Tailoring optical fields emitted by nanometric sources

Here we study a simple way of controlling the emitted fields of sub-wavelength nanometric sources. The system consists of arrays of nanoparticles (NPs) embedded in optical active media. The key concept is the careful tuning of NP's damping factors, which changes the eigenmode's decay rates of the whole array. This, at long time, leads to a locking of relative phases and frequencies of individual localized-surfaces-plasmons (LSPs) and, thus, controlls the emitted field. The amplitude of the LSP's oscillations can be kept constant by embedding the system in optical active media. In the case of full loss compensation, this implies that, not only the relative phases, but also the amplitudes of the LSPs remain fixed, leading us, additionally, to interpret the process as a new example of synchronization. The proposed approach can be used as a general way of controlling and designing the electromagnetic fields emitted by nanometric sources, which can find applications in optoelectronic, nanoscale lithography and probing microscopy

Desing of plasmomic nano-structures for SERS ultrasensitive spectroscopy: comparison between self-assembly and bioconjugation

En este trabajo, se presenta una estrategia sencilla para generar nanoestructuras plasmónicas por autoensamblado y bioconjugación de nanoesferas (NSs) de Au, para ser aplicadas como plataformas de espectroscopia Raman incrementada por superficie (SERS). Mediante el reconocimiento molecular altamente específico entre biotina y estreptavidina (STV) se generan dímeros con una distancia interpartícula de alrededor de 8 nm, mientras que en ausencia de STV la agregación no direccionada de la superficie de las NSs genera aglomerados compactos con distancia interpartícula de 5 nm debido a los puente hidrógeno que se establecen entre moléculas de biotina funcionalizadas. Ambos sustratos permiten detectar concentraciones de biotina picomolares (1x10-12 M). Sin embargo, los factores de incremento analíticos (AEF) son un orden de magnitud mayor en el caso de los dímeros (107) que en el caso de los aglomerados compactos (106). Utilizando los grandes incrementos de campo eléctrico se utilizaron estos sustratos para detectar un analito externo, Rodamina 6G (RH6G), y se determino que los dímeros generan incrementos de un orden de magnitud mayor (105) que el uso de aglomerados compactos (104). La dependencia de la longitud de onda y las diferencias en los AEF para los sustratos diméricos y los aglomerados compactos de NSs de Au se correlacionaron con simulaciones electrodinámicas rigurosas. Los dímeros generados son en sí un nuevo tipo de un sustrato SERS que puede ser autocalibrado donde selectivamente se puede “atrapar” moléculas biotiniladas por STV y situándolas en la zona de máximo incremento de campo electromagnético. Por otra parte, el estudio de las propiedades ópticas de los aglomerados compactos permitió el desarrollo de un procedimiento general para hacer una predicción cuantitativa de la respuesta SERS de este tipo de nanoestructuras.In this work, we report a simple strategy to obtain ultrasensitive SERS nanostructures by self-assembly and bioconjugation of Au nanospheres (NSs). Homodimer aggregates with an interparticle gap of around 8 nm are generated in aqueous dispersions by the highly specific molecular recognition of biotinylated Au NSs to streptavidin (STV), while compact-tight Au NS aggregates with a gap of 5 nm are formed in the absence of STV due to hydrogen bonding among biotinylated NSs. Both types of aggregates depict the capability to detect biotin concentrations lower than 1x10-12 M. Nevertheless, it was found that dimers are better SERS substrates as they generate enhancements one order of magnitude bigger than the compact-tight aggregates (107 and 106, respectively). Quite interesting, the AEF for an external analyte, Rhodamine 6G (RH6G), using the dimer aggregates is also 1 order of magnitude greater (105) than using compact-tight aggregates (around 104). The dependence on the wavelength and the differences of the AEF for Au random aggregates and dimers are rationalized with rigorous electrodynamic simulations. The dimers obtained afford a new type of an in situ self-calibrated and reliable SERS substrate where biotinylated molecules can selectively be “trapped” by STV and located in the nanogap enhanced plasmonic field. On the other hand, the study of the optical properties of compact-tight aggregates allow to develop a general procedure to make a quantitative prediction of the SERS response tight-compact clusters that is demonstrated to be quite general independent of the metal (Ag or Au) and size of the individual NSs of the cluster.Fil: Fraire, Juan Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Coronado, Eduardo A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentin

Keys for designing hematite/plasmonic metal hybrid nanostructures with enhanced photoactive properties

