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Plasmonic solid-state nanopores with tunable hole diameters can be prepared via a photocatalytic effect resulting from the enhanced electromagnetic (EM) field inside a metallic ring on top of a dielectric nanotube. Under white light illumination, the plasmon-enhanced EM-field induces a site-selective metal nucleation and growth within the ring. This approach is used to prepare Au and bimetallic Au–Ag nano-rings and demonstrate the reduction of the initial inner diameter of the nanopore down to 4 nm. The tunability of the nanopore diameter can be used to enable optimized detection of single entities with different sizes. As a proof-of-concept, single object detection of double stranded DNA (dsDNA) and Au nanoparticles (AuNPs) with a diameter down to 15 nm is performed. Numerical simulations provide insights into the EM-field distribution and confinement, showing that a field intensity enhancement of up to 104 can be achieved inside the nanopores. This localized EM-field can be used to perform enhanced optical measurements and generate local heating, thereby modifying the properties of the nanopore. Such a flexible approach also represents a valuable tool to investigate plasmon-driven photochemical reactions, and it can represent an important step toward the realization of new plasmonic devices.

Aptamers that undergo conformational changes upon small-molecule recognition have been shown to gate the ionic flux through nanopores by rearranging charge density within the aptamer-occluded orifice. However, mechanistic insight into such systems where biomolecular interactions are confined in nanoscale spaces, is limited. To shed light on the fundamental mechanisms that facilitate the detection of small-molecule analytes inside structure-switching aptamer-modified nanopores, we correlated experimental observations to theoretical models. We developed a novel dopamine aptamer-functionalized nanopore sensor with femtomolar detection limits and compared the sensing behavior with a serotonin sensor fabricated with the same methodology. When sensing these two neurotransmitters with comparable mass and equal charge, the sensors showed an opposite electronic behavior. This distinctive phenomenon was extensively studied using complementary experimental techniques such as quartz crystal microbalance with dissipation monitoring, in combination with theoretical assessment by the finite element method and molecular dynamic simulations. Taken together, our studies demonstrate that the sensing behavior of highly sensitive aptamer-modified nanopores correlates with the structure-switching mechanisms unique to the selected aptamers targeting specific small-molecule analytes. We believe that such investigations not only improve our understanding of the complex interactions occurring in confined nanoscale environments, but will also drive further innovations in biomimetic nanopore technologies.

With the total amount of worldwide data skyrocketing, the global data storage demand is predicted to grow to 1.75 x 10¹⁴ GB by 2025. Traditional storage methods have difficulties keeping pace given that current storage media have a maximum density of 103 GB/mm3. As such, data production will far exceed the capacity of currently available storage methods. The costs of maintaining and transferring data, as well as the limited lifespans and significant data losses associated with current technologies also demand advanced solutions for information storage. Nature offers a powerful alternative through the storage of information that defines living organisms in unique orders of four bases (A, T, C, G) located in molecules called deoxyribonucleic acid (DNA). DNA molecules as information carriers have many advantages over traditional storage media. Their high storage density, potentially low maintenance cost, ease of synthesis, and chemical modification make them an ideal alternative for information storage. To this end, rapid progress has been made over the past decade by exploiting user-defined DNA materials to encode information. In this review, we discuss the most recent advances of DNA-based data storage with a major focus on the challenges that remain in this promising field, including the current intrinsic low speed in data writing and reading and the high cost per byte stored. Alternatively, data storage relying on DNA nanostructures (as opposed to DNA sequence) as well as on other combinations of nanomaterials and biomolecules are proposed with promising technological and economic advantages. In summarizing the advances that have been made and underlining the challenges that remain, we provide a roadmap for the ongoing research in this rapidly growing field, which will enable the development of technological solutions to the global demand for superior storage methodologies., ACS Nano, 16 (11), ISSN:1936-0851, ISSN:1936-086X

Control over multiple optical elements that can be dynamically rearranged to yield substantial three-dimensional structural transformations is of great importance to realize reconfigurable plasmonic nanoarchitectures with sensitive and distinct optical feedback. In this work, we demonstrate a transformable plasmonic helix system, in which multiple gold nanoparticles (AuNPs) can be directly transported by DNA swingarms to target positions without undergoing consecutive stepwise movements. The swingarms allow for programmable AuNP translocations in large leaps within plasmonic nanoarchitectures, giving rise to tailored circular dichroism spectra. Our work provides an instructive bottom-up solution to building complex dynamic plasmonic systems, which can exhibit prominent optical responses through cooperative rearrangements of the constituent optical elements with high fidelity and programmability.

