Mixed chloridometallate(ii) ionic liquids with tunable color and optical response for potential ammonia sensors.

Eight d-metal-containing N-butylpyridinium ionic liquids (ILs) with the nominal composition (C4Py)2[Ni0.5M0.5Cl4] or (C4Py)2[Zn0.5M0.5Cl4] (M = Cu, Co, Mn, Ni, Zn; C4Py = N-butylpyridinium) were synthesized, characterized, and investigated for their optical properties. Single crystal and powder X-ray analysis shows that the compounds are isostructural to existing examples based on other d-metal ions. Inductively coupled plasma optical emission spectroscopy measurements confirm that the metal/metal ratio is around 50 : 50. UV-Vis spectroscopy shows that the optical absorption can be tuned by selection of the constituent metals. Moreover, the compounds can act as an optical sensor for the detection of gases such as ammonia as demonstrated via a simple prototype setup.

Photothermomechanical Nanopump: A Flow-Through Plasmonic Sensor at the Fiber Tip.

Optical fibers equipped with plasmonic flow sensors at their tips are fabricated and investigated as photothermomechanical nanopumps for the active transport of target analytes to the sensor surface. The nanopumps are prepared using a bottom-up strategy: i.e., by sequentially stacking a monolayer of a thermoresponsive polymer and a plasmonic nanohole array on an optical fiber tip. The temperature-dependent collapse and swelling of the polymer is used to create a flow-through pumping mechanism. The heat required for pumping is generated by exploiting the photothermal effect in the plasmonic nanohole array upon irradiation with laser light (405 nm). Simultaneous detection of analytes by the plasmonic sensor is achieved by monitoring changes in its optical response at longer wavelengths (∼500-800 nm). Active mass transport by pumping through the holes of the plasmonic nanohole array is visualized by particle imaging velocimetry. Finally, the performance of the photothermomechanical nanopumps is investigated for two types of analytes, namely nanoscale objects (gold nanoparticles) and molecules (11-mercaptoundecanoic acid). In the presence of the pumping mechanism, a 4-fold increase in sensitivity was observed compared to the purely photothermal effect, demonstrating the potential of the presented photothermomechanical nanopumps for sensing applications.

Microscopic Understanding of Reaction Rates Observed in Plasmon Chemistry of Nanoparticle-Ligand Systems.

Surface-enhanced Raman scattering (SERS) is an effective and widely used technique to study chemical reactions induced or catalyzed by plasmonic substrates, since the experimental setup allows us to trigger and track the reaction simultaneously and identify the products. However, on substrates with plasmonic hotspots, the total signal mainly originates from these nanoscopic volumes with high reactivity and the information about the overall consumption remains obscure in SERS measurements. This has important implications; for example, the apparent reaction order in SERS measurements does not correlate with the real reaction order, whereas the apparent reaction rates are proportional to the real reaction rates as demonstrated by finite-difference time-domain (FDTD) simulations. We determined the electric field enhancement distribution of a gold nanoparticle (AuNP) monolayer and calculated the SERS intensities in light-driven reactions in an adsorbed self-assembled molecular monolayer on the AuNP surface. Accordingly, even if a high conversion is observed in SERS due to the high reactivity in the hotspots, most of the adsorbed molecules on the AuNP surface remain unreacted. The theoretical findings are compared with the hot-electron-induced dehalogenation of 4-bromothiophenol, indicating a time dependency of the hot-carrier concentration in plasmon-mediated reactions. To fit the kinetics of plasmon-mediated reactions in plasmonic hotspots, fractal-like kinetics are well suited to account for the inhomogeneity of reactive sites on the substrates, whereas also modified standard kinetics model allows equally well fits. The outcomes of this study are on the one hand essential to derive a mechanistic understanding of reactions on plasmonic substrates by SERS measurements and on the other hand to drive plasmonic reactions with high local precision and facilitate the engineering of chemistry on a nanoscale.

The disappearance and return of nanoparticles upon low energy ion irradiation.

Ion irradiation of bulk and thin film materials is tightly connected to well described effects such as sputtering or/and ion beam mixing. However, when a nanoparticle is ion irradiated and the ion range is comparable to the nanoparticle size, these effects are to be reconsidered essentially. This study investigates the morphology changes of silver nanoparticles on top of silicon substrates, being irradiated with Ga+ions in an energy range from 1 to 30 keV. The hemispherical shaped nanoparticles become conical due to an enhanced and curvature-dependent sputtering, before they finally disappear. The sputter yield and morphology changes can be well described by 3D Monte Carlo TRI3DYN simulations. However, the combination of sputtering, ion beam mixing, ion beam induced diffusion, and Ostwald ripening at ion energies lower than 8 keV results in the reappearance of new particles. These newly formed nanoparticles appear in various structures depending on the material and ion energy.

