770 research outputs found
Bioactive Seed Layer for Surface-Confined Self-Assembly of Peptides
International audienceThe design and control of molecular systems that self-assemble spontaneously and exclusively at or near an interface represents a real scientific challenge. We present here a new concept, an active seed layer that allows to overcome this challenge.It is based on enzyme-assisted self-assembly. An enzyme, alkaline phosphatase, which transforms an original peptide,Fmoc-FFY(PO 4 2À), into an efficient gelation agent by dephosphorylation, is embedded in a polyelectrolyte multilayer and constitutes the "reaction motor". A seed layer composed of a polyelectrolyte covalently modified by anchoring hydro-gelator peptides constitutes the top of the multilayer. This layer is the nucleation site for the Fmoc-FFY peptide self-assembly. When such a film is brought in contact with a Fmoc-FFY-(PO42-) solution, a nofiber network starts to form almost instantaneously which extents up to several micrometers into the solution after several hours. We demonstrate that the active seed layer allows convenient control over the self-assembly kinetics and the geometric features of the fiber network simply by changing its peptide density
Turbidity diagrams of polyanion/polycation complexes in solution as a potential tool to predict the occurrence of polyelectrolyte multilayer deposition.
Surface functionalization with polyelectrolyte multilayer films (PEM films) has become very popular owing to its simplicity and versatility. However, even if some research is already available, this field of surface chemistry lacks a systematic knowledge of how the polyelectrolyte structure and solution conditions influence the growth of PEM films. In this investigation, we focus on the possible relationship between turbidity of polycation and polyanion mixtures in solution, and the buildup of PEM films made from the same polyelectrolytes in the same physicochemical conditions, namely pH, temperature and ionic strength. It comes out that for six different polycation/polyanion combinations there is a clear correlation between the turbidity evolution of polycation/polyanion complexes with the salt concentration and the evolution of the film deposition with the same parameter. In this investigation, the complexes in solution were prepared in conditions where the ratio between the number of cationic to anionic groups was close to unity. Even if there is a correlation between turbidity in solution and PEM film deposition, we found some exceptions in the low salt concentration regime. This work is an extension of the preliminary works of Cohen Stuart (D. Kovačević et al. Langmuir 18 (2002) 5607-5612) and Sukishvili et al. (S.A. Sukhishvili, E. Kharlampieva and V. Izumrudov, Macromolecules 39 (2006) 8873-8881).journal articleresearch support, non-u.s. gov't2010 Jun 012010 02 21importe
Polyanionic Hydrogels as Reservoirs for Polycationic Antibiotic Substitutes Providing Prolonged Antibacterial Activity
Implantation of biomedical devices is often followed by bacterial infections that may seriously affect implant functionalities and lead to their failure. In the context of bacterial resistance to antibiotics, which is a growing problem worldwide, new strategies that are able to overcome these problems are needed. In this work, we introduce a new formulation of hyaluronic acid (HA)-based antimicrobial material: HA hydrogels loaded with polyarginine (PAR), a polycationic antibiotic substitute. The loading is possible through electrostatic interactions between negatively charged HA and positively charged PAR. Such hydrogels absorb high quantities of PAR, which are then gradually released from the hydrogel. This original system provides a long-lasting antibacterial effect on an in vitro model of repetitive infection, thus demonstrating a strong potential to fight multiple rounds of infections that are resistant to antibiotic treatment. In addition, HA-PAR hydrogels could be deposited onto/into medical devices such as wound dressings and mesh prostheses used in clinical applications. Finally, we performed first in vivo tests of hydrogel-coated mesh materials to verify their biocompatibility in a rat model, which show no difference between control HA hydrogel and PAR-loaded hydrogel in terms of inflammation
Bioaffinity sensor based on nanoarchitectonic films: control of the specific adsorption of proteins through the dual role of an ethylene oxide spacer.