Plasmonic nanocavities are able to engineer and confine electromagnetic fields to subwavelength volumes. In the past decade, they have enabled a large set of applications, in particular for sensing, optical trapping, and the investigation of physical and chemical phenomena at a few or single-molecule levels. This extreme sensitivity is possible thanks to the highly confined local field intensity enhancement, which depends on the geometry of plasmonic nanocavities. Indeed, suitably designed structures providing engineered local optical fields lead to enhanced optical sensing based on different phenomena such as surface enhanced Raman scattering, fluorescence, and Förster resonance energy transfer. In this mini-review, we illustrate the most recent results on plasmonic nanocavities, with specific emphasis on the detection of single molecules.

Single molecule protein sequencing would tremendously impact in proteomics and human biology and it would promote the development of novel diagnostic and therapeutic approaches. However, its technological realization can only be envisioned, and huge challenges need to be overcome. Major difficulties are inherent to the structure of proteins, which are composed by several different amino-acids. Despite long standing efforts, only few complex techniques, such as Edman degradation, liquid chromatography and mass spectroscopy, make protein sequencing possible. Unfortunately, these techniques present significant limitations in terms of amount of sample required and dynamic range of measurement. It is known that proteins can distinguish closely similar molecules. Moreover, several proteins can work as biological nanopores in order to perform single molecule detection and sequencing. Unfortunately, while DNA sequencing by means of nanopores is demonstrated, very few examples of nanopores able to perform reliable protein-sequencing have been reported so far. Here, we investigate, by means of molecular dynamics simulations, how a re-engineered protein, acting as biological nanopore, can be used to recognize the sequence of a translocating peptide by sensing the “shape” of individual amino-acids. In our simulations we demonstrate that it is possible to discriminate with high fidelity, 9 different amino-acids in a short peptide translocating through the engineered construct. The method, here shown for fluorescence-based sequencing, does not require any labelling of the peptidic analyte. These results can pave the way for a new and highly sensitive method of sequencing.

The SERS-based detection of protein sequences with single-residue sensitivity suffers from signal dominance of aromatic amino acid residues and backbones, impeding detection of non-aromatic amino acid residues. Herein, we trap a gold nanoparticle in a plasmonic nanohole to generate a single SERS hot spot for single-molecule detection of 2 similar polypeptides (vasopressin and oxytocin) and 10 distinct amino acids that constitute the 2 polypeptides. Significantly, both aromatic and non-aromatic amino acids are detected and discriminated at the single-molecule level either at individual amino acid molecules or within the polypeptide chains. Correlated with molecular dynamics simulations, our results suggest that the signal dominance due to large spatial occupancy of aromatic rings of the polypeptide sidechains on gold surfaces can be overcome by the high localization of the single hot spot. The superior spectral and spatial discriminative power of our approach can be applied to single-protein analysis, fingerprinting, and sequencing.

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.

Numerous efforts have been undertaken to develop rectifying antennas operatingat high frequencies, especially dedicated to light harvesting and photodetectionapplications. However, the development of efficient high frequencyrectifying antennas has been a major technological challenge both due to a lackof comprehension of the underlying physics and limitations in the fabrication techniques. Various rectification strategies have been implemented, includingmetal-insulator-metal traveling-wave diodes, plasmonic nanogap opticalantennas, and whisker diodes, although all show limited high-frequency operation and modest conversion efficiencies. Here a new type of rectifying antennabased on plasmonic carrier generation is demonstrated. The proposed structureconsists of a resonant metallic conical nano-antenna tip in contact with the oxide surface of an oxide/metal bilayer. The conical shape allows for an improvedcurrent generation based on plasmon-mediated electromagnetic-to-electronconversion, an effect exploiting the nanoscale-tip contact of the rectifying antenna, and proportional to the antenna resonance and to the surface-electronscattering. Importantly, this solution provides rectification operation at 280 THz(1064 nm) with a 100-fold increase in efficiency compared to previously reported results. Finally, the conical rectifying antenna is also demonstrated to operateat 384 THz (780 nm), hence paving a way toward efficient rectennas toward thevisible range.

