate hydrophobic contributions from other interactions. The data demonstrate that the addition of TMAO to the aqueous solvent destabilizes hydrophobic contact pairs formed between alkyl and phenyl moieties. In other words, TMAO acts as a "denaturant" for hydrophobic interactions.

  9. Approximate Inference for Time-Varying Interactions and Macroscopic Dynamics of Neural Populations

    Science.gov (United States)

    Obermayer, Klaus

    2017-01-01

    The models in statistical physics such as an Ising model offer a convenient way to characterize stationary activity of neural populations. Such stationary activity of neurons may be expected for recordings from in vitro slices or anesthetized animals. However, modeling activity of cortical circuitries of awake animals has been more challenging because both spike-rates and interactions can change according to sensory stimulation, behavior, or an internal state of the brain. Previous approaches modeling the dynamics of neural interactions suffer from computational cost; therefore, its application was limited to only a dozen neurons. Here by introducing multiple analytic approximation methods to a state-space model of neural population activity, we make it possible to estimate dynamic pairwise interactions of up to 60 neurons. More specifically, we applied the pseudolikelihood approximation to the state-space model, and combined it with the Bethe or TAP mean-field approximation to make the sequential Bayesian estimation of the model parameters possible. The large-scale analysis allows us to investigate dynamics of macroscopic properties of neural circuitries underlying stimulus processing and behavior. We show that the model accurately estimates dynamics of network properties such as sparseness, entropy, and heat capacity by simulated data, and demonstrate utilities of these measures by analyzing activity of monkey V4 neurons as well as a simulated balanced network of spiking neurons. PMID:28095421

  10. Interaction forces for symmetric hydrophilic and hydrophobic systems in aqueous isopropanol solutions.

    Science.gov (United States)

    Hupka, Lukasz; Nalaskowski, Jakub; Miller, Jan D

    2010-02-16

    Interaction force measurements were performed for a silica-silica hydrophilic system and for a silanated silica-silanated silica hydrophobic system using the atomic force microscopy colloidal probe technique. The influence of the solution composition on interaction forces was investigated. The hydrophilic silica-silica interactions were found to be described as a typical Derjaguin-Landau-Verwey-Overbeek (DLVO) system in solutions of various compositions, whereas silanated silica-silanated silica interactions were dominated by a long-range hydrophobic force. An increase in the isopropyl alcohol content of the solution diminishes both the repulsive forces in the case of the hydrophilic system and the attractive interactions in the case of the hydrophobic system.

  11. Inversion of the balance between hydrophobic and hydrogen bonding interactions in protein folding and aggregation.

    Directory of Open Access Journals (Sweden)

    Anthony W Fitzpatrick

    2011-10-01

    Full Text Available Identifying the forces that drive proteins to misfold and aggregate, rather than to fold into their functional states, is fundamental to our understanding of living systems and to our ability to combat protein deposition disorders such as Alzheimer's disease and the spongiform encephalopathies. We report here the finding that the balance between hydrophobic and hydrogen bonding interactions is different for proteins in the processes of folding to their native states and misfolding to the alternative amyloid structures. We find that the minima of the protein free energy landscape for folding and misfolding tend to be respectively dominated by hydrophobic and by hydrogen bonding interactions. These results characterise the nature of the interactions that determine the competition between folding and misfolding of proteins by revealing that the stability of native proteins is primarily determined by hydrophobic interactions between side-chains, while the stability of amyloid fibrils depends more on backbone intermolecular hydrogen bonding interactions.

  12. Affinity chromatography of acetylcholinesterase. The importance of hydrophobic interactions.

    Science.gov (United States)

    Massoulié, J; Bon, S

    1976-09-15

    An easily prepared affinity column for acetylcholinesterase is described, which may be operated at ionic strength high enough to prevent aggregation of the asymmetric forms of the enzyme. Specific elution by tetraethylammonium or decamethonium was quantitative. The performance of this column is comparable to that of the column described by Dudai and Silman. It is shown that the hexyl 'spacer arm' strongly participates in the enzyme binding and that its replacement with the more hydrophilic spermine chain lowers the affinity. The hexyl chain itself is shown to bind acetylcholinesterase, although with lower affinity and capacity than the complete column. This binding is also partly reversed by inhibitors. Such hydrophobic columns bind the native asymmetric forms of the enzyme more strongly than the lytic globular ones. The aromatic quaternary ligang inhibits Electrophorus but not Torpedo acetylcholinesterase; therefore the column does not retain the Torpedo enzyme. Differences in Km between acetylcholinesterases of the two species also point to differences in their active sites.

  13. Hydrophobically Modified Polyelectrolytes: V. Interaction of Fluorocarbon Modified Poly (acrylic acid) with Various Added Surfactants

    Institute of Scientific and Technical Information of China (English)

    ZHOU,Hui(周晖); SONG,Guo-Qaiang(宋国强); GUO,Jin-Feng(郭金峰); ZHANG,Yun-xiang (章云祥); DIEING,Reinhold; MA,Lian(马莲); HAEUSSLING,Lukas

    2001-01-01

    The interactions between fiuorocarbon-medified pol(sodium acrylate) and various kinds of added surfactant have been studied by means of viscometric measurement. Association behavior was found in both hydrogenated and fluorinated anionic, nonionic and cationic surfactants. Among them, the interactions between fluorocarbon-modified poly ( sodium acrylate) and cationic surfactants are the strongest, owing to the cooperation of both electrostatic attractions and hydrophobic associations. The anionic surfactants have the weakest effects on the solution properties because of the existence of unfavorable electrostatic repulsion. The hydrophobic interactions between copolymers and fluorinated surfactants are much stronger than those between copolymers and hydrogenated surfactants.

  14. Molecular-scale hydrophobic interactions between hard-sphere reference solutes are attractive and endothermic

    Science.gov (United States)

    Chaudhari, Mangesh I.; Holleran, Sinead A.; Ashbaugh, Henry S.; Pratt, Lawrence R.

    2013-01-01

    The osmotic second virial coefficients, B2, for atomic-sized hard spheres in water are attractive (B2 statistical mechanical theory. These results constitute an initial step toward detailed molecular theory of additional intermolecular interaction features, specifically, attractive interactions associated with hydrophobic solutes. PMID:24297918

  15. A conserved patch of hydrophobic amino acids modulates Myb activity by mediating protein-protein interactions.

    Science.gov (United States)

    Dukare, Sandeep; Klempnauer, Karl-Heinz

    2016-07-01

    The transcription factor c-Myb plays a key role in the control of proliferation and differentiation in hematopoietic progenitor cells and has been implicated in the development of leukemia and certain non-hematopoietic tumors. c-Myb activity is highly dependent on the interaction with the coactivator p300 which is mediated by the transactivation domain of c-Myb and the KIX domain of p300. We have previously observed that conservative valine-to-isoleucine amino acid substitutions in a conserved stretch of hydrophobic amino acids have a profound effect on Myb activity. Here, we have explored the function of the hydrophobic region as a mediator of protein-protein interactions. We show that the hydrophobic region facilitates Myb self-interaction and binding of the histone acetyl transferase Tip60, a previously identified Myb interacting protein. We show that these interactions are affected by the valine-to-isoleucine amino acid substitutions and suppress Myb activity by interfering with the interaction of Myb and the KIX domain of p300. Taken together, our work identifies the hydrophobic region in the Myb transactivation domain as a binding site for homo- and heteromeric protein interactions and leads to a picture of the c-Myb transactivation domain as a composite protein binding region that facilitates interdependent protein-protein interactions of Myb with regulatory proteins.

  16. Interplay between the hydrophobic effect and dipole interactions in peptide aggregation at interfaces.

    Science.gov (United States)

    Ganesan, Sai J; Matysiak, Silvina

    2016-01-28

    Protein misfolding is an intrinsic property of polypeptides, and misfolded conformations have a propensity to aggregate. In the past decade, the development of various coarse-grained models for proteins has provided key insights into the driving forces in folding and aggregation. We recently developed a low resolution Water Explicit Polarizable PROtein coarse-grained Model (WEPPROM) by adding oppositely charged dummy particles inside protein backbone beads. With this model, we were able to achieve significant α/β secondary structure content, without any added bias. We now extend the model to study peptide aggregation at hydrophobic-hydrophilic interfaces and draw comparisons to aggregation in explicit water solvent. Elastin-like octapeptides (GV)4 are used as a model system for this study. A condensation-ordering mechanism of aggregation is observed in water. Our results suggest that backbone interpeptide dipolar interactions, not hydrophobicity, plays a more significant role in fibril-like peptide aggregation. We observe a cooperative effect in hydrogen bonding or dipolar interactions, with an increase in aggregate size in water and at interfaces. Based on this cooperative effect, we provide a potential explanation for the observed nucleus size in peptide aggregation pathways. The presence of a hydrophobic-hydrophilic interface increases both (a) order of aggregates formed, and (b) rate of the aggregation process. Without dipolar particles, peptide aggregation is not observed at the hydrophilic-hydrophobic interface. Thus, the presence of dipoles, not hydrophobicity, plays a key role in aggregation observed at hydrophobic interfaces.

  17. Modulation of graft architectures for enhancing hydrophobic interaction of biomolecules with thermoresponsive polymer-grafted surfaces.

    Science.gov (United States)

    Idota, Naokazu; Kikuchi, Akihiko; Kobayashi, Jun; Sakai, Kiyotaka; Okano, Teruo

    2012-11-01

    This paper describes the effects of graft architecture of poly(N-isopropylacrylamide) (PIPAAm) brush surfaces on thermoresponsive aqueous wettability changes and the temperature-dependent hydrophobic interaction of steroids in silica capillaries (I.D.: 50 μm). PIPAAm brushes were grafted onto glass substrates by surface-initiated atom transfer radical polymerization (ATRP) that is one of the living radical polymerization techniques. Increases in the graft density and chain length of PIPAAm brushes increased the hydration of polymer brushes, resulting in the increased hydrophilic properties of the surface below the transition temperature of PIPAAm at 32 °C. More hydrophobic surface properties were also observed on surfaces modified with the block copolymers of IPAAm and n-butyl methacrylate (BMA) than that with IPAAm homopolymer-grafted surfaces over the transition temperature. Using PBMA-b-PIPAAm-grafted silica capillaries, the baseline separation of steroids was successfully achieved by only changing temperature. The incorporation of hydrophobic PBMA chains in grafted PIPAAm enhanced the hydrophobic interaction with testosterone above the transition temperature. The surface modification of hydrophobicity-enhanced thermoresponsive polymers is a promising method for the preparation of thermoresponsive biointerfaces that can effectively modulated their biomolecule and cell adsorption with the wide dynamic range of hydrophilic/hydrophobic property change across the transition temperature.

  18. Ionic interactions. Subnanoscale hydrophobic modulation of salt bridges in aqueous media.

    Science.gov (United States)

    Chen, Shuo; Itoh, Yoshimitsu; Masuda, Takuya; Shimizu, Seishi; Zhao, Jun; Ma, Jing; Nakamura, Shugo; Okuro, Kou; Noguchi, Hidenori; Uosaki, Kohei; Aida, Takuzo

    2015-05-01

    Polar interactions such as electrostatic forces and hydrogen bonds play an essential role in biological molecular recognition. On a protein surface, polar interactions occur mostly in a hydrophobic environment because nonpolar amino acid residues cover ~75% of the protein surface. We report that ionic interactions on a hydrophobic surface are modulated by their subnanoscale distance to the surface. We developed a series of ionic head groups-appended self-assembled monolayers with C2, C6, C8, and C12 space-filling alkyl chains, which capture a dendritic guest via the formation of multiple salt bridges. The guest release upon protonolysis is progressively suppressed when its distance from the background hydrophobe changes from 1.2 (C2) to 0.2 (C12) nanometers, with an increase in salt bridge strength of ~3.9 kilocalories per mole.

  19. Asymmetric electrostatic and hydrophobic-hydrophilic interaction forces between mica surfaces and silicone polymer thin films.

    Science.gov (United States)

    Donaldson, Stephen H; Das, Saurabh; Gebbie, Matthew A; Rapp, Michael; Jones, Louis C; Roiter, Yuri; Koenig, Peter H; Gizaw, Yonas; Israelachvili, Jacob N

    2013-11-26

    We have synthesized model hydrophobic silicone thin films on gold surfaces by a two-step covalent grafting procedure. An amino-functionalized gold surface reacts with monoepoxy-terminated polydimethylsiloxane (PDMS) via a click reaction, resulting in a covalently attached nanoscale thin film of PDMS, and the click chemistry synthesis route provides great selectivity, reproducibility, and stability in the resulting model hydrophobic silicone thin films. The asymmetric interaction forces between the PDMS thin films and mica surfaces were measured with the surface forces apparatus in aqueous sodium chloride solutions. At an acidic pH of 3, attractive interactions are measured, resulting in instabilities during both approach (jump-in) and separation (jump-out from adhesive contact). Quantitative analysis of the results indicates that the Derjaguin-Landau-Verwey-Overbeek theory alone, i.e., the combination of electrostatic repulsion and van der Waals attraction, cannot fully describe the measured forces and that the additional measured adhesion is likely due to hydrophobic interactions. The surface interactions are highly pH-dependent, and a basic pH of 10 results in fully repulsive interactions at all distances, due to repulsive electrostatic and steric-hydration interactions, indicating that the PDMS is negatively charged at high pH. We describe an interaction potential with a parameter, known as the Hydra parameter, that can account for the extra attraction (low pH) due to hydrophobicity as well as the extra repulsion (high pH) due to hydrophilic (steric-hydration) interactions. The interaction potential is general and provides a quantitative measure of interfacial hydrophobicity/hydrophilicity for any set of interacting surfaces in aqueous solution.

  20. A closer look at the complex hydrophilic/hydrophobic interactions forces at the human hair surface

    Science.gov (United States)

    Baghdadli, N.; Luengo, G. S.; Recherche, L.

    2008-03-01

    The complex chemical structure of the hair surface is far from being completely understood. Current understanding is based on Rivett's model1 that was proposed to explain the macroscopic hydrophobic nature of the surface of natural hair. In this model covalently-linked fatty acids are chemically grafted to the amorphous protein (keratin) through a thio-ester linkage2,3. Nevertheless, experience like wetting and electrical properties of human hair surface4 shows that the complexity of the hair surface is not fully understand based on this model in literature. Recent studies in our laboratory show for the first time microscopic evidence of the heterogeneous physico-chemical character of the hair surface. By using Chemical Force Microscopy, the presence of hydrophobic and ionic species are detected and localized, before and after a cosmetic treatment (bleaching). Based on force curve analysis the mapping of the local distribution of hydrophilic and hydrophobic groups of hair surface is obtained. A discussion on a more plausible hair model and its implications will be presented based on these new results.

  1. A closer look at the complex hydrophilic/hydrophobic interactions forces at the human hair surface

    Energy Technology Data Exchange (ETDEWEB)

    Baghdadli, N; Luengo, G S; Recherche, L [Avenue Eugene Schueller, Aulnay-Sous Bois, 93100 (France)], E-mail: nbaghdadli@rd.loreal.com, E-mail: gluengo@rd.loreal.com

    2008-03-15

    The complex chemical structure of the hair surface is far from being completely understood. Current understanding is based on Rivett's model{sup 1} that was proposed to explain the macroscopic hydrophobic nature of the surface of natural hair. In this model covalently-linked fatty acids are chemically grafted to the amorphous protein (keratin) through a thio-ester linkage{sup 2,3}. Nevertheless, experience like wetting and electrical properties of human hair surface{sup 4} shows that the complexity of the hair surface is not fully understand based on this model in literature. Recent studies in our laboratory show for the first time microscopic evidence of the heterogeneous physico-chemical character of the hair surface. By using Chemical Force Microscopy, the presence of hydrophobic and ionic species are detected and localized, before and after a cosmetic treatment (bleaching). Based on force curve analysis the mapping of the local distribution of hydrophilic and hydrophobic groups of hair surface is obtained. A discussion on a more plausible hair model and its implications will be presented based on these new results.

  2. Force nanoscopy of hydrophobic interactions in the fungal pathogen Candida glabrata.

    Science.gov (United States)

    El-Kirat-Chatel, Sofiane; Beaussart, Audrey; Derclaye, Sylvie; Alsteens, David; Kucharíková, Soňa; Van Dijck, Patrick; Dufrêne, Yves F

    2015-02-24

    Candida glabrata is an opportunistic human fungal pathogen which binds to surfaces mainly through the Epa family of cell adhesion proteins. While some Epa proteins mediate specific lectin-like interactions with human epithelial cells, others promote adhesion and biofilm formation on plastic surfaces via nonspecific interactions that are not yet elucidated. We report the measurement of hydrophobic forces engaged in Epa6-mediated cell adhesion by means of atomic force microscopy (AFM). Using single-cell force spectroscopy, we found that C. glabrata wild-type (WT) cells attach to hydrophobic surfaces via strongly adhesive macromolecular bonds, while mutant cells impaired in Epa6 expression are weakly adhesive. Nanoscale mapping of yeast cells using AFM tips functionalized with hydrophobic groups shows that Epa6 is massively exposed on WT cells and conveys strong hydrophobic properties to the cell surface. Our results demonstrate that Epa6 mediates strong hydrophobic interactions, thereby providing a molecular basis for the ability of this adhesin to drive biofilm formation on abiotic surfaces.

  3. Interaction of O-acylated chitosans with biomembrane models: probing the effects from hydrophobic interactions and hydrogen bonding.

    Science.gov (United States)

    Pavinatto, Adriana; Souza, Adriano L; Delezuk, Jorge A M; Pavinatto, Felippe J; Campana-Filho, Sérgio P; Oliveira, Osvaldo N

    2014-02-01

    One of the major challenges in establishing the mechanisms responsible for the chitosan action in biomedical applications lies in the determination of the molecular-level interactions with the cell membrane. In this study, we probed hydrophobic interactions and H-bonding in experiments with O,O'-diacetylchitosan (DACT) and O,O'-dipropionylchitosan (DPPCT) incorporated into monolayers of distinct phospholipids, the zwitterionic dipalmitoyl phosphatidyl choline (DPPC), and the negatively charged dipalmitoyl phosphatidyl glycerol (DPPG) and dimyristoyl phosphatidic acid (DMPA). The importance of hydrophobic interactions was confirmed with the larger effects observed for DACT and DPPCT than for parent chitosan (Chi), particularly for the more hydrophobic DPPCT. Such larger effects were noted in surface pressure isotherms and elasticity of the monolayers. Since H-bonding is hampered for the chitosan derivatives, which have part of their hydroxyl groups shielded by O-acylation, these effects indicate that H-bonding does not play an important role in the chitosan-membrane interactions. Using polarization-modulated infrared reflection absorption (PM-IRRAS) spectroscopy, we found that the chitosan derivatives were incorporated into the hydrophobic chain of the phospholipids, even at high surface pressures comparable to those in a real cell membrane. Taken together, these results indicate that the chitosan derivatives containing hydrophobic moieties would probably be more efficient than parent chitosan as antimicrobial agents, where interaction with the cell membrane is crucial.

  4. Understanding the mutual impact of interaction between hydrophobic nanoparticles and pulmonary surfactant monolayer.

    Science.gov (United States)

    Sachan, Amit K; Galla, Hans-Joachim

    2014-03-26

    Interaction between hydrophobic nanoparticles (NPs) and a pulmonary surfactant (PS) film leads to a shift in molecular packing of surfactant molecules in the PS film around the interacting NPs. The resultant structural arrangement of surfactants around the NPs may be a potential structural factor responsible for their high retention ability within the film. Moreover, during this interaction, surfactant molecules coat the NPs and change their surface properties.

  5. Interactions between halide anions and a molecular hydrophobic interface.

    Science.gov (United States)

    Rankin, Blake M; Hands, Michael D; Wilcox, David S; Fega, K Rebecca; Slipchenko, Lyudmila V; Ben-Amotz, Dor

    2013-01-01

    Interactions between halide ions (fluoride and iodide) and t-butyl alcohol (TBA) dissolved in water are probed using a recently developed hydration-shell spectroscopic technique and theoretical cluster and liquid calculations. High ignal-to-noise Raman spectroscopic measurements are combined with multivariate curve resolution (Raman-MCR) to reveal that while there is little interaction between aqueous fluoride ions and TBA, iodide ions break down the tetrahedral hydration-shell structure of TBA and produce a red-shift in its CH stretch frequency, in good agreement with the theoretical effective fragment potential (EFP) molecular dynamics simulations and hybrid quantum/EFP frequency calculations. The results imply that there is a significantly larger probability of finding iodide than fluoride in the first hydration shell of TBA, although the local iodide concentration is apparently not as high as in the surrounding bulk aqueous NaI solution.

  6. Immobilization of molecular cobalt electrocatalyst by hydrophobic interaction with hematite photoanode for highly stable oxygen evolution

    KAUST Repository

    Joya, Khurram

    2015-07-15

    A unique modification of a hematite photoanode with perfluorinated Co-phthalocyanine (CoFPc) by strong binding associated with hydrophobic interaction is demonstrated. The resultant molecular electrocatalyst – hematite photoanode hybrid material showed significant onset shift and high stability for photoelectrochemical oxidation evolution reaction (OER).

  7. Reference interaction site model with hydrophobicity induced density inhomogeneity: An analytical theory to compute solvation properties of large hydrophobic solutes in the mixture of polyatomic solvent molecules

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Siqin [The HKUST Shenzhen Research Institute, Shenzhen (China); Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon (Hong Kong); Sheong, Fu Kit [Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon (Hong Kong); Huang, Xuhui, E-mail: xuhuihuang@ust.hk [The HKUST Shenzhen Research Institute, Shenzhen (China); Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon (Hong Kong); Division of Biomedical Engineering, Center of Systems Biology and Human Health, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon (Hong Kong)

    2015-08-07

    Reference interaction site model (RISM) has recently become a popular approach in the study of thermodynamical and structural properties of the solvent around macromolecules. On the other hand, it was widely suggested that there exists water density depletion around large hydrophobic solutes (>1 nm), and this may pose a great challenge to the RISM theory. In this paper, we develop a new analytical theory, the Reference Interaction Site Model with Hydrophobicity induced density Inhomogeneity (RISM-HI), to compute solvent radial distribution function (RDF) around large hydrophobic solute in water as well as its mixture with other polyatomic organic solvents. To achieve this, we have explicitly considered the density inhomogeneity at the solute-solvent interface using the framework of the Yvon-Born-Green hierarchy, and the RISM theory is used to obtain the solute-solvent pair correlation. In order to efficiently solve the relevant equations while maintaining reasonable accuracy, we have also developed a new closure called the D2 closure. With this new theory, the solvent RDFs around a large hydrophobic particle in water and different water-acetonitrile mixtures could be computed, which agree well with the results of the molecular dynamics simulations. Furthermore, we show that our RISM-HI theory can also efficiently compute the solvation free energy of solute with a wide range of hydrophobicity in various water-acetonitrile solvent mixtures with a reasonable accuracy. We anticipate that our theory could be widely applied to compute the thermodynamic and structural properties for the solvation of hydrophobic solute.

  8. A microcalorimetric study of molecular interactions between immunoglobulin G and hydrophobic charge-induction ligand.

    Science.gov (United States)

    Yuan, Xiao-Ming; Lin, Dong-Qiang; Zhang, Qi-Lei; Gao, Dong; Yao, Shan-Jing

    2016-04-22

    Hydrophobic charge-induction chromatography (HCIC) with 4-mercaptoethyl-pyridine (MEP) as the ligand is a novel technology for antibody purification. In this study, isothermal titration calorimetry (ITC) was used to evaluate the molecular interactions between MEP ligand and immunoglobulin G (IgG). Three types of IgG molecules including human IgG (hIgG), bovine IgG (bIgG) and a monoclonal antibody (mAb) were investigated with human serum albumins (HSA) and bovine serum albumin (BSA) as the comparison. The thermodynamic parameters obtained from ITC were compared with the adsorption data. The results indicated that MEP binding to protein at neutral pH was entropy driven and induced by multimodal molecular interactions that was dominated by hydrophobic forces. The interactions between MEP and IgGs were stronger than that of albumins, which resulted in high binding affinity of IgGs. Moreover, the effects of pH and salt addition on MEP-hIgG binding were studied. The change of enthalpy increased obviously with the decrease of pH, which revealed that the electrostatic forces dominated the MEP-hIgG interactions at acidic condition and caused typical charge-induced elution of HCIC. Salt addition influenced both hydrophobic and electrostatic interactions. With the increase of salt concentration, the hydrophobic interactions decreased first and then increased, while the electrostatic interactions showed the opposite trend. This resulted in trade-off between the multimodal interactions, which caused the salt-tolerant property of MEP resin. In general, ITC studies revealed the molecular mechanism of three critical characteristics of HCIC, multimodal interactions, pH-dependent and salt-tolerant properties.

  9. Effect of hydrophobic interactions on the folding mechanism of β-hairpins.

    Science.gov (United States)

    Popp, Alexander; Wu, Ling; Keiderling, Timothy A; Hauser, Karin

    2014-12-11

    Hydrophobic interactions are essential in stabilizing protein structures. How they affect the folding pathway and kinetics, however, is less clear. We used time-resolved infrared spectroscopy to study the dynamics of hydrophobic interactions of β-hairpin variants of the sequence Trpzip2 (SWTWENGKWTWK-NH2) that is stabilized by two cross-strand Trp-Trp pairs. The hydrophobicity strength was varied by substituting the tryptophans pairwise by either tyrosines or valines. Relaxation dynamics were induced by a laser-excited temperature jump, which separately probed for the loss of the cross-strand β-hairpin interaction and the rise of the disordered structure. All substitutions tested result in reduced thermal stability, lower transition temperatures, and faster dynamics compared to Trpzip2. However, the changes in folding dynamics depend on the amino acid substituted for Trp. The aromatic substitution of Tyr for Trp results in the same kinetics for the unfolding of sheet and growth of disorder, with similar activation energies, independent of the substitution position. Substitution of Trp with a solely hydrophobic Val results in even faster kinetics than substitution with Tyr but is additionally site-dependent. If the hairpin has a Val pair close to its termini, the rate constants for loss of sheet and gain of disorder are the same, but if the pair is close to the turn, the sheet and disorder components show different relaxation kinetics. The Trp → Val substitutions reveal that hydrophobic interactions alone weakly stabilize the hairpin structure, but adding edge-to-face aromatic interaction strengthens it, and both modify the complex folding process.

  10. Hydrophobic, Polar and Hydrogen Bonding Based Drug-Receptor Interaction of Tetrahydroimidazobenzodiazepinones

    Directory of Open Access Journals (Sweden)

    V. K. Sahu

    2008-01-01

    Full Text Available Anti-HIV drug discovery has been increasingly focusing on HIV-1-RT (reverse transcriptase as a potential therapeutic target. Tetrahydroimidazobenzodiazepinone (TIBO belongs to non-nucleoside group of reverse transcriptase inhibitors (NNRTIs. A computational chemistry study has been performed on a series of tetrahydroimidazo-benzodiazepinones as HIV-1-NNRT inhibitors. Problem statement: In order to search out new drug of desired activity from the lead compounds, there was need to know the interaction of drugs with their receptor i.e., type of force(s that have predominant role. Approach: Log P and SASA have been used for measurement of hydrophobic interaction, energy of protonation for measurement of most favorable hydrogen bond acceptor site, bond length and bond strain for measurement of strength of hydrogen bond formed between drug and receptor, atomic charges, ionization potential, electronegativity, E‡n and E‡m and their difference ΔE‡nm for measurement of polar interaction. The 3D modeling and geometry optimization of the compounds and receptor amino acids have been done by semiempirical method with MOPAC2002 associated with CAChe software. Results: The study has shown that hydrophobic interaction is predominant and made major contribution, while hydrogen bonding and polar interactions help in proper orientation of the compound (or its functional groups to make maximam interaction. Conclusion: In this study theoretical technique has been discussed by which new hypothetical HIV-1-NNRT inhibitors can be developed prior to their synthesis only by introducing effective hydrophobic substituents at specific sites.

  11. Antibody-ligand interactions for hydrophobic charge-induction chromatography: a surface plasmon resonance study.

    Science.gov (United States)

    Cheng, Fang; Li, Ming-Yang; Wang, Han-Qi; Lin, Dong-Qiang; Qu, Jing-Ping

    2015-03-24

    This article describes the use of surface plasmon resonance (SPR) spectroscopy to study antibody-ligand interactions for hydrophobic charge-induction chromatography (HCIC) and its versatility in investigating the surface and solution factors affecting the interactions. Two density model surfaces presenting the HCIC ligand (mercapto-ethyl-pyridine, MEP) were prepared on Au using a self-assembly technique. The surface chemistry and structure, ionization, and protein binding of such model surfaces were characterized by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), contact-angle titration, and SPR, respectively. The influences of the surface and solution factors, e.g., ligand density, salt concentration, and solution pH, on protein adsorption were determined by SPR. Our results showed that ligand density affects both equilibrium and dynamic aspects of the interactions. Specifically, a dense ligand leads to an increase in binding strength, rapid adsorption, slow desorption, and low specificity. In addition, both hydrophobic interactions and hydrogen bonding contribute significantly to the protein adsorption at neutral pH, while the electrostatic repulsion is overwhelmed under acidic conditions. The hydrophobic interaction at a high concentration of lyotropic salt would cause drastic conformational changes in the adsorbed protein. Combined with the self-assembly technique, SPR proves to be a powerful tool for studying the interactions between an antibody and a chromatographic ligand.

  12. Protein-spanning water networks and implications for prediction of protein-protein interactions mediated through hydrophobic effects.

    Science.gov (United States)

    Cui, Di; Ou, Shuching; Patel, Sandeep

    2014-12-01

    Hydrophobic effects, often conflated with hydrophobic forces, are implicated as major determinants in biological association and self-assembly processes. Protein-protein interactions involved in signaling pathways in living systems are a prime example where hydrophobic effects have profound implications. In the context of protein-protein interactions, a priori knowledge of relevant binding interfaces (i.e., clusters of residues involved directly with binding interactions) is difficult. In the case of hydrophobically mediated interactions, use of hydropathy-based methods relying on single residue hydrophobicity properties are routinely and widely used to predict propensities for such residues to be present in hydrophobic interfaces. However, recent studies suggest that consideration of hydrophobicity for single residues on a protein surface require accounting of the local environment dictated by neighboring residues and local water. In this study, we use a method derived from percolation theory to evaluate spanning water networks in the first hydration shells of a series of small proteins. We use residue-based water density and single-linkage clustering methods to predict hydrophobic regions of proteins; these regions are putatively involved in binding interactions. We find that this simple method is able to predict with sufficient accuracy and coverage the binding interface residues of a series of proteins. The approach is competitive with automated servers. The results of this study highlight the importance of accounting of local environment in determining the hydrophobic nature of individual residues on protein surfaces.

  13. Interaction mechanism between hydrophobic and hydrophilic surfaces: using polystyrene and mica as a model system.

    Science.gov (United States)

    Faghihnejad, Ali; Zeng, Hongbo

    2013-10-08

    The interactions between hydrophobic and hydrophilic molecules, particles, or surfaces occur in many biological phenomena and industrial processes. In this work, polystyrene (PS) and mica were chosen as a model system to investigate the interaction mechanism between hydrophilic and hydrophobic surfaces. Using a surface forces apparatus (SFA) coupled with a top-view optical microscope, interaction forces between PS and mica surfaces were directly probed in five different electrolyte solutions (i.e., NaCl, CaCl2, NaOH, HCl, and CH3COOH) of various concentrations. Long-range repulsion was observed in low electrolyte concentration (e.g., 0.001 M) which was mainly due to the presence of microscopic and submicroscopic bubbles on PS surface. A modified Derjaguin-Landau-Verwey-Overbeek (DLVO) theory well fits the interaction forces by taking into account the effect of bubbles on PS surface. The range of the repulsion was dramatically reduced in 1.0 M solutions of NaCl, CaCl2, and NaOH but did not significantly change in 1.0 M HCl and CH3COOH, which was due to ion specificity effect on the formation and stability of bubbles on PS surface. The range of repulsion was also significantly reduced to forces dominate the interaction between hydrophilic surface (i.e., mica) and hydrophobic polymer (i.e., PS), while the types of electrolytes (ion specificity), electrolyte concentration, degassing, and surface hydrophobicity can significantly affect the formation and stability of bubbles on the interacting surfaces, thus affecting the range and magnitude of the interaction forces.

  14. Synthesis of Hydrophobically Modified Poly(acrylic acid) Gels and Interaction of the Gels with Cationic/Anionic Surfactants

    Institute of Scientific and Technical Information of China (English)

    TIAN,Qin(田琴); TANG,Xiao-Zhen(唐小真); ZHUANG,Dong-Qing(庄东青); ZHANG,Yun-Xiang(章云祥)

    2002-01-01

    Poly( acrylic acid) (PAA) gel network with only chemical crosslinking and hydrophobically modified PAA (HM-PAA)gels with both chemical and physical crosslinking were synthesized by radical polymerization in tert-butanol, using ethylene glycol dimethacrylate (EGDMA) as crosslinker, and 2-(Nethylperfiuorooctanesulfoamido) ethyl methacrylate ( FMA ),stearyl acrylate (SA) or lauryl acrylate (LA) as hydrophobic comonomer respectively. The effect of the fractions and the species of the hydrophobes on swelling properties of HM-PAA gels and the interaction of gels and surfactants were studied.The results showed that the swelling ratio of HM-PAA gels exhibited a sharp decrease with increasing hydrophobic comonomer concentration, which could be ascribed to the formation of strong hydrophobic association among hydrophobic groups. It was proved that two kinds of binding mechanisms of surfactant/gel and different kinds of hydrophobic dusters existed in gels containing both physical and chemical networks.

  15. Cooperative hydrophobic/hydrophilic interactions in the hydration of dimethyl ether.

    Science.gov (United States)

    Utiramerur, S; Paulaitis, M E

    2010-04-21

    Cooperative interactions in the hydration of dimethyl ether (DME) relative to its purely hydrophobic analog, propane, are analyzed by expressing the free energy of hydration in terms of an "inner-shell" contribution from water molecular packing and chemical association, and an "outer-shell" contribution described by the mean binding energy of the solute to the solution and fluctuations in this binding energy. We find that nonadditive, cooperative interactions associated with strong correlations in the binding energy fluctuations of the methyl groups and ether oxygen play a dominant role in the hydration of DME relative to propane. The electrostatic nature of these interactions is revealed in a multi-Gaussian analysis of hydration substates, which shows that the formation of favorable ether oxygen-water hydrogen bonds is correlated with less favorable methyl group-water interactions, and vice versa. We conclude that the group additive distinction between the hydrophobic hydration of the DME methyl groups and hydrophilic hydration of the ether oxygen is lost in the context of these cooperative interactions. Our results also suggest that the binding energy fluctuations of constituent hydrophobic/hydrophilic groups are more sensitive than local water density fluctuations for characterizing the hydration of heterogeneous interfaces.

  16. Nisin adsorption on hydrophilic and hydrophobic surfaces: evidence of its interactions and antibacterial activity.

    Science.gov (United States)

    Karam, Layal; Jama, Charafeddine; Nuns, Nicolas; Mamede, Anne-Sophie; Dhulster, Pascal; Chihib, Nour-Eddine

    2013-06-01

    Study of peptides adsorption on surfaces remains a current challenge in literature. A complementary approach, combining X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to investigate the antimicrobial peptide nisin adsorption on hydrophilic and hydrophobic surfaces. The native low density polyethylene was used as hydrophobic support and it was grafted with acrylic acid to render it hydrophilic. XPS permitted to confirm nisin adsorption and to determine its amount on the surfaces. ToF-SIMS permitted to identify the adsorbed bacteriocin type and to observe its distribution and orientation behavior on both types of surfaces. Nisin was more oriented by its hydrophobic side to the hydrophobic substrate and by its hydrophilic side to the outer layers of the adsorbed peptide, in contrast to what was observed on the hydrophilic substrate. A correlation was found between XPS and ToF-SIMS results, the types of interactions on both surfaces and the observed antibacterial activity. Such interfacial studies are crucial for better understanding the peptides interactions and adsorption on surfaces and must be considered when setting up antimicrobial surfaces.

  17. Hydrophilic-hydrophobic polymer blend for modulation of crystalline changes and molecular interactions in solid dispersion.

    Science.gov (United States)

    Van Ngo, Hai; Nguyen, Phuc Kien; Van Vo, Toi; Duan, Wei; Tran, Van-Thanh; Tran, Phuong Ha-Lien; Tran, Thao Truong-Dinh

    2016-11-20

    This research study aimed to develop a new strategy for using a polymer blend in solid dispersion (SD) for dissolution enhancement of poorly water-soluble drugs. SDs with different blends of hydrophilic-hydrophobic polymers (zein/hydroxypropyl methylcellulose - zein/HPMC) were prepared using spray drying to modulate the drug crystal and polymer-drug interactions in SDs. Physicochemical characterizations, including power X-ray diffraction and Fourier transform infrared spectroscopy, were performed to elucidate the roles of the blends in SDs. Although hydrophobic polymers played a key role in changing the model drug from a crystal to an amorphous state, the dissolution rate was limited due to the wetting property. Fortunately, the hydrophilic-hydrophobic blend not only reduced the drug crystallinity but also resulted in a hydrogen bonding interaction between the drugs and the polymer for a dissolution rate improvement. This work may contribute to a new generation of solid dispersion using a blend of hydrophilic-hydrophobic polymers for an effective dissolution enhancement of poorly water-soluble drugs.

  18. The Hydrophobic Effect.

    Science.gov (United States)

    Huque, Entazul M.

    1989-01-01

    Discusses the physical basis and current understanding of hydrophobic effects. The thermodynamic background of the effects, hydrophobic hydration, and hydrophobic interactions are described. Four existing controversies are outlined. (YP)

  19. Urea's action on the hydrophobic interaction in physical and biophysical systems

    Science.gov (United States)

    Berne, B. J.

    2009-03-01

    For more than a century, urea has been commonly used as an agent for denaturing proteins. However, the mechanism behind its denaturing power is still not well understood. The mechanism of denaturation of proteins by urea is explored using all-atom microseconds molecular dynamics simulations of hen lysozyme generated on BlueGene/L. Accumulation of urea around lysozyme shows that water molecules are expelled from the first hydration shell of the protein. We observe a two stage penetration of the protein, with urea penetrating the hydrophobic core before water, forming a ``dry globule." The direct dispersion interaction between urea and the protein backbone and sidechains is stronger than for water, which gives rise to the intrusion of urea into the protein interior and also to urea's preferential binding to all regions of the protein. This is augmented by preferential hydrogen bond formation between the urea carbonyl and the backbone amides which contributes to the breaking of intra-backbone hydrogen bonds. Our study supports the ``direct interaction mechanism" whereby urea has a stronger dispersion interaction with protein than water. We also show by molecular dynamics simulations that a 7 M aqueous urea solution unfolds a chain of purely hydrophobic groups which otherwise adopts a compact structure in pure water. The unfolding process arises due to a weakening of hydrophobic interactions between the polymer groups. Again the action of urea is found to be direct, through its preferential binding to the polymer or plates. It is, therefore, acting like a surfactant capable of forming hydrogen bonds with the solvent. The preferential binding and the consequent weakened hydrophobic interactions are driven by enthalpy and are related to the difference in the strength of the attractive dispersion interactions of urea and water with the polymer chain or plate. We also show that the indirect mechanism, in which urea acts as a chaotrope, is not a likely cause of urea

  20. Isoentropic and Isoenthalpic Temperatures of Protein Unfolding in Hydrophobic Interaction Chromatography

    Institute of Scientific and Technical Information of China (English)

    Yan YAN; Rui Xian LIU; Yin Mao WEI; Ye Hua SHEN; Xin Du GENG

    2006-01-01

    The thermal behaviors of five proteins in hydrophobic interaction chromatography (HIC) were investigated in the temperature range from 0 to 50℃. The thermodynamic parameters (△H°,△S°, △Cp°and △G°) of these proteins in the process of retention and unfolding were determined.The existence of enthalpy and entropy convergence with temperature was confirmed. The differences of the isoentropic and isoenthalpic temperatures for protein unfolding in HIC system from the traditional solution were elucidated.

  1. Separation of mAbs molecular variants by analytical hydrophobic interaction chromatography HPLC: overview and applications

    OpenAIRE

    Haverick, Mark; Mengisen, Selina; Shameem, Mohammed; Ambrogelly, Alexandre

    2014-01-01

    Hydrophobic interaction chromatography-high performance liquid chromatography (HIC-HPLC) is a powerful analytical method used for the separation of molecular variants of therapeutic proteins. The method has been employed for monitoring various post-translational modifications, including proteolytic fragments and domain misfolding in etanercept (Enbrel®); tryptophan oxidation, aspartic acid isomerization, the formation of cyclic imide, and α amidated carboxy terminus in recombinant therapeutic...

  2. Adaptive hydrophobic and hydrophilic interactions of mussel foot proteins with organic thin films.

    Science.gov (United States)

    Yu, Jing; Kan, Yajing; Rapp, Michael; Danner, Eric; Wei, Wei; Das, Saurabh; Miller, Dusty R; Chen, Yunfei; Waite, J Herbert; Israelachvili, Jacob N

    2013-09-24

    The adhesion of mussel foot proteins (Mfps) to a variety of specially engineered mineral and metal oxide surfaces has previously been investigated extensively, but the relevance of these studies to adhesion in biological environments remains unknown. Most solid surfaces exposed to seawater or physiological fluids become fouled by organic conditioning films and biofilms within minutes. Understanding the binding mechanisms of Mfps to organic films with known chemical and physical properties therefore is of considerable theoretical and practical interest. Using self-assembled monolayers (SAMs) on atomically smooth gold substrates and the surface forces apparatus, we explored the force-distance profiles and adhesion energies of three different Mfps, Mfp-1, Mfp-3, and Mfp-5, on (i) hydrophobic methyl (CH3)- and (ii) hydrophilic alcohol (OH)-terminated SAM surfaces between pH 3 and pH 7.5. At acidic pH, all three Mfps adhered strongly to the CH3-terminated SAM surfaces via hydrophobic interactions (range of adhesive interaction energy = -4 to -9 mJ/m(2)) but only weakly to the OH-terminated SAM surfaces through H- bonding (adhesive interaction energy ≤ -0.5 mJ/m(2)). 3, 4-Dihydroxyphenylalanine (Dopa) residues in Mfps mediate binding to both SAM surface types but do so through different interactions: typical bidentate H-bonding by Dopa is frustrated by the longer spacing of OH-SAMs; in contrast, on CH3-SAMs, Dopa in synergy with other nonpolar residues partitions to the hydrophobic surface. Asymmetry in the distribution of hydrophobic residues in intrinsically unstructured proteins, the distortion of bond geometry between H-bonding surfaces, and the manipulation of physisorbed binding lifetimes represent important concepts for the design of adhesive and nonfouling surfaces.

  3. Separation of proteins from human plasma by sample displacement chromatography in hydrophobic interaction mode

    OpenAIRE

    Josic, Djuro; Breen, Lucas; Clifton, James; Gajdosik, Martina Srajer; Gaso-Sokac, Dajana; Rucevic, Marijana; Müller, Egbert

    2012-01-01

    Sample displacement chromatography (SDC) in reversed-phase and ion-exchange modes was introduced approximately twenty years ago. This method was first used for the preparative purification of peptides and proteins. Recently, SDC in ion-exchange mode was also successfully used for enrichment of low abundance proteins from human plasma. In this paper, the use of SDC for the separation of plasma proteins in hydrophobic interaction mode is demonstrated. By use of two or more columns coupled in se...

  4. Mechanism of simultaneously refolding and purification of proteins by hydrophobic interaction chromatographic unit and applications

    Institute of Scientific and Technical Information of China (English)

    GENG; Xindu(耿信笃); BAI; Quan(白泉)

    2002-01-01

    The hydrophobic amino acid residues of a denatured protein molecule tend to react with the particles of the stationary phase of hydrophobic interaction chromatography (STHIC). These hydrophobic interactions prevent the denatured protein molecules from aggregating with each other. The STHIC can provide high enough energy to a denatured protein molecule to make it dehydration and to refold it into its native or various intermediate states. The outcome not only depends on the specific interactions between amino acids, the structure of STHIC, but also depends on the association between the STHIC and mobile phase. The mechanism of protein refolding and the principle of its quality control by HPHIC were also presented. By appropriate selection of the chromatographic condition, several denatured proteins can be refolded and separated simultaneously in a single chromatographic run. A specially designed unit, with diameter much larger than its length, was designed and employed for both laboratory and preparative scales. That unit for the simultaneous renaturation and purification of proteins (USRPP) had the following four functions: to completely remove denaturant, to renature proteins, to separate renatured proteins from impurities, and to easily recycle waste denaturant. The efficiencies of refolding and purification of proteins by the USRPP are almost comparable to a usual long chromatographic column in laboratory. In preparative scale, USRPP can be easily, rapidly, and economically applied requiring a low pressure gradient. As an example, recombinant human interferon-? is employed to elucidate the application of the preparative USRPP.

  5. Molecular Dynamics Simulation of Behaviours of Non-Polar Droplets Merging and Interactions with Hydrophobic Surfaces

    Institute of Scientific and Technical Information of China (English)

    Y.Y.Yan; C.Y.Ji

    2008-01-01

    This paper presents a molecular dynamics simulation of the behaviours of non-polar droplets merging and also the fluid molecules interacting with a hydrophobic surface. Such behaviours and transport phenomena are popular in general micro-channel flow boiling and two-phase flow. The droplets are assumed to be composed of Lennards-Jones type molecules. Periodic boundary conditions are applied in three coordinate directions ofa 3-D system, where there exist two liquid droplets and their vapour. The two droplets merge when they come within the prescribed small distance. The merging of two droplets apart from each other at different initial distances is tested and the possible larger (or critical) non-dimensional distance, in which droplets merging can occur, is discussed. The evolution of the merging process is simulated numerically by employing the Molecular Dynamics (MD) method. For interactions with hydrophobic solid wail, a system with fluid confined between two walls is used to study the wetting phenomena of fluid and solid wail. The results are compared with those of hydrophilic wall to show the unique characteristics of hydrophobic interactions by microscopic methods.

  6. Synthesis of Hydrophobically Modified Poly(acrylic acid) gels and Interaction of the gels with Cationic/Anionic Surfactants

    Institute of Scientific and Technical Information of China (English)

    田琴; 唐小真; 庄东青; 章云祥

    2002-01-01

    Poly(acrylic acid)(PAA) gel network with only chemical crosslinking and hydorophobically modified PAA(HM-PAA)gels with both chemical and physical crosslinking were synthesized by radical polymerization in tert-butanol,using ethylene glycol dimethacrylate (EGDMA) as crossliker,and 2-(N-ethylperfluorooctanesulfoamido)ethyl methacrylate (FMA),stearyl acrylate (SA) or lauryl acrylate (LA) as Hydrophobic comonomer respectively.The effcet of the fractions and the species of the hydrophobes on swelling properties of HM-PAA gels and the interaction of gels and surfactants were studied.The results showed that the swelling ratio of HM-PAA gels exhibited a sharp decrease with increasing hydrophobic comomomer comcentration,Which Could be sacribed to the formation of strong hydrophobic association among hydrophobic groups.It was proved that two kinds of binding mechanisms of surfactan/gel and different kinds of hydrophobic clusters existed in gels containing both physical and chemical networks.

  7. MACROSCOPIC RIVERS

    NARCIS (Netherlands)

    VANDENBERG, IP

    1991-01-01

    We present a mathematical model for the ''river-phenomenon'': striking concentrations of trajectories of ordinary differential equations. This model of ''macroscopic rivers'' is formulated within nonstandard analysis, and stated in terms of macroscopes and singular perturbations. For a subclass, the

  8. Increasing the bioavailability of Ru(III) anticancer complexes through hydrophobic albumin interactions.

    Science.gov (United States)

    Webb, Michael I; Wu, Boris; Jang, Thalia; Chard, Ryan A; Wong, Edwin W Y; Wong, May Q; Yapp, Donald T T; Walsby, Charles J

    2013-12-09

    A series of pyridine-based derivatives of the clinically successful Ru(III)-based complexes indazolium [trans-RuCl4(1H-indazole)2] (KP1019) and sodium [trans-RuCl4(1H-indazole)2] (KP1339) have been synthesized to probe the effect of hydrophobic interactions with human serum albumin (hsA) on anticancer activity. The solution behavior and protein interactions of the new compounds were characterized by using electron paramagnetic resonance (EPR) and UV/Vis spectroscopy. These studies have revealed that incorporation of hydrophobic substituents at the 4'-position of the axial pyridine ligand stabilizes non-coordinate interactions with hsA. As a consequence, direct coordination to the protein is inhibited, which is expected to increase the bioavailability of the complexes, thus potentially leading to improved anticancer activity. By using this approach, the lifetimes of hydrophobic protein interactions were extended from 2 h for the unsubstituted pyridine complex, to more than 24 h for several derivatives. Free complexes were tested for their anticancer activity against the SW480 human colon carcinoma cell line, exhibiting low cytotoxicity. Pre-treatment with hsA improved the solubility of every compound and led to some changes in activity. Particularly notable was the difference in activity between the methyl- and dibenzyl-functionalized complexes. The former shows reduced activity after incubation with hsA, indicating reduced bioavailability due to protein coordination. The latter exhibits little activity on its own but, following treatment with hsA, exhibited significant cytotoxicity, which is consistent with its ability to form non-coordinate interactions with the protein. Overall, our studies demonstrate that non-coordinate interactions with hsA are a viable target for enhancing the activity of Ru(III)-based complexes in vivo.

  9. Efficient separation of homologous alpha-lactalbumin from transgenic bovine milk using optimized hydrophobic interaction chromatography.

    Science.gov (United States)

    Zhang, Yan; Luo, Jian; Bi, Jingxiu; Wang, Jun; Sun, Lijing; Liu, Yongdong; Zhang, Guifeng; Ma, Guanghui; Su, Zhiguo

    2010-06-04

    Transgenic bovine milk could be a rich source of recombinant human proteins. However, the co-presence of bovine and human homologous proteins can be a challenge for product purification. In this study, the average surface hydrophobicity and electric potential of human alpha-lactalbumin (HLA) and bovine alpha-lactalbumin (BLA) were analyzed and compared through the exposure area calculation of different amino acids. Based on the analysis, calcium independent hydrophobic interaction chromatography was selected for separation of recombinant human alpha-lactalbumin (rHLA) from BLA in transgenic bovine milk. The operating conditions for the best separation of two proteins were predicted by fluorescence data. Three commercially available HIC resins (Butyl Sepharose 4 FF, Octyl Sepharose 4 FF, Phenyl Sepharose 6 FF) were compared. The transgenic milk was skimmed and treated by pH adjustment to remove a large quantity of casein protein. The supernatant was loaded on the hydrophobic interaction chromatographic matrix. The correct elution fraction was further treated with gel filtration chromatography. The overall recovery of rHLA was up to 67.1% with the purity greater than 95%. Circular dichroism spectroscopy (CD) and mass spectrogram (MS) confirmed the native state and glycosylated form of the purified rHLA.

  10. Characterization and Correlation of Particle-Level Interactions to the Macroscopic Rheology of Powders, Granular Slurries, and Colloidal Suspensions

    Energy Technology Data Exchange (ETDEWEB)

    Poloski, Adam P.; Daniel, Richard C.; Rector, David R.; Bredt, Paul R.; Buck, Edgar C.; Berg, John C.; Saez, Avelino E.

    2006-09-29

    Hanford TRU tank sludges are complex mixtures of undissolved minerals and salt solids in an aqueous phase of high ionic strength. They show complex rheological behavior resulting from interactions at the macroscopic level, such as interparticle friction between grains in the coarse fraction, as well as from interactions at the nano-scale level, such as the agglomeration of colloidal particles. An understanding of how phenomena such as interparticle friction and aggregate stability under shear will allow better control of Hanford TRU tank sludges being processed for disposal. The project described in this report had two objectives. The first was to understand the physical properties and behavior of the Hanford transuranic (TRU) tank sludges under conditions that might exist during retrieval, treatment, packaging, and transportation for disposal at the Waste Isolation Pilot Plant (WIPP). The second objective was to develop a fundamental understanding of sludge physical properties by correlating the macroscopic behavior with interactions occurring at the particle/colloidal scale. These objectives were accomplished by: 1) developing continuum models for coarse granular slurries and 2) studying the behavior of colloidal agglomerates under shear and under irradiation.

  11. Hydrophobic Interactions Are Key To Drive the Association of Tapasin with Peptide Transporter Subunit TAP2.

    Science.gov (United States)

    Rufer, Elke; Kägebein, Danny; Leonhardt, Ralf M; Knittler, Michael R

    2015-12-01

    The transporter associated with Ag processing (TAP) translocates proteasomally derived cytosolic peptides into the endoplasmic reticulum. TAP is a central component of the peptide-loading complex (PLC), to which tapasin (TPN) recruits MHC class I (MHC I) and accessory chaperones. The PLC functions to facilitate and optimize MHC I-mediated Ag presentation. The heterodimeric peptide transporter consists of two homologous subunits, TAP1 and TAP2, each of which contains an N-terminal domain (N-domain) in addition to a conserved transmembrane (TM) core segment. Each N-domain binds to the TM region of a single TPN molecule, which recruits one MHC I molecule to TAP1 and/or TAP2. Although both N-domains act as TPN-docking sites, various studies suggest a functional asymmetry within the PLC resulting in greater significance of the TAP2/TPN interaction for MHC loading. In this study, we demonstrate that the leucine-rich hydrophobic sequence stretches (with the central leucine residues L20 and L66) in the first and second TM helix of TAP2 form a functional unit acting as a docking site for optimal TPN/MHC I recruitment, whereas three distinct highly conserved arginine and/or aspartate residues inside or flanking these TM helices are dispensable. Moreover, we show that the physical interaction between TAP2 and TPN is disrupted by benzene, a compound known to interfere with hydrophobic interactions, such as those between pairing leucine zippers. No such effects were observed for the TAP1/TAP2 interaction or the complex formation between TPN and MHC I. We propose that TAP/TPN complex formation is driven by hydrophobic interactions via leucine zipper-like motifs.

  12. Effects of hydrophobic and dipole-dipole interactions on the conformational transitions of a model polypeptide

    Science.gov (United States)

    Mu, Yan; Gao, Yi Qin

    2007-09-01

    We studied the effects of hydrophobicity and dipole-dipole interactions between the nearest-neighbor amide planes on the secondary structures of a model polypeptide by calculating the free energy differences between different peptide structures. The free energy calculations were performed with low computational costs using the accelerated Monte Carlo simulation (umbrella sampling) method, with a bias-potential method used earlier in our accelerated molecular dynamics simulations. It was found that the hydrophobic interaction enhances the stability of α helices at both low and high temperatures but stabilizes β structures only at high temperatures at which α helices are not stable. The nearest-neighbor dipole-dipole interaction stabilizes β structures under all conditions, especially in the low temperature region where α helices are the stable structures. Our results indicate clearly that the dipole-dipole interaction between the nearest neighboring amide planes plays an important role in determining the peptide structures. Current research provides a more unified and quantitative picture for understanding the effects of different forms of interactions on polypeptide structures. In addition, the present model can be extended to describe DNA/RNA, polymer, copolymer, and other chain systems.

  13. Spontaneous association of hydrophobized dextran and poly-beta-cyclodextrin into nanoassemblies. Formation and interaction with a hydrophobic drug.

    Science.gov (United States)

    Daoud-Mahammed, S; Ringard-Lefebvre, C; Razzouq, N; Rosilio, V; Gillet, B; Couvreur, P; Amiel, C; Gref, R

    2007-03-01

    New nanoassemblies were instantaneously prepared by mixing two aqueous solutions, one containing a beta-cyclodextrin polymer (pbetaCD), and the other a hydrophobically modified by alkyl chains dextran (MD). The formation mechanism and the inner structure of these nanoassemblies were analysed using surface tension measurements and (1)H NMR spectroscopy. The effect of a hydrophobic guest molecule, such as benzophenone (BZ), on the formation and stability of the nanoassemblies was also evaluated. MD exhibited the typical behaviour of a soluble amphiphilic molecule and adsorbed at the air/water interface. Whereas the injection of native beta-CDs in the solution beneath the adsorbed MD monolayer did not produce any change in the surface tension, that of the pbetaCD resulted in an increase in the surface tension, indicating the desorption of the polymer from the interface. This result accounts for a cooperative effect of beta-CDs linked together in the pbetaCD polymer on dextran desorption. The presence of benzophenone in the system hindered the sequestration of dextran alkyl moieties by beta-CD in the polymer without impeding the formation of associative nanoassemblies of 100-200 nm. (1)H NMR investigations demonstrated that, in the BZ-loaded nanoassemblies, the hydrophobic molecule was mainly located into the cyclodextrin cavities.

  14. Desing of a virtual interactive tutorial of the equine encephalon macroscopic anatomy for veterinary students

    Directory of Open Access Journals (Sweden)

    Carlos Alberto Venegas Cortes

    2006-06-01

    Full Text Available In order to answer the problem of what could be the most appropriate innovative didactic to improve the learning process of equine encephalon anatomy in the School of Veterinary Medicine of La Salle University, this project began to design, apply and evaluate a didactic prototype Computerized Educative Media CEM in macroscopic anatomy of equine encephalon, to improve the «significant learning» in this subject. The project was developed in three phases regarding the Galviz software engineering, as well as the selected environment for learning, within the framework of the conceptual Novak maps, the significant learning of Ausubel, and the test of usability adapted and applied to the anatomy students, as a MEC evaluation.

  15. Thermodynamic Molecular Switch in Sequence-Specific Hydrophobic Interaction: Two Computational Models Compared

    Directory of Open Access Journals (Sweden)

    Paul Chun

    2003-01-01

    Full Text Available We have shown in our published work the existence of a thermodynamic switch in biological systems wherein a change of sign in ΔCp°(Treaction leads to a true negative minimum in the Gibbs free energy change of reaction, and hence, a maximum in the related Keq. We have examined 35 pair-wise, sequence-specific hydrophobic interactions over the temperature range of 273–333 K, based on data reported by Nemethy and Scheraga in 1962. A closer look at a single example, the pair-wise hydrophobic interaction of leucine-isoleucine, will demonstrate the significant differences when the data are analyzed using the Nemethy-Scheraga model or treated by the Planck-Benzinger methodology which we have developed. The change in inherent chemical bond energy at 0 K, ΔH°(T0 is 7.53 kcal mol-1 compared with 2.4 kcal mol-1, while ‹ts› is 365 K as compared with 355 K, for the Nemethy-Scheraga and Planck-Benzinger model, respectively. At ‹tm›, the thermal agitation energy is about five times greater than ΔH°(T0 in the Planck-Benzinger model, that is 465 K compared to 497 K in the Nemethy-Scheraga model. The results imply that the negative Gibbs free energy minimum at a well-defined ‹ts›, where TΔS° = 0 at about 355 K, has its origin in the sequence-specific hydrophobic interactions, which are highly dependent on details of molecular structure. The Nemethy-Scheraga model shows no evidence of the thermodynamic molecular switch that we have found to be a universal feature of biological interactions. The Planck-Benzinger method is the best known for evaluating the innate temperature-invariant enthalpy, ΔH°(T0, and provides for better understanding of the heat of reaction for biological molecules.

  16. Free energetics of rigid body association of ubiquitin binding domains: a biochemical model for binding mediated by hydrophobic interaction.

    Science.gov (United States)

    Cui, Di; Ou, Shuching; Patel, Sandeep

    2014-07-01

    Weak intermolecular interactions, such as hydrophobic associations, underlie numerous biomolecular recognition processes. Ubiquitin is a small protein that represents a biochemical model for exploring thermodynamic signatures of hydrophobic association as it is widely held that a major component of ubiquitin's binding to numerous partners is mediated by hydrophobic regions on both partners. Here, we use atomistic molecular dynamics simulations in conjunction with the Adaptive Biasing Force sampling method to compute potentials of mean force (the reversible work, or free energy, associated with the binding process) to investigate the thermodynamic signature of complexation in this well-studied biochemical model of hydrophobic association. We observe that much like in the case of a purely hydrophobic solute (i.e., graphene, carbon nanotubes), association is favored by entropic contributions from release of water from the interprotein regions. Moreover, association is disfavored by loss of enthalpic interactions, but unlike in the case of purely hydrophobic solutes, in this case protein-water interactions are lost and not compensated for by additional water-water interactions generated upon release of interprotein and moreso, hydration, water. We further find that relative orientations of the proteins that mutually present hydrophobic regions of each protein to its partner are favored over those that do not. In fact, the free energy minimum as predicted by a force field based method recapitulates the experimental NMR solution structure of the complex.

  17. Hydrophobic pore array surfaces: wetting and interaction forces in water/ethanol mixtures.

    Science.gov (United States)

    Hansson, Petra M; Hormozan, Yashar; Brandner, Birgit D; Linnros, Jan; Claesson, Per M; Swerin, Agne; Schoelkopf, Joachim; Gane, Patrick A C; Thormann, Esben

    2013-04-15

    Interactions between and wetting behavior of structured hydrophobic surfaces using different concentrations of water/ethanol mixtures have been investigated. Silica surfaces consisting of pore arrays with different pore spacings and pore depths were made hydrophobic by silanization. Their static and dynamic contact angles were found to be independent of the pore depth while fewer pores on the surface, i.e. a closer resemblance to a flat surface, gave a lower contact angle. As expected, a higher amount of ethanol facilitated wetting on all the surfaces tested. Confocal Raman microscopy measurements proved both water and ethanol to penetrate into the pores. AFM colloidal probe force measurements clearly showed that formation of air cavitation was hindered between the hydrophobic surfaces in presence of ethanol, and an increase in ethanol concentration was followed by a smaller jump-in distance and a weaker adhesion force. On separation, an immediate jump-out of contact occurred. The measured forces were interpreted as being due to capillary condensation of ethanol between the surfaces giving rise to very unstable cavities immediately rupturing on surface separation.

  18. Different assembly of type IV collagen on hydrophilic and hydrophobic substrata alters endothelial cells interaction.

    Science.gov (United States)

    Coelho, N Miranda; González-García, C; Planell, J A; Salmerón-Sánchez, M; Altankov, G

    2010-06-09

    Considering the structural role of type IV collagen (Col IV) in the assembly of the basement membrane (BM) and the perspective of mimicking its organization for vascular tissue engineering purposes, we studied the adsorption pattern of this protein on model hydrophilic (clean glass) and hydrophobic trichloro(octadecyl)silane (ODS) surfaces known to strongly affect the behavior of other matrix proteins. The amount of fluorescently labeled Col IV was quantified showing saturation of the surface for concentration of the adsorbing solution of about 50microg/ml, but with approximately twice more adsorbed protein on ODS. AFM studies revealed a fine - nearly single molecular size - network arrangement of Col IV on hydrophilic glass, which turns into a prominent and growing polygonal network consisting of molecular aggregates on hydrophobic ODS. The protein layer forms within minutes in a concentration-dependent manner. We further found that human umbilical vein endothelial cells (HUVEC) attach less efficiently to the aggregated Col IV (on ODS), as judged by the significantly altered cell spreading, focal adhesions formation and the development of actin cytoskeleton. Conversely, the immunofluorescence studies for integrins revealed that the fine Col IV network formed on hydrophilic substrata is better recognized by the cells via both alpha1 and alpha2 heterodimers which support cellular interaction, apart from these on hydrophobic ODS where almost no clustering of integrins was observed.

  19. Different assembly of type IV collagen on hydrophilic and hydrophobic substrata alters endothelial cells interaction

    Directory of Open Access Journals (Sweden)

    NM Coelho

    2010-06-01

    Full Text Available Considering the structural role of type IV collagen (Col IV in the assembly of the basement membrane (BM and the perspective of mimicking its organization for vascular tissue engineering purposes, we studied the adsorption pattern of this protein on model hydrophilic (clean glass and hydrophobic trichloro(octadecylsilane (ODS surfaces known to strongly affect the behavior of other matrix proteins. The amount of fluorescently labeled Col IV was quantified showing saturation of the surface for concentration of the adsorbing solution of about 50μg/ml, but with approximately twice more adsorbed protein on ODS. AFM studies revealed a fine – nearly single molecular size – network arrangement of Col IV on hydrophilic glass, which turns into a prominent and growing polygonal network consisting of molecular aggregates on hydrophobic ODS. The protein layer forms within minutes in a concentration-dependent manner. We further found that human umbilical vein endothelial cells (HUVEC attach less efficiently to the aggregated Col IV (on ODS, as judged by the significantly altered cell spreading, focal adhesions formation and the development of actin cytoskeleton. Conversely, the immunofluorescence studies for integrins revealed that the fine Col IV network formed on hydrophilic substrata is better recognized by the cells via both α1 and α2 heterodimers which support cellular interaction, apart from these on hydrophobic ODS where almost no clustering of integrins was observed.

  20. Preferential hydrophobic interactions are responsible for a preference of D-amino acids in the aminoacylation of 5'-AMP with hydrophobic amino acids

    Science.gov (United States)

    Lacey, J. C. Jr; Wickramasinghe, N. S.; Sabatini, R. S.

