Spectral Tuning Research Articles

Electrostatic Spectral Tuning Maps for Biological Chromophores.

The mechanism by which the absorption wavelength of a molecule is modified by a protein is known as spectral tuning. Spectral tuning is often achieved by electrostatic interactions that stabilize/destabilize or modify the shape of the excited and ground-state potential energy surfaces of the chromophore. We present a protocol for the construction of three-dimensional "electrostatic spectral tuning maps" that describe how vertical excitation energies in a chromophore are influenced by nearby charges. The maps are built by moving a charge on the van der Waals surface of the chromophore and calculating the change in its excitation energy. The maps are useful guides for protein engineering of color variants, for interpreting spectra of chromophores that act as probes of their environment, and as starting points for further quantum mechanical/molecular mechanical studies. The maps are semiquantitative and can approximate the magnitude of the spectral shift induced by a point charge at a given position with respect to the chromophore. We generate and discuss electrostatic spectral tuning maps for model chromophores of photoreceptor proteins, fluorescent proteins, and aromatic amino acids. Such maps may be extended to other properties such as oscillator strengths, absolute energies (stability), ionization energies, and electron affinities.

Evolution of the eyes of vipers with and without infrared-sensing pit organs

We examined lens and brille transmittance, photoreceptors, visual pigments, and visual opsin gene sequences of viperid snakes with and without infrared-sensing pit organs. Ocular media transmittance is high in both groups. Contrary to previous reports, small as well as large single cones occur in pit vipers. Non-pit vipers differ from pit vipers in having a twotiered retina, but few taxa have been examined for this poorly understood feature. All vipers sampled express rh1, sws1 and lws visual opsin genes. Opsin spectral tuning varies but not in accordance with the presence/absence of pit organs, and not always as predicted from gene sequences. The visual opsin genes were generally under purifying selection, with positive selection at spectral tuning amino acids in RH1 and SWS1 opsins, and at retinal pocket stabilization sites in RH1 or LWS (and without substantial differences between pit and nonpit vipers). Lack of evidence for sensory trade-off between viperid eyes (in the aspects examined) and pit organs might be explained by the high degree of neural integration of vision and infrared detection; the latter representing an elaboration of an existing sense with addition of a novel sense organ, rather than involving the evolution of a wholly novel sensory system.

Photoreceptors morphology and genetics of the visual pigments of Bothrops jararaca and Crotalus durissus terrificus (Serpentes, Viperidae)

Snakes inhabit a great variety of habitats, whose spectral quality of light may vary a lot and influence specific adaptations of their visual system. In this study, we investigated the genetics of the visual opsins and the morphology of retinal photoreceptors, of two nocturnal snakes from the Viperidae family, Bothrops jararaca and Crotalus durissus terrificus, which inhabit preferentially the Atlantic Rain Forest and the Brazilian Savannah, respectively. Total RNA was extracted from homogenized retinas and converted to cDNA. The opsin genes expressed in snake retinas, LWS, RH1, and SWS1, were amplified by polymerase chain reactions (PCRs) and sequenced. The absorption peak (λmax) of the opsins were estimated based on amino acids located at specific spectral tuning sites. Photoreceptor cell populations were analyzed using immunohistochemistry with anti-opsin antibodies. Results showed the same morphological cell populations and same opsins absorption peaks, in both viperid species: double and single cones with LWS photopigment and λmax at ∼555 nm; single cones with SWS1 photopigment and λmax at ∼360 nm; and rods with the rhodopsin RH1 photopigment and λmax at ∼500 nm. The results indicate adaptations to nocturnal habit in both species despite the differences in habitat, and the possibility of a dichromatic color vision at photopic conditions.

Spectral Tuning by a Single Nucleotide Controls the Fluorescence Properties of a Fluorogenic Aptamer.

Fluorogenic aptamers are genetically encoded RNA aptamers that bind and induce the fluorescence of otherwise nonfluorescent small molecule dyes. These RNA-fluorophore complexes can be highly fluorescent and useful for RNA visualization and genetically encoded biosensors. Notably, different RNA aptamers can bind the same fluorophore, resulting in complexes that exhibit spectrally distinct fluorescence properties. The basis for spectral tuning of small molecule fluorophores has not yet been studied. Here we explore the mechanism of spectral tuning in three highly related RNA aptamers, Broccoli, Orange Broccoli, and Red Broccoli, each of which binds the DFHO (3,5-difluoro-4-hydroxybenzylidene imidazolinone-2-oxime) fluorophore and generates distinct spectral emissions. We show that DFHO fluorescence spectral tuning is controlled by interaction of the oxime moiety of the fluorophore and one specific nucleotide that is different in each RNA aptamer. Our finding presents, for the first time, a mechanism by which RNA can control the properties of a bound small molecule fluorophore. More broadly, our finding can guide further development of fluorogenic aptamers with novel spectral properties.

Control of vocal loudness in singing

Vocal loudness in sones is quantified on the basis of changes in spectral slope and harmonic tuning in a range of singing fundamental frequencies of 125 Hz to 1000 Hz. Spectral slope of the mouth output pressure is bracketed in the range of -3 dB/octave to -12 dB/octave to reflect a typical glottal spectrum from breathy to pressed adduction. To approximate formant tuning of harmonics, the SPL level of the first three harmonics is raised by 10, 20, and 30 dB. It is shown that spectral slope change is more effective in increasing vocal loudness than tuning a single harmonic with a vocal tract resonance. Some applications to amplified and unamplified vocal production and respective training are given.

