Fluorescent ionene-dye nanoparticles by electrostatic self-assembly

It is investigated that the association of linear cationic model polyelectrolytes with oppositely charged pyrenetetrasulfonate (PY) in aqueous solution. For this purpose water soluble ionenes were prepared via Menschutkin reaction from 1-4-diazabicyclo [2.2.2] octane and e.g. 1,6-dibromohexane and 1,4 dibromotransbuten. The complex formation between dye molecules PY and oppositely charged ionenes (PD4, PD6, PD4-2 and PD4coPD6) of different chemical structures in aqueous solution was studied by light scattering (LS), small angle neutron scattering (SANS), UV-Vis, fluorescence spectroscopy and atomic force microscopy (AFM). Spectrophotometric titration results revealed that PY molecules were bind to ionenes cooperative process due to π-π interaction. Cooperative binding constant KD was determined as 6.4 x 10^6 M^-1 (+ or - 10^5 M^-1). It was found that binding mode and geometry of PY is predominantly depending on inter-charge distances of corresponding ionenes. Resultant complexes have exhibited size and structure variation as a function of charge ratio (L), ionic strength, inter-charge distances. Spherical dye-ionene complexes of which radius of gyration ranging between (RG) 50 and 190 nm have been observed in PD4-PY system while this was not possible with a different ionene (PD6) or either case ionene excess. It was found that most of the PD4-PY complexes had RG / RH ~ 0.78. Based on the AFM and LS results, spherical complexes have certain colloidal stability and their size can effectively controlled by changing the L.

Electrochemiluminescence-based DNA detection using guanine oxidation at electrostatic self-assembly of Ru(bpy)(3)(2+)-doped silica nanoparticles on indium tin oxide electrode

A Ru(bpy)(3)(2+)-doped silica nanoparticle-[Ru@Silica] modified indium tin oxide electrode was prepared by simple electrostatic self-assembly technique, and one-electron catalytic oxidation of guanine bases in double-strand and denatured DNA was realized using the electrochemiluminescence detection means.

Tunable wettability of polyimide films based on electrostatic self-assembly of ionic liquids

We have demonstrated that the surface wettability of negatively charged polyimide films could be turned by electrostatic self-assembly of ionic liquids. The water contact angles of the polyimide films varied in the range 27-80 degrees for 13 different ionic liquids based on imidazolium and ammonium salts. The surface morphology of the resulting surfaces was characterized using atomic force microscopy. The results revealed that the assembly of longer-substituent cations was characterized by the formation of spherical nanoparticles that were formed due to sequent aggregation of cations on those electrostatically assembled ones via hydrophobic interaction. In this case, the counteranions are present in the assembled layers and the wettability is accordingly affected. Whereas for shorter-substituent cations, no aggregates were formed due to the less hydrophobic interaction than the electrostatic repulsive interaction between the cations, and the counteranions were absent from the assembled layers. This method can also be utilized to quantify the hydrophobicity of various ionic liquids.

Polyhedral oligomeric silsesquioxane nanocomposite thin films via layer-by-layer electrostatic self-assembly

Fabrication of ultrathin polymer composite films with low dielectric constants has been demonstrated. Octa( aminophenyl) silsesquioxane (OAPS) was synthesized and assembled with poly( acrylic acid) (PAA) and poly( styrene sulfonate) (PSS) via a layer-by-layer electrostatic self-assembly technique to yield nanoporous ultrathin films. The OAPS was soluble in water at pH 3 or lower, and suitable pH conditions for the OAPS/PAA and OAPS/PSS assemblies were determined. The multilayer formation process was studied by contact angle analysis, X-ray photoelectron spectroscopy, atomic force microscopy, quartz crystal microgravimetry, UV-vis spectroscopy, and ellipsometry. The multilayer growth was found to be steady and uniform, and the analysis of the film surface revealed a rough topography due to OAPS aggregates. The incorporation of porous OAPS molecules into the thin films significantly lowered their dielectric constants. The OAPS/PAA multilayer thin film thus prepared exhibited a dielectric constant of 2.06 compared to 2.58 for pure PAA film. The OAPS/PAA multilayer film was heated to effect cross-linking between the OAPS and the PAA layers, and the transformation was verified by reflection-absorption Fourier transform infrared spectroscopy.