    1992-01-01

    We have studied the chemistry of aminoacyl AMP to model reactions at the 3' terminus of aminoacyl tRNA for the purpose of understanding the origin of protein synthesis. The present studies relate to the D, L preference in the esterification of 5'-AMP. All N-acetyl amino acids we studied showed faster reaction of the D-isomer, with a generally decreasing preference for D-isomer as the hydrophobicity of the amino acid decreased. The beta-branched amino acids, Ile and Val, showed an extreme preference for D-isomer. Ac-Leu, the gamma-branched amino acid, showed a slightly low D/L ratio relative to its hydrophobicity. The molecular basis for these preferences for D-isomer is understandable in the light of our previous studies and seems to be due to preferential hydrophobic interaction of the D-isomer with adenine. The preference for hydrophobic D-amino acids can be decreased by addition of an organic solvent to the reaction medium. Conversely, peptidylation with Ac-PhePhe shows a preference for the LL isomer over the DD isomer.

  1. Construction of PS/PNIPAM core-shell particles and hollow spheres by using hydrophobic interaction and thermosensitive phase separation

    Institute of Scientific and Technical Information of China (English)

    Dongmei ZHU; Fei WANG; Cuiling GAO; Zheng XU

    2008-01-01

    This paper reports an easy and effective way tofabricate polystyrene/poly (N-isopropylacrylamide) (PS/PNIPAM) core-shell particles and PNIPAM hollow spheres.The main point of the method is to take advantage of the hydrophobic interaction between initiator and PS particles.The hydrophobic azodiisobutyronitriles automat-ically concentrate around the PS particles and initiate poly-merization of N-isopropylacrylamide (NIPAM) and thecrosslinker methylene bisacrylamide (MBA),which dissolve in the aqueous phase,at the surface of the PS nanoparticles.Then,PNIPAM adheres to the PS particles to form a core-shell structure as a result of their hydrophobic interaction.This interaction is due to the unique property of PNIPAM,namely,its ability to transition from hydrophilic to hydro-phobic when the temperature rises to 32℃.Furthermore,the hollow PNIPAM spheres were obtained by etching the PS core with chloroform.

  2. Hydrophobic interactions are involved in the inhibition of human leukocyte elastase by alkyltrimethylammonium salts.

    Science.gov (United States)

    Kouadri-Boudjelthia, A; Wallach, J M

    1997-02-01

    Electrostatic forces and hydrophobic interactions had been suggested to modify the adsorption of elastases onto insoluble fibrous elastin, which is the initial stage of elastolysis, but conflicting results had been obtained, and comparison between compounds with different structures was difficult. In order to explore these observations, we have studied the effect of six alkyltrimethylammonium bromides, with alkyl chain length ranging from six to 16 carbon atoms, on human leucocyte elastase activities, either with a synthetic substrate or with insoluble elastin. The enzymatic studies were performed either spectrophotometrically or using conductimetry, and direct binding on to elastin was conductimetrically measured. Binding of the alkyltrimethylammonium salts is increasing with alkyl chain length and we could demonstrate a cooperative binding for tetra- and hexadecyl chains. No effect of the six compounds could be evidenced on hydrolysis of a specific synthetic substrate. With insoluble elastin, elastolysis inhibition could be demonstrated for alkyl chain longer than ten carbon atoms, the effect increasing with chain length. A similar inhibition was observed with the soluble kappa-elastin, but it was less effective. The study shows that the interaction between the alkyltrimethylammonium salts and elastin plays a major role in the inhibitory potency of these molecules. As this effect is enhanced with alkyl chain length, it was concluded that hydrophobic interactions favour their binding, protecting elastin against elastase adsorption.

  3. Automated Hydrophobic Interaction Chromatography Column Selection for Use in Protein Purification

    Science.gov (United States)

    Murphy, Patrick J. M.; Stone, Orrin J.; Anderson, Michelle E.

    2011-01-01

    In contrast to other chromatographic methods for purifying proteins (e.g. gel filtration, affinity, and ion exchange), hydrophobic interaction chromatography (HIC) commonly requires experimental determination (referred to as screening or "scouting") in order to select the most suitable chromatographic medium for purifying a given protein 1. The method presented here describes an automated approach to scouting for an optimal HIC media to be used in protein purification. HIC separates proteins and other biomolecules from a crude lysate based on differences in hydrophobicity. Similar to affinity chromatography (AC) and ion exchange chromatography (IEX), HIC is capable of concentrating the protein of interest as it progresses through the chromatographic process. Proteins best suited for purification by HIC include those with hydrophobic surface regions and able to withstand exposure to salt concentrations in excess of 2 M ammonium sulfate ((NH4)2SO4). HIC is often chosen as a purification method for proteins lacking an affinity tag, and thus unsuitable for AC, and when IEX fails to provide adequate purification. Hydrophobic moieties on the protein surface temporarily bind to a nonpolar ligand coupled to an inert, immobile matrix. The interaction between protein and ligand are highly dependent on the salt concentration of the buffer flowing through the chromatography column, with high ionic concentrations strengthening the protein-ligand interaction and making the protein immobile (i.e. bound inside the column) 2. As salt concentrations decrease, the protein-ligand interaction dissipates, the protein again becomes mobile and elutes from the column. Several HIC media are commercially available in pre-packed columns, each containing one of several hydrophobic ligands (e.g. S-butyl, butyl, octyl, and phenyl) cross-linked at varying densities to agarose beads of a specific diameter 3. Automated column scouting allows for an efficient approach for determining which HIC media

  4. Automated hydrophobic interaction chromatography column selection for use in protein purification.

    Science.gov (United States)

    Murphy, Patrick J M; Stone, Orrin J; Anderson, Michelle E

    2011-09-21

    In contrast to other chromatographic methods for purifying proteins (e.g. gel filtration, affinity, and ion exchange), hydrophobic interaction chromatography (HIC) commonly requires experimental determination (referred to as screening or "scouting") in order to select the most suitable chromatographic medium for purifying a given protein (1). The method presented here describes an automated approach to scouting for an optimal HIC media to be used in protein purification. HIC separates proteins and other biomolecules from a crude lysate based on differences in hydrophobicity. Similar to affinity chromatography (AC) and ion exchange chromatography (IEX), HIC is capable of concentrating the protein of interest as it progresses through the chromatographic process. Proteins best suited for purification by HIC include those with hydrophobic surface regions and able to withstand exposure to salt concentrations in excess of 2 M ammonium sulfate ((NH(4;))(2;)SO(4;)). HIC is often chosen as a purification method for proteins lacking an affinity tag, and thus unsuitable for AC, and when IEX fails to provide adequate purification. Hydrophobic moieties on the protein surface temporarily bind to a nonpolar ligand coupled to an inert, immobile matrix. The interaction between protein and ligand are highly dependent on the salt concentration of the buffer flowing through the chromatography column, with high ionic concentrations strengthening the protein-ligand interaction and making the protein immobile (i.e. bound inside the column) (2). As salt concentrations decrease, the protein-ligand interaction dissipates, the protein again becomes mobile and elutes from the column. Several HIC media are commercially available in pre-packed columns, each containing one of several hydrophobic ligands (e.g. S-butyl, butyl, octyl, and phenyl) cross-linked at varying densities to agarose beads of a specific diameter (3). Automated column scouting allows for an efficient approach for determining

  5. Volatile anesthetics inhibit the activity of calmodulin by interacting with its hydrophobic site

    Institute of Scientific and Technical Information of China (English)

    ZHOU Miao-miao; XIA Hui-min; LIU Jiao; XU You-nian; XIN Nai-xin; ZHANG Shi-hai

    2012-01-01

    Background Volatile anesthetics (VAs) may affect varied and complex physiology processes by manipulating Ca2+-calmodulin (CaM).However,the detailed mechanism about the action of VAs on CaM has not been elucidated.This study was undertaken to examine the effects of VAs on the conformational change,hydrophobic site,and downstream signaling pathway of CaM,to explore the possible mechanism of anesthetic action of VAs.Methods Real-time second-harmonic generation (SHG) was performed to monitor the conformational change of CaM in the presence of VAs, each plus 100 μmol/L Ca2+. A hydrophobic fluorescence indicator,8-anilinonaphthalene-1-sulfonate (ANS),was utilized to define whether the VAs would interact with CaM at the hydrophobic site or not.High-performance liquid chromatography (HPLC) was carried out to analyze the activity of CaM-dependent phosphodiesterase (PDE1) in the presence of VAs.The VAs studied were ether,enflurane,isoflurane,and sevoflurane,with their aqueous concentrations 7.6,9.5,11.4 mmol/L; 0.42,0.52,0.62 mmol/L; 0.25,0.31,0.37 mmol/L and 0.47,0.59,0.71 mmol/L respectively,each were equivalent to their 0.8,1.0 and 1.2 concentration for 50% of maximal effect (EC50) for general anesthesia.Results The second-harmonic radiation of CaM in the presence of Ca2+ was largely inhibited by the VAs.The fluorescence intensity of ANS,generated by binding of Ca2+ to CaM,was reversed by the VAs.HPLC results also showed that AMP,the product of the hydrolysis of cAMP by CaM-dependent PDE1,was reduced by the VAs.Conclusions Our findings demonstrate that the above VAs interact with the hydrophobic core of Ca2+-CaM and the interaction results in the inhibition of the conformational change and activity of CaM.This in vitro study may provide us insight into the possible mechanism of anesthetic action of VAs in vivo.

  6. Bending of the Flexible Spacer Chain of Gemini Surfactant Induced by Hydrophobic Interaction

    Institute of Scientific and Technical Information of China (English)

    YOU,Yi; JIANG,Rong; LING,Tingting; ZHAO,Jianxi

    2009-01-01

    In order to understand the special role of the flexible alkylene spacer of gemini surfactant in the self-assembly,three gemini surfactants,alkylene-α,ω-bis(didodecylmethylammonium bromide)that is designated as 2C12-s-2C12·2Br (s=3,6,8),were synthesized.When the spread films of 2C12-s-2C12·2Br on the surface of water were con-structed,they form the dense layer of the alkyl tails owing to four dodecyl chains per molecule.This induced the bending of the spacer chain toward the air-side at the s smaller than that of C12-s-C12·2Br adsorbed on the air/water interface owing to the enhanced hydrophobic interaction between the alkyl tails and the spacer chain, where C12-s-C12·2Br has only two alkyl tails per molecule. Conclusively.,the enhanced hydrophobic interaction between the alkyl tails and the spacer chain can effectively induce the bending of the latter toward the air-side.

  7. Purification of tracer for somatomedin C radioimmunoassay by hydrophobic interaction chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Baxter, R.C.; Brown, A.S.

    1982-03-01

    A tracer for use in the somatomedin C radiommunoassay by hydrophobic interaction chromatography was purified. Material showing greatest immunoreactivity binds to Octyl Sepharose CL-4B (Pharmacia) in a buffer mixture consisting of 130 mL of acetonitrile and 870 mL of 0.1 mol/L NH/sub 4/HCO/sub 3/, pH 7.8, but is eluted by increasing the acetonitrile content to 180 mL/L. As compared with tracer purified by binding to specific antiserum in liquid phase, precipitating the complex with second antibody, and then dissociating by gel chromatography at acid pH, this tracer shows equal immunoreactivity against specific somatomedin C antiserum. Either preparation allows excellent discrimination between extracts of normal, acromegalic, and hypopituitary plasma samples; thus either is suitable for use in the somatomedin C radioimmunoassay. Tracer purification by hydrophobic interaction chromatography is rapid and inexpensive. It may be useful in preparing highly immunoreactive tracers for other peptide radioimmunoassays.

  8. Sorption of nano-C60 clusters in soil: hydrophilic or hydrophobic interactions?

    Science.gov (United States)

    Forouzangohar, Mohsen; Kookana, Rai S

    2011-05-01

    We studied the sorption behaviour of fullerene nano-C(60) particles (nC(60)) in soil from binary solvent mixtures of ethanol-water in order to critically evaluate the previous reports in the literature that the partitioning mechanism explains the soil sorption of fullerene C(60) as hydrophobic molecules. The sorption of nC(60) particles was studied in a range of solvent mixtures by changing volume fractions of ethanol from 20 to 100 percent. Sorption and particle characteristics were found to be very different in ethanol : water mixtures above and below 60% ethanol. In the range of 20-60% ethanol, sorption increased from 1.2 to 14.6 L kg(-1) accompanied by a change in zeta (ζ) potential from -32.4 to -7.2 mV. This observation can be attributed to hydrophilic interactions that negatively charged nC(60) particles undergo with soil colloids and water molecules. From 60% to 100% ethanol volume fractions, hydrophobic interactions of weakly charged nanoparticles may control the overall extent of soil sorption. The findings of this study indicate the importance of hydrophilic forces in controlling the sorption behaviour of nC(60) particles which are stabilized in water dominated solvent mixtures. The validity of the partitioning mechanism and K(OC) modelling approach in describing and estimating the sorption of nC(60) particles in soil (previously suggested in the literature) are, therefore, questioned.

  9. Characterization and Correlation of Particle-Level Interactions to the Macroscopic Rheology of Powders, Granular Slurries, and Colloidal Suspensions

    Energy Technology Data Exchange (ETDEWEB)

    A.P. Poloski; R.C. Daniel; D.R. Rector; P.R. Bredt; E.C. Buck; Berg, J.C.; Saez, A.E.

    2006-09-29

    This project had two primary objectives. The first was to understand the physical properties and behavior of select Hanford tank sludges under conditions that might exist during retrieval, treatment, packaging, and transportation for disposal at the Waste Isolation Pilot Plant (WIPP). The second objective was to develop a fundamental understanding of these sludge suspensions by correlating the macroscopic properties with particle interactions occurring at the colloidal scale. The specific tank wastes considered herein are contained in thirteen Hanford tanks including three double-shell tanks (DSTs) (AW-103, AW-105, and SY-102) and ten single-shell tanks (SSTs) (B-201 through B-204, T-201 through T-204, T-110, and T-111). At the outset of the project, these tanks were designated as potentially containing transuranic (TRU) process wastes that would be treated and disposed of in a manner different from the majority of the tank wastes.

  10. Thermodynamic modelling of hydrophobic interaction chromatography of biomolecules in the presence of salt.

    Science.gov (United States)

    Mirani, Mohammad Reza; Rahimpour, Farshad

    2015-11-27

    Hydrophobic interaction chromatography (HIC) is a useful method for isolation and purification of macromolecules. HIC separates proteins on the basis of surface hydrophobicity while generally retaining the activity of proteins. Aqueous mobile phases with high salt concentrations are often used to adsorb the proteins on a mildly hydrophobic support. In this research, the thermodynamic model of Chen and Sun, which predicts the adsorption isotherms of protein in presence of different type of salts, was modified by substitution the protein and salt activities in the mobile phase instead of their concentrations. In addition, model was examined for studying the adsorption of BSA, HSA, α-lactalbumin and Trypsinogen on different sepharose gels. The model parameters of Chen and Sun are adsorption equilibrium constant (KP), protein dehydration equilibrium constant (Ks), salt coefficient (α) and number of ligand binding (n). By substitution activity instead of salt and protein concentration, two other parameters (c1 and As), which related to the activity coefficients, are added to the model. The parameters of this nonlinear model are calculated by genetic algorithm (GA). The maximum average absolute percentage deviation (AAD) for the data which are obtained from the adsorption isotherm of BSA on phenyl sepharose gel, in the presence of different concentration of NaCl was 4.8%, while for Chen and Sun model, was 22.0%. Also maximum ADD for HSA, α-lactalbumin, and Trypsinogen adsorption was 7.8, 6.9, and 8.4, respectively. The results indicate that the modified model has adequate accuracy to predict protein HIC behaviour.

  11. Rheological and structural characterization of the interactions between cyclodextrin compounds and hydrophobically modified alginate.

    Science.gov (United States)

    Burckbuchler, Virginie; Kjøniksen, Anna-Lena; Galant, Céline; Lund, Reidar; Amiel, Catherine; Knudsen, Kenneth D; Nyström, Bo

    2006-06-01

    Interactions in semidilute solutions of a hydrophobically modified alginate (HM-alginate) in the presence of hydroxypropyl-beta-cyclodextrin (HP-beta-CD) monomer or a beta-cyclodextrin polymer (poly(beta-CD)) have been characterized at different temperatures with the aid of rheology and small-angle neutron scattering (SANS). The viscosity results for the HM-alginate/HP-beta-CD system reveal progressive deactivation of the hydrophobic associations as the concentration of HP-beta-CD increases. For the HM-alginate/poly(beta-CD) system, on the other hand, addition of poly(beta-CD) sets up bridges between adjacent polymer chains and thereby strengthens the associative network. A novel shear-thickening effect is observed at fairly high shear rates for the HM-alginate/poly(beta-CD) system, and this feature is influenced by temperature. Elevated temperature induces higher chain mobility and the formation of weaker network associations. Analyses of the SANS data disclosed that the association strength in HM-alginate/poly(beta-CD) mixtures increases strongly with increasing cosolute concentration, whereas no effect or a moderate weakening of the strength can be traced in HM-alginate/HP-beta-CD solutions upon addition of HP-beta-CD. The value of the correlation length xi is virtually not affected by the addition of cosolute for the HM-alginate/poly(beta-CD) system, whereas the decoupling of hydrophobic moieties of the polymer upon addition of HP-beta-CD gives rise to a smaller value of xi, suggesting that the size of the heterogeneity patches is reduced. The SANS results suggest that compact association structures are formed in the HM-alginate/poly(beta-CD) solutions.

  12. Impact of organic modifier and temperature on protein denaturation in hydrophobic interaction chromatography.

    Science.gov (United States)

    Bobaly, Balázs; Beck, Alain; Veuthey, Jean-Luc; Guillarme, Davy; Fekete, Szabolcs

    2016-11-30

    The goal of this study was to better understand the chromatographic conditions in which monoclonal antibodies (mAbs) of broad hydrophobicity scale and a cysteine conjugated antibody-drug conjugate (ADCs), namely brentuximab-vedotin, could denaturate. For this purpose, some experiments were carried out in HIC conditions using various organic modifier in natures and proportions, different mobile phase temperatures and also different pHs. Indeed, improper analytical conditions in hydrophobic interaction chromatography (HIC) may create reversed-phase (RP) like harsh conditions and therefore protein denaturation. In terms of organic solvents, acetonitrile (ACN) and isopropanol (IPA) were tested with proportions ranging from 0 to 40%. It appeared that IPA was a less denaturating solvent than ACN, but should be used in a reasonable range (10-15%). Temperature should also be kept reasonable (below 40°C), to limit denaturation under HIC conditions. However, the combined increase of temperature and organic content induced denaturation of protein biopharmaceuticals in all cases. Indeed, above 30-40°C and 10-15% organic modifier in mobile phase B, heavy chain (HC) and light chain (LC) fragments dissociated. Mobile phase pH was also particularly critical and denaturation was significant even under moderately acidic conditions (pH of 5.4). Today, HIC is widely used for measuring drug-to-antibody ratio (DAR) of ADCs, which is a critical quality attribute of such samples. Here, we demonstrated that the estimation of average DAR can be dependent on the amount of organic modifier in the mobile phase under HIC conditions, due to the better recovery of the most hydrophobic proteins in presence of organic solvent (IPA). So, special care should be taken when measuring the average DAR of ADCs in HIC. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Retention model of protein for mixed-mode interaction mechanism in ion exchange and hydrophobic interaction chromatography

    Institute of Scientific and Technical Information of China (English)

    WEI, Yin-Mao; LUO, Quan-Zhou; LIU,Tong; GENG, Xin-Du

    2000-01-01

    A unified retention equation of proteins was proved to be valid for a mixed-mode interaction mechanism in ion exchange chromatography (IEC) and hydrophobic interaction chromatography (HIC). The reason to form a “U” shape retention curve of proteins in both HIC and IEC was explained and the concentration range of the strongest elution ability for the mobile phase was determined with this equation. The parameters in this equation could be used to characterize the difference for either HIC or IEC adsorbents and the changes in the molecular conformation of proteins. With the parameters in this equation, the contributions of salt and water in the mobile phase to the protein retention in HIC and IEC were discussed,respectively. In addition, the comparison between the unified equation and Melander's three-parameter equation for mixedmode interaction chromatography was also investigated and better results were obtained in former equation.

  14. Hydrophobic noncovalent interactions of inosine-phenylalanine: a theoretical model for investigating the molecular recognition of nucleobases.

    Science.gov (United States)

    Santos, Lucas A; da Cunha, Elaine F F; Freitas, Matheus P; Ramalho, Teodorico C

    2014-08-07

    Understanding the molecular recognition process of nucleobases is one of the greatest challenges for both computational chemistry and biophysics fields. In fact, our results point out that it is a hard task to take into account the hydrophobic interactions, such as π-π and T-stacking interactions, by theoretical calculations using conventional force fields due to quantum effects of hyperconjugation and electronic correlation. In this line, our findings put in evidence that simple modifications in the Lennard-Jones potential can improve theoretical predictions in scenarios where hydrophobic interactions can drive the molecular recognition.

  15. Predicting the influence of long-range molecular interactions on macroscopic-scale diffusion by homogenization of the Smoluchowski equation

    Energy Technology Data Exchange (ETDEWEB)

    Kekenes-Huskey, P. M., E-mail: pkekeneshuskey@ucsd.edu [Department of Pharmacology, University of California San Diego, La Jolla, California 92093-0636 (United States); Gillette, A. K. [Department of Mathematics, University of Arizona, Tucson, Arizona 85721-0089 (United States); McCammon, J. A. [Department of Pharmacology, University of California San Diego, La Jolla, California 92093-0636 (United States); Department of Chemistry, Howard Hughes Medical Institute, University of California San Diego, La Jolla, California 92093-0636 (United States)

    2014-05-07

    The macroscopic diffusion constant for a charged diffuser is in part dependent on (1) the volume excluded by solute “obstacles” and (2) long-range interactions between those obstacles and the diffuser. Increasing excluded volume reduces transport of the diffuser, while long-range interactions can either increase or decrease diffusivity, depending on the nature of the potential. We previously demonstrated [P. M. Kekenes-Huskey et al., Biophys. J. 105, 2130 (2013)] using homogenization theory that the configuration of molecular-scale obstacles can both hinder diffusion and induce diffusional anisotropy for small ions. As the density of molecular obstacles increases, van der Waals (vdW) and electrostatic interactions between obstacle and a diffuser become significant and can strongly influence the latter's diffusivity, which was neglected in our original model. Here, we extend this methodology to include a fixed (time-independent) potential of mean force, through homogenization of the Smoluchowski equation. We consider the diffusion of ions in crowded, hydrophilic environments at physiological ionic strengths and find that electrostatic and vdW interactions can enhance or depress effective diffusion rates for attractive or repulsive forces, respectively. Additionally, we show that the observed diffusion rate may be reduced independent of non-specific electrostatic and vdW interactions by treating obstacles that exhibit specific binding interactions as “buffers” that absorb free diffusers. Finally, we demonstrate that effective diffusion rates are sensitive to distribution of surface charge on a globular protein, Troponin C, suggesting that the use of molecular structures with atomistic-scale resolution can account for electrostatic influences on substrate transport. This approach offers new insight into the influence of molecular-scale, long-range interactions on transport of charged species, particularly for diffusion-influenced signaling events

  16. Macroscopic properties and dynamical large deviations of the boundary driven Kawasaki process with long range interaction

    CERN Document Server

    Mourragui, Mustapha

    2011-01-01

    We consider a boundary driven exclusion process associated to particles evolving under Kawasaki (conservative) dynamics and long range interaction in a regime in which at equilibrium phase separation might occur. We show that the empirical density under the diffusive scaling solves a non linear integro differential evolution equation with Dirichlet boundary conditions and we prove the associated dynamical large deviations principle. Further, tuning suitable the intensity of the interaction, in the uniqueness phase regime, we show that under the stationary measure the empirical density solves a non local, stationary, transport equation.

  17. Online Hydrophobic Interaction Chromatography-Mass Spectrometry for Top-Down Proteomics.

    Science.gov (United States)

    Chen, Bifan; Peng, Ying; Valeja, Santosh G; Xiu, Lichen; Alpert, Andrew J; Ge, Ying

    2016-02-01

    Recent progress in top-down proteomics has led to a demand for mass spectrometry (MS)-compatible chromatography techniques to separate intact proteins using volatile mobile phases. Conventional hydrophobic interaction chromatography (HIC) provides high-resolution separation of proteins under nondenaturing conditions but requires high concentrations of nonvolatile salts. Herein, we introduce a series of more-hydrophobic HIC materials that can retain proteins using MS-compatible concentrations of ammonium acetate. The new HIC materials appear to function as a hybrid form of conventional HIC and reverse phase chromatography. The function of the salt seems to be preserving protein structure rather than promoting retention. Online HIC-MS is feasible for both qualitative and quantitative analysis. This is demonstrated with standard proteins and a complex cell lysate. The mass spectra of proteins from the online HIC-MS exhibit low charge-state distributions, consistent with those commonly observed in native MS. Furthermore, HIC-MS can chromatographically separate proteoforms differing by minor modifications. Hence, this new HIC-MS combination is promising for top-down proteomics.

  18. Electrocatalytic tuning of biosensing response through electrostatic or hydrophobic enzyme-graphene oxide interactions.

    Science.gov (United States)

    Baptista-Pires, Luis; Pérez-López, Briza; Mayorga-Martinez, Carmen C; Morales-Narváez, Eden; Domingo, Neus; Esplandiu, Maria Jose; Alzina, Francesc; Sotomayor-Torres, Clivia M; Merkoçi, Arben

    2014-11-15

    The effect of graphene oxidative grades upon the conductivity and hydrophobicity and consequently the influence on an enzymatic biosensing response is presented. The electrochemical responses of reduced graphene oxide (rGO) have been compared with the responses obtained from the oxide form (oGO) and their performances have been accordingly discussed with various evidences obtained by optical techniques. We used tyrosinase enzyme as a proof of concept receptor with interest for phenolic compounds detection through its direct adsorption onto a screen-printed carbon electrode previously modified with oGO or rGO with a carbon-oxygen ratio of 1.07 or 1.53 respectively. Different levels of oGO directly affect the (bio)conjugation properties of the biosensor due to changes at enzyme/graphene oxide interface coming from the various electrostatic or hydrophobic interactions with biomolecules. The developed biosensor was capable of reaching a limit of detection of 0.01 nM catechol. This tuning capability of the biosensor response can be of interest for building several other biosensors, including immunosensors and DNA sensors for various applications.

  19. The N-terminus of IntDOT forms hydrophobic interactions during Holliday Junction resolution.

    Science.gov (United States)

    Kolakowski, Adam J; Gardner, Jeffrey F

    DOT Integrase (IntDOT) is a member of the tyrosine recombinase family. It catalyzes the integration and excision reactions of an integrative and conjugative element (ICE) called CTnDOT. Like other tyrosine recombinases, the integration reaction proceeds by two sets of strand exchanges between the attDOT site on CTnDOT and an attB site in the host chromosome. The strand exchanges occur seven bases apart and define an overlap region. After the first strand exchanges a Holliday Junction (HJ) intermediate is formed. Previous work showed that a valine (V95) in a predicted alpha helix in the N-terminus of IntDOT is required for resolution of HJs to substrates and products. We have identified two additional hydrophobic residues in the helix (A92 and F99) that are involved in resolution of HJs. IntDOT proteins with substitutions at these residues form aberrant complexes in an electrophoretic mobility shift assay. We propose that these three residues participate in hydrophobic interactions that are involved in forming higher-order complexes and resolution of HJs. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Paper-PEG-based membranes for hydrophobic interaction chromatography: purification of monoclonal antibody.

    Science.gov (United States)

    Yu, Deqiang; Chen, Xiaonong; Pelton, Robert; Ghosh, Raja

    2008-04-15

    This article discusses the preparation of novel Paper-PEG interpenetrating polymer network-based membranes as inexpensive alternative to currently available adsorptive membranes. The Paper-PEG membranes were developed for carrying out hydrophobic interaction membrane chromatography (HIMC). PEG is normally very hydrophilic but can undergo phase separation and become hydrophobic in the presence of high antichaotropic salt concentrations. Two variants of the Paper-PEG membranes, Paper-PEG 1 and Paper-PEG 2 were prepared by grafting different amounts of the polymer on filter paper and these were tested for their hydraulic properties and antibody binding capacity. The better of the two membranes (Paper-PEG 1) was then used for purifying the monoclonal antibody hIgG1-CD4 from simulated mammalian cell culture supernatant. The processing conditions required for purification were systematically optimized. The dynamic antibody binding capacity of the Paper-PEG 1 membrane was about 9 mg/mL of bed volume. A single step membrane chromatographic process using Paper-PEG 1 membrane gave high monoclonal antibody purity and recovery. The hydraulic permeability of the paper-based membrane was high and was maintained even after many runs, indicating that membrane fouling was negligible and the membrane was largely incompressible.

  1. Mimicking bubble use in nature: propulsion of Janus particles due to hydrophobic-hydrophilic interactions.

    Science.gov (United States)

    Pinchasik, Bat-El; Möhwald, Helmuth; Skirtach, Andre G

    2014-07-09

    Bubbles are widely used by animals in nature in order to fulfill important functions. They are used by animals in order to walk underwater or to stabilize themselves at the water/air interface. The main aim of this work is to imitate such phenomena, which is the essence of biomimetics. Here, bubbles are used to propel and to control the location of Janus particles in an aqueous medium. The synthesis of Janus SiO2-Ag and polystyrene-Ag (PS-Ag) particles through embedment in Parafilm is presented. The Janus particles, partially covered with catalytically active Ag nanoparticles, are redispersed in water and placed on a glass substrate. The active Ag sites are used for the splitting of H2O2 into water and oxygen. As a result, an oxygen bubble is formed on one side of the particle and promotes its propulsion. Once formed, the bubble-particle complex is stable and therefore, can be manipulated by tuning hydrophilic-hydrophobic interactions with the surface. In this way a transition between two- and three- dimensional motion is possible by changing the hydrophobicity of the substrate. Similar principles are used in nature.

  2. Hsp90 protein interacts with phosphorothioate oligonucleotides containing hydrophobic 2'-modifications and enhances antisense activity.

    Science.gov (United States)

    Liang, Xue-Hai; Shen, Wen; Sun, Hong; Kinberger, Garth A; Prakash, Thazha P; Nichols, Joshua G; Crooke, Stanley T

    2016-05-05

    RNase H1-dependent antisense oligonucleotides (ASOs) are chemically modified to enhance pharmacological properties. Major modifications include phosphorothioate (PS) backbone and different 2'-modifications in 2-5 nucleotides at each end (wing) of an ASO. Chemical modifications can affect protein binding and understanding ASO-protein interactions is important for better drug design. Recently we identified many intracellular ASO-binding proteins and found that protein binding could affect ASO potency. Here, we analyzed the structure-activity-relationships of ASO-protein interactions and found 2'-modifications significantly affected protein binding, including La, P54nrb and NPM. PS-ASOs containing more hydrophobic 2'-modifications exhibit higher affinity for proteins in general, although certain proteins, e.g. Ku70/Ku80 and TCP1, are less affected by 2'-modifications. We found that Hsp90 protein binds PS-ASOs containing locked-nucleic-acid (LNA) or constrained-ethyl-bicyclic-nucleic-acid ((S)-cEt) modifications much more avidly than 2'-O-methoxyethyl (MOE). ASOs bind the mid-domain of Hsp90 protein. Hsp90 interacts with more hydrophobic 2' modifications, e.g. (S)-cEt or LNA, in the 5'-wing of the ASO. Reduction of Hsp90 protein decreased activity of PS-ASOs with 5'-LNA or 5'-cEt wings, but not with 5'-MOE wing. Together, our results indicate Hsp90 protein enhances the activity of PS/LNA or PS/(S)-cEt ASOs, and imply that altering protein binding of ASOs using different chemical modifications can improve therapeutic performance of PS-ASOs. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.

  3. The role of hydrophobic interactions in positioning of peripheral proteins in membranes

    Directory of Open Access Journals (Sweden)

    Lomize Mikhail A

    2007-06-01

    Full Text Available Abstract Background Three-dimensional (3D structures of numerous peripheral membrane proteins have been determined. Biological activity, stability, and conformations of these proteins depend on their spatial positions with respect to the lipid bilayer. However, these positions are usually undetermined. Results We report the first large-scale computational study of monotopic/peripheral proteins with known 3D structures. The optimal translational and rotational positions of 476 proteins are determined by minimizing energy of protein transfer from water to the lipid bilayer, which is approximated by a hydrocarbon slab with a decadiene-like polarity and interfacial regions characterized by water-permeation profiles. Predicted membrane-binding sites, protein tilt angles and membrane penetration depths are consistent with spin-labeling, chemical modification, fluorescence, NMR, mutagenesis, and other experimental studies of 53 peripheral proteins and peptides. Experimental membrane binding affinities of peripheral proteins were reproduced in cases that did not involve a helix-coil transition, specific binding of lipids, or a predominantly electrostatic association. Coordinates of all examined peripheral proteins and peptides with the calculated hydrophobic membrane boundaries, subcellular localization, topology, structural classification, and experimental references are available through the Orientations of Proteins in Membranes (OPM database. Conclusion Positions of diverse peripheral proteins and peptides in the lipid bilayer can be accurately predicted using their 3D structures that represent a proper membrane-bound conformation and oligomeric state, and have membrane binding elements present. The success of the implicit solvation model suggests that hydrophobic interactions are usually sufficient to determine the spatial position of a protein in the membrane, even when electrostatic interactions or specific binding of lipids are substantial. Our

  4. Transcriptional, microscopic and macroscopic investigations into monogenic and polygenic interactions of tomato and powdery mildew

    NARCIS (Netherlands)

    Li Chengwei,

    2005-01-01

    Powdery mildew ( Oidium neolycopersici) is a worldwide obligate fungal disease of tomato ( Solanum lycopersicum ). Six monogenic Ol genes and three major QTLs were identified and mapped on tomato genome. In this thesis, the mechanisms of both compatible and incompatible interactions of tomato and O.

  5. MICROBIAL CELL-SURFACE HYDROPHOBICITY - THE INVOLVEMENT OF ELECTROSTATIC INTERACTIONS IN MICROBIAL ADHESION TO HYDROCARBONS (MATH)

    NARCIS (Netherlands)

    GEERTSEMADOORNBUSCH, GI; VANDERMEI, HC; BUSSCHER, HJ

    Microbial adhesion to hydrocarbons (MATH) is the most commonly used method to determine microbial cell surface hydrophobicity. Since, however, the assay is based on adhesion, it is questionable whether the results reflect only the cell surface hydrophobicity or an interplay of hydrophobicity and

  6. Stabilization of cancer-specific gene carrier via hydrophobic interaction for a clear-cut response to cancer signaling.

    Science.gov (United States)

    Kim, Chan Woo; Toita, Riki; Kang, Jeong-Hun; Li, Kai; Lee, Eun Kyung; Zhao, Guo Xi; Funamoto, Daiki; Nobori, Takanobu; Nakamura, Yuta; Mori, Takeshi; Niidome, Takuro; Katayama, Yoshiki

    2013-09-28

    Here, we developed a new gene carrier, comprising a linear polyethylenimine (LPEI) grafted with a hydrophobically modified cationic peptide containing a long alkyl chain, for use in cancer-specific gene delivery. The cationic peptide is a substrate of protein kinase Cα (PKCα), which is known to be activated specifically in cancer cells. The hydrophobically modified LPEI-peptide conjugate (LPEI-C10-peptide) could form a polyplex with DNA through electrostatic and hydrophobic interactions between the anionic DNA strands and the cationic peptide substrate. The hydrophobic modification of the peptide did not affect the reactivity of the peptide toward PKCα, while the polyplex showed improved intracellular uptake. Because of the efficient endosomal escape and enhanced stability, the polyplex significantly improved the transgene regulation responding to intracellular PKCα activity.

  7. Numerical Simulation on Faulting: Microscopic evolution, macroscopic interaction and rupture process of earthquakes

    CERN Document Server

    Aochi, Hideo

    2010-01-01

    We review the recent researches of numerical simulations on faulting, which are interpreted in this paper as the evolution of the state of the fault plane and the evolution of fault structure. The theme includes the fault constitutive (friction) law, the properties of the gauge particles, the initial phase of the rupture, the dynamic rupture process, the interaction of the fault segments, the fault zone dynamics, and so on. Many numerical methods have been developed: boundary integral equation methods (BIEM), finite difference methods (FDM), finite or spectral element methods (FEM, SEM) as well as distinct element methods (DEM), discrete element methods (again DEM) or lattice solid models (LSM). The fault dynamics should be solved as a complex non-linear system, which shows multiple hierarchical structures on its property and behavior. The researches have progressively advanced since the 1990's both numerically and physically thanks to high performance computing environments. The interaction at small scales i...

  8. The Interaction of Radio-Frequency Fields With Dielectric Materials at Macroscopic to Mesoscopic Scales

    Science.gov (United States)

    Baker-Jarvis, James; Kim, Sung

    2012-01-01

    The goal of this paper is to overview radio-frequency (RF) electromagnetic interactions with solid and liquid materials from the macroscale to the nanoscale. The overview is geared toward the general researcher. Because this area of research is vast, this paper concentrates on currently active research areas in the megahertz (MHz) through gigahertz (GHz) frequencies, and concentrates on dielectric response. The paper studies interaction mechanisms both from phenomenological and fundamental viewpoints. Relaxation, resonance, interface phenomena, plasmons, the concepts of permittivity and permeability, and relaxation times are summarized. Topics of current research interest, such as negative-index behavior, noise, plasmonic behavior, RF heating, nanoscale materials, wave cloaking, polaritonic surface waves, biomaterials, and other topics are overviewed. Relaxation, resonance, and related relaxation times are overviewed. The wavelength and material length scales required to define permittivity in materials is discussed. PMID:26900513

  9. Interaction of Phenylalanine with DPPC Model Membranes: More Than a Hydrophobic Interaction.

    Science.gov (United States)

    Rosa, A S; Cutro, A C; Frías, M A; Disalvo, E A

    2015-12-31

    The negative free energy previously reported is explained by the stabilization of a PC-Phe (phosphocholine-phenylalanine) complex in the presence of water shown by the decrease in the symmetric stretching frequency of the phosphate group of the lipid (PO2(-)). An entropic contribution due to the disruption of the water network around the phenyl and in the membrane defect may be invoked. The dipole potential decrease is explained by the orientation of the carboxylate opposing to the CO of the lipids with oxygen moiety toward the low hydrated hydrocarbon core. The symmetric bending frequency of NH3(+) group of Phe, decreases in 5.2 cm(-1) in relation to water congruent with zeta potential shift to positive values. The Phe to DPPC dissociation constant is Kd = 2.23 ± 0.09 mM, from which the free energy change is about -4.54 kcal/mol at 25 °C. This may be due to hydrophobic contributions and two hydrogen bonds.

  10. Implications of promiscuous Pim-1 kinase fragment inhibitor hydrophobic interactions for fragment-based drug design.

    Science.gov (United States)

    Good, Andrew C; Liu, Jinyu; Hirth, Bradford; Asmussen, Gary; Xiang, Yibin; Biemann, Hans-Peter; Bishop, Kimberly A; Fremgen, Trisha; Fitzgerald, Maria; Gladysheva, Tatiana; Jain, Annuradha; Jancsics, Katherine; Metz, Markus; Papoulis, Andrew; Skerlj, Renato; Stepp, J David; Wei, Ronnie R

    2012-03-22

    We have studied the subtleties of fragment docking and binding using data generated in a Pim-1 kinase inhibitor program. Crystallographic and docking data analyses have been undertaken using inhibitor complexes derived from an in-house surface plasmon resonance (SPR) fragment screen, a virtual needle screen, and a de novo designed fragment inhibitor hybrid. These investigations highlight that fragments that do not fill their binding pocket can exhibit promiscuous hydrophobic interactions due to the lack of steric constraints imposed on them by the boundaries of said pocket. As a result, docking modes that disagree with an observed crystal structure but maintain key crystallographically observed hydrogen bonds still have potential value in ligand design and optimization. This observation runs counter to the lore in fragment-based drug design that all fragment elaboration must be based on the parent crystal structure alone.

  11. Separation of mAbs molecular variants by analytical hydrophobic interaction chromatography HPLC: overview and applications.

    Science.gov (United States)

    Haverick, Mark; Mengisen, Selina; Shameem, Mohammed; Ambrogelly, Alexandre

    2014-01-01

    Hydrophobic interaction chromatography-high performance liquid chromatography (HIC-HPLC) is a powerful analytical method used for the separation of molecular variants of therapeutic proteins. The method has been employed for monitoring various post-translational modifications, including proteolytic fragments and domain misfolding in etanercept (Enbrel®); tryptophan oxidation, aspartic acid isomerization, the formation of cyclic imide, and α amidated carboxy terminus in recombinant therapeutic monoclonal antibodies; and carboxy terminal heterogeneity and serine fucosylation in Fc and Fab fragments. HIC-HPLC is also a powerful analytical technique for the analysis of antibody-drug conjugates. Most current analytical columns, methods, and applications are described, and critical method parameters and suitability for operation in regulated environment are discussed, in this review.

  12. Mechanism of reversible self-association of a monoclonal antibody: role of electrostatic and hydrophobic interactions.

    Science.gov (United States)

    Esfandiary, Reza; Parupudi, Arun; Casas-Finet, Jose; Gadre, Dhanesh; Sathish, Hasige

    2015-02-01

    Reversible self-association of protein therapeutics, the phenomenon of formation of native reversible oligomeric species as a result of noncovalent intermolecular interactions, can add additional manufacturing, stability, delivery, and safety complexities in biopharmaceutical development. Its early detection, characterization, and mitigation can therefore contribute to the success of drug development. A variety of structural and environmental factors can contribute to the modulation of self-association with mechanisms still elusive in some cases due to the inherent structural complexity of proteins. By combining the capabilities of dynamic and static light scattering techniques, the modulatory effects of a variety of solution conditions on a model IgG1's (mAbA) intermolecular interactions have been utilized to derive mechanism of its self-association at relatively low-protein concentration. The analysis of the effect of pH, buffer type, Hofmeister salts, and aromatic amino acids utilizing light scattering supported a combined role of hydrophobic and electrostatic interactions in mAbA self-association. Fitting of the data into the equilibrium models obtained from the multiangle static light scattering provided the enthalpic and entropic contributions of self-association, highlighting the more dominant effect of electrostatic interactions. In addition, studies of the Fab and Fc fragments of mAbA suggested the key role of the former in observed self-association. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

  13. Interaction between human BAP31 and respiratory syncytial virus small hydrophobic (SH) protein

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yan; Jain, Neeraj; Limpanawat, Suweeraya; To, Janet [School of Biological Sciences, Nanyang Technological University, 637551 (Singapore); Quistgaard, Esben M. [Department of Medical Biochemistry and Biophysics, Karolinska Institutet, Stockholm (Sweden); Nordlund, Par [School of Biological Sciences, Nanyang Technological University, 637551 (Singapore); Department of Medical Biochemistry and Biophysics, Karolinska Institutet, Stockholm (Sweden); Thanabalu, Thirumaran [School of Biological Sciences, Nanyang Technological University, 637551 (Singapore); Torres, Jaume, E-mail: jtorres@ntu.edu.sg [School of Biological Sciences, Nanyang Technological University, 637551 (Singapore)

    2015-08-15

    The small hydrophobic (SH) protein is a short channel-forming polypeptide encoded by the human respiratory syncytial virus (hRSV). Deletion of SH protein leads to the viral attenuation in mice and primates, and delayed apoptosis in infected cells. We have used a membrane-based yeast two-hybrid system (MbY2H) and a library from human lung cDNA to detect proteins that bind SH protein. This led to the identification of a membrane protein, B-cell associated protein 31 (BAP31). Transfected SH protein co-localizes with transfected BAP31 in cells, and pulls down endogenous BAP31. Titration of purified C-terminal endodomain of BAP31 against isotopically labeled SH protein in detergent micelles suggests direct interaction between the two proteins. Given the key role of BAP31 in protein trafficking and its critical involvement in pro- and anti-apoptotic pathways, this novel interaction may constitute a potential drug target. - Highlights: • A yeast two-hybrid system (MbY2H) detected BAP31 as a binder of RSV SH protein. • Transfected SH and BAP31 co-localize in lung epithelial cells. • Endogenous BAP31 is pulled down by RSV SH protein. • BAP31 endodomain interacts with the N-terminal α-helix of SH protein in micelles. • This interaction is proposed to be a potential drug target.

  14. Role of a Hydrophobic Pocket in Polyamine Interactions with the Polyspecific Organic Cation Transporter OCT3.

    Science.gov (United States)

    Li, Dan C; Nichols, Colin G; Sala-Rabanal, Monica

    2015-11-13

    Organic cation transporter 3 (OCT3, SLC22A3) is a polyspecific, facilitative transporter expressed in astrocytes and in placental, intestinal, and blood-brain barrier epithelia, and thus elucidating the molecular mechanisms underlying OCT3 substrate recognition is critical for the rational design of drugs targeting these tissues. The pharmacology of OCT3 is distinct from that of other OCTs, and here we investigated the role of a hydrophobic cavity tucked within the translocation pathway in OCT3 transport properties. Replacement of an absolutely conserved Asp by charge reversal (D478E), neutralization (D478N), or even exchange (D478E) abolished MPP(+) uptake, demonstrating this residue to be obligatory for OCT3-mediated transport. Mutations at non-conserved residues lining the putative binding pocket of OCT3 to the corresponding residue in OCT1 (L166F, F450L, and E451Q) reduced the rate of MPP(+) transport, but recapitulated the higher sensitivity pharmacological profile of OCT1. Thus, interactions of natural polyamines (putrescine, spermidine, spermine) and polyamine-like potent OCT1 blockers (1,10-diaminodecane, decamethonium, bistriethylaminodecane, and 1,10-bisquinuclidinedecane) with wild-type OCT3 were weak, but were significantly potentiated in the mutant OCT3s. Conversely, a reciprocal mutation in OCT1 (F161L) shifted the polyamine-sensitivity phenotype toward that of OCT3. Further analysis indicated that OCT1 and OCT3 can recognize essentially the same substrates, but the strength of substrate-transporter interactions is weaker in OCT3, as informed by the distinct makeup of the hydrophobic cleft. The residues identified here are key contributors to both the observed differences between OCT3 and OCT1 and to the mechanisms of substrate recognition by OCTs in general.

  15. Adsorption of sodium ions and hydrated sodium ions on a hydrophobic graphite surface via cation-π interactions

    Institute of Scientific and Technical Information of China (English)

    Shi Guo-Sheng; Wang Zhi-Gang; Zhao Ji-Jun; Hu Jun; Fang Hai-Ping

    2011-01-01

    Using density functional theory computation, we show that sodium ions and hydrated sodium ions can be strongly adsorbed onto a hydrophobic graphite surface via cation-π interactions. The key to this cation-π interaction is the coupling of the delocalized π states of graphite and the empty orbitals of sodium ions. This finding implies that the property of the graphite surface is extremely dependent on the existence of the ions on the surface, suggesting that the hydrophobic property of the graphite surface may be affected by the existence of the sodium ions.

  16. Assessment of hydrophobic interactions and their contributions through the analysis of the methane dimer.

    Science.gov (United States)

    Alaniz, Víctor Duarte; Rocha-Rinza, Tomás; Cuevas, Gabriel

    2015-03-01

    Hydrophobic Interactions (HIs) are important in many phenomena of molecular recognition in chemistry and biology. Still, the relevance of HIs is sometimes difficult to evaluate particularly in large systems and intramolecular interactions. We put forward a method to estimate the magnitude and the different contributions of a given HI of the C···C, H-C···H, and H···H type through (i) the analysis of the electron density in the intermolecular region for eleven relative orientations of the methane dimer and (ii) the subsequent decomposition of the corresponding interaction energy in physically significant contributions using Symmetry Adapted Perturbation Theory (SAPT). Strong correlations were found between the topological properties of ρ(r) calculated at intermolecular bond critical points and Eint(SAPT) plus its different contributions with the C···C distance of the considered orientations of (CH4 )2 . These correlations were used to construct Mollier-like diagrams of Eint(SAPT) and its components as a function of the separation between two carbons and the orientation of the groups bonded to these atoms. The ethane dimer and tert-butylcyclohexane are used as representative examples of this new approach. Overall, we anticipate that this new method might prove useful in the study of both intramolecular and intermolecular HIs particularly of those within large systems wherein SAPT or electronic structure calculations are computationally expensive or even prohibitive.

  17. pH-programmable self-assembly of plasmonic nanoparticles: hydrophobic interaction versus electrostatic repulsion

    Science.gov (United States)

    Li, Weikun; Kanyo, Istvan; Kuo, Chung-Hao; Thanneeru, Srinivas; He, Jie

    2014-12-01

    We report a general strategy to conceptualize a new design for the pH-programmable self-assembly of plasmonic gold nanoparticles (AuNPs) tethered by random copolymers of poly(styrene-co-acrylic acid) (P(St-co-AA)). It is based on using pH as an external stimulus to reversibly change the surface charge of polymer tethers and to control the delicate balance of interparticle attractive and repulsive interactions. By incorporating -COOH moieties locally within PSt hydrophobic segments, the change in the ionization degree of -COOH moieties can dramatically disrupt the hydrophobic attraction within a close distance. pH acts as a key parameter to control the deprotonation of -COOH moieties and ``programs'' the assembled nanostructures of plasmonic nanoparticles in a stepwise manner. At a higher solution pH where -COOH groups of polymer tethers became highly deprotonated, electrostatic repulsion dominated the self-assembly and favored the formation of end-to-end, anisotropic assemblies, e.g. 1-D single-line chains. At a lower pH, the less deprotonated -COOH groups led to the decrease of electrostatic repulsion and the side-to-side aggregates, e.g. clusters and multi-line chains of AuNPs, became favorable. The pH-programmable self-assembly allowed us to engineer a ``manual'' program for a sequential self-assembly by changing the pH of the solution. We demonstrated that the two-step pH-programmable assembly could generate more sophisticated ``multi-block'' chains using two differently sized AuNPs. Our strategy offers a general means for the programmable design of plasmonic nanoparticles into the specific pre-ordained nanostructures that are potentially useful for the precise control over their plasmon coupling.We report a general strategy to conceptualize a new design for the pH-programmable self-assembly of plasmonic gold nanoparticles (AuNPs) tethered by random copolymers of poly(styrene-co-acrylic acid) (P(St-co-AA)). It is based on using pH as an external stimulus to

  18. The use of UV-visible spectroscopy for the determination of hydrophobic interactions between neuropeptides and membrane model systems.

    Science.gov (United States)

    Young, J K; Graham, W H; Beard, D J; Hicks, R P

    1992-08-01

    Ultraviolet-visible spectroscopy has been used as a rapid method to evaluate the hydrophobic interactions between a series of cationic and zwitterionic neuropeptides and dipeptides with the hydrophobic core of two membrane model systems; sodium dodecyl sulfate and lysophosphatidylcholine micelles. If a hydrophobic interaction occurs, a 1-nm bathochromic shift is observed in the uv-visible spectrum of the aromatic side chains when going from aqueous solution to a micellar solution. The aromatic residues of substance P, bradykinin, and Des-Arg9 bradykinin all exhibited the 1-nm bathochromic shift in the presence of sodium dodecyl sulfate while those of Met-enkephalin did not. The opposite effects were observed in the presence of lysophosphatidylcholine micelles.

  19. Purification of plasmid (pVaxLacZ by hydrophobic interaction chromatography

    Directory of Open Access Journals (Sweden)

    Keila Aparecida Moreira

    2005-06-01

    Full Text Available This paper describes a method for the plasmid DNA purification, which includes an ammonium sulphate precipitation, followed by hydrophobic interaction chromatography (HIC using Phenyl Sepharose 6 Fast Flow (low sub. The use of HIC took advantage of the more hydrophobic character of single stranded nucleic acid impurities as compared with double-stranded plasmid DNA.O DNA plasmidial tem sua aplicação na terapia gênica, tendo que apresentar elevado grau de pureza. Um método de purificação foi descrito neste trabalho, que inclui precipitação com sulfato de amônio seguida da cromatografia de interação hidrofóbica, usando a resina phenyl sepharose 6 fast flow. Ocorreu aumento da pureza das amostras analisadas, em torno de 30% após a precipitação com sulfato de amônio. Houve significativa redução dos contaminantes após a eluição das amostras na cromatografia de interação. O maior rendimento obtido foi 53% e fator de purificação 3,1 vezes após a eluição na cromatografia de interação hidrofóbica. A vantagem deste método é a possibilidade de explorar o caráter hidrofóbico, constituído de material genético de fita simples, tais como RNA e DNA genômico e proteínas, que podem interferir na liberação deste material para possíveis aplicações em terapia gênica.

  20. Optimized hydrophobic interactions and hydrogen bonding at the target-ligand interface leads the pathways of drug-designing.

    Directory of Open Access Journals (Sweden)

    Rohan Patil

    Full Text Available BACKGROUND: Weak intermolecular interactions such as hydrogen bonding and hydrophobic interactions are key players in stabilizing energetically-favored ligands, in an open conformational environment of protein structures. However, it is still poorly understood how the binding parameters associated with these interactions facilitate a drug-lead to recognize a specific target and improve drugs efficacy. To understand this, comprehensive analysis of hydrophobic interactions, hydrogen bonding and binding affinity have been analyzed at the interface of c-Src and c-Abl kinases and 4-amino substituted 1H-pyrazolo [3, 4-d] pyrimidine compounds. METHODOLOGY: In-silico docking studies were performed, using Discovery Studio software modules LigandFit, CDOCKER and ZDOCK, to investigate the role of ligand binding affinity at the hydrophobic pocket of c-Src and c-Abl kinase. Hydrophobic and hydrogen bonding interactions of docked molecules were compared using LigPlot program. Furthermore, 3D-QSAR and MFA calculations were scrutinized to quantify the role of weak interactions in binding affinity and drug efficacy. CONCLUSIONS: The in-silico method has enabled us to reveal that a multi-targeted small molecule binds with low affinity to its respective targets. But its binding affinity can be altered by integrating the conformationally favored functional groups at the active site of the ligand-target interface. Docking studies of 4-amino-substituted molecules at the bioactive cascade of the c-Src and c-Abl have concluded that 3D structural folding at the protein-ligand groove is also a hallmark for molecular recognition of multi-targeted compounds and for predicting their biological activity. The results presented here demonstrate that hydrogen bonding and optimized hydrophobic interactions both stabilize the ligands at the target site, and help alter binding affinity and drug efficacy.

  1. Model of waterlike fluid under confinement for hydrophobic and hydrophilic particle-plate interaction potentials.

    Science.gov (United States)

    Krott, Leandro B; Barbosa, Marcia C

    2014-01-01

    Molecular dynamic simulations were employed to study a waterlike model confined between hydrophobic and hydrophilic plates. The phase behavior of this system is obtained for different distances between the plates and particle-plate potentials. For both hydrophobic and hydrophilic walls, there are the formation of layers. Crystallization occurs at lower temperature at the contact layer than at the middle layer. In addition, the melting temperature decreases as the plates become more hydrophobic. Similarly, the temperatures of maximum density and extremum diffusivity decrease with hydrophobicity.

  2. Interaction between human BAP31 and respiratory syncytial virus small hydrophobic (SH) protein.

    Science.gov (United States)

    Li, Yan; Jain, Neeraj; Limpanawat, Suweeraya; To, Janet; Quistgaard, Esben M; Nordlund, Par; Thanabalu, Thirumaran; Torres, Jaume

    2015-08-01

    The small hydrophobic (SH) protein is a short channel-forming polypeptide encoded by the human respiratory syncytial virus (hRSV). Deletion of SH protein leads to the viral attenuation in mice and primates, and delayed apoptosis in infected cells. We have used a membrane-based yeast two-hybrid system (MbY2H) and a library from human lung cDNA to detect proteins that bind SH protein. This led to the identification of a membrane protein, B-cell associated protein 31 (BAP31). Transfected SH protein co-localizes with transfected BAP31 in cells, and pulls down endogenous BAP31. Titration of purified C-terminal endodomain of BAP31 against isotopically labeled SH protein in detergent micelles suggests direct interaction between the two proteins. Given the key role of BAP31 in protein trafficking and its critical involvement in pro- and anti-apoptotic pathways, this novel interaction may constitute a potential drug target.

  3. Difference of carboxybetaine and oligo(ethylene glycol) moieties in altering hydrophobic interactions: a molecular simulation study.

    Science.gov (United States)

    Shao, Qing; White, Andrew D; Jiang, Shaoyi

    2014-01-01

    Polycarboxybetaine and poly(ethylene glycol) materials resist nonspecific protein adsorption but differ in influencing biological functions such as enzymatic activity. To investigate this difference, we studied the influence of carboxybetaine and oligo(ethylene glycol) moieties on hydrophobic interactions using molecular simulations. We employed a model system composed of two non-polar plates and studied the potential of mean force of plate-plate association in carboxybetaine, (ethylene glycol)4, and (ethylene glycol)2 solutions using well-tempered metadynamics simulations. Water, trimethylamine N-oxide, and urea solutions were used as reference systems. We analyzed the variation of the potential of mean force in various solutions to study how carboxybetaine and oligo(ethylene glycol) moieties influence the hydrophobic interactions. To study the origin of their influence, we analyzed the normalized distributions of moieties and water molecules using molecular dynamics simulations. The simulation results showed that oligo(ethylene glycol) moieties repel water molecules away from the non-polar plates and weaken the hydrophobic interactions. Carboxybetaine moieties do not repel water molecules away from the plates and therefore do not influence the hydrophobic interactions.

  4. Study of the feasibility of separation of carrier ampholytes from peptides by hydrophobic interaction chromatography on octyl-sepharose

    NARCIS (Netherlands)

    Gelsema, W.J.; Ligny, C.L. de; Blanken, W.M.; Hamer, R.J.; Roozen, A.M.P.

    1980-01-01

    The merits of hydrophobic interaction chromatography on octyl-Sepharose as a method for the separation of carrier ampholytes from peptides have been investigated. K values for the association of octyl groups with small model peptides and with carrier ampholytes in aqueous sodium chloride-containing

  5. A Colorful Laboratory Investigation of Hydrophobic Interactions, the Partition Coefficient, Gibbs Energy of Transfer, and the Effect of Hofmeister Salts

    Science.gov (United States)

    McCain, Daniel F.; Allgood, Ottie E.; Cox, Jacob T.; Falconi, Audrey E.; Kim, Michael J.; Shih, Wei-Yu

    2012-01-01

    Only a few pedagogical experiments have been published dealing specifically with the hydrophobic interaction though it plays a central role in biochemistry. A set of experiments is presented in which students partition a variety of colorful indicator dyes in biphasic water/organic solvent mixtures. Students monitor the partitioning visually and…

  6. Interactions between nano-TiO{sub 2} and the oral cavity: Impact of nanomaterial surface hydrophilicity/hydrophobicity

    Energy Technology Data Exchange (ETDEWEB)

    Teubl, Birgit J.; Schimpel, Christa [Institute of Pharmaceutical Sciences, Department of Pharmaceutical Technology, University of Graz, 8010 (Austria); Leitinger, Gerd [Institute of Cell Biology, Histology and Embryology, Research Unit Electron Microscopic Techniques, Medical University of Graz, 8010 (Austria); Center for Medical Research, Medical University of Graz, 8010 (Austria); BioTechMed, Graz 8010 (Austria); Bauer, Bettina [Institute of Pharmaceutical Sciences, Department of Pharmaceutical Technology, University of Graz, 8010 (Austria); Fröhlich, Eleonore [Center for Medical Research, Medical University of Graz, 8010 (Austria); BioTechMed, Graz 8010 (Austria); Zimmer, Andreas [Institute of Pharmaceutical Sciences, Department of Pharmaceutical Technology, University of Graz, 8010 (Austria); BioTechMed, Graz 8010 (Austria); Roblegg, Eva, E-mail: eva.roblegg@uni-graz.at [Institute of Pharmaceutical Sciences, Department of Pharmaceutical Technology, University of Graz, 8010 (Austria); BioTechMed, Graz 8010 (Austria)

    2015-04-09

    Highlights: • Hydrophilic as well as hydrophobic TiO{sub 2} NPs agglomerated under oral physiological conditions. • Particles penetrated the upper and lower buccal epithelium, independent on the degree of hydrophilicity. • Most of the hydrophobic particles were found in vesicular structures, while hydrophilic particles were freely distributed in the cytoplasm. • Hydrophilic particles had a higher potential to trigger toxic effects (e.g., ROS) than hydrophobic particles. - Abstract: Titanium dioxide (TiO{sub 2}) nanoparticles are available in a variety of oral applications, such as food additives and cosmetic products. Thus, questions about their potential impact on the oro-gastrointestinal route rise. The oral cavity represents the first portal of entry and is known to rapidly interact with nanoparticles. Surface charge and size contribute actively to the particle–cell interactions, but the influence of surface hydrophilicity/hydrophobicity has never been shown before. This study addresses the biological impact of hydrophilic (NM 103, rutile, 20 nm) and hydrophobic (NM 104, rutile, 20 nm) TiO{sub 2} particles within the buccal mucosa. Particle characterization was addressed with dynamic light scattering and laser diffraction. Despite a high agglomeration tendency, 10% of the particles/agglomerates were present in the nanosized range and penetrated into the mucosa, independent of the surface properties. However, significant differences were observed in intracellular particle localization. NM 104 particles were found freely distributed in the cytoplasm, whereas their hydrophobic counterparts were engulfed in vesicular structures. Although cell viability/membrane integrity was not affected negatively, screening assays demonstrated that NM 104 particles showed a higher potential to decrease the physiological mitochondrial membrane potential than NM 103, resulting in a pronounced generation of reactive oxygen species.

  7. Isolation of soybean protein P34 from oil bodies using hydrophobic interaction chromatography

    Directory of Open Access Journals (Sweden)

    Seidel-Morgenstern Andreas

    2008-03-01

    Full Text Available Abstract Background Soybeans play a prominent role in allergologic research due to the high incidence of allergic reactions. For detailed studies on specific proteins it is necessary to have access to a large amount of pure substance. Results In this contribution, a method for purifying soybean (Glycine max protein P34 (also called Gly m Bd 30 K or Gly m 1 using hydrophobic interaction chromatography is presented. After screening experiments using 1 mL HiTrap columns, Butyl Sepharose 4 FF was selected for further systematic investigations. With this stationary phase, suitable operation conditions for two-step gradient elution using ammonium sulphate were determined experimentally. The separation conditions obtained in a small column could be scaled up successfully to column volumes of 7.5 and 75 mL, allowing for high product purities of almost 100% with a yield of 27% for the chromatographic separation step. Conditions could be simplified further using a onestep gradient, which gave comparable purification in a shorter process time. The identity of the purified protein was verified using in-gel digestion and mass spectrometry as well as immunological techniques. Conclusion With the technique presented it is possible to produce, within a short timeframe, pure P34, suitable for further studies where an example antigen is needed.

  8. Hydrophobic interaction chromatography of proteins. IV. Protein adsorption capacity and transport in preparative mode.

    Science.gov (United States)

    To, Brian C S; Lenhoff, Abraham M

    2011-01-21

    The adsorption isotherms of four model proteins (lysozyme, α-lactalbumin, ovalbumin, and BSA) on eight commercial phenyl hydrophobic interaction chromatography media were measured. The isotherms were softer than those usually seen in ion-exchange chromatography of proteins, and the static capacities of the media were lower, ranging from 30 to 110 mg/mL, depending on the ammonium sulfate concentration and the protein and adsorbent types. The protein-accessible surface area appears to be the main factor determining the binding capacity, and little correlation was seen with the protein affinities of the adsorbents. Breakthrough experiments showed that the dynamic capacities of the adsorbents at 10% breakthrough were 20-80% of the static capacities, depending on adsorbent type. Protein diffusivities in the adsorbents were estimated from batch uptake experiments using the pore diffusion and homogeneous diffusion models. Protein transport was affected by the adsorbent pore structures. Apparent diffusivities were higher at lower salt concentrations and column loadings, suggesting that adsorbed proteins may retard intraparticle protein transport. The diffusivities estimated from the batch uptake experiments were used to predict column breakthrough behavior. Analytical solutions developed for ion-exchange systems were able to provide accurate predictions for lysozyme breakthrough but not for ovalbumin. Impurities in the ovalbumin solutions used for the breakthrough experiments may have affected the ovalbumin uptake and led to the discrepancies between the predictions and the experimental results.

  9. Effective protein separation by coupling hydrophobic interaction and reverse phase chromatography for top-down proteomics.