The identification and quantification of biomarkers or proteins is a real challenge in allowing the early detection of diseases. The functionalization of the biosensor surface has to be properly designed to prevent nonspecific interactions and to detect the biomolecule of interest specifically. A multilayered nanoarchitecture, based on polyelectrolyte multilayers (PEM) and the sequential immobilization of streptavidin and a biotinylated antibody, was elaborated as a promising platform for the label-free sensing of targeted proteins. We choose ovalbumin as an example. Thanks to the versatility of PEM films, the platform was built on two types of sensor surface and was evaluated using both optical- and viscoelastic-based techniques, namely, optical waveguide lightmode spectroscopy and the quartz crystal microbalance, respectively. A library of biotinylated poly(acrylic acids) (PAAs) was synthesized by grafting biotin moieties at different grafting ratios (GR). The biotin moieties were linked to the PAA chains through ethylene oxide (EO) spacers of different lengths. The adsorption of the PAA-EOn-biotin (GR) layer on a PEM precursor film allows tuning the surface density in biotin and thus the streptavidin adsorption mainly through the grafting ratio. The nonspecific adsorption of serum was reduced and even suppressed depending on the length of the EO arms. We showed that to obtain an antifouling polyelectrolyte the grafting of EO9 or EO19 chains at 25% in GR is sufficient. Thus, the spacer has a dual role: ensuring the antifouling property and allowing the accessibility of biotin moieties. Finally, an optimized platform based on the PAA-EO9-biotin (25%)/streptavidin/biotinylated-antibody architecture was built and demonstrated promising performance as interface architecture for bioaffinity sensing of a targeted protein, in our case, ovalbumin.journal articleresearch support, non-u.s. gov't2013 Jun 182013 02 11importe
Collagen-based fibrillar multilayer films cross-linked by a natural agent.
Surface functionalization plays an important role in the design of biomedical implants, especially when layer forming cells, such as endothelial or epithelial cells, are needed. In this study, we define a novel nanoscale surface coating composed of collagen/alginate polyelectrolyte multilayers and cross-linked for stability with genipin. This buildup follows an exponential growth regime versus the number of deposition cycles with a distinct nanofibrillar structure that is not damaged by the cross-linking step. Stability and cell compatibility of the cross-linked coatings were studied with human umbilical vein endothelial cells. The surface coating can be covered by a monolayer of vascular endothelial cells within 5 days. Genipin cross-linking renders the surface more suitable for cell attachment and proliferation compared to glutaraldehyde (more conventional cross-linker) cross-linked surfaces, where cell clumps in dispersed areas were observed. In summary, it is possible with the defined system to build fibrillar structures with a nanoscale control of film thickness, which would be useful for in vivo applications such as inner lining of lumens for vascular and tracheal implants.journal articleresearch support, non-u.s. gov't2012 Jul 092012 06 13importe
Effect of the supporting electrolyte anion on the thickness of PSS/PAH multilayer films and on their permeability to an electroactive probe.
Quartz crystal microbalance and cyclic voltammetry are used to investigate the influence of the supporting salt of polyelectrolyte solutions on the buildup and the structure of PSS/PAH polyelectrolyte multilayers (PSS: poly(4-styrene sulfonate); PAH: poly(allylamine hydrochloride)). This film constitutes a model polyelectrolyte multilayer system. The supporting electrolytes were sodium salts where the nature of the anion was changed by following the Hofmeister series from cosmotropic to chaotropic anions (F-, Cl-, NO3-, ClO4-). For all the investigated anions, the film thickness increases linearly with the number of deposition steps.Wefind that chaotropic anions lead to larger thickness increments per bilayer during the film buildup than cosmotropic ones, confirming results found on PSS/PDADMA multilayers (PDADMA:poly(diallyldimethylammonium)). Films constituted by more than nine PSS/PAH bilayers are still permeable to hexacyanoferrate(II) ions, Fe(CN)(6)4-, whatever the nature of the supporting salt anion. On the other hand, these films are impermeable to ruthenium(II) hexamine ions, Ru(NH3)(6)2+, after the third PAH layer in the presence of NaF, NaCl, or NaNO3. These results are explained by the presence of an excess of positive charges in the film, which leads to a positive Donnan potential. We find that this potential is more positive when more chaotropic anions are used during the film buildup. We also find that a film constructed in the presence of chaotropic anions swells and becomes more permeable to Fe(CN)(6)4- ions when the film is brought into contact with a solution containing more cosmotropic anions. All our experimental findings can be explained by a strong interaction between chaotropic anions with the NH3+groups of PAH that is equivalent, as far as the multilayer buildup and electrochemical response is concerned, to a deprotonation of PAH as it is observed when the film is constructed at a higher pH. We thus arrive to a coherent explanation of the effect of the nature of the anions of the supporting electrolyte on the polyelectrolyte multilayer. We also find that great care must be taken when investigating polyelectrolyte multilayer films by electrochemical probing because electrochemical reactions involving the probes can appreciably modify the multilayer structure.journal articleresearch support, non-u.s. gov't2009 Feb 17importe
Polymer multilayer films obtained by electrochemically catalyzed click chemistry.
