arXiv subjects

Guillermo P. Acuna

Publications and source records attributed to Guillermo P. Acuna.

17 recordsLinked to original sources

arXiv2026

Probing individual phonon-polaritonic nanoparticle-on-mirror cavities by infrared nanospectroscopy

Nanoparticle-on-mirror (NPoM) cavities enable extreme light confinement and strong light-matter interactions, but their realization with phonon-polariton materials in the mid-infrared spectral range remains largely unexplored. Here, we use nano-FTIR spectroscopy to study the near-field response of individual phononic NPoM cavities formed by gold nanoparticles on a quartz substrate supporting phonon-polaritons. By placing a metal tip on top of the NPoM and recording the tip-scattered field, we observe two reproducible cavity resonances, identified as the fundamental and a second-order antenna modes by numerical simulations. The calculations show that, in absence of the tip, the NPoM cavity exhibits ultrasmall mode volumes ($V \sim 10^3$ nm$^3$) and high quality factors ($Q \sim 100$), resulting in extraordinary field intensity enhancements ($F \sim 10^4$) and Purcell factors ($P_F \sim 10^9$). They also indicate that the nano-FTIR tip enables efficient excitation and readout of these phononic NPoM modes without perturbing them, while enhancing the intrinsic local field intensity in the NPoM gap by two orders of magnitude. Our results establish phononic NPoM cavities as a promising platform for mid-infrared nanophotonics and pave the way for ultrasensitive vibrational spectroscopy based on nano-FTIR measurements of individual cavities.

physics.optics↗

arXiv2026

Modifying Electrochemical Doping in Light-Emitting Electrochemical Cells with Gold Nanoparticles

Electrochemical doping offers dynamic control of the electronic properties of organic semiconductors, and it is the enabling feature of a range of technologies, including electrochemical transistors, energy-storage devices, light-emitting electrochemical cells (LECs), and bioelectronics. Electrochemical doping is commonly controlled by the selection of the constituents in the active material of the device or the applied voltage bias, but herein we report that the incorporation of Au nanoparticles (Au-NPs) at an electrode interface can constitute an alternative control parameter. The LEC features balanced p- and n-type electrochemical doping that forms a p-n junction doping structure in its active material, and we find that it is possible to reshape this doping profile by incorporating Au-NPs at an electrode interface. Specifically, we establish that the inclusion of neat non-capped Au-NPs at the anodic interface shifts the p-n junction (i.e., the emission zone) away from the anode. In contrast, the inclusion of Au-NPs capped with sodium citrate is found to reverse this behavior, so that the emission zone is instead moved towards the anode. We utilize this control parameter to shift the emission zone towards a position of constructive (destructive) interference, as manifested in a strong increase (decrease) of the LEC emission efficiency. Our findings establish an interfacial strategy for modulating the spatial profile of electrochemical doping and tuning device performance without altering the chemistry of the active material, relying instead on the surface modification of one electrode. This approach is important because it provides a versatile and minimally invasive route to optimize electrochemical devices while preserving the intrinsic properties and formulation of the active material.

cond-mat.mtrl-sci↗

arXiv2026

DNA-Origami-Assembled Rhodium Nanoantennas for Deep-UV Label-Free Single-Protein Detection

Nanoparticles of plasmonic metals have significantly to the development of spectroscopic techniques, enabling strong confinement of electromagnetic fields at the nanoscale and corresponding signal amplification. However, to date, plasmonic applications have been limited mainly to the visible and near-infrared range, as materials supporting ultraviolet resonances typically exhibit poor chemical stability and lack robust surface functionalisation methods. In this work, we address these limitations by introducing a fully programmable approach to UV plasmonics based on rhodium nanocube dimers assembled using DNA origami templates. We have developed a reliable ligand exchange strategy that allows the functionalisation of rhodium nanocubes with DNA while maintaining their colloidal stability. These DNA-modified nanocubes act as modular building blocks that can be assembled into dimers with 69% efficiency and an average gap size of 10 nm. The DNA origami design also allows for the deterministic placement of a single streptavidin protein in the plasmonic gap, unlike previous methods based on stochastic diffusion. Experiments with single-molecule autofluorescence in UV, supported by numerical simulations, show an increase in brightness of up to 22, a reduction in fluorescence lifetime, and a more than tenfold increase in the total number of detected photons. By creating a robust and versatile platform for the production of UV-resonant plasmonic nanoantennas, this work extends the functionality of plasmonics to the deep UV spectrum and opens up new possibilities for labelling-free single-protein spectroscopy.