Electrostatically self-assembled nanoparticles based on biomolecules

In this work, two different systems were investigated to develop fundamental understanding of the self-assembly behavior of polyelectrolytes and small organic counterions with a certain geometry. Complexes formed were characterized by light scattering in solution, as well as UV-Vis spectroscopy, analytical ultracentrifugation, gel electrophoresis, zeta potential and IR spectroscopy. The morphologies of the aggregates were observed by AFM in dried state on surface. The charge ratio, the valence and the structure of the counterion were shown to represent key parameters in the complexation. The influence of polyelectrolyte type and molecular weights was also determined for the structure formed.rnrnOne system was mainly focused on the association of double-strand DNA with non-intercalating divalent and tetravalent organic counterions. The other model system involved linear NaPSS and oligolysines. In addition, various influences on the morphology of the charged self-assembly complexes in AFM studies were discussed. It was shown that electrostatic self-assembly of DNA and non-intercalating counterions as well as of a linear synthetic polyelectrolyte with oligolysine counterions that can build mutual hydrogen bonds can yield supramolecular aggregates of a defined size. Various morphologies (flower-like, rod-like, toroidal and spherical) of the assemblies were obtained for different combinations of polyelectrolyte and counterions. Results presented in this work are of importance for the fundamental understanding of the association behavior of various polyelectrolytes and organic counterions. The selection of biopolymers for the study may give an opportunity to transfer the basic research results into biological applications, such as gene therapy or drug delivery.rn

Silver nanoparticles coated with adenine: preparation, self-assembly and application in surface-enhanced Raman scattering

We describe herein the preparation of silver nanoparticles (AgNPs) using nucleobase adenine as protecting agent through the in situ chemical reduction of AgNO3 with NaBH4 in an aqueous medium at room temperature. As-prepared AgNPs were characterized by UV-visible spectra, transmission electron microscopy and x-ray photoelectron spectroscopy. All these data confirmed the formation of AgNPs. On the basis of electrostatic interactions between as-prepared AgNPs and anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS), we successfully fabricated (PSS/AgNP)n (n = 0-9) multilayers on a 3-mercaptopropyltrimethoxysilane/AgNP functionalized indium tin oxide (ITO) substrate via the layer-by-layer self-assembly technique and characterized as-formed multilayers with UV-visible spectra. Furthermore, these ITO substrates coated with multilayers of different thickness were investigated as surface-enhanced Raman scattering (SERS)-active substrates using p-aminothiophenol as a probe molecule, implying that these multilayers substrates may be promising for a new type of SERS-active substrate.

Didodecyldimethylammonium bromide lipid bilayer-protected gold nanoparticles: Synthesis, characterization, and self-assembly

Didodecyldimethylammonium bromide (DDAB) lipid bilayer-protected gold nanoparticles (AuNPs), which were stable and hydrophilic, were synthesized by in situ reduction of HAuCl4 with NaBH4 in an aqueous medium in the presence of DDAB. As-prepared nanoparticles were characterized by UV-vis spectra, transmission electron microscopy, dynamic light scattering analysis, and X-ray photoelectron spectroscopy. All these data supported the formation of AuNPs. Fourier transform infrared spectroscopy (FTIR) and differential thermal analysis/thermogravimetric analysis data revealed that DDAB existed in a bilayer structure formed on the particle surface, resulting in a positively charged particle surface. The FTIR spectra also indicated that the DDAB bilayer coated on the surface of AuNPs was probably in the ordered gel phase with some end-gauche defects. On the basis of electrostatic interactions between such AuNPs and anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS), we successfully fabricated (PSS/AuNP)(n) multilayers on a cationic polyelectrolyte poly(ethylenimine) coated indium tin oxide substrate via the layer-by-layer self-assembly technique and characterized as-formed multilayers with UV-vis spectra and atomic force microscopy.

Effect of substrate on particle arrangement in arrays formed by self-assembly of polymer grafted nanoparticles

We show that the substrate affects the interparticle spacing in monolayer arrays with hexagonal order formed by self-assembly of polymer grafted nanoparticles. Remarkably, arrays with square packing were formed due to convective shearing at a liquid surface induced by miscibility of colloidal solution with the substrate.

