Search

Morphological characterization of nanoparticle assemblies and hybrid nanomaterials is critical in determining their structure-property relationships as well as in the development of structures with desired properties. Electron tomography has become a widely utilized technique for the three-dimensional characterization of nanoparticle assemblies. However, the extraction of quantitative morphological parameters from the reconstructed volume can be a complex and labor-intensive task. In this study, we aim to overcome this challenge by automating the volumetric segmentation process applied to three-dimensional reconstructions of nanoparticle assemblies. The key to enabling automated characterization is to assess the performance of different volumetric segmentation methods in accurately extracting predefined quantitative descriptors for morphological characterization. In our methodology, we compare the quantitative descriptors obtained through manual segmentation with those obtained through automated segmentation methods, to evaluate their accuracy and effectiveness. To show generality, our study focuses on the characterization of assemblies of CdSe/CdS quantum dots, gold nanospheres and CdSe/CdS encapsulated in polymeric micelles, and silica-coated gold nanorods decorated with both CdSe/CdS or PbS quantum dots. We use two unsupervised segmentation algorithms: the watershed transform and the spherical Hough transform. Our results demonstrate that the choice of automated segmentation method is crucial for accurately extracting the predefined quantitative descriptors. Specifically, the spherical Hough transform exhibits superior performance in accurately extracting quantitative descriptors, such as particle size and interparticle distance, thereby allowing for an objective, efficient, and reliable volumetric segmentation of complex nanoparticle assemblies.

Micro-and nanorobots have the potential to perform non-invasive drug delivery, sensing, and surgery in living organisms, with the aid of diverse medical imaging techniques. To perform such actions, microrobots require high spatiotemporal resolution tracking with real-time closed-loop feedback. To that end, photoacoustic imaging has appeared as a promising technique for imaging microrobots in deep tissue with higher molecular specificity and contrast. Here, we present different strategies to track magnetically-driven micromotors with improved contrast and specificity using dedicated contrast agents (Au nanorods and nanostars). Furthermore, we discuss the possibility of improving the light absorption properties of the employed nanomaterials considering possible light scattering and coupling to the underlying metal-oxide layers on the micromotor’s surface. For that, 2D COMSOL simulation and experimental results were correlated, confirming that an increased spacing between the Au-nanostructures and the increase of thickness of the underlying oxide layer lead to enhanced light absorption and preservation of the characteristic absorption peak. These characteristics are important when visualizing the micromotors in a complex in vivo environment, to distinguish them from the light absorption properties of the surrounding natural chromophores.

The mechanical properties and stability of metal nanoparticle colloids under high-pressure conditions are investigated by means of optical extinction spectroscopy and small-angle X-ray scattering (SAXS), for colloidal dispersions of gold nanorods and gold nanospheres. SAXS allows us to follow in situ the structural evolution of the nanoparticles induced by pressure, regarding both nanoparticle size and shape (form factor) and their aggregation through the interparticle correlation function S(q) (structure factor). The observed behavior changes under hydrostatic and nonhydrostatic conditions are discussed in terms of liquid solidification processes yielding nanoparticle aggregation. We show that pressure-induced diffusion and aggregation of gold nanorods take place after solidification of the solvent. The effect of nanoparticle shape on the aggregation process is additionally discussed. We thank Professor Jan Dhont for helpful comments about nanoparticle diffusion in solid ethanol. F.R. acknowledges financial support from Projects PID2021-127656NB-I00 and MALTA-Consolider Team (RED2018-102612-T), and L.M.L.-M. from PID2020-117779RB-I00 and MDM-2017-0720, from the State Research Agency of Spain, Ministry of Science and Innovation. C.M.-S. acknowledges funding from the Spanish Ministry of Universities and the European Union-NextGeneration EU through the Margarita Salas research grant (C21.I4.P1). We acknowledge SOLEIL for the provision of synchrotron radiation facilities, and we would like to thank Dr. Javier Pérez, beamline supervisor, for assistance in using beamline SWING (proposals 20191731 and 20210678). This work benefited from the use of the SasView application, originally developed under NSF award DMR-0520547. SasView contains code developed with funding from the European Union’s Horizon 2020 research and innovation program under the SINE2020 project, grant agreement no. 654000.

Understanding the thermal stability of bimetallic nanoparticles is of vital importance to preserve their functionalities during their use in a variety of applications. In contrast to well-studied bimetallic systems such as Au@Ag, heat-induced morphological and compositional changes in Au@Pt nanoparticles are insufficiently understood, even though Au@Pt is an important material for catalysis. To investigate the thermal instability of Au@Pt nanorods at temperatures below their bulk melting point, we combined in situ heating with two- and three-dimensional electron microscopy techniques, including three-dimensional energy-dispersive X-ray spectroscopy. The experimental results were used as input for molecular dynamics simulations, to unravel the mechanisms behind the morphological transformation of Au@Pt core–shell nanorods. We conclude that thermal stability is influenced not only by the degree of coverage of Pt on Au but also by structural details of the Pt shell.