physics.optics↗

arXiv2025

Color Routing and Beam Steering of Single-Molecule Emission with a Spherical Silicon Nanoantenna

Single-photon emitters radiate as electric dipoles, which limits light collection efficiency and complicates integration into flat photonic devices. Developing nanophotonic structures capable of directing photon emission with tunable angular distributions in the visible spectrum has been pursued for applications ranging from integrated optical systems to discrimination of molecular species. To date, such directional control has been achieved using components whose overall footprint is larger than the emission wavelength and often rely on lossy plasmonic components. Here, we employ the DNA origami technique for deterministic nanoscale assembly, positioning single fluorophores in nanometric proximity to a single silicon spherical nanoparticle and demonstrate unidirectional emission with forward-to-backward intensity ratios up to ~7 dB. Furthermore, we show that a single silicon nanosphere antenna can function as a color router or a beam steerer depending on its size, emitter spectral range and emitter-nanoparticle distance.

physics.optics↗

arXiv2025

Distance dependent interaction between a single emitter and a single dielectric nanoparticle using DNA origami

Optical nanoantennas can manipulate light-matter interactions at the nanoscale, modifying the emission properties of nearby single photon emitters. To date, most optical antennas are based on metallic nanostructures that exhibit unmatched performance in terms of electric field enhancement but suffer from substantial ohmic losses that limit their applications. To circumvent these limitations, there is a growing interest in alternative materials. In particular, high-refractive-index dielectrics have emerged as promising candidates, offering negligible ohmic losses, and supporting both electric and magnetic resonances in the visible and near-infrared range that can unlock novel effects. Currently, the few available studies on dielectric nanoantennas focus on ensemble measurements. Here, we exploit the DNA origami technique to study the interaction between silicon nanoparticles and organic fluorophores at the single molecule level, in controlled geometries and at different spectral ranges within the visible spectrum. We characterize their distance-dependent interaction in terms of fluorescence intensity and lifetime, revealing a significant modification of the decay rate together with minimal quenching and a high fluorescence quantum yield even at short distances from the dielectric nanoparticle. This work demonstrates the advantages of dielectric nanoantennas over their metallic counterparts and paves the way for their applications in single-molecule spectroscopy and sensing.

physics.optics↗

arXiv2024

Coupling single-molecules to DNA-based optical antennas with position and orientation control

Optical antennas have been extensively employed to manipulate the photophysical properties of single photon emitters. Coupling between an emitter and a given resonant mode of an optical antenna depends mainly on three parameters: spectral overlap, relative distance, and relative orientation between the emitter's transition dipole moment and the antenna. While the first two have been already extensively demonstrated, achieving full coupling control remains unexplored due to the challenges in manipulating at the same time both the position and orientation of single molecules. Here, we use the DNA origami technique to assemble a dimer optical antenna and position a single fluorescent molecule at the antenna gap with controlled orientation, predominately parallel or perpendicular to the antenna's main axis. We study the coupling for both conditions through fluorescence measurements correlated with scanning electron microscopy images, revealing a 5-fold higher average fluorescence intensity when the emitter is aligned with the antenna's main axis and a maximum fluorescence enhancement of ~ 1400-fold. A comparison to realistic numerical simulations suggests that the observed distribution of fluorescence enhancement arises from small variations in emitter orientation and gap size. This work establishes DNA origami as a versatile platform to fully control the coupling between emitters and optical antennas, trailblazing the way for self-assembled nanophotonic devices with optimized and more homogenous performance.

physics.optics↗

arXiv2024

Towards full control of molecular exciton energy transfer via FRET in DNA origami assemblies

