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PubMedDate not supplied

Polyelectrolyte complexes and layer-by-layer capsules from chitosan/chitosan sulfate.

Polyelectrolyte complex formation of chitosans of varying average molecular weight and degree of acetylation with chitosan sulfate or poly(styrene sulfonate) was studied by static light scattering in dilute solution at various ionic strengths. Unlike the molecular weight, the degree of acetylation was found to have a significant effect on the resultant structural densities of the complexes. The same system was applied to the preparation of micrometer-sized hollow shells by means of a layer-by-layer technique (in total eight layers). Their behavior toward fluorescent probes such as fluorescein and rhodamin 6G or fluorescein isothiocyanate labeled dextrans at various ionic strengths and pH (observed by confocal laser light scanning microscopy) could be understood through a discussion of electrostatic forces between the highly charged shells and the probes to be dominant. At an ionic strength of 0.1 M and above, charge effects are largely suppressed (screening effect) and a size-dependent "cutoff" for the permeation of the macromolecular fluorophore was observed.

Acetylation↗

PubMedDate not supplied

Light-induced storage in layer-by-layer films of chitosan and an azo dye.

The buildup of layer-by-layer (LBL) films from chitosan and the azodye Ponceau-S (PS) was investigated under various experimental conditions, and the resulting films were used in optical storage experiments. The kinetics for the writing process in optical storage was faster for LBL films prepared at low pHs, probably because the films had a larger free volume for isomerization of the chromophores. The nanostructured nature of the LBL films also affected the crystallinity of chitosan, which was considerably decreased in this type of film as chitosan became protonated because of the electrostatic interactions between adjacent layers.

Azo Compounds↗

PubMedDate not supplied

Incorporation of alkaline phosphatase into layer-by-layer polyelectrolyte films on the surface of affi-gel heparin beads: physicochemical characterization and evaluation of the enzyme stability.

The preparation of functionalized beads in the micrometer size range that can be used to probe the action of immobilized biomolecules on cell cultures during controlled periods of time is of fundamental importance in cell biology. However, the preparation and characterization of such particles is tedious because of their fast sedimentation. It is hence difficult to prepare such beads in a reproducible manner. This highlights the need to prepare an important batch of functionnalized particles and to store them under conditions where the loss of biological activity is minimized. The aim of this paper was to immobilize alkaline phosphatase (AP) as a model enzyme on the surface of Affi-gel heparin beads functionnalized by means of a layer-by-layer (LBL) film made of poly-l-glutamic (PGA) acid and poly-l-lysine (PLL). The enzyme has been adsorbed either on the top of the LBL film or embedded under five polyelectrolyte layers. When embedded, the enzyme was not released in buffer and retained more than 30% of its initial activity after 3 months of storage at 4 degrees C. However, when the enzyme was adsorbed on top of the LBL film, about 80% of the adsorbed enzyme was released in the buffer after a few days of storage. Longer storage did not lead to any further desorption and the remaining enzyme displayed the same evolution of its activity with time as the embedded enzyme. The time evolution of the enzyme activity on the beads is compared with that in solution alone and in the presence of PGA and PLL separately.

Alkaline Phosphatase↗

PubMedDate not supplied

Surface-relief gratings and photoinduced birefringence in layer-by-layer films of chitosan and an azopolymer.

Layer-by-layer (LBL) films of chitosan alternated with an azopolymer, PS119, have been used for optical storage and fabrication of surface-relief gratings. The optical properties stem from the trans-cis-trans isomerization cycles undergone by the azochromophore, with a kinetics for writing the birefringence pattern that is much slower than in the spin-coated or cast films of azopolymers. The long writing times, of the order of 100 s, are due to the electrostatic interactions between adjacent chitosan and PS119 layers. Such interactions are also responsible for other features in the LBL films, namely the increase in the amount of adsorbed material when the pH of the preparation solution is decreased and the large residual birefringence after the writing laser is switched off. Gratings could be inscribed with s-polarized but not with p-polarized light, indicating a mass transport process associated with photodegradation.

Azo Compounds↗

PubMed2003

Layer-by-layer growth of metal-metal bonded supramolecular thin films and its use in the fabrication of lateral nanoscale devices.