    Science.gov (United States)

    Xiu, Lichen; Valeja, Santosh G; Alpert, Andrew J; Jin, Song; Ge, Ying

    2014-08-05

    One of the challenges in proteomics is the proteome's complexity, which necessitates the fractionation of proteins prior to the mass spectrometry (MS) analysis. Despite recent advances in top-down proteomics, separation of intact proteins remains challenging. Hydrophobic interaction chromatography (HIC) appears to be a promising method that provides high-resolution separation of intact proteins, but unfortunately the salts conventionally used for HIC are incompatible with MS. In this study, we have identified ammonium tartrate as a MS-compatible salt for HIC with comparable separation performance as the conventionally used ammonium sulfate. Furthermore, we found that the selectivity obtained with ammonium tartrate in the HIC mobile phases is orthogonal to that of reverse phase chromatography (RPC). By coupling HIC and RPC as a novel two-dimensional chromatographic method, we have achieved effective high-resolution intact protein separation as demonstrated with standard protein mixtures and a complex cell lysate. Subsequently, the separated intact proteins were identified by high-resolution top-down MS. For the first time, these results have shown the high potential of HIC as a high-resolution protein separation method for top-down proteomics.

  10. Fluorescence turn-on responses of anionic and cationic conjugated polymers toward proteins: effect of electrostatic and hydrophobic interactions.

    Science.gov (United States)

    Pu, Kan-Yi; Liu, Bin

    2010-03-11

    Cationic and anionic poly(fluorenyleneethynylene-alt-benzothiadiazole)s (PFEBTs) are designed and synthesized via Sonagashira coupling reaction to show light-up signatures toward proteins. Due to the charge transfer character of the excited states, the fluorescence of PFEBTs is very weak in aqueous solution, while their yellow fluorescence can be enhanced by polymer aggregation. PFEBTs show fluorescence turn-on rather than fluorescence quenching upon complexation with proteins. Both electrostatic and hydrophobic interactions between PFEBTs and proteins are found to improve the polymer fluorescence, the extent of which is dependent on the nature of the polymer and the protein. Changes in solution pH adjust the net charges of proteins, providing an effective way to manipulate electrostatic interactions and in turn the increment in the polymer fluorescence. In addition, the effect of protein digestion on the fluorescence of polymer/protein complexes is probed. The results indicate that electrostatic interaction induced polymer fluorescence increase cannot be substantially reduced through cleaving protein into peptide fragments. In contrast, hydrophobic interactions, mainly determined by the hydrophobicity of proteins, can be minimized by digestion, imparting a light-off signature for the polymer/protein complexes. This study thus not only highlights the opportunities of exerting nonspecific interactions for protein sensing but also reveals significant implications for biosensor design.

  11. A water-like model under confinement for hydrophobic and hydrophilic particle-plate interaction potentials

    OpenAIRE

    Krott, Leandro B.; BARBOSA, Marcia C.

    2013-01-01

    Molecular dynamic simulations were employed to study a water-like model confined between hydrophobic and hydrophilic plates. The phase behavior of this system is obtained for different distances between the plates and particle-plate potentials. For both hydrophobic and hydrophilic walls there are the formation of layers. Crystallization occurs at lower temperature at the contact layer than at the middle layer. In addition, the melting temperature decreases as the plates become more hydrophobi...

  12. The macroscopic pancake bounce

    Science.gov (United States)

    Andersen Bro, Jonas; Sternberg Brogaard Jensen, Kasper; Nygaard Larsen, Alex; Yeomans, Julia M.; Hecksher, Tina

    2017-01-01

    We demonstrate that the so-called pancake bounce of millimetric water droplets on surfaces patterned with hydrophobic posts (Liu et al 2014 Nat. Phys. 10 515) can be reproduced on larger scales. In our experiment, a bed of nails plays the role of the structured surface and a water balloon models the water droplet. The macroscopic version largely reproduces the features of the microscopic experiment, including the Weber number dependence and the reduced contact time for pancake bouncing. The scalability of the experiment confirms the mechanisms of pancake bouncing, and allows us to measure the force exerted on the surface during the bounce. The experiment is simple and inexpensive and is an example where front-line research is accessible to student projects.

  13. Selective adsorption of norfloxacin in aqueous media by an imprinted polymer based on hydrophobic and electrostatic interactions.

    Science.gov (United States)

    Xu, Zhifeng; Kuang, Daizhi; Liu, Lan; Deng, Qinying

    2007-09-21

    Based on hydrophobic and electrostatic interactions, a norfloxacin (NOF) imprinted polymer (P1) was prepared by the combined use of bismethacryloyl-beta-cyclodextrin (BMA-beta-CD) and 2-(diethylamino)ethylmethacrylate (DEAEM) as functional monomers. Compared with the molecularly imprinted polymers (MIPs) using only BMA-beta-CD or DEAEM as a functional monomer, P2 and P3, respectively, P1 showed higher binding affinity and specificity for NOF in aqueous media. Scatchard plot analysis revealed that two classes of binding sites were formed in the imprinted polymer with dissociation constants of 0.32 micromol/ml and 1.19 micromol/ml, respectively. It demonstrated that the combination of hydrophobic effect and electrostatic interaction in molecular imprinting was essential for the improvement of the selective ability of the imprinted polymer. Factors that influenced rebinding of the imprinted polymer including pH, water content in the adsorbed solution were explored.

  14. The hydrophobic effect: Molecular dynamics simulations of water confined between extended hydrophobic and hydrophilic surfaces

    DEFF Research Database (Denmark)

    Jensen, Morten Østergaard; Mouritsen, Ole G.; Peters, Günther H.J.

    2004-01-01

    experimental data from x-ray reflectivity measurements, reveal a uniform weak de-wetting characteristic for the extended hydrophobic surface, while the hydrophilic surface is weakly wetted. These microscopic data are consistent with macroscopic contact angle measurements. Specific water orientation is present......-correlation functions reveal that water molecules have characteristic diffusive behavior and orientational ordering due to the lack of hydrogen bonding interactions with the surface. These observations suggest that the altered dynamical properties of water in contact with extended hydrophobic surfaces together......Structural and dynamic properties of water confined between two parallel, extended, either hydrophobic or hydrophilic crystalline surfaces of n-alkane C36H74 or n-alcohol C35H71OH, are studied by molecular dynamics simulations. Electron density profiles, directly compared with corresponding...

  15. New shell crosslinked micelles from dextran with hydrophobic end groups and their interaction with bioactive molecules.

    Science.gov (United States)

    Mocanu, Georgeta; Nichifor, Marieta; Stanciu, Magdalena C

    2015-03-30

    Micelles formed in aqueous solution by dextran with hydrophobic (alkyl) end-groups were stabilized through divinyl sulfone crosslinking of the dextran shell. The efficacy of the crosslinking reaction was influenced by the divinyl sulfone amount, the pH and micelle concentration. Crosslinked micelles with a moderate crosslinking degree were further functionalized by attachment of 10 and 17 moles% N-(2-hydroxypropyl)-N,N-dimethyl-N-benzylammonium chloride groups along the dextran chain. The size and shape of both crosslinked micelles and their cationic derivatives were analyzed by DLS and TEM. The prepared micelles were able to bind anionic diclofenac (60-370 mg/g), hydrophobic anionic indometacin (70-120 mg/g), and hydrophobic alpha-tocopherol (170-220 mg/g) or ergocalciferol (90-110 mg/g) by hydrophobic or/and electrostatic forces. The release experiments and the antioxidant activity of bound alpha-tocopherol highlighted the potential of the new nano-sized micelles mainly as carriers for prolonged and controlled delivery of hydrophobic drugs.

  16. Collagen mimetic peptide discs promote assembly of a broad range of natural protein fibers through hydrophobic interactions.

    Science.gov (United States)

    McGuinness, Kenneth; Nanda, Vikas

    2017-07-19

    Collagen mimetic peptides that alone formed two-dimensional nanoscale discs driven by hydrophobic interactions were shown in electron microscopy studies to also co-assemble with natural fibrous proteins to produce discs-on-a-string (DoS) nanostructures. In most cases, peptide discs also facilitated bundling of the protein fibers. This provides insight into how synthetic and natural proteins may be combined to develop multicomponent, multi-dimensional architectures at the nanoscale.

  17. Preparation of a weak anion exchange/hydrophobic interaction dual-function mixed-mode chromatography stationary phase for protein separation using click chemistry.

    Science.gov (United States)

    Zhao, Kailou; Yang, Fan; Xia, Hongjun; Wang, Fei; Song, Qingguo; Bai, Quan

    2015-03-01

    In this study, 3-diethylamino-1-propyne was covalently bonded to the azide-silica by a click reaction to obtain a novel dual-function mixed-mode chromatography stationary phase for protein separation with a ligand containing tertiary amine and two ethyl groups capable of electrostatic and hydrophobic interaction functionalities, which can display hydrophobic interaction chromatography character in a high-salt-concentration mobile phase and weak anion exchange character in a low-salt-concentration mobile phase employed for protein separation. As a result, it can be employed to separate proteins with weak anion exchange and hydrophobic interaction modes, respectively. The resolution and selectivity of the stationary phase were evaluated in both hydrophobic interaction and ion exchange modes with standard proteins, respectively, which can be comparable to that of conventional weak anion exchange and hydrophobic interaction chromatography columns. Therefore, the synthesized weak anion exchange/hydrophobic interaction dual-function mixed-mode chromatography column can be used to replace two corresponding conventional weak anion exchange and hydrophobic interaction chromatography columns to separate proteins. Based on this mixed-mode chromatography stationary phase, a new off-line two-dimensional liquid chromatography technology using only a single dual-function mixed-mode chromatography column was developed. Nine kinds of tested proteins can be separated completely using the developed method within 2.0 h.

  18. Turning hydrophilic bacteria into biorenewable hydrophobic material with potential antimicrobial activity via interaction with chitosan.

    Science.gov (United States)

    Hanpanich, Orakan; Wongkongkatep, Pravit; Pongtharangkul, Thunyarat; Wongkongkatep, Jirarut

    2017-04-01

    Alteration of a bacteriocin-producing hydrophilic bacterium, Lactococcus lactis IO-1, into a hydrophobic material with potential antimicrobial activity using chitosan was investigated and compared with five other bacterial species with industrial importance. The negatively charged bacterial cells were neutralized by positively charged chitosan, resulting in a significant increase in the hydrophobicity of the bacterial cell surface. The largest Gram-positive B. megaterium ATCC 14581 showed a moderate response to chitosan while the smaller E. coli DH5α, L. lactis IO-1 and P. putida F1 exhibited a significant response to an increase in chitosan concentration. Because L. lactis IO-1 is a good source for natural peptide lantibiotic that is highly effective against several strains of food spoilage organisms and pathogens, hydrophobic material derived from L. lactis IO-1 and chitosan is a promising novel material with antimicrobial activity for the food and pharmaceutical industries. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. The effect of aqueous solutions of trimethylamine-N-oxide on pressure induced modifications of hydrophobic interactions.

    Science.gov (United States)

    Sarma, Rahul; Paul, Sandip

    2012-09-07

    To understand the mechanism of protein protection by the osmolyte trimethylamine-N-oxide (TMAO) at high pressure, using molecular dynamics (MD) simulations, solvation of hydrophobic group is probed in aqueous solutions of TMAO over a wide range of pressures relevant to protein denaturation. The hydrophobic solute considered in this study is neopentane which is a considerably large molecule. The concentrations of TMAO range from 0 to 4 M and for each TMAO concentration, simulations are performed at five different pressures ranging from 1 atm to 8000 atm. Potentials of mean force are calculated and the relative stability of solvent-separated state over the associated state of hydrophobic solute are estimated. Results suggest that high pressure reduces association of hydrophobic solutes. From computations of site-site radial distribution function followed by analysis of coordination number, it is found that water molecules are tightly packed around the nonpolar particle at high pressure and the hydration number increases with increasing pressure. On the other hand, neopentane interacts preferentially with TMAO over water and although hydration of neopentane reduces in presence of this osmolyte, TMAO does not show any tendency to prevent the pressure-induced dispersion of neopentane moieties. It is also observed that TMAO molecules prefer a side-on orientation near the neopentane surface, allowing its oxygen atom to form favorable hydrogen bonds with water while maintaining some hydrophobic contacts with neopentane. Analysis of hydrogen-bond properties and solvation characteristics of TMAO reveals that TMAO can form hydrogen bonds with water and it reduces the identical nearest neighbor water molecules caused by high hydrostatic pressures. Moreover, TMAO enhances life-time of water-water hydrogen bonds and makes these hydrogen bonds more attractive. Implication of these results for counteracting effect of TMAO against protein denaturation at high pressures are

  20. Reversible Interactions of Proteins with Mixed Shell Polymeric Micelles: Tuning the Surface Hydrophobic/Hydrophilic Balance toward Efficient Artificial Chaperones.

    Science.gov (United States)

    Wang, Jianzu; Song, Yiqing; Sun, Pingchuan; An, Yingli; Zhang, Zhenkun; Shi, Linqi

    2016-03-22

    Molecular chaperones can elegantly fine-tune its hydrophobic/hydrophilic balance to assist a broad spectrum of nascent polypeptide chains to fold properly. Such precious property is difficult to be achieved by chaperone mimicking materials due to limited control of their surface characteristics that dictate interactions with unfolded protein intermediates. Mixed shell polymeric micelles (MSPMs), which consist of two kinds of dissimilar polymeric chains in the micellar shell, offer a convenient way to fine-tune surface properties of polymeric nanoparticles. In the current work, we have fabricated ca. 30 kinds of MSPMs with finely tunable hydrophilic/hydrophobic surface properties. We investigated the respective roles of thermosensitive and hydrophilic polymeric chains in the thermodenaturation protection of proteins down to the molecular structure. Although the three kinds of thermosensitive polymers investigated herein can form collapsed hydrophobic domains on the micellar surface, we found distinct capability to capture and release unfolded protein intermediates, due to their respective affinity for proteins. Meanwhile, in terms of the hydrophilic polymeric chains in the micellar shell, poly(ethylene glycol) (PEG) excels in assisting unfolded protein intermediates to refold properly via interacting with the refolding intermediates, resulting in enhanced chaperone efficiency. However, another hydrophilic polymer-poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) severely deteriorates the chaperone efficiency of MSPMs, due to its protein-resistant properties. Judicious combination of thermosensitive and hydrophilic chains in the micellar shell lead to MSPM-based artificial chaperones with optimal efficacy.

  1. A new model for humic materials and their interactions with hydrophobic organic chemicals in soil-water or sediment-water systems

    Science.gov (United States)

    Wershaw, R. L.

    1986-01-01

    A generalized model of humic materials in soils and sediments, which is consistent with their observed properties, is presented. This model provides a means of understanding the interaction of hydrophobic pollutants with humic materials. In this model, it is proposed that the humic materials in soils and sediments consist of a number of different oligomers and simple compounds which result from the partial degradation of plant remains. These degradation products are stabilized by incorporation into humic aggregates bound together by weak bonding mechanisms, such as hydrogen bonding, pi bonding, and hydrophobic interactions. The resulting structures are similar to micelles or membranes, in which the interiors of the structures are hydrophobic and the exteriors are hydrophilic. Hydrophobic compounds will partition into the hydrophobic interiors of the humic micelles or "membrane-like" structures. ?? 1986.

  2. Surfactant-cobalt(III) complexes: The impact of hydrophobicity on interaction with HSA and DNA - insights from experimental and theoretical approach.

    Science.gov (United States)

    Veeralakshmi, Selvakumar; Sabapathi, Gopal; Nehru, Selvan; Venuvanalingam, Ponnambalam; Arunachalam, Sankaralingam

    2017-05-01

    To develop surfactant-based metallodrugs, it is very important to know about their hydrophobicity, micelle forming capacity, their interaction with biomacromolecules such as proteins and nucleic acids, and biological activities. Here, diethylenetriamine (dien) and tetradecylamine ligand (TA) based surfactant-cobalt(III) complexes with single chain domain, [Co(dien)(TA)Cl2]ClO4 (1) and double chain domain [Co(dien)(TA)2Cl](ClO4)2 (2) were chosen to study the effect of hydrophobicity on the interaction with human serum albumin and calf thymus DNA. The obtained results showed that (i) single chain surfactant-cobalt(III) complex (1) interact with HSA and DNA via electrostatic interaction and groove binding, respectively; (ii) double chain surfactant-cobalt(III) complex (2) interact with HSA and DNA via hydrophobic interaction and partial intercalation, respectively, due to the play of hydrophobicity by single and double chain domains. Further it is noted that, double chain surfactant-cobalt(III) complex interact strongly with HSA and DNA, compared single chain surfactant-cobalt(III) complex due to their more hydrophobicity nature. DFT and molecular docking studies offer insights into the mechanism and mode of binding towards the molecular target CT-DNA and HSA. Hence, the present findings will create new avenue towards the use of hydrophobic metallodrugs for various therapeutic applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Molecular dynamics analysis of conserved hydrophobic and hydrophilic bond-interaction networks in ErbB family kinases.

    Science.gov (United States)

    Shih, Andrew J; Telesco, Shannon E; Choi, Sung-Hee; Lemmon, Mark A; Radhakrishnan, Ravi

    2011-06-01

    The EGFR (epidermal growth factor receptor)/ErbB/HER (human EGFR) family of kinases contains four homologous receptor tyrosine kinases that are important regulatory elements in key signalling pathways. To elucidate the atomistic mechanisms of dimerization-dependent activation in the ErbB family, we have performed molecular dynamics simulations of the intracellular kinase domains of three members of the ErbB family (those with known kinase activity), namely EGFR, ErbB2 (HER2) and ErbB4 (HER4), in different molecular contexts: monomer against dimer and wild-type against mutant. Using bioinformatics and fluctuation analyses of the molecular dynamics trajectories, we relate sequence similarities to correspondence of specific bond-interaction networks and collective dynamical modes. We find that in the active conformation of the ErbB kinases, key subdomain motions are co-ordinated through conserved hydrophilic interactions: activating bond-networks consisting of hydrogen bonds and salt bridges. The inactive conformations also demonstrate conserved bonding patterns (albeit less extensive) that sequester key residues and disrupt the activating bond network. Both conformational states have distinct hydrophobic advantages through context-specific hydrophobic interactions. We show that the functional (activating) asymmetric kinase dimer interface forces a corresponding change in the hydrophobic and hydrophilic interactions that characterize the inactivating bond network, resulting in motion of the αC-helix through allostery. Several of the clinically identified activating kinase mutations of EGFR act in a similar fashion to disrupt the inactivating bond network. The present molecular dynamics study reveals a fundamental difference in the sequence of events in EGFR activation compared with that described for the Src kinase Hck.

  4. Microbial interactions with naturally occurring hydrophobic sediments: Influence on sediment and associated contaminant mobility.

    Science.gov (United States)

    Droppo, I G; Krishnappan, B G; Lawrence, J R

    2016-04-01

    The erosion, transport and fate of sediments and associated contaminants are known to be influenced by both particle characteristics and the flow dynamics imparted onto the sediment. The influential role of bitumen containing hydrophobic sediments and the microbial community on sediment dynamics are however less understood. This study links an experimental evaluation of sediment erosion with measured sediment-associated contaminant concentrations and microbial community analysis to provide an estimate of the potential for sediment to control the erosion, transport and fate of contaminants. Specifically the paper addresses the unique behaviour of hydrophobic sediments and the role that the microbial community associated with hydrophobic sediment may play in the transport of contaminated sediment. Results demonstrate that the hydrophobic cohesive sediment demonstrates unique transport and particle characteristics (poor settling and small floc size). Biofilms were observed to increase with consolidation/biostabilization times and generated a unique microbial consortium relative to the eroded flocs. Natural oil associated with the flocs appeared to be preferentially associated with microbial derived extracellular polymeric substances. While PAHs and naphthenic acid increased with increasing shear (indicative of increasing loads), they tended to decrease with consolidation/biostabilization (CB) time at similar shears suggesting a chemical and/or biological degradation. PAH and napthenic acid degrading microbes decreased with time as well, which may suggest that there was a reduced pool of PAHs and naphthenic acids available resulting in their die off. This study emphasizes the importance that any management strategies and operational assessments for the protection of human and aquatic health incorporate the sediment (suspended and bed sediment) and biological (biofilm) compartments and the energy dynamics within the system in order to better predict contaminant

  5. Modeling bubble-particle interactions in flotation using hydrophobic solid surfaces

    OpenAIRE

    Flinn, Darrin Heinz

    1996-01-01

    An atomic force microscope (AFM) was used to measure surface forces between a glass sphere and a flat fused silica plate under a number of conditions. Hydrophobic surfaces exhibiting contact angles ranging from 0 to 109° were prepared by reacting silica with octadecyltrichlorosilane (OTS). Contact angles, AFM images, and infrared transmission spectra showed that OTS forms clusters on the silica surface. The presence of water in the reaction was shown to greatly influence the f...

  6. A model of protein association based on their hydrophobic and electric interactions.

    Directory of Open Access Journals (Sweden)

    Angel Mozo-Villarías

    Full Text Available The propensity of many proteins to oligomerize and associate to form complex structures from their constituent monomers, is analyzed in terms of their hydrophobic (H, and electric pseudo-dipole (D moment vectors. In both cases these vectors are defined as the product of the distance between their positive and negative centroids, times the total hydrophobicity or total positive charge of the protein. Changes in the magnitudes and directions of H and D are studied as monomers associate to form larger complexes. We use these descriptors to study similarities and differences in two groups of associations: a open associations such as polymers with an undefined number of monomers (i.e. actin polymerization, amyloid and HIV capsid assemblies; b closed symmetrical associations of finite size, like spherical virus capsids and protein cages. The tendency of the hydrophobic moments of the monomers in an association is to align in parallel arrangements following a pattern similar to those of phospholipids in a membrane. Conversely, electric dipole moments of monomers tend to align in antiparallel associations. The final conformation of a given assembly is a fine-tuned combination of these forces, limited by steric constraints. This determines whether the association will be open (indetermined number of monomers or closed (fixed number of monomers. Any kinetic, binding or molecular peculiarities that characterize a protein assembly, comply with the vector rules laid down in this paper. These findings are also independent of protein size and shape.

  7. Two hydrophobic residues can determine the specificity of mitogen-activated protein kinase docking interactions.

    Science.gov (United States)

    Bardwell, A Jane; Bardwell, Lee

    2015-10-30

    MAPKs bind to many of their upstream regulators and downstream substrates via a short docking motif (the D-site) on their binding partner. MAPKs that are in different families (e.g. ERK, JNK, and p38) can bind selectively to D-sites in their authentic substrates and regulators while discriminating against D-sites in other pathways. Here we demonstrate that the short hydrophobic region at the distal end of the D-site plays a critical role in determining the high selectivity of JNK MAPKs for docking sites in their cognate MAPK kinases. Changing just 1 or 2 key hydrophobic residues in this submotif is sufficient to turn a weak JNK-binding D-site into a strong one, or vice versa. These specificity-determining differences are also found in the D-sites of the ETS family transcription factors Elk-1 and Net. Moreover, swapping two hydrophobic residues between these D-sites switches the relative efficiency of Elk-1 and Net as substrates for ERK versus JNK, as predicted. These results provide new insights into docking specificity and suggest that this specificity can evolve rapidly by changes to just 1 or 2 amino acids.

  8. Water structure near single and multi-layer nanoscopic hydrophobic plates of varying separation and interaction potentials

    Indian Academy of Sciences (India)

    Malay Rana; Amalendu Chandra

    2008-06-01

    We have performed a series of molecular dynamics simulations of water containing two nanoscopic hydrophobic plates to investigate the modifications of the density and hydrogen bond distributions of water in the vicinity of the surfaces. Our primary goal is to look at the effects of plate thickness, solute–solvent interaction and also interplate separation on the solvent structure in the confined region between two graphite-like plates and also near the outer surfaces of the plates. The thickness of the plates is varied by considering single and triple-layer graphite plates and the interaction potential is varied by tuning the attractive strength of the 12–6 pair interaction potential between a carbon atom of the graphite plates and a water molecule. The calculations are done for four different values of the tuning parameter ranging from fully Lennard–Jones to pure repulsive pair interactions. It is found that both the solvation characteristics and hydrogen bond distributions can depend rather strongly on the strength of the attractive part of the solute–water interaction potential. The thickness of the plates, however, is found to have only minor effects on the density profiles and hydrogen bond network. This indicates that the long range electrostatic interactions between water molecules on the two opposite sides of the same plate do not make any significant contribution to the overall solvation structure of these hydrophobic plates. The solvation characteristics are primarily determined by the balance between the loss of energy due to hydrogen bond network disruption, cavity repulsion potential and offset of the same by attractive component of the solute–water interactions. Our studies with different system sizes show that the essential features of solvation properties, e.g. wetting and dewetting characteristics for different interplate separations and interaction potentials, are also present in relatively smaller systems consisting of a few hundred

  9. Hair-inspired crystal growth of HOA in cavities of cellulose matrix via hydrophobic-hydrophilic interface interaction.

    Science.gov (United States)

    He, Meng; Kwok, Ryan T K; Wang, Zhenggang; Duan, Bo; Tang, Ben Zhong; Zhang, Lina

    2014-06-25

    As one of the most ordinary phenomena in nature, numerous pores on animal skins induce the growth of abundant hairs. In this study, cavities of a cellulose matrix were used as hard templates to lead the hair-inspired crystal growth of 12-hydroxyoctadecanoic acid (HOA) through hydrophobic-hydrophilic interface interaction, and short hair-like HOA crystals with a smooth surface were formed on cellulose films. In our findings, by using solvent evaporation induced crystallization, hydrophobic HOA grew along the hydrophilic cellulose pore wall to form regular vertical worm-like and pillar-like crystals with an average diameter of about 200 nm, depending on the experimental conditions and HOA concentration. The formation mechanism of the short hair-like HOA crystals as well as the structure and properties of the cellulose/HOA submicrometer composite films were studied. The pores of the cellulose matrix supplied not only cavities for the HOA crystals fixation but also hydrophilic shells to favor the vertical growth of the relatively hydrophobic HOA crystals. The cellulose/HOA submicrometer composite films exhibited high hydrophobicity, as a result of the formation of the solid/air composite surface. Furthermore, 4-(1,2,2-triphenylethenyl) benzoic acid, an aggregation-induced emission luminogen, was used to aggregate on the cellulose surface with HOA to emit and monitor the HOA crystal growth, showing bifunctional photoluminscence and self-cleaning properties. This work opens up a novel one-step pathway to design bio-inspired submicrometer materials by utilizing natural products, showing potential applications in self-cleaning optical devices.

  10. Hydrophobic Forces in Flotation

    OpenAIRE

    Pazhianur, Rajesh R

    1999-01-01

    An atomic force microscope (AFM) has been used to conduct force measurements to better understand the role of hydrophobic forces in flotation. The force measurements were conducted between a flat mineral substrate and a hydrophobic glass sphere in aqueous solutions. It is assumed that the hydrophobic glass sphere may simulate the behavior of air bubbles during flotation. The results may provide information relevant to the bubble-particle interactions occurring during flotation. The glass ...

  11. The tendency of smooth and rough Salmonella typhimurium bacteria and lipopolysaccharide to hydrophobic and ionic interaction, as studied in aqueous polymer two-phase systems.

    Science.gov (United States)

    Magnusson, K E; Stendahl, O; Tagesson, C; Edebo, L; Johansson, G

    1977-06-01

    In aqueous two-phase system, the partition of bacteria and lipopolysaccharide from a rough (R) strain (Rd-mutant) of Salmonella typhimurium is influenced by polymers with covalently linked hydrophobic groups indicating hydrophobic structures accessible at the cell surface. Furthermore, the partition of the R bacteria is influenced by a number of inorganic positive and negative ions, presumably as a consequence of interaction with negatively charged surface structures. In contrast, smooth (S) bacteria and lipopolysaccharide from the parent strain do not seem to participate in either hydrophobic or charge interaction indicating extensive hydrophilicity without charge. Thus, the S-specific polysaccharide side chain of S. typhimurium might serve the purpose of blindfolding aspecific host defence mechanisms dependent on hydrophobicity and charge. On the contrary, the R bacteria and R lipopolysaccharide have physico-chemical properties which predispose to interaction with several types of cells, organelles and molecules.

  12. Comparison of the Contributions of Tetrahydrofurfuryl Alcohol and PEG to α-Chymotrypsin Renaturation with High Performance Hydrophobic Interaction Chromatography

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The contributions of tetrahydrofurfuryl alcohol (THFA) and polyethylene glycol (PEG) to the renatured efficiency of α-chymotrypsin were investigated and compared with each other. The maximum increments of bioactivity recovery of α-Chy were found to be 25.1% for THFA, 10.4% for PEG, respectively. The experimental results indicated that the denaturant solution containing THFA contributed more to the renaturation of α-Chy in high performance hydrophobic interaction chromatography (HPHIC) than that containing PEG, when the concentration of THFA was 3.2%, the bioactivity recovery of α-Chy is the highest.

  13. The Interplay of Disulfide Bonds, α-Helicity, and Hydrophobic Interactions Leads to Ultrahigh Proteolytic Stability of Peptides.

    Science.gov (United States)

    Chen, Yaqi; Yang, Chaoqiong; Li, Tao; Zhang, Miao; Liu, Yang; Gauthier, Marc A; Zhao, Yibing; Wu, Chuanliu

    2015-08-10

    The contribution of noncovalent interactions to the stability of naturally occurring peptides and proteins has been generally acknowledged, though how these can be rationally manipulated to improve the proteolytic stability of synthetic peptides remains to be explored. In this study, a platform to enhance the proteolytic stability of peptides was developed by controllably dimerizing them into α-helical dimers, connected by two disulfide bonds. This platform not only directs peptides toward an α-helical conformation but permits control of the interfacial hydrophobic interactions between the peptides of the dimer. Using two model dimeric systems constructed from the N-terminal α-helix of RNase A and known inhibitors for the E3 ubiquitin ligase MDM2 (and its homologue MDMX), a deeper understanding into the interplay of disulfide bonds, α-helicity, and hydrophobic interactions on enhanced proteolytic stability was sought out. Results reveal that all three parameters play an important role on attaining ultrahigh proteolytic resistance, a concept that can be exploited for the development of future peptide therapeutics. The understanding gained through this study will enable this strategy to be tailored to new peptides because the proposed strategy displays substantial tolerance to sequence permutation. It thus appears promising for conveniently creating prodrugs composed entirely of the therapeutic peptide itself (i.e., in the form of a dimer).

  14. Enzymatic activity induced by interactions with a nanofabricated hydrophobic Si surface

    Science.gov (United States)

    Nishiyama, Katsuhiko

    2013-07-01

    The binding of peptides of 2-10 glycine residues (2-10Gly) to papain on nanofabricated hydrophobic Si surfaces was investigated by molecular dynamics and docking simulations. 5Gly, 7Gly, 9Gly, and 10Gly were distributed on sites near the active center of papain on the Si surface, while 6-10Gly were distributed on sites near the active center of free papain. The Si surface changed the substrate specificity of papain, and modification of this surface should allow full control of substrate specificity. Molecular surgery of proteins in cells may be realized using papain on specially designed surfaces.

  15. Purification of Mycobacterium bovis BCG Tokyo antigens by chromatofocusing, lectin-affinity chromatography, and hydrophobic interaction chromatography.

    Science.gov (United States)

    Sugden, E A; Stilwell, K; Watson, D C; Rohonczy, E B; Martineau, P

    1996-09-01

    A combination of chromatofocusing, lectin-affinity chromatography, and hydrophobic interaction chromatography resulted in a simple purification of protein antigens of Mycobacterium bovis BCG Tokyo culture filtrate. Identification was established on the basis of chromatographic separation, sodium dodecyl sulfate-polyacrylamide gel electrophoresis determination of molecular weights, and N-terminal amino acid determination. Chromatofocusing on PBE 94 accomplished the separation of BCG85B from other BCG85 complex antigens and partial separation of MPB64 and MPB70 antigens. Subsequently, MPB64 and MPB70 were completely separated on a high-performance liquid chromatography TSK Phenyl 5PW hydrophobic interaction chromatography column. This column also separated BCG85B from a 17-kDa protein with an N-terminal amino acid sequence of A-V-P-I-T-G-K-L-G-S-E-L-T-M-T-D-( )-V-G-Q, which is similar to the sequence of MPT63. Concanavalin A-Sepharose-affinity chromatography separated MPB64 from a 43- and 47-kDa doublet with an amino acid sequence of D-P-E-P-A-P-P-V-P-P-V-P-A-( )-A-A-S-P, which is similar to the sequence of MPT32 and which appears to be glycosylated.

  16. Hydrophobic Solvation: Aqueous Methane Solutions

    Science.gov (United States)

    Konrod, Oliver; Lankau, Timm

    2007-01-01

    A basic introduction to concept of a solvation shell around an apolar solute as well as its detection is presented. The hydrophobic solvation of toluene is found to be a good teaching example which connects macroscopic, phenomenological thermodynamic results with an atomistic point of view.

  17. Hydrophobic Solvation: Aqueous Methane Solutions

    Science.gov (United States)

    Konrod, Oliver; Lankau, Timm

    2007-01-01

    A basic introduction to concept of a solvation shell around an apolar solute as well as its detection is presented. The hydrophobic solvation of toluene is found to be a good teaching example which connects macroscopic, phenomenological thermodynamic results with an atomistic point of view.

  18. Lateral Protein-Protein Interactions at Hydrophobic and Charged Surfaces as a Function of pH and Salt Concentration.

    Science.gov (United States)

    Hladílková, Jana; Callisen, Thomas H; Lund, Mikael

    2016-04-07

    Surface adsorption of Thermomyces lanuginosus lipase (TLL)-a widely used industrial biocatalyst-is studied experimentally and theoretically at different pH and salt concentrations. The maximum achievable surface coverage on a hydrophobic surface occurs around the protein isoelectric point and adsorption is reduced when either increasing or decreasing pH, indicating that electrostatic protein-protein interactions in the adsorbed layer play an important role. Using Metropolis Monte Carlo (MC) simulations, where proteins are coarse grained to the amino acid level, we estimate the protein isoelectric point in the vicinity of charged surfaces as well as the lateral osmotic pressure in the adsorbed monolayer. Good agreement with available experimental data is achieved and we further make predictions of the protein orientation at hydrophobic and charged surfaces. Finally, we present a perturbation theory for predicting shifts in the protein isoelectric point due to close proximity to charged surfaces. Although this approximate model requires only single protein properties (mean charge and its variance), excellent agreement is found with MC simulations.

  19. The Non-Specific Binding of Fluorescent-Labeled MiRNAs on Cell Surface by Hydrophobic Interaction.

    Directory of Open Access Journals (Sweden)

    Ting Lu

    Full Text Available MicroRNAs are small noncoding RNAs about 22 nt long that play key roles in almost all biological processes and diseases. The fluorescent labeling and lipofection are two common methods for changing the levels and locating the position of cellular miRNAs. Despite many studies about the mechanism of DNA/RNA lipofection, little is known about the characteristics, mechanisms and specificity of lipofection of fluorescent-labeled miRNAs.Therefore, miRNAs labeled with different fluorescent dyes were transfected into adherent and suspension cells using lipofection reagent. Then, the non-specific binding and its mechanism were investigated by flow cytometer and laser confocal microscopy. The results showed that miRNAs labeled with Cy5 (cyanine fluorescent dye could firmly bind to the surface of adherent cells (Hela and suspended cells (K562 even without lipofection reagent. The binding of miRNAs labeled with FAM (carboxyl fluorescein to K562 cells was obvious, but it was not significant in Hela cells. After lipofectamine reagent was added, most of the fluorescently labeled miRNAs binding to the surface of Hela cells were transfected into intra-cell because of the high transfection efficiency, however, most of them were still binding to the surface of K562 cells. Moreover, the high-salt buffer which could destroy the electrostatic interactions did not affect the above-mentioned non-specific binding, but the organic solvent which could destroy the hydrophobic interactions eliminated it.These results implied that the fluorescent-labeled miRNAs could non-specifically bind to the cell surface by hydrophobic interaction. It would lead to significant errors in the estimation of transfection efficiency only according to the cellular fluorescence intensity. Therefore, other methods to evaluate the transfection efficiency and more appropriate fluorescent dyes should be used according to the cell types for the accuracy of results.

  20. Design and synthesis of an amphiphilic graft hydrogel having a hydrophobic domain formed by multiple interactions.

    Science.gov (United States)

    Nitta, Kyohei; Kimoto, Atsushi; Watanabe, Junji

    2016-11-01

    A novel hydrogel having hydrophobic oligo segments and hydrophilic poly(acrylamidoglycolic acid) (PAGA) as pH responsive polymer segments was designed and synthesized to be used as a soft biomaterial. Poly(trimethylene carbonate) (PTMC) as the side chain, for which the degrees of polymerization were 9, 19, and 49, and the composition ratios were 1, 5, and 10mol%, was used as the oligo segment in the hydrogel. The swelling ratio of the hydrogel was investigated under various changes in conditions such as pH, temperature, and hydrogen bonding upon urea addition. Under pH2-11 conditions, the graft gel reversibly swelled and shrank due to the effect of PAGA main chain. The interior morphology and skin layer of the hydrogel was observed by a scanning electron microscope. The hydrogel composed of PAGA as the hydrophilic polymer backbone had a sponge-like structure, with a pore size of approximately 100μm. On the other hand, upon increasing the ratio of trimethylene carbonate (TMC) units in the hydrogel, the pores became smaller or disappeared. Moreover, thickness of the skin layer significantly increased with the swelling ratio depended on the incorporation ratios of the PTMC macromonomer. Molecular incorporation in the hydrogel was evaluated using a dye as a model drug molecule. These features would play an important role in drug loading. Increasing the ratio of TMC units favored the adsorption of the dye and activation of the incorporation behavior.

  1. Epitope mapping of imidazolium cations in ionic liquid-protein interactions unveils the balance between hydrophobicity and electrostatics towards protein destabilisation.

    Science.gov (United States)

    Silva, Micael; Figueiredo, Angelo Miguel; Cabrita, Eurico J

    2014-11-14

    We investigated imidazolium-based ionic liquid (IL) interactions with human serum albumin (HSA) to discern the level of cation interactions towards protein stability. STD-NMR spectroscopy was used to observe the imidazolium IL protons involved in direct binding and to identify the interactions responsible for changes in Tm as accessed by differential scanning calorimetry (DSC). Cations influence protein stability less than anions but still significantly. It was found that longer alkyl side chains of imidazolium-based ILs (more hydrophobic) are associated with a higher destabilisation effect on HSA than short-alkyl groups (less hydrophobic). The reason for such destabilisation lies on the increased surface contact area of the cation with the protein, particularly on the hydrophobic contacts promoted by the terminus of the alkyl chain. The relevance of the hydrophobic contacts is clearly demonstrated by the introduction of a polar moiety in the alkyl chain: a methoxy or alcohol group. Such structural modification reduces the degree of hydrophobic contacts with HSA explaining the lesser extent of protein destabilisation when compared to longer alkyl side chain groups: above [C2mim](+). Competition STD-NMR experiments using [C2mim](+), [C4mim](+) and [C2OHmim](+) also validate the importance of the hydrophobic interactions. The combined effect of cation and anion interactions was explored using (35)Cl NMR. Such experiments show that the nature of the cation has no influence on the anion-protein contacts, still the nature of the anion modulates the cation-protein interaction. Herein we propose that more destabilising anions are likely to be a result of a partial contribution from the cation as a direct consequence of the different levels of interaction (cation-anion pair and cation-protein).

  2. Structural characteristics of the hydrophobic patch of azurin and its interaction with p53: a site-directed spin labeling study

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Site-directed spin labeling (SDSL) is a powerful tool for monitoring protein structure, dynamics and conformational changes. In this study, the domain-specific properties of azurin and its interaction with p53 were studied using this technique. Mutations of six residues, that are located in the hydrophobic patch of azurin, were prepared and spin labeled. Spectra of the six azurin mutants in solution showed that spin labeled residues 45 and 63 are in a very restricted environment, residues 59 and 65 are in a spacious environment and have free movement, and residues 49 and 51 are located in a relatively closed pocket. Polarity experiments confirmed these results. The changes observed in the spectra of spin labeled azurin upon interaction with p53 indicate that the hydrophobic patch is involved in this interaction. Our results provide valuable insight into the topographic structure of the hydrophobic domain of azurin, as well as direct evidence of its interaction with p53 in solution via the hydrophobic patch. Cytotoxicity studies of azurin mutants showed that residues along the hydrophobic patch are important for its cytotoxicity.

  3. Effect of hydrogen bonding and hydrophobic interaction on the formation of supramolecular hydrogels formed by L-phenylalanine derivative hydrogelator

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A new hydrogelator, pyridinium bromide salt of N-6-bromohexanoyl-L-phenylamino octadecane, was synthesized. Supramolecular hydrogels can be formed through the self-assembly of this hydrogelator in water. In this work, D2O was used instead of H2O as solvent for FT-IR measurement due to the fact that it is impossible to obtain useful FT-IR information on the hydrogen bonding in water. The investigation of FT-IR and steady-state fluorescence indicated that the driving forces for the self-assembly were mainly hydrogen bonding and hydrophobic interaction. Based on the data of XRD and molecular modeling, the possible mechanism of the formation of hydrogelator aggregates was proposed.

  4. Application of a pH responsive multimodal hydrophobic interaction chromatography medium for the analysis of glycosylated proteins.

    Science.gov (United States)

    Kallberg, K; Becker, K; Bülow, L

    2011-02-04

    Protein glycosylation has significant effects on the structure and function of proteins. The efficient separation and enrichment of glycoproteins from complex biological samples is one key aspect and represents a major bottleneck of glycoproteome research. In this paper, we have explored pH multimodal hydrophobic interaction chromatography to separate glycosylated from non-glycosylated forms of proteins. Three different proteins, ribonuclease, invertase and IgG, have been examined and different glycoforms have been identified. The media itself shows strong responsiveness to small variations in pH, which makes it possible to fine-tune the chromatographic conditions according to the properties of the protein isolated. Optimal glycoprotein separation has been obtained at pH 4. The pH responsive multimodal HIC medium in contrast to conventional HIC media is able to resolve contaminating DNA. Copyright © 2010 Elsevier B.V. All rights reserved.

  5. Solubilities of benzene, toluene and diphenyl in the t-butyl alcohol + water mixtures and hydrophobic interaction

    Institute of Scientific and Technical Information of China (English)

    邹立壮; 杨冠英; 韩布兴; 刘瑞麟; 阎海科

    1999-01-01

    The solubilitices of benzene, toluene and diphenyl in mixed solvents of t-butyl alcohol (TBA) and water at 283.15, 288.15, 293.15 and 298.15 K have been determined by spectrophotometry. The mole fraction of TBA [x (TBA)] in the mixed solvent are 0.000, 0.010, 0.020, 0.030, 0.040, 0.045, 0.050, 0.060, 0.080 and 0.100, respectively. The standard Gibbs energies of solution of benzene, toluene and diphenyl in the mixed solvent have also been calculated based on the solubility data. The hydrophobic interactions (HI) for the pairs of benzene-benzene, methane-benzene and methane-methane in the mixed solvent were calculated and discussed.

  6. Interaction of bovine serum albumin with N-acyl amino acid based anionic surfactants: Effect of head-group hydrophobicity.

    Science.gov (United States)

    Ghosh, Subhajit; Dey, Joykrishna

    2015-11-15

    The function of a protein depends upon its structure and surfactant molecules are known to alter protein structure. For this reason protein-surfactant interaction is important in biological, pharmaceutical, and cosmetic industries. In the present work, interactions of a series of anionic surfactants having the same hydrocarbon chain length, but different amino acid head group, such as l-alanine, l-valine, l-leucine, and l-phenylalanine with the transport protein, bovine serum albumin (BSA), were studied at low surfactant concentrations using fluorescence and circular dichroism (CD) spectroscopy, and isothermal titration calorimetry (ITC). The results of fluorescence measurements suggest that the surfactant molecules bind simultaneously to the drug binding site I and II of the protein subdomain IIA and IIIA, respectively. The fluorescence as well as CD spectra suggest that the conformation of BSA goes to a more structured state upon surfactant binding at low concentrations. The binding constants of the surfactants were determined by the use of fluorescence as well as ITC measurements and were compared with that of the corresponding glycine-derived surfactant. The binding constant values clearly indicate a significant head-group effect on the BSA-surfactant interaction and the interaction is mainly hydrophobic in nature.

  7. Thrombogenic collagen-mimetic peptides: Self-assembly of triple helix-based fibrils driven by hydrophobic interactions.

    Science.gov (United States)

    Cejas, Mabel A; Kinney, William A; Chen, Cailin; Vinter, Jeremy G; Almond, Harold R; Balss, Karin M; Maryanoff, Cynthia A; Schmidt, Ute; Breslav, Michael; Mahan, Andrew; Lacy, Eilyn; Maryanoff, Bruce E

    2008-06-24

    Collagens are integral structural proteins in animal tissues and play key functional roles in cellular modulation. We sought to discover collagen model peptides (CMPs) that would form triple helices and self-assemble into supramolecular fibrils exhibiting collagen-like biological activity without preorganizing the peptide chains by covalent linkages. This challenging objective was accomplished by placing aromatic groups on the ends of a representative 30-mer CMP, (GPO)(10), as with l-phenylalanine and l-pentafluorophenylalanine in 32-mer 1a. Computational studies on homologous 29-mers 1a'-d' (one less GPO), as pairs of triple helices interacting head-to-tail, yielded stabilization energies in the order 1a' > 1b' > 1c' > 1d', supporting the hypothesis that hydrophobic aromatic groups can drive CMP self-assembly. Peptides 1a-d were studied comparatively relative to structural properties and ability to stimulate human platelets. Although each 32-mer formed stable triple helices (CD) spectroscopy, only 1a and 1b self-assembled into micrometer-scale fibrils. Light microscopy images for 1a depicted long collagen-like fibrils, whereas images for 1d did not. Atomic force microscopy topographical images indicated that 1a and 1b self-organize into microfibrillar species, whereas 1c and 1d do not. Peptides 1a and 1b induced the aggregation of human blood platelets with a potency similar to type I collagen, whereas 1c was much less effective, and 1d was inactive (EC(50) potency: 1a/1b > 1c > 1d). Thus, 1a and 1b spontaneously self-assemble into thrombogenic collagen-mimetic materials because of hydrophobic aromatic interactions provided by the special end-groups. These findings have important implications for the design of biofunctional CMPs.

  8. Rational design of viscosity reducing mutants of a monoclonal antibody: Hydrophobic versus electrostatic inter-molecular interactions

    Science.gov (United States)

    Nichols, Pilarin; Li, Li; Kumar, Sandeep; Buck, Patrick M; Singh, Satish K; Goswami, Sumit; Balthazor, Bryan; Conley, Tami R; Sek, David; Allen, Martin J

    2015-01-01

    High viscosity of monoclonal antibody formulations at concentrations ≥100 mg/mL can impede their development as products suitable for subcutaneous delivery. The effects of hydrophobic and electrostatic intermolecular interactions on the solution behavior of MAB 1, which becomes unacceptably viscous at high concentrations, was studied by testing 5 single point mutants. The mutations were designed to reduce viscosity by disrupting either an aggregation prone region (APR), which also participates in 2 hydrophobic surface patches, or a negatively charged surface patch in the variable region. The disruption of an APR that lies at the interface of light and heavy chain variable domains, VH and VL, via L45K mutation destabilized MAB 1 and abolished antigen binding. However, mutation at the preceding residue (V44K), which also lies in the same APR, increased apparent solubility and reduced viscosity of MAB 1 without sacrificing antigen binding or thermal stability. Neutralizing the negatively charged surface patch (E59Y) also increased apparent solubility and reduced viscosity of MAB 1, but charge reversal at the same position (E59K/R) caused destabilization, decreased solubility and led to difficulties in sample manipulation that precluded their viscosity measurements at high concentrations. Both V44K and E59Y mutations showed similar increase in apparent solubility. However, the viscosity profile of E59Y was considerably better than that of the V44K, providing evidence that inter-molecular interactions in MAB 1 are electrostatically driven. In conclusion, neutralizing negatively charged surface patches may be more beneficial toward reducing viscosity of highly concentrated antibody solutions than charge reversal or aggregation prone motif disruption. PMID:25559441

  9. Rational design of viscosity reducing mutants of a monoclonal antibody: hydrophobic versus electrostatic inter-molecular interactions.

    Science.gov (United States)

    Nichols, Pilarin; Li, Li; Kumar, Sandeep; Buck, Patrick M; Singh, Satish K; Goswami, Sumit; Balthazor, Bryan; Conley, Tami R; Sek, David; Allen, Martin J

    2015-01-01

    High viscosity of monoclonal antibody formulations at concentrations ≥100 mg/mL can impede their development as products suitable for subcutaneous delivery. The effects of hydrophobic and electrostatic intermolecular interactions on the solution behavior of MAB 1, which becomes unacceptably viscous at high concentrations, was studied by testing 5 single point mutants. The mutations were designed to reduce viscosity by disrupting either an aggregation prone region (APR), which also participates in 2 hydrophobic surface patches, or a negatively charged surface patch in the variable region. The disruption of an APR that lies at the interface of light and heavy chain variable domains, VH and VL, via L45K mutation destabilized MAB 1 and abolished antigen binding. However, mutation at the preceding residue (V44K), which also lies in the same APR, increased apparent solubility and reduced viscosity of MAB 1 without sacrificing antigen binding or thermal stability. Neutralizing the negatively charged surface patch (E59Y) also increased apparent solubility and reduced viscosity of MAB 1, but charge reversal at the same position (E59K/R) caused destabilization, decreased solubility and led to difficulties in sample manipulation that precluded their viscosity measurements at high concentrations. Both V44K and E59Y mutations showed similar increase in apparent solubility. However, the viscosity profile of E59Y was considerably better than that of the V44K, providing evidence that inter-molecular interactions in MAB 1 are electrostatically driven. In conclusion, neutralizing negatively charged surface patches may be more beneficial toward reducing viscosity of highly concentrated antibody solutions than charge reversal or aggregation prone motif disruption.

  10. A dock and coalesce mechanism driven by hydrophobic interactions governs Cdc42 binding with its effector protein ACK.

    Science.gov (United States)

    Tetley, George J N; Mott, Helen R; Cooley, R Neil; Owen, Darerca

    2017-07-07

    Cdc42 is a Rho-family small G protein that has been widely studied for its role in controlling the actin cytoskeleton and plays a part in several potentially oncogenic signaling networks. Similar to most other small G proteins, Cdc42 binds to many downstream effector proteins to elicit its cellular effects. These effector proteins all engage the same face of Cdc42, the conformation of which is governed by the activation state of the G protein. Previously, the importance of individual residues in conferring binding affinity has been explored for residues within Cdc42 for three of its Cdc42/Rac interactive binding (CRIB) effectors, activated Cdc42 kinase (ACK), p21-activated kinase (PAK), and Wiskott-Aldrich syndrome protein (WASP). Here, in a complementary study, we have used our structure of Cdc42 bound to ACK via an intrinsically disordered ACK region to guide an analysis of the Cdc42 interface on ACK, creating a panel of mutant proteins with which we can now describe the complete energetic landscape of the Cdc42-binding site on ACK. Our data suggest that the binding affinity of ACK relies on several conserved residues that are critical for stabilizing the quaternary structure. These residues are centered on the CRIB region, with the complete binding region anchored at each end by hydrophobic interactions. These findings suggest that ACK adopts a dock and coalesce binding mechanism with Cdc42. In contrast to other CRIB-family effectors and indeed other intrinsically disordered proteins, hydrophobic residues likely drive Cdc42-ACK binding. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  11. Nuclear import of cutaneous beta genus HPV8 E7 oncoprotein is mediated by hydrophobic interactions between its zinc-binding domain and FG nucleoporins

    Energy Technology Data Exchange (ETDEWEB)

    Onder, Zeynep; Moroianu, Junona, E-mail: moroianu@bc.edu

    2014-01-20

    We have previously discovered and characterized the nuclear import pathways for the E7 oncoproteins of mucosal alpha genus HPVs, type 16 and 11. Here we investigated the nuclear import of cutaneous beta genus HPV8 E7 protein using confocal microscopy after transfections of HeLa cells with EGFP-8E7 and mutant plasmids and nuclear import assays in digitonin-permeabilized HeLa cells. We determined that HPV8 E7 contains a nuclear localization signal (NLS) within its zinc-binding domain that mediates its nuclear import. Furthermore, we discovered that a mostly hydrophobic patch {sub 65}LRLFV{sub 69} within the zinc-binding domain is essential for the nuclear import and localization of HPV8 E7 via hydrophobic interactions with the FG nucleoporins Nup62 and Nup153. Substitution of the hydrophobic residues within the {sub 65}LRLFV{sub 69} patch to alanines, and not R66A mutation, disrupt the interactions between the 8E7 zinc-binding domain and Nup62 and Nup153 and consequently inhibit nuclear import of HPV8 E7. - Highlights: • HPV8 E7 has a cNLS within its zinc-binding domain that mediates its nuclear import. • Discovery of a hydrophobic patch that is critical for the nuclear import of HPV8 E7. • HPV8 E7 nuclear import is mediated by hydrophobic interactions with FG-Nups, Nup62 and Nup153.

  12. Surface modification of hydrophobic polymers for improvement of endothelial cell-surface interactions

    NARCIS (Netherlands)

    Dekker, A.; Reitsma, K.; Beugeling, T.; Bantjes, A.; Feijen, J.; Kirkpatrick, C.J.; Aken, van W.G.

    1992-01-01

    The aim of this study is to improve the interaction of endothelial cells with polymers used in vascular prostheses. Polytetrafluoroethylene (PTFE; Teflon) films were treated by means of nitrogen and oxygen plasmas. Depending on the plasma exposure time, modified PTFE surfaces showed water-contact an

  13. Specific ion effects on the hydrophobic interaction of benzene self-assembled monolayers

    DEFF Research Database (Denmark)

    Dobberschütz, Sören; Pedersen, Morten Rimmen; Hassenkam, Tue;

    2015-01-01

    interaction of benzene self-assembled monolayers. Using the jump to contact phenomenon of an atomic force microscope (AFM) tip as an indicator of attractive forces between the surfaces of a sample and the tip, we discovered lower frequencies in the snap in as well as narrower distributions for the snap...

  14. Utilizing an Automated Home-Built Surface Plasmon Resonance Apparatus to Investigate How Water Interacts with a Hydrophobic Surface

    Science.gov (United States)

    Poynor, Adele

    2011-03-01

    By definition hydrophobic substances hate water. Water placed on a hydrophobic surface will form a drop in order to minimize its contact area. What happens when water is forced into contact with a hydrophobic surface? One theory is that an ultra-thin low- density region forms near the surface. We have employed an automated home-built Surface Plasmon Resonance (SPR) apparatus to investigate this boundary.

  15. Solid-state structure of gelatin-mono epoxy terminated polydimethylsiloxane polymer: effect of electrostatic and hydrophobic interactions.

    Science.gov (United States)

    Xu, Jing; Xia, Yongmei; Qiao, Cong-De; Zhu, Weiyue; Wang, Yuexia; Li, Tian-Duo

    2014-11-01

    In this study, a hybrid synthetic gelatin-mono epoxy terminated polydimethylsiloxane polymer (PDMS-E grafted gelatin (PGG)) was successfully synthesized on a large scale. Supramolecular structure of gelatin, which was decided by the sophisticated inter- and intra-molecular interactions, significantly affected the self-assembly and phase behavior of PGG. Interestingly, the supramolecular organization of PGG could be tuned finely by negatively charged surfactants, such as sodium dodecyl sulfate (SDS) and sodium tetradecyl sulfonate (STSo), as revealed by high-resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), light microscopy (LM), and atomic force microscopy (AFM). SEM images exhibited the presence of spherical aggregates in PGG/SDS films while hexagonal array was observed in PGG/STSo films. The results of LM revealed that when PGG/STSo solution was dried, a successive structural transformation from spheres to hexagons, via sticks and butterfly-shaped aggregates as intermediates, was observed. However, the morphologies of the aggregates formed in PGG/SDS system did not exhibit any obvious change upon drying. Attenuated total reflection-Fourier transform infrared spectra combined with AFM observations indicated that the secondary structure and aggregation behavior of gelatin was modified with the change in the electrostatic and hydrophobic interactions, leading to the formation of diversified solid-state structures of PGG.

  16. Protein-surfactant interactions at hydrophobic interfaces studied with total internal reflection fluorescence correlation spectroscopy (TIR-FCS).

    Science.gov (United States)

    Sonesson, Andreas W; Blom, Hans; Hassler, Kai; Elofsson, Ulla M; Callisen, Thomas H; Widengren, Jerker; Brismar, Hjalmar

    2008-01-15

    The aim of this work was to study the dynamics of proteins near solid surfaces in the presence or absence of competing surfactants by means of total internal reflection fluorescence correlation spectroscopy (TIR-FCS). Two different proteins were studied, bovine serum albumin (BSA) and Thermomyces lanuginosus lipase (TLL). A nonionic/anionic (C12E6/LAS) surfactant composition was used to mimic a detergent formulation and the surfaces used were C18 terminated glass. It was found that with increasing surfactant concentrations the term in the autocorrelation function (ACF) representing surface binding decreased. This suggested that the proteins were competed off the hydrophobic surface by the surfactant. When fitting the measured ACF to a model for surface kinetics, it was seen that with raised C12E6/LAS concentration, the surface interaction rate increased for both proteins. Under these experimental conditions this meant that the time the protein was bound to the surface decreased. At 10 microM C12E6/LAS the surface interaction was not visible for BSA, whereas it was still distinguishable in the ACF for TLL. This indicated that TLL had a higher affinity than BSA for the C18 surface. The study showed that TIR-FCS provides a useful tool to quantify the surfactant effect on proteins adsorption.

  17. Multivalent host-guest interactions between ss-cyclodextrin self-assembled monolayers and poly (isobutene-alt-maleic acid)s modified with hydrophobic guest moeties

    NARCIS (Netherlands)

    Crespo biel, O.; Péter, M.; Bruinink, C.M.; Ravoo, B.J.; Reinhoudt, David; Huskens, Jurriaan

    2005-01-01

    Poly(isobutene-alt-maleic acid)s modified with p-tert-butylphenyl or adamantyl groups interact with ß-cyclodextrin self-assembled monolayers (ß-CD SAMs) by inclusion of the hydrophobic substituents in the B-cyclodextrin cavities. The adsorption was shown to be strong, specific, and irreversible.

  18. Interaction of cationic hydrophobic surfactants at negatively charged surfaces investigated by atomic force microscopy.

    Science.gov (United States)

    McNamee, Cathy E; Butt, Hans-Jürgen; Higashitani, Ko; Vakarelski, Ivan U; Kappl, Michael

    2009-10-06

    Atomic force microscopy was used to study the adsorption of the surfactant octadecyl trimethyl ammonium chloride (C18TAC) at a low concentration (0.03 mM) to negatively charged surfaces in water. Atomic force microscopy tips were functionalized with dimethyloctadecyl(3-tripropyl)ammonium chloride (C18TAC-si) or N-trimethoxysilylpropyl-N,N,N-trimethylammomium chloride (hydrophilpos-si) to facilitate imaging of the adsorbed surfactant without artifacts. Tapping mode images and force measurements revealed C18TAC patches, identified as partial surfactant bilayers or hemimicelles. The forces controlling the adsorption process of the C18TAC to a negatively charged surface were investigated by measuring the forces between a C18TAC-si or a hydrophilpos-si tip and a silica surface in the presence of varying concentrations of either NaCl or NaNO3. Screening of forces with an increasing NaCl concentration was observed for the C18TAC-si and hydrophilpos-si tips, proving an electrostatic contribution. Screening was also observed for the hydrophilpos-si tip in NaNO3, whereas a long-range attraction was observed for the C18TAC-si tip for all NaNO3 concentrations. These results indicate that screening of the forces for the C18TAC-si tip depended on the type and/or size of the anion, possibly due to a different probability of the anions to enter the silane layers. The interaction of C18TAC patches with C18TAC-si tips in the presence of NaCl and the interaction of the patches with hydrophilpos-si tips in either NaCl or NaNO3 were repulsive and independent of the number of force curves measured, indicating a stable, positively charged C18TAC patch. However, the forces measured between the patches and a C18TAC-si tip in NaNO3 depended on the number of force curves measured, indicating a change in patch structure induced by the first interaction.

  19. Effect of ligand structure of stationary phase of high per-formance hydrophobic interaction chromatography on re-naturation efficiency of GuHCl-denatured α-chymotrypsin

    Institute of Scientific and Technical Information of China (English)

    SHEN; Yehua; WANG; Haibo; BAI; Quan; GENG; Xindu

    2005-01-01

    The renaturation of the denatured α-chymotrypsin (α-Chy) with 1.7 mol · L-1 guanidine hydrochloride (GuHCI) by three kinds of stationary phase of high performance hydrophobic interaction chromatography (STHIC) with a comparable hydrophobicity but different ligand structures was investigated. The obtained result indicates that the ligand structures of the three STHIC contribute to the renaturation efficiency of α-Chy in the order of the end ligands PEG-600< phenyl group < tetrahydrofurfuryl alcohol (THFA).

  20. Interference of macroscopic superpositions

    CERN Document Server

    Vecchi, I

    2000-01-01

    We propose a simple experimental procedure based on the Elitzur-Vaidman scheme to implement a quantum nondemolition measurement testing the persistence of macroscopic superpositions. We conjecture that its implementation will reveal the persistence of superpositions of macroscopic objects in the absence of a direct act of observation.

  1. A new class of organogelators based on triphenylmethyl derivatives of primary alcohols: hydrophobic interactions alone can mediate gelation

    Directory of Open Access Journals (Sweden)

    Wangkhem P. Singh

    2017-01-01

    Full Text Available In the present work, we have explored the use of the triphenylmethyl group, a commonly used protecting group for primary alcohols as a gelling structural component in the design of molecular gelators. We synthesized a small library of triphenylmethyl derivatives of simple primary alcohols and studied their gelation properties in different solvents. Gelation efficiency for some of the derivatives was moderate to excellent with a minimum gelation concentration ranging between 0.5–4.0% w/v and a gel–sol transition temperature range of 31–75 °C. 1,8-Bis(trityloxyoctane, the ditrityl derivative of 1,8-octanediol was the most efficient organogelator. Detailed characterizations of the gel were carried out using scanning electron microscopy, FTIR spectroscopy, rheology and powder XRD techniques. This gel also showed a good absorption profile for a water soluble dye. Given the non-polar nature of this molecule, gel formation is likely to be mediated by hydrophobic interactions between the triphenylmethyl moieties and alkyl chains. Possible self-assembled packing arrangements in the gel state for 1,8-bis(trityloxyoctane and (hexadecyloxymethanetriyltribenzene are presented. Results from this study strongly indicate that triphenylmethyl group is a promising gelling structural unit which may be further exploited in the design of small molecule based gelators.

  2. Understanding the fouling of algogenic organic matter in microfiltration using membrane-foulant interaction energy analysis: effects of organic hydrophobicity.

    Science.gov (United States)

    Huang, Weiwei; Chu, Huaqiang; Dong, Bingzhi

    2014-10-01

    Fouling caused by algogenic organic matter (AOM) in membrane filtration is a critical problem in algae-rich waters, and understanding fouling mechanisms, particularly by identifying the predominant membrane foulants, could have significant effects on algal fouling prediction and pretreatment. In this work, the fouling behavior of Aphanizomenon flos-aquae (APF)- and Anabaena flos-aquae (ANF)-AOM fractions was analyzed using the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory. The results show that the interfacial energy of membranes and foulants could be used for AOM membrane fouling analysis. The attractive energy was highest between the membrane and the neutral hydrophilic fractions (N-HPI) on clean membrane surfaces, followed by the energy associated with the hydrophobic fractions (HPO) and the transphilic fractions (TPI) in both of the AOMs; on the other hand, the negatively charged hydrophilic organics (C-HPI) in the APF-AOM suffered from repulsive interactions when nearing the membrane surface, which was consistent with their initial filtration flux. After the formation of an initial fouling layer on the membrane surface, membrane fouling was controlled mainly by the cohesion free energy between the approaching foulants and the foulants on the fouled membranes. In addition, it was observed that the interfacial energy between foulants was the dominant factor controlling membrane fouling in AOM filtration. Finally, the interfacial energies between the N-HPI fractions had the greatest effect on both APF-AOM and ANF-AOM membrane fouling. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Optimization of non-linear gradient in hydrophobic interaction chromatography for the analytical characterization of antibody-drug conjugates.

    Science.gov (United States)

    Bobály, Balázs; Randazzo, Giuseppe Marco; Rudaz, Serge; Guillarme, Davy; Fekete, Szabolcs

    2017-01-20

    The goal of this work was to evaluate the potential of non-linear gradients in hydrophobic interaction chromatography (HIC), to improve the separation between the different homologous species (drug-to-antibody, DAR) of commercial antibody-drug conjugates (ADC). The selectivities between Brentuximab Vedotin species were measured using three different gradient profiles, namely linear, power function based and logarithmic ones. The logarithmic gradient provides the most equidistant retention distribution for the DAR species and offers the best overall separation of cysteine linked ADC in HIC. Another important advantage of the logarithmic gradient, is its peak focusing effect for the DAR0 species, which is particularly useful to improve the quantitation limit of DAR0. Finally, the logarithmic behavior of DAR species of ADC in HIC was modelled using two different approaches, based on i) the linear solvent strength theory (LSS) and two scouting linear gradients and ii) a new derived equation and two logarithmic scouting gradients. In both cases, the retention predictions were excellent and systematically below 3% compared to the experimental values. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. A new class of organogelators based on triphenylmethyl derivatives of primary alcohols: hydrophobic interactions alone can mediate gelation.

