1. |
- Agmo Hernández, Víctor
(författare)
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An overview of surface forces and the DLVO theory
- 2023
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Ingår i: ChemTexts. - : Springer. - 2199-3793. ; 9:4
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Tidskriftsartikel (refereegranskat)abstract
- This lecture text focuses on surface forces and interactions in a liquid medium, with particular emphasis on the surface-surface interactions described by the DLVO theory, i.e., van der Waals attraction and electric double-layer repulsion. The text begins by describing the fundamental forces of nature, their connection to intermolecular interactions, and how the latter result in measurable forces between surfaces and macroscopical objects. A step-by-step reasoning on how DLVO forces arise is then presented, accompanied by a simplified description of the mathematical derivations of the main equations within the framework of the theory. The connection between the DLVO theory and the prediction of the stability of colloidal systems is presented. Examples on how the colloidal stability can be controlled or tuned are presented. The shortcomings of the original DLVO theory are discussed, and recent extended models dealing with these issues are briefly described. The text closes with a general overview of some of the most relevant non-DLVO interaction.
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2. |
- Agmo Hernández, Víctor, et al.
(författare)
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Electrochemistry of Adhesion and Spreading of Lipid Vesicles on Electrodes
- 2013
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Ingår i: Applications of Electrochemistry in Medicine. - Boston, MA : Springer US. - 9781461461487 ; , s. 189-247
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Bokkapitel (övrigt vetenskapligt/konstnärligt)abstract
- Biological membranes have developed to separate different compartments of organisms and cells. There is a large number of rather different functions which membranes have to fulfil: (1) they control the material and energy fluxes of metabolic processes, (2) they provide a wrapping protecting the compartments from chemical and physical attacks of the environment, (3) they provide interfaces at which specific biochemical machineries can operate (e.g., membrane bound enzymes), (4) they are equipped for signal transduction, (5) they possess the necessary stability and flexibility to allow cell division, and endo- and exocytosis as well as migration, (6) they present anchoring structures that enable cell-to-cell and cell-to-matrix physical interactions and intercellular communication. These are certainly not all functions of membranes as new functionalities are continuously reported. Since the biological membranes separate essentially aqueous solutions, such separating borders—if they should possess a reasonable stability and also flexibility combined with selective permeability—have to be built up of hydrophobic molecules exposing to both sides a similar interface. It was one of the most crucial and most lucky circumstances for the development and existence of life that certain amphiphilic molecules are able to assemble in bilayer structures (membranes), which—on one side—possess a rather high physical and chemical stability, and—on the other side—are able to incorporate foreign molecules for modifying both the physical properties as well as the permeability of the membranes for defined chemical species. The importance of the chemical function of membranes and all its constituents, e.g., ion channels, pore peptides, transport peptides, etc., is generally accepted. The fluid-mosaic model proposed by Singer and Nicolson [1] is still the basis to understand the biological, chemical, and physical properties of biological membranes. The importance of the purely mechanical properties of membranes came much later into the focus of research. The reasons are probably the dominance of biochemical thinking and biochemical models among biologists and medical researchers, as well as a certain lack of appropriate methods to probe mechanical properties of membranes. The last decades have changed that situation due to the development of techniques like the Atomic Force Microscopy, Fluorescence Microscopy, Micropipette Aspiration, Raman Microspectroscopy, advanced Calorimetry, etc. This chapter is aimed at elucidating how the properties of membranes can be investigated by studying the interaction of vesicles with a very hydrophobic surface, i.e., with the surface of a mercury electrode. This interaction is unique as it results in a complete disintegration of the bilayer membrane of the vesicles and the formation of an island of adsorbed lipid molecules, i.e., a monolayer island. This process can be followed by current-time measurements (chronoamperometry), which allow studying the complete disintegration process in all its details: the different steps of that disintegration can be resolved on the time scale and the activation parameters can be determined. Most interestingly, the kinetics of vesicle disintegration on mercury share important features with the process of vesicle fusion and, thus, sheds light also on mechanisms of endocytosis and exocytosis. Most importantly, not only artificial vesicles (liposomes) can be studied with this approach, but also reconstituted plasma membrane vesicles and even intact mitochondria. Hence, one can expect that the method may provide in future studies also information on the membrane properties of various other vesicles, including exosomes, and may allow investigating various aspects of drug action in relation to membrane properties (transmembrane transport, tissue targeting, bioavailability, etc.), and also the impact of pathophysiological conditions (e.g., oxidative modification) on membrane properties, on a hitherto not or only hardly accessible level.