Plasmonic Nanohole Arrays on Top of Porous Silicon Sensors: A Win-Win Situation.

Label-free optical sensors are attractive candidates, for example, for detecting toxic substances and monitoring biomolecular interactions. Their performance can be pushed by the design of the sensor through clever material choices and integration of components. In this work, two porous materials, namely, porous silicon and plasmonic nanohole arrays, are combined in order to obtain increased sensitivity and dual-mode sensing capabilities. For this purpose, porous silicon monolayers are prepared by electrochemical etching and plasmonic nanohole arrays are obtained using a bottom-up strategy. Hybrid sensors of these two materials are realized by transferring the plasmonic nanohole array on top of the porous silicon. Reflectance spectra of the hybrid sensors are characterized by a fringe pattern resulting from the Fabry-Pérot interference at the porous silicon borders, which is overlaid with a broad dip based on surface plasmon resonance in the plasmonic nanohole array. In addition, the hybrid sensor shows a significant higher reflectance in comparison to the porous silicon monolayer. The sensitivities of the hybrid sensor to refractive index changes are separately determined for both components. A significant increase in sensitivity from 213 ± 12 to 386 ± 5 nm/RIU is determined for the transfer of the plasmonic nanohole array sensors from solid glass substrates to porous silicon monolayers. In contrast, the spectral position of the interference pattern of porous silicon monolayers in different media is not affected by the presence of the plasmonic nanohole array. However, the changes in fringe pattern reflectance of the hybrid sensor are increased 3.7-fold after being covered with plasmonic nanohole arrays and could be used for high-sensitivity sensing. Finally, the capability of the hybrid sensor for simultaneous and independent dual-mode sensing is demonstrated.

Plasmonic biosensors fabricated by galvanic displacement reactions for monitoring biomolecular interactions in real time.

Optical sensors are prepared by reduction of gold ions using freshly etched hydride-terminated porous silicon, and their ability to specifically detect binding between protein A/rabbit IgG and asialofetuin/Erythrina cristagalli lectin is studied. The fabrication process is simple, fast, and reproducible, and does not require complicated lab equipment. The resulting nanostructured gold layer on silicon shows an optical response in the visible range based on the excitation of localized surface plasmon resonance. Variations in the refractive index of the surrounding medium result in a color change of the sensor which can be observed by the naked eye. By monitoring the spectral position of the localized surface plasmon resonance using reflectance spectroscopy, a bulk sensitivity of 296 nm ± 3 nm/RIU is determined. Furthermore, selectivity to target analytes is conferred to the sensor through functionalization of its surface with appropriate capture probes. For this purpose, biomolecules are deposited either by physical adsorption or by covalent coupling. Both strategies are successfully tested, i.e., the optical response of the sensor is dependent on the concentration of respective target analyte in the solution facilitating the determination of equilibrium dissociation constants for protein A/rabbit IgG as well as asialofetuin/Erythrina cristagalli lectin which are in accordance with reported values in literature. These results demonstrate the potential of the developed optical sensor for cost-efficient biosensor applications. Graphical abstract.

One Spot-Two Sensors: Porous Silicon Interferometers in Combination With Gold Nanostructures Showing Localized Surface Plasmon Resonance.

Sensors composed of a porous silicon monolayer covered with a film of nanostructured gold layer, which provide two optical signal transduction methods, are fabricated and thoroughly characterized concerning their sensing performance. For this purpose, silicon substrates were electrochemically etched in order to obtain porous silicon monolayers, which were subsequently immersed in gold salt solution facilitating the formation of a porous gold nanoparticle layer on top of the porous silicon. The deposition process was monitored by reflectance spectroscopy, and the appearance of a dip in the interference pattern of the porous silicon layer was observed. This dip can be assigned to the absorption of light by the deposited gold nanostructures leading to localized surface plasmon resonance. The bulk sensitivity of these sensors was determined by recording reflectance spectra in media having different refractive indices and compared to sensors exclusively based on porous silicon or gold nanostructures. A thorough analysis of resulting shifts of the different optical signals in the reflectance spectra on the wavelength scale indicated that the optical response of the porous silicon sensor is not influenced by the presence of a gold nanostructure on top. Moreover, the adsorption of thiol-terminated polystyrene to the sensor surface was solely detected by changes in the position of the dip in the reflectance spectrum, which is assigned to localized surface plasmon resonance in the gold nanostructures. The interference pattern resulting from the porous silicon layer is not shifted to longer wavelengths by the adsorption indicating the independence of the optical response of the two nanostructures, namely porous silicon and nanostructured gold layer, to refractive index changes and pointing to the successful realization of two sensors in one spot.