Self-Assembly and Catalytic Activity of Metal Nanoparticles Immobilized in Polymer Membrane Prepared via Layer-by-Layer Approach

Densely packed nanoparticles distributed in a stable and robust thin film is a highly preferred system for utilizing the various applications of nanoparticles. Here, we report covalent bond mediated layer-by-layer (LbL) self-assembled thin films of nanoparticles embedded in polymer membrane. Polymer with complementary functional group is utilized for fabrication of thin film via covalent bonding. UV-visible spectroscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to monitor the growth of LbL thin film. Subsequently, the composite thin film is used for catalysis of an organic electron transfer reaction of p-nitrophenol to p-aminophenol by sodium borohydride. The catalytic activity of these composite films is assayed multiple times, proving its applicability as a catalyst. The kinetic data obtained by monitoring reduction of p-nitrophenol suggest that the reaction rates are directly related to the sizes of the nanoparticle and porosity of the membrane.

A room temperature, templated synthesis of lanthanide trifluoride nanoparticles and their unusual self-assembly

A new methodology has been developed for synthesizing lanthanide trifluoride (LnF(3)) nanoparticles using a simple diffusion technique. The approach uses a lanthanide based hydrogel matrix to control the kinetics of the reaction, which also acts as a stabilizing platform, thus enabling the room temperature, in situ synthesis of finely sized (3-5 nm), monodisperse nanoparticles that were found to form in an ordered pattern on the gel fibers.

Bimodality and re-entrant behaviour in the hierarchical self-assembly of polymeric nanoparticles

We show that a film of a suspension of polymer grafted nanoparticles on a liquid substrate can be employed to create two-dimensional nanostructures with a remarkable variation in the pattern length scales. The presented experiments also reveal the emergence of concentration-dependent bimodal patterns as well as re-entrant behaviour that involves length scales due to dewetting and compositional instabilities. The experimental observations are explained through a gradient dynamics model consisting of coupled evolution equations for the height of the suspension film and the concentration of polymer. Using a Flory-Huggins free energy functional for the polymer solution, we show in a linear stability analysis that the thin film undergoes dewetting and/or compositional instabilities depending on the concentration of the polymer in the solution. We argue that the formation via `hierarchical self-assembly' of various functional nanostructures observed in different systems can be explained as resulting from such an interplay of instabilities.

Self-assembly of lambda-DNA networks/Ag nanoparticles: Hybrid architecture and active-SERS substrate

In this article, highly rough and stable surface enhanced Raman scattering (SERS)-active substrates had been fabricated by a facile layer by-layer technique. Unique lambda-DNA networks and CTAB capped silver nanoparticles (AgNP) were alternatively self-assembled on the charged mica surface until a desirable number of bilayers were reached. The as-prepared hybrid architectures were characterized by UV-vis spectroscopy, tapping mode atomic force microscopy (AFM) and confocal Raman microscopy, respectively.

Photochemical synthesis and self-assembly of gold nanoparticles

Colloidal gold was prepared by UV light irradiation of the mixture of HAuCl4 aqueous solution and poly(vinyl pyrrolidone) (PVP) ethanol solution in the presence of silver ions. The resulting sheet-like nanoparticles were found to self-assemble into nanoflowers by a centrifuging process. The results of control experiments reflected that only suitable size sheet-like nanoparticles could assemble into the flower-like structures. The presence of Ag ions and PVP are essential for the formation process of nanoflowers.

Reducing HAuCl4 by the C-60 dianion: C-60-directed self-assembly of gold nanoparticles into novel fullerene bound gold nanoassemblies

The C-60 dianion is used to reduce tetrachloroauric acid (HAuCl4) for the first time; three-dimensional C-60 bound gold (Au-C-60) nanoclusters are obtained from C-60-directed self-assembly of gold nanoparticles due to the strong affinities of Au-C-60 and C-60-C-60. The process was monitored in situ by UV-vis-NIR spectroscopy. The resulting Au-C-60 nanoclusters were characterized using transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy-dispersive spectroscopy (EDS), x-ray powder diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and FT-IR and Raman spectroscopies.

A one-dimensional network from the self-assembly of gold nanoparticles by a necklace-like polyelectrolyte template mediated by metallic ion coordination

A new approach to one-dimensional organization of gold nanoparticles (2-4 nm) is described, using poly(4-vinylpyridine) (P4VP) molecular chain as a template with the mediation of free Cu2+ ion coordination. The assembly was conducted on freshly prepared mica surfaces and in aqueous solution, respectively. The surface assembly was characterized by tapping mode atomic force microscopy (AFM), observing the physisorbed molecules in their chain-like conformation with an average height of 0.4 nm.