The fabrication of nanopores with a matched pore size, and the existence of multiple interferents make the reproducible detection of small-sized molecules by means of solid-state nanopores still challenging. A useful method to solve these problems is based on the detection of large DNA nanostructures related to the existence of small-sized targets. In particular, a DNA tetrahedron with a well-defined 3D nanostructure is the ideal candidate for use as a signal transducer. Here, we demonstrate the detection of an L1-encoding gene of HPV18 as a test DNA target sequence in a reaction buffer solution, where long single-stranded DNA linking DNA tetrahedra onto the surface of the magnetic beads is cleaved by a target DNA-activated CRISPR-cas12 system. The DNA tetrahedra are subsequently released and can be detected by the current pulse in a glassy nanopore. This approach has several advantages: (1) one signal transducer can be used to detect different targets; (2) a glassy nanopore with a pore size much larger than the target DNA fragment can boost the tolerance of the contaminants and interferents which often degrade the performance of a nanopore sensor.

Nowadays, there is a high demand for sensitive and selective real-time analytical methods suitable for a wide range of applications, from personalized telemedicine, drug discovery, food safety, and quality control, to defense, security, as well as environmental monitoring. Biosensors are analytical devices able to detect bio-chemical analytes (e.g., neurotransmitters, cancer biomarkers, bio-molecules, and ions), through the combination of a bio-recognition element and a bio-transduction device. The use of customized bio-recognition elements such as enzymes, antibodies, aptamers, and ion-selective membranes facilitates achieving high selectivity. Among the different bio-transduction devices currently available, electrolyte-gated field-effect transistors, in which the dielectric is represented by an ionic liquid buffer solution containing the targeted analyte, are gaining increasing attention. Indeed, these bio-transduction devices are characterized by superior electronic properties and intrinsic signal amplification that allow the detection of a wide range of bio-molecules with high sensitivity (down to pM concentration). A promising semiconducting material for bio-transduction devices is represented by carbon nanotubes, due to their unique electrical properties, nanosize, bio-compatibility, and their simple low-cost processability. This work provides a comprehensive and critical review of electrolyte-gated carbon nanotube field-effect transistor-based biosensors. First, an introduction to these bio-sensing devices is given. Next, the device configurations and operating principles are presented, and the most used materials and processes are reviewed with a particular focus on carbon nanotubes as the active material. Subsequently, different functionalization strategies reported in the literature, based on enzymes, antibodies, aptamers, and ion-selective membranes, are analyzed critically. Finally, present issues and challenges faced in the area are investigated, the conclusions are drawn, and a perspective outlook over the field of bio-sensing technologies, in general, is provided., Applied Physics Reviews, 8 (4), ISSN:1931-9401

A lightsail accelerated via directed energy is a candidate technology to send a probe into the deep space in a time period compatible with human life. The light emitted by a ground-based large-aperture phased laser array is directed onto the lightsail to produce a thrust by transferring the momentum of the incident photons. To achieve high efficiency propulsion, the lightsail must be characterized by extremely low mass, high reflectance and minimal absorption in the Doppler-shifted laser wavelength range, while high emissivity in the infrared is required for thermal management. Optimized multilayer structures allow ultralight spacecraft being accelerated by laser radiation pressure up to 20% of the light velocity, and eventually even above, as long as a compromise between efficiency and weight is achieved. Key aspect is the ability to survive to the temperature increase during the acceleration phase, which can be fateful for the system.

