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Cini N.,Technical University of Istanbul | Tulun T.,Technical University of Istanbul | Blanck C.,Charles Sadron Institute | Toniazzo V.,CRP Henri Tudor | And 5 more authors.
Physical Chemistry Chemical Physics | Year: 2012

Polyelectrolyte "complexes" have been studied for almost a century and find more and more applications in cosmetics and DNA transfection. Most of the available studies focused on the thermodynamic aspects of the "complex" formation, mainly to determine phase diagrams and the influence of diverse physicochemical aspects on the formation of "complexes", but conversely less effort has been given to the kinetics of such processes. We describe herein the "complexation" kinetics of a short linear sodium polyphosphate (PSP) with poly(allylamine hydrochloride) (PAH) in the presence of 10 mM, 0.15 M and 1 M NaCl. We find, by using a combination of physicochemical techniques, that mixtures containing a 1 to 1 molar ratio of phosphate and amino groups allow the formation of "complexes" having a few 100 nm in diameter which progressively grow to particles up to 1.5 microns in hydrodynamic diameter, the growth process being accompanied by some progressive sedimentation. During this slow aggregation kinetics, the polyelectrolytes undergo a release of counterions and the zeta potential changes from a positive value to a negative one of -20 mV which is close to the zeta potential of (PSP-PAH) n films deposited under identical physicochemical conditions. Even though the complexes have a negative electrophoretic mobility, they contain an equimolar amount of amino and phosphate groups. This allows us to make some assumption about the structure of such "complexes" and to compare them with other published structures. We will also compare them with the aggregates found during the "layer-by-layer" deposition of the same species under the same conditions. © 2012 The Owner Societies.

Kekicheff P.,Charles Sadron Institute | Schneider G.F.,Charles Sadron Institute | Schneider G.F.,Technical University of Delft | Decher G.,Charles Sadron Institute | And 2 more authors.
Langmuir | Year: 2013

Polyelectrolyte multilayers composed of poly(allylamine hydrochloride) and poly(styrene sulfonate) were assembled on 13 nm gold nanoparticles and characterized by Transmission Electron Microscopy and Atomic Force Microscopy. The direct measurement of the interactions at the molecular level using a Surface Force Apparatus revealed that the colloidal stability of such coated particles in aqueous media is brought about concomitantly by electrostatic and steric repulsive interactions. The cyanide induced dissolution of the gold cores yields either hollow nanocapsules or collapsed nanospheres, two species which are very difficult to distinguish. In contrast to the established micron sized hollow capsules, the dissolution of the nanosized gold cores may induce a substantial swelling of the polyelectrolyte complex into the central void as induced by the temporary local increase of the ionic strength. At least three layer pairs are required to maintain the structural integrity of the polyelectrolyte shells to yield hollow nanospheres. At about three layer pairs, thin nanocapsules are mechanically compressible and may collapse on themselves following mechanical stimulation to form even smaller spherical polyelectrolyte complex particles that retain the small polydispersity of the gold cores. Thus, the templating of polyelectrolyte shells around, e.g., gold nanoparticles followed by the dissolution of the respective cores constitutes a new method for the synthesis of extremely small polyelectrolyte complex particles with very low polydispersity. © 2013 American Chemical Society.

Qureshi S.S.,Charles Sadron Institute | Qureshi S.S.,Quaid-i-Azam University | Qureshi S.S.,Government of Pakistan | Zheng Z.,Charles Sadron Institute | And 6 more authors.
ACS Nano | Year: 2013

Layer-by-Layer (LbL) assembled films offer many interesting applications (e.g., in the field of nanoplasmonics), but are often mechanically feeble. The preparation of nanoprotective films of an oligomeric novolac epoxy resin with poly(ethyleneimine) using covalent LbL-assembly is described. The film growth is linear, and the thickness increment per layer pair is easily controlled by varying the polymer concentration and/or the adsorption times. The abrasion resistance of such cross-linked films was tested using a conventional rubbing machine and found to be greatly enhanced in comparison to that of classic LbL-films that are mostly assembled through electrostatic interactions. These robust LbL-films are then used to mechanically protect LbL-films that would completely be removed by a few rubbing cycles in the absence of a protective coating. A 45 nm thick LbL-film composed of gold nanoparticles and poly(allylamine hydrochloride) was chosen as an especially weak example for a functional multilayer system. The critical thickness for the protective LbL-coatings on top of the weak multilayer was determined to be about 6 layer pairs corresponding to about only 10 nm. At this thickness, the whole film withstands at least 25 abrasion cycles with a reduction of the total thickness of only about 2%. © 2013 American Chemical Society.

Gill R.,Charles Sadron Institute | Gill R.,Quaid-i-Azam University | Gill R.,Fatima Jinnah Women University | Mazhar M.,Quaid-i-Azam University | And 5 more authors.
Angewandte Chemie - International Edition | Year: 2010

Catching the end groups: A simple procedure was used for the covalent layer-by-layer assembly of homobifunctional H2N-poly(dimethoxysilane)-NH2 on SiO2 surfaces that leads to robust layer-by-layer films of optical quality (see picture; photo on left) despite the use of non-purified commercial starting materials. The films show a solvent memory for swelling and de-swelling when immersed in the corresponding solvent for each polymer. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

De Saint-Aubin C.,CNRS Mulhouse Institute of Materials Science | Hemmerle J.,French Institute of Health and Medical Research | Boulmedais F.,Charles Sadron Institute | Boulmedais F.,International Center for Frontier Research in Chemistry | And 4 more authors.
Langmuir | Year: 2012

Although never emphasized and increasingly used in organic electronics, PEDOT-PSS (poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)) layer-by-layer (lbl) film construction violates the alternation of polyanion and polycation rule stated as a prerequisit for a step-by-step film buildup. To demonstrate that this alternation is not always necessary, we studied the step-by-step construction of films using a single solution containing polycation/polyanion complexes. We investigated four different systems: PEDOT-PSS, bPEI-PSS (branched poly(ethylene imine)-poly(sodium 4-styrene sulfonate)), PDADMA-PSS (poly(diallyl dimethyl ammonium)-PSS), and PAH-PSS (poly(allylamine hydrochloride)-PSS). The film buildup obtained by spin-coating or dipping-and-drying process was monitored by ellipsometry, UV-vis-NIR spectrophotometry, and quartz-crystal microbalance. The surface morphology of the films was characterized by atomic force microscopy in tapping mode. After an initial transient regime, the different films have a linear buildup with the number of deposition steps. It appears that, when the particles composed of polyanion-polycation complex and complex aggregates in solution are more or less liquid (case of PEDOT-PSS and bPEI-PSS), our method leads to smooth films (roughness on the order of 1-2 nm). On the other hand, when these complexes are more or less solid particles (case of PDADMA-PSS and PAH-PSS), the resulting films are much rougher (typically 10 nm). Polycation/polyanion molar ratios in monomer unit of the liquid, rinsing, and drying steps are key parameters governing the film buildup process with an optimal polycation/polyanion molar ratio leading to the fastest film growth. This new and general lbl method, designated as 2-in-1 method, allows obtaining regular and controlled film buildup with a single liquid containing polyelectrolyte complexes and opens a new route for surface functionalization with polyelectrolytes. © 2012 American Chemical Society.

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