Impact of Optical Cavity on Refractive Index Sensitivity of Gold Nanohole Arrays.

Refractive index sensing based on surface plasmon resonance (SPR) is a highly efficient label-free technique for biomolecular detection. The performance of this method is defined by the dielectric properties of a sensing layer and its structure. Nanohole arrays in thin metal films provide good refractive index sensitivity but often suffer from a large resonance linewidth, which limits their broad practical application in biosensorics. Coupling the broad plasmon modes to sharp resonances can reduce the peak widths, but at the same time it can also degrade the sensitivity. Here, we use Finite-Difference Time Domain simulations to study the factors affecting the sensing performance of gold-silica-gold optical cavities with nanohole arrays in the dielectric and top metal layers. We demonstrate that by tuning resonator size and inter-hole spacing, the performance of the biosensor can be optimized and the figure of merit of the order of 5-7 is reached.

Protein Mobility Measurements through Oxidative Green-to-Red Photoconversion of EGFP.

Protein dynamics plays a key role in live cell functioning, stimulating the development of new experimental techniques for studying protein transport phenomena. Here, we introduce a relaxation method that is based on the rapid formation of a nonequilibrium concentration profile of the enhanced green fluorescent protein (EGFP) across a sample by its oxidative green-to-red photoconversion. Following the blue-light irradiation of a part of a sample containing EGFP and an oxidant, the diffusion-controlled response of a system is monitored. Changes in the concentration of the initial green-emitting and oxidized red-emitting forms are simultaneously tracked by fluorescence lifetime measurements using the time-correlated single photon counting. We show that the diffusion coefficient of EGFP in water, determined by this method, is in good agreement with previously published data. This approach opens a way for the studies of intracellular viscosity changes combined with sensing of elevated levels of reactive oxygen species.

Efficiency of Plasmon-Induced Dual-Mode Fluorescence Enhancement upon Two-Photon Excitation.

Anisotropic noble metal nanoparticles supporting more than one localized surface plasmon resonance can be tailored for efficient dual-mode fluorescence enhancement by ensuring an adequate coupling to both absorption and emission bands of fluorophores. This approach is naturally extended to two-photon excitation fluorescence, where a molecule is excited by simultaneous nonlinear absorption of two photons. However, the relative impact of plasmon coupling to excitation and emission on the overall fluorescence enhancement can be very different in this case. Here, by using the finite-difference time-domain method, we study the two-photon excitation fluorescence of near-infrared fluorescent protein (NirFP) eqFP670, which is the most red-shifted NirFP to date, in proximity to a silver nanobar. By optimizing the length and aspect ratio of the particle, we reach a fluorescence enhancement factor of 103. We show that the single mode coupling regime with highly tuned near-field significantly outperforms the dual-mode coupling enhancement. The plasmon-induced amplification of the fluorophore's excitation rate becomes of utmost importance due to its quadratic dependence on light intensity, defining the fluorescence enhancement upon two-photon excitation. Our results can be used for the rational design of hybrid nanosystems based on NirFP and plasmonic nanoparticles with greatly improved brightness important for developing whole-body imaging techniques.

Plasmon-Enhanced Fluorescence of EGFP on Short-Range Ordered Ag Nanohole Arrays.

Fluorescence of organic molecules can be enhanced by plasmonic nanostructures through coupling to their locally amplified electromagnetic field, resulting in higher brightness and better photostability of fluorophores, which is particularly important for bioimaging applications involving fluorescent proteins as genetically encoded biomarkers. Here, we show that a hybrid bionanosystem comprised of a monolayer of Enhanced Green Fluorescent Protein (EGFP) covalently linked to optically thin Ag films with short-range ordered nanohole arrays can exhibit up to 6-fold increased brightness. The largest enhancement factor is observed for nanohole arrays with a propagating surface plasmon mode, tuned to overlap with both excitation and emission of EGFP. The fluorescence lifetime measurements in combination with FDTD simulations provide in-depth insight into the origin of the fluorescence enhancement, showing that the effect is due to the local amplification of the optical field near the edges of the nanoholes. Our results pave the way to improving the photophysical properties of hybrid bionanosystems based on fluorescent proteins at the interface with easily fabricated and tunable plasmonic nanostructures.

Dynamic gas extraction of iodine in combination with a silver triangular nanoplate-modified paper strip for colorimetric determination of iodine and of iodine-interacting compounds.