Layered architectures for light-emitting diodes (LEDs) are the standard approach for solution-processable materials such as metal-halide perovskites. Upon designing the composition and thicknesses of the layers forming the LED, the primary focus is typically on the optimization of charge injection and balance. However, this approach only considers the process until electrons and holes recombine to generate photons, while for achieving optimized LED performance, the generated light must also be efficiently outcoupled. Our work focuses on the latter aspect. We assume efficient photon generation and analyze the effects of the geometrical configuration together with the dipole orientation, mimicking the light emission, on the main characteristics defining the LED, such as the Purcell effect and the outcoupling efficiency. We find that in-plane dipoles result in significantly increased outcoupling efficiency. Furthermore, the mismatch in refractive index among the layers and their different thicknesses can be tuned to maximize the Purcell effect and minimize internal losses. The combined optimization of dipole orientation and layer thicknesses can improve the efficiency of the LED up to a factor 10, hence highlighting the importance of considering also the photonic properties of the LED structures if the objective is to maximize the LED performance.

Surface plasmon resonance sensors are a well-established class of sensors that includes a very large variety of materials and detection schemes. However, the development of portable devices is still challenging due to the intrinsic complexity of the optical excitation/detection schemes. This work shows that nanoporous gold (NPG) films can overcome the said limitations by providing an excellent sensitivity without the need for sophisticated fabrication approaches and/or optical setups. The sensing mechanism is related to the co-localization of optical energy and analytes in the pores fostering an enhanced light–matter coupling. As a result, when molecules are adsorbed in the pores, the NPG film shows a significant spectral shift of the effective plasma frequency and an abrupt change of the reflectivity. By monitoring the reflectivity in the spectral region close to the plasma frequency (namely the plasma edge), it is possible to detect the analyte. Through a series of experiments, the authors demonstrated a sensitivity exceeding 15 000 nm per RIU in the near infrared range comparable with the state of the art of plasmonic metamaterials.

The phenomenon of coupling between light and surface plasmon polaritons requires specific momentum matching conditions. In the case of a single scattering object on a metallic surface, such as a nanoparticle or a nanohole, the coupling between a broadband effect, i.e., scattering, and a discrete one, such as surface plasmon excitation, leads to Fano-like resonance lineshapes. The necessary phase matching requirements can be used to engineer the light–plasmon coupling and to achieve a directional plasmonic excitation. Here, we investigate this effect by using a chiral nanotip to excite surface plasmons with a strong spin-dependent azimuthal variation. This effect can be described by a Fano-like interference with a complex coupling factor that can be modified thanks to a symmetry breaking of the nanostructure.

The phenomena of coupling between light and surface plasmon polaritons requires specific momentum matching conditions. In the case of a single scattering object on a metallic surface, like a nanoparticle or a nanohole, the coupling between a broadband effect, i.e. scattering, and a discrete one such as surface plasmon excitation, leads to Fano-like plasmonic resonance line-shapes. The necessary phase matching requirements can be used to engineer the light-plasmon coupling and to achieve a directional plasmonic excitation. Here we investigate this effect by using a chiral nanotip to excite surface plasmons with a strong spin-dependent azimuthal variation. This effect can be described by a Fano-like interference with a complex coupling factor that can be modified thanks to a symmetry breaking nanostructure.

The field of plasmonics has the potential to enable unique applications in the different wavelength ranges, from the ultraviolet to the visible and the infrared. The choice of plasmonic material and how this material is nanostructured have significant implications for the ultimate performance of any plasmonic device. Nanoporous metals (NPMs) (such as Au, Ag, Cu, Al, Mg, and Pt) have intriguing material properties that offer potential benefits for many applications due to their high specific surface area, high electrical conductivity, and reduced stiffness. The research on nanoporous metals has taken place on various fronts, including advanced microfabrication and characterization techniques to probe unusual nanoscale properties and applications spanning from fuel cells to electrochemical sensors. Here we report a short review of the available nanoporous materials, looking in particular at their properties as plasmonic materials.

