Two-state switchable plasmonic tweezers for dynamic manipulation of nano-objects.

In this work, we present a plasmonic platform capable of trapping nano-objects in two different spatial configurations. The switch between the two trapping states, localized on the tip and on the outer wall of a vertical gold nanochannel, can be activated by varying the focusing position of the excitation laser along the main axis of the nanotube. We show that the switching of the trapping site is induced by changes in the distribution of the electromagnetic field and of the trapping force. The "inner" and "outer" trapping states are characterized by a static and a dynamic behavior respectively, and their stiffness is measured by analyzing the positions of the trapped specimens as a function of time. In addition, we demonstrate that the stiffness of the static state is high enough to trap particles with diameter as small as 40 nm. These results show a simple, controllable way to generate a switchable two-state trapping regime, which could be used as a model for the study of dynamic trapping or as a mechanism for the development of nanofluidic devices.

Plasmon-Assisted Suppression of Surface Trap States and Enhanced Band-Edge Emission in a Bare CdTe Quantum Dot.

Colloidal quantum dots have emerged as a versatile photoluminescent and optoelectronic material. Limitations like fluorescence intermittency, nonradiative Auger recombination, and surface traps are commonly addressed by growing a wide-band-gap shell. However, the shell isolates the excitonic wave function and reduces its interaction with the external environment necessary for different applications. Furthermore, their long emission lifetime hinders their use in high-speed optoelectronics. Here, we demonstrate a high degree of control on the photophysics of a bare core CdTe quantum dot solely by plasmon coupling, showing that more than 99% of the surface defect-state emission from a trap-rich quantum dot can be quenched. Moreover, the band-edge state excitonic and biexcitonic emission rates are Purcell enhanced by 1460- and 613-fold, respectively. Our findings show how plasmon coupling on bare quantum dots could make chemical approaches developed for improving their optical properties unnecessary, with implications for nanoscale lasers, light-emitting devices, solar cells, and ultrafast single-photon sources.

Long-Range Capture and Delivery of Water-Dispersed Nano-objects by Microbubbles Generated on 3D Plasmonic Surfaces.

The possibility of investigating small amounts of molecules, moieties, or nano-objects dispersed in solution constitutes a central step for various application areas in which high sensitivity is necessary. Here, we show that the rapid expansion of a water bubble can act as a fast-moving net for molecules or nano-objects, collecting the floating objects in the surrounding medium in a range up to 100 µm. Thanks to an engineered 3D patterning of the substrate, the collapse of the bubble could be guided toward a designed area of the surface with micrometric precision. Thus, a locally confined high density of particles is obtained, ready for evaluation by most optical/spectroscopic detection schemes. One of the main relevant strengths of the long-range capture and delivery method is the ability to increase, by a few orders of magnitude, the local density of particles with no changes in their physiological environment. The bubble is generated by an ultrafast IR laser pulse train focused on a resonant plasmonic antenna; due to the excitation process, the technique is trustworthy and applicable to biological samples. We have tested the reliabilities of the process by concentrating highly dispersed fluorescence molecules and fluorescent beads. Lastly, as an ultimate test, we have applied the bubble clustering method on nanosized exosome vesicles dispersed in water; due to the clustering effect, we were able to effectively perform Raman spectroscopy on specimens that were otherwise extremely difficult to measure.

Reshaping the phonon energy landscape of nanocrystals inside a terahertz plasmonic nanocavity.

Phonons (quanta of collective vibrations) are a major source of energy dissipation and drive some of the most relevant properties of materials. In nanotechnology, phonons severely affect light emission and charge transport of nanodevices. While the phonon response is conventionally considered an inherent property of a nanomaterial, here we show that the dipole-active phonon resonance of semiconducting (CdS) nanocrystals can be drastically reshaped inside a terahertz plasmonic nanocavity, via the phonon strong coupling with the cavity vacuum electric field. Such quantum zero-point field can indeed reach extreme values in a plasmonic nanocavity, thanks to a mode volume well below λ3/107. Through Raman measurements, we find that the nanocrystals within a nanocavity exhibit two new "hybridized" phonon peaks, whose spectral separation increases with the number of nanocrystals. Our findings open exciting perspectives for engineering the optical phonon response of functional nanomaterials and for implementing a novel platform for nanoscale quantum optomechanics.