A method is described for sensitive and selective detection of iodine by using a paper strip modified with silver triangular nanoplates (AgTNPs). It is based on the extraction of iodine from a solution into a flow of air via dynamic gas extraction and transferring it through a reactive paper modified with AgTNPs. The interaction of AgTNPs with iodine results in a color change from blue to white. This can be visually detected and monitored by digital colorimetry. The dynamic gas extraction is highly selective for volatile compounds so that a sample pretreatment is minimal. Due to the sensitivity of AgTNPs for iodine, the limit of its detection is as low as 7 µg L-1, and the analytical range is of 20-200 µg L-1. The method also was applied in a new approach for determination of organic compounds that can interact with iodine. The organic compound is exposed to an excess of iodine, and this is followed by detection of residual iodine as described above. The method was applied to the determination of ascorbic acid, caffeine and the drug metamizole. Graphical abstract Schematic representation of a procedure of organic iodine-interacting compounds (Org.) determination. It is based on their iodination followed by gas extraction of the residual iodine, its interaction with silver triangular nanoplates and colorimetric detection with a scanner.

Chiral Plasmonic Biosensors.

Biosensing requires fast, selective, and highly sensitive real-time detection of biomolecules using efficient simple-to-use techniques. Due to a unique capability to focus light at nanoscale, plasmonic nanostructures provide an excellent platform for label-free detection of molecular adsorption by sensing tiny changes in the local refractive index or by enhancing the light-induced processes in adjacent biomolecules. This review discusses the opportunities provided by surface plasmon resonance in probing the chirality of biomolecules as well as their conformations and orientations. Various types of chiral plasmonic nanostructures and the most recent developments in the field of chiral plasmonics related to biosensing are considered.

Chiral plasmonic nanocrescents: large-area fabrication and optical properties.

Large-area arrays of substrate-supported plasmonic gold crescents are fabricated by using the new colloidal lithography technique, which is based on an in situ-deposited silica resistance layer. The method provides the means to control the particles' asymmetry just by changing the mutual deposition angle of gold and silica. Asymmetric crescent structures exhibit a pronounced circular dichroism in near-infrared region, with the chiral asymmetry factor reaching 0.2. According to the simulation, the optical chirality enhancement reaches between one and two orders of magnitude and is localized near the crescents' tips.

Dynamic protein coronas revealed as a modulator of silver nanoparticle sulphidation in vitro.

Proteins adsorbing at nanoparticles have been proposed as critical toxicity mediators and are included in ongoing efforts to develop predictive tools for safety assessment. Strongly attached proteins can be isolated, identified and correlated to changes in nanoparticle state, cellular association or toxicity. Weakly attached, rapidly exchanging proteins are also present at nanoparticles, but are difficult to isolate and have hardly been examined. Here we study rapidly exchanging proteins and show for the first time that they have a strong modulatory effect on the biotransformation of silver nanoparticles. Released silver ions, known for their role in particle toxicity, are found to be trapped as silver sulphide nanocrystals within the protein corona at silver nanoparticles in serum-containing cell culture media. The strongly attached corona acts as a site for sulphidation, while the weakly attached proteins reduce nanocrystal formation in a serum-concentration-dependent manner. Sulphidation results in decreased toxicity of Ag NPs.

Exploring plasmonic coupling in hole-cap arrays.

The plasmonic coupling between gold caps and holes in thin films was investigated experimentally and through finite-difference time-domain (FDTD) calculations. Sparse colloidal lithography combined with a novel thermal treatment was used to control the vertical spacing between caps and hole arrays and compared to separated arrays of holes or caps. Optical spectroscopy and FDTD simulations reveal strong coupling between the gold caps and both Bloch Wave-surface plasmon polariton (BW-SPP) modes and localized surface plasmon resonance (LSPR)-type resonances in hole arrays when they are in close proximity. The interesting and complex coupling between caps and hole arrays reveals the details of the field distribution for these simple to fabricate structures.

Extended temperature-accelerated dynamics: enabling long-time full-scale modeling of large rare-event systems.

A new method, the Extended Temperature-Accelerated Dynamics (XTAD), is introduced for modeling long-timescale evolution of large rare-event systems. The method is based on the Temperature-Accelerated Dynamics approach [M. Sørensen and A. Voter, J. Chem. Phys. 112, 9599 (2000)], but uses full-scale parallel molecular dynamics simulations to probe a potential energy surface of an entire system, combined with the adaptive on-the-fly system decomposition for analyzing the energetics of rare events. The method removes limitations on a feasible system size and enables to handle simultaneous diffusion events, including both large-scale concerted and local transitions. Due to the intrinsically parallel algorithm, XTAD not only allows studies of various diffusion mechanisms in solid state physics, but also opens the avenue for atomistic simulations of a range of technologically relevant processes in material science, such as thin film growth on nano- and microstructured surfaces.

Multifunctional biosensor based on localized surface plasmon resonance for monitoring small molecule-protein interaction.