Background A great challenge in nanomedicine, and more specifically in theranostics, is to improve the specificity and selectivity of nanomaterials towards target tissues or cells. The topical use of nanomedicines as adjuvants to systemic chemotherapy can significantly improve the survival of patients affected by localized carcinomas, reducing the side effects of traditional drugs and preventing local recurrences.Results Here we have used the Shiga toxin, to design a safe, high-affinity protein-ligand (ShTxB) to bind the globotriaosylceramide receptor (GB3) that is overexpressed on the surfaces of preneoplastic and malignant cancer cells in head and neck tumors. We find that ShTxB functionalized gold nanorods are efficiently retrotranslocated to the GB3 positive cell cytoplasms. After 3-10 minutes of laser radiation with a wavelength resonant with the AuNR longitudinal localized surface plasmon, the death of the targeted cancer cells is activated. Both preclinical models and patient biopsy cells show the non-cytotoxic nature of these functionalized nanoparticles prior to light activation and their treatment selectivity.Conclusions These results show how the topical use of nanomedicines targeted by natural ligands can represent an effective treatment for aggressive localized cancers, such as squamous cell carcinoma of the head and neck.

The localized surface plasmon resonance (LSPR) of gold nanospheres dispersed in methanol–ethanol 4:1 was measured as a function of pressure up to 60 GPa. The LSPR exhibits an intense red-shift with...

We present a study that allows us to explain the chemical changes behind the often observed but so far ununderstood drift of the plasmon resonance of chemically prepared gold nanorods in microfluid...

The effects of nonhydrostatic pressure on the morphology and stability of gold nanorods (AuNRs) and nanospheres (AuNSs) in 4:1 methanol-ethanol mixtures were studied by optical absorption spectroscopy and transmission electron microscopy at pressures of up to 23 and 30 GPa, respectively. Solvent solidification and associated nonhydrostatic stresses were found to have a negligible effect on the shape and size of AuNSs. On the contrary, while AuNRs maintained their initial morphology in the hydrostatic range, the uniaxial stress component induced under nonhydrostatic conditions had a shearing effect on the AuNRs, breaking them into smaller particles. Interestingly, colloidal stability was maintained in all cases, and the particles showed no sign of aggregation, despite the severe nonhydrostatic conditions to which both AuNR and AuNS colloids were subjected. Financial support from Projects PGC2018-101464−B-I00 (Ministerio de Ciencia, Innovación y Universidades) and MALTA-Consolider Team (RED2018-102612-T) is acknowledged. We acknowledge J. A. Barreda-Argüeso and J. RuizFuertes for support with high-pressure measurements. P.M. thanks the ARC for grant CE170100026. L.M.L.-M. acknowledges grant PID2020-117779R and the Maria de Maeztu Units of Excellence Program (grant MDM-2017-0720) from the Spanish Ministerio de Ciencia e Innovación.

International audience; The density and compressibility of nanoscale gold (both nanospheres and nanorods) and microscale gold (bulk) were simultaneously studied by X-ray diffraction with synchrotron radiation up to 30 GPa. Colloidal stability (aggregation state and nanoparticle shape and size) in both hydrostatic and nonhydrostatic regions was monitored by small-angle X-ray scattering. We demonstrate that nonhydrostatic effects due to solvent solidification had a negligible influence on the stability of the nanoparticles. Conversely, nonhydrostatic effects produced axial stresses on the nanoparticle up to a factor 10× higher than those on the bulk metal. Working under hydrostatic conditions (liquid solution), we determined the equation of state of individual nanoparticles. From the values of the lattice parameter and bulk modulus, we found that gold nanoparticles are slightly denser (0.3%) and stiffer (2%) than bulk gold: V 0 = 67.65(3) Å 3 , K 0 = 170(3)GPa, at zero pressure.

The incidence and mortality of cancer demand more innovative approaches and combination therapies to increase treatment efficacy and decrease off-target side effects. We describe a boron-rich nanoparticle composite with potential applications in both boron neutron capture therapy (BNCT) and photothermal therapy (PTT). Our strategy is based on gold nanorods (AuNRs) stabilized with polyethylene glycol and functionalized with the water-soluble complex cobalt bis(dicarbollide) ([3,3'-Co(1,2-C(2)B9H(11))(2)](-)), commonly known as COSAN. Radiolabeling with the positron emitter copper-64 (Cu-64) enabled in vivo tracking using positron emission tomography imaging. Cu-64-labeled multi-functionalized AuNRs proved to be radiochemically stable and capable of being accumulated in the tumor after intravenous administration in a mouse xenograft model of gastrointestinal cancer. The resulting multifunctional AuNRs showed high biocompatibility and the capacity to induce local heating under external stimulation and trigger cell death in heterogeneous cancer spheroids as well as the capacity to decrease cell viability under neutron irradiation in cancer cells. These results position our nanoconjugates as suitable candidates for combined BNCT/PTT therapies.