Fiber optic plasmonic sensors: Providing sensitive biosensor platforms with minimal lab equipment.

A simple, convenient, and inexpensive method to fabricate optical fiber based biosensors which utilize periodic hole arrays in gold films for signal transduction is reported. The process of hole array formation mainly relies on self-assembly of hydrogel microgels in combination with chemical gold film deposition and subsequent transfer of the perforated film onto an optical fiber tip. In the fabrication process solely chemical wet lab techniques are used, avoiding cost-intensive instrumentation or clean room facilities. The presented method for preparing fiber optic plasmonic sensors provides high throughput and is perfectly suited for commercialization using batch processing. The transfer of the perforated gold film onto an optical fiber tip does not affect the sensitivity of the biosensor ((420 ±â€¯83) nm/refractive index unit (RIU)), which is comparable to sensitivities of sensor platforms based on periodic hole arrays in gold films prepared by significantly more complex methods. Furthermore, real-time and in-line immunoassay studies with a specially designed 3D printed flow cell are presented exploiting the presented optical fiber based biosensors.

In Vitro Monitoring Conformational Changes of Polypeptide Monolayers Using Infrared Plasmonic Nanoantennas.

Proteins and peptides play a predominant role in biochemical reactions of living cells. In these complex environments, not only the constitution of the molecules but also their three-dimensional configuration defines their functionality. This so-called secondary structure of proteins is crucial for understanding their function in living matter. Misfolding, for example, is suspected as the cause of neurodegenerative diseases such as Alzheimer's and Parkinson's disease. Ultimately, it is necessary to study a single protein and its folding dynamics. Here, we report a first step in this direction, namely ultrasensitive detection and discrimination of in vitro polypeptide folding and unfolding processes using resonant plasmonic nanoantennas for surface-enhanced vibrational spectroscopy. We utilize poly-l-lysine as a model system which has been functionalized on the gold surface. By in vitro infrared spectroscopy of a single molecular monolayer at the amide I vibrations we directly monitor the reversible conformational changes between α-helix and ß-sheet states induced by controlled external chemical stimuli. Our scheme in combination with advanced positioning of the peptides and proteins and more brilliant light sources is highly promising for ultrasensitive in vitro studies down to the single protein level.

Dynamics of nanoparticle morphology under low energy ion irradiation.

If nanostructures are irradiated with energetic ions, the mechanism of sputtering becomes important when the ion range matches about the size of the nanoparticle. Gold nanoparticles with diameters of ∼50 nm on top of silicon substrates with a native oxide layer were irradiated by gallium ions with energies ranging from 1 to 30 keV in a focused ion beam system. High resolution in situ scanning electron microscopy imaging permits detailed insights in the dynamics of the morphology change and sputter yield. Compared to bulk-like structures or thin films, a pronounced shaping and enhanced sputtering in the nanostructures occurs, which enables a specific shaping of these structures using ion beams. This effect depends on the ratio of nanoparticle size and ion energy. In the investigated energy regime, the sputter yield increases at increasing ion energy and shows a distinct dependence on the nanoparticle size. The experimental findings are directly compared to Monte Carlo simulations obtained from iradina and TRI3DYN, where the latter takes into account dynamic morphological and compositional changes of the target.

Bottom-Up Fabrication of Hybrid Plasmonic Sensors: Gold-Capped Hydrogel Microspheres Embedded in Periodic Metal Hole Arrays.

The high potential of bottom-up fabrication strategies for realizing sophisticated optical sensors combining the high sensitivity of a surface plasmon resonance with the exceptional properties of stimuli-responsive hydrogel is demonstrated. The sensor is composed of a periodic hole array in a gold film whose holes are filled with gold-capped poly(N-isoproyl-acrylamide) (polyNIPAM) microspheres. The production of this sensor relies on a pure chemical approach enabling simple, time-efficient, and cost-efficient preparation of sensor platforms covering areas of cm2. The transmission spectrum of this plasmonic sensor shows a strong interaction between propagating surface plasmon polaritons at the metal film surface and localized surface plasmon resonance of the gold cap on top of the polyNIPAM microspheres. Computer simulations support this experimental observation. These interactions lead to distinct changes in the transmission spectrum, which allow for the simultaneous, sensitive optical detection of refractive index changes in the surrounding medium and the swelling state of the embedded polyNIPAM microsphere under the gold cap. The volume of the polyNIPAM microsphere located underneath the gold cap can be changed by certain stimuli such as temperature, pH, ionic strength, and distinct molecules bound to the hydrogel matrix facilitating the detection of analytes which do not change the refractive index of the surrounding medium significantly.