Chemical Functionalization of Plasmonic Surface Biosensors: A Tutorial Review on Issues, Strategies, and Costs.

In an ideal plasmonic surface sensor, the bioactive area, where analytes are recognized by specific biomolecules, is surrounded by an area that is generally composed of a different material. The latter, often the surface of the supporting chip, is generally hard to be selectively functionalized, with respect to the active area. As a result, cross talks between the active area and the surrounding one may occur. In designing a plasmonic sensor, various issues must be addressed: the specificity of analyte recognition, the orientation of the immobilized biomolecule that acts as the analyte receptor, and the selectivity of surface coverage. The objective of this tutorial review is to introduce the main rational tools required for a correct and complete approach to chemically functionalize plasmonic surface biosensors. After a short introduction, the review discusses, in detail, the most common strategies for achieving effective surface functionalization. The most important issues, such as the orientation of active molecules and spatial and chemical selectivity, are considered. A list of well-defined protocols is suggested for the most common practical situations. Importantly, for the reported protocols, we also present direct comparisons in term of costs, labor demand, and risk vs benefit balance. In addition, a survey of the most used characterization techniques necessary to validate the chemical protocols is reported.

Intracellular and Extracellular Recording of Spontaneous Action Potentials in Mammalian Neurons and Cardiac Cells with 3D Plasmonic Nanoelectrodes.

Three-dimensional vertical micro- and nanostructures can enhance the signal quality of multielectrode arrays and promise to become the prime methodology for the investigation of large networks of electrogenic cells. So far, access to the intracellular environment has been obtained via spontaneous poration, electroporation, or by surface functionalization of the micro/nanostructures; however, these methods still suffer from some limitations due to their intrinsic characteristics that limit their widespread use. Here, we demonstrate the ability to continuously record both extracellular and intracellular-like action potentials at each electrode site in spontaneously active mammalian neurons and HL-1 cardiac-derived cells via the combination of vertical nanoelectrodes with plasmonic optoporation. We demonstrate long-term and stable recordings with a very good signal-to-noise ratio. Additionally, plasmonic optoporation does not perturb the spontaneous electrical activity; it permits continuous recording even during the poration process and can regulate extracellular and intracellular contributions by means of partial cellular poration.

Time resolved and label free monitoring of extracellular metabolites by surface enhanced Raman spectroscopy.

Metabolomics is an emerging field of cell biology that aims at the comprehensive identification of metabolite levels in biological fluids or cells in a specific functional state. Currently, the major tools for determining metabolite concentrations are mass spectrometry coupled with chromatographic techniques and nuclear magnetic resonance, which are expensive, time consuming and destructive for the samples. Here, we report a time resolved approach to monitor metabolite dynamics in cell cultures, based on Surface Enhanced Raman Scattering (SERS). This method is label-free, easy to use and provides the opportunity to simultaneously study a broad range of molecules, without the need to process the biological samples. As proof of concept, NIH/3T3 cells were cultured in vitro, and the extracellular medium was collected at different time points to be analyzed with our engineered SERS substrates. By identifying individual peaks of the Raman spectra, we showed the simultaneous detection of several components of the conditioned medium, such as L-tyrosine, L-tryptophan, glycine, L-phenylalanine, L-histidine and fetal bovine serum proteins, as well as their intensity changes during time. Furthermore, analyzing the whole Raman data set with the Principal Component Analysis (PCA), we demonstrated that the Raman spectra collected at different days of culture and clustered by similarity, described a well-defined trajectory in the principal component plot. This approach was then utilized to determine indirectly the functional state of the macrophage cell line Raw 264.7, stimulated with the lipopolysaccharide (LPS) for 24 hours. The collected spectra at different time points, clustered by the PCA analysis, followed a well-defined trajectory, corresponding to the functional change of cells toward the activated pro-inflammatory state induced by the LPS. This study suggests that our engineered SERS surfaces can be used as a versatile tool both for the characterization of cell culture conditions and the functional state of cells over time.

Hot electrons in water: injection and ponderomotive acceleration by means of plasmonic nanoelectrodes.

