Fluorophore Interactions with the Surface Modes and Internal Modes of a Photonic Crystal.

The metal-ligand complex tris(2,2'-bipyridine)ruthenium(II) chloride (Ru probe) displays a broad emission spectrum ranging from 540 to 730 nm. The emission spectra of Ru probe were measured when placed on top of a one-dimensional photonic crystal (1DPC), which supports both Bloch surface wave (BSW) and internal modes for wavelengths below 640 nm and only internal modes above 640 nm. The S-polarized emission spectra, with the electric vector parallel to the 1DPC surface, were found to be strongly dependent on the observation angle through the coupling prism. Also, the usual single broad-emission spectrum of Ru probe on glass was converted into two or more narrow-band-spectrum on the 1DPC, with emission band maxima dependent on the observation angle. The two S-polarized emission band peaks for Ru probe were found to be consistent with coupling to the BSW and first internal mode (IM1) of the 1DPC. The same spectral shifts and changes in emission maxima were observed by using Kretschmann and reverse Kretschmann illuminations. As the coupling requires the emitter to be in proximity with the photonic structure, we calculated near- and far-field distributions of a dipole directly located on the 1DPC surface. Finite-Difference Time-Domain (FDTD) simulations were performed to confirm fluorophore coupling to the BSW and internal modes (IMs). Both the measured and simulated results showed that IM coupled emission is significant. Coupling to the IM mode occurred at longer wavelengths where the 1DPC did not support a BSW. These results demonstrate that a simple Bragg grating, without a BSW mode, can be used for detection of surface-bound fluorophores.

Plasmon- and Waveguide-Coupled Fluorescence at the Ultraviolet Region.

Surface plasmon-coupled emission (SPCE) has been well studied for its coupled, directional, and enhanced P-polarized radiation due to the interactions of fluorophores with surface plasmon polaritons (SPPs) on thin metal films. Such surface plasmon polariton-assisted directional fluorescence has various applications in biosensing. Herein, we demonstrate 2-aminopurine (2AP, a UV-absorbing and -emitting fluorophore) emission coupling to modes in aluminum-based plasmon-coupled waveguides (Al-PCWs). Directional emission from 2-aminopurine on plasmon-coupled waveguides was observed at specific angles as P-polarized SPCE and/or as P- or S-polarized waveguide-coupled emission (WGCE). All S-polarized waveguide modes showed clear angularly resolved emission as compared to that of P-polarized surface plasmon-coupled emission or P-polarized waveguide-coupled emission. The coupling angles, efficiencies, and polarizations of the modes were sensitive to the optical properties and overall dimensions of the top dielectric layer in PCWs. The effective plasmon-coupled waveguide can consist of either a thin probe-containing layer on top of the undoped silica film, or a single dielectric PVA layer with probes distributed throughout the film on the Al layer. The former structures with probes confined to the top of the undoped silica layer showed much higher angular resolutions and coupling efficiencies, as well as mode-dependent changes in lifetimes. These results demonstrate that the plasmon and waveguide modes can be used for selective detection of surface-bound and bulk fluorophores, simultaneously.

Remote Measurements of Tear Electrolyte Concentrations on Both Sides of an Inserted Contact Lens.

In this paper, a method is described to perform ion concentration measurements on both sides of an inserted contact lens, without physical contact with the eye or the contact lens. The outer surface of an eye is covered with a tear film that has multiple layers. The central aqueous layer contains electrolytes and proteins. When a contact lens is inserted, it becomes localized in the central layer, which creates two layers known as the pre-lens tear film (PLTF) and the post-lens tear film (PoLTF). The PoLTF is in direct contact with the sensitive corneal epithelial cells which control electrolyte concentrations in tears. It is difficult to measure the overall electrolyte concentration in tears because of the small 7 µL volume of bulk tears. No methods are known, and no method has been proposed, to selectively measure the concentrations of electrolytes in the smaller volumes of the PLTF and the PoLTF. In this paper, we demonstrate the ability to localize fluorophores on each side of a contact lens without probe mixing or diffusion across the lens. We measured the concentration of sodium in the region of the PoLTF using a sodium-sensitive fluorophore positioned on the inner surface of a contact lens. The fluorescence measurements do not require physical contact and are mostly independent of eye motion and fluorophore concentration. The method is generic and can be combined with ion-sensitive fluorophores for the other electrolytes in tears. Instrumentation for non-contact measurements is likely to be inexpensive with modern opto-electronic devices. We expect these lenses to be used for measurements of other ions in the PLTF and the PoLTF, and thus become useful for both research and in the diagnosis of infections, keratitis and biomarkers for diseases.