    Science.gov (United States)

    Singh, Wangkhem P; Singh, Rajkumar S

    2017-01-01

    In the present work, we have explored the use of the triphenylmethyl group, a commonly used protecting group for primary alcohols as a gelling structural component in the design of molecular gelators. We synthesized a small library of triphenylmethyl derivatives of simple primary alcohols and studied their gelation properties in different solvents. Gelation efficiency for some of the derivatives was moderate to excellent with a minimum gelation concentration ranging between 0.5-4.0% w/v and a gel-sol transition temperature range of 31-75 °C. 1,8-Bis(trityloxy)octane, the ditrityl derivative of 1,8-octanediol was the most efficient organogelator. Detailed characterizations of the gel were carried out using scanning electron microscopy, FTIR spectroscopy, rheology and powder XRD techniques. This gel also showed a good absorption profile for a water soluble dye. Given the non-polar nature of this molecule, gel formation is likely to be mediated by hydrophobic interactions between the triphenylmethyl moieties and alkyl chains. Possible self-assembled packing arrangements in the gel state for 1,8-bis(trityloxy)octane and (hexadecyloxymethanetriyl)tribenzene are presented. Results from this study strongly indicate that triphenylmethyl group is a promising gelling structural unit which may be further exploited in the design of small molecule based gelators.

  5. A new class of organogelators based on triphenylmethyl derivatives of primary alcohols: hydrophobic interactions alone can mediate gelation

    Science.gov (United States)

    Singh, Wangkhem P

    2017-01-01

    In the present work, we have explored the use of the triphenylmethyl group, a commonly used protecting group for primary alcohols as a gelling structural component in the design of molecular gelators. We synthesized a small library of triphenylmethyl derivatives of simple primary alcohols and studied their gelation properties in different solvents. Gelation efficiency for some of the derivatives was moderate to excellent with a minimum gelation concentration ranging between 0.5–4.0% w/v and a gel–sol transition temperature range of 31–75 °C. 1,8-Bis(trityloxy)octane, the ditrityl derivative of 1,8-octanediol was the most efficient organogelator. Detailed characterizations of the gel were carried out using scanning electron microscopy, FTIR spectroscopy, rheology and powder XRD techniques. This gel also showed a good absorption profile for a water soluble dye. Given the non-polar nature of this molecule, gel formation is likely to be mediated by hydrophobic interactions between the triphenylmethyl moieties and alkyl chains. Possible self-assembled packing arrangements in the gel state for 1,8-bis(trityloxy)octane and (hexadecyloxymethanetriyl)tribenzene are presented. Results from this study strongly indicate that triphenylmethyl group is a promising gelling structural unit which may be further exploited in the design of small molecule based gelators. PMID:28228855

  6. Sequence-specific purification of DNA oligomers in hydrophobic interaction chromatography using peptide nucleic acid amphiphiles: extended dynamic range.

    Science.gov (United States)

    Savard, Jeffrey M; Schneider, James W

    2007-06-01

    We present improvements on a previously reported method (Vernille JP, Schneider JW. 2004. Biotechnol Prog 20(6):1776-1782) to purify DNA oligomers by attachment of peptide nucleic acid amphiphiles (PNAA) to particular sequences on the oligomers, followed by their separation from unbound oligomers using hydrophobic interaction chromatography (HIC). Use of alkyl-modified HIC media (butyl and octyl sepharose) over phenyl-modified media (phenyl sepharose) reduced the elution time of unbound DNA while not affecting the elution time of the PNAA/DNA complex. Modifying the alkane tail length for PNAA from C(12) to C(18) increased slightly the retention of PNAA/DNA duplexes. By combining these two refinements, we show that sequence-specific purifications of DNA oligomers 60 bases in length or more can be achieved with high resolution, even when the PNAA alkane is attached to the center of the target strand. The insensitivity of the PNAA/DNA duplex binding to choice of HIC media appears to be due to a surface-induced aggregation phenomenon that does not occur in the case of untagged DNA. We also report on the use of batch HIC as an adequate predictor of elution profiles in linear gradient HIC, and its potential to considerably reduce purification times by applying step gradients. (c) 2006 Wiley Periodicals, Inc.

  7. Influence of binding pH and protein solubility on the dynamic binding capacity in hydrophobic interaction chromatography.

    Science.gov (United States)

    Baumann, Pascal; Baumgartner, Kai; Hubbuch, Jürgen

    2015-05-29

    Hydrophobic interaction chromatography (HIC) is one of the most frequently used purification methods in biopharmaceutical industry. A major drawback of HIC, however, is the rather low dynamic binding capacity (DBC) obtained when compared to e.g. ion exchange chromatography (IEX). The typical purification procedure for HIC includes binding at neutral pH, independently of the proteins nature and isoelectric point. Most approaches to process intensification are based on resin and salt screenings. In this paper a combination of protein solubility data and varying binding pH leads to a clear enhancement of dynamic binding capacity. This is shown for three proteins of acidic, neutral, and alkaline isoelectric points. High-throughput solubility screenings as well as miniaturized and parallelized breakthrough curves on Media Scout RoboColumns (Atoll, Germany) were conducted at pH 3-10 on a fully automated robotic workstation. The screening results show a correlation between the DBC and the operational pH, the protein's isoelectric point and the overall solubility. Also, an inverse relationship of DBC in HIC and the binding kinetics was observed. By changing the operational pH, the DBC could be increased up to 30% compared to the standard purification procedure performed at neutral pH. As structural changes of the protein are reported during HIC processes, the applied samples and the elution fractions were proven not to be irreversibly unfolded. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Cyclotides insert into lipid bilayers to form membrane pores and destabilize the membrane through hydrophobic and phosphoethanolamine-specific interactions.

    Science.gov (United States)

    Wang, Conan K; Wacklin, Hanna P; Craik, David J

    2012-12-21

    Cyclotides are a family of plant-derived circular proteins with potential therapeutic applications arising from their remarkable stability, broad sequence diversity, and range of bioactivities. Their membrane-binding activity is believed to be a critical component of their mechanism of action. Using isothermal titration calorimetry, we studied the binding of the prototypical cyclotides kalata B1 and kalata B2 (and various mutants) to dodecylphosphocholine micelles and phosphoethanolamine-containing lipid bilayers. Although binding is predominantly an entropy-driven process, suggesting that hydrophobic forces contribute significantly to cyclotide-lipid complex formation, specific binding to the phosphoethanolamine-lipid headgroup is also required, which is evident from the enthalpic changes in the free energy of binding. In addition, using a combination of dissipative quartz crystal microbalance measurements and neutron reflectometry, we elucidated the process by which cyclotides interact with bilayer membranes. Initially, a small number of cyclotides bind to the membrane surface and then insert first into the outer membrane leaflet followed by penetration through the membrane and pore formation. At higher concentrations of cyclotides, destabilization of membranes occurs. Our results provide significant mechanistic insight into how cyclotides exert their bioactivities.

  9. Pentamidine binds to tRNA through non-specific hydrophobic interactions and inhibits aminoacylation and translation.

    Science.gov (United States)

    Sun, Tao; Zhang, Yi

    2008-03-01

    The selective and potent inhibition of mitochondrial translation in Saccharomyces cerevisiae by pentamidine suggests a novel antimicrobial action for this drug. Electrophoresis mobility shift assay, T1 ribonuclease footprinting, hydroxyl radical footprinting and isothermal titration calorimetry collectively demonstrated that pentamidine non-specifically binds to two distinct classes of sites on tRNA. The binding was driven by favorable entropy changes indicative of a large hydrophobic interaction, suggesting that the aromatic rings of pentamidine are inserted into the stacked base pairs of tRNA helices. Pentamidine binding disrupts the tRNA secondary structure and masks the anticodon loop in the tertiary structure. Consistently, we showed that pentamidine specifically inhibits tRNA aminoacylation but not the cognate amino acid adenylation. Pentamidine inhibited protein translation in vitro with an EC(50) equivalent to that binds to tRNA and inhibits tRNA aminoacylation in vitro, but drastically higher than that inhibits translation in vivo, supporting the established notion that the antimicrobial activity of pentamidine is largely due to its selective accumulation by the pathogen rather than by the host cell. Therefore, interrupting tRNA aminoacylation by the entropy-driven non-specific binding is an important mechanism of pentamidine in inhibiting protein translation, providing new insights into the development of antimicrobial drugs.

  10. The influence of cosolvents on hydrophilic and hydrophobic interactions. Calorimetric studies of parent and alkylated cyclomaltooligosaccharides in concentrated aqueous solutions of ethanol or urea.

    Science.gov (United States)

    Castronuovo, Giuseppina; Niccoli, Marcella

    2008-11-03

    Heats of dilution in water and in aqueous 7 mol kg(-1) urea and 3 mol kg(-1) ethanol of binary solutions containing cyclomaltohexaose, cyclomaltoheptaose, cyclomaltooctaose, 2-hydroxypropyl-cyclomaltohexaose (HPαCD), 2-hydroxypropyl-cyclomaltoheptaose (HPβCD), methyl-cyclomaltohexaose (MeαCD), methyl-cyclomaltoheptaose (MeβCD) and 2-hydroxypropyl-cyclomaltooctaose (HPγCD) have been determined at 298.15K by flow microcalorimetry. The purpose of this study is to gain information about the influence of urea and ethanol, which have different effects on water structure, on hydrophilic and hydrophobic interactions. The pairwise interaction coefficients of the virial expansion of the excess enthalpies were evaluated and compared to those previously obtained for binary solutions of cyclomaltohexaose and cyclomaltoheptaose. The particular behaviour of cyclomaltooligosaccharides in water is put in evidence with respect to that shown by simple oligosaccharides. The values of the interaction coefficients greatly change in dependence of the solvent medium. They are negative in water for unsubstituted cyclomaltooligosaccharides, and positive for the alkyl-substituted ones, thus marking the major role of the hydrophobic interactions. In concentrated aqueous ethanol, coefficients are negative, while they are positive in concentrated aqueous urea. Urea solvates the hydroxyl group provoking the attenuation of hydrophilic and hydrophobic interactions. Instead, the presence of the cosolvent ethanol, which lowers the relative permittivity of the medium, enhances the strength of hydrophilic interactions.

  11. A control on hydrophobic and hydrophilic interactions between HEWL and metal Schiff-base complexes comprising of different metal ions and ligands

    Energy Technology Data Exchange (ETDEWEB)

    Koley Seth, Banabithi; Ray, Aurkie; Basu, Samita, E-mail: samita.basu@saha.ac.in

    2015-05-15

    The structural effects of different copper(II) and nickel(II) Schiff base complexes on hen egg white lysozyme (HEWL) have been investigated through steady state and time resolved absorption and fluorescence, and circular dichroism spectroscopy. The Schiff base ligands with N{sub 4} donor atoms show both hydrophobic and hydrophilic interactions, however hydrophilic interaction prevails with ligands having N{sub 2}O{sub 2} donor atoms. Variation of metal ions from Cu{sup 2+} to Ni{sup 2+} with each type of Schiff base ligand increases the probability of hydrophilic over hydrophobic interactions, which supports their significance in regulating the binding affinity between HEWL and metal complexes. On photo-excitation the complexes comprising of Cu{sup 2+} ion instead of Ni{sup 2+} ion and ligands with N{sub 4} donor system rather than N{sub 2}O{sub 2} donor system, increases the probability of intersystem crossing to populate the corresponding triplet state as observed from laser flash photolysis study. The better binding affinity of nickel complexes with different selectivities compared to copper complexes towards HEWL emphasizes the potentiality of less explored nickel complexes in drug–protein interactions. - Highlights: • Ni{sup II} and Cu{sup II} -Schiff base complexes bind hen egg white lysozyme spontaneously. • Both hydrophobic and hydrophilic interactions are effective for N{sub 4} ligands. • For N{sub 2}O{sub 2} ligands the hydrophilic is predominant over hydrophobic interaction. • Binding affinity and selectivity of Ni{sup II}-complexes are better than Cu{sup II}-complexes. • Replacement of Cu{sup 2+} by Ni{sup 2+} in a ligand enhances chance of hydrophilic interaction.

  12. Sequestration of hydrophobic organic contaminants by geosorbents

    Science.gov (United States)

    Luthy, Richard G.; Aiken, George R.; Brusseau, Mark L.; Cunningham, Scott D.; Gschwend, Philip M.; Pignatello, Joseph J.; Reinhard, Martin; Traina, Samuel J.; Weber, Walter J.; Westall, John C.

    1997-01-01

    The chemical interactions of hydrophobic organic contaminants (HOCs) with soils and sediments (geosorbents) may result in strong binding and slow subsequent release rates that significantly affect remediation rates and endpoints. The underlying physical and chemical phenomena potentially responsible for this apparent sequestration of HOCs by geosorbents are not well understood. This challenges our concepts for assessing exposure and toxicity and for setting environmental quality criteria. Currently there are no direct observational data revealing the molecular-scale locations in which nonpolar organic compounds accumulate when associated with natural soils or sediments. Hence macroscopic observations are used to make inferences about sorption mechanisms and the chemical factors affecting the sequestration of HOCs by geosorbents. Recent observations suggest that HOC interactions with geosorbents comprise different inorganic and organic surfaces and matrices, and distinctions may be drawn along these lines, particularly with regard to the roles of inorganic micropores, natural sorbent organic matter components, combustion residue particulate carbon, and spilled organic liquids. Certain manipulations of sorbates or sorbent media may help reveal sorption mechanisms, but mixed sorption phenomena complicate the interpretation of macroscopic data regarding diffusion of HOCs into and out of different matrices and the hysteretic sorption and aging effects commonly observed for geosorbents. Analytical characterizations at the microscale, and mechanistic models derived therefrom, are needed to advance scientific knowledge of HOC sequestration, release, and environmental risk.

  13. The Role of Hydrophobicity and Surface Receptors at Hyphae of Lyophyllum sp. Strain Karsten in the Interaction with Burkholderia terrae BS001 – Implications for Interactions in Soil

    Science.gov (United States)

    Vila, Taissa; Nazir, Rashid; Rozental, Sonia; dos Santos, Giulia M. P.; Calixto, Renata O. R.; Barreto-Bergter, Eliana; Wick, Lukas Y.; van Elsas, Jan Dirk

    2016-01-01

    The soil bacterium Burkholderia terrae strain BS001 can interact with varying soil fungi, using mechanisms that range from the utilization of carbon/energy sources such as glycerol to the ability to reach novel territories in soil via co-migration with growing fungal mycelia. Here, we investigate the intrinsic properties of the B. terrae BS001 interaction with the basidiomycetous soil fungus Lyophyllum sp. strain Karsten. In some experiments, the ascomycetous Trichoderma asperellum 302 was also used. The hyphae of Lyophyllum sp. strain Karsten were largely hydrophilic on water-containing media versus hydrophobic when aerial, as evidenced by contact angle analyses (CA). Co-migration of B. terrae strain BS001 cells with the hyphae of the two fungi occurred preferentially along the - presumably hydrophilic - soil-dwelling hyphae, whereas aerial hyphae did not allow efficient migration, due to reduced thickness of their surrounding mucous films. Moreover, the cell numbers over the length of the hyphae in soil showed an uneven distribution, i.e., the CFU numbers increased from minima at the inoculation point to maximal numbers in the middle of the extended hyphae, then decreasing toward the terminal side. Microscopic analyses of the strain BS001 associations with the Lyophyllum sp. strain Karsten hyphae in the microcosms confirmed the presence of B. terrae BS001 cells on the mucous matter that was present at the hyphal surfaces of the fungi used. Cell agglomerates were found to accumulate at defined sites on the hyphal surfaces, which were coined ‘fungal-interactive’ hot spots. Evidence was further obtained for the contention that receptors for a physical bacterium-fungus interaction occur at the Lyophyllum sp. strain Karsten hyphal surface, in which the specific glycosphingolipid ceramide monohexoside (CMH) plays an important role. Thus, bacterial adherence may be mediated by heterogeneously distributed fungal-specific receptors, implying the CMH moieties. This

  14. The role of hydrophobicity and surface receptors at hyphae of Lyophyllum sp strain Karsten in the interaction with Burkholderia terrae BS001 – implications for interactions in soil.

    Directory of Open Access Journals (Sweden)

    Taissa Vieira Machado Vila

    2016-10-01

    Full Text Available The soil bacterium Burkholderia terrae strain BS001 can interact with varying soil fungi, using mechanisms that range from the utilization of carbon/energy sources such as glycerol to the ability to reach novel territories in soil via co-migration with growing fungal mycelia. Here, we investigate the intrinsic properties of the B. terrae BS001 interaction with the basidiomycetous soil fungus Lyophyllum sp. strain Karsten. In some experiments, the ascomycetous Trichoderma asperellum 302 was also used. The hyphae of Lyophyllum sp. strain Karsten were largely hydrophilic on water-containing media versus hydrophobic when aerial, as evidenced by contact angle analyses (CA. Co-migration of B. terrae strain BS001 cells with the hyphae of the two fungi occurred preferentially along the - presumably hydrophilic - soil-dwelling hyphae, whereas aerial hyphae did not allow efficient migration, due to reduced thickness of their surrounding mucous films. Moreover, the cell numbers over the length of the hyphae in soil showed an uneven distribution, i.e. the CFU numbers increased from minima at the inoculation point to maximal numbers in the middle of the extended hyphae, then decreasing towards the terminal side. Microscopic analyses of the strain BS001 associations with the Lyophyllum sp. strain Karsten hyphae in the microcosms confirmed the presence of B. terrae BS001 cells on the mucous matter that was present at the hyphal surfaces of the fungi used. Cell agglomerates were found to accumulate at defined sites on the hyphal surfaces, which were coined ‘fungal-interactive’ hot spots. Evidence was further obtained for the contention that receptors for a physical bacterium-fungus interaction occur at the Lyophyllum sp. strain Karsten hyphal surface, in which the specific glycosphingolipid ceramide mono hexoside (CMH plays an important role. Thus, bacterial adherence may be mediated by heterogeneously-distributed fungal-specific receptors, implying the CMH

  15. Scaled Particle Theory and the Length-scales Involved in Hydrophobic Hydration of Aqueous Biomolecular Assemblies

    CERN Document Server

    Ashbaugh, H S; Ashbaugh, Henry S.; Pratt, Lawrence R.

    2003-01-01

    Hydrophobic hydration plays a crucial role in self-assembly processes over multiple-length scales, from the microscopic origins of inert gas solubility in water, to the mesoscopic organization of proteins and surfactant structures, to macroscopic phase separation. Many theoretical studies focus on the molecularly detailed interactions between oil and water, but the extrapolation of molecular-scale models to larger length scale hydration phenomena is sometimes not warranted. We revisit the scaled particle theory proposed thirty years ago by Stillinger, adopt a practical generalization, and consider the implications for hydrophobic hydration in light of our current understanding. The generalization is based upon identifying a molecular length, implicit in previous applications of scaled particle models, that provides an effective boundary radius for joining microscopic and macroscopic descriptions. We demonstrate that the generalized theory correctly reproduces many of the anomalous thermodynamic properties of ...

  16. Phase diagram and structures in mixtures of poly(styrenesulfonate anion) and alkyltrimethylammonium cations in water: significance of specific hydrophobic interaction.

    Science.gov (United States)

    Sitar, Simona; Goderis, Bart; Hansson, Per; Kogej, Ksenija

    2012-04-19

    Mixtures of polyelectrolytes and oppositely charged surfactants show very rich phase behavior that is influenced by surfactant-ion and polyion properties and by water content. A general feature is associative phase separation as a result of strong electrostatic interactions, whereas the effect of eventual more specific interactions (e.g., hydrophobic) has not been thoroughly investigated. In this paper, we report a detailed study on phase behavior and structures in poly(styrenesulfonate anion) (PSS(-))-cetyltrimethylammonium cation (CTA(+))-water mixtures that are characterized by a hydrophobic interaction between the styrene groups of PSS(-) and the micelle interior. Structures of various phases were determined by small-angle X-ray scattering, and results indicated the presence of a disordered micellar and an ordered hexagonal phase; no cubic phase was found. The general conclusion is that the highlighted hydrophobic interaction promotes dissolution of CTAPSS when the polyion salt is added and provides further stabilization of the dense phase when the surfactant salt is added.

  17. Semi-automated hydrophobic interaction chromatography column scouting used in the two-step purification of recombinant green fluorescent protein.

    Science.gov (United States)

    Stone, Orrin J; Biette, Kelly M; Murphy, Patrick J M

    2014-01-01

    Hydrophobic interaction chromatography (HIC) most commonly requires experimental determination (i.e., scouting) in order to select an optimal chromatographic medium for purifying a given target protein. Neither a two-step purification of untagged green fluorescent protein (GFP) from crude bacterial lysate using sequential HIC and size exclusion chromatography (SEC), nor HIC column scouting elution profiles of GFP, have been previously reported. Bacterial lysate expressing recombinant GFP was sequentially adsorbed to commercially available HIC columns containing butyl, octyl, and phenyl-based HIC ligands coupled to matrices of varying bead size. The lysate was fractionated using a linear ammonium phosphate salt gradient at constant pH. Collected HIC eluate fractions containing retained GFP were then pooled and further purified using high-resolution preparative SEC. Significant differences in presumptive GFP elution profiles were observed using in-line absorption spectrophotometry (A395) and post-run fluorimetry. SDS-PAGE and western blot demonstrated that fluorometric detection was the more accurate indicator of GFP elution in both HIC and SEC purification steps. Comparison of composite HIC column scouting data indicated that a phenyl ligand coupled to a 34 µm matrix produced the highest degree of target protein capture and separation. Conducting two-step protein purification using the preferred HIC medium followed by SEC resulted in a final, concentrated product with >98% protein purity. In-line absorbance spectrophotometry was not as precise of an indicator of GFP elution as post-run fluorimetry. These findings demonstrate the importance of utilizing a combination of detection methods when evaluating purification strategies. GFP is a well-characterized model protein, used heavily in educational settings and by researchers with limited protein purification experience, and the data and strategies presented here may aid in development other of HIC-compatible protein

  18. Semi-automated hydrophobic interaction chromatography column scouting used in the two-step purification of recombinant green fluorescent protein.

    Directory of Open Access Journals (Sweden)

    Orrin J Stone

    Full Text Available Hydrophobic interaction chromatography (HIC most commonly requires experimental determination (i.e., scouting in order to select an optimal chromatographic medium for purifying a given target protein. Neither a two-step purification of untagged green fluorescent protein (GFP from crude bacterial lysate using sequential HIC and size exclusion chromatography (SEC, nor HIC column scouting elution profiles of GFP, have been previously reported.Bacterial lysate expressing recombinant GFP was sequentially adsorbed to commercially available HIC columns containing butyl, octyl, and phenyl-based HIC ligands coupled to matrices of varying bead size. The lysate was fractionated using a linear ammonium phosphate salt gradient at constant pH. Collected HIC eluate fractions containing retained GFP were then pooled and further purified using high-resolution preparative SEC. Significant differences in presumptive GFP elution profiles were observed using in-line absorption spectrophotometry (A395 and post-run fluorimetry. SDS-PAGE and western blot demonstrated that fluorometric detection was the more accurate indicator of GFP elution in both HIC and SEC purification steps. Comparison of composite HIC column scouting data indicated that a phenyl ligand coupled to a 34 µm matrix produced the highest degree of target protein capture and separation.Conducting two-step protein purification using the preferred HIC medium followed by SEC resulted in a final, concentrated product with >98% protein purity. In-line absorbance spectrophotometry was not as precise of an indicator of GFP elution as post-run fluorimetry. These findings demonstrate the importance of utilizing a combination of detection methods when evaluating purification strategies. GFP is a well-characterized model protein, used heavily in educational settings and by researchers with limited protein purification experience, and the data and strategies presented here may aid in development other of HIC

  19. Biophysical insights into the intercalative interaction of surfactant cobalt(III) complexes of certain diimine ligands bound to yeast tRNA: Effects of hydrophobicity

    Science.gov (United States)

    Nagaraj, Karuppiah; Sakthinathan, Subramanian; Arunachalam, Sankaralingam

    2015-08-01

    The interaction of two surfactant cobalt(III) complexes, cis-[Co(ip)2(DA)2](ClO4)3 1 and cis-[Co(dpq)2(DA)2](ClO4)3 2 where ip = imidazo[4,5-f][1,10]phenanthroline and dpq = dipyrido[3,2-d:2‧-3‧-f]quinoxaline with yeast tRNA have been explored by using electronic absorption, competitive binding, electrochemical studies and viscosity measurements. The results suggest that these complexes can bind to tRNA by intercalation. The presence of hydrophobic diimine ligand and the long aliphatic double chains of these complexes facilitate its intercalative interaction with the hydrophobic interior of the tRNA. The extent of tRNA binding of complex 2 has greater affinity than that of complex containing imidazo[4,5-f][1,10]phenanthroline ligands.

  20. Biophysical insights into the intercalative interaction of surfactant cobalt(III) complexes of certain diimine ligands bound to yeast tRNA: Effects of hydrophobicity.

    Science.gov (United States)

    Nagaraj, Karuppiah; Sakthinathan, Subramanian; Arunachalam, Sankaralingam

    2015-08-01

    The interaction of two surfactant cobalt(III) complexes, cis-[Co(ip)₂(DA)₂](ClO₄)₃ 1 and cis-[Co(dpq)₂(DA)₂](ClO₄)₃ 2 where ip=imidazo[4,5-f][1,10]phenanthroline and dpq=dipyrido[3,2-d:2'-3'-f]quinoxaline with yeast tRNA have been explored by using electronic absorption, competitive binding, electrochemical studies and viscosity measurements. The results suggest that these complexes can bind to tRNA by intercalation. The presence of hydrophobic diimine ligand and the long aliphatic double chains of these complexes facilitate its intercalative interaction with the hydrophobic interior of the tRNA. The extent of tRNA binding of complex 2 has greater affinity than that of complex containing imidazo[4,5-f][1,10]phenanthroline ligands.

  1. Are the interactions between recombinant prion proteins and polymeric surfaces related to the hydrophilic/hydrophobic balance?

    Science.gov (United States)

    Vrlinic, Tjasa; Debarnot, Dominique; Legeay, Gilbert; Coudreuse, Arnaud; El Moualij, Benaissa; Zorzi, Willy; Perret-Liaudet, Armand; Quadrio, Isabelle; Mozetic, Miran; Poncin-Epaillard, Fabienne

    2012-06-01

    New non-fouling tubes are developed and their influence on the adhesion of neuroproteins is studied. Recombinant prion proteins are considered as a single component representative of hydrophobic proteins. Samples are stored for 24 h at 4 °C in tubes coated with two different coatings: poly(N-isopropylacrylamide) as a hydrophilic surface and a plasma-fluorinated coating as a hydrophobic one. The protein adhesion is monitored by ELISA tests, XPS and confocal microscopy. It appears that the highest recovery of recombinant prion protein in the liquid phase is obtained with the hydrophilic surface while the hydrophobic character of the storage tube induces an important amount of biological loss. However, the recovery is not complete even for tubes coated with poly(N-isopropylacrylamide).

  2. Hydrophobic interactions between polymeric carrier and palmitic acid-conjugated siRNA improve PEGylated polyplex stability and enhance in vivo pharmacokinetics and tumor gene silencing.

    Science.gov (United States)

    Sarett, Samantha M; Werfel, Thomas A; Chandra, Irene; Jackson, Meredith A; Kavanaugh, Taylor E; Hattaway, Madison E; Giorgio, Todd D; Duvall, Craig L

    2016-08-01

    Formation of stable, long-circulating siRNA polyplexes is a significant challenge in translation of intravenously-delivered, polymeric RNAi cancer therapies. Here, we report that siRNA hydrophobization through conjugation to palmitic acid (siPA) improves stability, in vivo pharmacokinetics, and tumor gene silencing of PEGylated nanopolyplexes (siPA-NPs) with balanced cationic and hydrophobic content in the core relative to the analogous polyplexes formed with unmodified siRNA, si-NPs. Hydrophobized siPA loaded into the NPs at a lower charge ratio (N(+):P(-)) relative to unmodified siRNA, and siPA-NPs had superior resistance to siRNA cargo unpackaging in comparison to si-NPs upon exposure to the competing polyanion heparin and serum. In vitro, siPA-NPs increased uptake in MDA-MB-231 breast cancer cells (100% positive cells vs. 60% positive cells) but exhibited equivalent silencing of the model gene luciferase relative to si-NPs. In vivo in a murine model, the circulation half-life of intravenously-injected siPA-NPs was double that of si-NPs, resulting in a >2-fold increase in siRNA biodistribution to orthotopic MDA-MB-231 mammary tumors. The increased circulation half-life of siPA-NPs was dependent upon the hydrophobic interactions of the siRNA and the NP core component and not just siRNA hydrophobization, as siPA did not contribute to improved circulation time relative to unmodified siRNA when delivered using polyplexes with a fully cationic core. Intravenous delivery of siPA-NPs also achieved significant silencing of the model gene luciferase in vivo (∼40% at 24 h after one treatment and ∼60% at 48 h after two treatments) in the murine MDA-MB-231 tumor model, while si-NPs only produced a significant silencing effect after two treatments. These data suggest that stabilization of PEGylated siRNA polyplexes through a combination of hydrophobic and electrostatic interactions between siRNA cargo and the polymeric carrier improves in vivo pharmacokinetics and

  3. Hydrophobic encapsulation of hydrocarbon gases.

    Science.gov (United States)

    Leontiev, Alexander V; Saleh, Anas W; Rudkevich, Dmitry M

    2007-04-26

    [reaction: see text] Encapsulation data for hydrophobic hydrocarbon gases within a water-soluble hemicarcerand in aqueous solution are reported. It is concluded that hydrophobic interactions serve as the primary driving force for the encapsulation, which can be used for the design of gas-separating polymers with intrinsic inner cavities.

  4. Macroscopic quantum resonators (MAQRO)

    CERN Document Server

    Kaltenbaek, Rainer; Kiesel, Nikolai; Romero-Isart, Oriol; Johann, Ulrich; Aspelmeyer, Markus

    2012-01-01

    Quantum physics challenges our understanding of the nature of physical reality and of space-time and suggests the necessity of radical revisions of their underlying concepts. Experimental tests of quantum phenomena involving massive macroscopic objects would provide novel insights into these fundamental questions. Making use of the unique environment provided by space, MAQRO aims at investigating this largely unexplored realm of macroscopic quantum physics. MAQRO has originally been proposed as a medium-sized fundamental-science space mission for the 2010 call of Cosmic Vision. MAQRO unites two experiments: DECIDE (DECoherence In Double-Slit Experiments) and CASE (Comparative Acceleration Sensing Experiment). The main scientific objective of MAQRO, which is addressed by the experiment DECIDE, is to test the predictions of quantum theory for quantum superpositions of macroscopic objects containing more than 10e8 atoms. Under these conditions, deviations due to various suggested alternative models to quantum th...

  5. Analysis of the macroscopic mechanisms produced by rotor/stator interactions in turbomachinery; Analyse des mecanismes macroscopiques produits par les interactions rotot/stator dans les turbomachines

    Energy Technology Data Exchange (ETDEWEB)

    Callot, St.

    2002-01-15

    Unsteady phenomena produced by the relative motion between fixed and moving rows in turbomachinery is characterized by different scales in space and time. From the numerical point of view, taking into account those effects requires new models. The purpose of this work is a better understanding of the unsteady mechanisms in a multistage turbomachinery. In order to cast of any restricting hypothesis over the spatial periodicities, numerical simulations are operated over the whole circumference of each row. In the single stage case, it is shown that the unsteady flow presents a phase-lagged periodic condition which may be described by the double Fourier decomposition proposed by Tyler and Sofrin. The spatial modes precise the interaction between rows and a comparison is made with the Adamczyk's decomposition. The numerical simulation of a one and a half stage brings an extension of the analysis of the interactions in a multistage machine. (author)

  6. New insights into the interactions between cork chemical components and pesticides. The contribution of π-π interactions, hydrogen bonding and hydrophobic effect.

    Science.gov (United States)

    Olivella, M À; Bazzicalupi, C; Bianchi, A; Fiol, N; Villaescusa, I

    2015-01-01

    The role of chemical components of cork in the sorption of several pesticides has been investigated. For this purpose raw cork and three cork extracted fractions (i.e. cork free of aliphatic extractives, cork free of all extractives and cork free of all extractives and suberin) were used as sorbent of three ionic pesticides (propazine, 2,4-dichlorophenoxy acetic acid (2,4-D) and alachlor) and five non-ionic pesticides (chlorpyrifos, isoproturon, metamitron, methomyl and oxamyl) with a logKow within the range -0.47 to 4.92. The effect of cations on the ionic pesticides, propazine and 2,4-D sorption was also analyzed. Results indicated that the highest yields were obtained for chlorpyrifos and alachlor sorption onto raw cork (>55%). After removal of aliphatic extractives sorption of all pesticides increased that ranged from 3% for propazine to 31% for alachlor. In contrast, removal of phenolic extractives caused a sorption decrease. Low sorption yields were obtained for hydrophobic pesticides such as metamitron, oxamyl and methomyl (cork fractions and extremely low when using raw cork (cork toward aromatic pesticides. Results presented in this paper gain insights into the cork affinities for pesticides and the interactions involved in the sorption process and also enables to envisage sorption affinity of cork for other organic pollutants.

  7. Defining process design space for a hydrophobic interaction chromatography (HIC) purification step: application of quality by design (QbD) principles.

    Science.gov (United States)

    Jiang, Canping; Flansburg, Lisa; Ghose, Sanchayita; Jorjorian, Paul; Shukla, Abhinav A

    2010-12-15

    The concept of design space has been taking root under the quality by design paradigm as a foundation of in-process control strategies for biopharmaceutical manufacturing processes. This paper outlines the development of a design space for a hydrophobic interaction chromatography (HIC) process step. The design space included the impact of raw material lot-to-lot variability and variations in the feed stream from cell culture. A failure modes and effects analysis was employed as the basis for the process characterization exercise. During mapping of the process design space, the multi-dimensional combination of operational variables were studied to quantify the impact on process performance in terms of yield and product quality. Variability in resin hydrophobicity was found to have a significant influence on step yield and high-molecular weight aggregate clearance through the HIC step. A robust operating window was identified for this process step that enabled a higher step yield while ensuring acceptable product quality.

  8. Hydrophobic Interactions Are a Key to MDM2 Inhibition by Polyphenols as Revealed by Molecular Dynamics Simulations and MM/PBSA Free Energy Calculations.

    Science.gov (United States)

    Verma, Sharad; Grover, Sonam; Tyagi, Chetna; Goyal, Sukriti; Jamal, Salma; Singh, Aditi; Grover, Abhinav

    2016-01-01

    p53, a tumor suppressor protein, has been proven to regulate the cell cycle, apoptosis, and DNA repair to prevent malignant transformation. MDM2 regulates activity of p53 and inhibits its binding to DNA. In the present study, we elucidated the MDM2 inhibition potential of polyphenols (Apigenin, Fisetin, Galangin and Luteolin) by MD simulation and MM/PBSA free energy calculations. All polyphenols bind to hydrophobic groove of MDM2 and the binding was found to be stable throughout MD simulation. Luteolin showed the highest negative binding free energy value of -173.80 kJ/mol followed by Fisetin with value of -172.25 kJ/mol. It was found by free energy calculations, that hydrophobic interactions (vdW energy) have major contribution in binding free energy.

  9. Hydrophobic Interactions Are a Key to MDM2 Inhibition by Polyphenols as Revealed by Molecular Dynamics Simulations and MM/PBSA Free Energy Calculations.

    Directory of Open Access Journals (Sweden)

    Sharad Verma

    Full Text Available p53, a tumor suppressor protein, has been proven to regulate the cell cycle, apoptosis, and DNA repair to prevent malignant transformation. MDM2 regulates activity of p53 and inhibits its binding to DNA. In the present study, we elucidated the MDM2 inhibition potential of polyphenols (Apigenin, Fisetin, Galangin and Luteolin by MD simulation and MM/PBSA free energy calculations. All polyphenols bind to hydrophobic groove of MDM2 and the binding was found to be stable throughout MD simulation. Luteolin showed the highest negative binding free energy value of -173.80 kJ/mol followed by Fisetin with value of -172.25 kJ/mol. It was found by free energy calculations, that hydrophobic interactions (vdW energy have major contribution in binding free energy.

  10. Multi-modal applicability of a reversed-phase/weak-anion exchange material in reversed-phase, anion-exchange, ion-exclusion, hydrophilic interaction and hydrophobic interaction chromatography modes.

    Science.gov (United States)

    Lämmerhofer, Michael; Nogueira, Raquel; Lindner, Wolfgang

    2011-06-01

    We recently introduced a mixed-mode reversed-phase/weak anion-exchange type separation material based on silica particles which consisted of a hydrophobic alkyl strand with polar embedded groups (thioether and amide functionalities) and a terminal weak anion-exchange-type quinuclidine moiety. This stationary phase was designed to separate molecules by lipophilicity and charge differences and was mainly devised for peptide separations with hydroorganic reversed-phase type elution conditions. Herein, we demonstrate the extraordinary flexibility of this RP/WAX phase, in particular for peptide separations, by illustrating its applicability in various chromatographic modes. The column packed with this material can, depending on the solute character and employed elution conditions, exploit attractive or repulsive electrostatic interactions, and/or hydrophobic or hydrophilic interactions as retention and selectivity increments. As a consequence, the column can be operated in a reversed-phase mode (neutral compounds), anion-exchange mode (acidic compounds), ion-exclusion chromatography mode (cationic solutes), hydrophilic interaction chromatography mode (polar compounds), and hydrophobic interaction chromatography mode (e.g., hydrophobic peptides). Mixed-modes of these chromatographic retention principles may be materialized as well. This allows an exceptionally flexible adjustment of retention and selectivity by tuning experimental conditions. The distinct separation mechanisms will be outlined by selected examples of peptide separations in the different modes.

  11. The Synthesis and Characterization of Aromatic Hybrid Anderson-Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions.

    Science.gov (United States)

    Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette

    2015-12-01

    Four aromatic hybrid Anderson polyoxomolybdates with Fe(3+) or Mn(3+) as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, (1) H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-FeMo6 -bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRISR=(HOCH2 )3 CR)), (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-FeMo6 -cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-MnMo6 -bzn), and (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-MnMo6 -cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mM) sodium salts Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-FeMo6 -bzn), Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-FeMo6 -cin), Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-MnMo6 -bzn), and Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-MnMo6 -cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern-Volmer analysis, which suggested the formation of a 1:1 POM-protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic

  12. Changing water affinity from hydrophobic to hydrophilic in hydrophobic channels.

    Science.gov (United States)

    Ohba, Tomonori; Yamamoto, Shotaro; Kodaira, Tetsuya; Hata, Kenji

    2015-01-27

    The behavior of water at hydrophobic interfaces can play a significant role in determining chemical reaction outcomes and physical properties. Carbon nanotubes and aluminophosphate materials have one-dimensional hydrophobic channels, which are entirely surrounded by hydrophobic interfaces. Unique water behavior was observed in such hydrophobic channels. In this article, changes in the water affinity in one-dimensional hydrophobic channels were assessed using water vapor adsorption isotherms at 303 K and grand canonical Monte Carlo simulations. Hydrophobic behavior of water adsorbed in channels wider than 3 nm was observed for both adsorption and desorption processes, owing to the hydrophobic environment. However, water showed hydrophilic properties in both adsorption and desorption processes in channels narrower than 1 nm. In intermediate-sized channels, the hydrophobic properties of water during the adsorption process were seen to transition to hydrophilic behavior during the desorption process. Hydrophilic properties in the narrow channels for both adsorption and desorption processes are a result of the relatively strong water-channel interactions (10-15 kJ mol(-1)). In the 2-3 nm channels, the water-channel interaction energy of 4-5 kJ mol(-1) was comparable to the thermal translational energy. The cohesive water interaction was approximately 35 kJ mol(-1), which was larger than the others. Thus, the water affinity change in the 2-3 nm channels for the adsorption and desorption processes was attributed to weak water-channel interactions and strong cohesive interactions. These results are inherently important to control the properties of water in hydrophobic environments.

  13. Mixed micelles of 7,12-dioxolithocholic acid and selected hydrophobic bile acids: interaction parameter, partition coefficient of nitrazepam and mixed micelles haemolytic potential.

    Science.gov (United States)

    Poša, Mihalj; Tepavčević, Vesna

    2011-09-01

    The formation of mixed micelles built of 7,12-dioxolithocholic and the following hydrophobic bile acids was examined by conductometric method: cholic (C), deoxycholic (D), chenodeoxycholic (CD), 12-oxolithocholic (12-oxoL), 7-oxolithocholic (7-oxoL), ursodeoxycholic (UD) and hiodeoxycholic (HD). Interaction parameter (β) in the studied binary mixed micelles had negative value, suggesting synergism between micelle building units. Based on β value, the hydrophobic bile acids formed two groups: group I (C, D and CD) and group II (12-oxoL, 7-oxoL, UD and HD). Bile acids from group II had more negative β values than bile acids from group I. Also, bile acids from group II formed intermolecular hydrogen bonds in aggregates with both smaller (2) and higher (4) aggregation numbers, according to the analysis of their stereochemical (conformational) structures and possible structures of mixed micelles built of these bile acids and 7,12-dioxolithocholic acid. Haemolytic potential and partition coefficient of nitrazepam were higher in mixed micelles built of the more hydrophobic bile acids (C, D, CD) and 7,12-dioxolithocholic acid than in micelles built only of 7,12-dioxolithocholic acid. On the other hand, these mixed micelles still had lower values of haemolytic potential than micelles built of C, D or CD. The mixed micelles that included bile acids: 12-oxoL, 7-oxoL, UD or HD did not significantly differ from the micelles of 7,12-dioxolithocholic acid, observing the values of their haemolytic potential.

  14. Hydrophobic interaction between contiguous residues in the S6 transmembrane segment acts as a stimuli integration node in the BK channel

    Science.gov (United States)

    Carrasquel-Ursulaez, Willy; Contreras, Gustavo F.; Sepúlveda, Romina V.; Aguayo, Daniel; González-Nilo, Fernando

    2015-01-01

    Large-conductance Ca2+- and voltage-activated K+ channel (BK) open probability is enhanced by depolarization, increasing Ca2+ concentration, or both. These stimuli activate modular voltage and Ca2+ sensors that are allosterically coupled to channel gating. Here, we report a point mutation of a phenylalanine (F380A) in the S6 transmembrane helix that, in the absence of internal Ca2+, profoundly hinders channel opening while showing only minor effects on the voltage sensor active–resting equilibrium. Interpretation of these results using an allosteric model suggests that the F380A mutation greatly increases the free energy difference between open and closed states and uncouples Ca2+ binding from voltage sensor activation and voltage sensor activation from channel opening. However, the presence of a bulky and more hydrophobic amino acid in the F380 position (F380W) increases the intrinsic open–closed equilibrium, weakening the coupling between both sensors with the pore domain. Based on these functional experiments and molecular dynamics simulations, we propose that F380 interacts with another S6 hydrophobic residue (L377) in contiguous subunits. This pair forms a hydrophobic ring important in determining the open–closed equilibrium and, like an integration node, participates in the communication between sensors and between the sensors and pore. Moreover, because of its effects on open probabilities, the F380A mutant can be used for detailed voltage sensor experiments in the presence of permeant cations. PMID:25548136

  15. Molecular mechanism of hydrophobic charge-induction chromatography: interactions between the immobilized 4-mercaptoethyl-pyridine ligand and IgG.

    Science.gov (United States)

    Lin, Dong-Qiang; Tong, Hong-Fei; Wang, Hong-Yin; Shao, Shuang; Yao, Shan-Jing

    2012-10-19

    Hydrophobic charge-induction chromatography (HCIC) is a novel bioseparation technology, especially for antibody purification. In order to better understand the molecular mechanism of HCIC, the typical ligand of 4-mercaptoethyl-pyridine (MEP) was coupled onto the cellulose matrix, and the binding and departing of IgG were studied with the molecular dynamics simulation. Based on the previous work with free MEP ligand (J. Phys. Chem. B, 116 (4) (2012) 1393-1400), the pocket around TYR319 and LEU309 on the CH2 domain of IgG was selected as the potential binding site for the Fc fragment of IgG (Fc-A), and the complex of matrix-ligand-Fc-A was formed for the molecular simulation. Both single ligand and ligand net were investigated in the present work. It was found that the MEP ligand immobilized on the cellulose matrix could capture the Fc-A at neutral pH during the simulation, and the Fc-A would depart quickly when pH was changed to 4.0. The hydrophobic interactions and hydrogen bonds controlled the binding of Fc-A on the immobilized ligands at neutral pH and the electrostatic repulsion caused the departing of Fc-A at acid condition. For the ligand net, multipoint binding was found, while one ligand dominated the binding of Fc-A and other ligands might enhance the adsorption of protein. In addition, the adsorption isotherm and the isothermal titration calorimetry (ITC) were used to evaluate the molecular interactions. The experimental results indicated that the hydrophobic interaction is the major driving force for the adsorption of IgG on the MEP resin, which was in good agreement with those findings of molecular simulation. The molecular simulation and thermodynamic results verified strongly the molecular mechanism of HCIC--the hydrophobic interactions for binding and the charge-induction repulsion for elution. Better understanding on the molecular interactions would be beneficial to design new HCIC ligands for improving the efficiency of antibody separation

  16. Hydrophobic interactions leading to a complex interplay between bioelectrocatalytic properties and multilayer meso-organization in layer-by-layer assemblies.

    Science.gov (United States)

    Lorena Cortez, M; De Matteis, Nicolás; Ceolín, Marcelo; Knoll, Wolfgang; Battaglini, Fernando; Azzaroni, Omar

    2014-10-14

    The present study explores the development of mesostructured bioelectrochemical interfaces with accurate compositional and topological control of the supramolecular architecture through the layer-by-layer assembly of ternary systems based on poly(allylamine) containing an osmium polypyridyl complex (OsPA), an anionic surfactant, sodium dodecyl sulfate (SDS) or sodium octodecyl sulfate (ODS), and glucose oxidase (GOx). We show that the introduction of the anionic surfactant allows a sensitive increase of the polyelectrolyte and the enzyme uptake at pH 7.0, enhancing its catalytic behavior in the presence of glucose as compared to the surfactant-free system (OsPA/GOx)n constructed at the same pH. Structural characterization of the multilayer films was performed by means of grazing-incidence small-angle X-ray scattering (GISAXS), which showed the formation of mesostructured domains within the composite assemblies. Experimental results indicate that the balance between ionic and hydrophobic interactions plays a leading role not only in the construction of the self-assembled system but also in the functional properties of the bioactive interface. The structure of the ternary multilayered films depends largely on the length of the alkyl chain of the surfactant. We show that surfactants incorporated into the film also play a role as chemical entities capable of tuning the hydrophobicity of the whole assembly. In this way, the deliberate introduction of short-range hydrophobic forces was exploited as an additional variable to manipulate the adsorption and coverage of protein during each assembly step. However, the integration of long-chain surfactants may lead to the formation of very well-organized interfacial architectures with poor electron transfer properties. This, in turn, leads to a complex trade-off between enzyme coverage and redox wiring that is governed by the meso-organization and the hydrophobic characteristics of the multilayer assembly.

  17. Ion-exchange and hydrophobic interactions affecting selectivity for neutral and charged solutes on three structurally similar agglomerated ion-exchange and mixed-mode stationary phases.

    Science.gov (United States)

    Kazarian, Artaches A; Taylor, Mark R; Haddad, Paul R; Nesterenko, Pavel N; Paull, Brett

    2013-11-25

    The nature and extent of mixed-mode retention mechanisms evident for three structurally related, agglomerated, particle-based stationary phases were evaluated. These three agglomerated phases were Thermo Fisher ScientificIon PacAS11-HC - strong anion exchange, Thermo Fisher Scientific IonPac CS10--strong cation-exchange PS-DVB, and the Thermo Fisher Scientific Acclaim Trinity P1silica-based substrate, which is commercially marketed as a mixed-mode stationary phase. All studied phases can exhibit zwitterionic and hydrophobic properties, which contribute to the retention of charged organic analytes. A systematic approach was devised to investigate the relative ion-exchange capacities and hydrophobicities for each of the three phases, together with the effect of eluent pH upon selectivity, using a specifically selected range of anionic, cationic and neutral aromatic compounds. Investigation of the strong anion-exchange column and the Trinity P1 mixed-mode substrate, in relation to ion-exchange capacity and pH effects, demonstrated similar retention behaviour for both the anionic and ampholytic solutes, as expected from the structurally related phases. Further evaluation revealed that the ion-exchange selectivity of the mixed-mode phase exhibited properties similar to that of the strong anion-exchange column, with secondary cation-exchange selectivity, albeit with medium to high anion-exchange and cation-exchange capacities, allowing selective retention for each of the anionic, cationic and ampholytic solutes. Observed mixed-mode retention upon the examined phases was found to be a sum of anion- and cation-exchange interactions, secondary ion-exchange and hydrophobic interactions, with possible additional hydrogen bonding. Hydrophobic evaluation of the three phases revealed logP values of 0.38-0.48, suggesting low to medium hydrophobicity. These stationary phases were also benchmarked against traditional reversed-phase substrates namely, octadecylsilica YMC-Pac Pro C18

  18. Effects of environmental factors on MSP21-25 aggregation indicate the roles of hydrophobic and electrostatic interactions in the aggregation process.

    Science.gov (United States)

    Zhang, Xuecheng; Dong, Yuanqiu; Yu, Jigang; Tu, Xiaoming

    2014-01-01

    Merozoite surface protein 2 (MSP2), one of the most abundant proteins on the merozoite surface of Plasmodium falciparum, is recognized to be important for the parasite's invasion into the host cell and is thus a promising malaria vaccine candidate. However, mediated mainly by its conserved N-terminal 25 residues (MSP21-25), MSP2 readily forms amyloid fibril-like aggregates under physiological conditions in vitro, which impairs its potential as a vaccine component. In addition, there is evidence that MSP2 exists in aggregated forms on the merozoite surface in vivo. To elucidate the aggregation mechanism of MSP21-25 and thereby understand the behavior of MSP2 in vivo and find ways to avoid the aggregation of relevant vaccine in vitro, we investigated the effects of agitation, pH, salts, 1-anilinonaphthalene-8-sulfonic acid (ANS), trimethylamine N-oxide dihydrate (TMAO), urea, and sub-micellar sodium dodecyl sulfate (SDS) on the aggregation kinetics of MSP21-25 using thioflavin T (ThT) fluorescence. The results showed that MSP21-25 aggregation was accelerated by agitation, while repressed by acidic pHs. The salts promoted the aggregation in an anion nature-dependent pattern. Hydrophobic surface-binding agent ANS and detergent urea repressed MSP21-25 aggregation, in contrast to hydrophobic interaction strengthener TMAO, which enhanced the aggregation. Notably, sub-micellar SDS, contrary to its micellar form, promoted MSP21-25 aggregation significantly. Our data indicated that hydrophobic interactions are the predominant driving force of the nucleation of MSP21-25 aggregation, while the elongation is controlled mainly by electrostatic interactions. A kinetic model of MSP21-25 aggregation and its implication were also discussed.

  19. The macroscopic pancake bounce

    DEFF Research Database (Denmark)

    Hecksher, Tina; Bro, Jonas Andersen; Jensen, Kasper Sternberg Brogaard

    2017-01-01

    We demonstrate that the so-called pancake bounce of millimetric water droplets on surfaces patterned with hydrophobic posts (Liu et al 2014 Nat. Phys. 10 515) can be reproduced on larger scales. In our experiment, a bed of nails plays the role of the structured surface and a water balloon models ...

  20. In vitro studies of serum albumin interaction with poly(D,L-lactide) nanospheres loaded by hydrophobic cargo.

    Science.gov (United States)

    Pietkiewicz, Jadwiga; Wilk, Kazimiera A; Bazylińska, Urszula

    2016-01-05

    The various polymer-based nanocarriers are very attractive for in vitro and in vivo bioapplications. A new type of a promising drug delivery systems for cancer tissues-poly(D,L-lactide) nanospheres stabilized with Cremophor EL and loaded with hydrophobic cyanines (IR-780 or ZnPc) or curcumin (CUR) were fabricated by the nanoprecipitation method. The Cremophor EL/PLA/water nanospheres demonstrated regular shape, low polydispersity (PdIcyanine IR-780 with albumin immobilized in the wells of polystyrene plate occurred with lower efficiency than analogs loaded with ZnPc or CUR. Similar relationships were observed after UV-vis spectra analysis of nanospheres in the presence of albumin at various protein concentrations.

  1. Combined effects of potassium chloride and ethanol as mobile phase modulators on hydrophobic interaction and reversed-phase chromatography of three insulin variants.

    Science.gov (United States)

    Johansson, Karolina; Frederiksen, Søren S; Degerman, Marcus; Breil, Martin P; Mollerup, Jørgen M; Nilsson, Bernt

    2015-02-13

    The two main chromatographic modes based on hydrophobicity, hydrophobic interaction chromatography (HIC) and reversed-phase chromatography (RPC), are widely used for both analytical and preparative chromatography of proteins in the pharmaceutical industry. Despite the extensive application of these separation methods, and the vast amount of studies performed on HIC and RPC over the decades, the underlying phenomena remain elusive. As part of a systematic study of the influence of mobile phase modulators in hydrophobicity-based chromatography, we have investigated the effects of both KCl and ethanol on the retention of three insulin variants on two HIC adsorbents and two RPC adsorbents. The focus was on the linear adsorption range, separating the modulator effects from the capacity effects, but some complementary experiments at higher load were included to further investigate observed phenomena. The results show that the modulators have the same effect on the two RPC adsorbents in the linear range, indicating that the modulator concentration only affects the activity of the solute in the mobile phase, and not that of the solute-ligand complex, or that of the ligand. Unfortunately, the HIC adsorbents did not show the same behavior. However, the insulin variants displayed a strong tendency toward self-association on both HIC adsorbents; on one in particular. Since this causes peak fronting, the retention is affected, and this could probably explain the lack of congruity. This conclusion was supported by the results from the non-linear range experiments which were indicative of double-layer adsorption on the HIC adsorbents, while the RPC adsorbents gave the anticipated increased tailing at higher load. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Hydrophobic interactions as key determinants to the KCa3.1 channel closed configuration. An analysis of KCa3.1 mutants constitutively active in zero Ca2+.

    Science.gov (United States)

    Garneau, Line; Klein, Hélène; Banderali, Umberto; Longpré-Lauzon, Ariane; Parent, Lucie; Sauvé, Rémy

    2009-01-02

    In this study we present evidence that residue Val282 in the S6 transmembrane segment of the calcium-activated KCa3.1 channel constitutes a key determinant of channel gating. A Gly scan of the S6 transmembrane segment first revealed that the substitutions A279G and V282G cause the channel to become constitutively active in zero Ca2+. Constitutive activity was not observed when residues extending from Cys276 to Ala286, other than Ala279 and Val282, were substituted to Gly. The accessibility of Cys engineered at Val275 deep in the channel cavity was next investigated for the ion-conducting V275C/V282G mutant and closed V275C channel in zero Ca2+ using Ag+ as probe. These experiments demonstrated that internal Ag+ ions have free access to the channel cavity independently of the channel conducting state, arguing against an activation gate located at the S6 segment C-terminal end. Experiments were also conducted where Val282 was substituted by residues differing in size and/or hydrophobicity. We found a strong correlation between constitutive activity in zero Ca2+ and the hydrophobic energy for side chain burial. Single channel recordings showed finally that constitutive activation in zero Ca2+ is better explained by a model where the channel is locked in a low conducting state with a high open probability rather than resulting from a change in the open/closed energy balance that would favor channel openings to a full conducting state in the absence of Ca2+. We conclude that hydrophobic interactions involving Val282 constitute key determinants to KCa3.1 gating by modulating the ion conducting state of the selectivity filter through an effect on the S6 transmembrane segment.

  3. Interaction of some hydrophobic amino acids, peptides, and protein with aqueous 3-chloro-1,2-propanediol and 3-chloro-1-propanol: Biophysical studies

    Energy Technology Data Exchange (ETDEWEB)

    Keswani, Neelam [Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076 (India); Kishore, Nand, E-mail: nandk@chem.iitb.ac.i [Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076 (India)

    2011-04-15

    Research highlights: Thermodynamic properties of amino acids, peptides and protein determined in solution. The solvents chosen were 3-chloropropan-1-ol and 3-chloropropan-1,2-diol. {yields}The results enabled understanding the interactions quantitatively in these systems affecting the protein stability. Fine details of interactions provided in-depth analysis. - Abstract: The apparent molar volume V{sub 2,{phi},} apparent molar isentropic compressibility K{sub S,2,{phi},} and heat of dilution (q) of aqueous glycine, alanine, {alpha}-amino butyric acid, valine, leucine, diglycine, triglycine, and hen egg white lysozyme have been determined in aqueous solutions of 3-chloropropano-1-ol and 3-chloropropan-1,2-diol solutions at T = 298.15 K. These data have been used to calculate the infinite dilution standard partial molar volume V{sub 2,m}{sup 0}, partial molar isentropic compressibility K{sub S,2,m}{sup 0}, and enthalpy of dilution {Delta}{sub dil}H{sup o} of the amino acids and peptides in aqueous 3-chloropropano-1-ol and 3-chloropropan-1,2-diol, and the standard partial molar quantities of transfer of the amino acids and peptides to the aqueous alcohol and diol solutions. The linear correlation of V{sub 2,m}{sup 0} for a homologous series of amino acids has been utilized to calculate the contribution of the charged end groups (NH{sub 3}{sup +},COO{sup -}), CH{sub 2} group and other alkyl chains of the amino acids to the values of V{sub 2,m}{sup 0}. The results on the standard partial molar volumes of transfer, compressibility and enthalpy of dilution from water to aqueous alcohol and diol solutions have been correlated and interpreted in terms of ion-polar, ion-hydrophobic, and hydrophobic-hydrophobic group interactions. The heat of dilution of these amino acids, peptides, and hen egg white lysozyme measured in aqueous solutions of 3-chloropropano-1-ol and 3-chloropropan-1,2-diol by using isothermal titration calorimetry along with the volumetric, compressibility

  4. Hydrophobic interactions between the S5 segment and the pore helix stabilizes the closed state of Slo2.1 potassium channels.

    Science.gov (United States)

    Suzuki, Tomoyuki; Hansen, Angela; Sanguinetti, Michael C

    2016-04-01

    Under normal physiological conditions, Slo2.1K(+) channels are in a closed state unless activated by an elevation in [Na(+)]i. Fenamates such as niflumic acid also activate Slo2.1. Previous studies suggest that activation of Slo2.1 channels is mediated by a conformational change in the selectivity filter, and not a widening of the aperture formed by the S6 segment bundle crossing as occurs in voltage-gated K(+) channels. It is unclear how binding of Na(+) or fenamates is allosterically linked to opening of the presumed selectivity filter activation gate in Slo2.1. Here we examined the role of the S5 transmembrane segment in the activation of Slo2.1. Channels were heterologously expressed in Xenopus laevis oocytes and whole cell currents measured with the voltage-clamp technique. Ala substitution of five residues located on a single face of the S5 α-helical segment induced constitutive channel activity. Leu-209, predicted to face towards Phe-240 in the pore helix was investigated by further mutagenesis. Mutation of Leu-209 to Glu or Gln induced maximal channel activation as did the combined mutation to Ala of all three hydrophobic S5 residues predicted to be adjacent to Phe-240. Together these results suggest that hydrophobic interactions between residues in S5 and the C-terminal end of the pore helix stabilize Slo2.1 channels in a closed state.

  5. NMR shows hydrophobic interactions replace glycine packing in the triple helix at a natural break in the (Gly-X-Y)n repeat.

    Science.gov (United States)

    Li, Yingjie; Brodsky, Barbara; Baum, Jean

    2007-08-03

    Little is known about the structural consequences of the more than 20 breaks in the (Gly-X-Y)(n) repeating sequence found in the long triple helix domain of basement membrane type IV collagen. NMR triple resonance studies of doubly labeled residues within a set of collagen model peptides provide distance and dihedral angle restraints that allow determination of model structures of both a standard triple helix and of a triple helix with a break in solution. Although the standard triple helix cannot continue when Gly is not every third residue, the NMR data support rod-like molecules that have standard triple-helical structures on both sides of a well defined and highly localized perturbation. The GAAVM break region may be described as a "pseudo triple helix," because it preserves the standard one-residue stagger of the triple helix but introduces hydrophobic interactions at the position normally occupied by the much smaller and hydrogen-bonded Gly residue of the repeating (Gly-X-Y)(n) sequence. This structure provides a rationale for the consensus presence of hydrophobic residues in breaks of similar length and defines a novel variant of a triple helix that could be involved in recognition.

  6. Macroscopic and microscopic observations of needle insertion into gels

    NARCIS (Netherlands)

    Veen, van Youri R.J.; Jahya, Alex; Misra, Sarthak

    2012-01-01

    Needle insertion into soft tissue is one of the most common medical interventions. This study provides macroscopic and microscopic observations of needle–gel interactions. A gelatin mixture is used as a soft-tissue simulant. For the macroscopic studies, system parameters, such as insertion velocity,

  7. An extended CCR5 ECL2 peptide forms a helix that binds HIV-1 gp120 through non-specific hydrophobic interactions.

    Science.gov (United States)

    Abayev, Meital; Moseri, Adi; Tchaicheeyan, Oren; Kessler, Naama; Arshava, Boris; Naider, Fred; Scherf, Tali; Anglister, Jacob

    2015-05-01

    C-C chemokine receptor 5 (CCR5) serves as a co-receptor for HIV-1. The CCR5 N-terminal segment, the second extracellular loop (ECL2) and the transmembrane helices have been implicated in binding the envelope glycoprotein gp120. Peptides corresponding to the sequence of the putative ECL2 as well as peptides containing extracellular loops 1 and 3 (ECL1 and ECL3) were found to inhibit HIV-1 infection. The aromatic residues in the C-terminal half of an ECL2 peptide were shown to interact with gp120. In the present study, we found that, in aqueous buffer, the segment Q188-Q194 in an elongated ECL2 peptide (R168-K197) forms an amphiphilic helix, which corresponds to the beginning of the fifth transmembrane helix in the crystal structure of CCR5. Two-dimensional saturation transfer difference NMR spectroscopy and dynamic filtering studies revealed involvement of Y187, F189, W190 and F193 of the helical segment in the interaction with gp120. The crystal structure of CCR5 shows that the aromatic side chains of F189, W190 and F193 point away from the binding pocket and interact with the membrane or with an adjacent CCR5 molecule, and therefore could not interact with gp120 in the intact CCR5 receptor. We conclude that these three aromatic residues of ECL2 peptides interact with gp120 through hydrophobic interactions that are not representative of the interactions of the intact CCR5 receptor. The HIV-1 inhibition by ECL2 peptides, as well as by ECL1 and ECL3 peptides and peptides corresponding to ECL2 of CXCR4, which serves as an alternative HIV-1 co-receptor, suggests that there is a hydrophobic surface in the envelope spike that could be a target for HIV-1 entry inhibitors. The structures and NMR data of ECL2S (Q186-T195) were deposited under Protein Data Bank ID 2mzx and BioMagResBank ID 25505. © 2015 FEBS.

  8. [Development of a new hydrophobic interaction chromatography absorbent and its application to the purification of recombinant hepatitis B surface antigen].

    Science.gov (United States)

    Wang, Yang-Mu; Bi, Jing-Xiu; Zhao, Lan; Zhou, Wei-Bin; Li, Yan; Huang, Yong-Dong; Zhang, Yan; Lin, Hai; Su, Zhi-Guo

    2006-03-01

    A new hydrophobic absorbent based on homemade highly cross-linked agarose beads was synthesized by immobilizing butyl derivative onto the matrix linkage. The density of ligand was controlled by adjusting the concentration of butanethiol and the synthesis route was optimized by evaluating the purification efficiency of recombinant Hepatitis B surface antigen (HBsAg) expressed by Chinese hamster ovary (CHO) cell line. A high performance absorbent was finally screened out with up to 80% of HBsAg recovery and purification-fold (PF) about 20. Furthermore, the column pressure was about 0.06 MPa under the flow rate of 500cm/h, and no leaked butyl were detected after exposing the gel in common buffers, chaotropic agents, high concentrations of denaturing agents such as guanidine hydrochloride, urea and polar organic solvents. These results demonstrated that the absorbent have high physico-chemical stability, so it was available for the downstream process. Finally, after scaled up to 2L wet gel/batch, the absorbent was applied to the integration of three-step chromatography and obtained the purified CHO-HBsAg with 95% purity by SDS-PAGE and HPLC, which meet the requirements of SFDA. The purification efficiency and the reproducible ability of the absorbents were also evaluated from batch-to-batch. The results demonstrated that the absorbent met the requirement of scalable, reproducible, economic effect as well. This absorbent is a promising alternative exported HIC gel for wildly being used in Chinese pharmaceutical industries.