We present a theoretical and experimental study of a plasmonic nanoelectrode architecture that is able to inject bunches of hot electrons into an aqueous environment. In this approach, electrons are accelerated in water by ponderomotive forces up to energies capable of exciting or ionizing water molecules. This ability is enabled by the nanoelectrode structure (extruding out of a metal baseplate), which allows for the production of an intense plasmonic hot spot at the apex of the structure while maintaining the electrical connection to a virtually unlimited charge reservoir. The electron injection is experimentally monitored by recording the current transmitted through the water medium, whereas the electron acceleration is confirmed by observation of the bubble generation for a laser power exceeding a proper threshold. An understanding of the complex physics involved is obtained via a numerical approach that explicitly models the electromagnetic hot spot generation, electron-by-electron injection via multiphoton absorption, acceleration by ponderomotive forces and electron-water interaction through random elastic and inelastic scattering. The model predicts a critical electron density for bubble nucleation that nicely matches the experimental findings and reveals that the efficiency of energy transfer from the plasmonic hot spot to the free electron cloud is much more efficient (17 times higher) in water than in a vacuum. Because of their high kinetic energy and large reduction potential, these proposed wet hot electrons may provide new opportunities in photocatalysis, electrochemical processes and hot-electron driven chemistry.

Morphological modulation of graphene-mediated hybridization in plasmonic systems.

We investigated the plasmonic response of a 2-dimensional ordered array of closely spaced (few-nm apart) Au nanoparticles covered by a large-area single-layer graphene sheet. The array consisted of coherently aligned nanoparticle chains, endowed with a characteristic uniaxial anisotropy. The joint effect of such a morphology and of the very small particle size and spacing led to a corresponding uniaxial wrinkling of graphene in the absence of detectable strain. The deposition of graphene redshifted the Au plasmon-resonance, strongly increased the optical absorption of the array and, most importantly, induced a marked optical anisotropy in the plasmonic response, absent in the pristine nanoparticle array. The experimental observations are accounted for by invoking a graphene-mediated resistive coupling between the Au nanoparticles, where the optical anisotropy arises from the wrinkling-induced anisotropic electron mobility in graphene at optical frequencies.

3D vertical nanostructures for enhanced infrared plasmonics.

The exploitation of surface plasmon polaritons has been mostly limited to the visible and near infrared range, due to the low frequency limit for coherent plasmon excitation and the reduction of confinement on the metal surface for lower energies. In this work we show that 3D--out of plane--nanostructures can considerably increase the intrinsic quality of the optical output, light confinement and electric field enhancement factors, also in the near and mid-infrared. We suggest that the physical principle relies on the combination of far field and near field interactions between neighboring antennas, promoted by the 3D out-of-plane geometry. We first analyze the changes in the optical behavior, which occur when passing from a single on-plane nanostructure to a 3D out-of-plane configuration. Then we show that by arranging the nanostructures in periodic arrays, 3D architectures can provide, in the mid-IR, a much stronger plasmonic response, compared to that achievable with the use of 2D configurations, leading to higher energy harvesting properties and improved Q-factors, with bright perspective up to the terahertz range.

Direct Synthesis of Carbon-Doped TiO2-Bronze Nanowires as Anode Materials for High Performance Lithium-Ion Batteries.

Carbon-doped TiO2-bronze nanowires were synthesized via a facile doping mechanism and were exploited as active material for Li-ion batteries. We demonstrate that both the wire geometry and the presence of carbon doping contribute to the high electrochemical performance of these materials. Direct carbon doping for example reduces the Li-ion diffusion length and improves the electrical conductivity of the wires, as demonstrated by cycling experiments, which evidenced remarkably higher capacities and superior rate capability over the undoped nanowires. The as-prepared carbon-doped nanowires, evaluated in lithium half-cells, exhibited lithium storage capacity of ∼306 mA h g(-1) (91% of the theoretical capacity) at the current rate of 0.1C as well as excellent discharge capacity of ∼160 mAh g(-1) even at the current rate of 10 C after 1000 charge/discharge cycles.

Spatially, Temporally, and Quantitatively Controlled Delivery of Broad Range of Molecules into Selected Cells through Plasmonic Nanotubes.

A Universal plasmonic/microfluidic platform for spatial and temporal controlled intracellular delivery is described. The system can inject/transfect the desired amount of molecules with an efficacy close to 100%. Moreover, it is highly scalable from single cells to large ensembles without administering the molecules to an extracellular bath. The latter enables quantitative control over the amount of injected molecules.

Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals.