We report the covalent layer-by-layer construction of polyelectrolyte multilayer (PEM) films by using an efficient electrochemically triggered Sharpless click reaction. The click reaction is catalyzed by Cu(I) which is generated in situ from Cu(II) (originating from the dissolution of CuSO(4)) at the electrode constituting the substrate of the film. The film buildup can be controlled by the application of a mild potential inducing the reduction of Cu(II) to Cu(I) in the absence of any reducing agent or any ligand. The experiments were carried out in an electrochemical quartz crystal microbalance cell which allows both to apply a controlled potential on a gold electrode and to follow the mass deposited on the electrode through the quartz crystal microbalance. Poly(acrylic acid) (PAA) modified with either alkyne (PAA(Alk)) or azide (PAA(Az)) functions grafted onto the PAA backbone through ethylene glycol arms were used to build the PEM films. Construction takes place on gold electrodes whose potentials are more negative than a critical value, which lies between -70 and -150 mV vs Ag/AgCl (KCl sat.) reference electrode. The film thickness increment per bilayer appears independent of the applied voltage as long as it is more negative than the critical potential, but it depends upon Cu(II) and polyelectrolyte concentrations in solution and upon the reduction time of Cu(II) during each deposition step. An increase of any of these latter parameters leads to an increase of the mass deposited per layer. For given buildup conditions, the construction levels off after a given number of deposition steps which increases with the Cu(II) concentration and/or the Cu(II) reduction time. A model based on the diffusion of Cu(II) and Cu(I) ions through the film and the dynamics of the polyelectrolyte anchoring on the film, during the reduction period of Cu(II), is proposed to explain the major buildup features.journal articleresearch support, non-u.s. gov't2010 Feb 16importe
Cyto-mechanoresponsive polyelectrolyte multilayer films.
Cell adhesion processes take place through mechanotransduction mechanisms where stretching of proteins results in biological responses. In this work, we present the first cyto-mechanoresponsive surface that mimics such behavior by becoming cell-adhesive through exhibition of arginine-glycine-aspartic acid (RGD) adhesion peptides under stretching. This mechanoresponsive surface is based on polyelectrolyte multilayer films built on a silicone sheet and where RGD-grafted polyelectrolytes are embedded under antifouling phosphorylcholine-grafted polyelectrolytes. The stretching of this film induces an increase in fibroblast cell viability and adhesion.journal articleresearch support, non-u.s. gov't2012 Jan 112011 12 20importe
Nucleon and hadron structure changes in the nuclear medium and impact on observables
We review the effect of hadron structure changes in a nuclear medium using
the quark-meson coupling (QMC) model, which is based on a mean field
description of non-overlapping nucleon (or baryon) bags bound by the
self-consistent exchange of scalar and vector mesons. This approach leads to
simple scaling relations for the changes of hadron masses in a nuclear medium.
It can also be extended to describe finite nuclei, as well as the properties of
hypernuclei and meson-nucleus deeply bound states. It is of great interest that
the model predicts a variation of the nucleon form factors in nuclear matter.
We also study the empirically observed, Bloom-Gilman (quark-hadron) duality.
Other applications of the model include subthreshold kaon production in heavy
ion collisions, D and D-bar meson production in antiproton-nucleus collisions,
and J/Psi suppression. In particular, the modification of the D and D-bar meson
properties in nuclear medium can lead to a large J/Psi absorption cross
section, which explains the observed J/Psi suppression in relativistic heavy
ion collisions.Comment: 143 pages, 77 figures, references added, a review article accepted in
Prog. Part. Nucl. Phy
Close-to-threshold Meson Production in Hadronic Interactions
Studies of meson production at threshold in the hadron--hadron interaction
began in the fifties when sufficient energies of accelerated protons were
available. A strong interdependence between developments in accelerator
physics, detector performance and theoretical understanding led to a unique
vivid field of physics. Early experiments performed with bubble chambers
revealed already typical ingredients of threshold studies, which were
superseded by more complete meson production investigations at the nucleon beam
facilities TRIUMF, LAMPF, PSI, LEAR and SATURNE. Currently, with the advent of
the new cooler rings as IUCF, CELSIUS and COSY the field is entering a new
domain of precision and the next step of further progress.
The analysis of this new data in the short range limit permits a more
fundamental consideration and a quantitative comparison of the production
processes for different mesons in the few--body final states. The
interpretation of the data take advantage of the fact that production reactions
close-to-threshold are characterized by only a few degrees of freedom between a
well defined combination of initial and exit channels. Deviations from
predictions of phase-space controlled one-meson-exchange models are indications
of new and exciting physics. Precision data on differential cross sections,
isospin and spin observables -- partly but by no means adequately available --
are presently turning up on the horizon. There is work for the next years and
excitement of the physics expected. Here we try to give a brief and at the same
time comprehensive overview of this field of hadronic threshold production
studies.Comment: 100 pages, Review article to be published in Prog. Part. Nucl. Phys.
Vol. 49, issue 1 (2002
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