Following blood administration, the pristine surface of nanoparticles (NPs) associates with biomolecules from the surrounding environment forming the so-called "biomolecular corona". It is well accepted that the biomolecular corona dramatically affects the NP fate in the biological medium while the pristine surface is no longer available for binding. Recent studies have shown that the glycans associated with the proteins forming the corona have a role in the NP interaction with macrophages, but the glycan identities remain unknown. We aim here to identify the glycan composition of the biomolecular corona and to assess the role of these glycans in the interaction of the proteins from the corona with glycan binding biomolecules, such as lectins.In this study, we have characterized the biomolecular corona of citrate stabilised gold NPs after exposure of the NPs to blood plasma at two different plasma concentrations, mimicking the in vitro and in vivo conditions. We have extensively characterized the biomolecular corona using HILIC chromatography and shotgun proteomics. Following this, a lectin binding assay was carried out using Dynamic Light Scattering (DLS) and Fluorescence Correlation Spectroscopy (FCS) to assess whether proteins with known affinity towards specific glycans would bind to the corona.Our findings highlighted that the protein corona composition is dependent on the exposing conditions. However, under both plasma concentrations, the biantennary sialylated glycans (A2G2S2) are enriched. DLS and FCS confirmed that the glycans are accessible for binding as the corona interacts with lectins with known affinity towards terminal sialic acids and the enzymatic removal of the glycans leads to a decrease in lectin affinity. This study shows for the first time that the glycans are present in the corona and that they could potentially be responsible for the modulation of NP biological processes as they can directly engage with glycan binding receptors that are highly expressed in an organism.

Environmental conditions during real-world application of bimetallic core-shell nanoparticles (NPs) often include the use of elevated temperatures, which are known to cause elemental redistribution, in turn significantly altering the properties of these nanomaterials. Therefore, a thorough understanding of such processes is of great importance. The recently developed combination of fast electron tomography with in situ heating holders is a powerful approach to investigate heat-induced processes at the single NP level, with high spatial resolution in 3D. In combination with 3D finite-difference diffusion simulations, this method can be used to disclose the influence of various NP parameters on the diffusion dynamics in Au@Ag core-shell systems. A detailed study of the influence of heating on atomic diffusion and alloying for Au@Ag NPs with varying core morphology and crystallographic details is carried out. Whereas the core shape and aspect ratio of the NPs play a minor role, twin boundaries are found to have a strong influence on the elemental diffusion.

The interaction of several components in the strong coupling regime yielding multiple Rabi splittings opens up remarkable possibilities for studies of multimode hybridization and energy transfer, which is of considerable interest in both fundamental and applied science. Here we demonstrate that three different components, such as core−shell Au@Ag nanorods and J-aggregates of two different dyes, can be integrated into a single hybrid structure, which leads to strong collective exciton− plasmon coupling and double-mode Rabi splitting totaling 338 meV. We demonstrate strong coupling in these multicomponent plexitonic nanostructures by means of magnetic circular dichroism spectroscopy and demonstrate strong magneto-optical activity for the three hybridized states resulting from this coupling. The J-aggregates of two different nonmagnetic dyes interact with metal nanoparticles effectively, achieving magnetic properties due to the hybridization of electronic excitations in the threecomponent system., This work was supported by MINECO (Ministerio de Economiá y Competitividad), Spain, Projects FIS2016-80174-P (PLASMOQUANTA) and MAT2017-86659-R (MULTIMAGE). I.R.N. and Y.P.R. acknowledge support from the Ministry of Education and Science of the Russian Federation under Grant No. 14.Y26.31.0011 and funding from the Basque Government (Grant No. IT1164-19). This work was coordinated under the Maria de Maeztu Units of Excellence Program from the Spanish State Research Agency (Grant No. MDM-2017-0720).

Plasmonic nanostructures, of which gold nanoparticles are the most elementary example, owe their unique properties to localized surface plasmons (LSP), the modes of free electron oscillation. LSP alter significantly electromagnetic field in the nanostructure neighborhood (i.e., near-field), which can modify the electric dipole transition rates in organic emitters. This study aims at investigating the influence of Au@SiO2 core–shell nanoparticles on the photophysics of porphyrins covalently attached to the nanoparticles surface. Guided by theoretical predictions, three sets of gold nanoparticles of different sizes were coated with a silica layer of similar thickness. The outer silica surface was functionalized with either free-base meso-tetraphenylporphyrin or its zinc complex. Absorption and emission bands of porphyrin overlap in energy with a gold nanoparticle LSP resonance that provides the field enhancement. Silica separates the emitters from the gold surface, while the gold core size tunes the energy of the LSP resonance. The signatures of weak-coupling regime have been observed. Apart from modified emission profiles and shortened S1 lifetimes, Q band part intensity of the excitation spectra significantly increased with respect to the Soret band. The results were explained using classical transfer matrix simulations and electronic states kinetics, taking into account the photophysical properties of each chromophore. The calculations could reasonably well predict and explain the experimental outcomes. The discrepancies between the two were discussed.