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3. |
- Agmo Hernández, Víctor, et al.
(författare)
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Enhanced interpretation of adsorption data generated by liquid chromatography and by modern biosensors
- 2013
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Ingår i: Journal of Chromatography A. - : Elsevier BV. - 0021-9673 .- 1873-3778. ; 1317, s. 22-31
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Tidskriftsartikel (refereegranskat)abstract
- In this study we demonstrate the importance of proper data processing in adsorption isotherm estimations. This was done by investigating and reprocessing data from five cases on two closely related platforms: liquid chromatography (LC) and biosensors. The previously acquired adsorption data were reevaluated and reprocessed using a three-step numerical procedure: (i) preprocessing of adsorption data, (ii) adsorption data analysis and (iii) final rival model fit. For each case, we will discuss what we really measure and what additional information can be obtained by numerical processing of the data. These cases clearly demonstrate that numerical processing of LC and biosensor data can be used to gain deeper understanding of molecular interactions with adsorption media. This is important because adsorption data, especially from biosensors, is often processed using old and simplified methods. (C) 2013 Elsevier B.V. All rights reserved.
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4. |
- Agmo Hernández, Víctor, et al.
(författare)
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Intrinsic Heterogeneity in Liposome Suspensions Caused by the Dynamic Spontaneous Formation of Hydrophobic Active Sites in Lipid Membranes
- 2011
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 27:8, s. 4873-4883
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Tidskriftsartikel (refereegranskat)abstract
- The spontaneous, dynamic formation of hydrophobic active sites in lipid bilayer membranes is studied and characterized. It is shown that the rates of formation and consumption of these active sites control at least two important properties of liposomes: their affinity for hydrophobic surfaces and the rate by which they spontaneously release encapsulated molecules. The adhesion and spreading of liposomes onto hydrophobic polystyrene nanoparticles and the spontaneous leakage of an encapsulated fluorescent dye were monitored for different liposome compositions employing Cryo-TEM, DLS, and fluorescence measurements. It was observed that an apparently homogeneous, monodisperse liposome suspension behaves as if composed by two different populations: a fast leaking population that presents affinity for the hydrophobic substrate employed, and a slow leaking population that does not attach immediately to it. The results reported here suggest that the proportion of liposomes in each population changes over time until a dynamic equilibrium is reached. It is shown that this phenomenom can lead to irreproducibility in, for example, spontaneous leakage experiments, as extruded liposomes leak much faster just after preparation than 24 h afterward. Our findings account for discrepancies in several experimental results reported in the literature. To our knowledge, this is the first systematic study addressing the issue of an existing intrinsic heterogeneity of liposome suspensions.
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5. |
- Agmo Hernández, Víctor, et al.
(författare)
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Label-Free Characterization of Peptide-Lipid Interactions Using Immobilized Lipodisks
- 2013
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Ingår i: Analytical Chemistry. - : American Chemical Society (ACS). - 0003-2700 .- 1520-6882. ; 85:15, s. 7377-7384
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Tidskriftsartikel (refereegranskat)abstract
- Lipodisks, planar lipid bilayer structures stabilized by PEG-ylated lipids, were in the present study covalently bound and immobilized onto sensors for quartz crystal microbalance with dissipation monitoring (QCM-D) studies. It is shown that the modified sensors can be used to characterize the interaction of lipodisks with α-helical amphiphilic peptides with an accuracy similar to that obtained with well established fluorimetric approximations. The method presented has the great advantage that it can be used with peptides in their native form even if no fluorescent residues are present. The potential of the method is illustrated by determining the parameters describing the association of melittin, mastoparan X, and mastoparan with immobilized lipodisks. Both thermodynamic and kinetic analyses are possible. The presented method constitutes a useful tool for fundamental studies of peptide–membrane interactions and can also be applied to optimize the design of lipodisks, for example, for sustained release of antimicrobial peptides in therapeutic applications.
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6. |
- Agmo Hernández, Víctor, et al.