Converting the guided-modes of Bloch surface waves with surface pattern.

The guided-modes of Bloch surface waves, such as the transverse electric modes (TE00 and TE01 modes), can simultaneously exist in a low-refractive-index ridge waveguide with subwavelength thickness that are deposited on an all dielectric one-dimension photonic crystal. By using the finite difference frequency domain method, coupled mode theory and finite-difference time-domain method, the conversion between the guided-modes has been investigated. This conversion can be realized in a broadband wavelength with surface pattern of this low-index ridge. This conversion is useful for developing lab-on-a-chip photonic devices, such as a mode converter that can maintain the output mode purity over 90% with working wavelength ranging from 590 to 680 nm, and a power splitter that can maintain the splitting ratio over 8:2 with wavelength ranging from 530 to 710 nm.

Fluorescence Coupling to Internal Modes of 1D Photonic Crystals Characterized by Back Focal Plane Imaging.

The coupling of fluorescence with surface electromagnetic modes, such as surface plasmons on thin metal films or Bloch surface waves (BSW) on truncated one-dimensional photonic crystals (1DPC), are presently utilized for many fluorescence-based applications. In addition to the surface wave, 1DPCs also support other electromagnetic modes that are confined within the 1DPC structure. These internal modes (IMs) have not received much attention for fluorescence coupling due to lack of spatial overlap of their electric fields with the surface bound fluorophores. However, our recent studies have indicated that the fluorescence coupling with IMs occurs quite efficiently. This observed internal mode-coupled emission (IMCE) is (similar to BSW-coupled emission) indeed wavelength dependent, directional and S-polarized. In this paper, we have carried out back-focal plane (BFP) imaging to reveal that the IMs of 1DPCs can couple with surface bound excited dye molecules, with or without a BSW mode presence. Depending on the emission wavelength, the coupling is observed with BSW and IMs or only IMs of the 1DPC structure. The experimental results are well matching with numerical simulations. The occurrence of IMCE regardless of the availability of BSWs removes the dependence on just the surface mode for obtaining coupled emission from 1DPCs. The observation of IMCE is expected to widen the scope of 1DPCs for surface-based fluorescence sensing and assays.

Sodium-Sensitive Contact Lens for Diagnostics of Ocular Pathologies.

The ability to measure all the electrolyte concentrations in tears would be valuable in ophthalmology for research and diagnosis of dry eye disease (DED) and other ocular pathologies. However, tear samples are difficult to collect and analyze because the total volume is small and the chemical composition changes rapidly. Measurements of electrolytes in tears is challenging because typical clinical assays for proteins and other biomarkers cannot be used to detect ion concentrations tears. Here, we report the contact lens which is sensitive to sodium ion (Na+), one of the dominant electrolytes in tears. The Na ions in tears is diagnostic for DED. Three sodium-sensitive fluorophores (SG-C16, SG-LPE and SG-PL) were synthesized by derivatizing the sodium green with 1-hexadecyl amine, 1-oleoyl-2-hydroxy-sn-glycero-3-phosphoethanolamine or poly-L-lysine, respectively. These probes were bound to modern silicone hydrogel (SiHG) contact lens, Biofinity from Cooper Vision. Doped lenses were tested for sodium ion dependent spectral properties of probes within the contact lens. The probes displayed changes in intensity and lifetime in response to Na+ concentration, were completely reversible, no significant probe wash-out from the lenses, were not affected by proteins in tears and were not removed after repeated washing. These results are the first step to our long-term goal, which is a lens sensitive to all the electrolytes in tears. We presented design, synthesis and implementation of three new sodium sensitive probes within a silicon hydrogel lens. Contact lenses to measure the other electrolytes in tears can be developed using the same approach by synthesis and testing of new ion-sensitive fluorophores.