Photoactive hybrid nanostructures composed of metal oxides and plasmonic metals are able to perform the conversion of radiant (solar) energy into electrical or chemical energy. However, their use in large-scale practical applications still requires their photoconversion efficiency to be improved. In this work, the light-harvesting properties of hematite/plasmonic metal rodlike hybrid nanostructures are investigated on the basis of discrete dipole approximation simulations. The effects of the length and nature of the metallic counterpart on the far- and near-field optical properties of the hybrid nanostructure are analyzed in detail. The implemented methodology allowed us to assess the contribution of each component of the hybrid nanostructure to the absorption efficiency, Qabs, separately. In turn, the Qabs values obtained were employed to determine the absorbed photon flux, ø, within the α-Fe2O3 component, a relevant quantity directly related to the photoconversion efficiency. It was found that both absorption efficiency Qabs and absorbed photon flux ø can be largely enhanced through a proper selection of the length and nature of the metallic counterpart of the nanostructure, evidencing plasmon-enhanced light absorption in the α-Fe2O3 component, which is attributed to a plasmon-induced energy transfer mechanism based on near-field enhancements. Importantly, it was found that the highest ø values achieved for nanostructures composed of Ag and Al (∼11 × 1016 photons cm-2 s-1) are nearly 3 times larger than those corresponding to nanostructures composed of Au (∼4 × 1016 photons cm-2 s-1). In addition, a direct relationship between the absorbed photon flux, ø, and optical characteristics of the nanostructures, that is, the bandgap energy of α-Fe2O3 and the energy and radiative line width of the localized surface plasmon resonance, was empirically obtained. Such a relationship not only complements but also overcomes the limitations of the reported useful criteria and provides helpful guidelines for the optimum design of hybrid nanostructures with enhanced photoactive properties.Fil: Encina, Ezequiel Roberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Coronado, Eduardo A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentin

Gold Nucleation Inhibition by Halide Ions: a Basis for a Seed-Mediated Approach

In the present work, we examine the effect of halide ions on gold nucleation, a typical synthetic variable in the wet-chemical production of gold nanostructures. It was found that the homogeneous nucleation of gold by the chemical reduction of aqueous gold ions is kinetically quenched by an increase in the concentration of halide ions, and this effect grows stronger as the Au–halide complex stability increases. The nucleation quenching is not exclusively related to a specific reducing agent, but appears to be a more general behavior, and is affected by the pH of the media. While no nucleation is observed, Au(I) metastable species coexist together with the reducer, constituting metastable solutions. It is demonstrated that nucleation inhibition by halide ions can be employed as a basis for a seed-mediated approach to produce gold nanostructures. The metastable solutions are proved to function as growth baths, where Au(I) reduction is triggered on the surface of previously synthesized gold nanoparticles, driving their growth in the absence of secondary nucleation. It is also shown how, with this approach, the synthesis conditions can be rationally designed to obtain gold nanoparticles with the desired properties in a controlled and reproducible fashion.Fil: Moiraghi, Raquel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Douglas Gallardo, Oscar Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Coronado, Eduardo A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Macagno, Vicente Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Perez, Manuel Alejo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentin

Buffering plasmons in nanoparticle waveguides at the virtual-localized transition

We study the plasmonic energy transfer from a locally excited nanoparticle (LE-NP) to a linear array of small NPs and we obtain the parametric dependence of the response function. An analytical expression allows us to distinguish the extended resonant states and the localized ones, as well as an elusive regime of virtual states. This last appears when the resonance width collapses and before it becomes a localized state. Contrary to common wisdom, the highest excitation transfer does not occur when the system has a well defined extended resonant state but just at the virtual-localized transition, where the main plasmonic modes have eigenfrequencies at the passband edge. The slow group velocity at this critical frequency enables the excitation buffering and hence favors a strong signal inside the chain. A similar situation should appear in many other physical systems. The extreme sensitivity of this transition to the waveguide and LE-NP parameters provides new tools for plasmonics.Comment: Regular article: 7 pages and 5 figure

A Plasmonic approach to study protein interaction kinetics through the dimerization of functionalized Ag Nanoparticles

Understanding the kinetics of protein interactions plays a key role in biology with significant implications for the design of analytical methods for disease monitoring and diagnosis in medical care, research and industrial applications. Herein, we introduce a novel plasmonic approach to study the binding kinetics of protein-ligand interactions following the formation of silver nanoparticles (Ag NPs) dimers by UV-Vis spectroscopy that can be used as probes for antigen detection and quantification. To illustrate and test the method, the kinetics of the prototype biotin-streptavidin (Biot-STV) pair interaction was studied. Controlled aggregates (dimers) of STV functionalized Ag NPs were produced by adding stoichiometric quantities of gliadin-specific biotinylated antibodies (IgG-Biot). The dimerization kinetics was studied in a systematic way as a function of Ag NPs size and at different concentrations of IgG-Biot. The kinetics data have shown to be consistent with a complex reaction mechanism in which only the Ag NPs attached to the IgG-Biot located in a specific STV site are able to form dimers. These results help in elucidating a complex reaction mechanism involved in the dimerization kinetics of functionalized Ag NPs, which can serve as probes in surface plasmon resonance-based bioassays for the detection and quantification of different biomarkers or analytes of interest.Fil: Mercadal, Pablo Agustin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Motrich, Ruben Dario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Córdoba. Centro de Investigaciones en Bioquímica Clínica e Inmunología; ArgentinaFil: Coronado, Eduardo A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentin

Quantum dynamical simulations of local field enhancement in metal nanoparticles

Field enhancements (Γ) around small Ag nanoparticles (NPs) are calculated using a quantum dynamical simulation formalism and the results are compared with electrodynamic simulations using the discrete dipole approximation (DDA) in order to address the important issue of the intrinsic atomistic structure of NPs. Quite remarkably, in both quantum and classical approaches the highest values of Γ are located in the same regions around single NPs. However, by introducing a complete atomistic description of the metallic NPs in optical simulations, a different pattern of the Γ distribution is obtained. Knowing the correct pattern of the Γ distribution around NPs is crucial for understanding the spectroscopic features of molecules inside hot spots. The enhancement produced by surface plasmon coupling is studied by using both approaches in NP dimers for different inter-particle distances. The results show that the trend of the variation of Γ versus inter-particle distance is different for classical and quantum simulations. This difference is explained in terms of a charge transfer mechanism that cannot be obtained with classical electrodynamics. Finally, time dependent distribution of the enhancement factor is simulated by introducing a time dependent field perturbation into the Hamiltonian, allowing an assessment of the localized surface plasmon resonance quantum dynamics.Fil: Negre, Christian Francisco Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Perassi, Eduardo Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Coronado, Eduardo A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Sanchez, Cristian Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentin

Near-Field Enhancement Contribution to the Photoactivity in Magnetite-Gold Hybrid Nanostructures

Hybrid nanostructures composed of magnetic iron oxides and plasmonic metals can convert light energy into chemical energy, and they can be easily manipulated through magnetic fields. As a consequence of these multifunctional features, they can be employed as magnetically recyclable heterogeneous photocatalysts. Herein, we report a two-step method for the preparation of magnetite (Fe3O4)-gold (Au) hybrid nanostructures in aqueous media. The obtained material resembles a core-satellite morphology of 60 nm Fe3O4 nanoparticles surrounded by nearly 20 nm spherical Au nanoparticles attached to their surface. The synthesized hybrid material exhibits enhanced capabilities for methylene blue photodegradation compared with bare Fe3O4 nanoparticles. Detailed electrodynamics simulations were performed to achieve further insight into the improved photoactive properties of the Fe3O4-Au hybrid nanostructures. The theoretical results show that the excitation of localized surface plasmon resonances in the Au component leads to greater light absorption in the Fe3O4 component, which ultimately impacts the improved photocatalytic properties of the hybrid nanostructure. Overall, this work provides a complementary approach toward a complete understanding of the enhanced photoactive properties of hybrid nanostructures and highlights the importance of considering their actual morphology into simulations.Fil: Guzman, Federico Valentin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Mercadal, Pablo Agustin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Coronado, Eduardo A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Encina, Ezequiel Roberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentin

SERS-based molecularly imprinted plasmonic sensor for highly sensitive PAH detection

A novel hybrid plasmonic platform based on the synergetic combination of a molecularly imprinted polymer (MIP) thin film with Au nanoparticle (NPs) assemblies, noted as Au@MIP, was developed for surface-enhanced Raman scattering (SERS) spectroscopy recognition of polycyclic aromatic hydrocarbons (PAHs). While the MIP trapped the PAH close to the Au surface, the plasmonic NPs enhanced the molecule's Raman signal. The Au@MIP fabrication comprises a two-step procedure, first, the layer-by-layer deposition of Au NPs on glass and their further coating with a uniform MIP thin film. Profilometry analysis demonstrated that the thickness and homogeneity of the MIP film could be finely tailored by tuning different parameters such as prepolymerization time or spin-coating rate. Two different PAH molecules, pyrene or fluoranthene, were used as templates for the fabrication of pyrene- or fluoranthene-based Au@MIP substrates. The use of pyrene or fluoranthene, as the template molecule to fabricate the Au@MIP thin films, enabled its ultradetection in the nM regime with a 100-fold improvement compared with the nonimprinted plasmonic sensors (Au@NIPs). The SERS data analysis allowed to estimate the binding constant of the template molecule to the MIP. The selectivity of both pyrene- and fluoranthene-based Au@MIPs was analyzed against three PAHs of different sizes. The results displayed the important role of the template molecule used for the Au@MIPs fabrication in the selectivity of the system. Finally, the practical applicability of pyrene-based Au@MIPs was shown by performing the detection of pyrene in two real samples: creek water and seawater. The design and optimization of this type of plasmonic platform will pave the way for the detection of other relevant (bio)molecules in a broad range of fields such as environmental control, food safety, or biomedicine.Fil: Castro-Grijalba, Alexander. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. Universidad Nacional de San Luis. Facultad de Ciencias de la Salud. Laboratorio de Quimica Analitica Ambiental.; Argentina. Universidad de Vigo; EspañaFil: Montes-García, Verónica. Universidad de Vigo; EspañaFil: Cordero-Ferradás, María José. Universidad de Vigo; EspañaFil: Coronado, Eduardo A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Pérez-Juste, Jorge. Universidad de Vigo; EspañaFil: Pastoriza-Santos, Isabel. Universidad de Vigo; Españ