Coronavirus disease 2019 (COVID-19) is probably the most commonly heard word of the last 12 months. The outbreak of this virus (SARS-CoV-2) is strongly compromising worldwide healthcare systems, social behavior, and everyone's lives. The early diagnosis of COVID-19 and isolation of positive cases has proven to be fundamental in containing the spread of the infection. Even though the polymerase chain reaction (PCR) based methods remain the gold standard for SARS-CoV-2 detection, the urgent demand for rapid and wide-scale diagnosis precipitated the development of alternative diagnostic approaches. The millions of tests performed every day worldwide are still insufficient to achieve the desired goal, that of screening the population during daily life. Probably the most appealing approach to consistently monitor COVID-19 spread is the direct detection of SARS-CoV-2 from exhaled breath. For instance, the challenging incorporation of reliable, highly sensitive, and cost-efficient detection methods in masks could represent a breakthrough in the development of portable and noninvasive point-of-care diagnosis for COVID-19. In this perspective paper, we discuss the critical technical aspects related to the application of breath analysis in the diagnosis of viral infection. We believe that, if achieved, it could represent a game-changer in containing the pandemic spread.

The field of plasmonics is capable of enabling interesting applications in different wavelength ranges, spanning from the ultraviolet up to the infrared. The choice of plasmonic material and how the material is nanostructured has significant implications for ultimate performance of any plasmonic device. Artificially designed nanoporous metals (NPMs) have interesting material properties including large specific surface area, distinctive optical properties, high electrical conductivity, and reduced stiffness, implying their potentials for many applications. This paper reviews the wide range of available nanoporous metals (such as Au, Ag, Cu, Al, Mg, and Pt), mainly focusing on their properties as plasmonic materials. While extensive reports on the use and characterization of NPMs exist, a detailed discussion on their connection with surface plasmons and enhanced spectroscopies as well as photocatalysis is missing. Here, we report on different metals investigated, from the most used nanoporous gold to mixed metal compounds, and discuss each of these plasmonic materials’ suitability for a range of structural design and applications. Finally, we discuss the potentials and limitations of the traditional and alternative plasmonic materials for applications in enhanced spectroscopy and photocatalysis.

23 pags., 5 figs., Mirrors are a subset of optical components essential for the success of current and future space missions. Most of the telescopes for space programs ranging from earth observation to astrophysics and covering the whole electromagnetic spectrum from x-rays to far-infrared are based on reflective optics. Mirrors operate in diverse and harsh environments that range from low-earth orbit to interplanetary orbits and deep space. The operational life of space observatories spans from minutes (sounding rockets) to decades (large observatories), and the performance of the mirrors within the mission lifetime is susceptible to degrading, resulting in a drop in the instrument throughput, which in turn affects the scientific return. Therefore, the knowledge of potential degradation mechanisms, how they affect mirror performance, and how to prevent them is of paramount importance to ensure the long-term success of space telescopes. In this review, we report an overview of current mirror technology for space missions with a focus on the importance of the degradation and radiation resistance of coating materials. Special attention is given to degradation effects on mirrors for far and extreme UV, as in these ranges the degradation is enhanced by the strong absorption of most contaminants., JIL acknowledges funding by Ministerio de Ciencia e Innovación, Gobierno de España (PID2019-105156GB-I00). LRM appreciates the support from the Center for Research and Explorationin Space Science and Technology II (CRESST II) program. MGP acknowledges ASI-INAF I/013/12/0 Solar Orbiter, METIS instrument European Space Agency (contract no. 4000122836/18/NL/PS/gp), Radiation Testing of Optical Coatings for Space.

The fabrication of nanopore with matched pore size, and the existence of multi interferents make the reproducible detection of small-sized molecules by means of solid-state nanopore still challenging. A useful method to solve these problems is based on the detection of large DNA nanostructure related to the existence of small-sized target. In particular, DNA tetrahedron with well-defined 3D nanostructure is the ideal candidate to be used as signal transducer. Here, we demonstrate the detection of L1-encoding gene of HPV18 as test DNA target sequence in a reaction buffering solution, where long single-stranded DNA linking DNA tetrahedrons onto the surface of magnetic beads are cleaved by target DNA-activated CRISPR-cas12 system. The DNA tetrahedrons are subsequently released and can be detected by the current pulse in a glassy nanopore. This approach has several advantages: (1) One signal transducer can be used to detect different targets; (2) Glassy nanopore with pore size much larger than the target DNA fragment can boost the tolerance of contaminants and interferents which often degrade the performance of nanopore sensor.

