Laura Rodriguez-Lorenzo

Zeptomol Detection Through Controlled Ultrasensitive Surface-Enhanced Raman Scattering

SERS permits identifying the nature of molecules in extremely low concentrations, but it is hindered by poor enhancement or low reproducibility. We demonstrate controllable approximately 10(10) signal amplification reaching the zeptomol detection limit for a nonresonant molecule by sandwiching the analyte between the tips of star-shaped gold nanoparticles and a planar gold surface using a simple synthetic procedure. This unprecedented control over light-intensity amplification opens a new avenue toward high-yield, fully reproducible, SERS-based, zeptomol detection and holds promise for nonlinear optics applications at the single-particle level.

Plasmonic nanosensors with inverse sensitivity by means of enzyme-guided crystal growth

Lowering the limit of detection is key to the design of sensors needed for food safety regulations, environmental policies and the diagnosis of severe diseases. However, because conventional transducers generate a signal that is directly proportional to the concentration of the target molecule, ultralow concentrations of the molecule result in variations in the physical properties of the sensor that are tiny, and therefore difficult to detect with confidence. Here we present a signal-generation mechanism that redefines the limit of detection of nanoparticle sensors by inducing a signal that is larger when the target molecule is less concentrated. The key step to achieve this inverse sensitivity is to use an enzyme that controls the rate of nucleation of silver nanocrystals on plasmonic transducers. We demonstrate the outstanding sensitivity and robustness of this approach by detecting the cancer biomarker prostate-specific antigen down to 10(-18) g ml(-1) (4 × 10(-20) M) in whole serum.

Tuning Size and Sensing Properties in Colloidal Gold Nanostars

Gold nanostars are multibranched nanoparticles with sharp tips, which display extremely interesting plasmonic properties but require optimization. We present a systematic investigation of the influence of different parameters on the size, morphology, and monodispersity of Au nanostars obtained via seeded growth in concentrated solutions of poly(vinylpyrrolidone) in N,N-dimethylformamide. Controlled prereduction of Au(3+) to Au(+) was found to influence monodispersity (narrower plasmon bands), while the [HAuCl(4)]/[seed] molar ratio significantly affects the morphology and tip plasmon resonance frequency. We also varied the size of the seeds (2-30 nm) and found a clear influence on the final nanostar dimensions as well as on the number of spikes, while synthesis temperature notably affects the morphology of the particles, with more rounded morphologies formed above 60 °C. This rounding effect allowed us to confirm the importance of sharp tips on the optical enhancing behavior of these nanoparticles in surface-enhanced raman scattering (SERS). Additionally, the sensitivity toward changes in the local refractive index was found to increase for larger nanostars, though lower figure of merit (FOM) values were obtained because of the larger polydispersity.

Surface-enhanced Raman scattering biomedical applications of plasmonic colloidal particles

This review article presents a general view of the recent progress in the fast developing area of surface-enhanced Raman scattering spectroscopy as an analytical tool for the detection and identification of molecular species in very small concentrations, with a particular focus on potential applications in the biomedical area. We start with a brief overview of the relevant concepts related to the choice of plasmonic nanostructures for the design of suitable substrates, their implementation into more complex materials that allow generalization of the method and detection of a wide variety of (bio)molecules and the strategies that can be used for both direct and indirect sensing. In relation to indirect sensing, we devote the final section to a description of SERS-encoded particles, which have found wide application in biomedicine (among other fields), since they are expected to face challenges such as multiplexing and high-throughput screening.

Design of SERS-Encoded, Submicron, Hollow Particles Through Confined Growth of Encapsulated Metal Nanoparticles

The synthetic architectures of complex inorganic nanostructures, including multifunctional hollow capsules, are expected to play key roles in many different applications, such as drug delivery, photonic crystals, nanoreactors, and sensing. Implementation of novel strategies for the fabrication of such materials is needed because of the infancy of this knowledge, which still limits progress in certain areas. Herein we report a straightforward synthetic approach for the development of multifunctional submicron reactors comprising catalytic gold nanoparticles (2-3 nm) confined inside hollow silica capsules. Additionally, the confined growth of encapsulated metal nanoparticles was carried out to evidence the usefulness and functionality of these reactors in catalytic applications and as an approach for the development of novel complex nanostructures. Their potential and multifunctionality have been pointed out by fabrication of SERS-encoded submicrometer particles with shape and size uniformity for use in antigen biosensing; this was accomplished via codification of gold nanoparticle islands grown onto their inner surfaces.