We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn(2+) and Cd(2+)) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu(2-x)Se) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces. No alloy or core-shell structures were observed. The role of phosphines, like tri-n-octylphosphine, in these reactions, is multifaceted: besides acting as selective solvating ligands for Cu(+) ions exiting the nanoparticles during exchange, they also enable anion diffusion, by extracting an appreciable amount of selenium to the solution phase, which may further promote the exchange process. In reactions run at a higher temperature (150 °C), copper vacancies were quickly eliminated from the nanocrystals and major differences in Cu stoichiometries, as well as in reactivities, between the initial Cu2Se and Cu(2-x)Se samples were rapidly smoothed out. These experiments indicate that cation exchange, under the specific conditions of this work, is more efficient at room temperature than at higher temperature.

Out-of-Plane Plasmonic Antennas for Raman Analysis in Living Cells.

Out-of-plane plasmonic nanoantennas protruding from the substrate are exploited to perform very sensitive surface enhanced Raman scattering analysis of living cells. Cells cultured on three-dimensional surfaces exhibit tight adhesion with nanoantenna tips where the plasmonic hot-spot resides. This fact provides observable cell adhesion sites combined with high plasmonic enhancement, resulting in an ideal system for Raman investigation of cell membranes.

Cu3-x P Nanocrystals as a Material Platform for Near-Infrared Plasmonics and Cation Exchange Reactions.

Synthesis approaches to colloidal Cu3P nanocrystals (NCs) have been recently developed, and their optical absorption features in the near-infrared (NIR) have been interpreted as arising from a localized surface plasmon resonance (LSPR). Our pump-probe measurements on platelet-shaped Cu3-x P NCs corroborate the plasmonic character of this absorption. In accordance with studies on crystal structure analysis of Cu3P dating back to the 1970s, our density functional calculations indicate that this material is substoichiometric in copper, since the energy of formation of Cu vacancies in certain crystallographic sites is negative, that is, they are thermodynamically favored. Also, thermoelectric measurements point to a p-type behavior of the majority carriers from films of Cu3-x P NCs. It is likely that both the LSPR and the p-type character of our Cu3-x P NCs arise from the presence of a large number of Cu vacancies in such NCs. Motivated by the presence of Cu vacancies that facilitate the ion diffusion, we have additionally exploited Cu3-x P NCs as a starting material on which to probe cation exchange reactions. We demonstrate here that Cu3-x P NCs can be easily cation-exchanged to hexagonal wurtzite InP NCs, with preservation of the anion framework (the anion framework in Cu3-x P is very close to that of wurtzite InP). Intermediate steps in this reaction are represented by Cu3-x P/InP heterostructures, as a consequence of the fact that the exchange between Cu+ and In3+ ions starts from the peripheral corners of each NC and gradually evolves toward the center. The feasibility of this transformation makes Cu3-x P NCs an interesting material platform from which to access other metal phosphides by cation exchange.

Hierarchical effect behind the supramolecular chirality of silver(I)-cysteine coordination polymers.

Cysteine is a sulfur-containing amino acid that easily coordinates to soft metal ions and grafts to noble metal surfaces. Recently, chiroptical activity of Ag(+)/cysteine coordination polymers has been widely studied, while, on the other hand, the appearance of a plasmon-enhanced circular dichroic signal (PECD) at the plasmonic spectral region (λ > 400 nm) has been observed for AgNPs capped with chiral sulfur-containing amino acids. These two events are both potentially exploited for sensing applications. However, the presence of Ag(+) ions in AgNP colloidal solution deals with the competition of cysteine grafting at the metal NP surface and/or metal ion coordination. Herein we demonstrate that the chiroptical activity observed by adding cysteine to AgNP colloids prepared by pulsed laser ablation in liquids (PLAL) is mainly related to the formation of CD-active Ag(+)/cysteine supramolecular polymers. The strict correlation between supramolecular chirality and hierarchical effects, driven by different chemical environments experienced by cysteine when different titration modalities are used, is pivotal to validate cysteine as a fast and reliable probe to characterize the surface oxidation of AgNPs prepared by pulsed laser ablation in liquids by varying the laser wavelengths.

Hollow plasmonic antennas for broadband SERS spectroscopy.

