Surface-enhanced spectroscopy on plasmonic oligomers assembled by AFM nanoxerography.

Surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF) from individual plasmonic oligomers are investigated by confocal Raman micro-spectroscopy and time-resolved fluorescence microscopy coupled to steady state micro-spectroscopy. The nanoparticle (NP) oligomers are made of either ligand protected Au or Au@SiO2 core-shell colloidal NPs, which were assembled into ordered arrays by atomic force microscopy (AFM) nanoxerography. A strong dependence of the SERS emission on the polarization of incident light relative to the specific geometry of the plasmonic oligomer was observed. The SEF studies, performed on a large collection of NP oligomers of various known configurations showed interesting fluorophore decay rate modification and red-shift of the emission spectra. The experimental results are analyzed theoretically by employing finite-difference time-domain (FDTD) simulations on equivalent realistic structures, within the local density of optical states (LDOS) framework. The presented results, together with the proven potential of the LDOS approach as a useful common tool for analyzing both SERS and SEF effects further the general understanding of plasmon-related phenomena in nanoparticle oligomers.

Small angle X-ray scattering coupled with in situ electromechanical probing of nanoparticle-based resistive strain gauges.

A comprehensive study on the electromechanical behavior of nanoparticle-based resistive strain gauges in action through normal and grazing incidence small angle X-ray scattering (SAXS/GISAXS) investigations is presented. The strain gauges were fabricated from arrays of colloidal gold nanoparticle (NP) wires assembled on flexible polyethylene terephthalate and polyimide substrates by convective self-assembly. Microstructural changes (mean interparticle distance variations) within these NP wires under uniaxial stretching estimated by SAXS/GISAXS are correlated to their macroscopic electrical resistance variations. SAXS measurements suggest a linear longitudinal extension and transversal contraction of the NP wires with applied strain (0 to ∼ 13%). The slope of this longitudinal variation is less than unity, implying a partial strain transfer from the substrate to the NP wires. The simultaneously measured electrical resistance of the strain gauges shows an exponential variation within the elastic domain of the substrate deformation, consistent with electron tunnelling through the interparticle gaps. A slower variation observed within the plastic domain suggests the formation of new electronic conduction pathways. Implications of transversal contraction of the NP wires on the directional sensitivities of strain gauges are evaluated by simulating electronic conduction in models mimicking a realistic NP arrangement. A loss of directionality of the NP-based strain gauges due to transversal current flow within the NP wires is deduced.

Vibrational and electronic excitations in gold nanocrystals.

An experimental analysis of all elementary excitations--phonons and electron-holes--in gold nanocrystals has been performed using plasmon resonance Raman scattering. Assemblies of monodisperse, single-crystalline gold nanoparticles, specific substrates and specific experimental configurations have been used. Three types of excitations are successively analyzed: collective quasi-acoustical vibrations of the particles (Lamb's modes), electron-hole excitations (creating the so-called "background" in surface-enhanced Raman scattering) and ensembles of atomic vibrations ("bulk" phonons). The experimental vibrational density of states extracted from the latter contribution is successfully compared with theoretical estimations performed using atomic simulations. The dominant role of surface atoms over the core ones on lattice dynamics is clearly demonstrated. Consequences on the thermodynamic properties of nanocrystals such as the decrease of the characteristic Debye temperature are also considered.

Dynamics of Dielectrophoretic-Force-Directed Assembly of NaYF4 Colloidal Nanocrystals into Tunable Multilayered Micropatterns.

The dynamics of dielectrophoretic-force-directed assembly of polarizable colloidal upconverting ß-NaYF4 nanocrystals into tunable multilayers on charge micropatterns written by atomic force microscopy is investigated. Multilayered nanocrystal assembly by this nanoxerography process occurs in two phases. During the first phase typically lasting a few minutes, the nanocrystal assemblies grow up to a maximum thickness under the influence of strong dielectrophoretic forces exerted by the charge patterns. Subsequently, the nanocrystals start to diffuse back into the solvent, leaving a single layer attached to the charge patterns. A theoretical model based on the Fokker-Planck equation is formulated to describe this dynamics involving an interplay of diffusive and dielectrophoretic forces. Being in good agreement with the experimental results, this approach may be reliably extended to simulate the directed assembly of other types of polarizable colloids from liquid phase by nanoxerography.

3D assembly of upconverting NaYF4 nanocrystals by AFM nanoxerography: creation of anti-counterfeiting microtags.