Fluorescent contact lens for continuous non-invasive measurements of sodium and chloride ion concentrations in tears.

Rapid and non-invasive measurement of hydration status is medically important because even mild levels of dehydration can have a significant impact on physical and cognitive performance. Despite the potential value of determining whole-body hydration based on the electrolytes found in tears, very few tests are available. An area of intense interest is the development of a contact lens which could measure ion concentrations in tears, specifically that of sodium (Na+) and chloride (Cl-) ions, the dominant electrolytes in blood plasma and tears. Here, we describe a method to make fluorescent contact lenses which allow determination of Na+ and Cl- ion concentrations in tears. Fluorophores known to be sensitive to Na+ and Cl- were derivatized to bind non-covalently to two commercially-available silicone hydrogel (SiHG) contact lenses-the Biofinity (Comfilcon A) or MyDay (Stenfilcon A) lenses. The sodium- and chloride-sensitive fluorophores displayed spectral changes in the physiological range for Na+ and Cl- ions in tears. The lenses for both Na+ and Cl- ions were completely reversible. The sodium responses were not sensitive to protein interference including human lysozyme, human serum albumin and mucin type 2. The chloride sensitivity was similar with both lenses, but the sodium-sensitive range was different in the Biofinity and MyDay lenses. We also fabricated a lens with both the Na+ and Cl- probes in a single MyDay lens resulting in a contact lens that independently measured Na+ and Cl- concentrations without physical separation of the fluorophores. Our findings indicated that a sodium and chloride-sensitive contact lens (NaCl-lens) could be used for rapid non-invasive detection of whole-body hydration, as well as associated diseases or other infections.

Fluorophore Coupling to Internal Modes of Bragg Gratings.

Multilayer structures with two dielectrics having different optical constants and no structural features in the x-y plane can display photonic band gaps (PBGs) and are called one-dimensional photonic crystals (1DPCs). If the top layer thickness is carefully selected, the electromagnetic energy can be trapped at the top surface. These highly enhanced fields are called Bloch surface waves (BSWs). The BSW resonance angles are sensitive to the dielectric constant above the top dielectric layer. As a result, BSW structures have been used for surface plasmon resonance-like measurements without the use of a metal film. However, the emphasis on surface-localized BSWs has resulted in limited interest in fluorophore interactions with other optical modes of 1DPCs or Bragg gratings without the different thickness top layer. Herein, three different fluorescent probes were used to cover the short, center, and long wavelengths of the PBG. We demonstrate efficient coupling of fluorophores to both the BSW and internal modes (IMs) of a 1DPC. Coupling to the IM is expected to be low because of the micron-scale distances between the fluorophores and IM, which exists inside the Bragg gratings. At different wavelengths or observation angles, the IM-coupled emission (IMCE) can occur with the first three modes of the multilayer. This coupling is not dependent on a BSW mode. IMCE was also observed for a monolayer of fluorophore-labeled protein. IMCE enables sensitive detection of surface-bound fluorophores. Applications are anticipated in high sensitivity detection and super-resolution imaging.

Coupling of Fluorophores in Single Nanoapertures to Tamm Plasmon Structures.

Metal nanostructures (such as plasmonic antennas) have been widely demonstrated to be excellent devices for beaming and sorting the fluorescence emission. These effects rely on the constructive scattering or diffraction from different elements (such as metal corrugations or nanorings) of the nanostructures. However, subwavelength-size nanoholes, without nearby nanoscale features, results in an angularly dispersed emission from the distal surface. Herein, we demonstrate for the first time the emission redirection capabilities of a single isolated nanoaperture milled in a thick silver film deposited on a dielectric multilayer. Specifically, we show that a dye dissolved in ethanol filling in the nanoaperture can couple to Tamm Plasmon Polariton (TPP) modes of the structure. Due to the small in-plane wavevectors of the TPPs, the fluorescence from Tamm-coupled dyes within the nanoaperture is emitted normally to the sample surface, with a minimum angular width of about 12.54°. This kind of fluorescence manipulation has proven to be effective with various nanoaperture shapes, such as circles, squares, and triangles. Our work is also the first experimental demonstration of lateral coupling of fluorophores with TPPs in nanoholes, with potential applications in bioanalysis and biosciences.