Layer-by-layer self-assembly of metal-metal bonded supramolecules is demonstrated and utilized to fabricate lateral nanoelectronic devices. Mercaptoethylpyridine is used to bind to Au substrates and to template the sequential assembly of alternating layers of redox active dirhodium complexes [Rh2(DAniF)2]2(O2CCH2CO2)2 (DAniF = N,N'-di-p-anisylformamidinate) and conjugated organic ligands trans-1,2-bis(4-pyridyl)ethylene. Optical spectroscopy and atomic force microscopy show that the structure and composition of these thin films are similar to those found in tightly packed single crystals. Electrochemical studies of these films grown on Au substrates reveal a reversible oxidation wave at approximately 406 mV, corresponding to the one electron oxidation of the Rh24+ center. This directed assembly technique has been used to fabricate lateral nano-electronic devices in which the supramolecules span the channels. Tailoring the chemistry of the templating ligand enables assembly on desired surfaces and engineering the chemistry of the supramolecules' dimetal units and coordinating ligands may tune the device characteristics.

Journal Article↗

PubMed2004

Probing the structure and dynamics of end-grafted flexible polymer chain layers by combined atomic force-electrochemical microscopy. Cyclic voltammetry within nanometer-thick macromolecular poly(ethylene glycol) layers.

The combined atomic force-electrochemical microscopy (AFM-SECM) technique was used in aqueous solution to determine both the static and dynamical properties of nanometer-thick monolayers of poly(ethylene glycol) (PEG) chains end-grafted to a gold substrate surface. Approach of a microelectrode tip from a redox end-labeled PEG layer triggered a tip-to-substrate cycling motion of the chains' free ends as a result of the redox heads' oxidation at the tip and re-reduction at the substrate surface. As few as approximately 200 chains at a time could be addressed in such a way. Quantitative analysis of the data, in the light of a simple model of elastic bounded diffusion SECM positive feedback, gave access to the end-tethered polymer layer thickness and the end-to-end diffusion coefficient of the chains. The thickness of the grafted PEG layer was shown to increase with the chain surface coverage, while the end-to-end diffusion coefficient was found to be constant and close to the one predicted by Rouse dynamics. At close tip-substrate separation, slowing of the chains' motion, as a consequence of their vertical confinement within the tip-substrate gap, was observed and quantitatively modeled.

Journal Article↗

PubMed2005

Increasing the oxidative stability of liquid and dried tuna oil-in-water emulsions with electrostatic layer-by-layer deposition technology.

Omega-3 Fatty acids have numerous health benefits, but their addition to foods is limited by oxidative rancidity. Engineering the interfacial membrane of oil-in-water emulsion droplets to produce a cationic and/or thick interface is an effective method to control lipid oxidation. Cationic and thick emulsion droplet interfacial membranes can be produced by an electrostatic layer-by-layer deposition technique resulting in droplets that are coated by multiple layers of emulsifiers. Tuna oil-in-water emulsion droplets coated by lecithin and chitosan produce cationic emulsion droplets that are more oxidatively stable than emulsions coated by lecithin alone. Ethylenediaminetetraacetic acid (EDTA) was able to increase the oxidative stability of emulsions stabilized with lecithin and chitosan more effectively than mixed tocopherols. The combination of EDTA and mixed tocopherols was not more effective than EDTA alone suggesting that control of prooxidant metals was the most important antioxidant technology. The production of emulsion droplets coated with lecithin and chitosan could be an excellent technology for stabilization of oxidatively unstable lipids for use in a variety of food products.

Animals↗

PubMed2004

Collective and individual plasmon resonances in nanoparticle films obtained by spin-assisted layer-by-layer assembly.

Nanoscale uniform films containing gold nanoparticle and polyelectrolyte multilayer structures were fabricated by the using spin-assembly or spin-assisted layer-by-layer (SA-LbL) deposition technique. These SA-LbL films with a general formula [Au/(PAH-PSS)nPAH]m possessed a well-organized microstructure with uniform surface morphology and high surface quality at a large scale (tens of micrometers across). Plasmon resonance peaks from isolated nanoparticles and interparticle interactions were revealed in the UV-visible extinction spectra of the SA-LbL films. All films showed the strong extinction peak in the region of 510-550 nm, which is due to the plasmon resonance of the individual gold nanoparticles redshifted because of a local dielectric environment. For films with sufficient density of gold nanoparticles within the layers, the second strong peak was consistently observed between 620 and 660 nm, which is the collective plasmon resonance from intralayer interparticle coupling. Finally, we suggested that, for certain film designs, interlayer interparticle resonance might be revealed as an independent contribution at 800 nm in UV-visible spectra. The observation of independent and concurrent individual, intralayer, and interlayer plasmon resonances can be critical for sensing applications, which involve monitoring of optomechanical properties of ultrathin optically active compliant membranes.