Devising Self-Assembled-Monolayers for Surface-Enhanced Infrared Spectroscopy of pH-Driven Poly-l-lysine Conformational Changes.

Surface-enhanced infrared absorption spectroscopy (SEIRA) is applied to study protein conformational changes. In general, the appropriate functionalization of metal surfaces with biomolecules remains a challenge if the conformation and activity of the biomolecule shall be preserved. Here we present a SEIRA study to monitor pH-induced conformational changes of poly-l-lysine (PLL) covalently bound to a thin gold layer via self-assembled monolayers (SAMs). We demonstrate that the composition of the SAM is crucial. A SAM of 11-mercaptoundecanonic acid (MUA) can link PLL to the gold layer, but pH-driven conformational transitions were hindered compared to poly-l-lysine in solution. To address this problem, we devised a variety of SAMs, i.e., mixed SAMs of MUA with either octanethiol (OT) or 11-mercapto-1-undecanol (MUoL) and furthermore SAMs of MT(PEG)4 and NHS-PEG10k-SH. These mixed SAMs modify the surface properties by changing the polarity and the morphology of the surface present to nearby PLL molecules. Our experiments reveal that mixed SAMs of MUA-MUoL and SAMs of NHS-PEG10k-SH-MT(PEG)4 are suitable to monitor pH-driven conformational changes of immobilized PLL. These SAMs might be applicable for chemoselective protein immobilization in general.

Enhanced sputter yields of ion irradiated Au nano particles: energy and size dependence.

Hexagonally arranged Au nanoparticles exhibiting a broad Gaussian-shaped size distribution ranging from 30 nm to 80 nm were deposited on Si substrates and irradiated with Ar(+) and Ga(+) ions with various energies from 20 to 350 keV and 1 to 30 keV, respectively. The size and energy dependence of the sputter yield were measured using high-resolution scanning electron microscopy image analysis. These results were compared to simulation results obtained by iradina, a Monte Carlo code, which takes the specifics of the nano geometry into account. The experimental sputter yields are significantly higher than simulated sputter yields for both bulk and the nano geometry. The difference can be clearly attributed to thermally driven effects, which significantly increase the measured sputter yields.

Bottom-up fabrication of nanohole arrays loaded with gold nanoparticles: extraordinary plasmonic sensors.

A chemical route to periodic hole arrays in gold films whose holes are loaded with single gold nanoparticles is presented, paving the road to mass production of highly sensitive plasmonic sensors on large areas.

Optical characterization of porous silicon monolayers decorated with hydrogel microspheres.

The optical response of porous silicon (pSi) films, covered with a quasi-hexagonal array of hydrogel microspheres, to immersion in ethanol/water mixtures was investigated. For this study, pSi monolayers were fabricated by electrochemical etching, stabilized by thermal oxidation, and decorated with hydrogel microspheres using spin coating. Reflectance spectra of pSi samples with and without deposited hydrogel microspheres were taken at normal incidence. The employed hydrogel microspheres, composed of poly-N-isopropylacrylamide (polyNIPAM), are stimuli-responsive and change their size as well as their refractive index upon exposure to alcohol/water mixtures. Hence, distinct differences in the interference pattern of bare pSi films and pSi layers covered with polyNIPAM spheres could be observed upon their immersion in the respective solutions using reflective interferometric Fourier transform spectroscopy (RIFTS). Here, the amount of reflected light (fast Fourier transform (FFT) amplitude), which corresponds to the refractive index contrast and light scattering at the pSi film interfaces, showed distinct differences for the two fabricated samples. Whereas the FFT amplitude of the bare porous silicon film followed the changes in the refractive index of the surrounding medium, the FFT amplitude of the pSi/polyNIPAM structure depended on the swelling/shrinking of the attached hydrogel spheres and exhibited a minimum in ethanol-water mixtures with 20 wt% ethanol. At this value, the polyNIPAM microgel is collapsed to its minimum size. In contrast, the effective optical thickness, which reflects the effective refractive index of the porous layer, was not influenced by the attached hydrogel spheres. PACS: 81.05.Rm; 81.16.Dn; 83.80Kn; 42.79.Pw.