Controlling the flow of excitons between organic molecules holds immense promise for various applications, including energy conversion, spectroscopy, photocatalysis, sensing, and microscopy. DNA nanotechnology has shown promise in achieving this control by using synthetic DNA as a platform for positioning and, very recently, for also orienting organic dyes. In this study, the orientation of doubly-linked dyes in DNA origami structures was manipulated to control energy transfer. By controlling independently the orientation of single donor and acceptor molecules, the average energy transfer efficiency was doubled. This work demonstrates the potential of DNA nanotechnology for precise control of the excitonic energy transfer with implications for artificial light-harvesting antennas.

cond-mat.soft↗

arXiv2023

Universal click-chemistry approach for the DNA functionalization of nanoparticles

Nanotechnology has revolutionized the fabrication of hybrid species with tailored functionalities. A milestone in this field is the DNA conjugation of nanoparticles, introduced almost 30 years ago, which typically exploits the affinity between thiol groups and metallic surfaces. Over the last decades, developments in colloidal research have enabled the synthesis of an assortment of non-metallic structures, such as high-index dielectric nanoparticles, with unique properties not previously accessible with traditional metallic nanoparticles. However, to stabilize, integrate and provide further functionality to non-metallic nanoparticles, reliable techniques for their functionalization with DNA will be crucial. Here, we combine well-established dibenzylcyclooctyne-azide click-chemistry with a simple freeze-thaw method to achieve the functionalization of silica and silicon nanoparticles, which form exceptionally stable colloids with a high DNA surface density of 0.2 molecules/nm2. Furthermore, we demonstrate that these functionalized colloids can be self-assembled into high-index dielectric optical antennas with a yield of up to 78% via the use of DNA origami. Finally, we extend this method to functionalize other important nanomaterials, including oxides, polymers, core-shell and metal nanostructures. Our results indicate that the method presented herein serves as a crucial complement to conventional thiol functionalization chemistry and thus greatly expands the toolbox of DNA-functionalized nanoparticles currently available.

physics.chem-ph↗

arXiv2023

DNA origami assembled nanoantennas for manipulating single-molecule spectral emission

Optical nanoantennas can affect the decay rates of nearby emitters by modifying the local density of photonic states around them. In the weak-coupling limit, and according to the Fermi's Golden Rule, the emission spectrum of a dye is given by the energy of all the possible radiative transitions weighted by the probability of each of them to occur. By engineering the resonance of a nanoantenna, one can selectively enhance specific vibronic transitions of a dye molecule, thus shaping its emission spectrum. Since interactions between emitters and nanoantennas are known to be position dependent, we make here use of DNA origami to precisely place an individual dye at different positions around a gold nanorod. We show how this relative position between the nanorod and the emitter affects the emission spectrum of the latter. In particular, we observe the appearance of a second fluorescence peak whose wavelength and intensity are correlated with the fundamental plasmonic resonance of the nanorod, which we extract from its photoluminescence spectrum. This second peak results from the selective enhancement of transitions to different vibrational levels of the excitonic ground state, whose energies are in resonance with the plasmonic one. Furthermore, we argue that the drastic alteration of the fluorescence spectrum in some of our samples cannot be accounted for with Kasha's rule, which indicates that radiative and vibrational relaxation dye lifetimes can become comparable through the coupling to the gold nanorods.

physics.optics↗

arXiv2022

Super-resolved FRET imaging by confocal fluorescence-lifetime single-molecule localization microscopy

FRET-based approaches are a unique tool for sensing the immediate surroundings and interactions of (bio)molecules. FRET imaging and FLIM (Fluorescence Lifetime Imaging Microscopy) enable the visualization of the spatial distribution of molecular interactions and functional states. However, conventional FLIM and FRET imaging provide average information over an ensemble of molecules within a diffraction-limited volume, which limits the spatial information, accuracy, and dynamic range of the observed signals. Here, we demonstrate an approach to obtain super-resolved FRET imaging based on single-molecule localization microscopy using an early prototype of a commercial time-resolved confocal microscope. DNA Points Accumulation for Imaging in Nanoscale Topography (DNA-PAINT) with fluorogenic probes provides a suitable combination of background reduction and blinking kinetics compatible with the scanning speed of usual confocal microscopes. A single laser is used to excite the donor, a broad detection band is employed to retrieve both donor and acceptor emission, and FRET events are detected from lifetime information.