Multiplex optical sensing with surface-enhanced Raman scattering: A critical review

Multiplex analysis permits the detection of several analytical targets at the same time. This approach may permit to draw a rapid and accurate diagnostic about the health of an individual or an environment. Among the analytical techniques with potential for multiplexing surface-enhanced Raman scattering (SERS) offer unique advantages such as ultrasensitive detection down low the deconvolution times, a unique signature containing all the vibrational information of the target molecules, and the possibility of performing the experiments even in very demanding environments such as natural or biological fluids. Here we review the late advances in multiplex SERS including the direct methods, those aided by the surface functionalization of the plasmonic nanoparticles and the use of SERS encoded particles.

Reshaping and LSPR tuning of Au nanostars in the presence of CTAB

Gold nanostars can easily undergo reshaping into spherical particles by simply adding a small amount of CTAB. Such reshaping can be understood in terms of Ostwald ripening involving dissolution of weakly bound surface atoms at areas with high convex curvature and re-deposition at concave areas. This process can be stopped at any time by adding silver ions, which block bromide and stabilize the surface. Because the localized surface plasmon resonance (LSPR) band of the nanostars colloid gradually changes during etching, stabilization of intermediate morphologies allows fine LSPR tuning, which can be exploited for plasmonic applications.

Reversible assembly of metal nanoparticles induced by penicillamine. Dynamic formation of SERS hot spots

We report a systematic study of the surface modification of gold and silver nanoparticles with DL-penicillamine (PEN) and N-acetyl-DL-penicillamine (NAP), motivated by the possibility of inducing pH-controlled reversible nanoparticle assembly. The interaction of PEN and NAP with the metal nanoparticle surface was studied by isothermal titration calorimetry (ITC). The results indicate that equilibrium is reached with the formation of a submonolayer corresponding to ca. 40% and 64% of total surface coverage for PEN and NAP, respectively. Both PEN and NAP modified nanoparticles could be reversibly aggregated at acidic pH due to the protonation of the carboxylic groups, leading to a decrease in their stability by electrostatic interactions and the advent of hydrogen bonding interactions which promote interparticle linkage. The process was monitored by UV-Vis spectroscopy, transmission electron microscopy (TEM) and surface enhanced Raman scattering (SERS) spectroscopy. Interestingly, the SERS characterization demonstrated the pH-controlled formation of hot-spots.

Growth of Sharp Tips on Gold Nanowires Leads to Increased Surface-Enhanced Raman Scattering Activity

We report the formation of gold nanoparticles with a novel and useful morphology, comprising nanowires fully covered with sharp tips (thorned nanowires). The synthesis is based on a seeded-growth approach based the rapid overgrowth of ultrathin gold wires in N,N-dimethylformamide, in the presence of poly(vinylpyrrolidone). The process allows a fine control over the thickness of the final wires, as well as the tunability of the number and sharpness of the thorns. These new plasmonic nanostructures display extremely strong optical enhancing properties and can be readily used as platforms for SERS and for integration in ultrasensitive optical devices.

Fluorescence‐Encoded Gold Nanoparticles: Library Design and Modulation of Cellular Uptake into Dendritic Cells

In order to harness the unique properties of nanoparticles for novel clinical applications and to modulate their uptake into specific immune cells we designed a new library of homo- and hetero-functional fluorescence-encoded gold nanoparticles (Au-NPs) using different poly(vinyl alcohol) and poly(ethylene glycol)-based polymers for particle coating and stabilization. The encoded particles were fully characterized by UV-Vis and fluorescence spectroscopy, zeta potential and dynamic light scattering. The uptake by human monocyte derived dendritic cells in vitro was studied by confocal laser scanning microscopy and quantified by fluorescence-activated cell sorting and inductively coupled plasma atomic emission spectroscopy. We show how the chemical modification of particle surfaces, for instance by attaching fluorescent dyes, can conceal fundamental particle properties and modulate cellular uptake. In order to mask the influence of fluorescent dyes on cellular uptake while still exploiting its fluorescence for detection, we have created hetero-functionalized Au-NPs, which again show typical particle dependent cellular interactions. Our study clearly prove that the thorough characterization of nanoparticles at each modification step in the engineering process is absolutely essential and that it can be necessary to make substantial adjustments of the particles in order to obtain reliable cellular uptake data, which truly reflects particle properties.