  9. Surfactant-soil interactions during surfactant-amended remediation of contaminated soils by hydrophobic organic compounds: a review.

    Science.gov (United States)

    Laha, Shonali; Tansel, Berrin; Ussawarujikulchai, Achara

    2009-01-01

    Surfactants are amphiphilic molecules that reduce aqueous surface tension and increase the solubility of hydrophobic organic compounds (HOCs). Surfactant-amended remediation of HOC-contaminated soils and aquifers has received significant attention as an effective treatment strategy - similar in concept to using soaps and detergents as washing agents to remove grease from soiled fabrics. The proposed mechanisms involved in surfactant-amended remediation include: lowering of interfacial tension, surfactant solubilization of HOCs, and the phase transfer of HOC from soil-sorbed to pseudo-aqueous phase. However, as with any proposed chemical countermeasures, there is a concern regarding the fate of the added surfactant. This review summarizes the current state of knowledge regarding nonionic micelle-forming surfactant sorption onto soil, and serves as an introduction to research on that topic. Surfactant sorption onto soil appears to increase with increasing surfactant concentration until the onset of micellization. Sorbed-phase surfactant may account for the majority of added surfactant in surfactant-amended remediation applications, and this may result in increased HOC partitioning onto soil until HOC solubilization by micellar phase surfactant successfully competes with increased HOC sorption on surfactant-modified soil. This review provides discussion of equilibrium partitioning theory to account for the distribution of HOCs between soil, aqueous phase, sorbed surfactant, and micellar surfactant phases, as well as recently developed models for surfactant sorption onto soil. HOC partitioning is characterized by apparent soil-water distribution coefficients in the presence of surfactant.

  10. Covariant Macroscopic Quantum Geometry

    CERN Document Server

    Hogan, Craig J

    2012-01-01

    A covariant noncommutative algebra of position operators is presented, and interpreted as the macroscopic limit of a geometry that describes a collective quantum behavior of the positions of massive bodies in a flat emergent space-time. The commutator defines a quantum-geometrical relationship between world lines that depends on their separation and relative velocity, but on no other property of the bodies, and leads to a transverse uncertainty of the geometrical wave function that increases with separation. The number of geometrical degrees of freedom in a space-time volume scales holographically, as the surface area in Planck units. Ongoing branching of the wave function causes fluctuations in transverse position, shared coherently among bodies with similar trajectories. The theory can be tested using appropriately configured Michelson interferometers.

  11. Canonical quantization of macroscopic electromagnetism

    Energy Technology Data Exchange (ETDEWEB)

    Philbin, T G, E-mail: tgp3@st-andrews.ac.u [School of Physics and Astronomy, University of St Andrews, North Haugh, St Andrews, Fife KY16 9SS (United Kingdom)

    2010-12-15

    Application of the standard canonical quantization rules of quantum field theory to macroscopic electromagnetism has encountered obstacles due to material dispersion and absorption. This has led to a phenomenological approach to macroscopic quantum electrodynamics where no canonical formulation is attempted. In this paper macroscopic electromagnetism is canonically quantized. The results apply to any linear, inhomogeneous, magnetodielectric medium with dielectric functions that obey the Kramers-Kronig relations. The prescriptions of the phenomenological approach are derived from the canonical theory.

  12. Canonical quantization of macroscopic electromagnetism

    CERN Document Server

    Philbin, T G

    2010-01-01

    Application of the standard canonical quantization rules of quantum field theory to macroscopic electromagnetism has encountered obstacles due to material dispersion and absorption. This has led to a phenomenological approach to macroscopic quantum electrodynamics where no canonical formulation is attempted. In this paper macroscopic electromagnetism is canonically quantized. The results apply to any linear, inhomogeneous, magnetoelectric medium with dielectric functions that obey the Kramers-Kronig relations. The prescriptions of the phenomenological approach are derived from the canonical theory.

  13. Effect of Different Salts on the Solubilities of Benzene and Diphenyl in t-Butyl Alcohol-Water Mixture and Hydrophobic Interaction

    Institute of Scientific and Technical Information of China (English)

    ZOU,Li-Zhuang(邹立壮); WANG,Xiao-Ling(王晓玲); ZHU,Shu-Quan(朱书全); HAN,Bu-Xing(韩布兴); LIU,Rui-Lin(刘瑞麟); YAN,Hai-Ke(阎海科)

    2002-01-01

    The solubilities of benzene and diphenyl in mixed solvents of tbutyl alcohol (TBA) and water with different salts have been determined at T = 298.15, 303.15, 308.15 and 313.15 K.The molar fraction of TBA [ x (TBA) ] in mixed solvent is 0.045, and the molality of the salts (ms) in mixed solvents are 0.000, 0.250, 0.500, 0.750 and 1.000 mol/kg, respectively. The standard Gibbs energies of solution of benzene and diphenyl in the mixed solvents have also been calculated based on the solubility data. The effects of different salts on the hydrophobic interaction (HI) for benzene-benzene pair in the systems were discussed.

  14. Recovery of infective virus particles in ion-exchange and hydrophobic interaction monolith chromatography is influenced by particle charge and total-to-infective particle ratio.

    Science.gov (United States)

    Sviben, Dora; Forcic, Dubravko; Ivancic-Jelecki, Jelena; Halassy, Beata; Brgles, Marija

    2017-06-01

    Viral particles are used in medical applications as vaccines or gene therapy vectors. In order to obtain product of high purity, potency and safety for medical use purification of virus particles is a prerequisite, and chromatography is gaining increased attention to meet this aim. Here, we report on the use of ion-exchange and hydrophobic interaction chromatography on monolithic columns for purification of mumps virus (MuV) and measles virus (MeV). Efficiency of the process was monitored by quantification of infective virus particles (by 50% cell culture infective dose assay) and total virus particles, and monitoring of their size (by Nanoparticle Tracking Analysis). Ion-exchange chromatography was shown to be inefficient for MuV and best results for MeV were obtained on QA column with recovery around 17%. Purification of MuV and MeV by hydrophobic interaction chromatography resulted in recoveries around 60%. Results showed that columns with small channels (d=1.4μm) are not suitable for MuV and MeV, although their size is below 400nm, whereas columns with large channels (6μm) showed to be efficient and recoveries independent on the flow rate up to 10mL/min. Heterogeneity of the virus suspension and its interday variability mostly regarding total-to-infective particle ratio was observed. Interestingly, a trend in recovery depending on the day of the harvest was also observed for both viruses, and it correlated with the total-to-infective particle ratio, indicating influence of the virus sample composition on the chromatography results. Copyright © 2017. Published by Elsevier B.V.

  15. Hydrophobicity of rare-earth oxide ceramics

    Science.gov (United States)

    Azimi, Gisele; Dhiman, Rajeev; Kwon, Hyuk-Min; Paxson, Adam T.; Varanasi, Kripa K.

    2013-04-01

    Hydrophobic materials that are robust to harsh environments are needed in a broad range of applications. Although durable materials such as metals and ceramics, which are generally hydrophilic, can be rendered hydrophobic by polymeric modifiers, these deteriorate in harsh environments. Here we show that a class of ceramics comprising the entire lanthanide oxide series, ranging from ceria to lutecia, is intrinsically hydrophobic. We attribute their hydrophobicity to their unique electronic structure, which inhibits hydrogen bonding with interfacial water molecules. We also show with surface-energy measurements that polar interactions are minimized at these surfaces and with Fourier transform infrared/grazing-angle attenuated total reflection that interfacial water molecules are oriented in the hydrophobic hydration structure. Moreover, we demonstrate that these ceramic materials promote dropwise condensation, repel impinging water droplets, and sustain hydrophobicity even after exposure to harsh environments. Rare-earth oxide ceramics should find widespread applicability as robust hydrophobic surfaces.

  16. Lipophilicity of amyloid β-peptide 12-28 and 25-35 to unravel their ability to promote hydrophobic and electrostatic interactions.

    Science.gov (United States)

    Ermondi, G; Catalano, F; Vallaro, M; Ermondi, I; Camacho Leal, M P; Rinaldi, L; Visentin, S; Caron, G

    2015-11-10

    The growing interest for peptide therapeutics calls for new strategies to determine the physico-chemical properties responsible for the interactions of peptides with the environment. This study reports about the lipophilicity of two fragments of the amyloid β-peptide, Aβ 25-35 and Aβ 12-28. Firstly, computational studies showed the limits of log D(7.4)oct in describing the lipophilicity of medium-sized peptides. Chromatographic lipophilicity indexes (expressed as log k', the logarithm of the retention factor) were then measured in three different systems to highlight the different skills of Aβ 25-35 and Aβ 12-28 in giving interactions with polar and apolar environments. CD studies were also performed to validate chromatographic experimental conditions. Results show that Aβ 12-28 has a larger skill in promoting hydrophobic and electrostatic interactions than Aβ 25-35. This finding proposes a strategy to determine the lipophilicity of peptides for drug discovery purposes but also gives insights in unraveling the debate about the aminoacidic region of Aβ responsible for its neurotoxicity.

  17. Two variables dominating the retention of intact proteins under gradient elution with simultaneous ultrafast high-resolution separation by hydrophobic interaction chromatography.

    Science.gov (United States)

    Geng, Xindu; Jia, Xiaodan; Liu, Peng; Wang, Fei; Yang, Xiaoming

    2015-10-07

    The retention of intact proteins under gradient elution in hydrophobic interaction chromatography (HIC) was found to be governed by two variables, the steady region (SR) and the migration region (MR). In the SR, the proteins are immobilized by the strong interactions with the stationary phase such that the retention time is independent of the column length. In the MR, the proteins also interact with the stationary phase, but they move normally, thus the retention time depends on their partition coefficients and the column length. The SR can be used as an operation space (OP) for high-throughput protein analysis by 1D-LC using short columns at high flow rates to maintain a high resolution. The OP can also be employed for all assisted operations in online 2D-LC. Based on the steady region/migration region optimization strategy developed in this study, five successive complete separations of seven intact proteins were performed in a HIC cake in less than 5 min, and a crude extract of ribonuclease A from bovine pancreas was purified using online 2D-LC to 95.8% purity with 93.2% mass recovery in 45 min. This approach can be used to expedite the purification of drug-target proteins and should therefore be of interest to the pharmaceutical industry.

  18. Influence of solution parameters on europium(III), α-Al2O3, and humic acid interactions: Macroscopic and time-resolved laser-induced luminescence data

    Science.gov (United States)

    Janot, Noémie; Benedetti, Marc F.; Reiller, Pascal E.

    2013-12-01

    Speciation of Eu(III) in the presence of purified Aldrich humic acid (PAHA) and/or α-Al2O3 has been studied by time-resolved luminescence spectroscopy as a function of pH, ionic strength and PAHA concentration. The comparisons of macroscopic and spectroscopic data (adsorption, spectra, and decay times analyses) between the ternary system, i.e., Eu(III)/PAHA/α-Al2O3, and the corresponding binary systems are comprehensively presented. As expected, results show almost no influence of ionic strength on Eu(III) adsorption onto α-Al2O3. However, in the binary Eu(III)/PAHA system, it is clearly shown that variations of electrolyte concentration, which modify PAHA conformation, influence the symmetry of the humic-bound Eu(III) at pH ⩾ 7. In the ternary system, adsorption of both Eu(III) and PAHA onto the surface decreases with ionic strength. At I = 0.01 M NaClO4, Eu(III) luminescence decay is much faster than at I = 0.1 M NaClO4. This is most likely due to the lower surface concentration of PAHA at lower ionic strength, leading to a less constrained environment for Eu(III) ions. At high pH, luminescence spectra are different at the two ionic strengths studied. Concerning the influence of PAHA concentration, spectroscopic results show that in the binary Eu(III)/PAHA system complete complexation of 1 μM Eu(III) is reached for 16 mgPAHA l-1 at pH 4, and for lower PAHA concentrations at higher pH. At the same PAHA concentration, asymmetry ratios are comparable between the binary Eu(III)/PAHA system and the ternary system between pH 4 and 7.7. This means that the presence of mineral surface has almost no influence on Eu(III) environment symmetry below pH 8; hence, under these acid to neutral pH conditions, the occurrence of Eu(III)-bridged humic surface complexes is not likely. In the ternary system, at different pH, luminescence decay times of Eu(III) increase with PAHA concentration. They are much higher in the ternary system than in the binary Eu(III)/PAHA system

  19. Synthesis of novel lanthanide acylpyrazolonato ligands with long aliphatic chains and immobilization of the Tb complex on the surface of silica pre-modified via hydrophobic interactions.

    Science.gov (United States)

    Pettinari, C; Marchetti, F; Pettinari, R; Belousov, Y A; Taydakov, I V; Krasnobrov, V D; Petukhov, D I; Drozdov, A A

    2015-09-01

    Five new complexes Ln(Q(C17))3(H2O)(Solv) (Ln = Y, Solv = H2O, Ln = Tb, Dy, Sm or Eu, Solv = EtOH) were synthesized with the acylpyrazolonato ligand Q(C17) bearing a long aliphatic C17H35 chain in the acyl moiety, and the crystal structure of Y(Q(C17))3(H2O)2 shows the three aliphatic chains from the coordinated ligands positioned in the same direction, affording plane layers built by Y(Q(C17))3(H2O)2 molecules connected through H-bonding interactions. The layers are stitched to each other like in "hook & loop" tapes. Luminescence of complexes was determined and the complex Tb(Q(C17))3(H2O)(EtOH) was immobilized on the surface of silica preprocessed using a C17H35CONH(CH2)3Si(OEt)3 reagent via hydrophobic interactions of long aliphatic chains. Luminescent properties and micromorphology of the obtained hybrid particles and hybrid films were investigated. Intensive green emission of the complex retains after grafting onto the silica surface. Inclusion of the complex on the surface of silica materials occurs as separate molecules, after the disruption of the H-bonding network present in the crystalline phase of the pure terbium sample.

  20. Nature of interactions between PEO-PPO-PEO triblock copolymers and lipid membranes: (I) effect of polymer hydrophobicity on its ability to protect liposomes from peroxidation.

    Science.gov (United States)

    Wang, Jia-Yu; Marks, Jeremy; Lee, Ka Yee C

    2012-09-10

    PEO-PPO-PEO triblock copolymers have opposing effects on lipid membrane integrity: they can behave either as membrane sealants or as membrane permeabilizers. To gain insights into their biomembrane activities, the fundamental interactions between a series of PEO-based polymers and phospholipid vesicles were investigated. Specifically, the effect of copolymer hydrophobicity on its ability to prevent liposomes from peroxidation was evaluated, and partitioning free energy and coefficient involved in the interactions were derived. Our results show that the high degree of hydrophilicity is a key feature of the copolymers that can effectively protect liposomes from peroxidation and the protective effect of the copolymers stems from their adsorption at the membrane surface without penetrating into the bilayer core. The origin of this protective effect induced by polymer absorption is attributed to the retardation of membrane hydration dynamics, which is further illustrated in the accompanying study on dynamic nuclear polarization (DNP)-derived hydration dynamics (Cheng, C.-Y.; Wang, J.-Y.; Kausik, R.; Lee, K. Y. C.; Han S. Biomacromolecules, 2012, DOI: 10.1021/bm300848c).

  1. Quantum equilibria for macroscopic systems

    Energy Technology Data Exchange (ETDEWEB)

    Grib, A [Department of Theoretical Physics and Astronomy, Russian State Pedagogical University, St. Petersburg (Russian Federation); Khrennikov, A [Centre for Mathematical Modelling in Physics and Cognitive Sciences Vaexjoe University (Sweden); Parfionov, G [Department of Mathematics, St. Petersburg State University of Economics and Finances (Russian Federation); Starkov, K [Department of Mathematics, St. Petersburg State University of Economics and Finances (Russian Federation)

    2006-06-30

    Nash equilibria are found for some quantum games with particles with spin-1/2 for which two spin projections on different directions in space are measured. Examples of macroscopic games with the same equilibria are given. Mixed strategies for participants of these games are calculated using probability amplitudes according to the rules of quantum mechanics in spite of the macroscopic nature of the game and absence of Planck's constant. A possible role of quantum logical lattices for the existence of macroscopic quantum equilibria is discussed. Some examples for spin-1 cases are also considered.

  2. Preparation of a novel weak cation exchange/hydrophobic interaction chromatography dual-function polymer-based stationary phase for protein separation using "thiol-ene click chemistry".

    Science.gov (United States)

    Yang, Fan; Bai, Quan; Zhao, Kailou; Gao, Dong; Tian, Lei

    2015-02-01

    A novel dual-function mixed-mode stationary phase based on poly(glycidyl methacrylate-co-ethylene dimethacrylate) microspheres was synthesized by thiol-ene click chemistry and characterized by infrared spectroscopy and elemental analysis. The new system displays both hydrophobic interaction chromatography (HIC) character in a high salt concentration mobile phase, and weak cation exchange (WCX) chromatography character in a low salt concentration mobile phase. It can be used to separate proteins in both ion-exchange chromatography (IEC) mode and HIC mode. The resolution and selectivity of the stationary phase were evaluated in both HIC mode and IEC mode using protein standards. In comparison with the conventional WCX and HIC columns, the results were satisfactory and acceptable. Protein mass and bioactivity recoveries of more than 96% can be achieved in both HIC mode and IEC mode using this column. The results indicate that the novel dual-function mixed-mode column in many cases can replace the use of two individual WCX and HIC columns. In addition, the effects on protein separation of different ligand structures in the dual-function stationary phase and the pH of the mobile phase used were also investigated in detail. The results show that electrostatic interaction of the ligand with proteins must match the hydrophobicity of the ligand, which is an important factor to prepare the dual-function stationary phase. On the basis of this dual-function mixed-mode chromatography column, a new two-dimensional liquid chromatography technology with a single column system was also developed in this study, and was used to renature and purify recombinant human interferon-γ from inclusion bodies. The mass recovery, purity, and specific bioactivity obtained for the purified recombinant human interferon-γ were 87.2%, 92.4%, and 2.8 × 10(7) IU/mg, respectively, in IEC mode, and 83.4%, 95.2%, and 4.3 × 10(7) IU/mg, respectively, in HIC mode. The results indicate that the

  3. Characterisation of nanomaterial hydrophobicity using engineered surfaces

    Science.gov (United States)

    Desmet, Cloé; Valsesia, Andrea; Oddo, Arianna; Ceccone, Giacomo; Spampinato, Valentina; Rossi, François; Colpo, Pascal

    2017-03-01

    Characterisation of engineered nanomaterials (NMs) is of outmost importance for the assessment of the potential risks arising from their extensive use. NMs display indeed a large variety of physico-chemical properties that drastically affect their interaction with biological systems. Among them, hydrophobicity is an important property that is nevertheless only slightly covered by the current physico-chemical characterisation techniques. In this work, we developed a method for the direct characterisation of NM hydrophobicity. The determination of the nanomaterial hydrophobic character is carried out by the direct measurement of the affinity of the NMs for different collectors. Each collector is an engineered surface designed in order to present specific surface charge and hydrophobicity degrees. Being thus characterised by a combination of surface energy components, the collectors enable the NM immobilisation with surface coverage in relation to their hydrophobicity. The experimental results are explained by using the extended DLVO theory, which takes into account the hydrophobic forces acting between NMs and collectors.

  4. Nanomechanical probing of soft matter through hydrophobic AFM tips fabricated by two-photon polymerization

    Science.gov (United States)

    Suriano, Raffaella; Zandrini, Tommaso; De Marco, Carmela; Osellame, Roberto; Turri, Stefano; Bragheri, Francesca

    2016-04-01

    Atomic force microscopy (AFM) nanoindentation of soft materials is a powerful tool for probing mechanical properties of biomaterials. Though many results have been reported in this field over the last decade, adhesion forces between the tip and the sample hinder the elastic modulus measurement when hydrophilic soft samples are investigated. Here, two-photon polymerization (2PP) technology was used to fabricate hydrophobic perfluoropolyether-based AFM tips. The hydrophobic 2PP tips allowed us to overcome the limitations of commercial and functionalized tips as well as to successfully measure the elastic modulus of medically relevant soft materials in air. Our results obtained in the characterization of poly(dimethyl siloxane) and polyethylene glycol hydrogels showed lower adhesion forces over a larger measurement range when compared to measurements performed with commercial tips. The elastic moduli measured by means of hydrophobic 2PP AFM tips were also found to be comparable to those obtained using conventional techniques for macroscopic samples. We successfully showed that the hydrophobic AFM tips developed by this highly versatile technology enable the study of mechanical properties of soft matter, benefiting from reduced sample-tip interactions, and a custom-made shape and dimension of the tips.

  5. Nanomechanical probing of soft matter through hydrophobic AFM tips fabricated by two-photon polymerization.

    Science.gov (United States)

    Suriano, Raffaella; Zandrini, Tommaso; De Marco, Carmela; Osellame, Roberto; Turri, Stefano; Bragheri, Francesca

    2016-04-15

    Atomic force microscopy (AFM) nanoindentation of soft materials is a powerful tool for probing mechanical properties of biomaterials. Though many results have been reported in this field over the last decade, adhesion forces between the tip and the sample hinder the elastic modulus measurement when hydrophilic soft samples are investigated. Here, two-photon polymerization (2PP) technology was used to fabricate hydrophobic perfluoropolyether-based AFM tips. The hydrophobic 2PP tips allowed us to overcome the limitations of commercial and functionalized tips as well as to successfully measure the elastic modulus of medically relevant soft materials in air. Our results obtained in the characterization of poly(dimethyl siloxane) and polyethylene glycol hydrogels showed lower adhesion forces over a larger measurement range when compared to measurements performed with commercial tips. The elastic moduli measured by means of hydrophobic 2PP AFM tips were also found to be comparable to those obtained using conventional techniques for macroscopic samples. We successfully showed that the hydrophobic AFM tips developed by this highly versatile technology enable the study of mechanical properties of soft matter, benefiting from reduced sample-tip interactions, and a custom-made shape and dimension of the tips.

  6. [Formation of 55-kDa Fragments under Impaired Coordination Bonds and Hydrophobic Interactions in Peripheral Light-Harvesting Complexes Isolated from Photosynthetic Purple Bacteria].

    Science.gov (United States)

    Solov'ev, A A; Erokhin, Y E

    2015-01-01

    Size exclusion chromatography was used to assess the relative size of intact and diphenylamine-treated (DPA, with suppressed carotenoid synthesis) peripheral light-harvesting complexes (LH2 complexes) of the sulfurbacterium Allochromatium minutissimum. Both LH2 complexes were nonamers and had the same elution volume V(e), coinciding with that for the LH2 complex of Rhodoblastus acidophilus (strain 10050). Their molecular mass was 150 kDa. Bot pheophytinization of bacteriochlorophyll (BChl) at low pH and treatment with the detergent LDAO, affecting the hydrophobic interactions between the neighboring protomers, result in the fragmentation of the ring of the isolated LH2 complexes and formation of 55-kDa fragments with molecular masses corresponding to one-third of the initial value. Fragmentation caused by both pheophytinization and detergent treatment was much more rapid in DPA-treated LH2 complexes than in the intact ones. The 55-kDa fragments formed at low pH values contained monomeric bacteriopheophytin, while the fragments of a similar molecular mass formed at pH 8.0 in the presence of the detergent contained monomeric BChl. The observed fragmentation was hypothesized to reflect the inherent C3 symmetry of the LH2 complexes, with the preliminarily assembled trimers used as building blocks.

  7. Three dimensional liquid chromatography coupling ion exchange chromatography/hydrophobic interaction chromatography/reverse phase chromatography for effective protein separation in top-down proteomics.

    Science.gov (United States)

    Valeja, Santosh G; Xiu, Lichen; Gregorich, Zachery R; Guner, Huseyin; Jin, Song; Ge, Ying

    2015-01-01

    To address the complexity of the proteome in mass spectrometry (MS)-based top-down proteomics, multidimensional liquid chromatography (MDLC) strategies that can effectively separate proteins with high resolution and automation are highly desirable. Although various MDLC methods that can effectively separate peptides from protein digests exist, very few MDLC strategies, primarily consisting of 2DLC, are available for intact protein separation, which is insufficient to address the complexity of the proteome. We recently demonstrated that hydrophobic interaction chromatography (HIC) utilizing a MS-compatible salt can provide high resolution separation of intact proteins for top-down proteomics. Herein, we have developed a novel 3DLC strategy by coupling HIC with ion exchange chromatography (IEC) and reverse phase chromatography (RPC) for intact protein separation. We demonstrated that a 3D (IEC-HIC-RPC) approach greatly outperformed the conventional 2D IEC-RPC approach. For the same IEC fraction (out of 35 fractions) from a crude HEK 293 cell lysate, a total of 640 proteins were identified in the 3D approach (corresponding to 201 nonredundant proteins) as compared to 47 in the 2D approach, whereas simply prolonging the gradients in RPC in the 2D approach only led to minimal improvement in protein separation and identifications. Therefore, this novel 3DLC method has great potential for effective separation of intact proteins to achieve deep proteome coverage in top-down proteomics.

  8. Purification of chimeric heavy chain monoclonal antibody EG2-hFc using hydrophobic interaction membrane chromatography: an alternative to protein-A affinity chromatography.

    Science.gov (United States)

    Sadavarte, Rahul; Spearman, Maureen; Okun, Natalie; Butler, Michael; Ghosh, Raja

    2014-06-01

    Heavy chain monoclonal antibodies are being considered as alternative to whole-IgG monoclonal antibodies for certain niche applications. Protein-A chromatography which is widely used for purifying IgG monoclonal antibodies is also used for purifying heavy chain monoclonal antibodies as these molecules possess fully functional Fc regions. However, the acidic conditions used to elute bound antibody may sometimes also leach protein-A, which is immunotoxic. Low pH conditions also tend to make the mAb molecules unstable and prone to aggregation. Moreover, protein-A affinity chromatography does not remove aggregates already present in the feed. Hydrophobic interaction membrane chromatography (or HIMC) has already been studied as an alternative to protein-A chromatography for purifying whole-IgG monoclonal antibodies. This paper describes the use of HIMC for capturing a humanized chimeric heavy chain monoclonal antibody (EG2-hFC). Binding and eluting conditions were suitably optimized using pure EG2-hFC. Based on this, an HIMC method was developed for capture of EG2-hFC directly from cell culture supernatant. The EG2-hFc purity obtained in this single-step process was high. The glycan profiles of protein-A and HIMC purified monoclonal antibody samples were similar, clearly demonstrating that both techniques captured similarly glycosylated population of EG2-hFc. Moreover, this technique was able to resolve aggregates from monomeric form of the EG2-hFc.

  9. Isolation of monoclonal antibody from a Chinese hamster ovary supernatant. II: dynamics of the integrated separation on ion exchange and hydrophobic interaction chromatography media.

    Science.gov (United States)

    Marek, Wojciech; Muca, Renata; Woś, Sylwia; Piątkowski, Wojciech; Antos, Dorota

    2013-08-30

    Dynamics of the purification process of a CHO derived monoclonal antibody by ion exchange chromatography (IEC), hydrophobic interaction chromatography (HIC) and their integration has been investigated. To quantify the adsorption behavior of the target protein (IgG1) and impurities contained in the supernatant, their elution course on IEC and HIC columns has been analyzed versus pH and/or the salt concentration in the mobile phase. A short-cut method has been proposed for mathematical modeling and determining underlying kinetic and thermodynamic parameters. The accuracy of the model predictions has been verified by comparing the simulated and experimental band profiles recorded in both chromatographic processes. After verification, the model was used to optimize operating conditions for the column loading and chromatographic elution in the integrated process IEC/HIC. Two alternative loading techniques based on the upstream and downstream feed dilution were taken into account in the optimization routine. In the first one the feed stream was diluted with the loading buffer prior to the column loading, while in the latter one the feed dilution was realized inside the column using the multiple-injection technique. It was shown that the downstream dilution allowed significant reduction of the contact time between the protein and the loading buffer.

  10. Time and Matter in the Interaction between Gravity and Quantum Fluids: Are there Macroscopic Quantum Transducers between Gravitational and Electromagnetic waves?

    CERN Document Server

    Chiao, R Y; Chiao, Raymond Y.; Fitelson, Walter J.

    2006-01-01

    Measurements of the tunneling time are briefly reviewed. Next, time and matter in general relativity and quantum mechanics is examined. In particular, the question arises: How does gravitational radiation interact with a coherent quantum many-body system (a ``quantum fluid'')? A minimal coupling rule for the coupling of the electron spin to curved spacetime in general relativity implies the possibility of a coupling between electromagnetic (EM) and gravitational (GR) radiation mediated by a quantum Hall fluid. This suggests that quantum transducers between these two kinds of radiation fields might exist. We report here on a first attempt at a Hertz-type experiment, in which a high-$\\rm{T_c}$ superconductor (YBCO) was the material used as a quantum transducer to convert EM into GR microwaves, and a second piece of YBCO in a separate apparatus was used to back-convert GR into EM microwaves. An upper limit on the conversion efficiency of YBCO was measured to be $1.6\\times10^{-5}$.

  11. The role of hydrophobicity and surface receptors at hyphae of Lyophyllum sp. strain Karsten in the interaction with Burkholderia terrae BS001 : Implications for interactions in soil

    NARCIS (Netherlands)

    Vila, Taissa; Nazir, Rashid; Rozental, Sonia; dos Santos, Giulia M. P.; Calixto, Renata O.R.; Barreto-Bergter, Eliana; Wick, Lukas Y.; van Elsas, Jan Dirk

    2016-01-01

    The soil bacterium Burkholderia terrae strain BS001 can interact with varying soil fungi, using mechanisms that range from the utilization of carbon/energy sources such as glycerol to the ability to reach novel territories in soil via co-migration with growing fungal mycelia. Here, we investigate th

  12. Macroscopic-microscopic mass models

    CERN Document Server

    Nix, J R; Nix, J Rayford; Moller, Peter

    1995-01-01

    We discuss recent developments in macroscopic-microscopic mass models, including the 1992 finite-range droplet model, the 1992 extended-Thomas-Fermi Strutinsky-integral model, and the 1994 Thomas-Fermi model, with particular emphasis on how well they extrapolate to new regions of nuclei. We also address what recent developments in macroscopic-microscopic mass models are teaching us about such physically relevant issues as the nuclear curvature energy, a new congruence energy arising from a greater-than-average overlap of neutron and proton wave functions, the nuclear incompressibility coefficient, and the Coulomb redistribution energy arising from a central density depression. We conclude with a brief discussion of the recently discovered rock of metastable superheavy nuclei near 272:110 that had been correctly predicted by macroscopic-microscopic models, along with a possible new tack for reaching an island near 290:110 beyond our present horizon.

  13. A new approach on the purification of recombinant human soluble catechol-O-methyltransferase from an Escherichia coli extract using hydrophobic interaction chromatography.

    Science.gov (United States)

    Passarinha, L A; Bonifácio, M J; Soares-da-Silva, P; Queiroz, J A

    2008-01-11

    Catechol-O-methyltransferase (COMT) is a significant target in protein engineering due to its role not only in normal brain function but also to its possible involvement in some human disorders. In this work, a new approach was employed for the purification of recombinant human soluble COMT (hSCOMT) using hydrophobic interaction chromatography, as the main isolation method, from an Escherichia coli culture broth. A simplified overall process flow is proposed. Indeed, with an optimized heterologous expression system for recombinant hSCOMT production, such as E. coli, it was possible to produce and recover the active monomeric enzyme directly from the cell crude culture broth either by a freeze/thaw or ultrasonication lysis step. The recombinant enzyme present in the bacterial soluble fraction, exhibited similar affinity for epinephrine (K(m) 276 [215; 337] microM) and the methyl donor (S-adenosyl-L-methionine, SAMe) (K(m) 36 [30; 41]microM) as human SCOMT. After the precipitation step by 55% of ammonium sulphate, a HIC step on the butyl-sepharose resin was found to be highly effective in selectively eluting a range of contaminating key proteins present in the concentrate soluble extract. Consequently, the partially purified eluate from HIC could then be loaded and polished by gel filtration in order to increase the process efficiency. The final product appeared as a single band in sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE). The procedure resulted in a global 10.9-fold purification with a specific activity of 5500 nmol/h/mg of protein. The widespread applicability of the process, here described, to different COMT sources could make this protocol highly useful for all studies requiring purified and active COMT proteins.

  14. 四苯硼钠在活性炭表面吸附过程的疏水相互作用%Hydrophobic interaction for the adsorption of sodium tetraphenylborate onto activated carbon

    Institute of Scientific and Technical Information of China (English)

    于玲; 王晓玲; 邹立壮; 支献华; 朱书全

    2003-01-01

    In this paper, the adsorption characteristics of sodium tetraphenylborate(NaBPh4) on activated carbon at 298.2,303.2,308.2,313..2 and 323.2 K was studied.The results show that the adsorption isotherm of NaBPh4 on activated carbon at different temperatures could be described using Langrnuir equation. Furthermore, the standard Gibbs energy, enthalpy, entropy and hydrophobic interaction Gibbs energy for the adsorption of NaBPh4 on activated carbon were studied, and the result shows that the hydrophobic interaction of BPh4- ion plays the most important role for the transfer of NaBPh4 from water to activated carbon surface.

  15. Macroscopic Quantum Criticality in a Circuit QED

    CERN Document Server

    Wang, Y D; Nori, F; Quan, H T; Sun, C P; Liu, Yu-xi; Nori, Franco

    2006-01-01

    Cavity quantum electrodynamic (QED) is studied for two strongly-coupled charge qubits interacting with a single-mode quantized field, which is provided by a on-chip transmission line resonator. We analyze the dressed state structure of this superconducting circuit QED system and the selection rules of electromagnetic-induced transitions between any two of these dressed states. Its macroscopic quantum criticality, in the form of ground state level crossing, is also analyzed, resulting from competition between the Ising-type inter-qubit coupling and the controllable on-site potentials.

  16. Terahertz Science and Technology of Macroscopically Aligned Carbon Nanotube Films

    Science.gov (United States)

    Kono, Junichiro

    One of the outstanding challenges in nanotechnology is how to assemble individual nano-objects into macroscopic architectures while preserving their extraordinary properties. For example, the one-dimensional character of electrons in individual carbon nanotubes leads to extremely anisotropic transport, optical, and magnetic phenomena, but their macroscopic manifestations have been limited. Here, we describe methods for preparing macroscopic films, sheets, and fibers of highly aligned carbon nanotubes and their applications to basic and applied terahertz studies. Sufficiently thick films act as ideal terahertz polarizers, and appropriately doped films operate as polarization-sensitive, flexible, powerless, and ultra-broadband detectors. Together with recently developed chirality enrichment methods, these developments will ultimately allow us to study dynamic conductivities of interacting one-dimensional electrons in macroscopic single crystals of single-chirality single-wall carbon nanotubes.

  17. Large Deviations for the Macroscopic Motion of an Interface

    Science.gov (United States)

    Birmpa, P.; Dirr, N.; Tsagkarogiannis, D.

    2017-03-01

    We study the most probable way an interface moves on a macroscopic scale from an initial to a final position within a fixed time in the context of large deviations for a stochastic microscopic lattice system of Ising spins with Kac interaction evolving in time according to Glauber (non-conservative) dynamics. Such interfaces separate two stable phases of a ferromagnetic system and in the macroscopic scale are represented by sharp transitions. We derive quantitative estimates for the upper and the lower bound of the cost functional that penalizes all possible deviations and obtain explicit error terms which are valid also in the macroscopic scale. Furthermore, using the result of a companion paper about the minimizers of this cost functional for the macroscopic motion of the interface in a fixed time, we prove that the probability of such events can concentrate on nucleations should the transition happen fast enough.

  18. Preparation of hydrophobic coatings

    Science.gov (United States)

    Branson, Eric D.; Shah, Pratik B.; Singh, Seema; Brinker, C. Jeffrey

    2009-02-03

    A method for preparing a hydrophobic coating by preparing a precursor sol comprising a metal alkoxide, a solvent, a basic catalyst, a fluoroalkyl compound and water, depositing the precursor sol as a film onto a surface, such as a substrate or a pipe, heating, the film and exposing the film to a hydrophobic silane compound to form a hydrophobic coating with a contact angle greater than approximately 150.degree.. The contact angle of the film can be controlled by exposure to ultraviolet radiation to reduce the contact angle and subsequent exposure to a hydrophobic silane compound to increase the contact angle.

  19. A Macroscopic Analogue of the Nuclear Pairing Potential

    Science.gov (United States)

    Dunlap, Richard A.

    2013-01-01

    A macroscopic system involving permanent magnets is used as an analogue to nucleons in a nucleus to illustrate the significance of the pairing interaction. This illustrates that the view of the total nuclear energy based only on the nucleon occupancy of the energy levels can yield erroneous results and it is only when the pairing interaction is…

  20. Prediction of coal hydrophobicity

    Energy Technology Data Exchange (ETDEWEB)

    Labuschagne, B.C.J. [Council for Scientific and Industrial Research, Pretoria (South Africa). Div. of Energy Technology; Wheelock, T.D.; Guo, R.K.; David, H.T. [Iowa State Univ. of Science and Technology, Ames, IA (United States); Markuszewski, R. [Ames Lab., IA (United States)

    1988-12-31

    Many coals exhibit a certain degree of native hydrophobicity. The more hydrophobic coals (the higher-rank coals) are easily beneficiated by froth flotation or oil agglomeration, while the more hydrophilic coals (the lower-rank coals) are floated or agglomerated with difficulty. Coals of different ranks and often even of the same rank sometimes differ greatly in hydrophobicity as measured by contact angle or natural floatability. Although the degree of hydrophobicity of a coal is related to its rank and has been correlated with other surface properties of the coal , the known information is still not sufficient to allow a good estimation to be made of the hydrophobicity of a given coal and does not explain the variation of coal hydrophobicity as a function of rank. A statistical analysis of previously published data, as well as newly acquired data, shows that coal hydrophobicity correlates better with moisture content than with carbon content, and better with the moisture/carbon molar ratio than with the hydrogen/carbon or oxygen/carbon atomic ratios. These findings indicate that there is a strong association between hydrophobicity and coal moisture content.

  1. Contacts Between Alcohols in Water Are Random Rather than Hydrophobic.

    Science.gov (United States)

    Rankin, Blake M; Ben-Amotz, Dor; van der Post, Sietse T; Bakker, Huib J

    2015-02-19

    Given the importance of water-mediated hydrophobic interactions in a wide range of biological and synthetic self-assembly processes, it is remarkable that both the sign and the magnitude of the hydrophobic interactions between simple amphiphiles, such as alcohols, remain unresolved. To address this question, we have performed Raman hydration-shell vibrational spectroscopy and polarization-resolved femtosecond infrared experiments, as well as random mixing and molecular dynamics simulations. Our results indicate that there are no more hydrophobic contacts in aqueous solutions of alcohols ranging from methanol to tertiary butyl alcohol than in random mixtures of the same concentration. This implies that the interaction between small hydrophobic groups is weaker than thermal energy fluctuations. Thus, the corresponding water-mediated hydrophobic interaction must be repulsive, with a magnitude sufficient to negate the attractive direct van der Waals interaction between the hydrophobic groups.

  2. Water structuring and hydroxide ion binding at the interface between water and hydrophobic Walls of varying rigidity and van der Waals interactions

    NARCIS (Netherlands)

    Vacha, Robert; Zangi, Ronen; Engberts, Jan B. F. N.; Jungwirth, Pavel

    2008-01-01

    The interfacial behavior of hydroxide ions has been investigated by means of molecular dynamics simulations of aqueous KOH solutions between hydrophobic carbon-like walls. In agreement with previous calculations, we show that a rigid, attractive wall strongly structures water molecules in neighborin

  3. High-Resolution Coarse-Grained Model of Hydrated Anion-Exchange Membranes that Accounts for Hydrophobic and Ionic Interactions through Short-Ranged Potentials.

    Science.gov (United States)

    Lu, Jibao; Jacobson, Liam C; Perez Sirkin, Yamila A; Molinero, Valeria

    2017-01-10

    Molecular simulations provide a versatile tool to study the structure, anion conductivity, and stability of anion-exchange membrane (AEM) materials and can provide a fundamental understanding of the relation between structure and property of membranes that is key for their use in fuel cells and other applications. The quest for large spatial and temporal scales required to model the multiscale structure and transport processes in the polymer electrolyte membranes, however, cannot be met with fully atomistic models, and the available coarse-grained (CG) models suffer from several challenges associated with their low-resolution. Here, we develop a high-resolution CG force field for hydrated polyphenylene oxide/trimethylamine chloride (PPO/TMACl) membranes compatible with the mW water model using a hierarchical parametrization approach based on Uncertainty Quantification and reference atomistic simulations modeled with the Generalized Amber Force Field (GAFF) and TIP4P/2005 water. The parametrization weighs multiple properties, including coordination numbers, radial distribution functions (RDFs), self-diffusion coefficients of water and ions, relative vapor pressure of water in the solution, hydration enthalpy of the tetramethylammonium chloride (TMACl) salt, and cohesive energy of its aqueous solutions. We analyze the interdependence between properties and address how to compromise between the accuracies of the properties to achieve an overall best representability. Our optimized CG model FFcomp quantitatively reproduces the diffusivities and RDFs of the reference atomistic model and qualitatively reproduces the experimental relative vapor pressure of water in solutions of tetramethylammonium chloride. These properties are of utmost relevance for the design and operation of fuel cell membranes. To our knowledge, this is the first CG model that includes explicitly each water and ion and accounts for hydrophobic, ionic, and intramolecular interactions explicitly

  4. Desalting of phosphopeptides by tandem polypyrrole-c18 reverse phase micropipette tip (TMTip{sub PPY-C18}) based on hybrid electrostatic, {Pi}-{Pi} stacking and hydrophobic interactions for mass spectrometric analysis

    Energy Technology Data Exchange (ETDEWEB)

    Zheng Shi; Wang Xiaoli; Fu Jieying; Hu Xuejiao; Xiao Xiao; Huang Lulu; Zhou Youe [Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079 (China); Zhong Hongying, E-mail: hyzhong@mail.ccnu.edu.cn [Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079 (China)

    2012-04-29

    Highlights: Black-Right-Pointing-Pointer A new micropipette tip TMTip{sub PPY-C18} was developed for desalting of phosphopeptides. Black-Right-Pointing-Pointer TMTip{sub PPY-C18} is based on polypyrrole in tandem with C18 chromatographic material. Black-Right-Pointing-Pointer TMTip{sub PPY-C18} combines electrostatic, {Pi}-{Pi} stacking and hydrophobic interactions. Black-Right-Pointing-Pointer TMTip{sub PPY-C18} can be used in both acidic and basic experimental conditions. - Abstract: Desalting and concentration of peptides using reverse phase (RP) C18 chromatographic material based on hydrophobic interaction is a routine approach used in mass spectrometry (MS)-based proteomics. However, MS detection of small hydrophilic peptides, in particular, phosphopeptides that bear multiple negative charges, is challenging due to the insufficient binding to C18 stationary phase. We described here the development of a new desalting method that takes the unique properties of polypyrrole (PPY). The presence of positively charged nitrogen atoms under acidic conditions and polyunsaturated bonds in polypyrrole provide a prospect for enhanced adsorption of phosphopeptides or hydrophilic peptides through extra electrostatic and {Pi}-{Pi} stacking interactions in addition to hydrophobic interactions. In tandem with reversed phase C18 chromatographic material, the new type of desalting method termed as TMTip{sub PPY-C18} can significantly improve the MS detection of phosphopeptides with multiple phosphate groups and other small hydrophilic peptides. It has been applied to not only tryptic digest of model proteins but also the analysis of complex lysates of zebrafish eggs. The number of detected phosphate groups on a peptide ranged from 1 to 6. Particularly, polypyrrole based method can also be used in basic condition. Thus it provides a useful means to handle peptides that may not be detectable in acidic condition. It can be envisioned that the TMTip{sub PPY-C18} should be able to

  5. Wetting in hydrophobic nanochannels: a challenge of classical capillarity.

    Science.gov (United States)

    Helmy, Roy; Kazakevich, Yuri; Ni, Chaoying; Fadeev, Alexander Y

    2005-09-14

    We report an investigation of the water-hydrophobic interface in well-defined nanochannels (R approximately 2-4 nm). Wetting in these systems cannot be described by classical (macroscopic) capillary theory: (1) water occupies only a fraction ( approximately 60%) of the pore volume, and (2) the capillary pressures are approximately 60-90% greater than predicted by the Laplace equation. The results suggest the presence of approximately 0.6 nm layer of low-density fluid (vapor) separating water from the hydrophobic solid.

  6. Macroscopic domain formation in the platelet plasma membrane

    DEFF Research Database (Denmark)

    Bali, Rachna; Savino, Laura; Ramirez, Diego A.;

    2009-01-01

    There has been ample debate on whether cell membranes can present macroscopic lipid domains as predicted by three-component phase diagrams obtained by fluorescence microscopy. Several groups have argued that membrane proteins and interactions with the cytoskeleton inhibit the formation of large d...

  7. The fundamental diagram : a macroscopic traffic flow model.

    NARCIS (Netherlands)

    Botma, H.

    1976-01-01

    In models of traffic flow, the interactions between vehicles are of prime interest, and are based on characteristics of the drivers, road and vehicles. The fundamental diagram is a representation of a relationship on a macroscopic level in the steady state between the quantity of traffic and a chara

  8. The physical origin of hydrophobic effects

    CERN Document Server

    Sun, Qiang

    2016-01-01

    Because the strength of hydrogen bonding in water is stronger than that of van der Waals Interaction, water should play an important role in the process of hydrophobic effects. According to our recent structural studies on bulk water and air/water interface, the hydrophobic solutes mainly affect the structure of the topmost water layer (interfacial water) at solute/water interface. In reference with bulk water, due to truncations of hydrogen bonding at the interface, the effects of solutes on water structure are ascribed to the loss of tetrahedral hydrogen bonding in interfacial water. From this, the hydration free energy is derived, and utilized to investigate the dissolved behaviors of hydrophobic solutes. With increasing the size of solutes, this leads to the increase of hydration free energy, which can be divided into the initial solvation and hydrophobic solvation processes, respectively. In the initial solvation process, the hydration free energy is dominated by the hydrogen bonding in interfacial water...

  9. Macroscopic Theory of Dark Sector

    Directory of Open Access Journals (Sweden)

    Boris E. Meierovich

    2014-01-01

    Full Text Available A simple Lagrangian with squared covariant divergence of a vector field as a kinetic term turned out to be an adequate tool for macroscopic description of the dark sector. The zero-mass field acts as the dark energy. Its energy-momentum tensor is a simple additive to the cosmological constant. Massive fields describe two different forms of dark matter. The space-like massive vector field is attractive. It is responsible for the observed plateau in galaxy rotation curves. The time-like massive field displays repulsive elasticity. In balance with dark energy and ordinary matter it provides a four-parametric diversity of regular solutions of the Einstein equations describing different possible cosmological and oscillating nonsingular scenarios of evolution of the Universe. In particular, the singular big bang turns into a regular inflation-like transition from contraction to expansion with the accelerated expansion at late times. The fine-tuned Friedman-Robertson-Walker singular solution is a particular limiting case at the lower boundary of existence of regular oscillating solutions in the absence of vector fields. The simplicity of the general covariant expression for the energy-momentum tensor allows displaying the main properties of the dark sector analytically. Although the physical nature of dark sector is still unknown, the macroscopic theory can help analyze the role of dark matter in astrophysical phenomena without resorting to artificial model assumptions.

  10. Experimental Study on Physical Mechanism of Drag Reduction of Hydrophobic Materials in Laminar Flow

    Institute of Scientific and Technical Information of China (English)

    YU Yong-Sheng; WEI Qin-Ding

    2006-01-01

    We experimentally study the physical mechanism of the drag reduction of hydrophobic materials in the macroscopic scale. The experiment includes the drag and velocity measurements of laminar boundary layer Sow over flat plates, and the observation of air bubbles on the surfaces. The plate surfaces have different wetting and roughness properties. In the drag measurements, the plates with bubbles on the surfaces lead to drag reduction, but not for those without bubbles. Velocity measurement confirms that the flow is laminar and gives apparent fluid slip on the plate wall with bubbles. In observation, air bubbles in macroscopic size emerge and enlarge on hydrophobic surfaces but not on hydrophilic surfaces. Therefore, the drag reduction of hydrophobic materials is explained by the generation of air bubbles of macroscopic size that cause the apparent velocity slip.

  11. Black Holes and Quantumness on Macroscopic Scales

    CERN Document Server

    Flassig, D; Wintergerst, N

    2012-01-01

    It has recently been suggested that black holes may be described as condensates of weakly interacting gravitons at a critical point, exhibiting strong quantum effects. In this paper, we study a model system of attractive bosons in one spatial dimension which is known to undergo a quantum phase transition. We demonstrate explicitly that indeed quantum effects are important at the critical point, even if the number of particles is macroscopic. Most prominently, we evaluate the entropy of entanglement between different momentum modes and observe it to become maximal at the critical point. Furthermore, we explicitly see that the leading entanglement is between long wavelength modes and is hence a feature independent of ultraviolet physics. If applicable to black holes, our findings substantiate the conjectured breakdown of semiclassical physics even for large black holes. This can resolve long standing mysteries, such as the information paradox and the no-hair theorem.

  12. Intrusion and extrusion of water in hydrophobic mesopores

    OpenAIRE

    Barrat, Jean-Louis; Lefevre, Benoit; Bocquet, Lyderic; Saugey, Anthony; Vigier, Gérard; Gobin, Pierre-François; Charlaix, Elisabeth

    2003-01-01

    We present experimental and theoretical results on intrusion-extrusion cycles of water in hydrophobic mesoporous materials, characterized by independent cylindrical pores. The intrusion, which takes place above the bulk saturation pressure, can be well described using a macroscopic capillary model. Once the material is saturated with water, extrusion takes place upon reduction of the externally applied pressure; Our results for the extrusion pressure can only be understood by assuming that th...

  13. Distance-dependent hydrophobic-hydrophobic contacts in protein folding simulations.

    Science.gov (United States)

    Onofrio, Angelo; Parisi, Giovanni; Punzi, Giuseppe; Todisco, Simona; Di Noia, Maria Antonietta; Bossis, Fabrizio; Turi, Antonio; De Grassi, Anna; Pierri, Ciro Leonardo

    2014-09-21

    Successful prediction of protein folding from an amino acid sequence is a challenge in computational biology. In order to reveal the geometric constraints that drive protein folding, highlight those constraints kept or missed by distinct lattices and for establishing which class of intra- and inter-secondary structure element interactions is the most relevant for the correct folding of proteins, we have calculated inter-alpha carbon distances in a set of 42 crystal structures consisting of mainly helix, sheet or mixed conformations. The inter-alpha carbon distances were also calculated in several lattice "hydrophobic-polar" models built from the same protein set. We found that helix structures are more prone to form "hydrophobic-hydrophobic" contacts than beta-sheet structures. At a distance lower than or equal to 3.8 Å (very short-range interactions), "hydrophobic-hydrophobic" contacts are almost absent in the native structures, while they are frequent in all the analyzed lattice models. At distances in-between 3.8 and 9.5 Å (short-/medium-range interactions), the best performing lattice for reproducing mainly helix structures is the body-centered-cubic lattice. If protein structures contain sheet portions, lattice performances get worse, with few exceptions observed for double-tetrahedral and body-centered-cubic lattices. Finally, we can observe that ab initio protein folding algorithms, i.e. those based on the employment of lattices and Monte Carlo simulated annealings, can be improved simply and effectively by preventing the generation of "hydrophobic-hydrophobic" contacts shorter than 3.8 Å, by monitoring the "hydrophobic-hydrophobic/polar-polar" contact ratio in short-/medium distance ranges and by using preferentially a body-centered-cubic lattice.

  14. Solute partitioning in aqueous surfactant assemblies: comparison of hydrophobic-hydrophilic interactions in micelles, alcohol-swollen micelles, microemulsions, and synthetic vesicles

    Energy Technology Data Exchange (ETDEWEB)

    Russell, J.C.; Whitten, D.G.

    1982-11-03

    The structures of anionic assemblies including sodium lauryl sulfate (SLS) micelles, alcohol-swollen SLS micelles, microemulsions, and vesicles of a mixture of dipalmitoyllecithin and dicetyl phosphate are investigated by using the ground-state complexation of a hydrophilic quencher (methyl viologen) with several hydrophobic fluorescent probes, including surfactant stilbenes and 1,4-diphenylbutadiene. In SLS micelles this complexation can be decreased nearly an order of magnitude by addition of 1-heptanol, indicating that the structure of the micelle can be adjusted from the highly open structure of the pure micelle to a much more closed structure in which hydrophobic solubilizates can be sequestered from hydrophilic reagents bound to the surface. The fluorescence quenching process in anionic vesicles is strongly dependent on temperature; at low temperatures quenching occurs, while at higher temperatures addition of methyl viologen appears to increase the stilbene fluorescence, indicating that the dicationic quencher binds to the vesicle surface, increasing the order of the system. These results indicate that the degree of organization of surfactant systems can be adjusted by simple changes in composition. 33 references.

  15. Measurement-Induced Macroscopic Superposition States in Cavity Optomechanics

    Science.gov (United States)

    Hoff, Ulrich B.; Kollath-Bönig, Johann; Neergaard-Nielsen, Jonas S.; Andersen, Ulrik L.

    2016-09-01

    A novel protocol for generating quantum superpositions of macroscopically distinct states of a bulk mechanical oscillator is proposed, compatible with existing optomechanical devices operating in the bad-cavity limit. By combining a pulsed optomechanical quantum nondemolition (QND) interaction with nonclassical optical resources and measurement-induced feedback, the need for strong single-photon coupling is avoided. We outline a three-pulse sequence of QND interactions encompassing squeezing-enhanced cooling by measurement, state preparation, and tomography.

  16. Macroscopically-Discrete Quantum Cosmology

    CERN Document Server

    Chew, Geoffrey F

    2008-01-01

    To Milne's Lorentz-group-based spacetime and Gelfand-Naimark unitary representations of this group we associate a Fock space of 'cosmological preons'-quantum-theoretic universe constituents. Milne's 'cosmological principle' relies on Lorentz invariance of 'age'--global time. We divide Milne's spacetime into 'slices' of fixed macroscopic width in age, with 'cosmological rays' defined on (hyperbolic) slice boundaries-Fock space attaching only to these exceptional universe ages. Each (fixed-age) preon locates within a 6-dimensional manifold, one of whose 3 'extra' dimensions associates in Dirac sense to a self-adjoint operator that represents preon (continuous) local time, the operator canonically-conjugate thereto representing preon (total) energy. Self-adjoint-operator expectations at any spacetime-slice boundary prescribe throughout the following slice a non-fluctuating 'mundane reality'- electromagnetic and gravitational potentials 'tethered' to current densities of locally-conserved electric charge and ener...

  17. Seismic scanning tunneling macroscope - Theory

    KAUST Repository

    Schuster, Gerard T.

    2012-09-01

    We propose a seismic scanning tunneling macroscope (SSTM) that can detect the presence of sub-wavelength scatterers in the near-field of either the source or the receivers. Analytic formulas for the time reverse mirror (TRM) profile associated with a single scatterer model show that the spatial resolution limit to be, unlike the Abbe limit of λ/2, independent of wavelength and linearly proportional to the source-scatterer separation as long as the point scatterer is in the near-field region; if the sub-wavelength scatterer is a spherical impedance discontinuity then the resolution will also be limited by the radius of the sphere. Therefore, superresolution imaging can be achieved as the scatterer approaches the source. This is analogous to an optical scanning tunneling microscope that has sub-wavelength resolution. Scaled to seismic frequencies, it is theoretically possible to extract 100 Hz information from 20 Hz data by imaging of near-field seismic energy.

  18. Evaporation-induced failure of hydrophobicity

    Science.gov (United States)

    Luo, H.; Liu, T.; Ma, J.; Wang, P.; Wang, Y.; Leprince-Wang, Y.; Jing, G.

    2016-09-01

    Hydrophobic coatings have tremendous applications in many fields of industries, and their robustness is an important subject of investigation. Here we experimentally demonstrate the detachment of hydrophobic coating and the formation of the residual deposit resulting from an evaporating drop of water. A hydrophobic octadecanethiol (ODT) coating is employed to enhance the hydrophobicity of ZnO nanowire arrays (advancing and receding contact angle of 165° and 128°, respectively). Being a model system of the unique bonding interaction between ODT and ZnO, water drop drying on the structure of ODT/ZnO is examined. Our experimental results showed the significant depression and even failure of the hydrophobicity on this composite surface resulting from collecting the deposits of ODT molecules during the drop drying. By analyzing energy criterion and force balance, surface tension at the moving contact line is identified as a dominating destructive force to unstick the coating molecules. Interestingly, a normal rinsing stream does not damage this coating to alter its hydrophobicity, but rather is overshadowed by the evaporation of the tinny water drop. The drops of rain or condensed water outdoor may thus play the same role to damage the functional coatings after their evaporation. Our findings indicate that more delicate designs are needed to prevent the destructive effects of drop evaporation on superhydrophobic surfaces.

  19. Silver Nanoparticles-Based Nano-drop Spectrophotometric Determination of Cationic Surfactants Coupled with Hydrophobic Interaction; An Application to Pharmaceuticals and Environmental

    Directory of Open Access Journals (Sweden)

    Ashima Sharma

    2016-10-01

    Full Text Available The proposed work describes the nanodrop spectrophotometric determination of cationic surfactants using citrate-modified silver nanoparticles based on the aggregation of silver nanoparticles induced by cationic surfactants due to the hydrophobic effect. The visible color change in the solution of silver nanoparticle includes a red shift with the quenching of the absorption spectra. The maximum absorbance was measured at wavelength,λmax400 nm. The concentrations of cationic surfactants were determined using a nanodrop spectrophotometer with limits of detection of 15.0, 8.0, 6.0, 5.8, and 13.0 µM for dodecyl trimethyl ammonium bromide, myristiltrimethyl ammonium bromide, cetrimoniumtrimethyl ammonium bromide, cetylpyridinium chloride and benzalkonium chloride, respectively. The proposed method was successfully applied for the determination of cetylpyridinium chloride in commercial mouthwasher, gum astringent and nasal spray pharmaceuticals and environmental samples.

  20. Hydrophobic, Porous Battery Boxes

    Science.gov (United States)

    Bragg, Bobby J.; Casey, John E., Jr.

    1995-01-01

    Boxes made of porous, hydrophobic polymers developed to contain aqueous potassium hydroxide electrolyte solutions of zinc/air batteries while allowing air to diffuse in as needed for operation. Used on other types of batteries for in-cabin use in which electrolytes aqueous and from which gases generated during operation must be vented without allowing electrolytes to leak out.

  1. Hydrophobic treatment of concrete

    NARCIS (Netherlands)

    Vries, J. de; Polder, R.B.

    1996-01-01

    As part of the maintenance policy of the Dutch Ministry of Transport, Civil Engineering Division, hydrophobic treatment of concrete was considered as an additional protective measure against penetration of aggressive substances, for instance deicing salts in bridge decks. A set of tests was designed

  2. Hydrophobic treatment of concrete

    NARCIS (Netherlands)

    Vries, J.de; Polder, R.B.

    1997-01-01

    As part of the maintenance policy of the dutch Ministry of Transport, Civil Engineering Division, hydrophobic treatment of concrete was considered as an additional protective measure against penetration of aggressive substances, for instance deicing salts in bridge decks. A set of tests was designed

  3. Effects of varying interfacial surface tension on macroscopic polymer lenses

    Science.gov (United States)

    Zimmerman, Charlotte; White, Mason; Baylor, Martha-Elizabeth

    2015-09-01

    We investigate macroscopic polymer lenses (0.5- to 2.5-cm diameter) fabricated by dropping hydrophobic photocurable resin onto the surface of various hydrophilic liquid surfaces. Due to the intermolecular forces along the interface between the two liquids, a lens shape is formed. We find that we can vary the lens geometry by changing the region over which the resin is allowed to spread and the surface tension of the substrate to produce lenses with theoretically determined focal lengths ranging from 5 to 25 mm. These effects are varied by changing the container width, substrate composition, and substrate temperature. We present data for five different variants, demonstrating that we can control the lens dimensions for polymer lens applications that require high surface quality.

  4. Assembly of tobacco mosaic virus into fibrous and macroscopic bundled arrays mediated by surface aniline polymerization.

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Z.; Bruckman, M.; Li, S.; Lee, A.; Lee, B.; Pingali, S.-V.; Thiyagarajan, P.; Wang, Q.; Univ. of South Carolina

    2007-06-05

    One-dimensional (1D) polyaniline/tobacco mosaic virus (TMV) composite nanofibers and macroscopic bundles of such fibers were generated via a self-assembly process of TMV assisted by in-situ polymerization of polyaniline on the surface of TMV. At near-neutral reaction pH, branched polyaniline formed on the surface of TMV preventing lateral association. Therefore, long 1D nanofibers were observed with high aspect ratios and excellent processibility. At a lower pH, transmission electron microscopy (TEM) analysis revealed that initially long nanofibers were formed which resulted in bundled structures upon long-time reaction, presumably mediated by the hydrophobic interaction because of the polyaniline on the surface of TMV. In-situ time-resolved small-angle X-ray scattering study of TMV at different reaction conditions supported this mechanism. This novel strategy to assemble TMV into 1D and 3D supramolecular composites could be utilized in the fabrication of advanced materials for potential applications including electronics, optics, sensing, and biomedical engineering.

  5. Macroscopic theory of dark sector

    CERN Document Server

    Meierovich, Boris E

    2013-01-01

    A simple Lagrangian with squared covariant divergence of a vector field as a kinetic term turned out an adequate tool for macroscopic description of the dark sector. The zero-mass field acts as the dark energy. Its energy-momentum tensor is a simple additive to the cosmological constant. Massive fields {\\phi}_{I} with {\\phi}^{K}{\\phi}_{K}0 describe two different forms of dark matter. The space-like ({\\phi}^{K}{\\phi}_{K}0) massive field displays repulsive elasticity. In balance with dark energy and ordinary matter it provides a four parametric diversity of regular solutions of the Einstein equations describing different possible cosmological and oscillating non-singular scenarios of evolution of the universe. In particular, the singular big bang turns into a regular inflation-like transition from contraction to expansion with the accelerate expansion at late times. The fine-tuned Friedman-Robertson-Walker singular solution is a particular limiting case at the boundary of existence of regular oscillating soluti...

  6. Protein-induced bilayer Perturbations: Lipid ordering and hydrophobic coupling

    DEFF Research Database (Denmark)

    Petersen, Frederic Nicolas Rønne; Laursen, Ib; Bohr, Henrik;

    2009-01-01

    The host lipid bilayer is increasingly being recognized as an important non-specific regulator of membrane protein function. Despite considerable progress the interplay between hydrophobic coupling and lipid ordering is still elusive. We use electron spin resonance (ESR) to study the interaction...... and hydrophobic mismatch. Our findings also show that at high protein:lipid ratios the lipids are motionally restricted but not completely immobilized. Both exchange on and off rate values for the lipid ↔ gramicidin interaction are lowest at optimal hydrophobic matching. Hydrophobic mismatch of few Å results...... in up to 10-fold increased exchange rates as compared to the ‘optimal’ match situation pointing to the regulatory role of hydrophobic coupling in lipid–protein interactions....

  7. Phactr3/scapinin, a member of protein phosphatase 1 and actin regulator (phactr family, interacts with the plasma membrane via basic and hydrophobic residues in the N-terminus.

    Directory of Open Access Journals (Sweden)

    Akihiro Itoh

    Full Text Available Proteins that belong to the protein phosphatase 1 and actin regulator (phactr family are involved in cell motility and morphogenesis. However, the mechanisms that regulate the actin cytoskeleton are poorly understood. We have previously shown that phactr3, also known as scapinin, localizes to the plasma membrane, including lamellipodia and membrane ruffles. In the present study, experiments using deletion and point mutants showed that the basic and hydrophobic residues in the N-terminus play crucial roles in the localization to the plasma membrane. A BH analysis (http://helixweb.nih.gov/bhsearch is a program developed to identify membrane-binding domains that comprise basic and hydrophobic residues in membrane proteins. We applied this program to phactr3. The results of the BH plot analysis agreed with the experimentally determined region that is responsible for the localization of phactr3 to the plasma membrane. In vitro experiments showed that the N-terminal itself binds to liposomes and acidic phospholipids. In addition, we showed that the interaction with the plasma membrane via the N-terminal membrane-binding sequence is required for phactr3-induced morphological changes in Cos7 cells. The membrane-binding sequence in the N-terminus is highly conserved in all members of the phactr family. Our findings may provide a molecular basis for understanding the mechanisms that allow phactr proteins to regulate cell morphogenesis.

  8. Insights into the Hendra virus NTAIL-XD complex: Evidence for a parallel organization of the helical MoRE at the XD surface stabilized by a combination of hydrophobic and polar interactions.