Glucose-sensitive silicone hydrogel contact lens toward tear glucose monitoring.

Accurate and reliable monitoring of blood glucose is needed for the treatment of diabetes, which has many challenges, including lack of patient compliance. Measuring tear glucose is an alternative to traditional finger-stick tests used to track blood sugar levels, but glucose sensing using tears has yet to be achieved. We report a methodology for possible tear glucose monitoring using glucose-sensitive silicone hydrogel (SiHG) contact lenses, the primary type of lenses available in today's market. Initially, we assessed the interpenetrating polymer network, with nearly pure silicone and water regions, existing in the SiHGs using a polarity-sensitive probe Prodan. We then synthesized a glucose-sensitive fluorophore Quin-C18 with a hydrophobic side chain for localization of probe at the interfacial region. Using our glucose-sensing contact lens, we were able to measure varying concentrations of glucose in an in-vitro system. The Quin-C18 strongly bound to the lenses with insignificant leaching even after multiple rinses. The lenses displayed a similar response to glucose after three months of storage in water. This study demonstrates that it may be possible to develop a contact lens for continuous glucose monitoring in the near term, using our concept of fluorophore binding at the silicone-water interface.

Extending the Propagation Distance of a Silver Nanowire Plasmonic Waveguide with a Dielectric Multilayer Substrate.

Chemical-synthesized silver nanowires have been proven as an efficient architecture for plasmonic waveguides, but the high propagation loss prevents their widely applications. Here, we demonstrate that the propagation distance of the plasmons along a silver nanowire can be extended if this nanowire was placed on a dielectric multilayer substrate containing a photonic band gap but not placed on a commonly used glass substrate. The propagation distance at 630 nm wavelength can reach 16 µm, even when the silver nanowire is as thin as 90 nm in diameter. Experimental and simulation results further show that the polarization of this propagating plasmon mode was nearly parallel to the surface of the dielectric multilayer, so it can be excited by a transverse-electric polarized Bloch surface wave propagating along a polymer nanowire with diameter at only about 170 nm on the same dielectric multilayer. Numerical simulations were also carried out and are consistent with the experiment results. Our work provides a platform with which to extend the propagation distance of the plasmonic waveguide and also for the integration between photonic and plasmonic waveguides on the nanometer scale.

Manipulating Propagation Constants of Silver Nanowire Plasmonic Waveguide Modes Using a Dielectric Multilayer Substrate.

Experiments and numerical simulations demonstrate that when a silver nanowire is placed on a dielectric multilayer, but not the commonly used bare glass slide, the effective refractive index of the propagating surface plasmons along the silver nanowire can be controlled. Furthermore, by increasing the thickness of the top dielectric layer, longer wavelength light can also propagate along a very thin silver nanowire. In the experiment, the diameter of the silver nanowire can be as thin as 70 nm, with the incident wavelength as long as 640 nm. The principle of this control is analysed from the existence of a photonic band gap and the Bloch surface wave with this dielectric multilayer substrate.

Conversion of isotropic fluorescence into a long-range non-diverging beam.

Fluorescent samples typically emit isotropically in all directions. Large lenses and other optical components are needed to capture a significant fraction of the emission, and complex confocal microscopes are required for high resolution focal-plane imaging. It is known that Bessel beams have remarkable properties of being able to travel over long distances, over 1000 times the wavelength, without diverging, and hence are called non-diffracting beams. In previous reports the Bessel beams were formed by an incident light source, typically with plane-wave illumination on a circular aperture. It was not known if Bessel beams could form from fluorescent light sources. We demonstrate transformation of the emission from fluorescent polystyrene spheres (FPS) into non-diverging beams which propagate up to 130 mm (13 cm) along the optical axis with a constant diameter. This is accomplished using a planar metal film, with no nanoscale features in the X-Y plane, using surface plasmon-coupled emission. Using samples which contain many FPS in the field-of-view, we demonstrate that an independent Bessel beam can be generated from any location on the metal film. The extremely long non-diffracted propagation distances, and self-healing properties of Bessel beams, offer new opportunities in fluorescence sensing and imaging.