Formation of 3D close-packed assemblies of upconverting NaYF4 colloidal nanocrystals (NCs) on surfaces, by Atomic Force Microscopy (AFM) nanoxerography is presented. The surface potential of the charge patterns, the NC concentration, the polarizability of the NCs and the polarity of the dispersing solvent are identified as the key parameters controlling the assembly of NaYF4 NCs into micropatterns of the desired 3D architecture. This insight allowed us to fabricate micrometer sized Quick Response (QR) codes encoded in terms of upconversion luminescence intensity or color. Topographically hidden messages could also be readily incorporated within these microtags. This work demonstrates that AFM nanoxerography has enormous potential for generating high-security anti-counterfeiting microtags.

Electron transport in gold colloidal nanoparticle-based strain gauges.

A systematic approach for understanding the electron transport mechanisms in resistive strain gauges based on assemblies of gold colloidal nanoparticles (NPs) protected by organic ligands is described. The strain gauges were fabricated from parallel micrometer wide wires made of 14 nm gold (Au) colloidal NPs on polyethylene terephthalate substrates, elaborated by convective self-assembly. Electron transport in such devices occurs by inter-particle electron tunneling through the tunnel barrier imposed by the organic ligands protecting the NPs. This tunnel barrier was varied by changing the nature of organic ligands coating the nanoparticles: citrate (CIT), phosphines (BSPP, TDSP) and thiols (MPA, MUDA). Electro-mechanical tests indicate that only the gold NPs protected by phosphine and thiol ligands yield high gauge sensitivity. Temperature-dependent resistance measurements are explained using the 'regular island array model' that extracts transport parameters, i.e., the tunneling decay constant ß and the Coulomb charging energy E(C). This reveals that the Au@CIT nanoparticle assemblies exhibit a behavior characteristic of a strong-coupling regime, whereas those of Au@BSPP, Au@TDSP, Au@MPA and Au@MUDA nanoparticles manifest a weak-coupling regime. A comparison of the parameters extracted from the two methods indicates that the most sensitive gauges in the weak-coupling regime feature the highest ß. Moreover, the E(C) values of these 14 nm NPs cannot be neglected in determining the ß values.

Microarrays of gold nanoparticle clusters fabricated by Stop&Go convective self-assembly for SERS-based sensor chips.

SERS substrates fabricated from chemically synthesized nanoparticles (NPs) offer a distinct advantage of localizing and enhancing the electromagnetic fields by facile tuning of NP size, shape and interparticle distances. In this report, two-dimensional arrays of micrometre-sized clusters of gold nanoparticles protected by (i) sodium citrate and (ii) tris(2,4-dimethyl-5-sulfonatophenyl)phosphine (TDSP) ligands were directly assembled from colloidal suspensions onto flat, non-patterned substrates by discontinuous ('Stop&Go') convective self-assembly. The micrometric spacing between the NP clusters makes it easy to address them individually by confocal Raman microscopy. The packing of the gold NPs within these clusters with interparticle spacings of the order of nanometres leads to an optical response dominated by coupled surface plasmon resonances, and favours a strong enhancement of electromagnetic fields useful for surface enhanced Raman scattering (SERS). These NP clusters make very uniform SERS substrates, with reproducible SERS responses from cluster to cluster. The potential of these NP clusters for optical biosensing is demonstrated by the SERS detection of a biologically relevant molecule, cytosine, adsorbed onto the NP clusters. The presented results are promising for designing an original class of nanoparticle-based SERS microarrays. The new paradigm of convective self-assembly could be exploited generally for the patterning of various other types of colloidal micro- and nano-objects, such as semiconducting NPs, magnetic NPs, bacteria or proteins.

Size-selective 2D ordering of gold nanoparticles using surface topography of self-assembled diamide template.

Size-selective organization of ~2 nm dodecanethiol stabilized gold nanoparticles (AuNPs) into periodic 1D arrays by using the surface topographical features of a soft template is described. The template consists of micrometer length nanotapes organized into nanosheets with periodic valleys running along their length and is generated by the hierarchical self-assembly of a diamide molecule (BHPB) in cyclohexane. The AuNP ordering achieved simply by mixing the preformed template with the readily available ~2 nm dodecanethiol stabilized AuNPs is comparable to those obtained using programmable DNA and functional block copolymers. The observed periodicity of the AuNP arrays provided valuable structural clues about the organization of nanotapes into nanosheets. Self-assembling BHPB molecules in the presence of AuNPs by heating and cooling the two components led to a comparatively disordered organization because the template structure was changed under these conditions. Moreover, the template could not order larger AuNPs (~5 nm) into a similar 1D array, owing to the steric restriction imposed by the dimension of the valleys on the template. Interestingly, this geometric constraint led to AuNP size sorting when a polydisperse sample (2.5 ± 0.9 nm) was used for organization, with AuNPs attached to the template edges being larger (≥2.2 ± 0.9 nm) than those associated to the inner valleys (1.6 ± 0.8 nm). This is a unique example of size-sorting induced by the surface topographical features of a soft template.