The detection of cancer biomarkers at an early stage of tumor development is vital for effective diagnosis and treatment of cancer. Current diagnostic tools can often detect cancer only when the biomarker levels are already too high, so that the tumors have spread and treatments are less effective. It is urgent therefore to develop highly sensitive assays for the detection of such biomarkers at the lowest possible concentration. In this context, we developed a sandwich immunoassay based on surface-enhanced Raman scattering (SERS) for the ultrasensitive detection of α-fetoprotein (AFP), which is typically present in human serum as a biomarker indicative of early stages of hepatocellular carcinoma. In the immunoassay design, molybdenum disulfide (MoS2) modified with a monoclonal antibody was used as a capture probe for AFP. A secondary antibody linked to an SERS-encoded nanoparticle was employed as the Raman signal reporter, that is, the transducer for AFP detection. The sandwich immunocomplex “capture probe/target/SERS tag” was deposited on a silicon wafer and decorated with silver-coated gold nanocubes to increase the density of “hot spots” on the surface of the immunosensor. The developed SERS immunosensor exhibits a wide linear detection range (1 pg mL–1 to 10 ng mL–1) with a limit of detection as low as 0.03 pg mL–1 toward AFP with good reproducibility (RSD < 6%) and stability. These parameters demonstrate that the proposed immunosensor has the potential to be used as an analytical platform for the detection of early-stage cancer biomarkers in clinical applications.

In a typical colloidal synthesis, the molecules of the reducing agent are irreversibly oxidized during nanocrystal growth. Such a scenario is of questionable sustainability when confronted with naturally occurring processes in which reducing agent molecules are cyclically regenerated. Here we show that cofactor molecules once consumed in the nucleation and growth of metallic nanocrystals can be photoregenerated using metallic nanocrystals as photocatalysts and reused in the subsequent nucleation process. Cyclic regeneration of cofactor molecules opens up the possibilities for the sustainable synthesis of inorganic nanoparticles., This work was supported by the Spanish MINECO (PID2019-111772RB-I00) and the BBVA Foundation – “Primera convocatoria de ayudas fundacion BBVA a investigadores, innovadores y creadores culturales”. A. C. acknowledges support from the Spanish MINECO under the Maria de Maeztu Units of Excellence Program (MDM-2016-0618).

This work was partially supported by the European Research Council ERC-CoG-648071-ProNANO, ERC-PoC-841063-NIMM, Agencia Estatal de Investigación, Spain (PID2019- 111649RB-I00; and MAT2017-88693-R), and the Basque Government (Elkartek KK-2017/00008), E.L-M thanks the Spanish Ministry of Science and Innovation for the FPI grant (BES-2017-079646). This work was performed under the Maria de Maeztu Units of Excellence Program from the Spanish State Research Agency – Grant No. MDM-2017-0720 (CIC biomaGUNE) and SEV-2016-0686 (IMDEA Nanociencia)., Protein-based materials are usually considered as insulators, although conductivity has been recently shown in proteins. This fact opens the door to develop new biocompatible conductive materials. While there are emerging efforts in this area, there is an open challenge related to the limited conductivity of protein-based systems. This work shows a novel approach to tune the charge transport properties of protein-based materials by using electron-dense AuNPs. Two strategies are combined in a unique way to generate the conductive solid films: (1) the controlled self-assembly of a protein building block; (2) the templating of AuNPs by the engineered building block. This bottom-up approach allows controlling the structure of the films and the distribution of the AuNPs within, leading to enhanced conductivity. This work illustrates a promising strategy for the development of effective hybrid protein-based bioelectrical materials., European Research Council (ERC) European Commission ERC-CoG-648071-ProNANO ERC-PoC-841063-NIMM, Agencia Estatal de Investigacion, Spain PID2019111649RB-I00 MAT2017-88693-R, Basque Government Elkartek KK-2017/00008, Spanish Government BES-2017-079646, Maria de Maeztu Units of Excellence Program from the Spanish State Research Agency MDM-2017-0720 SEV-2016-0686

Excitons in semiconductor quantum dots (QDs) feature high values of the two-photon absorption cross-sections (TPACSs), enabling applications of two-photon-excited photoluminescence (TPE PL) of QDs in biosensing and nonlinear optoelectronics. However, efficient TPE PL of QDs requires high-intensity laser fields, which limits these applications. There are two possible ways to increase the TPE PL of QDs: by increasing their photoluminescence quantum yield (PLQY) or by further increasing the TPACS. Plasmonic nanoparticles (PNPs) may act as open nanocavities for increasing the PLQY via the Purcell effect, but this enhancement is strictly limited by the maximum possible PLQY value of 100%. Here we directly investigated the effect of PNPs on the effective TPACS of excitons in QDs. We have found that effective TPACS of excitons in a QD–PMMA thin film can be increased by a factor of up to 12 near the linearly excited gold nanorods (GNRs). Using gold nanospheres (GNSs), in which plasmons cannot be excited in the infrared range, as a control system, we have shown that, although both GNSs and GNRs increase the recombination rate of excitons, the TPACS is increased only in the case of GNRs. We believe that the observed effect of TPACS enhancement is a result of the nonlinear interaction of the plasmons in GNRs with excitons in QDs, which we have supported by numerical simulations. The results show the way to the rational design of the spectral features of plasmon–exciton hybrids for using them in biosensing and nonlinear optoelectronics., V. K. acknowledges support from the Russian Science Foundation (Grant No. 18-72-10143) for the part of the study related to the investigation of the effects of PNPs on the effective TPACS of excitons in QDs and numerical simulations of these effects. Support from the Ministry of Education and Science of the Russian Federation (Grant No. 14.Y26.31.0011) for the part of this study related to the synthesis and functionalisation of the QDs and engineering of hybrid QD-GNR materials is also acknowledged. Y. R. acknowledges the support from the Basque Government (grant no. IT1164-19). Y. R. and M. G. acknowledge the support from the Spanish MINECO (PID2019-111772RB-I00). I. N. acknowledges the Ministry of Higher Education, Research and Innovation of the French Republic and Université de Reims Champagne-Ardenne.