Top-up fabrication of gold nanorings.

A simple method for the fabrication of gold nanorings with reliable material composition and reproducible morphology that relies on a combination of top-down and bottom-up techniques is presented. Here, lithographically defined hole arrays are used as templates for the deposition of gold nanoparticles. The resulting gold nanoparticle rings are joined by electroless deposition of gold, thereby leading to the formation of gold nanoring arrays that show plasmonic resonance in their optical spectra at theoretically predicted wavelengths. In addition, the gold nanorings can be released from the template by extensive rinsing with water, thereby enabling their further functionalization or assembly and the re-use of the template for the preparation of more nanorings.

Real-time monitoring of electrochemical controlled protein adsorption by a plasmonic nanowire based sensor.

A plasmonic sensor composed of a vertically aligned gold nanowire array was fabricated and employed for the optical detection of protein adsorption induced by an electric field.

Contact line motion on nanorough surfaces: a thermally activated process.

The motion of a solid-liquid-liquid contact line over nanorough surfaces is investigated. The surface nanodefects are varied in size, density, and shape. The dynamics of the three-phase contact line on all nanorough substrates studied is thermally activated. However, unlike the motion of a liquid-vapor interface over smooth surfaces, this thermally activated process is not adequately described by the molecular kinetic theory. The molecular parameters extracted from the experiments suggest that on the nanorough surfaces, the motion of the contact line is unlikely to simply consist of molecular adsorption-desorption steps. Thermally activated pinning-depinning events on the surface nanodefects are also important. We investigate the effect of surface nanotopography on the relative importance of these two mechanisms in governing contact line motion. Using a derivation for the hysteresis energy based on Joanny and de Gennes's model, we evaluate the effect of nanotopographical features on the wetting activation free energy and contact line friction. Our results suggest that both solid-liquid interactions and surface pinning strength contribute to the energy barriers hindering the three-phase contact line motion. For relatively low nanodefect densities, the activation free energy of wetting can be expressed as a sum of surface wettability and surface topography contributions, thus providing a direct link between contact line dynamics and roughness parameters.

Photonic crystal sensors based on porous silicon.

Porous silicon has been established as an excellent sensing platform for the optical detection of hazardous chemicals and biomolecular interactions such as DNA hybridization, antigen/antibody binding, and enzymatic reactions. Its porous nature provides a high surface area within a small volume, which can be easily controlled by changing the pore sizes. As the porosity and consequently the refractive index of an etched porous silicon layer depends on the electrochemial etching conditions photonic crystals composed of multilayered porous silicon films with well-resolved and narrow optical reflectivity features can easily be obtained. The prominent optical response of the photonic crystal decreases the detection limit and therefore increases the sensitivity of porous silicon sensors in comparison to sensors utilizing Fabry-Pérot based optical transduction. Development of porous silicon photonic crystal sensors which allow for the detection of analytes by the naked eye using a simple color change or the fabrication of stacked porous silicon photonic crystals showing two distinct optical features which can be utilized for the discrimination of analytes emphasize its high application potential.

Fabrication of porous silicon by metal-assisted etching using highly ordered gold nanoparticle arrays.

A simple method for the fabrication of porous silicon (Si) by metal-assisted etching was developed using gold nanoparticles as catalytic sites. The etching masks were prepared by spin-coating of colloidal gold nanoparticles onto Si. An appropriate functionalization of the gold nanoparticle surface prior to the deposition step enabled the formation of quasi-hexagonally ordered arrays by self-assembly which were translated into an array of pores by subsequent etching in HF solution containing H2O2. The quality of the pattern transfer depended on the chosen preparation conditions for the gold nanoparticle etching mask. The influence of the Si surface properties was investigated by using either hydrophilic or hydrophobic Si substrates resulting from piranha solution or HF treatment, respectively. The polymer-coated gold nanoparticles had to be thermally treated in order to provide a direct contact at the metal/Si interface which is required for the following metal-assisted etching. Plasma treatment as well as flame annealing was successfully applied. The best results were obtained for Si substrates which were flame annealed in order to remove the polymer matrix - independent of the substrate surface properties prior to spin-coating (hydrophilic or hydrophobic). The presented method opens up new resources for the fabrication of porous silicon by metal-assisted etching. Here, a vast variety of metal nanoparticles accessible by well-established wet-chemical synthesis can be employed for the fabrication of the etching masks.