The chemical environment of cells is an extremely complex and multifaceted system that includes many types of proteins, lipids, nucleic acids and various other components. With the final aim of studying these components in detail, we have developed multiband plasmonic antennas, which are suitable for highly sensitive surface enhanced Raman spectroscopy (SERS) and are activated by a wide range of excitation wavelengths. The three-dimensional hollow nanoantennas were produced on an optical resist by a secondary electron lithography approach, generated by fast ion-beam milling on the polymer and then covered with silver in order to obtain plasmonic functionalities. The optical properties of these structures have been studied through finite element analysis simulations that demonstrated the presence of broadband absorption and multiband enhancement due to the unusual geometry of the antennas. The enhancement was confirmed by SERS measurements, which showed a large enhancement of the vibrational features both in the case of resonant excitation and out-of-resonance excitation. Such characteristics indicate that these structures are potential candidates for plasmonic enhancers in multifunctional opto-electronic biosensors.

3D plasmonic nanoantennas integrated with MEA biosensors.

Neuronal signaling in brain circuits occurs at multiple scales ranging from molecules and cells to large neuronal assemblies. However, current sensing neurotechnologies are not designed for parallel access of signals at multiple scales. With the aim of combining nanoscale molecular sensing with electrical neural activity recordings within large neuronal assemblies, in this work three-dimensional (3D) plasmonic nanoantennas are integrated with multielectrode arrays (MEA). Nanoantennas are fabricated by fast ion beam milling on optical resist; gold is deposited on the nanoantennas in order to connect them electrically to the MEA microelectrodes and to obtain plasmonic behavior. The optical properties of these 3D nanostructures are studied through finite elements method (FEM) simulations that show a high electromagnetic field enhancement. This plasmonic enhancement is confirmed by surface enhancement Raman spectroscopy of a dye performed in liquid, which presents an enhancement of almost 100 times the incident field amplitude at resonant excitation. Finally, the reported MEA devices are tested on cultured rat hippocampal neurons. Neurons develop by extending branches on the nanostructured electrodes and extracellular action potentials are recorded over multiple days in vitro. Raman spectra of living neurons cultured on the nanoantennas are also acquired. These results highlight that these nanostructures could be potential candidates for combining electrophysiological measures of large networks with simultaneous spectroscopic investigations at the molecular level.

Sn cation valency dependence in cation exchange reactions involving Cu(2-x)Se nanocrystals.

We studied cation exchange reactions in colloidal Cu(2-x)Se nanocrystals (NCs) involving the replacement of Cu(+) cations with either Sn(2+) or Sn(4+) cations. This is a model system in several aspects: first, the +2 and +4 oxidation states for tin are relatively stable; in addition, the phase of the Cu(2-x)Se NCs remains cubic regardless of the degree of copper deficiency (that is, "x") in the NC lattice. Also, Sn(4+) ions are comparable in size to the Cu(+) ions, while Sn(2+) ones are much larger. We show here that the valency of the entering Sn ions dictates the structure and composition not only of the final products but also of the intermediate steps of the exchange. When Sn(4+) cations are used, alloyed Cu(2-4y)Sn(y)Se NCs (with y ≤ 0.33) are formed as intermediates, with almost no distortion of the anion framework, apart from a small contraction. In this exchange reaction the final stoichiometry of the NCs cannot go beyond Cu0.66Sn0.33Se (that is Cu2SnSe3), as any further replacement of Cu(+) cations with Sn(4+) cations would require a drastic reorganization of the anion framework, which is not possible at the reaction conditions of the experiments. When instead Sn(2+) cations are employed, SnSe NCs are formed, mostly in the orthorhombic phase, with significant, albeit not drastic, distortion of the anion framework. Intermediate steps in this exchange reaction are represented by Janus-type Cu(2-x)Se/SnSe heterostructures, with no Cu-Sn-Se alloys.

Pulsed laser ablation of a continuously-fed wire in liquid flow for high-yield production of silver nanoparticles.

Using wires of defined diameters instead of a planar target for pulsed laser ablation in liquid results in significant increase of ablation efficiency and nanoparticle productivity up to a factor of 15. We identified several competitive phenomena based on thermal conductivity, reflectivity and cavitation bubble shape that affect the ablation efficiency when the geometry of the target is changed. On the basis of the obtained results, this work represents an intriguing starting point for further developments related to the up-scaling of pulsed laser ablation in liquid environments at the industrial level.