High-sensitivity strain gauge based on a single wire of gold nanoparticles fabricated by stop-and-go convective self-assembly.

High-sensitivity strain gauges based on single wires of close-packed 14 nm colloidal gold nanoparticles are obtained by a novel variant of convective self-assembly (CSA). This CSA mode named stop-and-go CSA enables the fabrication of nanoparticle wires only a few micrometers wide, separated by distances that can be easily tuned over tens to hundreds of micrometers. Nanoparticle wires are obtained in a single step by direct deposition of nanoparticles from suspensions onto flexible polyethylene terephthalate films, without any lithographic prepatterning. When connected between two electrodes, such single nanoparticle wires function as miniature resistive strain gauges. The high sensitivity, repeatability, and robustness demonstrated by these single-wire strain gauges make them extremely promising for integration into micro-electromechanical systems or for high-resolution strain mapping.

Coulomb force directed single and binary assembly of nanoparticles from aqueous dispersions by AFM nanoxerography.

We present a simple protocol to obtain versatile assemblies of nanoparticles from aqueous dispersions onto charge patterns written by atomic force microscopy, on a 100 nm thin film of polymethylmethacrylate spin-coated on silicon wafers. This protocol of nanoxerography uses a two-stage development involving incubation of the desired aqueous colloidal dispersion on charge patterns and subsequent immersion in an adequate water-soluble alcohol. The whole process takes only a few minutes. Numerical simulations of the evolution of the electric field generated by charge patterns in various solvents are done to resolve the mechanism by which nanoparticle assembly occurs. The generic nature of this protocol is demonstrated by constructing various assemblies of charged organic/inorganic/metallic (latex, silica, gold) nanoparticles of different sizes (3 to 100 nm) and surface functionalities from aqueous dispersions onto charge patterns of complex geometries. We also demonstrate that it is possible to construct a binary assembly of nanoparticles on a pattern made of positive and negative charges generated in a single charge writing step, by sequential developments in two aqueous dispersions of oppositely charged particles. This protocol literally extends the spectra of eligible colloids that can be assembled by nanoxerography and paves the way for building complex assemblies of nanoparticles on predefined areas of surfaces, which could be useful for the elaboration of nanoparticle-based functional devices.

Facile ligand-exchange with polyvinylpyrrolidone and subsequent silica coating of hydrophobic upconverting beta-NaYF(4):Yb(3+)/Er(3+) nanoparticles.

A facile ligand-exchange strategy with a water-soluble polymer, i.e. polyvinylpyrrolidone (PVP), to replace the surface passivating oleate ligands on the beta-NaYF(4) nanoparticle surface is reported. Highly monodisperse oleate-stabilized beta-NaYF(4) nanoparticles were synthesized and the oleates were exchanged with a commercially available PVP allowing the phase transfer of these nanoparticles. The exchanged nanoparticles are readily dispersible in water and other polar solvents. To show the effectiveness of the exchange reaction we used the affinity of the PVP chains to silica and coated the nanoparticles with a uniform, thin silica shell. The PVP exchanged and silica-coated nanoparticles show longer colloidal stability and no surfactant related problems as compared to the reverse microemulsion-based silica-coated nanoparticles, which show a high tendency to aggregate, when removed from the microemulsion. The optical properties of the ligand-exchanged nanoparticles dispersed in water were compared with that of the oleate-stabilized nanoparticles in organic solvents. A decrease in the upconversion emission intensity and a different relative ratio of the green and red upconverted light were observed for the particles dispersed in water after ligand-exchange. PVP is a highly biocompatible polymer and is reported to have a longer blood circulation time and very low accumulation in vital organs, two highly desired properties for in vivo studies. This ligand-exchange strategy opens a new pathway to study the use of beta-NaYF(4) for biological applications in vivo.

Molecular hydrogels from bile acid analogues with neutral side chains: network architectures and viscoelastic properties. Junction zones, spherulites, and crystallites: phenomenological aspects of the gel metastability.