    Science.gov (United States)

    Erales, Jenny; Beltrandi, Matilde; Roche, Jennifer; Maté, Maria; Longhi, Sonia

    2015-08-01

    The Hendra virus is a member of the Henipavirus genus within the Paramyxoviridae family. The nucleoprotein, which consists of a structured core and of a C-terminal intrinsically disordered domain (N(TAIL)), encapsidates the viral genome within a helical nucleocapsid. N(TAIL) partly protrudes from the surface of the nucleocapsid being thus capable of interacting with the C-terminal X domain (XD) of the viral phosphoprotein. Interaction with XD implies a molecular recognition element (MoRE) that is located within N(TAIL) residues 470-490, and that undergoes α-helical folding. The MoRE has been proposed to be embedded in the hydrophobic groove delimited by helices α2 and α3 of XD, although experimental data could not discriminate between a parallel and an antiparallel orientation of the MoRE. Previous studies also showed that if the binding interface is enriched in hydrophobic residues, charged residues located close to the interface might play a role in complex formation. Here, we targeted for site directed mutagenesis two acidic and two basic residues within XD and N(TAIL). ITC studies showed that electrostatics plays a crucial role in complex formation and pointed a parallel orientation of the MoRE as more likely. Further support for a parallel orientation was afforded by SAXS studies that made use of two chimeric constructs in which XD and the MoRE were covalently linked to each other. Altogether, these studies unveiled the multiparametric nature of the interactions established within this complex and contribute to shed light onto the molecular features of protein interfaces involving intrinsically disordered regions. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. MACROSCOPIC DIVERSITY FOR CDMA MOBILE SYSTEM

    Institute of Scientific and Technical Information of China (English)

    Pei Xiaoyan; Hu Jiandong

    2002-01-01

    A novel system of macroscopic diversity with voting rule in CDMA cellular system is suggested in order to raise the coverage and quality of service of CDMA mobile communication system. The estimation of the impact of macroscopic diversity on performance of CDMA cellular system is analyzed and investigated.

  10. MACROSCOPIC DIVERSITY FOR CDMA MOBILE SYSTEM

    Institute of Scientific and Technical Information of China (English)

    PeiXiaoyan; HuJiandong

    2002-01-01

    A novel system of macroscopic diversity with voting rule in CDMA cellular system is suggested in order to raise the coverage and quality of service of CDMA mobile communication system.The estimation of the impact of macroscopic diversity on performance of CDMA cellular system is analyzed and investigated.

  11. Hydrophobic sugar holograms

    Science.gov (United States)

    Mejias-Brizuela, N. Y.; Olivares-Pérez, A.; Páez-Trujillo, G.; Hernández-Garay, M. P.; Fontanilla-Urdaneta, R.; Fuentes-Tapia, I.

    2008-02-01

    The sugar matrix is used to record of phase holograms; it was modified with the purpose of obtaining a hydrophobic material to improve the stability of the registered image and to stimulate the photosensitivity of the sugar. The new material is formed by a sugar, pectin and vanillin dissolution. The diffraction efficiency parameter increases in comparison with only the sugar matrix, obtaining already of 10%.

  12. Fluoroalkyl and alkyl chains have similar hydrophobicities in binding to the "hydrophobic wall" of carbonic anhydrase.

    Science.gov (United States)

    Mecinović, Jasmin; Snyder, Phillip W; Mirica, Katherine A; Bai, Serena; Mack, Eric T; Kwant, Richard L; Moustakas, Demetri T; Héroux, Annie; Whitesides, George M

    2011-09-07

    hydrophobic effect in this representative system of protein and ligand: hydrophobic interactions, here, seem to comprise approximately equal contributions from enthalpy (plausibly from strengthening networks of hydrogen bonds among molecules of water) and entropy (from release of water from configurationally restricted positions).

  13. Rank distributions: A panoramic macroscopic outlook

    Science.gov (United States)

    Eliazar, Iddo I.; Cohen, Morrel H.

    2014-01-01

    This paper presents a panoramic macroscopic outlook of rank distributions. We establish a general framework for the analysis of rank distributions, which classifies them into five macroscopic "socioeconomic" states: monarchy, oligarchy-feudalism, criticality, socialism-capitalism, and communism. Oligarchy-feudalism is shown to be characterized by discrete macroscopic rank distributions, and socialism-capitalism is shown to be characterized by continuous macroscopic size distributions. Criticality is a transition state between oligarchy-feudalism and socialism-capitalism, which can manifest allometric scaling with multifractal spectra. Monarchy and communism are extreme forms of oligarchy-feudalism and socialism-capitalism, respectively, in which the intrinsic randomness vanishes. The general framework is applied to three different models of rank distributions—top-down, bottom-up, and global—and unveils each model's macroscopic universality and versatility. The global model yields a macroscopic classification of the generalized Zipf law, an omnipresent form of rank distributions observed across the sciences. An amalgamation of the three models establishes a universal rank-distribution explanation for the macroscopic emergence of a prevalent class of continuous size distributions, ones governed by unimodal densities with both Pareto and inverse-Pareto power-law tails.

  14. Macroscopic Quantum Phenomena from the Correlation, Coupling and Criticality Perspectives

    Science.gov (United States)

    Chou, C. H.; Hu, B. L.; Subaşi, Y.

    2011-12-01

    In this sequel paper we explore how macroscopic quantum phenomena can be measured or understood from the behavior of quantum correlations which exist in a quantum system of many particles or components and how the interaction strengths change with energy or scale, under ordinary situations and when the system is near its critical point. We use the nPI (master) effective action related to the Boltzmann-BBGKY / Schwinger-Dyson hierarchy of equations as a tool for systemizing the contributions of higher order correlation functions to the dynamics of lower order correlation functions. Together with the large N expansion discussed in our first paper [1] we explore 1) the conditions whereby an H-theorem is obtained, which can be viewed as a signifier of the emergence of macroscopic behavior in the system. We give two more examples from past work: 2) the nonequilibrium dynamics of N atoms in an optical lattice under the large Script N (field components), 2PI and second order perturbative expansions, illustrating how N and Script N enter in these three aspects of quantum correlations, coherence and coupling strength. 3) the behavior of an interacting quantum system near its critical point, the effects of quantum and thermal fluctuations and the conditions under which the system manifests infrared dimensional reduction. We also discuss how the effective field theory concept bears on macroscopic quantum phenomena: the running of the coupling parameters with energy or scale imparts a dynamical-dependent and an interaction-sensitive definition of 'macroscopia'.

  15. Investigation of dissipative forces near macroscopic media

    Energy Technology Data Exchange (ETDEWEB)

    Becker, R.S.

    1982-12-01

    The interaction of classical charged particles with the fields they induce in macroscopic dielectric media is investigated. For 10- to 1000-eV electrons, the angular perturbation of the trajectory by the image potential for surface impact parameters of 50 to 100 A is shown to be of the order of 0.001 rads over a distance of 100 A. The energy loss incurred by low-energy particles due to collective excitations such as surface plasmons is shown to be observable with a transition probability of 0.01 to 0.001 (Becker, et al., 1981b). The dispersion of real surface plasmon modes in planar and cylindrical geometries is discussed and is derived for pinhole geometry described in terms of a single-sheeted hyperboloid of revolution. An experimental apparatus for the measurement of collective losses for medium-energy electrons translating close to a dielectric surface is described and discussed. Data showing such losses at electron energies of 500 to 900 eV in silver foils containing many small apertures are presented and shown to be in good agreement with classical stopping power calculations and quantum mechanical calculations carried out in the low-velocity limit. The data and calculations are compared and contrasted with earlier transmission and reflection measurements, and the course of further investigation is discussed.

  16. Cloud Macroscopic Organization: Order Emerging from Randomness

    Science.gov (United States)

    Yuan, Tianle

    2011-01-01

    Clouds play a central role in many aspects of the climate system and their forms and shapes are remarkably diverse. Appropriate representation of clouds in climate models is a major challenge because cloud processes span at least eight orders of magnitude in spatial scales. Here we show that there exists order in cloud size distribution of low-level clouds, and that it follows a power-law distribution with exponent gamma close to 2. gamma is insensitive to yearly variations in environmental conditions, but has regional variations and land-ocean contrasts. More importantly, we demonstrate this self-organizing behavior of clouds emerges naturally from a complex network model with simple, physical organizing principles: random clumping and merging. We also demonstrate symmetry between clear and cloudy skies in terms of macroscopic organization because of similar fundamental underlying organizing principles. The order in the apparently complex cloud-clear field thus has its root in random local interactions. Studying cloud organization with complex network models is an attractive new approach that has wide applications in climate science. We also propose a concept of cloud statistic mechanics approach. This approach is fully complementary to deterministic models, and the two approaches provide a powerful framework to meet the challenge of representing clouds in our climate models when working in tandem.

  17. Cloud macroscopic organization: order emerging from randomness

    Directory of Open Access Journals (Sweden)

    T. Yuan

    2011-01-01

    Full Text Available Clouds play a central role in many aspects of the climate system and their forms and shapes are remarkably diverse. Appropriate representation of clouds in climate models is a major challenge because cloud processes span at least eight orders of magnitude in spatial scales. Here we show that there exists order in cloud size distribution of low-level clouds and it follows a power-law distribution with exponent γ close to 2. γ is insensitive to yearly variations in environmental conditions, but has regional variations and land-ocean contrasts. More importantly, we demonstrate this self-organizing behavior of clouds emerges naturally from a complex network model with simple, physical organizing principles: random clumping and merging. We also show clear-cloudy sky symmetry in terms of macroscopic organization because of similar fundamental underlying organizing principles. The order in the apparently complex cloud-clear field thus has its root in random simple interactions. Studying cloud organization with complex network models is an attractive new approach that has wide applications in climate science. This approach is fully complementary to deterministic models and the two approaches provide a powerful framework to meet the challenge of representing clouds in our climate models when working in tandem.

  18. Gel formation driven by tunable hydrophobic domain: design of acrylamide macromonomer with oligo hydrophobic segment.

    Science.gov (United States)

    Nitta, Kyohei; Miyake, Junpei; Watanabe, Junji; Ikeda, Yoshiyuki

    2012-04-09

    Nowadays, biomaterials with amphiphilic properties are undergoing remarkable development. Here, we present one such development, in which we prepared amphiphilic graft copolymers, with a main chain composed of hydroxyethyl acrylamide (HEAA), to introduce hydrophilicity, and a side chain composed of poly(trimethylene carbonate) (PTMC) to introduce tunable hydrophobicity. These macromonomers were created with a novel molecular design, which introduced a ring-opening polymerization by the hydroxyl end group of HEAA in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene, and were analyzed by (1)H NMR and gel permeation chromatography. The amphiphilic graft copolymers were shown to form a hydrogel, the swelling ratio of which was greatly influenced by the number of trimethylene carbonate units. These copolymers also exhibited the Tyndall phenomenon in aqueous solution; they aggregated spontaneously due to hydrogen bonding and hydrophobic interactions, and a sodium 8-anilino-1-naphthalenesulfonate (ANS) fluorescence probe was introduced into the hydrophobic domain. The solution property of ANS in the polymer solution was analyzed by fluorescence measurement and (1)H NMR. The maximum fluorescence wavelength of ANS shifted to shorter wavelengths as the degree of polymerization of the hydrophobic PTMC, the composition of the macromonomer, and the concentration of the copolymer increased. The resulting copolymer formed a polymer micelle structure due to the tunable hydrophobic domain formation in selected solvents. Therefore, these amphiphilic graft copolymers containing a PTMC segment are excellent candidates for use as hydrophobic drug delivery carriers.

  19. Heterocoagulation of hydrophobic particle and bubble during microflotation

    NARCIS (Netherlands)

    Mishchuk, N.A.; Koopal, L.K.; Dukhin, S.S.

    2002-01-01

    The laws of the interaction between a gas bubble and a hydrophobic solid particle were studied. The range of the system parameters that can ensure the heterocoagulation of the particle and the bubble was determined.

  20. Heterocoagulation of hydrophobic particle and bubble during microflotation

    NARCIS (Netherlands)

    Mishchuk, N.A.; Koopal, L.K.; Dukhin, S.S.

    2002-01-01

    The laws of the interaction between a gas bubble and a hydrophobic solid particle were studied. The range of the system parameters that can ensure the heterocoagulation of the particle and the bubble was determined.

  1. Hydrophobic mismatch sorts SNARE proteins into distinct membrane domains

    Science.gov (United States)

    Milovanovic, Dragomir; Honigmann, Alf; Koike, Seiichi; Göttfert, Fabian; Pähler, Gesa; Junius, Meike; Müllar, Stefan; Diederichsen, Ulf; Janshoff, Andreas; Grubmüller, Helmut; Risselada, Herre J.; Eggeling, Christian; Hell, Stefan W.; van den Bogaart, Geert; Jahn, Reinhard

    2015-01-01

    The clustering of proteins and lipids in distinct microdomains is emerging as an important principle for the spatial patterning of biological membranes. Such domain formation can be the result of hydrophobic and ionic interactions with membrane lipids as well as of specific protein-protein interactions. Here using plasma membrane-resident SNARE proteins as model, we show that hydrophobic mismatch between the length of transmembrane domains (TMDs) and the thickness of the lipid membrane suffices to induce clustering of proteins. Even when the TMDs differ in length by only a single residue, hydrophobic mismatch can segregate structurally closely homologous membrane proteins in distinct membrane domains. Domain formation is further fine-tuned by interactions with polyanionic phosphoinositides and homo and heterotypic protein interactions. Our findings demonstrate that hydrophobic mismatch contributes to the structural organization of membranes.

  2. Macroscopic transport by synthetic molecular machines

    NARCIS (Netherlands)

    Berna, J; Leigh, DA; Lubomska, M; Mendoza, SM; Perez, EM; Rudolf, P; Teobaldi, G; Zerbetto, F

    2005-01-01

    Nature uses molecular motors and machines in virtually every significant biological process, but demonstrating that simpler artificial structures operating through the same gross mechanisms can be interfaced with - and perform physical tasks in - the macroscopic world represents a significant hurdle

  3. Assessments of macroscopicity for quantum optical states

    DEFF Research Database (Denmark)

    Laghaout, Amine; Neergaard-Nielsen, Jonas Schou; Andersen, Ulrik Lund

    2015-01-01

    With the slow but constant progress in the coherent control of quantum systems, it is now possible to create large quantum superpositions. There has therefore been an increased interest in quantifying any claims of macroscopicity. We attempt here to motivate three criteria which we believe should...... enter in the assessment of macroscopic quantumness: The number of quantum fluctuation photons, the purity of the states, and the ease with which the branches making up the state can be distinguished. © 2014....

  4. Quantum Bell Inequalities from Macroscopic Locality

    CERN Document Server

    Yang, Tzyh Haur; Sheridan, Lana; Scarani, Valerio

    2010-01-01

    We propose a method to generate analytical quantum Bell inequalities based on the principle of Macroscopic Locality. By imposing locality over binary processings of virtual macroscopic intensities, we establish a correspondence between Bell inequalities and quantum Bell inequalities in bipartite scenarios with dichotomic observables. We discuss how to improve the latter approximation and how to extend our ideas to scenarios with more than two outcomes per setting.

  5. Interaction of angiogenically stimulated intermediate CD163+ monocytes/macrophages with soft hydrophobic poly(n-butyl acrylate) networks with elastic moduli matched to that of human arteries.

    Science.gov (United States)

    Mayer, Anke; Kratz, Karl; Hiebl, Bernhard; Lendlein, Andreas; Jung, Friedrich

    2012-03-01

    The cell population of peripheral blood monocytes/macrophages (MO) is heterogeneous: The majority of the MO are CD14++ CD16- and named "classical" (= MO1). Furthermore, two other subpopulations were described: CD14++ CD16+ ("intermediate" = MO2) and CD14+ CD16++ ("non-classical" = MO3). It is reported that MO2 possess anti-inflammatory properties and express the MO lineage marker CD163. On a hydrophilic neutrally charged acrylamide-based hydrogel human intermediate (CD14++ CD16+ ), angiogenically stimulated CD163++ monocytes/macrophages (aMO2) maintained a proangiogenic and noninflammatory status for at least 14 days. Here, we explored whether this aMO2 subset adhered to hydrophobic poly(n-butyl acrylate) networks (cPnBA) and also remained in its proangiogenic and noninflammatory status. Because substrate elasticity can impact adherence, morphology, and function of cells, cPnBAs with different Young's modulus (250 and 1100 kPa) were investigated, whereby their elasticity was tailored by variation of the cross-linker content and matched to the elasticity of human arteries. The cPnBAs exhibited similar surface properties (e.g., surface roughness), which were maintained after ethylene oxide sterilization and exposure in serum-free cell culture medium for 18 h at 37°C. aMO2 were seeded on cPnBA samples (1.7 × 10(5) cells/1.33 cm(2) ) in Dulbecco's modified Eagle medium (DMEM high glucose) supplemented with vascular endothelial growth factor 165 (VEGF-A(165) , 10 ng/mL) and fetal calf serum (10 vol%) for 3 and 72 h. On both polymeric samples (n = 3 each), the numbers of adherent cells per unit area were significantly higher (P glass, 3 h: 6 ± 3 cells/mm(2) , 72 h: 130 ± 83 cells/mm(2) ) and showed a typically spread morphology. The mRNA expression profile of the aMO2 was not influenced by the substrate elasticity. In the supernatant of aMO2 on cPnBA0250, significantly less VEGF-A(165) product was found than expected based on

  6. Indirect measurement of interfacial melting from macroscopic ice observations.

    Science.gov (United States)

    Saruya, Tomotaka; Kurita, Kei; Rempel, Alan W

    2014-06-01

    Premelted water that is adsorbed to particle surfaces and confined to capillary regions remains in the liquid state well below the bulk melting temperature and can supply the segregated growth of ice lenses. Using macroscopic measurements of ice-lens initiation position in step-freezing experiments, we infer how the nanometer-scale thicknesses of premelted films depend on temperature depression below bulk melting. The interfacial interactions between ice, liquid, and soda-lime glass particles exhibit a power-law behavior that suggests premelting in our system is dominated by short-range electrostatic forces. Using our inferred film thicknesses as inputs to a simple force-balance model with no adjustable parameters, we obtain good quantitative agreement between numerical predictions and observed ice-lens thickness. Macroscopic observations of lensing behavior have the potential as probes of premelting behavior in other systems.

  7. Measurement-induced macroscopic superposition states in cavity optomechanics

    CERN Document Server

    Hoff, Ulrich B; Neergaard-Nielsen, Jonas S; Andersen, Ulrik L

    2016-01-01

    We present a novel proposal for generating quantum superpositions of macroscopically distinct states of a bulk mechanical oscillator, compatible with existing optomechanical devices operating in the readily achievable bad-cavity limit. The scheme is based on a pulsed cavity optomechanical quantum non-demolition (QND) interaction, driven by displaced non-Gaussian states, and measurement-induced feedback, avoiding the need for strong single-photon optomechanical coupling. Furthermore, we show that single-quadrature cooling of the mechanical oscillator is sufficient for efficient state preparation, and we outline a three-pulse protocol comprising a sequence of QND interactions for squeezing-enhanced cooling, state preparation, and tomography.

  8. Generating giant and tunable nonlinearity in a macroscopic mechanical resonator from a single chemical bond

    Science.gov (United States)

    Huang, Pu; Zhou, Jingwei; Zhang, Liang; Hou, Dong; Lin, Shaochun; Deng, Wen; Meng, Chao; Duan, Changkui; Ju, Chenyong; Zheng, Xiao; Xue, Fei; Du, Jiangfeng

    2016-05-01

    Nonlinearity in macroscopic mechanical systems may lead to abundant phenomena for fundamental studies and potential applications. However, it is difficult to generate nonlinearity due to the fact that macroscopic mechanical systems follow Hooke's law and respond linearly to external force, unless strong drive is used. Here we propose and experimentally realize high cubic nonlinear response in a macroscopic mechanical system by exploring the anharmonicity in chemical bonding interactions. We demonstrate the high tunability of nonlinear response by precisely controlling the chemical bonding interaction, and realize, at the single-bond limit, a cubic elastic constant of 1 × 1020 N m-3. This enables us to observe the resonator's vibrational bi-states transitions driven by the weak Brownian thermal noise at 6 K. This method can be flexibly applied to a variety of mechanical systems to improve nonlinear responses, and can be used, with further improvements, to explore macroscopic quantum mechanics.

  9. Polar solvents decrease the viscosity of high concentration IgG1 solutions through hydrophobic solvation and interaction: formulation and biocompatibility considerations.

    Science.gov (United States)

    Kamerzell, Tim J; Pace, Amanda L; Li, Megan; Danilenko, Dimitry M; McDowell, Michelle; Gokarn, Yatin R; Wang, Y John

    2013-04-01

    Low-volume protein dosage forms for subcutaneous injection pose unique challenges to the pharmaceutical scientist. Indeed, high protein concentrations are often required to achieve acceptable bioavailability and efficacy for many indications. Furthermore, high solution viscosities are often observed with formulations containing protein concentrations well above 150 mg/mL. In this work, we explored the use of polar solvents for reducing solution viscosity of high concentration protein formulations intended for subcutaneous injection. An immunoglobulin, IgG1, was used in this study. The thermodynamic preferential interaction parameter (Γ23 ) measured by differential scanning calorimetry, as well as Fourier transform infrared, Raman, and second-derivative UV spectroscopy, were used to characterize the effects of polar solvents on protein structure and to reveal important mechanistic insight regarding the nature of the protein-solvent interaction. Finally, the hemolytic potential and postdose toxicity in rats were determined to further investigate the feasibility of using these cosolvents for subcutaneous pharmaceutical formulations. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 102:1182-1193, 2013.

  10. Experimental and computational surface hydrophobicity analysis of a non-enveloped virus and proteins.

    Science.gov (United States)

    Heldt, Caryn L; Zahid, Amna; Vijayaragavan, K Saagar; Mi, Xue

    2017-05-01

    The physical characteristics of viruses needs to be understood in order to manipulate the interaction of viruses with host cells, as well as to create specific molecular recognition techniques to detect, purify, and remove viruses. Viruses are generally believed to be positively charged at physiological pH, but there are few other defining characteristics. Here, we have experimentally and computationally demonstrated that a non-enveloped virus is more hydrophobic than a panel of model proteins. Reverse-phase and hydrophobic interaction chromatography and ANS fluorescence determined the experimental hydrophobic strength of each entity. Computational surface hydrophobicity was calculated by the solvent exposed surface area of the protein weighted by the hydrophobicity of each amino acid. The results obtained indicate a strong correlation between the computational surface hydrophobicity and experimentally determined hydrophobicity using reverse-phase chromatography and ANS fluorescence. The surface hydrophobicity did not compare strongly to the weighted average of the amino acid sequence hydrophobicity. This demonstrates that our simple method of calculating the surface hydrophobicity gives general hydrophobicity information about proteins and viruses with crystal structures. In the process, this method demonstrated that porcine parvovirus (PPV) is more hydrophobic than the model proteins used in this study. This adds an additional dimension to currently known virus characteristics and can improve our manipulation of viruses for gene therapy targeting, surface adsorption and general understanding of virus interactions. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Ligand and counterion control of Ag(I) architectures: assembly of a {Ag8} ring cluster mediated by hydrophobic and Ag...Ag interactions.

    Science.gov (United States)

    Fielden, John; Long, De-liang; Slawin, Alexandra M Z; Kögerler, Paul; Cronin, Leroy

    2007-10-29

    A strategy combining ligand design and counterion variation has been used to investigate the assembly of silver(I) complexes. As a result, dinuclear, octanuclear, and polymeric silver(I) species have been synthesized by complexation of the rigid aliphatic amino ligands cis-3,5-diamino-trans-hydroxycyclohexane (DAHC), cis-3,5-diamino-trans-methoxycyclohexane (DAMC), and cis-3,5-diamino-trans-tert-butyldimethylsilylanyloxycyclohexane (DATC) with silver(I) triflate, nitrate, and perchlorate. The compositions of these aggregates, established by X-ray crystallography and elemental analysis, are [{Ag(DAHC)}2](CF3SO3)2 (1), [{Ag(DAMC)}2](CF3SO3)2 (2), [{Ag(DAMC)}2](NO3)2 (3), [{Ag(DATC)}6{Ag(DAHC)}2](NO3)8 (4), and [{Ag(DATC}n](NO3)n (5), where the DAHC present in 4 is formed by in situ hydrolysis of the acid labile silyl ether group. The type of aggregate formed depends both upon the noncoordinating O-substituent of the ligand and the (also noncoordinating) counterion, with the normal preference of the ligand topology for forming Ag2L2 structures being broken by introduction of the bulky, lipophilic O-tert-butyldimethylsilyl (TBDMS) group. Of particular note is the octanuclear silver ring structure 4, which is isolated only when both the O-TBDMS group and the nitrate counteranion are present and is formed from four Ag2L2 dimers connected by Ag...Ag and hydrogen-bonding interactions. Diffusion rate measurement of this {Ag8} complex by 1H NMR (DOSY) indicates dissociation in CD3OD and CD3CN, showing that this supramolecular ring structure is formed upon crystallization, and establishing a qualitative limit to the strength of Ag...Ag interactions in solution. When solutions of the {Ag8} cluster in methanol are kept for several days though, a new UV-vis absorption is observed at around 430 nm, consistent with the formation of silver nanoparticles.

  12. Hydrogels with micellar hydrophobic (nanodomains

    Directory of Open Access Journals (Sweden)

    Miloslav ePekař

    2015-01-01

    Full Text Available Hydrogels containing hydrophobic domains or nanodomains, especially of the micellar type, are reviewed. Examples of the reasons for introducing hydrophobic domains into hydrophilic gels are given; typology of these materials is introduced. Synthesis routes are exemplified and properties of a variety of such hydrogels in relation with their intended applications are described. Future research needs are identified briefly.

  13. Macroscopic optical response and photonic bands

    CERN Document Server

    Perez-Huerta, J S; Mendoza, Bernardo S; Mochan, W Luis

    2012-01-01

    We develop a formalism for the calculation of the macroscopic dielectric response of composite systems made of particles of one material embedded periodically within a matrix of another material, each of which is characterized by a well defined dielectric function. The nature of these dielectric functions is arbitrary, and could correspond to dielectric or conducting, transparent or opaque, absorptive and dispersive materials. The geometry of the particles and the Bravais lattice of the composite are also arbitrary. Our formalism goes beyond the longwavelenght approximation as it fully incorporates retardation effects. We test our formalism through the study the propagation of electromagnetic waves in 2D photonic crystals made of periodic arrays of cylindrical holes in a dispersionless dielectric host. Our macroscopic theory yields a spatially dispersive macroscopic response which allows the calculation of the full photonic band structure of the system, as well as the characterization of its normal modes, upo...

  14. A macroscopic challenge for quantum spacetime

    CERN Document Server

    Amelino-Camelia, Giovanni

    2013-01-01

    Over the last decade a growing number of quantum-gravity researchers has been looking for opportunities for the first ever experimental evidence of a Planck-length quantum property of spacetime. These studies are usually based on the analysis of some candidate indirect implications of spacetime quantization, such as a possible curvature of momentum space. Some recent proposals have raised hope that we might also gain direct experimental access to quantum properties of spacetime, by finding evidence of limitations to the measurability of the center-of-mass coordinates of some macroscopic bodies. However I here observe that the arguments that originally lead to speculating about spacetime quantization do not apply to the localization of the center of mass of a macroscopic body. And I also analyze some popular formalizations of the notion of quantum spacetime, finding that when the quantization of spacetime is Planckian for the constituent particles then for the composite macroscopic body the quantization of spa...

  15. On Macroscopic Complexity and Perceptual Coding

    CERN Document Server

    Scoville, John

    2010-01-01

    While Shannon information establishes limits to the universal data compression of binary data, no existing theory provides an equivalent characterization of the lossy data compression algorithms prevalent in audiovisual media. The current paper proposes a mathematical framework for perceptual coding and inference which quantifies the complexity of objects indistinguishable to a particular observer. A definition of the complexity is presented and related to a generalization of Boltzmann entropy for these equivalence classes. When the classes are partitions of phase space, corresponding to classical observations, this is the proper Boltzmann entropy and the macroscopic complexity agrees with the Algorithmic Entropy. For general classes, the macroscopic complexity measure determines the optimal lossy compression of the data. Conversely, perceptual coding algorithms may be used to construct upper bounds on certain macroscopic complexities. Knowledge of these complexities, in turn, allows perceptual inference whic...

  16. Nanoplasmon-enabled macroscopic thermal management

    CERN Document Server

    Jonsson, Gustav Edman; Dmitriev, Alexandre

    2013-01-01

    In numerous applications of energy harvesting via transformation of light into heat the focus recently shifted towards highly absorptive materials featuring nanoplasmons. It is currently established that noble metals-based absorptive plasmonic platforms deliver significant light-capturing capability and can be viewed as super-absorbers of optical radiation. However, direct experimental evidence of plasmon-enabled macroscopic temperature increase that would result from these efficient absorptive properties is scarce. Here we derive a general quantitative method of characterizing light-capturing properties of a given heat-generating absorptive layer by macroscopic thermal imaging. We further monitor macroscopic areas that are homogeneously heated by several degrees with plasmon nanostructures that occupy a mere 8% of the surface, leaving it essentially transparent and evidencing significant heat generation capability of nanoplasmon-enabled light capture. This has a direct bearing to thermophotovoltaics and othe...

  17. Roles of nonpolar and polar intermolecular interactions in the improvement of the drug loading capacity of PEO-b-PCL with increasing PCL content for two hydrophobic Cucurbitacin drugs.

    Science.gov (United States)

    Patel, Sarthak K; Lavasanifar, Afsaneh; Choi, Phillip

    2009-09-14

    Molecular dynamics (MD) simulation was used to study the roles of nonpolar and polar intermolecular interactions in the improvement of the drug loading capacity of poly(ethylene oxide)-b-poly(epsilon-caprolactone) (PEO-b-PCL) with increasing PCL content for two water insoluble anticancer drugs: Cucurbitacin B (CuB) and Cucurbitacin I (CuI). In particular, random binary mixture models containing 10-12 wt % drug and remaining PEO-b-PCL with three different PCL/PEO (w/w) ratios (0.5, 1, and 2) were used to calculate their Flory-Huggins interaction parameters (chi). The MD simulation results show that, for both CuB and CuI, the computed chi decreases (i.e., affinity increases) with increasing PCL/PEO ratio. Such results are consistent with our experimental observation that increasing the PCL/PEO (w/w) ratio from 1 to 4.8 significantly increases the drug loading capacity of micelles formed by PEO-b-PCL for both drugs. Analysis of the energy data shows that increasing affinity (loading) at higher PCL/PEO ratio is attributed to the increase in favorable polar interactions and to the formation of additional hydrogen bonds (H-bonds) between the drugs and the PCL block rather than to the increase in the hydrophobic characteristics of the diblock copolymer as one would normally expect. In fact, the nonpolar intermolecular interactions became more unfavorable at higher PCL/PEO ratio. Analysis of the radial distribution functions of the model mixtures indicates that at high PCL/PEO ratio, multiple H-bond sites on the PCL block interacted with single H-bond sites on the drug molecules. However, at low PCL/PEO ratio, only single H-bonds formed between various H-bond sites on the drug molecules and those of the PCL and PEO blocks. It seems that formation of H-bonds between multiple H-bond sites on the PCL block and single H-bond sites on the drug molecules is responsible for inducing drug/PEO-b-PCL affinity. The finding also explains the experimental observation that release rates

  18. Flagella bending affects macroscopic properties of bacterial suspensions

    Energy Technology Data Exchange (ETDEWEB)

    Potomkin, M.; Tournus, M.; Berlyand, L. V.; Aranson, I. S.

    2017-05-01

    To survive in harsh conditions, motile bacteria swim in complex environments and respond to the surrounding flow. Here, we develop a mathematical model describing how flagella bending affects macroscopic properties of bacterial suspensions. First, we show how the flagella bending contributes to the decrease in the effective viscosity observed in dilute suspension. Our results do not impose tumbling (random reorientation) as was previously done to explain the viscosity reduction. Second, we demonstrate how a bacterium escapes from wall entrapment due to the self-induced buckling of flagella. Our results shed light on the role of flexible bacterial flagella in interactions of bacteria with shear flow and walls or obstacles.

  19. Modelling and simulations of macroscopic multi-group pedestrian flow

    CERN Document Server

    Mahato, Naveen K; Tiwari, Sudarshan

    2016-01-01

    We consider a multi-group microscopic model for pedestrian flow describing the behaviour of large groups. It is based on an interacting particle system coupled to an eikonal equation. Hydrodynamic multi-group models are derived from the underlying particle system as well as scalar multi-group models. The eikonal equation is used to compute optimal paths for the pedestrians. Particle methods are used to solve the macroscopic equations. Numerical test cases are investigated and the models and, in particular, the resulting evacuation times are compared for a wide range of different parameters.

  20. Separation of the Microscopic and Macroscopic Domains

    Science.gov (United States)

    Van Zandt, L. L.

    1977-01-01

    Examines the possibility of observing interference in quantum magnification experiments such as the celebrated "Schroedinger cat". Uses the possibility of observing interference for separating the realm of microscopic from macroscopic dynamics; estimates the dividing line to fall at system sizes of about 100 Daltons. (MLH)

  1. Entropy, Macroscopic Information, and Phase Transitions

    OpenAIRE

    Parrondo, Juan M. R.

    1999-01-01

    The relationship between entropy and information is reviewed, taking into account that information is stored in macroscopic degrees of freedom, such as the order parameter in a system exhibiting spontaneous symmetry breaking. It is shown that most problems of the relationship between entropy and information, embodied in a variety of Maxwell demons, are also present in any symmetry breaking transition.

  2. Macroscopic Modeling of Polymer-Electrolyte Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Weber, A.Z.; Newman, J.

    2007-04-01

    In this chapter, the various approaches for the macroscopic modeling of transport phenomena in polymer-electrolyte membranes are discussed. This includes general background and modeling methodologies, as well as exploration of the governing equations and some membrane-related topic of interest.

  3. Lozenge Tilings, Glauber Dynamics and Macroscopic Shape

    Science.gov (United States)

    Laslier, Benoît; Toninelli, Fabio Lucio

    2015-09-01

    We study the Glauber dynamics on the set of tilings of a finite domain of the plane with lozenges of side 1/ L. Under the invariant measure of the process (the uniform measure over all tilings), it is well known (Cohn et al. J Am Math Soc 14:297-346, 2001) that the random height function associated to the tiling converges in probability, in the scaling limit , to a non-trivial macroscopic shape minimizing a certain surface tension functional. According to the boundary conditions, the macroscopic shape can be either analytic or contain "frozen regions" (Arctic Circle phenomenon Cohn et al. N Y J Math 4:137-165, 1998; Jockusch et al. Random domino tilings and the arctic circle theorem, arXiv:math/9801068, 1998). It is widely conjectured, on the basis of theoretical considerations (Henley J Statist Phys 89:483-507, 1997; Spohn J Stat Phys 71:1081-1132, 1993), partial mathematical results (Caputo et al. Commun Math Phys 311:157-189, 2012; Wilson Ann Appl Probab 14:274-325, 2004) and numerical simulations for similar models (Destainville Phys Rev Lett 88:030601, 2002; cf. also the bibliography in Henley (J Statist Phys 89:483-507, 1997) and Wilson (Ann Appl Probab 14:274-325, 2004), that the Glauber dynamics approaches the equilibrium macroscopic shape in a time of order L 2+ o(1). In this work we prove this conjecture, under the assumption that the macroscopic equilibrium shape contains no "frozen region".

  4. Macroscopic invisibility cloaking of visible light

    DEFF Research Database (Denmark)

    Chen, Xianzhong; Luo, Y.; Zhang, Jingjing

    2011-01-01

    to a few wavelengths. Here, we report the first realization of a macroscopic volumetric invisibility cloak constructed from natural birefringent crystals. The cloak operates at visible frequencies and is capable of hiding, for a specific light polarization, three-dimensional objects of the scale...

  5. An exploration for the macroscopic physical meaning of entropy

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The macroscopic physical meaning of entropy is analyzed based on the exergy (availability) of a combined system (a closed system and its environment), which is the maximum amount of useful work obtainable from the system and the environment as the system is brought into equilibrium with the environment. The process the system experiences can be divided in two sequent sub-processes, the process at constant volume, which represents the heat interaction of the system with the environment, and the adiabatic process, which represents the work interaction of the system with the environment. It is shown that the macroscopic physical meaning of entropy is a measure of the unavailable energy of a closed system for doing useful work through heat interaction. This statement is more precise than those reported in prior literature. The unavailability function of a closed system can be defined as T0S and p0V in volume constant process and adiabatic process, respectively. Their changes, that is, AiTgS) and A (p0V) represent the unusable parts of the internal energy of a closed system for doing useful work in corresponding processes. Finally, the relation between Clausius entropy and Boltzmann entropy is discussed based on the comparison of their expressions for absolute entropy.

  6. PROPERTIES OF DILUTE SOLUTIONS OF HYDROPHOBICALLY MODIFIED POLY(4-VINYL PYRIDINE) (POLYSOAPS)

    Institute of Scientific and Technical Information of China (English)

    1998-01-01

    Hydrophobically modified poly(4-vinyl pyridines) by alkyl bromides are kinds of polysoap similar to the surfactant. Properties of dilute solutions were studied through the viscosity measurements in pure water and NaCl solutions. In aqueous solutions of polysoaps hydrophobic interaction can be attributed to aggregation of hydrophobic groups of the polysoap main chains. The hydrophobic groups of polysoap can aggregate to form hydrophobic microdomains (micelles) in aqueous solution. This is a compact conformation. The formation of such microdomains is a process of dynamic equilibrium.

  7. Method for producing hydrophobic aerogels

    Science.gov (United States)

    Hrubesh, Lawrence W.; Poco, John F.; Coronado, Paul R.

    1999-01-01

    A method for treating a dried monolithic aerogel containing non-dispersed particles, with an organometallic surface modifying agent to produce hydrophobic aerogels. The dried, porous hydrophobic aerogels contain a protective layer of alkyl groups, such as methyl groups, on the modified surfaces of the pores of the aerogel. The alkyl groups at the aerogel surface typically contain at least one carbon-metal bond per group.

  8. Macroscopic quantum mechanics in a classical spacetime.

    Science.gov (United States)

    Yang, Huan; Miao, Haixing; Lee, Da-Shin; Helou, Bassam; Chen, Yanbei

    2013-04-26

    We apply the many-particle Schrödinger-Newton equation, which describes the coevolution of a many-particle quantum wave function and a classical space-time geometry, to macroscopic mechanical objects. By averaging over motions of the objects' internal degrees of freedom, we obtain an effective Schrödinger-Newton equation for their centers of mass, which can be monitored and manipulated at quantum levels by state-of-the-art optomechanics experiments. For a single macroscopic object moving quantum mechanically within a harmonic potential well, its quantum uncertainty is found to evolve at a frequency different from its classical eigenfrequency-with a difference that depends on the internal structure of the object-and can be observable using current technology. For several objects, the Schrödinger-Newton equation predicts semiclassical motions just like Newtonian physics, yet quantum uncertainty cannot be transferred from one object to another.

  9. Macroscopic Invisibility Cloaking of Visible Light

    CERN Document Server

    Chen, Xianzhong; Zhang, Jingjing; Jiang, Kyle; Pendry, John B; Zhang, Shuang

    2010-01-01

    Invisibility cloaks of light, which used to be confined to the imagination, have now been turned into a scientific reality, thanks to the enabling theoretical tools of transformation optics and conformal mapping. Inspired by those theoretical works, the experimental realisation of electromagnetic invisibility cloaks has been reported at various electromagnetic frequencies. All the invisibility cloaks demonstrated thus far, however, have relied on nano- or micro-fabricated artificial composite materials with spatially varying electromagnetic properties, which limit the size of the cloaked region to a few wavelengths. Here we report realisation of a macroscopic volumetric invisibility cloak constructed from natural birefringent crystals. The cloak operates at visible frequencies and is capable of hiding three-dimensional objects of the scale of centimetres and millimetres. Our work opens avenues for future applications with macroscopic cloaking devices.

  10. Macroscopic spin and charge transport theory

    Institute of Scientific and Technical Information of China (English)

    Li Da-Fang; Shi Jun-Ren

    2009-01-01

    According to the general principle of non-equilibrium thermodynamics, we propose a set of macroscopic transport equations for the spin transport and the charge transport. In particular, the spin torque is introduced as a generalized 'current density' to describe the phenomena associated with the spin non-conservation in a unified framework. The Einstein relations and the Onsager relations between different transport phenomena are established. Specifically, the spin transport properties of the isotropic non-magnetic and the isotropic magnetic two-dimensional electron gases are fully described by using this theory, in which only the macroscopic-spin-related transport phenomena allowed by the symmetry of the system are taken into account.

  11. Macroscopic entrainment of periodically forced oscillatory ensembles.

    Science.gov (United States)

    Popovych, Oleksandr V; Tass, Peter A

    2011-03-01

    Large-amplitude oscillations of macroscopic neuronal signals, such as local field potentials and electroencephalography or magnetoencephalography signals, are commonly considered as being generated by a population of mutually synchronized neurons. In a computational study in generic networks of phase oscillators and bursting neurons, however, we show that this common belief may be wrong if the neuronal population receives an external rhythmic input. The latter may stem from another neuronal population or an external, e.g., sensory or electrical, source. In that case the population field potential may be entrained by the rhythmic input, whereas the individual neurons are phase desynchronized both mutually and with their field potential. Intriguingly, the corresponding large-amplitude oscillations of the population mean field are generated by pairwise desynchronized neurons oscillating at frequencies shifted far away from the frequency of the macroscopic field potential.

  12. Adsorption modeling for macroscopic contaminant dispersal analysis

    Energy Technology Data Exchange (ETDEWEB)

    Axley, J.W.

    1990-05-01

    Two families of macroscopic adsorption models are formulated, based on fundamental principles of adsorption science and technology, that may be used for macroscopic (such as whole-building) contaminant dispersal analysis. The first family of adsorption models - the Equilibrium Adsorption (EA) Models - are based upon the simple requirement of equilibrium between adsorbent and room air. The second family - the Boundary Layer Diffusion Controlled Adsorption (BLDC) Models - add to the equilibrium requirement a boundary layer model for diffusion of the adsorbate from the room air to the adsorbent surface. Two members of each of these families are explicitly discussed, one based on the linear adsorption isotherm model and the other on the Langmuir model. The linear variants of each family are applied to model the adsorption dynamics of formaldehyde in gypsum wall board and compared to measured data.

  13. Macroscopic Invisible Cloak for Visible Light

    CERN Document Server

    Zhang, Baile; Liu, Xiaogang; Barbastathis, George

    2011-01-01

    Invisibility cloaks, a subject that usually occurs in science fiction and myths, have attracted wide interest recently because of their possible realization. The biggest challenge to true invisibility is known to be the cloaking of a macroscopic object in the broad range of wavelengths visible to the human eye. Here we experimentally solve this problem by incorporating the principle of transformation optics into a conventional optical lens fabrication with low-cost materials and simple manufacturing techniques. A transparent cloak made of two pieces of calcite is created. This cloak is able to conceal a macroscopic object with a maximum height of 2 mm, larger than 3500 free-space-wavelength, inside a transparent liquid environment. Its working bandwidth encompassing red, green and blue light is also demonstrated.

  14. Macroscopic Quantum Resonators (MAQRO): 2015 update

    Energy Technology Data Exchange (ETDEWEB)

    Kaltenbaek, Rainer [University of Vienna, Vienna Center for Quantum Science and Technology, Vienna (Austria); Aspelmeyer, Markus; Kiesel, Nikolai [University of Vienna, Vienna Center for Quantum Science and Technology, Vienna (Austria); Barker, Peter F.; Bose, Sougato [University College London, Department of Physics and Astronomy, London (United Kingdom); Bassi, Angelo [University of Trieste, Department of Physics, Trieste (Italy); INFN - Trieste Section, Trieste (Italy); Bateman, James [University of Swansea, Department of Physics, College of Science, Swansea (United Kingdom); Bongs, Kai; Cruise, Adrian Michael [University of Birmingham, School of Physics and Astronomy, Birmingham (United Kingdom); Braxmaier, Claus [University of Bremen, Center of Applied Space Technology and Micro Gravity (ZARM), Bremen (Germany); Institute of Space Systems, German Aerospace Center (DLR), Bremen (Germany); Brukner, Caslav [University of Vienna, Vienna Center for Quantum Science and Technology, Vienna (Austria); Austrian Academy of Sciences, Institute of Quantum Optics and Quantum Information (IQOQI), Vienna (Austria); Christophe, Bruno; Rodrigues, Manuel [The French Aerospace Lab, ONERA, Chatillon (France); Chwalla, Michael; Johann, Ulrich [Airbus Defence and Space GmbH, Immenstaad (Germany); Cohadon, Pierre-Francois; Heidmann, Antoine; Lambrecht, Astrid; Reynaud, Serge [ENS-PSL Research University, Laboratoire Kastler Brossel, UPMC-Sorbonne Universites, CNRS, College de France, Paris (France); Curceanu, Catalina [Laboratori Nazionali di Frascati dell' INFN, Frascati (Italy); Dholakia, Kishan; Mazilu, Michael [University of St. Andrews, School of Physics and Astronomy, St. Andrews (United Kingdom); Diosi, Lajos [Wigner Research Center for Physics, P.O. Box 49, Budapest (Hungary); Doeringshoff, Klaus; Peters, Achim [Humboldt-Universitaet zu Berlin, Institut fuer Physik, Berlin (Germany); Ertmer, Wolfgang; Rasel, Ernst M. [Leibniz Universitaet Hannover, Institut fuer Quantenoptik, Hannover (Germany); Gieseler, Jan; Novotny, Lukas; Rondin, Loic [ETH Zuerich, Photonics Laboratory, Zuerich (Switzerland); Guerlebeck, Norman; Herrmann, Sven; Laemmerzahl, Claus [University of Bremen, Center of Applied Space Technology and Micro Gravity (ZARM), Bremen (Germany); Hechenblaikner, Gerald [Airbus Defence and Space GmbH, Immenstaad (Germany); European Southern Observatory (ESO), Garching bei Muenchen (Germany); Hossenfelder, Sabine [KTH Royal Institute of Technology and Stockholm University, Nordita, Stockholm (Sweden); Kim, Myungshik [Imperial College London, QOLS, Blackett Laboratory, London (United Kingdom); Milburn, Gerard J. [University of Queensland, ARC Centre for Engineered Quantum Systems, Brisbane (Australia); Mueller, Holger [University of California, Department of Physics, Berkeley, CA (United States); Paternostro, Mauro [Queen' s University, Centre for Theoretical Atomic, Molecular and Optical Physics, School of Mathematics and Physics, Belfast (United Kingdom); Pikovski, Igor [Harvard-Smithsonian Center for Astrophysics, ITAMP, Cambridge, MA (United States); Pilan Zanoni, Andre [Airbus Defence and Space GmbH, Immenstaad (Germany); CERN - European Organization for Nuclear Research, EN-STI-TCD, Geneva (Switzerland); Riedel, Charles Jess [Perimeter Institute for Theoretical Physics, Waterloo, ON (Canada); Roura, Albert [Universitaet Ulm, Institut fuer Quantenphysik, Ulm (Germany); Schleich, Wolfgang P. [Universitaet Ulm, Institut fuer Quantenphysik, Ulm (Germany); Texas A and M University Institute for Advanced Study (TIAS), Institute for Quantum Science and Engineering (IQSE), and Department of Physics and Astronomy, College Station, TX (United States); Schmiedmayer, Joerg [Vienna University of Technology, Vienna Center for Quantum Science and Technology, Institute of Atomic and Subatomic Physics, Vienna (Austria); Schuldt, Thilo [Institute of Space Systems, German Aerospace Center (DLR), Bremen (Germany); Schwab, Keith C. [California Institute of Technology, Applied Physics, Pasadena, CA (United States)

    2016-12-15

    Do the laws of quantum physics still hold for macroscopic objects - this is at the heart of Schroedinger's cat paradox - or do gravitation or yet unknown effects set a limit for massive particles? What is the fundamental relation between quantum physics and gravity? Ground-based experiments addressing these questions may soon face limitations due to limited free-fall times and the quality of vacuum and microgravity. The proposed mission Macroscopic Quantum Resonators (MAQRO) may overcome these limitations and allow addressing such fundamental questions. MAQRO harnesses recent developments in quantum optomechanics, high-mass matter-wave interferometry as well as state-of-the-art space technology to push macroscopic quantum experiments towards their ultimate performance limits and to open new horizons for applying quantum technology in space. The main scientific goal is to probe the vastly unexplored 'quantum-classical' transition for increasingly massive objects, testing the predictions of quantum theory for objects in a size and mass regime unachievable in ground-based experiments. The hardware will largely be based on available space technology. Here, we present the MAQRO proposal submitted in response to the 4th Cosmic Vision call for a medium-sized mission (M4) in 2014 of the European Space Agency (ESA) with a possible launch in 2025, and we review the progress with respect to the original MAQRO proposal for the 3rd Cosmic Vision call for a medium-sized mission (M3) in 2010. In particular, the updated proposal overcomes several critical issues of the original proposal by relying on established experimental techniques from high-mass matter-wave interferometry and by introducing novel ideas for particle loading and manipulation. Moreover, the mission design was improved to better fulfill the stringent environmental requirements for macroscopic quantum experiments. (orig.)

  15. A macroscopic approach to creating exotic matter

    OpenAIRE

    Ridgely, C. T.

    2000-01-01

    Herein the Casimir effect is used to present a simple macroscopic view on creating exotic matter. The energy arising between two nearly perfectly conducting parallel plates is shown to become increasingly negative as the plate separation is reduced. It is proposed that the Casimir energy appears increasingly negative simply because the vacuum electromagnetic zero-point field performs positive work in pushing the plates together, transforming field energy into kinetic energy of the plates. Nex...

  16. Shot noise in linear macroscopic resistors

    OpenAIRE

    Gomila Lluch, Gabriel; Pennetta, C.; Reggiani, L.; Ferrari, G; Sampietro, M.; G. Bertuccio(Politecnico di Milano, Italy)

    2004-01-01

    We report on direct experimental evidence of shot noise in a linear macroscopic resistor. The origin of the shot noise comes from the fluctuation of the total number of charge carriers inside the resistor associated with their diffusive motion under the condition that the dielectric relaxation time becomes longer than the dynamic transit time. The present results show that neither potential barriers nor the absence of inelastic scattering are necessary to observe shot noise in electronic devi...

  17. Shot Noise in Linear Macroscopic Resistors

    Science.gov (United States)

    Gomila, G.; Pennetta, C.; Reggiani, L.; Sampietro, M.; Ferrari, G.; Bertuccio, G.

    2004-06-01

    We report on direct experimental evidence of shot noise in a linear macroscopic resistor. The origin of the shot noise comes from the fluctuation of the total number of charge carriers inside the resistor associated with their diffusive motion under the condition that the dielectric relaxation time becomes longer than the dynamic transit time. The present results show that neither potential barriers nor the absence of inelastic scattering are necessary to observe shot noise in electronic devices.

  18. Macroscopic Objects, Intrinsic Spin, and Lorentz Violation

    CERN Document Server

    Atkinson, David W; Tasson, Jay D

    2013-01-01

    The framework of the Standard-Model Extension (SME) provides a relativistic quantum field theory for the study of Lorentz violation. The classical, nonrelativistic equations of motion can be extracted as a limit that is useful in various scenarios. In this work, we consider the effects of certain SME coefficients for Lorentz violation on the motion of macroscopic objects having net intrinsic spin in the classical, nonrelativistic limit.

  19. Active Polar Two-Fluid Macroscopic Dynamics

    Science.gov (United States)

    Pleiner, Harald; Svensek, Daniel; Brand, Helmut R.

    2014-03-01

    We study the dynamics of systems with a polar dynamic preferred direction. Examples include the pattern-forming growth of bacteria (in a solvent, shoals of fish (moving in water currents), flocks of birds and migrating insects (flying in windy air). Because the preferred direction only exists dynamically, but not statically, the macroscopic variable of choice is the macroscopic velocity associated with the motion of the active units. We derive the macroscopic equations for such a system and discuss novel static, reversible and irreversible cross-couplings connected to this second velocity. We find a normal mode structure quite different compared to the static descriptions, as well as linear couplings between (active) flow and e.g. densities and concentrations due to the genuine two-fluid transport derivatives. On the other hand, we get, quite similar to the static case, a direct linear relation between the stress tensor and the structure tensor. This prominent ``active'' term is responsible for many active effects, meaning that our approach can describe those effects as well. In addition, we also deal with explicitly chiral systems, which are important for many active systems. In particular, we find an active flow-induced heat current specific for the dynamic chiral polar order.

  20. 21 CFR 584.700 - Hydrophobic silicas.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Hydrophobic silicas. 584.700 Section 584.700 Food... DRINKING WATER OF ANIMALS Listing of Specific Substances Affirmed as GRAS § 584.700 Hydrophobic silicas. (a) Product. Amorphous fumed hydrophobic silica or precipitated hydrophobic silica (CAS Reg. No....

  1. Hydrophobic hydration from small to large lengthscales: Understanding and manipulating the crossover

    OpenAIRE

    Rajamani, Sowmianarayanan; Truskett, Thomas M.; Garde, Shekhar

    2005-01-01

    Small and large hydrophobic solutes exhibit remarkably different hydration thermodynamics. Small solutes are accommodated in water with minor perturbations to water structure, and their hydration is captured accurately by theories that describe density fluctuations in pure water. In contrast, hydration of large solutes is accompanied by dewetting of their surfaces and requires a macroscopic thermodynamic description. A unified theoretical description of these lengthscale dependencies was pres...

  2. Hydrophobic aggregation of ultrafine kaolinite

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xiao-ping; HU Yue-hua; LIU Run-Qing

    2008-01-01

    The hydrophobic aggregation of ultrafine kaolinite in cationic surfactant suspension was investigated by sedimentation test, zeta potential measurement and SEM observation. SEM images reveal that kaolinite particles show the self-aggregation of edge-face in acidic media, the aggregation of edge-face and edge-edge in neutral media, and the dispersion in alkaline media due to electrostatic repulsion. In the presence of the dodecylammonium acetate cationic surfactant and in neutral and alkaline suspension, the hydrophobic aggregation of face-face is demonstrated. The zeta potential of kaolinite increases with increasing the concentration of cationic surfactant. The small and loose aggregation at a low concentration but big and tight aggregation at a high concentration is presented At pH=7 alkyl quarterly amine salt CTAB has the best hydrophobic aggregation among three cationic surfactants, namely, dodecylammonium acetate, alkyl quarterly amine salts 1227 and CTAB.

  3. Fluoroalkyl and Alkyl Chains Have Similar Hydrophobicities in Binding to the “Hydrophobic Wall” of Carbonic Anhydrase

    Energy Technology Data Exchange (ETDEWEB)

    J Mecinovic; P Snyder; K Mirica; S Bai; E Mack; R Kwant; D Moustakas; A Heroux; G Whitesides

    2011-12-31

    entropic contributions to the hydrophobic effect in this representative system of protein and ligand: hydrophobic interactions, here, seem to comprise approximately equal contributions from enthalpy (plausibly from strengthening networks of hydrogen bonds among molecules of water) and entropy (from release of water from configurationally restricted positions).

  4. Macroscopic Quantum Phenomena from the Correlation, Coupling and Criticality Perspectives

    CERN Document Server

    Chou, C H; Subasi, Y

    2011-01-01

    In this sequel paper we explore how macroscopic quantum phenomena can be measured or understood from the behavior of quantum correlations which exist in a quantum system of many particles or components and how the interaction strengths change with energy or scale, under ordinary situations and when the system is near its critical point. We use the nPI (master) effective action related to the Boltzmann-BBGKY / Schwinger-Dyson hierarchy of equations as a tool for systemizing the contributions of higher order correlation functions to the dynamics of lower order correlation functions. Together with the large N expansion discussed in our first paper(MQP1) we explore 1) the conditions whereby an H-theorem is obtained, which can be viewed as a signifier of the emergence of macroscopic behavior in the system. We give two more examples from past work: 2) the nonequilibrium dynamics of N atoms in an optical lattice under the large $\\cal N$ (field components), 2PI and second order perturbative expansions, illustrating h...

  5. Residence time dependent desorption of Staphylococcus epidermidis from hydrophobic and hydrophilic substrata.

    Science.gov (United States)

    Boks, Niels P; Kaper, Hans J; Norde, Willem; Busscher, Henk J; van der Mei, Henny C

    2008-12-01

    Adhesion and desorption are simultaneous events during bacterial adhesion to surfaces, although desorption is far less studied than adhesion. Here, desorption of Staphylococcus epidermidis from substratum surfaces is demonstrated to be residence time dependent. Initial desorption rate coefficients were similar for hydrophilic and hydrophobic dimethyldichlorosilane (DDS)-coated glass, likely because initial desorption is controlled by attractive Lifshitz-Van der Waals interactions, which are comparable on both substratum surfaces. However, significantly slower decay times of the desorption rate coefficients are found for hydrophilic glass than for hydrophobic DDS-coated glass. This difference is suggested to be due to the acid-base interactions between staphylococci and these surfaces, which are repulsive on hydrophilic glass and attractive on hydrophobic DDS-coated glass. Final desorption rate coefficients are higher on hydrophilic glass than on hydrophobic DDS-coated glass, due to the so called hydrophobic effect, facilitating a closer contact on hydrophobic DDS-coated glass.

  6. Condensation Dynamics on Mimicked Metal Matrix Hydrophobic Nanoparticle-Composites

    Science.gov (United States)

    Damle, Viraj; Sun, Xiaoda; Rykaczewski, Konrad

    2014-11-01

    Use of hydrophobic surfaces promotes condensation in the dropwise mode, which is significantly more efficient than the common filmwise mode. However, limited longevity of hydrophobic surface modifiers has prevented their wide spread use in industry. Recently, metal matrix composites (MMCs) having microscale hydrophobic heterogeneities dispersed in hydrophilic metal matrix have been proposed as durable and self-healing alternative to hydrophobic surface coatings interacting with deposited water droplets. While dispersion of hydrophobic microparticles in MMC is likely to lead to surface flooding during condensation, the effect of dispersion of hydrophobic nanoparticles (HNPs) with size comparable to water nuclei critical radii and spacing is not obvious. To this end, we fabricated highly ordered arrays of Teflon nanospheres on silicon substrates that mimic the top surface of the MMCs with dispersed HNPs. We used light and electron microscopy to observe breath figures resulting from condensation on these surfaces at varied degrees of subcooling. Here, we discuss the relation between the droplet size distribution, Teflon nanosphere diameter and spacing, and condensation mode. KR acknowledges startup funding from ASU.

  7. Influence of aqueous electrolytes on the wetting behavior of hydrophobic solid polymers-low-rate dynamic liquid/fluid contact angle measurements using axisymmetric drop shape analysis.

    Science.gov (United States)

    Welzel, Petra B; Rauwolf, Cordula; Yudin, Olexandr; Grundke, Karina

    2002-07-01

    The interaction of inorganic ions with low-energy hydrophobic surfaces was examined using model systems of solid polymers without ionizable functional surface groups in aqueous electrolyte solutions. Low-rate dynamic contact angle measurements with captive bubbles in conjunction with axisymmetric drop shape analysis (ADSA) were performed to study the influence of electrolyte ions (in the aqueous test solutions) on the wettability of the polymers. When various types of ions were used, no significant change in advancing and receding contact angles was observed. The contact angle hysteresis was small. The zeta potential of the model polymers in aqueous electrolyte solutions was determined from streaming potential measurements. The variation of the zeta potential at different pH levels indicates preferential adsorption of hydroxyl ions at this interface. However, the presence of electrolytes at the interface between water and the different model polymers did not influence the macroscopic contact angle. The results may suggest the absence of any specific interaction between the ions and the solid polymer, as this should result in changes of hydrophobicity. Similar to the air/water interface, the composition and the potential of the polymer/water interface are obviously determined predominantly by the aqueous phase with only slight influence from the solid phase.

  8. Estimation of atomic hydrophobicities using molecular dynamics simulation of peptides

    Science.gov (United States)

    Held, Marie; Nicolau, Dan V.

    2007-12-01

    The hydrophobic force is one of the main driving forces in protein folding and binding. However, its nature is not yet well understood and consequently there are more than 80 different scales published trying to quantify it. Most of the hydrophobicity scales are amino acid-based, but the interaction between the molecular surface of the proteins (and DNA) and surfaces they are immobilized on, e.g., on biomedical micro/nanodevices, occurs on fractions of, rather than whole amino acids. This fragmented structure of the biomolecular surface requires the derivation of atom-level hydrophobicity. Most attempts for the evaluation of atomic hydrophobicities are derived from amino acid-based values, which ignore dynamic and steric factors. This contribution reports on the Molecular Dynamics simulations that aim to overcome this simplification. The calculations examine various tripeptides in an aqueous solution and the analysis focuses on the distance of the nearest water molecules to the individual atoms in the peptides. Different environments result in a variation of average distances for similar atoms in different tripeptides. Comparison with the atomic hydrophobicities derived from the amino acid-based hydrophobicity obtained from peptide partition in water-octanol (Dgoct) and transport through the membrane interface (Dgwif) shows a similar trend to the calculated distances. The variations are likely due to the steric differences of similar types of atoms in different geometric contexts. Therefore, Molecular Dynamics simulations proved convenient for the evaluation of atomic hydrophobicities and open new research avenues. The atomic hydrophobicities can be used to design surfaces that mimic the biomolecular surfaces and therefore elicit an expected biomolecular activity from the immobilized biomolecules.

  9. Rainbow correlation imaging with macroscopic twin beam

    Science.gov (United States)

    Allevi, Alessia; Bondani, Maria

    2017-06-01

    We present the implementation of a correlation-imaging protocol that exploits both the spatial and spectral correlations of macroscopic twin-beam states generated by parametric downconversion. In particular, the spectral resolution of an imaging spectrometer coupled to an EMCCD camera is used in a proof-of-principle experiment to encrypt and decrypt a simple code to be transmitted between two parties. In order to optimize the trade-off between visibility and resolution, we provide the characterization of the correlation images as a function of the spatio-spectral properties of twin beams generated at different pump power values.

  10. Fingerprint Feature Extraction Based on Macroscopic Curvature

    Institute of Scientific and Technical Information of China (English)

    Zhang Xiong; He Gui-ming; Zhang Yun

    2003-01-01

    In the Automatic Fingerprint Identification System (AFIS), extracting the feature of fingerprint is very important. The local curvature of ridges of fingerprint is irregular, so people have the barrier to effectively extract the fingerprint curve features to describe fingerprint. This article proposes a novel algorithm; it embraces information of few nearby fingerprint ridges to extract a new characteristic which can describe the curvature feature of fingerprint. Experimental results show the algorithm is feasible, and the characteristics extracted by it can clearly show the inner macroscopic curve properties of fingerprint. The result also shows that this kind of characteristic is robust to noise and pollution.

  11. Fingerprint Feature Extraction Based on Macroscopic Curvature

    Institute of Scientific and Technical Information of China (English)

    Zhang; Xiong; He; Gui-Ming; 等

    2003-01-01

    In the Automatic Fingerprint Identification System(AFIS), extracting the feature of fingerprint is very important. The local curvature of ridges of fingerprint is irregular, so people have the barrier to effectively extract the fingerprint curve features to describe fingerprint. This article proposes a novel algorithm; it embraces information of few nearby fingerprint ridges to extract a new characterstic which can describe the curvature feature of fingerprint. Experimental results show the algorithm is feasible, and the characteristics extracted by it can clearly show the inner macroscopic curve properties of fingerprint. The result also shows that this kind of characteristic is robust to noise and pollution.

  12. Macroscopic fluctuations theory of aerogel dynamics

    CERN Document Server

    Lefevere, Raphael; Zambotti, Lorenzo

    2010-01-01

    We consider extensive deterministic dynamics made of $N$ particles modeling aerogels under a macroscopic fluctuation theory description. By using a stochastic model describing those dynamics after a diffusive rescaling, we show that the functional giving the exponential decay in $N$ of the probability of observing a given energy and current profile is not strictly convex as a function of the current. This behaviour is caused by the fact that the energy current is carried by particles which may have arbitrary low speed with sufficiently large probability.

  13. Synthesis and Aqueous Solution Viscosity of Hydrophobically Modified Xanthan Gum

    Institute of Scientific and Technical Information of China (English)

    QIAN Xiao-lin; WU Wen-hui; YU Pei-zhi; WANG Jian-quan

    2007-01-01

    Two xanthan gum derivatives hydrophobically modified by 4 or 8 tetradecyl chains per 100 xanthan gum structure units were synthesized. The derivatives were studied by scanning electron microscope and pyrene fluorescence spectrometry. And the aqueous solution apparent viscosity of the derivatives was investigated. The results indicate that the network of the derivatives with more hydrophobic groups is closer and tighter. With increasing of alkyl chain substitution degree, the hydrophobically associating interactions enhance in aqueous solution. Aqueous solution apparent viscosity of the derivatives increases with increasing of polymer concentration and alkyl substitution degree, and decreases with the increase of temperature. In the brine solution, the strong viscosity enhancement phenomenon appears. The interaction between the derivatives and surfactant sodium dodecylbenzene sulfonate is strong.