Recent advances in nanotechnology have prompted the need for tools to accurately and noninvasively manipulate individual nano-objects. Among the possible strategies, optical forces have been widely used to enable nano-optical tweezers capable of trapping or moving a specimen with unprecedented accuracy. Here, we propose an architecture consisting of a nanotip excited with a plasmonic vortex enabling effective dynamic control of nanoparticles in three dimensions. The structure illuminated by a beam with angular momentum can generate an optical field that can be used to manipulate single dielectric nanoparticles. We demonstrate that it is possible to stably trap or push the particle from specific points, thus enabling a new, to the best of our knowledge, platform for nanoparticle manipulation.

There is a growing interest in extending plasmonics applications into the ultraviolet region of the electromagnetic spectrum. Noble metals are commonly used in plasmonic, but their intrinsic optical properties limit their use above 350 nm. Aluminum is probably the most suitable material for UV plasmonics, and in this work we fabricated substrates of nanoporous aluminum starting from an alloy of Al2Mg3. The porous metal is obtained by means of a galvanic replacement reaction. Such nanoporous metal can be exploited to achieve a plasmonic material suitable for enhanced UV Raman spectroscopy and fluorescence. Thanks to the large surface to volume ratio, this material represents a powerful platform for promoting interaction between plasmonic substrates and molecules in the UV.

Ultrafast control of light−matter interactions is fundamental in view of new technological frontiers of information processing. However, conventional optical elements are either static or feature switching speeds that are extremely low with respect to the time scales at which it is possible to control light. Here, we exploit the artificial epsilon-near-zero (ENZ) modes of a metal-insulator-metal nanocavity to tailor the linear photon absorption of our system and realize a nondegenerate all-optical ultrafast modulation of the reflectance at a specific wavelength. Optical pumping of the system at its high energy ENZ mode leads to a strong redshift of the low energy mode because of the transient increase of the local dielectric function, which leads to a sub-3-ps control of the reflectance at a specific wavelength with a relative modulation depth approaching 120%. All-optical switching allows control of one optical signal using another, holding potential to overcome the limitations of electrical switches via ultrafast manipulation of light. In this work, sub-3 ps all-optical switching is achieved in an epsilon-near-zero nanocavity, exhibiting a relative modulation depth of 120% at a specific wavelength.

The spontaneous interaction between noble metals and biological scaffolds enables simple and cost-effective synthesis of nanomaterials with unique features. Here, plasmonic silver nanorings are synthesized on a ring-like protein, i.e., a peroxiredoxin (PRX), and used to assemble large arrays of functional nanostructures. The PRX drives the seeding growth of metal silver under wet reducing conditions, yielding nanorings with outer and inner diameters down to 28 and 3 nm, respectively. The obtained hybrid nanostructures are selectively deposited onto a solid-state 2D membrane made of graphene in order to prepare plasmonic nanopores. In particular, the interaction between the graphene and the PRX allows for the simple preparation of ordered arrays of plasmonic nanorings on a 2D-material membrane. This fabrication process can be finalized by drilling a nanometer scale pore in the middle of the ring. Fluorescence spectroscopic measurements in combination with numerical simulations demonstrate the plasmonic effects induced in the metallic nanoring cavity. The prepared nanopores represent one of the first examples of hybrid plasmonic nanopore structures integrated on a 2D-material membrane. The diameter of the nanopore and the atomically thick substrate make this proof-of-concept approach particularly interesting for nanopore-based technologies and applications such as next-generation sequencing and single-molecule detection.

Engineered electromagnetic fields in plasmonic nanopores enable enhanced optical detection for single molecule sensing and sequencing. Here, a plasmonic nanopore prepared in a thick nanoporous film...