The detection of cancer biomarkers at an early stage of tumor development is vital for effective diagnosis and treatment of cancer. Current diagnostic tools can often detect cancer only when the biomarker levels are already too high, so that the tumors have spread and treatments are less effective. It is urgent therefore to develop highly sensitive assays for the detection of such biomarkers at the lowest possible concentration. In this context, we developed a sandwich immunoassay based on surface-enhanced Raman scattering (SERS) for the ultrasensitive detection of alpha-fetoprotein (AFP), which is typically present in human serum as a biomarker indicative of early stages of hepatocellular carcinoma. In the immunoassay design, molybdenum disulfide (MoS2) modified with a monoclonal antibody was used as a capture probe for AFP. A secondary antibody linked to an SERS-encoded nanoparticle was employed as the Raman signal reporter, that is, the transducer for AFP detection. The sandwich immunocomplex "capture probe/target/SERS tag" was deposited on a silicon wafer and decorated with silver-coated gold nanocubes to increase the density of "hot spots" on the surface of the immunosensor. The developed SERS immunosensor exhibits a wide linear detection range (1 pg mL(-1) to 10 ng mL(-1)) with a limit of detection as low as 0.03 pg mL(-1) toward AFP with good reproducibility (RSD < 6%) and stability. These parameters demonstrate that the proposed immunosensor has the potential to be used as an analytical platform for the detection of early-stage cancer biomarkers in clinical applications E.E. is grateful for a fellowship from the Scientific and Technological Research Council of Turkey (TUBITAK). A.C. and A.S. thank MINECO for their research grant (Juan de la Cierva.Incorporacion/no. IJCI-2016-31113, Juan de la Cierva. Formacion/no. FJC2018-036777-I, respectively). We thank Dr. Judith Langer for support in the interpretation of SERS results. This work was supported by the European Union's Horizon 2020 research and innovation program under Grant Agreements 785219 and 881603 Graphene Flagship. L.M.L.-M. acknowledges funding from the European Research Council (ERC-AdG-2017#787510). M.P., as the recipient of the AXA Bionanotechnology Chair, is grateful to the AXA Research Fund for financial support. This work was performed under the Maria de Maeztu Units of Excellence Program from the Spanish State Research Agency.grant no. MDM-20170720

Strong exciton–plasmon interaction enables effective control of the photonic properties of hybrid organic–inorganic nanostructures encompassing light absorption, scattering and luminescence. Whereas the manifestations of light-matter interactions in the absorption and scattering are reasonably well understood their relation to the luminescence as well as luminescence properties themselves in strongly coupled plexcitonic hybrids is still largely underexplored especially for a system with a complex mechanism of hybridisation of states. Here we report on investigation of the interaction between localized and hybridized plasmons in gold nanostars and excitons in J-aggregates under ambient conditions. Our findings demonstrate the quality performance of the formed plexciton system with multiple hybridization channels in terms of the parameters of strong coupling, such as Rabi splitting (230 meV), coupling-strength-to-transition energy ratio (0.07), and cooperativity (2.03). The results of time-resolved experiments elucidate the observed enhanced spontaneous emission rate with regard to the Purcell effect, whose value was estimated from the extinction spectra of the strongly coupled plexciton system., Financial supports from Projects PID2019-111772RB-I00 of the Spanish MINECO and the Ministry of Science and Higher Education of the Russian Federation (Grant No. 14.Y26.31.0011) are acknowledged. Y. R. acknowledges the support from the Basque Government (grant no. IT1164-19). P.S. and I.N acknowledge support from the Russian Science Foundation (grant no. 21-79-30048) of the part of this work related to nanomaterials manufacturing and functionalisation. I.N. acknowledges support from the Université de Reims Champagne-Ardenne. A.S.-I. acknowledges the Maria de Maeztu Units of Excellence Program from the Spanish State Research Agency (Grant No. MDM-2017-0720).

Hybridized plexcitonic states have unique properties which have been widely studied in recent decades in many research fields targeted at both fundamental science and innovative applications. However, to make these applications come true one needs to ensure the stabilization and preservation of electronic states and optical transitions in hybrid nanostructures, especially under the influence of external stressors, in regimes, that have not yet been comprehensively investigated. The present work shows that the nanohybrid system, composed of plasmonic nanoparticles and J-aggregates of organic molecules, displays outstanding resistance to harsh environmental stressors such as temperature, pH and strong light irradiation as well as demonstrates long-term stability and processability of the nanostructures both in weak and strong coupling regimes. These findings contribute to a deeper understanding of the physicochemical properties of plexcitonic nanoparticles and may find important implications for the development of potential applications in optoelectronics, optical imaging and chemo-bio-sensing and, in general, in the field of optical materials science., Authors acknowledge the financial support from the Ministry of Education and Science of the Russian Federation (grant no. 14.Y26.31.0011). Y. R. acknowledges the support from the Basque Government (grant no. IT1164-19). M. G. acknowledges support from the Basque Government (PIBA 2018-34), and Diputación Foral de Guipúzcoa (RED 2018, RED 2019). A. S. I. acknowledges the Maria de Maeztu Units of Excellence Programme – Grant No. MDM-2017-0720 Ministry of Science, Innovation and Universities.