  14. Theoretical and computational studies of hydrophobic and hydrophilic hydration: Towards a molecular description of the hydration of proteins

    Science.gov (United States)

    Garde, Shekhar

    The unique balance of forces underlying biological processes-such as protein folding, aggregation, molecular recognition, and the formation of biological membranes-owes its origin in large part to the surrounding aqueous medium. A quantitative description of fundamental noncovalent interactions, in particular hydrophobic and electrostatic interactions at molecular- scale separations, requires an accurate description of water structure. Thus, the primary goals of our research are to understand the role of water in mediating interactions between molecules and to incorporate this understanding into molecular theories for calculating water-mediated interactions. We have developed a molecular model of hydrophobic interactions that uses methods of information theory to relate hydrophobic effects to the density fluctuations in liquid water. This model provides a quantitative description of small-molecule hydration thermodynamics, as well as insights into the entropies of unfolding globular proteins. For larger molecular solutes, we relate the inhomogeneous water structure in their vicinity to their hydration thermodynamics. We find that the water structure in the vicinity of nonpolar solutes is only locally sensitive to the molecular details of the solute. Water structures predicted using this observation are used to study the association of two neopentane molecules and the conformational equilibria of n-pentane molecule. We have also studied the hydration of a model molecular ionic solute, a tetramethylammonium ion, over a wide range of charge states of the solute. We find that, although the charge dependence of the ion hydration free energy is quadratic, negative ions are more favorably hydrated compared to positive ions. Moreover, this asymmetry of hydration can be reconciled by considering the differences in water organization surrounding positive and negative ions. We have also developed methods for predicting water structure surrounding molecular ions and relating

  15. Macroscopic and microscopic spectral properties of brain networks during local and global synchronization

    NARCIS (Netherlands)

    Maksimenko, V.A.; Lüttjohann, A.; Makarov, V.V.; Goremyko, M.V.; Koronovskii, A.A.; Nedaivozov, V.; Runnova, A.E.; Luijtelaar, E.L.J.M. van; Hramov, A.E.; Boccaletti, S.

    2017-01-01

    We introduce a practical and computationally not demanding technique for inferring interactions at various microscopic levels between the units of a network from the measurements and the processing of macroscopic signals. Starting from a network model of Kuramoto phase oscillators which evolve

  16. Reservoir engineering of a mechanical resonator: generating a macroscopic superposition state and monitoring its decoherence

    Science.gov (United States)

    Asjad, Muhammad; Vitali, David

    2014-02-01

    A deterministic scheme for generating a macroscopic superposition state of a nanomechanical resonator is proposed. The nonclassical state is generated through a suitably engineered dissipative dynamics exploiting the optomechanical quadratic interaction with a bichromatically driven optical cavity mode. The resulting driven dissipative dynamics can be employed for monitoring and testing the decoherence processes affecting the nanomechanical resonator under controlled conditions.

  17. Spin models as microfoundation of macroscopic market models

    Science.gov (United States)

    Krause, Sebastian M.; Bornholdt, Stefan

    2013-09-01

    Macroscopic price evolution models are commonly used for investment strategies. There are first promising achievements in defining microscopic agent based models for the same purpose. Microscopic models allow a deeper understanding of mechanisms in the market than the purely phenomenological macroscopic models, and thus bear the chance for better models for market regulation. However microscopic models and macroscopic models are commonly studied separately. Here, we exemplify a unified view of a microscopic and a macroscopic market model in a case study, deducing a macroscopic Langevin equation from a microscopic spin market model closely related to the Ising model. The interplay of the microscopic and the macroscopic view allows for a better understanding and adjustment of the microscopic model, as well, and may guide the construction of agent based market models as basis of macroscopic models.

  18. Hydrophobic patches on protein surfaces

    NARCIS (Netherlands)

    Lijnzaad, P.

    2007-01-01

    Hydrophobicity is a prime determinant of the structure and function of proteins. It is the driving force behind the folding of soluble proteins, and when exposed on the surface, it is frequently involved in recognition and binding of ligands and other proteins. The energetic cost of exposing hydroph

  19. Metastable states and macroscopic quantum tunneling in a cold atom josephson ring

    Energy Technology Data Exchange (ETDEWEB)

    Solenov, Dmitry [Los Alamos National Laboratory; Mozyrsky, Dmitry [Los Alamos National Laboratory

    2009-01-01

    We study macroscopic properties of a system of weakly interacting neutral bosons confined in a ring-shaped potential with a Josephson junction. We derive an effective low energy action for this system and evaluate its properties. In particular we find that the system possesses a set of metastable current-carrying states and evaluate the rates of transitions between these states due to macroscopic quantum tunneling. Finally we discuss signatures of different metastable states in the time-of-flight images and argue that the effect is observable within currently available experimental technique.

  20. MACROSCOPIC STRAIN POTENTIALS IN NONLINEAR POROUS MATERIALS

    Institute of Scientific and Technical Information of China (English)

    刘熠; 黄筑平

    2003-01-01

    By taking a hollow sphere as a representative volume element (RVE), the macroscopic strain potentials of porous materials with power-law incompressible matrix are studied in this paper.According to the principles of the minimum potential energy in nonlinear elasticity and the variational procedure, static admissible stress fields and kinematic admissible displacement fields are constructed,and hence the upper and the lower bounds of the macroscopic strain potential are obtained. The bounds given in the present paper differ so slightly that they both provide perfect approximations of the exact strain potential of the studied porous materials. It is also found that the upper bound proposed by previous authors is much higher than the present one, and the lower bounds given by Cocks is much lower. Moreover, the present calculation is also compared with the variational lower bound of Ponte Castafneda for statistically isotropic porous materials. Finally, the validity of the hollow spherical RVE for the studied nonlinear porous material is discussed by the difference between the present numerical results and the Cocks bound.

  1. Macroscopic theory for capillary-pressure hysteresis.

    Science.gov (United States)

    Athukorallage, Bhagya; Aulisa, Eugenio; Iyer, Ram; Zhang, Larry

    2015-03-03

    In this article, we present a theory of macroscopic contact angle hysteresis by considering the minimization of the Helmholtz free energy of a solid-liquid-gas system over a convex set, subject to a constant volume constraint. The liquid and solid surfaces in contact are assumed to adhere weakly to each other, causing the interfacial energy to be set-valued. A simple calculus of variations argument for the minimization of the Helmholtz energy leads to the Young-Laplace equation for the drop surface in contact with the gas and a variational inequality that yields contact angle hysteresis for advancing/receding flow. We also show that the Young-Laplace equation with a Dirichlet boundary condition together with the variational inequality yields a basic hysteresis operator that describes the relationship between capillary pressure and volume. We validate the theory using results from the experiment for a sessile macroscopic drop. Although the capillary effect is a complex phenomenon even for a droplet as various points along the contact line might be pinned, the capillary pressure and volume of the drop are scalar variables that encapsulate the global quasistatic energy information for the entire droplet. Studying the capillary pressure versus volume relationship greatly simplifies the understanding and modeling of the phenomenon just as scalar magnetic hysteresis graphs greatly aided the modeling of devices with magnetic materials.

  2. Adsorption of Rotavirus, MS2 Bacteriophage and Surface-Modified Silica Nanoparticles to Hydrophobic Matter.

    Science.gov (United States)

    Farkas, Kata; Varsani, Arvind; Pang, Liping

    2015-09-01

    Adsorption to aquifer media is an important process in the removal of viruses from groundwater. Even though hydrophobic interactions have been shown to contribute to adsorption, little is known about the hydrophobicity of viruses found in groundwater. In this study, the hydrophobicity of rotavirus, MS2 bacteriophage and DNA-labelled silica nanoparticles (SiNPs) coated with glycoprotein, protein A and alpha-1-microglobulin/bikunin precursor (AMBP) was investigated. The hydrophobicity was experimentally determined by using a modified microbial adhesion to hydrocarbons (MATH) assay. The results were compared with the theoretical hydrophobicity of the viral capsid proteins and the proteins used to coat the nanoparticles, and with the results of adsorption tests with unmodified and organosilane-coated (hydrophobic) silica sand. While most theoretical protein hydrophobicity values were similar, the results of the MATH assay suggested fundamental differences in the hydrophobicity of the viruses and the SiNPs. MS2 was found to be highly hydrophobic as based on the MATH hydrophobicity and a significantly enhanced adsorption to hydrophobic sand, whereas rotavirus was relatively hydrophilic. The MATH assay revealed that protein-coating of SiNP introduced some degree of hydrophobicity to hydrophilic SiNPs, enabling them to more closely mimic viral hydrophobicity. Our study also demonstrated that the protein-coated SiNPs better mimicked rotavirus adsorption to sand media (coated or not coated with hydrophobic organic matter) than the MS2. This further supports previous findings that these surface-modified SiNPs are useful surrogates in mimicking rotavirus retention and transport in porous media.

  3. Quantum correlations of lights in macroscopic environments

    Science.gov (United States)

    Sua, Yong Meng

    This dissertation presents a detailed study in exploring quantum correlations of lights in macroscopic environments. We have explored quantum correlations of single photons, weak coherent states, and polarization-correlated/polarization-entangled photons in macroscopic environments. These included macroscopic mirrors, macroscopic photon number, spatially separated observers, noisy photons source and propagation medium with loss or disturbances. We proposed a measurement scheme for observing quantum correlations and entanglement in the spatial properties of two macroscopic mirrors using single photons spatial compass state. We explored the phase space distribution features of spatial compass states, such as chessboard pattern by using the Wigner function. The displacement and tilt correlations of the two mirrors were manifested through the propensities of the compass states. This technique can be used to extract Einstein-Podolsky-Rosen correlations (EPR) of the two mirrors. We then formulated the discrete-like property of the propensity P b(m,n), which can be used to explore environmental perturbed quantum jumps of the EPR correlations in phase space. With single photons spatial compass state, the variances in position and momentum are much smaller than standard quantum limit when using a Gaussian TEM 00 beam. We observed intrinsic quantum correlations of weak coherent states between two parties through balanced homodyne detection. Our scheme can be used as a supplement to decoy-state BB84 protocol and differential phase-shift QKD protocol. We prepared four types of bipartite correlations +/- cos2(theta1 +/- theta 2) that shared between two parties. We also demonstrated bits correlations between two parties separated by 10 km optical fiber. The bits information will be protected by the large quantum phase fluctuation of weak coherent states, adding another physical layer of security to these protocols for quantum key distribution. Using 10 m of highly nonlinear

  4. Macroscopic quantum electrodynamics of high-Q cavities

    Energy Technology Data Exchange (ETDEWEB)

    Khanbekyan, Mikayel

    2009-10-27

    In this thesis macroscopic quantum electrodynamics in linear media was applied in order to develop an universally valid quantum theory for the description of the interaction of the electromagnetic field with atomic sources in high-Q cavities. In this theory a complete description of the characteristics of the emitted radiation is given. The theory allows to show the limits of the applicability of the usually applied theory. In order to establish an as possible generally valid theory first the atom-field interaction was studied in the framework of macroscopic quantum electrodynamics in dispersive and absorptive media. In order to describe the electromagnetic field from Maxwell's equations was started, whereby the noise-current densities, which are connected with the absorption of the medium, were included. The solution of these equations expresses the electromagnetic field variables by the noise-current densities by means of Green's tensor of the macroscopic Maxwell equations. The explicit quantization is performed by means of the noise-current densities, whereby a diagonal Hamiltonian is introduced, which then guarantees the time development according to Maxwell's equation and the fulfillment of the fundamental simultaneous commutation relations of the field variables. In the case of the interaction of the medium-supported field with atoms the Hamiltonian must be extended by atom-field interactions energies, whereby the canonical coupling schemes of the minimal or multipolar coupling can be used. The dieelectric properties of the material bodies as well as their shape are coded in the Green tensor of the macroscopic Maxwell equations. As preparing step first the Green tensor was specified in order to derive three-dimensional input-output relations for the electromagnetic field operators on a plane multilayer structure. Such a general dewscription of the electromagnetic field allows the inclusion both of dispersion and absorption of the media and the

  5. Macroscopic electromagnetic response of metamaterials with toroidal resonances

    CERN Document Server

    Savinov, V; Zheludev, N I

    2013-01-01

    Toroidal dipole, first described by Ia. B. Zeldovich [Sov. Phys. JETP 33, 1184 (1957)], is a distinct electromagnetic excitation that differs both from the electric and the magnetic dipoles. It has a number of intriguing properties: static toroidal nuclear dipole is responsible for parity violation in atomic spectra; interactions between static toroidal dipole and oscillating magnetic dipole are claimed to violate Newton's Third Law while non-stationary charge-current configurations involving toroidal multipoles have been predicted to produce vector potential in the absence of electromagnetic fields. Existence of the toroidal response in metamaterials was recently demonstrated and is now a growing field of research. However, no direct analytical link has yet been established between the transmission and reflection of macroscopic electromagnetic media and toroidal dipole excitations. To address this essential gap in electromagnetic theory we have developed an analytical approach linking microscopic and macrosc...

  6. Macroscopic acousto-mechanical analogy of a microbubble

    CERN Document Server

    Chaline, Jennifer; Mehrem, Ahmed; Bouakaz, Ayache; Santos, Serge Dos; Sánchez-Morcillo, Víctor J

    2015-01-01

    Microbubbles, either in the form of free gas bubbles surrounded by a fluid or encapsulated bubbles used currently as contrast agents for medical echography, exhibit complex dynamics under specific acoustic excitations. Nonetheless, considering their micron size and the complexity of their interaction phenomenon with ultrasound waves, expensive and complex experiments and/or simulations are required for their analysis. The behavior of a microbubble along its equator can be linked to a system of coupled oscillators. In this study, the oscillatory behavior of a microbubble has been investigated through an acousto-mechanical analogy based on a ring-shaped chain of coupled pendula. Observation of parametric vibration modes of the pendula ring excited at frequencies between $1$ and $5$ Hz is presented. Simulations have been carried out and show mode mixing phenomena. The relevance of the analogy between a microbubble and the macroscopic acousto-mechanical setup is discussed and suggested as an alternative way to in...

  7. Macroscopic quantum electrodynamics of high-Q cavities

    Energy Technology Data Exchange (ETDEWEB)

    Khanbekyan, Mikayel

    2009-10-27

    In this thesis macroscopic quantum electrodynamics in linear media was applied in order to develop an universally valid quantum theory for the description of the interaction of the electromagnetic field with atomic sources in high-Q cavities. In this theory a complete description of the characteristics of the emitted radiation is given. The theory allows to show the limits of the applicability of the usually applied theory. In order to establish an as possible generally valid theory first the atom-field interaction was studied in the framework of macroscopic quantum electrodynamics in dispersive and absorptive media. In order to describe the electromagnetic field from Maxwell's equations was started, whereby the noise-current densities, which are connected with the absorption of the medium, were included. The solution of these equations expresses the electromagnetic field variables by the noise-current densities by means of Green's tensor of the macroscopic Maxwell equations. The explicit quantization is performed by means of the noise-current densities, whereby a diagonal Hamiltonian is introduced, which then guarantees the time development according to Maxwell's equation and the fulfillment of the fundamental simultaneous commutation relations of the field variables. In the case of the interaction of the medium-supported field with atoms the Hamiltonian must be extended by atom-field interactions energies, whereby the canonical coupling schemes of the minimal or multipolar coupling can be used. The dieelectric properties of the material bodies as well as their shape are coded in the Green tensor of the macroscopic Maxwell equations. As preparing step first the Green tensor was specified in order to derive three-dimensional input-output relations for the electromagnetic field operators on a plane multilayer structure. Such a general dewscription of the electromagnetic field allows the inclusion both of dispersion and absorption of the media and the

  8. On the macroscopic quantization in mesoscopic rings and single-electron devices

    Science.gov (United States)

    Semenov, Andrew G.

    2016-05-01

    In this letter we investigate the phenomenon of macroscopic quantization and consider particle on the ring interacting with the dissipative bath as an example. We demonstrate that even in presence of environment, there is macroscopically quantized observable which can take only integer values in the zero temperature limit. This fact follows from the total angular momentum conservation combined with momentum quantization for bare particle on the ring. The nontrivial thing is that the model under consideration, including the notion of quantized observable, can be mapped onto the Ambegaokar-Eckern-Schon model of the single-electron box (SEB). We evaluate SEB observable, originating after mapping, and reveal new physics, which follows from the macroscopic quantization phenomenon and the existence of additional conservation law. Some generalizations of the obtained results are also presented.

  9. Intermolecular Vibrations of Hydrophobic Amino Acids

    Science.gov (United States)

    Williams, Michael Roy Casselman

    Hydrophobic amino acids interact with their chemical environment through a combination of electrostatic, hydrogen bonding, dipole, induced dipole, and dispersion forces. These interactions all have their own characteristic energy scale and distance dependence. The low-frequency (0.1-5 THz, 5-150 cm-1) vibrational modes of amino acids in the solid state are a direct indicator of the interactions between the molecules, which include interactions between an amino acid functional group and its surroundings. This information is central to understanding the dynamics and morphology of proteins. The alpha-carbon is a chiral center for all of the hydrophobic amino acids, meaning that they exist in two forms, traditionally referred to as L- and D-enantiomers. This nomenclature indicates which direction the molecule rotates plane-polarized visible light (levorotory and dextrorotory). Chiral a-amino acids in proteins are exclusively the L-variety In the solid state, the crystal lattice of the pure L-enantiomer is the mirror image of the D-enantiomer crystal lattice. These solids are energetically identical. Enantiomers also have identical spectroscopic properties except when the measurement is polarization sensitive. A mixture of equal amounts D- and L-amino acid enantiomers can crystallize into a racemic (DL-) structure that is different from that of the pure enantiomers. Whether a solution of both enantiomers will crystallize into a racemic form or spontaneously resolve into a mixture of separate D- and L-crystals largely depends on the interactions between molecules available in the various possible configurations. This is an active area of research. Low-frequency vibrations with intermolecular character are very sensitive to changes in lattice geometry, and consequently the vibrational spectra of racemic crystals are usually quite distinct from the spectra of the crystals of the corresponding pure enantiomers in the far-infrared (far-IR). THz time-domain spectroscopy (THz

  10. Scaling Properties and Asymptotic Spectra of Finite Models of Phase Transitions as They Approach Macroscopic Limits

    Science.gov (United States)

    Rowe, D. J.; Turner, P. S.; Rosensteel, G.

    2004-11-01

    The asymptotic spectra and scaling properties of a mixed-symmetry Hamiltonian, which exhibits a second-order phase transition in its macroscopic limit, are examined for a system of N interacting bosons. A second interacting boson-model Hamiltonian, which exhibits a first-order phase transition, is also considered. The latter shows many parallel characteristics and some notable differences, leaving it open to question as to the nature of its asymptotic critical-point properties.

  11. Macroscopic Quantum Coherence in Antiferromagnetic Molecular Magnets

    Institute of Scientific and Technical Information of China (English)

    HU Hui; LO Rong; ZHU Jia-Lin; XIONG Jia-Jiong

    2001-01-01

    The macroscopic quantum coherence in a biaxial antiferromagnetic molecular magnet in the presence of magnetic field acting parallel to its hard anisotropy axis is studied within the two-sublattice model. On the basis of instanton technique in the spin-coherent-state path-integral representation, both the rigorous Wentzel-Kramers-Brillouin exponent and pre-exponential factor for the ground-state tunnel splitting are obtained. We find that the quantum fluctuations around the classical paths can not only induce a new quantum phase previously reported by Chiolero and Loss (Phys. Rev. Lett. 80 (1998) 169), but also have great influence on the intensity of the ground-state tunnel splitting. Those features clearly have no analogue in the ferromagnetic molecular magnets. We suggest that they may be the universal behaviors in all antiferromagnetic molecular magnets. The analytical results are complemented by exact diagonalization calculation.

  12. Micro- and macroscopic simulation of periodic metamaterials

    Directory of Open Access Journals (Sweden)

    R. Schuhmann

    2008-05-01

    Full Text Available In order to characterize three-dimensional, left-handed metamaterials (LHM we use electromagnetic field simulations of unit cells. For waves traveling in one of the main directions of the periodic LHM-arrays, the analysis is concentrated on the calculation of global quantities of the unit cells, such as scattering parameters or dispersion diagrams, and a careful interpretation of the results. We show that the concept of equivalent material values – which may be negative in a narrow frequency range – can be validated by large "global" simulations of a wedge structure. We also discuss the limitations of this concept, since in some cases the macroscopic behavior of an LHM cannot be accurately described by equivalent material values.

  13. Microscopic versus macroscopic calculation of dielectric nanospheres

    Science.gov (United States)

    Kühn, M.; Kliem, H.

    2008-12-01

    The issue of nanodielectrics has recently become an important field of interest. The term describes nanometric dielectrics, i. e. dielectric materials with structural dimensions typically smaller than 100 run. In contrast to the behaviour of a bulk material the nanodielectrics can behave completely different. With shrinking dimensions the surface or rather boundary effects outweigh the volume effects. This leads to a different observable physics at the nanoscale. A crucial point is the question whether a continuum model for the calculation of dielectric properties is still applicable for these nanomaterials. In order to answer this question we simulated dielectric nanospheres with a microscopic local field method and compared the results to the macroscopic mean field theory.

  14. Partitioning a macroscopic system into independent subsystems

    Science.gov (United States)

    Delle Site, Luigi; Ciccotti, Giovanni; Hartmann, Carsten

    2017-08-01

    We discuss the problem of partitioning a macroscopic system into a collection of independent subsystems. The partitioning of a system into replica-like subsystems is nowadays a subject of major interest in several fields of theoretical and applied physics. The thermodynamic approach currently favoured by practitioners is based on a phenomenological definition of an interface energy associated with the partition, due to a lack of easily computable expressions for a microscopic (i.e. particle-based) interface energy. In this article, we outline a general approach to derive sharp and computable bounds for the interface free energy in terms of microscopic statistical quantities. We discuss potential applications in nanothermodynamics and outline possible future directions.

  15. Casimir effect from macroscopic quantum electrodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Philbin, T G, E-mail: tgp3@st-andrews.ac.uk [School of Physics and Astronomy, University of St Andrews, North Haugh, St Andrews, Fife KY16 9SS (United Kingdom)

    2011-06-15

    The canonical quantization of macroscopic electromagnetism was recently presented in (Philbin 2010 New J. Phys. 12 123008). This theory is used here to derive the Casimir effect, by considering the special case of thermal and zero-point fields. The stress-energy-momentum tensor of the canonical theory follows from Noether's theorem, and its electromagnetic part in thermal equilibrium gives the Casimir energy density and stress tensor. The results hold for arbitrary inhomogeneous magnetodielectrics and are obtained from a rigorous quantization of electromagnetism in dispersive, dissipative media. Continuing doubts about the status of the standard Lifshitz theory as a proper quantum treatment of Casimir forces do not apply to the derivation given here. Moreover, the correct expressions for the Casimir energy density and stress tensor inside media follow automatically from the simple restriction to thermal equilibrium, without the need for complicated thermodynamical or mechanical arguments.

  16. Taming macroscopic jamming in transportation networks

    CERN Document Server

    Ezaki, Takahiro; Nishinari, Katsuhiro

    2015-01-01

    In transportation networks, a spontaneous jamming transition is often observed, e.g in urban road networks and airport networks. Because of this instability, flow distribution is significantly imbalanced on a macroscopic level. To mitigate the congestion, we consider a simple control method, in which congested nodes are closed temporarily, and investigate how it influences the overall system. Depending on the timing of the node closure and opening, and congestion level of a network, the system displays three different phases: free-flow phase, controlled phase, and deadlock phase. We show that when the system is in the controlled phase, the average flow is significantly improved, whereas when in the deadlock phase, the flow drops to zero. We study how the control method increases the network flow and obtain their transition boundary analytically.

  17. Variability of macroscopic dimensions of Moso bamboo.

    Science.gov (United States)

    Cui, Le; Peng, Wanxi; Sun, Zhengjun; Sun, Zhengjun; Sun, Zhengjun; Lu, Huangfei; Chen, Guoning

    2015-03-01

    In order to the macroscopic geometry distributions of vascular bundles in Moso bamboo tubes. The circumference of bamboo tubes was measured, used a simple quadratic diameter formula to analyze the differences between the tubes in bamboo culm, and the arrangement of vascular bundles was investigated by cross sectional images of bamboo tubes. The results shown that the vascular bundles were differently distributed in a bamboo tube. In the outer layer, the vascular bundles had a variety of shapes, and were aligned parallel to each other. In the inner layers, the vascular bundles weren't aligned but uniform in shape. It was concluded that the vascular bundle sections arranged in parallel should be separated from the non-parallel sections for the maximum bamboo utilization.

  18. Robust macroscopic entanglement without complex encodings

    CERN Document Server

    Chaves, Rafael; Acín, Antonio

    2011-01-01

    One of the main challenges for the experimental manipulation and storage of macroscopic entanglement is its fragility under noise. We present a simple recipe for the systematic enhancement of the resistance of multipartite entanglement against any local noise with a privileged direction in the Bloch sphere. For the case of exact local dephasing along any given basis, and for all noise strengths, our prescription grants full robustness: even states whose entanglement decays exponentially with the number of parts are mapped to states whose entanglement is constant. In contrast to previous techniques resorting to complex logical-qubit encodings, such enhancement is attained simply by performing local unitary rotations before the noise acts. The scheme is therefore highly experimentally-friendly, as it brings no overhead of extra physical qubits to encode logical ones. In addition, we show that, apart from entanglement, the resilience of the states as resources for useful practical tasks such as metrology and non...

  19. Macroscopic Quantum Coherence in Antiferromagnetic Molecular Magnets

    Institute of Scientific and Technical Information of China (English)

    HUHui; LURong; 等

    2001-01-01

    The macroscopic quantum coherence in a biaxial antiferromagnetic molecular magnet in the presence of magnetic field acting parallel to its hard anisotropy axis is studied within the two-sublattice model.On the basis of instanton technique in the spin-coherent-state path-integral representation,both the rigorous Wentzel-Kramers-Brillouin exponent and pre-exponential factor for the ground-state tunnel splitting are obtained.We find that the quantum fluctuations around the classical paths can not only induce a new quantum phase previously reported by Chiolero and Loss (Phys.Rev.Lett.80(1998)169),but also have great influence on the intensity of the ground-state tunnel splitting.Those features clearly have no analogue in the ferromagnetic molecular magnets.We suggest that they may be the universal behaviors in all antiferromagnetic molecular magnets.The analytical results are complemented by exact diagonalization calculation.

  20. Hydrophobic environment is a key factor for the stability of thermophilic proteins.

    Science.gov (United States)

    Gromiha, M Michael; Pathak, Manish C; Saraboji, Kadhirvel; Ortlund, Eric A; Gaucher, Eric A

    2013-04-01

    The stability of thermophilic proteins has been viewed from different perspectives and there is yet no unified principle to understand this stability. It would be valuable to reveal the most important interactions for designing thermostable proteins for such applications as industrial protein engineering. In this work, we have systematically analyzed the importance of various interactions by computing different parameters such as surrounding hydrophobicity, inter-residue interactions, ion-pairs and hydrogen bonds. The importance of each interaction has been determined by its predicted relative contribution in thermophiles versus the same contribution in mesophilic homologues based on a dataset of 373 protein families. We predict that hydrophobic environment is the major factor for the stability of thermophilic proteins and found that 80% of thermophilic proteins analyzed showed higher hydrophobicity than their mesophilic counterparts. Ion pairs, hydrogen bonds, and interaction energy are also important and favored in 68%, 50%, and 62% of thermophilic proteins, respectively. Interestingly, thermophilic proteins with decreased hydrophobic environments display a greater number of hydrogen bonds and/or ion pairs. The systematic elimination of mesophilic proteins based on surrounding hydrophobicity, interaction energy, and ion pairs/hydrogen bonds, led to correctly identifying 95% of the thermophilic proteins in our analyses. Our analysis was also applied to another, more refined set of 102 thermophilic-mesophilic pairs, which again identified hydrophobicity as a dominant property in 71% of the thermophilic proteins. Further, the notion of surrounding hydrophobicity, which characterizes the hydrophobic behavior of residues in a protein environment, has been applied to the three-dimensional structures of elongation factor-Tu proteins and we found that the thermophilic proteins are enriched with a hydrophobic environment. The results obtained in this work highlight the

  1. Rheological Properties in Aqueous Solution for Hydrophobically Modified Polyacrylamides Prepared in Inverse Emulsion Polymerization

    Directory of Open Access Journals (Sweden)

    Shirley Carro

    2017-01-01

    Full Text Available Inverse emulsion polymerization technique was employed to synthesize hydrophobically modified polyacrylamide polymers with hydrophobe contents near to feed composition. Three different structures were obtained: multisticker, telechelic, and combined. N-Dimethyl-acrylamide (DMAM, n-dodecylacrylamide (DAM, and n-hexadecylacrylamide (HDAM were used as hydrophobic comonomers. The effect of the hydrophobe length of comonomer, the initial monomer, and surfactant concentrations on shear viscosity was studied. Results show that the molecular weight of copolymer increases with initial monomer concentration and by increasing emulsifier concentration it remained almost constant. Shear viscosity measurements results show that the length of the hydrophobic comonomer augments the hydrophobic interactions causing an increase in viscosity and that the polymer thickening ability is higher for combined polymers.

  2. Intrinsic Hydrophobicity of Rammed Earth

    Science.gov (United States)

    Holub, M.; Stone, C.; Balintova, M.; Grul, R.

    2015-11-01

    Rammed earth is well known for its vapour diffusion properties, its ability to regulate humidity within the built environment. Rammed earth is also an aesthetically iconic material such as marble or granite and therefore is preferably left exposed. However exposed rammed earth is often coated with silane/siloxane water repellents or the structure is modified architecturally (large roof overhangs) to accommodate for the hydrophilic nature of the material. This paper sets out to find out optimal hydrophobicity for rammed earth based on natural composite fibres and surface coating without adversely affecting the vapour diffusivity of the material. The material is not required to be waterproof, but should resist at least driving rain. In order to evaluate different approaches to increase hydrophobicity of rammed earth surface, peat fibres and four types of repellents were used.

  3. Determining the Macroscopic Properties of Relativistic Jets

    Science.gov (United States)

    Hardee, P. E.

    2004-08-01

    The resolved relativistic jets contain structures whose observed proper motions are typically assumed to indicate the jet flow speed. In addition to structures moving with the flow, various normal mode structures such as pinching or helical and elliptical twisting can be produced by ejection events or twisting perturbations to the jet flow. The normal mode structures associated with relativistic jets, as revealed by numerical simulation, theoretical calculation, and suggested by observation, move more slowly than the jet speed. The pattern speed is related to the jet speed by the sound speed in the jet and in the surrounding medium. In the event that normal mode structures are observed, and where proper motions of pattern and flow speed are available or can be estimated, it is possible to determine the sound speed in the jet and surrounding medium. Where spatial development of normal mode structures is observed, it is possible to make inferences as to the heating rate/macroscopic viscosity of the jet fluid. Ultimately it may prove possible to separate the microscopic energization of the synchrotron radiating particles from the macroscopic heating of the jet fluid. Here I present the relevant properties of useful normal mode structures and illustrate the use of this technique. Various aspects of the work presented here have involved collaboration with I. Agudo (Max-Planck, Bonn), M.A. Aloy (Max-Planck, Garching), J. Eilek (NM Tech), J.L. Gómez (U. Valencia), P. Hughes (U. Michigan), A. Lobanov (Max-Planck, Bonn), J.M. Martí (U. Valencia), & C. Walker (NRAO).

  4. Hydrophobic effect at aqueous interfaces

    Science.gov (United States)

    Pohorille, Andrew

    2005-01-01

    Conceptual basis for hydrophobic effects in bulk water and at aqueous interfaces have similar conceptual basis but often manifests itself differently. Using a wide range of computer simulations as the basis, I will review different forms of hydrophobic effects at a variety of interfaces starting from simple liquid-vapor and water-oil interfaces and progressing to water-membrane interfaces. I will start with discussing how water is organized at different interfaces, stressing both similarities and differences. The main thread is that, as in the bulk liquid, hydrophobic effects have profound influence on conformational equilibria and organization of both small molecules and macromolecules, but the result of this influence is quite different. Specifically, it will be shown that many small, but not necessarily amphiphilic molecules tend to accumulate at the interface and, and this tendency will be explained. Furthermore, I will show that many short peptides that are disordered in water spontaneously fold into well-defined structures in the interfacial environment. Biological implications of this self-organizing effect will be discussed.

  5. Combining a polarizable force-field and a coarse-grained polarizable solvent model. II. Accounting for hydrophobic effects.

    Science.gov (United States)

    Masella, Michel; Borgis, Daniel; Cuniasse, Philippe

    2011-09-01

    A revised and improved version of our efficient polarizable force-field/coarse grained solvent combined approach (Masella, Borgis, and Cuniasse, J. Comput. Chem. 2008, 29, 1707) is described. The polarizable pseudo-particle solvent model represents the macroscopic solvent polarization by induced dipoles placed on mobile pseudo-particles. In this study, we propose a new formulation of the energy term handling the nonelectrostatic interactions among the pseudo-particles. This term is now able to reproduce the energetic and structural response of liquid water due to the presence of a hydrophobic spherical cavity. Accordingly, the parameters of the energy term handling the nonpolar solute/solvent interactions have been refined to reproduce the free-solvation energy of small solutes, based on a standard thermodynamic integration scheme. The reliability of this new approach has been checked for the properties of solvated methane and of the solvated methane dimer, as well as by performing 10 × 20 ns molecular dynamics (MD) trajectories for three solvated proteins. A long-time stability of the protein structures along the trajectories is observed. Moreover, our method still provides a measure of the protein solvation thermodynamic at the same accuracy as standard Poisson-Boltzman continuum methods. These results show the relevance of our approach and its applicability to massively coupled MD schemes to accurately and intensively explore solvated macromolecule potential energy surfaces.

  6. Zero time tunneling: macroscopic experiments with virtual particles

    Directory of Open Access Journals (Sweden)

    Nimtz Günter

    2015-01-01

    Full Text Available Feynman introduced virtual particles in his diagrams as intermediate states of an interaction process. They represent necessary intermediate states between observable real states. Such virtual particles were introduced to describe the interaction process between an electron and a positron and for much more complicated interaction processes. Other candidates for virtual particles are evanescent modes in optics and in elastic fields. Evanescent modes have a purely imaginary wave number, they represent the mathematical analogy of the tunneling solutions of the Schrödinger equation. Evanescent modes exist in the forbidden frequency bands of a photonic lattice and in undersized wave guides, for instance. The most prominent example for the occurrence of evanescent modes is the frustrated total internal reflection (FTIR at double prisms. Evanescent modes and tunneling lie outside the bounds of the special theory of relativity. They can cause faster than light (FTL signal velocities. We present examples of the quantum mechanical behavior of evanescent photons and phonons at a macroscopic scale. The evanescent modes of photons are described by virtual particles as predicted by former QED calculations.

  7. Single-file diffusion of macroscopic charged particles.

    Science.gov (United States)

    Coste, C; Delfau, J-B; Even, C; Saint Jean, M

    2010-05-01

    In this paper, we study a macroscopic system of electrically interacting metallic beads organized as a sequence along an annulus. A random mechanical shaking mimics the thermal excitation. We exhibit non-Fickian diffusion (single-file diffusion) at large time. We measure the mobility of the particles and compare it to theoretical expectations. We show that our system cannot be accurately described by theories assuming only hard-sphere interactions. Its behavior is qualitatively described by a theory extended to more realistic potentials [M. Kollmann, Phys. Rev. Lett. 90, 180602 (2003)]. A correct quantitative agreement is shown and we interpret the discrepancies by the violation of the assumption of overdamped dynamics, which is a key point in the theory. We recast previous results on colloids with known interaction potentials and compare them quantitatively to the theory. Focusing on the transition between ordinary and single-file diffusions, we exhibit a dimensionless crossover time that is of order 1 both for colloids and our system, although the time and length scales differ by several orders of magnitude.

  8. Observability of relative phases of macroscopic quantum states

    CERN Document Server

    Pati, A K

    1998-01-01

    After a measurement, to observe the relative phases of macroscopically distinguishable states we have to ``undo'' a quantum measurement. We generalise an earlier model of Peres from two state to N-state quantum system undergoing measurement process and discuss the issue of observing relative phases of different branches. We derive an inequality which is satisfied by the relative phases of macroscopically distinguishable states and consequently any desired relative phases can not be observed in interference setups. The principle of macroscopic complementarity is invoked that might be at ease with the macroscopic world. We illustrate the idea of limit on phase observability in Stern-Gerlach measurements and the implications are discussed.

  9. Cell-surface hydrophobicity of Staphylococcus saprophyticus.

    Science.gov (United States)

    Schneider, P. F.; Riley, T. V.

    1991-01-01

    The cell-surface hydrophobicity of 100 urinary isolates of Staphylococcus saprophyticus, cultured from symptomatic females in the general population, was assessed using a two-phase aqueous:hydrocarbon system. Relatively strong cell-surface hydrophobicity was exhibited by 79 isolates using the criteria employed, while only 2 of the remaining 21 isolates failed to demonstrate any detectable hydrophobicity. Cell-surface hydrophobicity may be a virulence factor of S. saprophyticus, important in adherence of the organism to uroepithelia. Additionally, the data support the concept that cell-surface hydrophobicity may be a useful predictor of clinical significance of coagulase-negative staphylococci isolated from clinical sources. PMID:1993454

  10. Hydrophobic-Core Microcapsules and Their Formation

    Science.gov (United States)

    Calle, Luz M. (Inventor); Li, Wenyan (Inventor); Buhrow, Jerry W. (Inventor); Jolley, Scott T. (Inventor)

    2016-01-01

    Hydrophobic-core microcapsules and methods of their formation are provided. A hydrophobic-core microcapsule may include a shell that encapsulates a hydrophobic substance with a core substance, such as dye, corrosion indicator, corrosion inhibitor, and/or healing agent, dissolved or dispersed therein. The hydrophobic-core microcapsules may be formed from an emulsion having hydrophobic-phase droplets, e.g., containing the core substance and shell-forming compound, dispersed in a hydrophilic phase. The shells of the microcapsules may be capable of being broken down in response to being contacted by an alkali, e.g., produced during corrosion, contacting the shell.

  11. Use of hybrid discrete cellular models for identification of macroscopic nutrient loss in reaction-diffusion models of tissues.

    Science.gov (United States)

    Aristotelous, Andreas C; Haider, Mansoor A

    2014-08-01

    Macroscopic models accounting for cellular effects in natural or engineered tissues may involve unknown constitutive terms that are highly dependent on interactions at the scale of individual cells. Hybrid discrete models, which represent cells individually, were used to develop and apply techniques for modeling diffusive nutrient transport and cellular uptake to identify a nonlinear nutrient loss term in a macroscopic reaction-diffusion model of the system. Flexible and robust numerical methods were used, based on discontinuous Galerkin finite elements in space and a Crank-Nicolson temporal discretization. Scales were bridged via averaging operations over a complete set of subdomains yielding data for identification of a macroscopic nutrient loss term that was accurately captured via a fifth-order polynomial. Accuracy of the identified macroscopic model was demonstrated by direct, quantitative comparisons of the tissue and cellular scale models in terms of three error norms computed on a mesoscale mesh. Copyright © 2014 John Wiley & Sons, Ltd.

  12. Graphene-based macroscopic assemblies and architectures: an emerging material system.

    Science.gov (United States)

    Cong, Huai-Ping; Chen, Jia-Fu; Yu, Shu-Hong

    2014-11-07

    Due to the outstanding physicochemical properties arising from its truly two-dimensional (2D) planar structure with a single-atom thickness, graphene exhibits great potential for use in sensors, catalysts, electrodes, and in biological applications, etc. With further developments in the theoretical understanding and assembly techniques, graphene should enable great changes both in scientific research and practical industrial applications. By the look of development, it is of fundamental and practical significance to translate the novel physical and chemical properties of individual graphene nanosheets into the macroscale by the assembly of graphene building blocks into macroscopic architectures with structural specialities and functional novelties. The combined features of a 2D planar structure and abundant functional groups of graphene oxide (GO) should provide great possibilities for the assembly of GO nanosheets into macroscopic architectures with different macroscaled shapes through various assembly techniques under different bonding interactions. Moreover, macroscopic graphene frameworks can be used as ideal scaffolds for the incorporation of functional materials to offset the shortage of pure graphene in the specific desired functionality. The advantages of light weight, supra-flexibility, large surface area, tough mechanical strength, and high electrical conductivity guarantee graphene-based architectures wide application fields. This critical review mainly addresses recent advances in the design and fabrication of graphene-based macroscopic assemblies and architectures and their potential applications. Herein, we first provide overviews of the functional macroscopic graphene materials from three aspects, i.e., 1D graphene fibers/ribbons, 2D graphene films/papers, 3D network-structured graphene monoliths, and their composite counterparts with either polymers or nano-objects. Then, we present the promising potential applications of graphene-based macroscopic

  13. Tunable Surface Hydrophobicity and Fluid Transport through Nanoporous Membranes

    Science.gov (United States)

    Ostrowski, Joseph H. J.

    There are more than three billion people across the globe that struggle to obtain clean drinkable water. One of the most promising avenues for generating potable water is through reverse osmosis and nanofiltration. Both solutions require a semipermeable membrane that prohibits passage of unwanted solute particles but allows passage of the solvent. Atomically thin two-dimensional membranes based on porous graphene show great promise as semipermeable materials, but modeling fluid flow on length scales between the microscopic (nanometer and smaller) and macroscopic (micron and larger) regimes presents formidable challenges. This thesis explores both equilibrium and nonequilibrium aspects of this problem and develops new methodology for simulating systems away from thermal equilibrium. First, we hypothesize that there is a wetting penalty for water as it tries to breach a sheet of graphene that should be naturally hydrophobic. By using equilibrium molecular dynamics simulations, we show that the hydrophobicity depends sensitively on the degree of electrical doping, offering an opportunity to tune the hydrophobic effect of graphene using small amounts of doping. The wetting contact angle, a measure of hydrophobicity, changes dramatically with the voltage applied to single layer graphene. We find that the sensitivity of the hydrophobic effect to voltage depends not on hydrogen bonding motifs at the interface between graphene and water, but instead on a phenomenon known as electrowetting. The theory of electrowetting predicts that the difference in surface tensions that defines the contact angle is quartic in the voltage, rather than quadratic, as it would be in bilayer graphene or in a two-dimensional metal. To explore the nonequilibrium aspects of fluid passage through atomically thin membranes, we developed a molecular dynamics methodology for simulating fluid flow at constant flux based on Gauss's principle of least constraint. This method develops microscopic

  14. Drying Induced Hydrophobic Polymer Collapse

    OpenAIRE

    ten Wolde, Pieter Rein; Chandler, David

    2002-01-01

    We have used computer simulation to study the collapse of a hydrophobic chain in water. We find that the mechanism of collapse is much like that of a first-order phase transition. The evaporation of water in the vicinity of the polymer provides the driving force for collapse, and the rate limiting step is the nucleation of a sufficiently large vapor bubble. The study is made possible through the application of transition path sampling and a coarse-grained treatment of liquid water. Relevance ...

  15. Dropwise Condensation on Hydrophobic Cylinders

    CERN Document Server

    Park, Kyoo-Chul; Hoang, Michelle; McManus, Brendan; Aizenberg, Joanna

    2016-01-01

    In this work, we studied the effect of the diameter of horizontal hydrophobic cylinders on droplet growth. We postulate that the concentration gradient created by natural convection around a horizontal circular cylinder is related to the droplet growth on the cylinder by condensation. We derive a simple scaling law of droplet growth and compare it with experimental results. The predicted negative exponent of drop diameter (d) as a function of cylinder diameter (D) at different time points is similar to the general trend of experimental data. Further, this effect of cylinder diameter on droplet growth is observed to be stronger than the supersaturation conditions created by different surface temperatures.

  16. Searching for the nanoscopic–macroscopic boundary

    Energy Technology Data Exchange (ETDEWEB)

    Velásquez, E.A. [GICM and GES Groups, Instituto de Física-FCEN, Universidad de Antioquia UdeA, Calle 70 No. 52-21 Medellín (Colombia); Grupo de Investigación en Modelamiento y Simulación Computacional, Universidad de San Buenaventura Sec. Medellín, A.A. 5222, Medellín (Colombia); Altbir, D. [Departamento de Física, Universidad de Santiago de Chile (USACH), CEDENNA, Santiago (Chile); Mazo-Zuluaga, J. [GICM and GES Groups, Instituto de Física-FCEN, Universidad de Antioquia UdeA, Calle 70 No. 52-21 Medellín (Colombia); Duque, L.F. [GICM and GES Groups, Instituto de Física-FCEN, Universidad de Antioquia UdeA, Calle 70 No. 52-21 Medellín (Colombia); Grupo de Física Teórica, Aplicada y Didáctica, Facultad de Ciencias Exactas y Aplicadas Instituto Tecnológico Metropolitano, Medellín (Colombia); Mejía-López, J., E-mail: jmejia@puc.cl [Facultad de Física, Pontificia Universidad Católica de Chile, CEDENNA, Santiago (Chile)

    2013-12-15

    Several studies have focused on the size-dependent properties of elements, looking for a unique definition of the nanoscopic–macroscopic boundary. By using a novel approach consisting of an energy variational method combined with a quantum Heisenberg model, here we address the size at which the ordering temperature of a magnetic nanoparticle reaches its bulk value. We consider samples with sizes in the range 1–500 nm, as well as several geometries and crystalline lattices and observe that, contrarily to what is commonly argued, the nanoscopic-microscopic boundary depends on both factors: shape and crystalline structure. This suggests that the surface-to-volume ratio is not the unique parameter that defines the behavior of a nanometric sample whenever its size increases reaching the bulk dimension. Comparisons reveal very good agreement with experimental evidence with differences less than 2%. Our results have broad implications for practical issues in measurements on systems at the nanometric scale. - Highlights: • A novel quantum-Heisenberg variational energy method is implemented. • The asymptotic behavior toward the thermodynamic limit is explored. • An important dependence of the nano-bulk boundary on the geometry is found. • And also an important dependence on the crystalline lattice. • We obtain a very good agreement with experimental evidence with differences <2%.

  17. The Proell Effect: A Macroscopic Maxwell's Demon

    Science.gov (United States)

    Rauen, Kenneth M.

    2011-12-01

    Maxwell's Demon is a legitimate challenge to the Second Law of Thermodynamics when the "demon" is executed via the Proell effect. Thermal energy transfer according to the Kinetic Theory of Heat and Statistical Mechanics that takes place over distances greater than the mean free path of a gas circumvents the microscopic randomness that leads to macroscopic irreversibility. No information is required to sort the particles as no sorting occurs; the entire volume of gas undergoes the same transition. The Proell effect achieves quasi-spontaneous thermal separation without sorting by the perturbation of a heterogeneous constant volume system with displacement and regeneration. The classical analysis of the constant volume process, such as found in the Stirling Cycle, is incomplete and therefore incorrect. There are extra energy flows that classical thermo does not recognize. When a working fluid is displaced across a regenerator with a temperature gradient in a constant volume system, complimentary compression and expansion work takes place that transfers energy between the regenerator and the bulk gas volumes of the hot and cold sides of the constant volume system. Heat capacity at constant pressure applies instead of heat capacity at constant volume. The resultant increase in calculated, recyclable energy allows the Carnot Limit to be exceeded in certain cycles. Super-Carnot heat engines and heat pumps have been designed and a US patent has been awarded.

  18. Macroscopic superpositions and gravimetry with quantum magnetomechanics

    Science.gov (United States)

    Johnsson, Mattias T.; Brennen, Gavin K.; Twamley, Jason

    2016-11-01

    Precision measurements of gravity can provide tests of fundamental physics and are of broad practical interest for metrology. We propose a scheme for absolute gravimetry using a quantum magnetomechanical system consisting of a magnetically trapped superconducting resonator whose motion is controlled and measured by a nearby RF-SQUID or flux qubit. By driving the mechanical massive resonator to be in a macroscopic superposition of two different heights our we predict that our interferometry protocol could, subject to systematic errors, achieve a gravimetric sensitivity of Δg/g ~ 2.2 × 10-10 Hz-1/2, with a spatial resolution of a few nanometres. This sensitivity and spatial resolution exceeds the precision of current state of the art atom-interferometric and corner-cube gravimeters by more than an order of magnitude, and unlike classical superconducting interferometers produces an absolute rather than relative measurement of gravity. In addition, our scheme takes measurements at ~10 kHz, a region where the ambient vibrational noise spectrum is heavily suppressed compared the ~10 Hz region relevant for current cold atom gravimeters.

  19. Distributivity breaking and macroscopic quantum games

    CERN Document Server

    Grib, A A; Parfionov, G N; Starkov, K A

    2005-01-01

    Examples of games between two partners with mixed strategies, calculated by the use of the probability amplitude as some vector in Hilbert space are given. The games are macroscopic, no microscopic quantum agent is supposed. The reason for the use of the quantum formalism is in breaking of the distributivity property for the lattice of yes-no questions arising due to the special rules of games. The rules of the games suppose two parts: the preparation and measurement. In the first part due to use of the quantum logical orthocomplemented non-distributive lattice the partners freely choose the wave functions as descriptions of their strategies. The second part consists of classical games described by Boolean sublattices of the initial non-Boolean lattice with same strategies which were chosen in the first part. Examples of games for spin one half are given. New Nash equilibria are found for some cases. Heisenberg uncertainty relations without the Planck constant are written for the "spin one half game".

  20. The membranotropic activity of N-terminal peptides from the pore-forming proteins sticholysin I and II is modulated by hydrophobic and electrostatic interactions as well as lipid composition

    Indian Academy of Sciences (India)

    Uris Ros; Lohans Pedrera; Daylín Díaz; Juan C De Karam; Tatiane P Sudbrack; Pedro A Valiente; Diana Martínez; Eduardo M Cilli; Fabiola Pazos; Rosangela Itri; Maria E Lanio; Shirley Schreier; Carlos Álvarez

    2011-12-01

    The sea anemone Stichodactyla helianthus produces two pore-forming proteins, sticholysins I and II (St I and St II). Despite their high identity (93%), these toxins exhibit differences in hemolytic activity that can be related to those found in their N-terminal. To clarify the contribution of the N-terminal amino acid residues to the activity of the toxins, we synthesized peptides spanning residues 1–31 of St I (StI1-31) or 1–30 of St II (StII1-30) and demonstrated that StII1-30 promotes erythrocyte lysis to a higher extent than StI1-31. For a better understanding of the molecular mechanism underlying the peptide activity, here we studied their binding to lipid monolayers and pemeabilizing activity in liposomes. For this, we examined the effect on peptide membranotropic activity of including phospatidic acid and cholesterol in a lipid mixture of phosphatidylcholine and sphingomyelin. The results suggest the importance of continuity of the 1–10 hydrophobic sequence in StII1-30 for displaying higher binding and activity, in spite of both peptides’ abilities to form pores in giant unilamellar vesicles. Thus, the different peptide membranotropic action is explained in terms of the differences in hydrophobic and electrostatic peptide properties as well as the enhancing role of membrane inhomogeneities.

  1. Water repellency in hydrophobic nanocapsules--molecular view on dewetting.

    Science.gov (United States)

    Müller, Achim; Garai, Somenath; Schäffer, Christian; Merca, Alice; Bögge, Hartmut; Al-Karawi, Ahmed Jasim M; Prasad, Thazhe Kootteri

    2014-05-26

    The hydrophobic effect plays a major role in a variety of important phenomena in chemistry, materials science and biology, for instance in protein folding and protein-ligand interactions. Studies--performed within cavities of the unique metal oxide based porous capsules of the type {(pentagon)12(linker)30}≡{(W)W5}12{Mo2(ligand)}30 with different acetate/water ligand ratios--have provided unprecedented results revealing segregation/repellency of the encapsulated "water" from the internal hydrophobic ligand walls of the capsules, while the disordered water molecules, interacting strongly with each other via hydrogen bonding, form in all investigated cases the same type of spherical shell. The present results can be (formally) compared--but only regarding the repellency effect--with the amazing "action" of the (super)hydrophobic Lotus (Nelumbo) leaves, which are self-cleaning based on water repellency resulting in the formation of water droplets picking up dirt. The present results were obtained by constructing deliberately suitable hydrophobic interiors within the mentioned capsules.

  2. Anionic and cationic Hofmeister effects on hydrophobic and hydrophilic surfaces.

    Science.gov (United States)

    Schwierz, Nadine; Horinek, Dominik; Netz, Roland R

    2013-02-26

    Using a two-step modeling approach, we address the full spectrum of direct, reversed, and altered ionic sequences as the charge of the ion, the charge of the surface, and the surface polarity are varied. From solvent-explicit molecular dynamics simulations, we extract single-ion surface interaction potentials for halide and alkali ions at hydrophilic and hydrophobic surfaces. These are used within Poisson-Boltzmann theory to calculate ion density and electrostatic potential distributions at mixed polar/unpolar surfaces for varying surface charge. The resulting interfacial tension increments agree quantitatively with experimental data and capture the Hofmeister series, especially the anomaly of lithium, which is difficult to obtain using continuum theory. Phase diagrams that feature different Hofmeister series as a function of surface charge, salt concentration, and surface polarity are constructed from the long-range force between two surfaces interacting across electrolyte solutions. Large anions such as iodide have a high hydrophobic surface affinity and increase the effective charge magnitude on negatively charged unpolar surfaces. Large cations such as cesium also have a large hydrophobic surface affinity and thereby compensate an external negative charge surface charge most efficiently, which explains the well-known asymmetry between cations and anions. On the hydrophilic surface, the size-dependence of the ion surface affinity is reversed, explaining the Hofmeister series reversal when comparing hydrophobic with hydrophilic surfaces.

  3. An Experimental Proposal for Demonstration of Macroscopic Quantum Effects

    Directory of Open Access Journals (Sweden)

    Jensen R.

    2010-10-01

    Full Text Available An experiment is proposed, whose purpose is to determine whether quantum indeterminism can be observed on a truly macroscopic scale. The experiment involves using a double-slit plate or interferometer and a macroscopic mechanical switch. The objective is to determine whether or not the switch can take on an indeterminate state.

  4. An Experimental Proposal for Demonstration of Macroscopic Quantum Effects

    Directory of Open Access Journals (Sweden)

    Jensen R.

    2010-10-01

    Full Text Available An experiment is proposed, whose purpose is to determine whether quantum indeter- minism can be observed on a truly macroscopic scale. The experiment involves using a double-slit plate or interferometer and a macroscopic mechanical switch. The objective is to determine whether or not the switch can take on an indeterminate state.

  5. High-affinity DNA base analogs as supramolecular, nanoscale promoters of macroscopic adhesion.

    Science.gov (United States)

    Anderson, Cyrus A; Jones, Amanda R; Briggs, Ellen M; Novitsky, Eric J; Kuykendall, Darrell W; Sottos, Nancy R; Zimmerman, Steven C

    2013-05-15

    Adhesion phenomena are essential to many biological processes and to synthetic adhesives and manufactured coatings and composites. Supramolecular interactions are often implicated in various adhesion mechanisms. Recently, supramolecular building blocks, such as synthetic DNA base-pair mimics, have drawn attention in the context of molecular recognition, self-assembly, and supramolecular polymers. These reversible, hydrogen-bonding interactions have been studied extensively for their adhesive capabilities at the nano- and microscale, however, much less is known about their utility for practical adhesion in macroscopic systems. Herein, we report the preparation and evaluation of supramolecular coupling agents based on high-affinity, high-fidelity quadruple hydrogen-bonding units (e.g., DAN·DeUG, Kassoc = 10(8) M(-1) in chloroform). Macroscopic adhesion between polystyrene films and glass surfaces modified with 2,7-diamidonaphthyridine (DAN) and ureido-7-deazaguanine (DeUG) units was evaluated by mechanical testing. Structure-property relationships indicate that the designed supramolecular interaction at the nanoscale plays a key role in the observed macroscopic adhesive response. Experiments probing reversible adhesion or self-healing properties of bulk samples indicate that significant recovery of initial strength can be realized after failure but that the designed noncovalent interaction does not lead to healing during the process of adhesion loss.

  6. Sialic Acid-Responsive Polymeric Interface Material: From Molecular Recognition to Macroscopic Property Switching

    Science.gov (United States)

    Xiong, Yuting; Jiang, Ge; Li, Minmin; Qing, Guangyan; Li, Xiuling; Liang, Xinmiao; Sun, Taolei

    2017-01-01

    Biological systems that utilize multiple weak non-covalent interactions and hierarchical assemblies to achieve various bio-functions bring much inspiration for the design of artificial biomaterials. However, it remains a big challenge to correlate underlying biomolecule interactions with macroscopic level of materials, for example, recognizing such weak interaction, further transforming it into regulating material’s macroscopic property and contributing to some new bio-applications. Here we designed a novel smart polymer based on polyacrylamide (PAM) grafted with lactose units (PAM-g-lactose0.11), and reported carbohydrate-carbohydrate interaction (CCI)-promoted macroscopic properties switching on this smart polymer surface. Detailed investigations indicated that the binding of sialic acid molecules with the grafted lactose units via the CCIs induced conformational transformation of the polymer chains, further resulted in remarkable and reversible switching in surface topography, wettability and stiffness. With these excellent recognition and response capacities towards sialic acid, the PAM-g-lactose0.11 further facilitated good selectivity, strong anti-interference and high adsorption capacity in the capture of sialylated glycopeptides (important biomarkers for cancers). This work provides some enlightenment for the development of biointerface materials with tunable property, as well as high-performance glycopeptide enrichment materials. PMID:28084463

  7. Sialic Acid-Responsive Polymeric Interface Material: From Molecular Recognition to Macroscopic Property Switching

    Science.gov (United States)

    Xiong, Yuting; Jiang, Ge; Li, Minmin; Qing, Guangyan; Li, Xiuling; Liang, Xinmiao; Sun, Taolei

    2017-01-01

    Biological systems that utilize multiple weak non-covalent interactions and hierarchical assemblies to achieve various bio-functions bring much inspiration for the design of artificial biomaterials. However, it remains a big challenge to correlate underlying biomolecule interactions with macroscopic level of materials, for example, recognizing such weak interaction, further transforming it into regulating material’s macroscopic property and contributing to some new bio-applications. Here we designed a novel smart polymer based on polyacrylamide (PAM) grafted with lactose units (PAM-g-lactose0.11), and reported carbohydrate-carbohydrate interaction (CCI)-promoted macroscopic properties switching on this smart polymer surface. Detailed investigations indicated that the binding of sialic acid molecules with the grafted lactose units via the CCIs induced conformational transformation of the polymer chains, further resulted in remarkable and reversible switching in surface topography, wettability and stiffness. With these excellent recognition and response capacities towards sialic acid, the PAM-g-lactose0.11 further facilitated good selectivity, strong anti-interference and high adsorption capacity in the capture of sialylated glycopeptides (important biomarkers for cancers). This work provides some enlightenment for the development of biointerface materials with tunable property, as well as high-performance glycopeptide enrichment materials.

  8. Preparation of hydrophobic organic aeorgels

    Science.gov (United States)

    Baumann, Theodore F.; Satcher, Jr., Joe H.; Gash, Alexander E.

    2007-11-06

    Synthetic methods for the preparation of hydrophobic organics aerogels. One method involves the sol-gel polymerization of 1,3-dimethoxybenzene or 1,3,5-trimethoxybenzene with formaldehyde in non-aqueous solvents. Using a procedure analogous to the preparation of resorcinol-formaldehyde (RF) aerogels, this approach generates wet gels that can be dried using either supercritical solvent extraction to generate the new organic aerogels or air dried to produce an xerogel. Other methods involve the sol-gel polymerization of 1,3,5 trihydroxy benzene (phloroglucinol) or 1,3 dihydroxy benzene (resorcinol) and various aldehydes in non-aqueous solvents. These methods use a procedure analogous to the one-step base and two-step base/acid catalyzed polycondensation of phloroglucinol and formaldehyde, but the base catalyst used is triethylamine. These methods can be applied to a variety of other sol-gel precursors and solvent systems. These hydrophobic organics aerogels have numerous application potentials in the field of material absorbers and water-proof insulation.

  9. Peptide adsorption on a hydrophobic surface results from an interplay of solvation, surface, and intrapeptide forces

    OpenAIRE

    Horinek, D.; Serr, A; Geisler, M.; Pirzer, T.; Slotta, U.; Lud, S. Q.; Garrido, J. A.; Scheibel, T.; Hugel, T; Netz, R. R.

    2008-01-01

    The hydrophobic effect, i.e., the poor solvation of nonpolar parts of molecules, plays a key role in protein folding and more generally for molecular self-assembly and aggregation in aqueous media. The perturbation of the water structure accounts for many aspects of protein hydrophobicity. However, to what extent the dispersion interaction between molecular entities themselves contributes has remained unclear. This is so because in peptide folding interactions and structural changes occur on ...

  10. Design of Macroscopically Ordered Liquid Crystalline Hydrogel Columns Knitted with Nanosilver for Topical Applications.

    Science.gov (United States)

    Lali Raveendran, Reshma; Kumar Sasidharan, Nishanth; Devaki, Sudha J

    2017-04-19

    The design of liquid crystalline hydrogels knitted with silver nanoparticles in macroscopic ordering is becoming a subject of research interest due to their promising multifunctional applications in biomedical and optoelectronic applications. The present work describes the development of liquid crystalline Schiff-based hydrogel decorated with silver nanoparticles and the demonstration of its antifungal applications. Schiff base was prepared from polyglucanaldehyde and chitosan, and the former was prepared by the oxidation of amylose (polyglucopyranose) isolated from abundantly available unutilized jackfruit seed starch. Self-assembled silver columns decorated with macroscopically ordered networks were prepared in a single step of in situ condensation and a reduction/complexation process. The various noncovalent interactions among the -OH, -C═O, and -NH impart rigidity and ordering for the formation of macroscopically ordered liquid crystalline hydrogel and the Ag(I) complexation evidenced from the studies made by FT-IR spectroscopy in combination with rheology and microscopic techniques such as SEM, TEM, AFM, XRD, and PLM. The antifungal studies were screened using species of Candida by disc diffusion method. The MIC and MFC values, in vitro antifungal studies, reactive oxygen species (ROS) production, and propidium iodide (PI) uptake results suggest that the present macroscopically ordered liquid crystalline hydrogel system can be considered an excellent candidate for topical applications. All these results suggest that this design strategy can be exploited for the incorporation of biologically relevant metal nanoparticles for developing unique robust hydrogels for multifunctional applications.

  11. X-ray-generated heralded macroscopical quantum entanglement of two nuclear ensembles

    Science.gov (United States)

    Liao, Wen-Te; Keitel, Christoph H.; Pálffy, Adriana

    2016-09-01

    Heralded entanglement between macroscopical samples is an important resource for present quantum technology protocols, allowing quantum communication over large distances. In such protocols, optical photons are typically used as information and entanglement carriers between macroscopic quantum memories placed in remote locations. Here we investigate theoretically a new implementation which employs more robust x-ray quanta to generate heralded entanglement between two crystal-hosted macroscopical nuclear ensembles. Mössbauer nuclei in the two crystals interact collectively with an x-ray spontaneous parametric down conversion photon that generates heralded macroscopical entanglement with coherence times of approximately 100 ns at room temperature. The quantum phase between the entangled crystals can be conveniently manipulated by magnetic field rotations at the samples. The inherent long nuclear coherence times allow also for mechanical manipulations of the samples, for instance to check the stability of entanglement in the x-ray setup. Our results pave the way for first quantum communication protocols that use x-ray qubits.

  12. Macroscopic quasilinear theory of parallel electron firehose instability associated with solar wind electrons

    Science.gov (United States)

    Sarfraz, M.; Yoon, P. H.; Saeed, Sundas; Abbas, G.; Shah, H. A.

    2017-01-01

    A number of different microinstabilities are known to be responsible for regulating the upper bound of temperature anisotropies in solar wind protons, alpha particles, and electrons. In the present paper, quasilinear kinetic theory is employed to investigate the time variation in electron temperature anisotropies in response to the excitation of parallel electron firehose instability in homogeneous and non-collisional solar wind plasma under the condition of T∥e>T⊥e . By assuming the bi-Maxwellian form of velocity distribution functions, various velocity moments of the particle kinetic equation are taken in order to reduce the theory to macroscopic model in which the wave-particle interaction is incorporated, hence, the macroscopic quasilinear theory. The threshold condition for the parallel electron firehose instability, empirically constructed as a curve in (β∥e,T⊥e/T∥e) phase space, is implicit in the present macroscopic quasilinear calculation. Even though the present calculation excludes the oblique firehose instability, which is known to possess a higher growth rate, the basic methodology may be further extended to include such a mode. Among the findings is that the parallel electron firehose instability dynamically couples the electrons and protons, which implies that this instability may be important for overall solar wind dynamics. The present analysis shows that the macroscopic quasilinear approach may eventually be incorporated in global-kinetic models of the solar wind electrons and ions.