Live intracellular imaging is a valuable tool in modern diagnostics and pharmacology. Surface Enhanced Raman Spectroscopy (SERS) stands out as a non-destructive and multiplexed technique, but intracellular SERS imaging still suffers from interfering background from endogenous components. Here we show the assembly of small colloidal SERS probes with Raman signal in the cell-silent window of 1800–2900 cm−1 for biorthogonal intracellular SERS imaging of dopamine that was undistinguishable from the endogenous cell background. By linking colloidal silver nanoparticles with alkyne-dopamine adducts, clusters are formed by 2–6 nanoparticles spaced by tight interparticle gaps that exhibited high electric field enhancement and strong SERS signals of alkyne and dopamines. Due to the cell-silent signals of the alkyne, intracellular in-vitro Raman imaging shows that the dopamines on the internalized clusters remain distinguishable across the cytoplasm with good spatial resolution. Our method can be a general-purpose method for real-time imaging of biomolecules, such as proteins, peptides, DNA and drugs.

In this work, we show that modulating the fractal dimension of nanoporous gold allows its effective dielectric response to be tailored over a wide spectral range of infrared wavelengths. In particular, the plasma edge and effective plasma frequency depend linearly on the fractal dimension, which can be controlled by varying the pore and ligament sizes. Importantly, the fractal porous metal exhibits superior plasmonic properties compared to its bulk counterpart. These properties, combined with a longer skin depth on the order of 100-200 nm, enables the penetration of optical energy deep into the nanopores where molecules can be loaded, thus, achieving more effective light-matter coupling. These findings may open new pathways to engineering the optical response of fractal-like or self-similar metamaterials without the need for sophisticated lithographic patterning.

We have investigated three-dimensional (3D) MoS2 nanoarchitectures doped with different amount of Ni to boost the hydrogen evolution reaction (HER) in alkaline environment, where this reaction is normally hindered. As a comparison, the activity in acidic media was also investigated to determine and compare the role of the Ni sites in both media. The doping of MoS2, especially at high loadings, can modify its structural and/or electronic properties, which can also affect the HER activity. The structural and electronic properties of the Ni doped 3D-MoS2 nanoarchitecture were studied by X-ray diffraction (XRD), Raman spectroscopy, scanning and transmission electronic microscopy (SEM, TEM), and X-ray photoemission Spectroscopy (XPS). XPS also allowed us to determine the Ni-based species formed as a function of the dopant loading. The HER activity of the materials was investigated by linear sweep voltammetry (LSV) in 0.5 M H2SO4 and 1.0 M KOH. By combining the physicochemical and electrochemical results, we concluded that the Ni sites have a different role in the HER mechanism and kinetics in acidic and in alkaline media. Thus, NiSx species are essential to promote HER in alkaline medium, whereas the Ni-Mo-S ones enhance the HER in acid medium.

Surface-enhanced Raman spectroscopy (SERS) sensing of DNA bases by plasmonic nanopores could pave a way to novel methods for DNA analyses and new generation single-molecule sequencing platforms. The SERS discrimination of single DNA bases depends critically on the time that a DNA strand resides within the plasmonic hot spot. In fact, DNA molecules flow through the nanopores so rapidly that the SERS signals collected are not sufficient for single-molecule analysis. Here, we report an approach to control the residence time of molecules in the hot spot by an electro-plasmonic trapping effect. By directly adsorbing molecules onto a gold nanoparticle and then trapping the single nanoparticle in a plasmonic nanohole up to several minutes, we demonstrate single-molecule SERS detection of all four DNA bases as well as discrimination of single nucleobases in a single oligonucleotide. Our method can be extended easily to label-free sensing of single-molecule amino acids and proteins., Sensing DNA bases by surface-enhanced Raman spectroscopy (SERS) in plasmonic nanopores has suffered from rapid flow through of molecules. Here, the authors attach DNA molecules to gold nanoparticles which, due to electro-plasmonic trapping, allow for controlled residence times and discrimination of single nucleotides.