(författare)
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Ubiquinone-10 alters mechanical properties and increases stability of phospholipid membranes
- 2015
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Ingår i: Biochimica et Biophysica Acta - Biomembranes. - : Elsevier BV. - 0005-2736 .- 1879-2642. ; 1848:10, s. 2233-2243
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Tidskriftsartikel (refereegranskat)abstract
- Abstract Ubiquinone-10 is mostly known for its role as an electron and proton carrier in aerobic cellular respiration and its function as a powerful antioxidant. Accumulating evidence suggest, however, that this well studied membrane component could have several other important functions in living cells. The current study reports on a previously undocumented ability of ubiquinone-10 to modulate the mechanical strength and permeability of lipid membranes. Investigations of DPH fluorescence anisotropy, spontaneous and surfactant induced leakage of carboxyfluorescein, and interactions with hydrophobic and hydrophilic surfaces were used to probe the effects caused by inclusion of ubiquinone-10 in the membrane of phospholipid liposomes. The results show that ubiquinone in concentrations as low as 2 mol.% increases the lipid packing order and condenses the membrane. The altered physicochemical properties result in a slower rate of release of hydrophilic components, and render the membrane more resistant towards rupture. As judged from comparative experiments using the polyisoprenoid alcohol solanesol, the quinone moiety is essential for the membrane stabilizing effects to occur. Our findings imply that the influence of ubiquinone-10 on the permeability and mechanical properties of phospholipid membranes is similar to that of cholesterol. The reported data indicate, however, that the molecular mechanisms are different in the two cases.
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7. |
- Agmo Hernandez, Victor, et al.
(författare)
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Study of the temporal distribution of the adhesion-spreading events of liposomes on a mercury electrode
- 2009
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Ingår i: Journal of Solid State Electrochemistry. - : Springer Science and Business Media LLC. - 1432-8488 .- 1433-0768. ; 13:7, s. 1111-1114
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Tidskriftsartikel (refereegranskat)abstract
- The formal analysis of the mechanism of adhesion spreading of liposomes at mercury electrodes shares several characteristics with the mechanism of metal nucleation at electrodes. It is shown that the description of the temporal distribution of the adhesion-spreading events is similar to that of the temporal distribution of metal clusters. Both processes are stochastic in nature and can be described by the Poisson distribution. Using this approach, a previously proposed model for the overall adhesion-spreading mechanism, considering the formation of active sites on the liposome and the actual attachment of the liposomes to the mercury surface, is validated.
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8. |
- Agmo Hernández, Víctor, 1980-, et al.
(författare)
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The electrochemistry of liposomes
- 2008
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Ingår i: Israel Journal of Chemistry. - 0021-2148. ; 48, s. 169-184
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Recension (refereegranskat)
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9. |
- Agmo Hernández, Víctor, et al.
(författare)
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The lipid composition determines the kinetics of adhesion and spreading of liposomes on mercury electrodes
- 2008
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Ingår i: Bioelectrochemistry. - : Elsevier BV. - 1567-5394 .- 1878-562X. ; 74:1, s. 149-156
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Tidskriftsartikel (refereegranskat)abstract
- The dependence of membrane properties on their composition was studied by following the adhesion and spreading of unilamellar and multilamellar liposomes on static mercury electrodes with the help of chronoamperometry. The analysis of the peak-shaped signals allows determining the kinetic parameters of the three-step adhesion-spreading process. The presence of cholesterol in the membrane stabilizes the bilayer in the liquid-crystal line phase, and destabilizes the gel phase. The kinetic parameters also show the effect of superlattice formation in the DMPC-cholesterol system. The detergent triton X-100 is only incorporated in the liquid-crystalline DMPC membranes, and it is expelled to the solution when the membrane is transformed to the gel phase. In the liquid-crystalline membrane, it enhances the adhesion-spreading of liposomes on mercury. The lyric peptides mastoparan X and melittin affect the adhesion-spreading in a similar manner. For the rupture-spreading step, their effect is explained by pore formation. The results obtained with lecithins of different length suggest that the bilayer opening process has much in common with flip-flop translocations. For this process the activation energies were found to be independent of the chain length of the lecithin molecules, while the preexponential factor in the Arthenius equation decreases drastically for longer chains.
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10. |
- Agmo Hernandez, Victor, et al.
(författare)
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The overall adhesion-spreading process of liposomes on a mercury electrode is controlled by a mixed diffusion and reaction kinetics mechanism
- 2009
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Ingår i: Journal of Solid State Electrochemistry. - : Springer Science and Business Media LLC. - 1432-8488 .- 1433-0768. ; 13:4, s. 639-649
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Tidskriftsartikel (refereegranskat)abstract
- Using high-resolution chronoamperometric measurements, with sampling each 1.333 micro s, the initial step of the adhesion-spreading of liposomes on a mercury electrode was studied. These measurements allow getting a deeper insight into the first interaction of the liposomes with the mercury electrode, and they show that the overall adhesion-spreading process at different potentials is partially controlled by a fast but weak interaction equilibrium resulting in a mixed diffusion- and reaction-kinetics-controlled mechanism of the overall reaction.
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