Although high-quality gold nanorods can be routinely synthesized, within a wide range of sizes and aspect ratios, a similar level of control has not been reached for silver nanorods. Whereas seeded-growth processes have been developed, the reported methods have not met sufficient interest, mainly because of limited quality, particularly when small size (short diameter) and small aspect ratios are targeted. In the surfactant-driven seeded growth of gold nanorods, the success of the synthesis is largely dependent on the quality and stability of the seeds, and thus related methods have been reported for the seeded growth of Ag nanorods, using penta-twinned Au nanorods and bipyramids as seeds. However, Ag nanorods with diameters of >30 nm are consistently obtained, restricting their potential applications. We report the preparation of high-quality silver nanorods, using either small bipyramids or small decahedra as seeds, with special attention to the location of the seeds, either at the center (bipyramids) or at one end (decahedra) of the resulting nanorods.

Plasmonic nanoparticles (PNPs) can significantly modify the optical properties of nearby organic molecules and thus present an attractive opportunity for sensing applications. However, the utilization of PNPs in conventional absorption, fluorescence, or Raman spectroscopy techniques is often ineffective due to strong absorption background and light scattering, particularly in the case of turbid solutions, cell suspensions, and biological tissues. Here we show that nonmagnetic organic molecules may exhibit magneto-optical response due to binding to a PNP. Specifically, we detect strong magnetic circular dichroism signal from supramolecular J-aggregates, a representative organic dye, upon binding to silver-coated gold nanorods. We explain this effect by strong coupling between the J-aggregate exciton and the nanoparticle plasmon, leading to the formation of a hybrid state in which the exciton effectively acquires magnetic properties from the plasmon. Our findings are fully corroborated by theoretical modeling and constitute a novel magnetic method for chemo- and biosensing, which (upon adequate PNP functionalization) is intrinsically insensitive to the organic background and thus offers a significant advantage over conventional spectroscopy techniques., We acknowledge financial support from Project Fis2016.80174-P (PLASMOQUANTA) from MINECO (Ministerio de Economia y Competitividad). L.L.-M. acknowledges funding from the European Research Council (ERC Advanced Grant 267867, Plasmaquo).

Semiconductor quantum dots (QDs) are known for their ability to exhibit multiphoton emission caused by recombination of biexcitons (BX). However, the quantum yield (QY) of BX emission is low due to the fast Auger process. Plasmonic nanoparticles (PNPs) provide an attractive opportunity to accelerate BX radiative recombination. Here, we demonstrate the PNPs induced distance-controlled enhancement of BX emission of single QDs. Studying the same single QD before and after its integration with the PNPs, we observed a plasmon-mediated increase in the QY of BX emission. Remarkably, the enhancement of BX emission remains pronounced even at distances of 170 nm. We attribute this effect to efficient coupling, which results in the trade-off between resonance energy transfer from QD to gold nanorods and the Purcell effect at small QD-PNP separations and the predominant influence of the Purcell effect at longer distances. Our findings constitute a reliable approach to managing the efficiency of multiexciton emission over a wide span of distances, thus paving the way for new applications., The authors acknowledge the financial support from the Ministry of Education and Science of the Russian Federation (Grant 14.Y26.31.0011). Y.R. acknowledges support from MINECO (Ministerio de Economiá y Competitividad, Spain), Project Fis2016.80174-P (PLASMOQUANTA).

The hydrophobic collapse is a structural transition of grafted polymer chains in a poor solvent. Although such a transition seems an intrinsic event during clustering of polymer-stabilized nanoparticles in the liquid phase, it has not been resolved in real time. In this work, we implemented a microfluidic 3D-flow-focusing mixing reactor equipped with real-time analytics, small-angle X-ray scattering (SAXS), and UV–vis–NIR spectroscopy to study the early stage of cluster formation for polystyrene-stabilized gold nanoparticles. The polymer shell dynamics obtained by in situ SAXS analysis and numerical simulation of the solvent composition allowed us to map the interaction energy between the particles at early state of solvent mixing, 30 ms behind the crossing point. We found that the rate of hydrophobic collapse depends on water concentration, ranging between 100 and 500 nm/s. Importantly, we confirmed that the polymer shell collapses prior to the commencement of clustering.

Semiconductor quantum dots (QDs) are known for their unique photophysical properties and, in particular, their ability to multiphoton emission caused by recombination of biexcitons. However, the luminescence quantum yield of biexciton states is relatively low due to the fast Auger non-radiative process. Plasmonic nanoparticles can significantly accelerate the radiative rate of QDs. In this study we demonstrate the distance-controlled enhancement of the biexciton emission of single CdSe/ZnS/CdS/ZnS QDs due to their coupling with gold nanorods. We explain this enhancement as the distancedependent trade-off between the energy transfer and the Purcell effect. Our findings constitute a reliable approach to managing the efficiency of multiphoton emission over a wide span of distances.