Contact lens to measure individual ion concentrations in tears and applications to dry eye disease.

Dry eye disease (DED) affects millions of individuals in the United States and worldwide, and the incidence is increasing with an aging population. There is widespread agreement that the measurement of total tear osmolarity is the most reliable test, but this procedure provides only the total ionic strength and does not provide the concentration of each ionic species in tears. Here, we describe an approach to determine the individual ion concentrations in tears using modern silicone hydrogel (SiHG) contact lenses. We made pH (or H3O+, hydronium cation,/OH-, hydroxyl ion) and chloride ion (two of the important electrolytes in tear fluid) sensitive SiHG contact lenses. We attached hydrophobic C18 chains to water-soluble fluorescent probes for pH and chloride. The resulting hydrophobic ion sensitive fluorophores (H-ISF) bind strongly to SiHG lenses and could not be washed out with aqueous solutions. Both H-ISFs provide measurements which are independent of total intensity by use of wavelength-ratiometric measurements for pH or lifetime-based sensing for chloride. Our approach can be extended to fabricate a contact lens which provides measurements of the six dominant ionic species in tears. This capability will be valuable for research into the biochemical processes causing DED, which may improve the ability to diagnose the various types of DED.

Silver Nanowires for Reconfigurable Bloch Surface Waves.

The use of a single silver nanowire as a flexible coupler to transform a free space beam into a Bloch surface wave propagating on a dielectric multilayer is proposed. Based on Huygens' Principle, when a Gaussian beam is focused onto a straight silver nanowire, a Bloch surface wave is generated and propagates perpendicular to the nanowire. By curving the silver nanowire, the surface wave can be focused. Furthermore, the spatial phase of the incident laser beam can be actively controlled with the aid of a spatial light modulator, resulting in the reconfigurable or dynamically controlled Bloch surface waves. The low cost of the chemically synthesized silver nanowires and the high flexibility with regard to tuning the spatial phase of the incident light make this approach very promising for various applications including optical micromanipulation, fluorescence imaging, and sensing.

Diffraction-Free Bloch Surface Waves.

Here, we demonstrate a diffraction-free Bloch surface wave sustained on all-dielectric multilayers that does not diffract after being passed through three obstacles or across a single mode fiber. It can propagate in a straight line for distances longer than 110 µm at a wavelength of 633 nm and could be applied as an in-plane optical virtual probe both in air and in an aqueous environment. Its ability to be used in water, its long diffraction-free distance, and its tolerance to multiple obstacles make this wave ideal for certain applications in areas such as the biological sciences, where many measurements are made on glass surfaces or for which an aqueous environment is required, and for high-speed interconnections between chips, where low loss is necessary.

Radiative decay engineering 8: Coupled emission microscopy for lens-free high-throughput fluorescence detection.