physics.optics↗

arXiv2022

Reconfigurable chirality with achiral excitonic materials in the strong-coupling regime

We introduce and theoretically analyze the concept of manipulating optical chirality via strong coupling of the optical modes of chiral nanostructures with excitonic transitions in molecular layers or semiconductors. With chirality being omnipresent in chemistry and biomedicine, and highly desirable for technological applications related to efficient light manipulation, the design of nanophotonic architectures that sense the handedness of molecules or generate the desired light polarization in an externally controllable manner is of major interdisciplinary importance. Here we propose that such capabilities can be provided by the mode splitting resulting from polaritonic hybridization. Starting with an object with well-known chiroptical response -- here, for a proof of concept, a chiral sphere -- we show that strong coupling with a nearby excitonic material generates two distinct frequency regions that retain the object's chirality density and handedness, which manifest most clearly through anticrossings in circular-dichroism or differential-scattering dispersion diagrams. These windows can be controlled by the intrinsic properties of the excitonic layer and the strength of the interaction, enabling thus the post-fabrication manipulation of optical chirality. Our findings are further verified via simulations of the circular dichroism of a realistic chiral architecture, namely a helical assembly of plasmonic nanospheres embedded in a resonant matrix.

physics.optics↗

arXiv2022

DNA self-assembly of single molecules with deterministic position and orientation

An ideal nanofabrication method should allow the organization of nanoparticles and molecules with nanometric positional precision, stoichiometric control and well-defined orientation. The DNA origami technique has evolved into a highly versatile bottom-up nanofabrication methodology that fulfils almost all of these features. It enables the nanometric positioning of molecules and nanoparticles with stoichiometric control, and even the orientation of asymmetrical nanoparticles along predefined directions. However, orienting individual molecules has been a standing challenge, mainly due to unspecific electrostatic interactions. Here, we show how single molecules, namely Cy5 and Cy3 fluorophores, can be incorporated in a DNA origami with controlled orientation by doubly linking them to oligonucleotide strands that are hybridized while leaving enough unpaired bases to induce a stretching force. Particularly, we explore the effects of leaving 0, 2, 4, 6, and 8 unpaired bases and find extreme orientations for 0 and 8 unpaired bases, corresponding to the molecules being perpendicular and parallel to the DNA double helix, respectively. We foresee that these results will expand the application field of DNA origami towards the fabrication of nanodevices involving a wide range of orientation-dependent molecular interactions, such as energy transfer, intermolecular electron transport, catalysis, exciton delocalization, or the electromagnetic coupling of a molecule to specific resonant nano-antennas modes.

cond-mat.soft↗

arXiv2022

Unidirectional ultracompact DNA-templated optical antennas

Optical nanoantennas are structures designed to manipulate light-matter interactions at the nanoscale by interfacing propagating light with localized optical fields. In recent years, a plethora of devices have been realized that are able to efficiently tailor the absorption and/or emission rates of fluorophores. By contrast, modifying the spatial characteristics of their radiation fields remains a challenge. Up to date, the designs providing directionality to fluorescence emission have required compound, complex geometries with overall dimensions comparable to the operating wavelength. Here, we present the fabrication and characterization of DNA-templated ultracompact optical antennas, with sub-wavelength sizes and capable of directing single-molecule fluorescence into predefined directions. Using the DNA origami methodology, two gold nanorods are assembled side-to-side with a separation gap of 5 nm. We show that a single fluorescent molecule placed at the tip of one of the nanorods drives the dimer antenna in anti-phase, leading to unidirectional emission.

physics.optics↗

arXiv2022

Optical ultracompact directional antenna based on a dimer nanorod structure

Controlling directionality of optical emitters is of utmost importance for their application in communication and biosensing devices. Metallic nanoantennas have been proven to affect both excitation and emission properties of nearby emitters, including directionality of their emission. In this regard, optical directional nanoantennas based on a Yagi-Uda design have been demonstrated in the visible range. Despite this impressive proof of concept, their overall size and considerable number of elements represent obstacles for the exploitation of these antennas in nanophotonic applications and for their incorporation onto photonic chips. In order to address these challenges, we investigate an alternative design. In particular, we numerically demonstrate unidirectionality of an ultracompact optical antenna based on two parallel gold nanorods (side-by-side dimer). Our results show that exciting the antiphase mode by an emitter placed in the near-field can lead to unidirectional emission. Furthermore, in order to verify the feasibility of this design, we study the effect on the directionality of several parameters such as shape of the nanorods, possible defects in dimer assembly, and different position and orientation of the emitter. We conclude that this design is robust to changes, making it experimentally achievable.