  13. X-ray-generated heralded macroscopical quantum entanglement of two nuclear ensembles.

    Science.gov (United States)

    Liao, Wen-Te; Keitel, Christoph H; Pálffy, Adriana

    2016-09-19

    Heralded entanglement between macroscopical samples is an important resource for present quantum technology protocols, allowing quantum communication over large distances. In such protocols, optical photons are typically used as information and entanglement carriers between macroscopic quantum memories placed in remote locations. Here we investigate theoretically a new implementation which employs more robust x-ray quanta to generate heralded entanglement between two crystal-hosted macroscopical nuclear ensembles. Mössbauer nuclei in the two crystals interact collectively with an x-ray spontaneous parametric down conversion photon that generates heralded macroscopical entanglement with coherence times of approximately 100 ns at room temperature. The quantum phase between the entangled crystals can be conveniently manipulated by magnetic field rotations at the samples. The inherent long nuclear coherence times allow also for mechanical manipulations of the samples, for instance to check the stability of entanglement in the x-ray setup. Our results pave the way for first quantum communication protocols that use x-ray qubits.

  14. The relation between a microscopic threshold-force model and macroscopic models of adhesion

    Science.gov (United States)

    Hulikal, Srivatsan; Bhattacharya, Kaushik; Lapusta, Nadia

    2017-01-01

    This paper continues our recent work on the relationship between discrete contact interactions at the microscopic scale and continuum contact interactions at the macroscopic scale (Hulikal et al., J. Mech. Phys. Solids 76, 144-161, 2015). The focus of this work is on adhesion. We show that a collection of a large number of discrete elements governed by a threshold-force based model at the microscopic scale collectively gives rise to continuum fracture mechanics at the macroscopic scale. A key step is the introduction of an efficient numerical method that enables the computation of a large number of discrete contacts. Finally, while this work focuses on scaling laws, the methodology introduced in this paper can also be used to study rough-surface adhesion.

  15. Macroscopic irreversibility and microscopic paradox: A Constructal law analysis of atoms as open systems

    Science.gov (United States)

    Lucia, Umberto

    2016-10-01

    The relation between macroscopic irreversibility and microscopic reversibility is a present unsolved problem. Constructal law is introduced to develop analytically the Einstein’s, Schrödinger’s, and Gibbs’ considerations on the interaction between particles and thermal radiation (photons). The result leads to consider the atoms and molecules as open systems in continuous interaction with flows of photons from their surroundings. The consequent result is that, in any atomic transition, the energy related to the microscopic irreversibility is negligible, while when a great number of atoms (of the order of Avogadro’s number) is considered, this energy related to irreversibility becomes so large that its order of magnitude must be taken into account. Consequently, macroscopic irreversibility results related to microscopic irreversibility by flows of photons and amount of atoms involved in the processes.

  16. How fast is protein hydrophobic collapse?

    OpenAIRE

    Sadqi, Mourad; Lapidus, Lisa J.; Muñoz, Victor

    2003-01-01

    One of the most recurring questions in protein folding refers to the interplay between formation of secondary structure and hydrophobic collapse. In contrast with secondary structure, it is hard to isolate hydrophobic collapse from other folding events. We have directly measured the dynamics of protein hydrophobic collapse in the absence of competing processes. Collapse was triggered with laser-induced temperature jumps in the acid-denatured form of a simple protein and monitored by fluoresce...

  17. Nanocomposites fabrication by self-assembly method to modify macroscopic properties

    Science.gov (United States)

    Lopez-Barbosa, N.; Osma, J. F.

    2017-01-01

    Polymeric nanocomposites have been in the scope of scientists for the last decade due to their multiple applications and simple synthesis. Self-assembly fabrication can be performed through different methods such as layer-by-layer or the controlled growth of nanostructures on a surface. These methods allow fast elaboration of nanocomposites that can be readily integrated in sensors or films. The current work exposes the self-assembly of nanocomposites for the modification of material’s macroscopic properties such as hydrophobicity and temperature’s resistance on textiles. Hydrophobicity properties of cotton textiles were modified by the application of functionalized silica nanoparticles on their surfaces. Thermal resistance of cotton textiles was achieved by incorporating TiO2 nanoparticles into the matrix, increasing the scope of their applications. Functionalization was attained by chloro-trimethyl-silane (CTS) and γ-amino(propyl) triethoxy silane (APTES) in organic and inorganic solvents. Wetting phenomena characteristics appeared to highly depend on the synthesis parameters.

  18. The physical origin of hydrophobic effects

    Science.gov (United States)

    Sun, Qiang

    2017-03-01

    From the structural studies on water and air/water interface, hydration free energy is derived, and used to investigate the origin of hydrophobic effects. As a solute is dissolved into water, hydration free energy increases, and is divided into initial and hydrophobic solvation processes. In the initial process, hydration free energy is dominated by hydrogen bonding in interfacial water (topmost water layer at solute/water interface). For hydrophobic process, hydration free energy is related to the hydrogen bonding in bulk and interfacial water. Therefore, hydrophobic effects originate from the structural competition between hydrogen bonding in bulk water and that in interfacial water.

  19. Method for making nanoporous hydrophobic coatings

    Science.gov (United States)

    Fan, Hongyou; Sun, Zaicheng

    2013-04-23

    A simple coating method is used to form nanoporous hydrophobic films that can be used as optical coatings. The method uses evaporation-induced self-assembly of materials. The coating method starts with a homogeneous solution comprising a hydrophobic polymer and a surfactant polymer in a selective solvent. The solution is coated onto a substrate. The surfactant polymer forms micelles with the hydrophobic polymer residing in the particle core when the coating is dried. The surfactant polymer can be dissolved and selectively removed from the separated phases by washing with a polar solvent to form the nanoporous hydrophobic film.

  20. Study of Hydrophobic and Ionizable Hydrophilic Copolymers at Polymer/Solid and Polymer/Liquid Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Perahia, Dvora

    2011-11-01

    Joint experimental-computational efforts were set to characterize the interfacial effects on the structure and dynamics of polymers consisting of highly rigid hydrophilic-ionizable and hydrophobic sub-units within one polymeric chain casted into thin films of several molecular dimensions. Focusing on the ultra thin film region we separate out the interfacial effects from bulk characteristics. Specifically, the study sought to: identify the parameters that control the formation of a stable polymer-solid interface. The study consists of two components, experimental investigations and computational efforts. The experimental component was designed to derive empirical trends that can be used to correlate the set of coupled polymer molecular parameters with the interfacial characteristics of these polymers, and their response to presence of solvents. The computational study was designed to provide molecular insight into the ensemble averages provided by the experimental efforts on multiple length scales from molecular dimensions, to the nanometer lengths to a macroscopic understanding of solvent interactions with structured polymers. With the ultimate goal of correlating molecular parameters to structure, dynamics and properties of ionic polymers, the first stage of the research began with the study of two systems, one which allowed tailoring the flexibility of the backbone without the presence of ionic groups, but with a potential to sulfonate groups at a later stage, and a polymer whose backbone is rigid and the density of the ionic group can be varied. The combined experimental and computational studies significantly extended the understanding of polymers at interfaces from model systems to polydispersed copolymers with blocks of varying nature and complexity. This new insight directly affects the design of polymers for sustainable energy applications from batteries and fuel cells to solar energy.

  1. Thermophoresis of dissolved molecules and polymers: Consideration of the temperature-induced macroscopic pressure gradient.

    Science.gov (United States)

    Semenov, Semen; Schimpf, Martin

    2004-01-01

    The movement of molecules and homopolymer chains dissolved in a nonelectrolyte solvent in response to a temperature gradient is considered a consequence of temperature-induced pressure gradients in the solvent layer surrounding the solute molecules. Local pressure gradients are produced by nonuniform London-van der Waals interactions, established by gradients in the concentration (density) of solvent molecules. The density gradient is produced by variations in solvent thermal expansion within the nonuniform temperature field. The resulting expression for the velocity of the solute contains the Hamaker constants for solute-solvent and solute-solute interactions, the radius of the solute molecule, and the viscosity and cubic coefficient of thermal expansion of the solvent. In this paper we consider an additional force that arises from directional asymmetry in the interaction between solvent molecules. In a closed cell, the resulting macroscopic pressure gradient gives rise to a volume force that affects the motion of dissolved solutes. An expression for this macroscopic pressure gradient is derived and the resulting force is incorporated into the expression for the solute velocity. The expression is used to calculate thermodiffusion coefficients for polystyrene in several organic solvents. When these values are compared to those measured in the laboratory, the consistency is better than that found in previous reports, which did not consider the macroscopic pressure gradient that arises in a closed thermodiffusion cell. The model also allows for the movement of solute in either direction, depending on the relative values of the solvent and solute Hamaker constants.

  2. Experimental demonstration of macroscopic quantum coherence in Gaussian states

    DEFF Research Database (Denmark)

    Marquardt, C.; Andersen, Ulrik Lund; Leuchs, G.

    2007-01-01

    We witness experimentally the presence of macroscopic coherence in Gaussian quantum states using a recently proposed criterion [E. G. Cavalcanti and M. D. Reid, Phys. Rev. Lett. 97 170405 (2006)]. The macroscopic coherence stems from interference between macroscopically distinct states in phase...... space, and we prove experimentally that a coherent state contains these features with a distance in phase space of 0.51 +/- 0.02 shot noise units. This is surprising because coherent states are generally considered being at the border between classical and quantum states, not yet displaying any...

  3. Synthesis and Solution Properties of Hydrophobic Associating Polymers

    Institute of Scientific and Technical Information of China (English)

    任鲲; 姜桂元; 徐春明; 林梅钦

    2005-01-01

    Acrylamide/2-acrylamido alkane sulfonic acid hydrophobic associating copolymers were synthesized by micellar copolymerization. Effects of hydrophobe content, polymer concentration, salinity and surfactant on rheological behavior of copolymers were investigated and the conformation of polymers in solution was studied by means of environmental scanning electronic microscopy and dynamic light scattering. The experimental results showed that in the dilute regime the hydrophobic parts could interact intramolecularly, while in the regime where the polymer concentration was higher than the critical association concentration, intermolecular hydrophobic association became predominant. Within the limit of the solubility, the critical association concentration of the polymer decreased with the increase of the salinity. The experimental results of the solution conformation indicated the presence of the three-dimensional network structure in deionized water and the size of the mesh in the network varied with the polymer concentration. In NaG1 solution, above the critical association concentration, an increase in polymer concentration enhanced the intermolecular association and also enlarged the hydrodynamic radius. It would result in the imorovement of the thickening power of polvmers.

  4. Nanocarriers from GRAS Zein Proteins to Encapsulate Hydrophobic Actives.

    Science.gov (United States)

    Weissmueller, Nikolas T; Lu, Hoang D; Hurley, Amanda; Prud'homme, Robert K

    2016-11-14

    One factor limiting the expansion of nanomedicines has been the high cost of the materials and processes required for their production. We present a continuous, scalable, low cost nanoencapsulation process, Flash Nanoprecipitation (FNP) that enables the production of nanocarriers (NCs) with a narrow size distribution using zein corn proteins. Zein is a low cost, GRAS protein (having the FDA status of "Generally Regarded as Safe") currently used in food applications, which acts as an effective encapsulant for hydrophobic compounds using FNP. The four-stream FNP configuration allows the encapsulation of very hydrophobic compounds in a way that is not possible with previous precipitation processes. We present the encapsulation of several model active compounds with as high as 45 wt % drug loading with respect to zein concentration into ∼100 nm nanocarriers. Three examples are presented: (1) the pro-drug antioxidant, vitamin E-acetate, (2) an anticholera quorum-sensing modulator CAI-1 ((S)-3-hydroxytridecan-4-one; CAI-1 that reduces Vibrio cholerae virulence by modulating cellular communication), and (3) hydrophobic fluorescent dyes with a range of hydrophobicities. The specific interaction between zein and the milk protein, sodium caseinate, provides stabilization of the NCs in PBS, LB medium, and in pH 2 solutions. The stability and size changes in the three media provide information on the mechanism of assembly of the zein/active/casein NC.

  5. Towards a macroscopic modeling of the complexity in traffic flow.

    Science.gov (United States)

    Rosswog, Stephan; Wagner, Peter

    2002-03-01

    Based on the assumption of a safe velocity U(e)(rho) depending on the vehicle density rho, a macroscopic model for traffic flow is presented that extends the model of the Kühne-Kerner-Konhäuser by an interaction term containing the second derivative of U(e)(rho). We explore two qualitatively different forms of U(e): a conventional Fermi-type function and, motivated by recent experimental findings, a function that exhibits a plateau at intermediate densities, i.e., in this density regime the exact distance to the car ahead is only of minor importance. To solve the fluid-like equations a Lagrangian particle scheme is developed. The suggested model shows a much richer dynamical behavior than the usual fluid-like models. A large variety of encountered effects is known from traffic observations, many of which are usually assigned to the elusive state of "synchronized flow." Furthermore, the model displays alternating regimes of stability and instability at intermediate densities. It can explain data scatter in the fundamental diagram and complicated jam patterns. Within this model, a consistent interpretation of the emergence of very different traffic phenomena is offered: they are determined by the velocity relaxation time, i.e., the time needed to relax towards U(e)(rho). This relaxation time is a measure of the average acceleration capability and can be attributed to the composition (e.g., the percentage of trucks) of the traffic flow.

  6. Semiconductor spintronics in a participating phonon medium: Macroscopic equations

    Directory of Open Access Journals (Sweden)

    A. Rossani

    2013-09-01

    Full Text Available In the last two decades considerable interest has arisen on the spin related phenomena in semiconductor devices. In semiconductor materials two essential mechanisms act on the spin dynamics: the spin-orbit coupling and the spin-flip interactions. Here the novelty is that we adopt the asymptotic approach developed in previous papers of mine [A. Rossani, Physica A 305, 323 (2002; A. Rossani, G. Spiga, and A. Domaingo, J. Phys. A 36, 11955 (2003; A. Rossani and G. Spiga, J. Math. Phys. 47, 013301 (2006; A. Rossani and A. M. Scarfone, Physica B 334, 292 (2003; A. Rossani, J. Phys. A 43, 165002 (2010]. The aim of this paper is to derive macroscopic equations starting from a kinetic approach. Moreover an equation for the evolution of the spin density is added, which account for a general dispersion relation. The treatment of spin-flip processes, derived from first principles, is new and leads to an explicit expression of the relaxation time as a function of the temperature.

  7. On the Boundary Condition for Water at a Hydrophobic, Dense Surface

    Science.gov (United States)

    Walther, J. H.; Jaffe, R. L.; Werder, T.; Halicioglu, T.; Koumoutsakos, P.

    2002-01-01

    We study the no-slip boundary conditions for water at a hydrophobic (graphite) surface using non-equilibrium molecular-dynamics simulations. For the planar Couette flow, we find a slip length of 64 nm at 1 bar and 300 K, decreasing with increasing system pressure to a value of 31 nm at 1000 bar. Changing the properties of the interface to from hydrophobic to strongly hydrophilic reduces the slip to 14 nm. Finally, we study the flow of water past an array of carbon nanotubes mounted in an inline configuration with a spacing of 16.4 x 16.4 nm. For tube diameters of 1.25 and 2.50 nm we find drag coefficients in good agreement with the macroscopic, Navier-Stokes values. For carbon nanotubes, the no-slip condition is valid to within the definition of the position of the interface.

  8. Molecular docking using the molecular lipophilicity potential as hydrophobic descriptor: impact on GOLD docking performance.

    Science.gov (United States)

    Nurisso, Alessandra; Bravo, Juan; Carrupt, Pierre-Alain; Daina, Antoine

    2012-05-25

    GOLD is a molecular docking software widely used in drug design. In the initial steps of docking, it creates a list of hydrophobic fitting points inside protein cavities that steer the positioning of ligand hydrophobic moieties. These points are generated based on the Lennard-Jones potential between a carbon probe and each atom of the residues delimitating the binding site. To thoroughly describe hydrophobic regions in protein pockets and properly guide ligand hydrophobic moieties toward favorable areas, an in-house tool, the MLP filter, was developed and herein applied. This strategy only retains GOLD hydrophobic fitting points that match the rigorous definition of hydrophobicity given by the molecular lipophilicity potential (MLP), a molecular interaction field that relies on an atomic fragmental system based on 1-octanol/water experimental partition coefficients (log P(oct)). MLP computations in the binding sites of crystallographic protein structures revealed that a significant number of points considered hydrophobic by GOLD were actually polar according to the MLP definition of hydrophobicity. To examine the impact of this new tool, ligand-protein complexes from the Astex Diverse Set and the PDB bind core database were redocked with and without the use of the MLP filter. Reliable docking results were obtained by using the MLP filter that increased the quality of docking in nonpolar cavities and outperformed the standard GOLD docking approach.

  9. Hydrophobicity of peritoneal tissues in the rat

    NARCIS (Netherlands)

    Gomez-Suarez, C; Bruinsma, GM; Rakhorst, G; van der Mei, HC; Busscher, HJ

    2002-01-01

    In this study, an inventory of the hydrophobicity of peritoneal tissues in the living rat was made. Peritoneal tissues were divided into mesentery (i.e., omentum) and parietal and visceral peritoneum and their hydrophobicity was determined by the sessile drop method. All peritoneal tissues were hydr

  10. Hydrogels with Micellar Hydrophobic (Nano)Domains

    OpenAIRE

    Pekař, Miloslav

    2015-01-01

    Hydrogels containing hydrophobic domains or nanodomains, especially of the micellar type, are reviewed. Examples of the reasons for introducing hydrophobic domains into hydrophilic gels are given; typology of these materials is introduced. Synthesis routes are exemplified and properties of a variety of such hydrogels in relation with their intended applications are described. Future research needs are identified briefly.

  11. Hydrogels with micellar hydrophobic (nano)domains

    OpenAIRE

    Miloslav ePekař

    2015-01-01

    Hydrogels containing hydrophobic domains or nanodomains, especially of the micellar type, are reviewed. Examples of the reasons for introducing hydrophobic domains into hydrophilic gels are given; typology of these materials is introduced. Synthesis routes are exemplified and properties of a variety of such hydrogels in relation with their intended applications are described. Future research needs are identified briefly.

  12. Hydrogels with micellar hydrophobic (nano)domains

    Science.gov (United States)

    Pekař, Miloslav

    2014-12-01

    Hydrogels containing hydrophobic domains or nanodomains, especially of the micellar type, are reviewed. Examples of the reasons for introducing hydrophobic domains into hydrophilic gels are given; typology of these materials is introduced. Synthesis routes are exemplified and properties of a variety of such hydrogels in relation with their intended applications are described. Future research needs are identified briefly.

  13. Durability of hydrophobic treatment of concrete

    NARCIS (Netherlands)

    Vries, J. de; Polder, R.B.; Borsje, H.

    1998-01-01

    The subject of this study was the performance of hydrophobic treatment to protect concrete against chloride penetration from de-icing salts. Hydrophobic treatment makes a concrete surface absorb less water and less chloride. Several types of tests were carried out to study the performance of hydroph

  14. Durability of hydrophobic treatment of concrete

    NARCIS (Netherlands)

    Vries, J. de; Polder, R.B.; Borsje, H.

    1998-01-01

    The subject of this study was the performance of hydrophobic treatment to protect concrete against chloride penetration from de-icing salts. Hydrophobic treatment makes a concrete surface absorb less water and less chloride. Test methods and requirements for commercial products were established. In

  15. Composite, nanostructured, super-hydrophobic material

    Science.gov (United States)

    D'Urso, Brian R.; Simpson, John T.

    2007-08-21

    A hydrophobic disordered composite material having a protrusive surface feature includes a recessive phase and a protrusive phase, the recessive phase having a higher susceptibility to a preselected etchant than the protrusive phase, the composite material having an etched surface wherein the protrusive phase protrudes from the surface to form a protrusive surface feature, the protrusive feature being hydrophobic.

  16. Accumulation of small protein molecules in a macroscopic complex coacervate

    NARCIS (Netherlands)

    Lindhoud, S.; Claessens, M.M.A.E.

    2016-01-01

    To obtain insight into the accumulation of proteins into macroscopic complex coacervate phases, the lysozyme concentration in complex coacervates containing the cationic polyelectrolyte poly-(N,N dimethylaminoethyl methacrylate) and the anionic polyelectrolyte polyacrylic acid was investigated as a

  17. Macroscopic cumulative fatigue damage of material under nonsymmetrical cycle

    Institute of Scientific and Technical Information of China (English)

    盖秉政

    2002-01-01

    Hashin's macroscopic theory of fatigue damage is further discussed and a new method has been proposed for prediction of cumulative fatigue damage of material and its lifetime under nonsymmetrical cyclic loading.

  18. Quantum fluctuations, gauge freedom and mesoscopic/macroscopic stability

    Energy Technology Data Exchange (ETDEWEB)

    Del Giudice, E [Istituto Nazionale di Fisica Nucleare, Via Celoria 16, I-20133 Milan (Italy); Vitiello, G [Dipartimento di Matematica e Informatica, Universita di Salerno and Istituto Nazionale di Fisica Nucleare, Gruppo Collegato di Salerno, 84100 Salerno (Italy)

    2007-11-15

    We study how the mesoscopic/macroscopic stability of coherent extended domains is generated out of the phase locking between gauge field and matter field. The role of the radiative gauge field in sustaining the coherent regime is discussed.

  19. New Tests of Macroscopic Local Realism using Continuous Variable Measurements

    CERN Document Server

    Reid, M D

    2001-01-01

    We show that quantum mechanics predicts an Einstein-Podolsky-Rosen paradox (EPR), and also a contradiction with local hidden variable theories, for photon number measurements which have limited resolving power, to the point of imposing an uncertainty in the photon number result which is macroscopic in absolute terms. We show how this can be interpreted as a failure of a new, very strong premise, called macroscopic local realism. We link this premise to the Schrodinger-cat paradox. Our proposed experiments ensure all fields incident on each measurement apparatus are macroscopic. We show that an alternative measurement scheme corresponds to balanced homodyne detection of quadrature phase amplitudes. The implication is that where either EPR correlations or failure of local realism is predicted for continuous variable (quadrature phase amplitude) measurements, one can perform a modified experiment which would lead to conclusions about the much stronger premise of macroscopic local realism.

  20. HYDROPHOBICITY OF CONTAMINATED SILICONE RUBBER SURFACES

    Institute of Scientific and Technical Information of China (English)

    Zhi-min Zheng; Cai-hong Xu; Jian Jiang; Chang-yu Ren; Wei Gao; Ze-min Xie

    2002-01-01

    Silicone rubber (SIR) shows superior performance when used outdoors, but its surface can be transformed frominherently hydrophobic to hydrophilic by the adsorption of contaminants. Al(OH)3, Al2O3, quartz powder and active carbonwere selected as authentic contaminants. Hydrophobicity of the surface was determined using contact angle measurement.The results indicate that the adsorbability of the contaminants can strongly affect the hydrophobicity of contaminated SIRsurface. The increasing rate of contact angle of specimens contaminated by Al(OH)3 was much faster than that by Al2O3 andquartz due to the adsorption of migrated low molecular weight (LMW) polydimethylsiloxanes. Specimens contaminated byactive carbon could achieve surface hydrophobicity within 15 min because active carbon has high adsorbability. Surfaces ofcontaminated ultrapure SIR, polytetrafluoroethylene (PTFE) and glass remain hydrophilic because they contain no mobileLMW components. The addition of oligomeric polydimethylsiloxanes has little effect on the hydrophobicity of contaminantscovered on SIR surface.

  1. Effect of surface energy of solid surfaces on the micro- and macroscopic properties of adsorbed BSA and lysozyme.

    Science.gov (United States)

    Sharma, Indu; Pattanayek, Sudip K

    2017-07-01

    The surface energy, a macroscopic property, depends on the chemical functionality and micro- and macroscopic roughness of the surface. The adsorption of two widely used proteins bovine serum albumin (BSA) and lysozyme on surfaces of four different chemical functionalities were done to find out the interrelation between macroscopic and microscopic properties. We have observed the secondary structure of protein after its adsorption. In addition, we observed the variation of surface energy of proteins due to variation in adsorption time, change in protein concentration and effect of a mixture of proteins. Surfaces of three different chemical functionalities namely, amine, hydroxyl and octyl were obtained through self-assembled monolayer on silica surfaces and were tested for responses towards adsorption of lysozyme and BSA. The adsorbed lysozyme has higher surface energy than the adsorbed BSA on amine and octyl surfaces. On hydroxyl functional surface, the surface energy due to the adsorbed lysozyme or BSA increases slowly with time. The surface energy of the adsorbed protein increases gradually with increasing protein concentration on hydrophobic surfaces. On hydrophilic surfaces, with increasing BSA concentration in bulk solution, the surface energy of the adsorbed protein on GPTMS and amine surfaces is maximum at 1μM concentration. During the adsorption from a mixture of BSA and lysozyme on octyl surface, first lysozyme adsorbs and subsequent BSA adsorption leads to a high surface energy. Copyright © 2016. Published by Elsevier B.V.

  2. Macroscopic description of complex adaptive networks co-evolving with dynamic node states

    CERN Document Server

    Wiedermann, Marc; Heitzig, Jobst; Lucht, Wolfgang; Kurths, Jürgen

    2015-01-01

    In many real-world complex systems, the time-evolution of the network's structure and the dynamic state of its nodes are closely entangled. Here, we study opinion formation and imitation on an adaptive complex network which is dependent on the individual dynamic state of each node and vice versa to model the co-evolution of renewable resources with the dynamics of harvesting agents on a social network. The adaptive voter model is coupled to a set of identical logistic growth models and we show that in such systems, the rate of interactions between nodes as well as the adaptive rewiring probability play a crucial role for the sustainability of the system's equilibrium state. We derive a macroscopic description of the system which provides a general framework to model and quantify the influence of single node dynamics on the macroscopic state of the network and is applicable to many fields of study, such as epidemic spreading or social modeling.

  3. Cavity-Assisted Generation of Sustainable Macroscopic Entanglement of Ultracold Gases

    Directory of Open Access Journals (Sweden)

    Chaitanya Joshi

    2015-08-01

    Full Text Available Prospects for reaching persistent entanglement between two spatially-separated atomic Bose–Einstein condensates are outlined. The system setup comprises two condensates loaded in an optical lattice, which, in return, is confined within a high-Q optical resonator. The system is driven by an external laser that illuminates the atoms, such that photons can scatter into the cavity. In the superradiant phase, a cavity field is established, and we show that the emerging cavity-mediated interactions between the two condensates is capable of entangling them despite photon losses. This macroscopic atomic entanglement is sustained throughout the time-evolution apart from occasions of sudden deaths/births. Using an auxiliary photon mode and coupling it to a collective quadrature of the two condensates, we demonstrate that the auxiliary mode’s squeezing is proportional to the atomic entanglement, and as such, it can serve as a probe field of the macroscopic entanglement.

  4. Investigating macroscopic quantum superpositions and the quantum-to-classical transition by optical parametric amplification

    CERN Document Server

    De Martini, Francesco

    2012-01-01

    The present work reports on an extended research endeavor focused on the theoretical and experimental realization of a macroscopic quantum superposition (MQS) made up with photons. As it is well known, this intriguing, fundamental quantum condition is at the core of a famous argument conceived by Erwin Schroedinger, back in 1935. The main experimental challenge to the actual realization of this object resides generally on the unavoidable and uncontrolled interactions with the environment, i.e. the decoherence leading to the cancellation of any evidence of the quantum features associated with the macroscopic system. The present scheme is based on a nonlinear process, the "quantum injected optical parametric amplification", that maps by a linearized cloning process the quantum coherence of a single - particle state, i.e. a Micro - qubit, into a Macro - qubit, consisting in a large number M of photons in quantum superposition. Since the adopted scheme was found resilient to decoherence, the MQS\\ demonstration wa...

  5. Solution properties of hydrophobically modified

    Directory of Open Access Journals (Sweden)

    A.M. Al-Sabagh

    2016-12-01

    Full Text Available We tested nine hydrophobically modified polyacrylamides with molecular weights situated between 1.58 and 0.89 × 106 g/mol for enhanced oil recovery applications. Their solution properties were investigated in the distilled water, brine solution, formation water and sea water. Their critical association concentrations were determined from the relationship between their concentrations and the corresponding apparent viscosities (ηapp at 30 °C at shear rate 6 s−1. They were between 0.4 and 0.5 g/dl. The brine solutions of 0.5 g/dl of HM-PAMs were investigated at different conditions regarding their apparent viscosities. Such conditions were mono and divalent cations, temperature ranging from 30 to 90 °C, the shear rate ranging from 6 to 30 s−1 and the aging time for 45 days. The surface and interfacial tensions for the HM-PAMs were measured for concentration range from 0.01 to 1 g/dl brine solutions at 30 °C and their emulsification efficiencies were investigated for 7 days. The discrepancy in the properties and efficiencies of the tested copolymers was discussed in the light of their chemical structure.

  6. Simultaneous Interaction of Hydrophilic and Hydrophobic Solvents with Ethylamino Neurotransmitter Radical Cations: Infrared Spectra of Tryptamine(+)-(H2O)m-(N2)n Clusters (m,n ≤ 3).

    Science.gov (United States)

    Schütz, Markus; Sakota, Kenji; Moritz, Raphael; Schmies, Matthias; Ikeda, Takamasa; Sekiya, Hiroshi; Dopfer, Otto

    2015-10-01

    Solvation of biomolecules by a hydrophilic and hydrophobic environment strongly affects their structure and function. Here, the structural, vibrational, and energetic properties of size-selected clusters of the microhydrated tryptamine cation with N2 ligands, TRA(+)-(H2O)m-(N2)n (m,n ≤ 3), are characterized by infrared photodissociation spectroscopy in the 2800-3800 cm(-1) range and dispersion-corrected density functional theory calculations at the ωB97X-D/cc-pVTZ level to investigate the simultaneous solvation of this prototypical neurotransmitter by dipolar water and quadrupolar N2 ligands. In the global minimum structure of TRA(+)-H2O generated by electron ionization, H2O is strongly hydrogen-bonded (H-bonded) as proton acceptor to the acidic indolic NH group. In the TRA(+)-H2O-(N2)n clusters, the weakly bonded N2 ligands do not affect the H-bonding motif of TRA(+)-H2O and are preferentially H-bonded to the OH groups of the H2O ligand, whereas stacking to the aromatic π electron system of the pyrrole ring of TRA(+) is less favorable. The natural bond orbital analysis reveals that the H-bond between the N2 ligand and the OH group of H2O cooperatively strengthens the adjacent H-bond between the indolic NH group of TRA(+) and H2O, while π stacking is slightly noncooperative. In the larger TRA(+)-(H2O)m clusters, the H2O ligands form a H-bonded solvent network attached to the indolic NH proton, again stabilized by strong cooperative effects arising from the nearby positive charge. Comparison with the corresponding neutral TRA-(H2O)m clusters illustrates the strong impact of the excess positive charge on the structure of the microhydration network.

  7. A simple atomic-level hydrophobicity scale reveals protein interfacial structure.

    Science.gov (United States)

    Kapcha, Lauren H; Rossky, Peter J

    2014-01-23

    Many amino acid residue hydrophobicity scales have been created in an effort to better understand and rapidly characterize water-protein interactions based only on protein structure and sequence. There is surprisingly low consistency in the ranking of residue hydrophobicity between scales, and their ability to provide insightful characterization varies substantially across subject proteins. All current scales characterize hydrophobicity based on entire amino acid residue units. We introduce a simple binary but atomic-level hydrophobicity scale that allows for the classification of polar and non-polar moieties within single residues, including backbone atoms. This simple scale is first shown to capture the anticipated hydrophobic character for those whole residues that align in classification among most scales. Examination of a set of protein binding interfaces establishes good agreement between residue-based and atomic-level descriptions of hydrophobicity for five residues, while the remaining residues produce discrepancies. We then show that the atomistic scale properly classifies the hydrophobicity of functionally important regions where residue-based scales fail. To illustrate the utility of the new approach, we show that the atomic-level scale rationalizes the hydration of two hydrophobic pockets and the presence of a void in a third pocket within a single protein and that it appropriately classifies all of the functionally important hydrophilic sites within two otherwise hydrophobic pores. We suggest that an atomic level of detail is, in general, necessary for the reliable depiction of hydrophobicity for all protein surfaces. The present formulation can be implemented simply in a manner no more complex than current residue-based approaches.

  8. Novel hydrophobically associative polyacrylamide with tunable viscosity

    Institute of Scientific and Technical Information of China (English)

    Xu Feng Zhang; Wen Hui Wu

    2009-01-01

    Hydrophobically associative polyacrylamide (HAPAM) were prepared in aqueous solution by radical copolymerization of novel cationic surface-active monomer, dimethylhexadecyl(3-acrylamidopropyl)ammonium bromide (DMHAB), with acrylarnide (AM) in the presence of DMHAB/CTAB mixed micelles. The length of hydrophobic microblock (N_H) in HAPAM is controlled by the molar fraction of DMHAB in mixed micelles, which can be mediated by the ratio of CTAB to DMHAB. The results of steady-state fluorescence probe and viscometry experiments showed the ability of HAPAM association was determined by the length of the hydrophobic microblock. HAPAM with tunable association ability are promising materials for thickening agent.

  9. Super-hydrophobic fluorine containing aerogels

    Science.gov (United States)

    Coronado, Paul R.; Poco, John F.; Hrubesh, Lawrence W.

    2007-05-01

    An aerogel material with surfaces containing fluorine atoms which exhibits exceptional hydrophobicity, or the ability to repel liquid water. Hydrophobic aerogels are efficient absorbers of solvents from water. Solvents miscible with water are separated from it because the solvents are more volatile than water and they enter the porous aerogel as a vapor across the liquid water/solid interface. Solvents that are immisicble with water are separated from it by selectively wetting the aerogel. The hydrophobic property is achieved by formulating the aerogel using fluorine containing molecules either directly by addition in the sol-gel process, or by treating a standard dried aerogel using the vapor of fluorine containing molecules.

  10. Molecular explanation for why talc surfaces can be both hydrophilic and hydrophobic

    CERN Document Server

    Rotenberg, Benjamin; Chandler, David

    2011-01-01

    While individual water molecules adsorb strongly on a talc surface (hydrophilic behavior), a droplet of water beads up on the same surface (hydrophobic behavior). To rationalize this dichotomy, we investigate the influence of the microscopic structure of the surface and the strength of adhesive (surface-water) interactions on surface hydrophobicity. We show that at low relative humidity, the competition between adhesion and the favorable entropy of being in the vapor phase determines the surface coverage. However, at saturation, it is the competition between adhesion and cohesion (water-water interactions) that determines surface hydrophobicity. The adhesive interactions in talc are strong enough to overcome the unfavorable entropy, and water adsorbs strongly on talc surfaces. However, they are too weak to overcome the cohesive interactions, and water thus beads up on talc surfaces. Surprisingly, even (talc-like) surfaces that are highly adhesive, do not fully wet at saturation. Instead, a water droplet forms...

  11. Electrostatic Binding and Hydrophobic Collapse of Peptide-Nucleic Acid Aggregates Quantified Using Force Spectroscopy

    CERN Document Server

    Camunas-Soler, Joan; Bizarro, Cristiano V; de Loreno, Sara; Fuentes-Perez, Maria Eugenia; Ramsch, Roland; Vilchez, Susana; Solans, Conxita; Moreno-Herrero, Fernando; Albericio, Fernando; Eritja, Ramon; Giralt, Ernest; Dev, Sukhendu B; Ritort, Felix

    2014-01-01

    Knowledge of the mechanisms of interaction between self-aggregating peptides and nucleic acids or other polyanions is key to the understanding of many aggregation processes underlying several human diseases (e.g. Alzheimer's and Parkinson's diseases). Determining the affinity and kinetic steps of such interactions is challenging due to the competition between hydrophobic self-aggregating forces and electrostatic binding forces. Kahalalide F (KF) is an anticancer hydrophobic peptide which contains a single positive charge that confers strong aggregative properties with polyanions. This makes KF an ideal model to elucidate the mechanisms by which self-aggregation competes with binding to a strongly charged polyelectrolyte such as DNA. We use optical tweezers to apply mechanical forces to single DNA molecules and show that KF and DNA interact in a two-step kinetic process promoted by the electrostatic binding of DNA to the aggregate surface followed by the stabilization of the complex due to hydrophobic interact...

  12. Unruh effect and macroscopic quantum interference

    CERN Document Server

    Steane, Andrew

    2015-01-01

    We investigate the influence of Unruh radiation on matter-wave interferometry experiments using neutral objects modeled as dielectric spheres. The Unruh effect leads to a loss of coherence through momentum diffusion. This is a fundamental source of decoherence that affects all objects having electromagnetic interactions. However, the effect is not large enough to prevent the observation of interference for objects of any size, even when the path separation is larger than the size of the object. When the acceleration in the interferometer arms is large, inertial tidal forces will disrupt the material integrity of the interfering objects before the Unruh decoherence of the centre of mass motion is sufficient to prevent observable interference.

  13. Electro-hydrodynamics near Hydrophobic Surfaces

    CERN Document Server

    Maduar, S R; Lobaskin, V; Vinogradova, O I

    2014-01-01

    We show that the dynamics of the electrostatic diffuse layer at the slippery hydrophobic surface depends strongly on the mobility of surface charges. For a hydrophobic surface with immobile charges the fluid transport is considerably amplified by the existence of a hydrodynamic slippage. In contrast, near the hydrophobic surface with mobile adsorbed charges it is also controlled by an additional electric force, which increases the shear stress at the slipping interface. To account for this we formulate electro-hydrodynamic boundary conditions at the slipping interface, which are applied to quantify electro-osmotic flows. Our theoretical predictions are fully supported by dissipative particle dynamics simulations with explicit charges. These results lead to a new general concept of zeta-potential of hydrophobic surfaces.

  14. Surface analysis of selected hydrophobic materials

    Science.gov (United States)

    Wisniewska, Sylwia Katarzyna

    This dissertation contains a series of studies on hydrophobic surfaces by various surface sensitive techniques such as contact angle measurements, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and atomic force microscopy (AFM). Hydrophobic surfaces have been classified as mineral surfaces, organic synthetic surfaces, or natural biological surfaces. As a model hydrophobic mineral surface, elemental sulfur has been selected. The sulfur surface has been characterized for selected allotropic forms of sulfur such as rhombic, monoclinic, plastic, and cyclohexasulfur. Additionally, dextrin adsorption at the sulfur surface was measured. The structure of a dextrin molecule showing hydrophobic sites has been presented to support the proposed hydrophobic bonding nature of dextrin adsorption at the sulfur surface. As a model organic hydrophobic surface, primary fatty amines such as dodecylamine, hexadecylamine, and octadecylamine were chosen. An increase of hydrophobicity, significant changes of infrared bands, and surface topographical changes with time were observed for each amine. Based on the results it was concluded that hydrocarbon chain rearrangement associated with recrystallization took place at the surface during contact with air. A barley straw surface was selected as a model of biological hydrophobic surfaces. The differences in the contact angles for various straw surfaces were explained by the presence of a wax layer. SEM images confirmed the heterogeneity and complexity of the wax crystal structure. AFM measurements provided additional structural details including a measure of surface roughness. Additionally, straw degradation as a result of conditioning in an aqueous environment was studied. Significant contact angle changes were observed as soon as one day after conditioning. FTIR studies showed a gradual wax layer removal due to straw surface decomposition. SEM and AFM images revealed topographical changes and biological

  15. Extended Macroscopic Study of Dilute Gas Flow within a Microcavity

    Directory of Open Access Journals (Sweden)

    Mohamed Hssikou

    2016-01-01

    Full Text Available The behaviour of monatomic and dilute gas is studied in the slip and early transition regimes using the extended macroscopic theory. The gas is confined within a two-dimensional microcavity where the longitudinal sides are in the opposite motion with constant velocity ±Uw. The microcavity walls are kept at the uniform and reference temperature T0. Thus, the gas flow is transported only by the shear stress induced by the motion of upper and lower walls. From the macroscopic point of view, the regularized 13-moment equations of Grad, R13, are solved numerically. The macroscopic gas proprieties are studied for different values of the so-called Knudsen number (Kn, which gives the gas-rarefaction degree. The results are compared with those obtained using the classical continuum theory of Navier-Stokes and Fourier (NSF.

  16. Geometric aspects of Schnakenberg's network theory of macroscopic nonequilibrium observables

    Science.gov (United States)

    Polettini, M.

    2011-03-01

    Schnakenberg's network theory deals with macroscopic thermodynamical observables (forces, currents and entropy production) associated to the steady states of diffusions on generic graphs. Using results from graph theory and from the theory of discrete differential forms we recast Schnakenberg's treatment in the form of a simple discrete gauge theory, which allows to interpret macroscopic forces as the Wilson loops of a real connection. We discuss the geometric properties of transient states, showing that heat fluxes allow for a notion of duality of macroscopic observables which interchanges the role of the environment and that of the system. We discuss possible generalizations to less trivial gauge groups and the relevance for nonequilibrium fluctuation theorems. Based on work in collaboration with professor A. Maritan, University of Padua, to be published.

  17. Broadband Macroscopic Cortical Oscillations Emerge from Intrinsic Neuronal Response Failures

    Directory of Open Access Journals (Sweden)

    Amir eGoldental

    2015-10-01

    Full Text Available Broadband spontaneous macroscopic neural oscillations are rhythmic cortical firing which was extensively examined during the last century, however, their possible origination is still controversial. In this work we show how macroscopic oscillations emerge in solely excitatory random networks and without topological constraints. We experimentally and theoretically show that these oscillations stem from the counterintuitive underlying mechanism - the intrinsic stochastic neuronal response failures. These neuronal response failures, which are characterized by short-term memory, lead to cooperation among neurons, resulting in sub- or several- Hertz macroscopic oscillations which coexist with high frequency gamma oscillations. A quantitative interplay between the statistical network properties and the emerging oscillations is supported by simulations of large networks based on single-neuron in-vitro experiments and a Langevin equation describing the network dynamics. Results call for the examination of these oscillations in the presence of inhibition and external drives.

  18. Reconciling power laws in microscopic and macroscopic neural recordings

    CERN Document Server

    Pettersen, Klas H; Tetzlaff, Tom; Einevoll, Gaute T

    2013-01-01

    Power laws, characterized by quantities following 1/x^\\alpha{} distributions, are commonly reported when observing nature or society, and the question of their origin has for a long time intrigued physicists. Power laws have also been observed in neural recordings, both at the macroscopic and microscopic levels: at the macroscopic level, the power spectral density (PSD) of the electroencephalogram (EEG) has been seen to follow 1/f^\\alpha{} distributions; at the microscopic level similar power laws have been observed in single-neuron recordings of the neuronal soma potential and soma current, yet with different values of the power-law exponent \\alpha. In this theoretical study we find that these observed macroscopic and microscopic power laws may, despite the widely different spatial scales and different exponents, have the same source. By a combination of simulation on a biophysical detailed, pyramidal neuron model and analytical investigations of a simplified ball and stick neuron, we find that the transfer ...

  19. Characterization of surface hydrophobicity of engineered nanoparticles.

    Science.gov (United States)

    Xiao, Yao; Wiesner, Mark R

    2012-05-15

    The surface chemistry of nanoparticles, including their hydrophobicity, is a key determinant of their fate, transport and toxicity. Engineered NPs often have surface coatings that control the surface chemistry of NPs and may dominate the effects of the nanoparticle core. Suitable characterization methods for surface hydrophobicity at the nano-scale are needed. Three types of methods, surface adsorption, affinity coefficient and contact angle, were investigated in this study with seven carbon and metal based NPs with and without coatings. The adsorption of hydrophobic molecules, Rose Bengal dye and naphthalene, on NPs was used as one measure of hydrophobicity and was compared with the relative affinity of NPs for octanol or water phases, analogous to the determination of octanol-water partition coefficients for organic molecules. The sessile drop method was adapted for measuring contact angle of a thin film of NPs. Results for these three methods were qualitatively in agreement. Aqueous-nC(60) and tetrahydrofuran-nC(60) were observed to be more hydrophobic than nano-Ag coated with polyvinylpyrrolidone or gum arabic, followed by nano-Ag or nano-Au with citrate-functionalized surfaces. Fullerol was shown to be the least hydrophobic of seven NPs tested. The advantages and limitations of each method were also discussed.

  20. Hydrophobicity of silver surfaces with microparticle geometry

    Science.gov (United States)

    Macko, Ján; Oriňaková, Renáta; Oriňak, Andrej; Kovaľ, Karol; Kupková, Miriam; Erdélyi, Branislav; Kostecká, Zuzana; Smith, Roger M.

    2016-11-01

    The effect of the duration of the current deposition cycle and the number of current pulses on the geometry of silver microstructured surfaces and on the free surface energy, polarizability, hydrophobicity and thus adhesion force of the silver surfaces has been investigated. The changes in surface hydrophobicity were entirely dependent on the size and density of the microparticles on the surface. The results showed that formation of the silver microparticles was related to number of current pulses, while the duration of one current pulse played only a minor effect on the final surface microparticle geometry and thus on the surface tension and hydrophobicity. The conventional geometry of the silver particles has been transformed to the fractal dimension D. The surface hydrophobicity depended predominantly on the length of the dendrites not on their width. The highest silver surface hydrophobicity was observed on a surface prepared by 30 current pulses with a pulse duration of 1 s, the lowest one when deposition was performed by 10 current pulses with a duration of 0.1 s. The partial surface tension coefficients γDS and polarizability kS of the silver surfaces were calculated. Both parameters can be applied in future applications in living cells adhesion prediction and spectral method selection. Silver films with microparticle geometry showed a lower variability in final surface hydrophobicity when compared to nanostructured surfaces. The comparisons could be used to modify surfaces and to modulate human cells and bacterial adhesion on body implants, surgery instruments and clean surfaces.

  1. Hyperactivation of Rhizomucor miehei lipase by hydrophobic xerogels.

    Science.gov (United States)

    Aucoin, Marc G; Erhardt, Frank A; Legge, Raymond L

    2004-03-20

    Although a variety of approaches exist for the immobilization of enzymes, the "science" of enzyme immobilization is still in its infancy. In recent years, considerable interest has developed regarding the use of xerogels for enzyme immobilization. There are several advantages to xerogels for enzyme immobilization, including the opportunity to produce them in defined shapes or thin films and the ability to manipulate their physical characteristics (e.g., porosity, hydrophobicity, and optical properties). In this study we examined the effect of xerogel hydrophobicity on the activity of lipase (EC 3.2.2.3) from Rhizomucor miehei. The hydrophobicity of the xerogels was manipulated by generating xerogels with various molar ratios of propyltrimethoxysilane (PTMS) to tetramethoxysilane (TMOS), from 1:1 to 10:1. The belief was that, by increasing the proportion of propyl groups, the hydrophobicity of the resulting xerogel would be increased. Differences in the hydrophobicity of the resulting xerogels were confirmed using water-affinity studies. Two approaches were taken for water-affinity determinations by examining the ability of the xerogels to remove water from air (controlled humidity) and from water-saturated isopropyl ether. Xerogels with higher propyl content showed a reduced affinity for water. A crude lipase preparation from Rhizomucor miehei was then contacted with sized xerogel particulates and the effect of the xerogel on lipase activity was determined. The presence of the xerogel resulted in hyperactivation of the lipase. Analysis of the protein adsorption revealed changes in the profile of proteins adsorbed to the xerogel based on the hydrophobicity of the xerogel. Based on estimations of the specific activity of the hyperactivated lipase, a minimum hyperactivation of 207% was observed. Part of the hyperactivation may be attributable to xerogel-lipase interactions, but also to the adsorption of a component from the crude lipase preparation that may complex

  2. Flocculation, hydrophobic agglomeration and filtration of ultrafine coal

    Science.gov (United States)

    Yu, Zhimin

    In coal preparation plant circuits, fine coal particles are aggregated either by oil agglomeration or by flocculation. In a new hydrophobic agglomeration process, recently developed hydrophobic latices are utilized. While the selectivity of such aggregation processes determines the beneficiation results, the degree of aggregation has a strong effect on fine coal filtration. The aim of this research was to study the fundamentals and analyze the common grounds for these processes, including the potential effect of the coal surface properties. The selective flocculation tests, in which three types of coal, which differed widely in surface wettability, and three additives (hydrophobic latices, a semi-hydrophobic flocculant and a typical hydrophilic polyelectrolyte) were utilized, showed that coal wettability plays a very important role in selective flocculation. The abstraction of a hydrophobic latex on coal and silica revealed that the latex had a much higher affinity towards hydrophobic coal than to hydrophilic mineral matter. As a result, the UBC-1 hydrophobic latex flocculated only hydrophobic coal particles while the polyelectrolyte (PAM) flocculated all the tested coal samples and minerals, showing no selectivity in the fine coal beneficiation. The oil agglomeration was tested using kerosene emulsified with various surfactants (e.g. cationic, anionic and non-ionic). Surfactants enhance not only oil emulsification, hence reducing oil consumption (down to 0.25--0.5%), but also entirely change the electrokinetic properties of the droplets and affect the interaction energy between oil droplets and coal particles. Consequently, the results found in the course of the experimental work strongly indicate that even oxidized coals can be agglomerated if cationic surfactants are used to emulsify the oil. Oil agglomeration of the Ford-4 ultrafine coal showed that even at extremely low oil consumption (0.25 to 0.5%), a clean coal product with an ash content around 5% at over

  3. Microscopic and macroscopic infarct complicating pediatric epilepsy surgery.

    Science.gov (United States)

    Rubinger, Luc; Hazrati, Lili-Naz; Ahmed, Raheel; Rutka, James; Snead, Carter; Widjaja, Elysa

    2017-03-01

    There is some suggestion that microscopic infarct could be associated with invasive monitoring, but it is unclear if the microscopic infarct is also visible on imaging and associated with neurologic deficits. The aims of this study were to assess the rates of microscopic and macroscopic infarct and other major complications of pediatric epilepsy surgery, and to determine if these complications were higher following invasive monitoring. We reviewed the epilepsy surgery data from a tertiary pediatric center, and collected data on microscopic infarct on histology and macroscopic infarct on postoperative computed tomography (CT) or magnetic resonance imaging (MRI) done one day after surgery and major complications. Three hundred fifty-two patients underwent surgical resection and there was one death. Forty-two percent had invasive monitoring. Thirty patients (9%) had microscopic infarct. Univariable analyses showed that microscopic infarct was higher among patients with invasive monitoring relative to no invasive monitoring (20% vs. 0.5%, respectively, p microscopic infarct had transient right hemiparesis, and two with both macroscopic and microscopic infarct had unexpected persistent neurologic deficits. Thirty-two major complications (9.1%) were reported, with no difference in major complications between invasive monitoring and no invasive monitoring (10% vs. 7%, p = 0.446). In the multivariable analysis, invasive monitoring increased the odds of microscopic infarct (odds ratio [OR] 15.87, p = 0.009), but not macroscopic infarct (OR 2.6, p = 0.173) or major complications (OR 1.4, p = 0.500), after adjusting for age at surgery, sex, age at seizure onset, operative type, and operative location. Microscopic infarct was associated with invasive monitoring, and none of the patients had permanent neurologic deficits. Macroscopic infarct was not associated with invasive monitoring, and two patients with macroscopic infarct had persistent neurologic deficits. Wiley

  4. Approximating macroscopic observables in quantum spin systems with commuting matrices

    CERN Document Server

    Ogata, Yoshiko

    2011-01-01

    Macroscopic observables in a quantum spin system are given by sequences of spatial means of local elements $\\frac{1}{2n+1}\\sum_{j=-n}^n\\gamma_j(A_{i}), \\; n\\in{\\mathbb N},\\; i=1,...,m$ in a UHF algebra. One of their properties is that they commute asymptotically, as $n$ goes to infinity. It is not true that any given set of asymptotically commuting matrices can be approximated by commuting ones in the norm topology. In this paper, we show that for macroscopic observables, this is true.

  5. On the notion of a macroscopic quantum system

    CERN Document Server

    Khrenikov, A Yu

    2004-01-01

    We analyse the notion of macroscopic quantum system from the point of view of the statistical structure of quantum theory. We come to conclusion that the presence of interference of probabilities should be used the main characteristic of quantumness (in the opposition to N. Bohr who permanently emphasized the crucial role of quantum action). In the light of recent experiments with statistical ensembles of people who produced interference of probabilities for special pairs of questions (which can be considered as measurements on people) human being should be considered as a macroscopic quantum system. There is also discussed relation with experiments of A. Zeilinger on interference of probabilities for macromoleculas.

  6. Stimuli-deformable graphene materials: from nanosheet to macroscopic assembly

    Directory of Open Access Journals (Sweden)

    Fei Zhao

    2016-04-01

    Full Text Available Stimulus-induced deformation (SID of graphene-based materials has triggered rapidly increasing research interest due to the spontaneous response to external stimulations, which enables precise configurational regulation of single graphene nanosheets (GNSs through control over the environmental conditions. While the micro-strain of GNS is barely visible, the deformation of graphene-based macroscopic assemblies (GMAs is remarkable, thereby presenting significant potential for future application in smart devices. This review presents the current progress of SID of graphene in the manner of nanosheets and macroscopic assemblies in both the experimental and theoretical fronts, and summarizes recent advancements of SID of graphene for applications in smart systems.

  7. Statistical thermodynamics understanding the properties of macroscopic systems

    CERN Document Server

    Fai, Lukong Cornelius

    2012-01-01

    Basic Principles of Statistical PhysicsMicroscopic and Macroscopic Description of StatesBasic PostulatesGibbs Ergodic AssumptionGibbsian EnsemblesExperimental Basis of Statistical MechanicsDefinition of Expectation ValuesErgodic Principle and Expectation ValuesProperties of Distribution FunctionRelative Fluctuation of an Additive Macroscopic ParameterLiouville TheoremGibbs Microcanonical EnsembleMicrocanonical Distribution in Quantum MechanicsDensity MatrixDensity Matrix in Energy RepresentationEntropyThermodynamic FunctionsTemperatureAdiabatic ProcessesPressureThermodynamic IdentityLaws of Th

  8. Hydrophobic character of surface regions and total hydrophobicity of four variants of chromosomal class C beta-lactamase from Pseudomonas aeruginosa are identical. Chromatographic comparison of the hydrophobic character of the variants and the effect of focusing buffer composition on the separation of the variants by chromatofocusing with internal and external pH gradients.

    Science.gov (United States)

    Walther-Rasmussen, J; Høiby, N

    2000-09-15

    The hydrophobic character of class C beta-lactamase molecular variants from Pseudomonas aeruginosa was compared by hydrophobic interaction chromatography and reversed-phase liquid chromatography, respectively. Separation of the variants by hydrophobic interaction chromatography was not achieved by modifying salt and pH of mobile phases. Reversed-phase liquid chromatography of the variants resulted in almost identical retention times. The results showed that the hydrophobic character of surface regions as well as total hydrophobicity of the variants are identical. The resolving power of external, internal and gradient chromatofocusing of the variants on strong and weak anion exchangers using low-molecular-mass buffers was compared to that of commercial ampholytes and showed no difference in separation pattern of the variants. Comparisons of variant isoelectric point (pI) values determined by chromatofocusing and isoelectric focusing showed that pI values determined by gradient chromatofocusing were most similar to the pI values determined by isoelectric focusing.

  9. Water-based adhesives with tailored hydrophobic association: dilution resistance and improved setting behavior.

    Science.gov (United States)

    Dundua, Alexander; Landfester, Katharina; Taden, Andreas

    2014-11-01

    Hydrophobic association and stimuli-responsiveness is a powerful tool towards water-based adhesives with strongly improved properties, which is demonstrated based on the example of hydrophobically modified alkali-soluble latexes (HASE) with modulated association. Their rheological properties are highly tunable due to the hydrophobic domains that act as physical crosslinking sites of adjustable interaction strength. Ethanol, propanol, and butanol are used as water-soluble model additives with different hydrophobicity in order to specifically target the association sites and impact the viscoelastic properties and stimuli-responsiveness. The rheological and mechanical property response upon dilution with water can be tailored, and dilution-resistant or even dilution-thickening systems are obtained. The investigations are of high importance for water-based adhesives, as our findings provide insight into general structure-property relationships to improve their setting behavior, especially upon contact with wet substrates.

  10. Explaining Ionic Liquid Water Solubility in Terms of Cation and Anion Hydrophobicity

    Directory of Open Access Journals (Sweden)

    Johannes Ranke

    2009-03-01

    Full Text Available The water solubility of salts is ordinarily dictated by lattice energy and ion solvation. However, in the case of low melting salts also known as ionic liquids, lattice energy is immaterial and differences in hydrophobicity largely account for differences in their water solubility. In this contribution, the activity coefficients of ionic liquids in water are split into cation and anion contributions by regression against cation hydrophobicity parameters that are experimentally determined by reversed phase liquid chromatography. In this way, anion hydrophobicity parameters are derived, as well as an equation to estimate water solubilities for cation-anion combinations for which the water solubility has not been measured. Thus, a new pathway to the quantification of aqueous ion solvation is shown, making use of the relative weakness of interactions between ionic liquid ions as compared to their hydrophobicities.

  11. Solvent fluctuations induce non-Markovian kinetics in hydrophobic pocket-ligand binding

    CERN Document Server

    Weiß, R Gregor; Dzubiella, Joachim

    2016-01-01

    We investigate the impact of water fluctuations on the key-lock association kinetics of a hydrophobic ligand (key) binding to a hydrophobic pocket (lock) by means of a minimalistic stochastic model system. It describes the collective hydration behavior of the pocket by bimodal fluctuations of a water-pocket interface that dynamically couples to the diffusive motion of the approaching ligand via the hydrophobic interaction. This leads to a set of overdamped Langevin equations in 2D-coordinate-space, that is Markovian in each dimension. Numerical simulations demonstrate locally increased friction of the ligand, decelerated binding kinetics, and local non-Markovian (memory) effects in the ligand's reaction coordinate as found previously in explicit-water molecular dynamics studies of model hydrophobic pocket-ligand binding [1,2]. Our minimalistic model elucidates the origin of effectively enhanced friction in the process that can be traced back to long-time decays in the force-autocorrelation function induced by...

  12. Heating and reduction affect the reaction with tannins of wine protein fractions differing in hydrophobicity.

    Science.gov (United States)

    Marangon, Matteo; Vincenzi, Simone; Lucchetta, Marco; Curioni, Andrea

    2010-02-15

    During the storage, bottled white wines can manifest haziness due to the insolubilisation of the grape proteins that may 'survive' in the fermentation process. Although the exact mechanism of this occurrence is not fully understood, proteins and tannins are considered two of the key factors involved in wine hazing, since their aggregation leads to the formation of insoluble particles. To better understand this complex interaction, proteins and tannins from the same unfined Pinot grigio wine were separated. Wine proteins were then fractionated by hydrophobic interaction chromatography (HIC). A significant correlation between hydrophobicity of the wine protein fractions and the haze formed after reacting with wine tannins was found, with the most reactive fractions revealing (by SDS-PAGE and RP-HPLC analyses) the predominant presence of thaumatin-like proteins. Moreover, the effects of both protein heating and disulfide bonds reduction (with dithiotreithol) on haze formation in the presence of tannins were assessed. These treatments generally resulted in an improved reactivity with tannins, and this phenomenon was related to both the surface hydrophobicity and composition of the protein fractions. Therefore, haze formation in wines seems to be related to hydrophobic interactions occurring among proteins and tannins. These interactions should occur on hydrophobic tannin-binding sites, whose exposition on the proteins can depend on both protein heating and reduction.

  13. Hydrophobically modified polyelectrolytes: Characterization, aggregation and adsorption

    Science.gov (United States)

    Islam, Mohammad Ferdous

    The focus of our work was to experimentally study the aggregation and adsorption behavior of model HM polyelectrolytes. Hydrophobically modified alkali soluble emulsions (HASE), the model HM polyelectrolytes, were chosen because they had complex architecture yet possessed key variables for systematic study. The HASE polymers have methacrylic acid (MAA) and ethyl acrylate (EA) in the backbone with pendent hydrophobic groups. Characterization of a single molecule is an important first step in understanding the aggregation and adsorption of these polymers. However, characterizations of the HASE polymers using conventional techniques such as gel permeation chromatography or static light scattering were difficult because of the hydrophobic association. In this study, two different approaches have been taken to prevent the hydrophobic association in aqueous solution: (1) hydrolyze the polymer to cleave the hydrophobic constituents, and (2) use methyl beta-cyclodextrin that has a hydrophobic cavity and a hydrophilic outer shell, to shield the hydrophobes from associating. By taking these two approaches and using gel permeation chromatography (GPC), dynamic (DLS) and static (SLS) light scattering techniques, the molecular weight, hydrodynamic radius and radius of gyration of a single molecule were determined. Except for one chemical site, we were able to determine that branching or grafting did not occur in the polymer chain during synthesis. Our aggregation studies showed that, in aqueous solutions, the HASE polymers formed small aggregates (presumably single micelles of single or a few chains) and large aggregates (presumably formed by bridging between micelles). The radii and masses of the larger aggregates, measured using DLS and SLS, were found to increase with an increase in the polymer concentration, indicating an open association process for the HASE polymers. Our SLS results also showed that, at high salt concentration, the aggregates of the HASE polymer with

  14. Adsorption of an endoglucanase from the hyperthermophilic Pyrococcus furiosus of hydrophobic (polysterene) and hydrophilic (silica) surfaces increases protein heat stability

    NARCIS (Netherlands)

    Koutsopoulos, S.; Oost, van der J.; Norde, W.

    2004-01-01

    The interaction of an endoglucanase from the hyperthermophilic microorganism Pyrococcus furiosus with two types of surfaces, that is, hydrophobic polystyrene and hydrophilic silica, was investigated, and the adsorption isotherms were determined. The adsorbed hyperthermostable enzyme did not undergo

  15. Adsorption of an endoglucanase from the hyperthermophilic Pyrococcus furiosus on hydrophobic (polystyrene) and hydrophilic (silica) surfaces increases protein heat stability

    NARCIS (Netherlands)

    Koutsopoulos, S.; van der Oost, J.; Norde, Willem

    2004-01-01

    The interaction of an endoglucanase from the hyperthermophilic microorganism Pyrococcus furiosus with two types of surfaces, that is, hydrophobic polystyrene and hydrophilic silica, was investigated, and the adsorption isotherms were determined. The adsorbed hyperthermostable enzyme did not undergo

  16. Nonminimal Macroscopic Models of a Scalar Field Based on Microscopic Dynamics. II. Transport Equations

    CERN Document Server

    Ignat'ev, Yu G

    2015-01-01

    The article proposes generalizations of the macroscopic model of plasma of scalar charged particles to the cases of inter-particle interaction with multiple scalar fields and negative effective masses of these particles. The model is based on the microscopic dynamics of a particle at presence of scalar fields. The theory is managed to be generalized naturally having strictly reviewed a series of its key positions depending on a sign of particle masses. Thereby, it is possible to remove the artificial restriction contradicting the more fundamental principle of action functional additivity. Additionally, as a condition of internal consistency of the theory, particle effective mass function is found.

  17. Quantum statistical derivation of the macroscopic Maxwell equations

    NARCIS (Netherlands)

    Schram, K.

    1960-01-01

    The macroscopic Maxwell equations in matter are derived on a quantum statistical basis from the microscopic equations for the field operators. Both the density operator formalism and the Wigner distribution function method are discussed. By both methods it can be proved that the quantum statistical

  18. Macroscopic and Microscopic Gradient Structures of Bamboo Culms

    Directory of Open Access Journals (Sweden)

    Suwat SUTNAUN

    2005-01-01

    Full Text Available This work studied the structure of bamboo culms which is naturally designed to retard the bending stress caused by a wind load. A macroscopic gradient structure (diameter, thickness and internodal length and a microscopic one (distribution of fiber of three sympodial bamboo species i.e. Tong bamboo (Dendrocalamus asper Backer., Pah bamboo (Gigantochloa bambos and Pak bamboo (Gigantochloa hasskarliana were examined. From the macroscopic point of view, the wind-load generated bending stress for the tapered hollow tube of bamboo was found to vary uniformly with height, especially at the middle of the culms. Furthermore, the macroscopic shape of bamboo culm is about 2-6 times stiffer in bending mode than one with a solid circular section for the same amount of wood material. Microscopically, the distribution of fiber in the radial direction linearly decreases from the outer surface to the inner surface in the same manner as that of the distribution of the bending stress in the radial direction. Distribution of fiber along the vertical length of bamboos at each height is proportional to the level of bending stress generated by the wind load. Both macroscopic and microscopic gradient structures of sympodial type bamboos were found to be less effective to retard the bending stress than those of monopodial type bamboo.

  19. Microstructure and macroscopic properties of polydisperse systems of hard spheres

    NARCIS (Netherlands)

    Ogarko, Vitaliy Anatolyevich

    2014-01-01

    This dissertation describes an investigation of systems of polydisperse smooth hard spheres. This includes the development of a fast contact detection algorithm for computer modelling, the development of macroscopic constitutive laws that are based on microscopic features such as the moments of the

  20. Photoinduced macroscopic chiral structures in a series of azobenzene copolyesters

    DEFF Research Database (Denmark)

    Nedelchev, L.; Nikolova, L.; Matharu, A.

    2002-01-01

    A study of the propagation of elliptically polarized light and the resulting formation of macroscopic chiral structures in a series of azobenzene side-chain copolyesters, in which the morphology is varied from liquid crystalline to amorphous, is reported. Real-time measurements are presented...