Journal Article↗

PubMed2004

Self-doping effect in poly(o-methoxyaniline)/poly(3-thiopheneacetic acid) layer-by-layer films.

Nanostructured films from two conducting polymers, poly(o-methoxyaniline) (POMA) and poly(3-thiopheneacetic acid) (PTAA), were fabricated with the layer-by-layer (LBL) technique. The electrochemical response of the LBL films differs from that of a POMA cast film, even in a potential range where PTAA is inactive. This is attributed to differences in the diffusion-controlled charge and mass transport, where distinct ionic species participate in the LBL films, as demonstrated by quartz crystal microbalance measurements. The results show that the transport properties of conducting polymers can be changed by alternation with layers of appropriate materials in LBL films.

Journal Article↗

PubMed2004

Polyelectrolyte multilayer films of different charge density copolymers with synergistic nonelectrostatic interactions prepared by the layer-by-layer technique.

Random copolymers composed of diallyldimethylammonium chloride (DADMAC) and acrylamide with varying contents (8-100 mol %) of the cationic DADMAC component were alternated with polyanionic, fully charged poly(styrenesulfonate) to form multilayer thin films. UV-vis spectrophotometry, FTIR spectroscopy, and quartz-crystal microgravimetry (QCM) were employed to follow multilayer buildup. Atomic force microscopy was used to obtain structural information. Layer thicknesses have been determined with small-angle X-ray scattering and ellipsometry, in addition to values calculated from QCM. While in previous work, a critical charge density limit could be observed, below which no layer growth is possible; in this system, multilayer formation takes place with copolymers with charge densities as low as 8 mol %. Instead of a continuous increase of adsorbed amounts with decreasing charge density above the critical charge density, as found in previous work, similar layer thicknesses for films with 100 and 8 mol % charged polyelectrolytes and maximally adsorbed amounts for copolymers in an intermediate charge density region have been found. This adsorption behavior is explained in terms of synergistic nonelectrostatic interactions between the polyelectrolytes used.

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PubMed2004

Layer by layer characterization of 1-octadecanol films on a Au(111) electrode surface. "In situ" polarization modulation infrared reflection absorption spectroscopy and electrochemical studies.

Bilayers of 1-octadecanol were transferred from the gas-solution interface onto a Au(111) electrode surface using either the horizontal touch or the Langmuir-Blodgett (LB) technique. The horizontal touch method gives an X-type film in which the molecule in the bottom layer is oriented with the tail toward the metal and the head toward the tail of the molecule in the top layer (head to tail orientation). The LB technique allows one to build not only X but also a Y bilayer, in which the molecules in the two leaflets are oriented tail to tail with the polar heads facing the metal and the solution. The properties of these films were characterized by electrochemistry and polarization modulation infrared reflection absorption spectroscopy (PM IRRAS). The freshly prepared X bilayer is defect free and is characterized by a low capacity of 0.84 microF cm(-2). The bilayer may be desorbed from the electrode surface at E < -0.6 V and readsorbed again at more positive potentials. The potential-driven readsorption gives a Y film with a higher capacity of 2.2 microF cm(-2). The IR studies of a mixed bilayer composed of one hydrogenated leaflet and a second deuterated leaflet showed that 1-octadecanol molecules assume a more vertical orientation in the leaflet facing the solution than in the leaflet in contact with the metal. Upon desorption of the X film, the molecules in the bottom layer flip-flop and the readsorbed film assumes the Y structure. Smaller tilt angles are observed in the X film as opposed to the Y film.

Journal Article↗

PubMed2004

Layer-by-layer assembly of ordinary and composite coordination multilayers.