physics.optics↗

arXiv2021

In Situ Photothermal Response of Single Gold Nanoparticles Through Hyperspectral Imaging AntiStokes Thermometry

Several fields of applications require a reliable characterization of the photothermal response and heat dissipation of nanoscopic systems, which remains a challenging task both for modeling and experimental measurements. Here, we present a new implementation of anti-Stokes thermometry that enables the in situ photothermal characterization of individual nanoparticles (NPs) from a single hyperspectral photoluminescence confocal image. The method is label-free, applicable to any NP with detectable anti-Stokes emission, and does not require any prior information about the NP itself or the surrounding media. With it, we first studied the photothermal response of spherical gold NPs of different sizes on glass substrates, immersed in water, and found that heat dissipation is mainly dominated by the water for NPs larger than 50 nm. Then, the role of the substrate was studied by comparing the photothermal response of 80 nm gold NPs on glass with sapphire and graphene, two materials with high thermal conductivity. For a given irradiance level, the NPs reach temperatures 18% lower on sapphire and 24% higher on graphene than on bare glass. The fact that the presence of a highly conductive material such as graphene leads to a poorer thermal dissipation demonstrates that interfacial thermal resistances play a very significant role in nanoscopic systems, and emphasize the need for in situ experimental thermometry techniques. The developed method will allow addressing several open questions about the role of temperature in plasmon-assisted applications, especially ones where NPs of arbitrary shapes are present in complex matrixes and environments.

physics.optics↗

arXiv2021

Watching Single Unmodified Enzymes at Work

Many proteins undergo conformational changes during their activity. A full understanding of the function of these proteins can only be obtained if different conformations and transitions between them can be monitored in aqueous solution, with adequate temporal resolution and, ideally, on a single-molecule level. Interrogating conformational dynamics of single proteins remains, however, exquisitely challenging and typically requires site-directed chemical modification combined with rigorous minimization of possible artifacts. These obstacles limit the number of single-protein investigations. The work presented here introduces an approach that traps single unmodified proteins from solution in a plasmonic hotspot and makes it possible to assign changes in refractive index to changes in protein conformation while monitoring these changes for minutes to hours with a temporal resolution at least as fast as 40 microseconds. The resulting single molecule data reveals that adenylate kinase employs a hidden enzymatic sub-cycle during catalysis, that citrate synthase populates a previously unknown intermediate conformation, which is more important for its enzymatic activity than its well-known open conformation, that hemoglobin transitions in several steps from its deoxygenated and rigid T state to its oxygenated and flexible R state, and that apo-calmodulin thermally unfolds and refolds in steps that correspond to conformational changes of individual protein domains.

physics.bio-ph↗

arXiv2021

DNA Origami Route for Nanophotonics

The specificity and simplicity of the Watson-Crick base pair interactions make DNA one of the most versatile construction materials for creating nanoscale structures and devices. Among several DNA-based approaches, the DNA origami technique excels in programmable self-assembly of complex, arbitrary shaped structures with dimensions of hundreds of nanometers. Importantly, DNA origami can be used as templates for assembly of functional nanoscale components into three-dimensional structures with high precision and controlled stoichiometry. This is often beyond the reach of other nanofabrication techniques. In this Perspective, we highlight the capability of the DNA origami technique for realization of novel nanophotonic systems. First, we introduce the basic principles of designing and fabrication of DNA origami structures. Subsequently, we review recent advances of the DNA origami applications in nanoplasmonics, single-molecule and super-resolution fluorescent imaging, as well as hybrid photonic systems. We conclude by outlining the future prospects of the DNA origami technique for advanced nanophotonic systems with tailored functionalities.

physics.optics↗