A thorough understanding of the thermal stability and potential reshaping of anisotropic gold nanostars is required for various potential applications. Combination of a tomographic heating holder with fast tilt series acquisition has been used to monitor temperature-induced morphological changes of Au nanostars. The outcome of our 3D investigations can be used as an input for boundary element method simulations, enabling us to investigate the influence of reshaping on the nanostars’ plasmonic properties. Our work leads to a better understanding of the mechanism behind thermal reshaping. In addition, the approach presented here is generic and can hence be applied to a wide variety of nanoparticles made of different materials and with arbitrary morphology.

It is commonly agreed that the crystalline structure of seeds dictates the crystallinity of final nanoparticles in a seeded-growth process. Although the formation of monocrystalline particles does require the use of single-crystal seeds, twin planes may stem from either single-or polycrystalline seeds. However, experimental control over twin-plane formation remains difficult to achieve synthetically. Here, we show that a careful interplay between kinetics and selective surface passivation offers a unique handle over the emergence of twin planes (in decahedra and triangles) during the growth over single-crystalline gold nanoparticles of quasi-spherical shape. Twinning can be suppressed under conditions of slow kinetics in the presence of silver ions, yielding single-crystalline particles with high-index facets.

The anisotropic morphology of gold nanorods (AuNRs) has been shown to lead to nonuniform ligand distribution and preferential etching through their tips. We have recently demonstrated that this effect can be achieved by biocatalytic oxidation with hydrogen peroxide, catalyzed by the enzyme horseradish peroxidase (HRP). We report here that modification of AuNRs with thiol-containing organic molecules such as glutathione and thiocholine hinders enzymatic AuNR etching. Higher concentrations of thiol-containing molecules in the reaction mixture gradually decrease the rate of enzymatic etching, which can be monitored by UV–vis spectroscopy through changes in the AuNR longitudinal plasmon band. This effect can be applied to develop novel optical assays for acetylcholinesterase (AChE) activity. The biocatalytic hydrolysis of acetylthiocholine by AChE yields thiocholine, which prevents enzymatic AuNR etching in the presence of HRP. Additionally, the same bioassay can be used for the detection of nanomolar concentrations of AChE inhibitors such as paraoxon and galanthamine.

Nanoparticle assemblies can be investigated in 3 dimensions using electron tomography. However, it is not straightforward to obtain quantitative information such as the number of particles or their relative position. This becomes particularly difficult when the number of particles increases. We propose a novel approach in which prior information on the shape of the individual particles is exploited. It improves the quality of the reconstruction of these complex assemblies significantly. Moreover, this quantitative Sparse Sphere Reconstruction approach yields directly the number of particles and their position as an output of the reconstruction technique, enabling a detailed 3D analysis of assemblies with as many as 10 000 particles. The approach can also be used to reconstruct objects based on a very limited number of projections, which opens up possibilities to investigate beam sensitive assemblies where previous reconstructions with the available electron tomography techniques failed.

The light harvesting capacity of plasmonic nanoparticles is a fundamental feature for catalysing chemical reactions close to their surface. The efficiency of the photochemical processes depends not only on the geometrical aspects on a single particle level but also on the complexity of the multiparticle architectures. Although, the effect of the particle geometry is progressively understood in the relevant photochemical processes (water splitting and hydrogen evolution), there are experimental and theoretical needs for understanding the role of the shape in the multiparticle systems in the photocatalytic processes. Here we have shown that macroscopic plasmonic substrates comprising gold nanostars exhibit better efficiencies than nanorods or cubes in the photoregeneration of cofactor molecules. We performed photochemical and photoelectrochemical measurements, supported by theoretical simulations, showing that the unique geometry of nanostars – radially distributed spikes – contributes to stronger light absorption by the plasmonic film containing that type of nanoparticles.

Gold and silver nanoclusters aggregates have gained significant attention as their optical properties and chemical stability surpasses those of individual nanoclusters. Here, we present a systematic investigation of aggregation-induced changes of morphology and optical properties of glutathione-stabilized silver-doped gold nanoclusters (AuAg NCs). We show that the silver-doped clusters have the ability to spontaneously aggregate in solution, but in order to stabilize their structure and enhance the one-photon (1 P) and two-photon (2 P) properties we used poly(allylamine hydrochloride) (PAH) matrix. This resulted in obtaining NCs superstructures having narrow size distribution and efficient 1 P and 2 P excited photoluminescence.

Fabrication of protein-based biomaterials is an arduous and time-consuming procedure with multiple steps. In this work, we describe a portable toolkit that integrates both cell-free protein synthesis (CFPS) and protein immobilization in one pot just by mixing DNA, solid materials, and a CFPS system. We have constructed a modular set of plasmids that fuse the N-terminus of superfolded green fluorescent protein (sGFP) with different peptide tags (poly(6X)Cys, poly(6X)His, and poly(6X)Lys), which drive the immobilization of the protein on the tailored material (agarose beads with different functionalities, gold nanorods, and silica nanoparticles). This system also enables the incorporation of azide-based amino acids into the nascent protein for its selective immobilization through copper-free click reactions. Finally, this technology has been expanded to the synthesis and immobilization of enzymes and antibody-binding proteins for the fabrication of functional biomaterials. This synthetic biological platform has emerged as a versatile tool for on-demand fabrication of therapeutic, diagnostic, and sensing biomaterials.