Coordination self-assembly of bishydroxamate-based metal-organic multilayers on gold employing a layer-by-layer (LbL) approach was investigated. It is shown that the solution chemistry of the participating metal ion has a marked influence on the composition and properties of the multilayers. Use of Ce4+ and particularly zirconium(IV) acetylacetonate (Zr(acac)4) solutions in the ion-binding step of multilayer construction leads to multilayers with a near-stoichiometric metal ion-to-ligand ratio, suggesting a structure close to that predicted by a simple coordination self-assembly scheme. On the other hand use of a ZrCl4 solution as the source of metal ions in the multilayer construction leads to a multilayer with greater thickness and a large excess of Zr(IV), evenly distributed between the organic layers. In the latter case, a ratio of ca. 1:2 between the excess Zr and oxygen, as well as long-term Zr4+ binding experiments showing deposition of ZrO2, suggest the formation of a zirconia-type nanophase between the bishydroxamate organic repeat units during multilayer self-assembly. Hence, while the multilayer prepared using Zr(acac)4 solution appears to represent a "true" coordination-based structure, the one prepared using ZrCl4 is best described as a composite organic-ceramic multilayer. Composite multilayers prepared in this way display different properties from those of the stoichiometric ones, such as improved dielectric behavior and higher stiffness. Even greater mechanical stability is obtained with multilayers constructed using alternate binding of ZrCl4 and Ce4+. The concept of LbL formation of coordination-based composite organic-ceramic structures may be useful in obtaining nanometer-scale structures with tunable properties.

Cesium↗

PubMed2004

X-ray nanoscale profiling of layer-by-layer assembled metal/organophosphonate films.

The nanoscale structure of multilayer metal/phosphonate thin films prepared via a layer-by-layer assembly process was studied using specular X-ray reflectivity (XRR), X-ray fluorescence (XRF), and long-period X-ray standing wave (XSW) analysis. After the SiO(2) X-ray mirror surfaces were functionalized with a monolayer film terminated with phosphonate groups, the organic multilayer films were assembled by alternating immersions in (a) aqueous solutions containing Zr(4+), Hf(4+), or Y(3+) cations and then (b) organic solvent solutions of PO(3)-R-PO(3), where R was a porphyrin or porphyrin-square spacer molecule. The different heavy metal cations provided X-ray fluorescence marker layers at different heights within the different multilayer assemblies. The XSW measurements used a 22 nm period Si/Mo multilayer mirror. The long-period XSW generated by the zeroth-order (total external reflection) through fourth-order Bragg diffraction conditions made it possible to examine the Fourier transforms of the fluorescent atom distributions over a much larger q(z)() range in reciprocal space than previously achieved.

Membranes, Artificial↗

PubMed2004

Electrostatic layer-by-layer assembled carbon nanotube multilayer film and its electrocatalytic activity for O2 reduction.

Multilayer films of shortened multiwalled carbon nanotubes (MWNTs) are homogeneously and stably assembled on glassy carbon electrodes with the layer-by-layer (LBL) method, based on electrostatic interaction of positively charged poly(diallyldimethylammonium chloride) and negatively charged and shortened MWNTs. The film assembly and electrochemical property as well as the electrocatalytic activity toward O2 reduction of the MWNT multilayer film are studied. Scanning electron microscopy, the quartz crystal microbalance technique, ultraviolet-visible-near-infrared spectroscopy, and cyclic voltammetry are used for characterization of film assembly. Experimental results revealed that film growth is uniform, almost with the same coverage of the MWNTs in each layer, and that the assembled MWNTs are mainly in the form of small bundles or single tubes on the electrodes. Electrochemical studies indicate that the LBL assembled MWNT films possess a remarkable electrocatalytic activity toward O2 reduction in alkaline media. This property, combined with the well-dispersed, porous and conductive features of the MWNT film illustrated with the LBL method, suggests the potential application of the MWNT film for constructing an efficient alkaline air electrode for energy conversions.

Journal Article↗

PubMed2004

Highly ion conductive poly(ethylene oxide)-based solid polymer electrolytes from hydrogen bonding layer-by-layer assembly.

We report the development of a solid polymer electrolyte film from hydrogen bonding layer-by-layer (LBL) assembly that outperforms previously reported LBL assembled films and approaches battery integration capability. Films were fabricated by alternating deposition of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) layers from aqueous solutions. Film quality benefits from increasing PEO molecular weight even into the 10(6) range due to the intrinsically low PEO/PAA cross-link density. Assembly is disrupted at pH near the PAA ionization onset, and a potential mechanism for modulating PEO:PAA ratio within assembled films by manipulating pH is discussed. Ionic conductivity of 5 x 10(-5) S/cm is achievable after short exposure to 100% relative humidity (RH) for plasticization. Adding free ions by exposing PEO/ PAA films to lithium salt solutions enhanced conductivity to greater than 10(-5) S/cm at only 52% RH and tentatively greater than 10(-4) S/cm at 100% RH. The excellent stability of PEO/PAA films even when exposed to 1.0 M salt solutions led to an exploration of LBL assembly with added electrolyte present in the adsorption step. Fortuitously, the modulation of PEO/PAA assembly by ionic strength is analogous to that of electrostatic LBL assembly and can be attributed to electrolyte interactions with PEO and PAA. Dry ionic conductivity was enhanced in films assembled in the presence of salt as compared to films that were merely exposed to salt after assembly, implying different morphologies. These results reveal clear directions for the evolution of these promising solid polymer electrolytes into elements appropriate for electrochemical power storage and generation applications.