Fluorescence spectroscopy and imaging are now used throughout the biosciences. Fluorescence microscopes, spectrofluorometers, microwell plate readers and microarray imagers all use multiple optical components to collect, redirect and focus the emission onto single point or array imaging detectors. For almost all biological samples, except those with regular nanoscale features, emission occurs in all directions. With the exception of complex microscope objectives with large collection angles (NA ≤ 0.5), all these instruments collect only a small fraction of the total emission. Because of the increasing knowledge base on fluorophores within near-field (<200 nm) distances from plasmonic and photonic structures we can anticipate the development of compact devices in which the sample to be detected is located directly on solid state detectors such as CCDs or CMOS cameras. Near-field interactions of fluorophores with metallic or dielectric multi-layer structures (MLSs) can capture a large fraction of the total emission. Depending on the composition and dimensions of the MLSs, the spatial distribution of the sample emission results in distinct optical patterns on the detector surface. With either plain glass slides or MLSs the most commonly used front focal plane (FFP) images reveal the x-y spatial distribution of emission from the sample. Another approach, which is often used with two or three-dimensional nanostructures, is back focal plane (BFP) imaging. The BFP images reveal the angular distribution of the emission. The FFP and BFP images occur at certain distances from the sample which is determined by the details of the optical components. Obtaining these images requires multiple optical components and distances which are too large for the compact devices. For devices described in this paper, the images will be detected at a fixed distance between the sample and some arbitrary distance below the MLS which is determined by the geometry and thicknesses of the components. We refer to measurements at these locations as out-of-focal plane (OFP) imaging. Herein we describe a method to measure the optical fields at micron and multi-micron distances below the MLS, which will represent the images seen by an optically coupled array detector. The possibility of sub-surface optical images is illustrated using five different multi-layer structures. This is accomplished using an optical configuration which allows measurement at a front focal plane (FFP), back focal plane (BFP) or any OFP locations. Our OFP imaging method provides a link between the FFP images which reveals the surface distribution of fluorophores with the BFP images that reveal the angular distribution of emission. This linkage can be useful when examining structures which have nanoscale features due to fluorescence or leakage radiation from nanostructures.

Bloch surface waves confined in one dimension with a single polymeric nanofibre.

Polymeric fibres with small radii (such as ≤125 nm) are delicate to handle and should be laid down on a solid substrate to obtain practical devices. However, placing these nanofibres on commonly used glass substrates prevents them from guiding light. In this study, we numerically and experimentally demonstrate that when the nanofibre is placed on a suitable dielectric multilayer, it supports a guided mode, a Bloch surface wave (BSW) confined in one dimension. The physical origin of this new mode is discussed in comparison with the typical two-dimensional BSW mode. Polymeric nanofibres are easily fabricated to contain fluorophores, which make the dielectric nanofibre and multilayer configuration suitable for developing a large range of new nanometric scale devices, such as processor-memory interconnections, devices with sensitivity to target analytes, incident polarization and multi-colour BSW modes.

Out-of-Focal Plane Imaging by Leakage Radiation Microscopy.

Leakage radiation microscopy (LRM) is used to investigate the optical properties of surfaces. The front-focal plane (FFP) image with LRM reveals structural features on the surfaces. Back-focal plane (BFP) image with LRM reveals the angular distribution of the radiation. Herein we experimentally demonstrate that the out-of-focal plane (OFP) images present a link between the FFP and BFP images and provide optical information that cannot be resolved by either FFP or BFP images. The OFP image provides a linkage between the spatial location of the emission and the angular distribution from the same location, and thus information about the film's discontinuity, nonuniformity or variable thickness can be uncovered. The use of OFP imaging will extend the scope and applications of the LRM and coupled emission imaging which are powerful tools in nanophotonics and high throughput fluorescence screening.

Imaging optical fields below metal films and metal-dielectric waveguides by a scanning microscope.

Laser scanning confocal fluorescence microscopy (LSCM) is now an important method for tissue and cell imaging when the samples are located on the surfaces of glass slides. In the past decade, there has been extensive development of nano-optical structures that display unique effects on incident and transmitted light, which will be used with novel configurations for medical and consumer products. For these applications, it is necessary to characterize the light distribution within short distances from the structures for efficient detection and elimination of bulky optical components. These devices will minimize or possibly eliminate the need for free-space light propagation outside of the device itself. We describe the use of the scanning function of a LSCM to obtain 3D images of the light intensities below the surface of nano-optical structures. More specifically, we image the spatial distributions inside the substrate of fluorescence emission coupled to waveguide modes after it leaks through thin metal films or dielectric-coated metal films. The observed spatial distribution were in general agreement with far-field calculations, but the scanning images also revealed light intensities at angles not observed with classical back focal plane imaging. Knowledge of the subsurface optical intensities will be crucial in the combination of nano-optical structures with rapidly evolving imaging detectors.