The efficacy of drug delivery and other nanomedicine-related therapies largely relies on the ability of nanoparticles to reach the target organ. However, when nanoparticles are injected into the bloodstream, their surface is instantly modified upon interaction with blood components, principally with proteins. It is well known that a dynamic and multi-layered protein structure is formed spontaneously on the nanoparticle upon contact with physiological media, which has been termed protein corona. Although several determinant factors involved in protein corona formation have been identified from in vitro studies, specific relationships between the nanomaterial synthetic identity and its ensuing biological identity under realistic in vivo conditions remain elusive. We present here a detailed study of in vivo protein corona formation after blood circulation of anisotropic gold nanoparticles (nanorods and nanostars). Plasmonic gold nanoparticles of different shapes and sizes were coated with polyethyleneglycol, intravenously administered in CD-1 mice and subsequently recovered. The results from gel electrophoresis and mass spectrometry analysis revealed the formation of complex protein coronas, as early as 10 minutes post-injection. The total amount of protein adsorbed onto the particle surface and the protein corona composition were found to be affected by both the particle size and shape.

The presence of iodide ions during the growth of gold nanorods strongly affects the shape of the final products, which is proposed to be due to selective iodide adsorption on certain crystallographic facets. Therefore, a detailed structural and morphological characterization of the starting rods is crucial toward understanding this effect. Electron tomography is used to determine the crystallographic indices of the lateral facets of gold nanorods, as well as those present at the tips. Based on this information, density functional theory calculations are used to determine the surface and interface energies of the observed facets and provide insight into the relationship between the amount of iodide ions in the growth solution and the final morphology of anisotropic gold nanoparticles.

A limiting factor of solvent-induced nanoparticle self-assembly is the need for constant sample dilution in assembly/disassembly cycles. Changes in the nanoparticle concentration alter the kinetics of the subsequent assembly process, limiting optical signal recovery. Herein, we show that upon confining hydrophobic nanoparticles in permeable silica nanocapsules, the number of nanoparticles participating in cyclic aggregation remains constant despite bulk changes in solution, leading to highly reproducible plasmon band shifts at different solvent compositions.

Pt nanoparticles play an essential role in a wide variety of catalytic reactions. The activity of the particles strongly depends on their three-dimensional (3D) structure and exposed facets, as well as on the reactive environment. High-resolution electron microscopy has often been used to characterize nanoparticle catalysts but unfortunately most observations so far have been either performed in vacuum and/or using conventional (2D) in situ microscopy. The latter however does not provide direct 3D morphological information. We have implemented a quantitative methodology to measure variations of the 3D atomic structure of nanoparticles under the flow of a selected gas. We were thereby able to quantify refaceting of Pt nanoparticles with atomic resolution during various oxidation–reduction cycles. In a H2 environment, a more faceted surface morphology of the particles was observed with {100} and {111} planes being dominant. On the other hand, in O2 the percentage of {100} and {111} facets decreased and a significant increase of higher order facets was found, resulting in a more rounded morphology. This methodology opens up new opportunities toward in situ characterization of catalytic nanoparticles because for the first time it enables one to directly measure 3D morphology variations at the atomic scale in a specific gaseous reaction environment.

Three dimensional (3D) characterization of structural defects in nanoparticles by transmission electron microscopy is far from straightforward. We propose the use of a dose-efficient approach, so-called multimode tomography, during which tilt series of low and high angle annular dark field scanning transmission electron microscopy projection images are acquired simultaneously. In this manner, not only reliable information can be obtained concerning the shape of the nanoparticles, but also the twin planes can be clearly visualized in 3D. As an example, we demonstrate the application of this approach to identify the position of the seeds with respect to the twinning planes in anisotropic gold nanoparticles synthesized using a seed mediated growth approach.

The three-dimensional (3D) atomic structure of nanomaterials, including strain, is crucial to understand their properties. Here, we investigate lattice strain in Au nanodecahedra using electron tomography. Although different electron tomography techniques enabled 3D characterizations of nanostructures at the atomic level, a reliable determination of lattice strain is not straightforward. We therefore propose a novel model-based approach from which atomic coordinates are measured. Our findings demonstrate the importance of investigating lattice strain in 3D.

Resumen del trabajo presentado a la 19th International Conference on Transparent Optical Networks (ICTON), celebrada en Girona (España) del 2 al 6 de julio de 2017., We report our recent results of investigation of the interactions between localized plasmons in gold nanorods and excitons in J-aggregates. We were able to track an anticrossing behavior of the hybridized modes both in the extinction and in the photoluminescence spectra of this hybrid system. We identified the nonlinear optical behavior of this system by transient absorption spectroscopy. Finally using magnetic circular dichroism spectroscopy, we show that nonmagnetic organic molecules exhibit magneto-optical response due to binding to a plasmonic nanoparticles. In our experiments, we also studied the effect of detuning as well as the effect of off- and on resonance excitation on the hybrid states.