Journal Article↗

PubMed2005

Molecular dynamics simulations of layer-by-layer assembly of polyelectrolytes at charged surfaces: effects of chain degree of polymerization and fraction of charged monomers.

We performed molecular dynamics simulations of the electrostatic assembly of multilayers of flexible polyelectrolytes at a charged surface. The multilayer build-up was achieved through sequential adsorption of oppositely charged polymers in a layer-by-layer fashion from dilute polyelectrolyte solutions. The steady-state multilayer growth proceeds through a charge reversal of the adsorbed polymeric film which leads to a linear increase in the polymer surface coverage after completion of the first few deposition steps. Moreover, substantial intermixing between chains adsorbed during different deposition steps is observed. This intermixing is consistent with the observed requirement for several deposition steps to transpire for completion of a single layer. However, despite chain intermixing, there are almost perfect periodic oscillations of the density difference between monomers belonging to positively and negatively charged macromolecules in the adsorbed film. Weakly charged chains show higher polymer surface coverage than strongly charged ones.

Journal Article↗

PubMed2005

Layer-by-layer assembly of nacre-like nanostructured composites with antimicrobial properties.

In a recent report, we have presented the layer-by-layer (LBL) assembly of a biomimetic nanostructured composite from Na(+)-montmorillonite clay nanosheets and poly(diallylmethylammonium chloride) (Tang, Z.; Kotov, N.; Magonov, S.; Ozturk, B. Nat. Mater. 2003, 2, 413). The structure, deformation mechanism, and mechanical properties of the material are very similar to those of natural nacre and lamellar bones. This fact prompts further investigation of these composites as potential bone implants. LBL assembly affords preparation of multifunctional composites, and here we demonstrate that not only mechanical strength, but also antibacterial activity, can be introduced in these implantable materials by alternating clay layers with starch-stabilized silver nanoparticles. The resulting composite showed excellent structural stability with no detectable levels of silver lost over a 1 month period. Evaluation of the antibacterial properties showed almost complete growth inhibition of E. coli over an 18 h period. The amount of silver eluted from the LBL composite over a 1 month period was determined to be only 0.5-3.0 microg/L. This concentration of silver did not prevent the growth of the mammalian tissue cultures. The LBL composite has shown biocompatibility with the human osteoblast cell line.

Animals↗

PubMed2006

Fuzzy ternary particle systems by surface-initiated atom transfer radical polymerization from layer-by-layer colloidal core-shell macroinitiator particles.

We report the synthesis of ternary polymer particle material systems composed of (a) a spherical colloidal particle core, coated with (b) a polyelectrolyte intermediate shell, and followed by (c) a grafted polymer brush prepared by surface-initiated polymerization as the outer shell. The layer-by-layer (LbL) deposition process was utilized to create a functional intermediate shell of poly(diallyl-dimethylammonium chloride)/poly(acrylic acid) multilayers on the colloid template with the final layer containing an atom transfer radical polymerization (ATRP) macroinitiator polyelectrolyte. The intermediate core-shell architecture was analyzed with FT-IR, electrophoretic mobililty (zeta-potential) measurements, atomic force microscopy, and transmission electron microscopy (TEM) techniques. The particles were then utilized as macroinitiators for the surface-initiated ATRP grafting process for poly(methyl methacrylate) polymer brush. The polymer grafting was confirmed with thermo gravimetric analysis, FT-IR, and TEM. The polymer brush formed the outermost shell for a ternary colloidal particle system. By combining the LbL and surface-initiated ATRP methods to produce controllable multidomain core-shell architectures, interesting functional properties should be obtainable based on independent polyelectrolyte and polymer brush behavior.

Journal Article↗