Structural and rheological properties of hydrogels made up of neutral bile acid derivatives are studied. Complementary scattering, diffraction, and microscopy techniques provide a precise structural description of the network architecture and its variation as a function of concentration, aging time, composition of the solvent, and type of gelator. Two derivatives (TH and PH) are considered as presenting favorable scattering features to approach the issue of the competition between gelation versus crystallization. PH and TH fibers are semirigid cylinders with monodisperse cross-sections (R(0) = 92 and 80 A, respectively) involving 25 or 12 molecules per cross-sectional repeating unit along the fiber axis. Bundles are cross-links in the networks, and a scattering protocol is developed to determine the nodal and fibrillar fractions in the networks. The effects of alcoholic mixtures, dimethylsulfoxide, and temperature on the network properties are analyzed in terms of the bending modulus of the fibers, the degree of nonaffine character of the regime of deformation, and the dispersion degree of the nodal heterogeneities. It is shown that fibers are semirigid and the scaling laws of the elasticity of the gels with the concentration (exponent (5)/(2)) also support the theoretical context. Head-to-tail molecular arrangements are shown to be similar in the solid and gel phases. Birefringent textures show that spherulitic microdomains coexist in the network texture and are the seeds for a slow crystallization process. The whole pattern might be more general for numerous other self-assembled fibrillar networks found in molecular gels.

Ammonium lithocholate nanotubes: stability and copper metallization.

Ammonium lithocholate nanotubes (NHLC) have been prepared in alkaline ammonia solutions and exhibited remarkable monodisperse cross-sectional dimensions (external diameter = 52 nm) as shown by cryo-transmission electron microscopy measurements. A classical electroless metallic replication method was used with a single poly(ethylene-imine) PEI layer coating the negatively charged NHLC nanotubes. Short copper rods (external diameter ∼ 80 nm) were observed by scanning electron microscopy that corresponded to the original organic templates. The results obtained in acidic conditions are analyzed in terms of the lifetime of the self-assembled structures and formation of bundles of tubes. Dynamic light scattering measurements and optical observations show that the system in the presence of controlled amounts of hydrochloric acid is stable enough to account for a metallic replication in acidic conditions. An average apparent diffusion coefficient of the organic NHLC assemblies is extracted (∼ 9.8 × 10 nm s) in homogeneous suspensions where bundles have been dispersed by the acidic additions.

Supramolecular gels: functions and uses.

In recent years there has been immense interest in studying gels derived from low molecular mass gelators (supramolecular, or simply molecular gels). The motivation for this is not only to understand the fundamental aggregate structures in the gels at different length scales, but also to explore their potential for futuristic technological applications. Gels have been made sensitive to external stimuli like light and chemical entities by incorporating a spectroscopically active or a receptor unit as part of the gelator molecule. This makes them suitable for applications such as sensing and actuating. The diversity of gel structural architectures has allowed them to be utilized as templates to prepare novel inorganic superstructures for possible applications in catalysis and separation. Gels derived from liquid crystals (anisotropy gels) that can act as dynamically functional materials have been prepared, for example, for (re-writable) information recording. Supramolecular gels can be important in controlled release applications, in oil recovery, for gelling cryogenic fuels etc. They can also serve as media for a range of applications. This tutorial review highlights some of the instructive work done by various groups to develop smart and functional gels, and covers a wide spectrum of scientific interest ranging from medicine to materials science.

Self-assembled networks of ribbons in molecular hydrogels of cationic deoxycholic acid analogues.

Aqueous gels derived from three cationic 24-nor 3,12-dihydroxy cholane (DC) derivatives with N-methyl-2-pyrrolidinone (NMP), N-methylmorpholine (NMM), and 1,4-diazabicyclo[2.2.2]octane (DABCO) at the side chain positions have been exhaustively characterized by small-angle neutron-scattering experiments. Although the molecular structures differ slightly by the heterocycle grafted to the steroid core, the derived gels exhibit a range of structural behaviors at the nanoscale that depart from those observed with simple deoxycholate systems. The NMM-DC aggregates are ribbons with a bimolecular thickness of t = 37 A and an anisotropy of the section b/a approximately 0.1. DABCO-DC exhibits a remarkable transition from ribbons (t = 29.5 A, b/a = 0.18) to thicker cylindrical fibers (R approximately 59 A), involving four original ribbons, upon a concentration increase. The NMP-DC system forms thick cylindrical fibers (R approximately 68 A) with steroid molecules organized in a specific morphology. Bilayered or interdigited structures are formed and favored by the presence of multiple polar interaction centers in the DC molecules. Secondary aggregation mechanisms are invoked in the formation of bundles having a lower cross-sectional anisotropic symmetry and exhibiting Bragg peaks corresponding to molecular length periodicities. The relations between the structural information and the rheological properties are discussed.