We report an optical sensor based on localized surface plasmon resonance (LSPR) to study small-molecule protein interaction combining high sensitivity refractive index sensing for quantitative binding information and subsequent conformation-sensitive plasmon-activated circular dichroism spectroscopy. The interaction of α-amylase and a small-size molecule (PGG, pentagalloyl glucose) was log concentration-dependent from 0.5 to 154 µM. In situ tests were additionally successfully applied to the analysis of real wine samples. These studies demonstrate that LSPR sensors to monitor small molecule­protein interactions in real time and in situ, which is a great advance within technological platforms for drug discovery.

Spatial mapping and quantification of soft and hard protein coronas at silver nanocubes.

Protein coronas around silver nanocubes were quantified in serum-containing media using localized surface plasmon resonances. Both soft and hard coronas showed exposure-time and concentration-dependent changes in protein surface density with time-dependent hardening. We observed spatially dependent kinetics of the corona-formation at cube edges/corners versus facets at short incubation times, where the polymer stabilization agent delayed corona hardening. The soft corona contained more protein than the hard corona at all time-points (8-fold difference with 10% serum conditions).

Onset of bonding plasmon hybridization preceded by gap modes in dielectric splitting of metal disks.

Dielectric splitting of nanoscale disks was studied experimentally and via finite-difference time-domain (FDTD) simulations through systematic introduction of multiple ultrathin dielectric layers. Tunable, hybridized dark bonding modes were seen with first-order gap modes preceding the appearance of bonding dipole-dipole disk modes. The observed bright dipolar mode did not show the energy shift expected from plasmon hybridization but activated dark higher order gap modes. Introducing lateral asymmetry was shown to remodel the field distribution resulting in 3D asymmetry that reoriented the dipole orientation away from the dipole of the elementary disk modes.

Enhanced refractive index sensitivity of elevated short-range ordered nanohole arrays in optically thin plasmonic Au films.

A simple development of the colloidal lithography technique is demonstrated for fabrication of perforated plasmonic metal films elevated above the substrate surface. The bulk refractive index sensitivity of short-range ordered nanohole arrays in 20 nm thick Au films exhibits an increase of up to 37% due to reduction of substrate effect caused by lifting with a 40 nm silica layer. Analysis of the local electric field distribution suggests that the sensitivity increase is due to revealing of the enhanced field near the holes.

From rings to crescents: a novel fabrication technique uncovers the transition details.

A novel fabrication route is reported for the generation of substrate-supported symmetric and asymmetric metal nanostructures. We combine a colloidal template and angled evaporation to deposit in situ mask materials for subsequent lithographic pattern transfer. The technique is demonstrated for the fabrication of concentric and nonconcentric gold rings and crescents. Optical properties of localized plasmon resonances in such structures are studied by UV-vis-NIR spectroscopy and finite-difference time domain simulations during the transition from rings to crescents revealing the development of strong quadrupolar modes.

Complex protein nanopatterns over large areas via colloidal lithography.

The patterning of biomolecules at the nanoscale provides a powerful method to investigate cellular adhesion processes. A novel method for patterning is presented that is based on colloidal monolayer templating combined with multiple and angled deposition steps. Patterns of gold and SiO2 layers are used to generate complex protein nanopatterns over large areas. Simple circular patches or more complex ring structures are produced in addition to hierarchical patterns of smaller patches. The gold regions are modified through alkanethiol chemistry, which enables the preparation of extracellular matrix proteins (vitronectin) or cellular ligands (the extracellular domain of E-cadherin) in the nanopatterns, whereas the selective poly(l-lysine)-poly(ethylene glycol) functionalization of the SiO2 matrix renders it protein repellent. Cell studies, as a proof of principle, demonstrate the potential for using sets of systematically varied samples with simpler or more complex patterns for studies of cellular adhesive behavior and reveal that the local distribution of proteins within a simple patch critically influences cell adhesion.

HArF in solid argon revisited: transition from unstable to stable configuration.

The thermal conversion of HArF configurations in solid argon has been investigated both experimentally and theoretically. The matrix isolation experiments have been concentrated on temperatures 25-27 K, promoting the transition from the unstable to stable HArF configuration. The combined quantum mechanical-molecular mechanical and temperature-accelerated dynamics approach has been developed to study the real-time evolution of HArF trapped in different matrix-site morphologies. Two realistic pathways of the stable HArF formation are found for annealing at 25-27 K. The conversion mechanism in both pathways involves the local mobility of matrix vacancies in the vicinity of the HArF molecule. These two relaxation processes occurring within different timescales can cause the multiexponential decay of unstable HArF observed experimentally. The theoretical values of the activation energy of 64 meV as well as the corresponding pre-exponential factor of exp(28) s(-1), obtained for one of the unstable HArF configurations, are well consistent with the experimental estimates of 70 meV and exp(30 +/- 3) s(-1), respectively.