Spectroscopic photoacoustic imaging for cardiovascular interventions

Alongside ultrasound imaging, photoacoustic imaging (PA) augments the imaging system with tissue composition information. Indeed, PA primarily maps tissue optical absorption and thus can reveal tissue composition. Localizing and identifying specific biomolecules can be very useful for both diagnostic imaging and evaluation of the treatment effect in various applications. PA imaging can for instance discern lipid-rich atherosclerotic plaques from fibrotic ones. It can also distinguish highly vascularized or highly oxygenated tissue from hypoxic areas in tumors. However, multiple parameters affect the PA signal received, rendering a direct mapping from signal received to absorption challenging. For instance, at selected wavelengths, multiple chromophores may contribute to the signal observed. In order to separate the different chromophores, judicious spectral tuning of imaging wavelengths can help. We call this technique spectroscopic photoacoustic imaging (sPA). Based on sPA imaging, we were capable to super-localize sources down to 1/20th of the imaging system point spread function (PSF). sPA can also improve the imaging specificity and sensitivity of targeted tissue features. In this talk, we showcase the many benefits of sPA imaging for image enhancement. We also discuss challenges and feasibility to integrate in surgical tools for minimally invasive interventions. In particular, we focus on how sPA studies can take the specific problem of visualization of RF ablation for atrial fibrillation from bench to bedside.

Spectrally Matched Quantum Dot Photoluminescence in GaAs-Si Tandem Luminescent Solar Concentrators

Luminescent solar concentrators (LSCs) can capture both direct and diffuse irradiance via isotropic absorption of waveguide-embedded luminophores. Additionally, LSCs have the potential to reduce the overall cost of a photovoltaic (PV) module by concentrating incident irradiance onto an array of smaller cells. Historically, LSC efficiencies have suffered in part from incomplete light absorption and non-unity quantum yield (QY) of the luminophores. Inorganic quantum dot (QD) luminophores allow the spectral tuning of the absorption and photoluminescence bands, and have near-unity QYs. In a four-terminal tandem LSC module scheme, visible light is trapped within the LSC waveguide and is converted by GaAs cells, and near infrared light is optically coupled to a Si subcell. Here, we investigate the efficiency of a GaAs/Si tandem LSC as a function of luminophore absorption edge and emission wavelength for QD luminophores dispersed in an LSC waveguide with embedded, coplanar GaAs cells. We find that positioning the luminophore absorption edge at 660 nm yields a maximum module power efficiency of approximately 26%, compared with 21% for the non-optimized luminophore and 19% for the bare Si cases.

SyLMAND: a microfabrication beamline with wide spectral and beam power tuning range at the Canadian Light Source.

SyLMAND, the Synchrotron Laboratory for Micro and Nano Devices, is a recently commissioned microfabrication bend magnet beamline with ancillary cleanroom facilities at the Canadian Light Source. The synchrotron radiation is applied to pattern high-aspect-ratio polymer microstructures used in the area of micro-electro-mechanical systems (MEMS). SyLMAND particularly focuses on spectral and beam power adjustability and large exposable area formats in an inert gas atmosphere; a rotating-disk intensity chopper allows for independent beam-power reduction, while continuous spectral tuning between 1-2 keV and >15 keV photon energies is achieved using a double-mirror system and low-atomic-number filters. Homogeneous exposure of samples up to six inches in diameter is performed in the experimental endstation, a vertically scanning precision stage (scanner) with tilt and rotation capabilities under 100 mbar helium. Commissioning was completed in late 2017, and SyLMAND is currently ramping up its user program, mostly in the areas of RF MEMS, micro-fluidics/life sciences and micro-optics.

Anomalously Large Spectral Shifts near the Quantum Tunnelling Limit in Plasmonic Rulers with Subatomic Resolution.

The resonance wavelength of a coupled plasmonic system is extremely sensitive to the distance between its metallic surfaces, resulting in "plasmon rulers". We explore this behavior in the subnanometer regime using self-assembled monolayers of bis-phthalocyanine molecules in a nanoparticle-on-mirror (NPoM) construct. These allow unprecedented subangstrom control over spacer thickness via choice of metal center, in a gap-size regime at the quantum-mechanical limit of plasmonic enhancement. A dramatic shift in the coupled plasmon resonance is observed as the gap size is varied from 0.39 to 0.41 nm. Existing theoretical models are unable to account for the observed spectral tuning, which requires inclusion of the quantum-classical interface, emphasizing the need for new treatments of light at the subnanoscale.

The Effective Conjugation Length Is Responsible for the Red/Green Spectral Tuning in the Cyanobacteriochrome Slr1393g3.

The origin of the spectral shift from a red- to a green-absorbing form in a cyanobacteriochrome, Slr1393g3, was identified by combined quantum mechanics/molecular mechanics simulations. This protein, related to classical phytochromes, carries the open-chain tetrapyrrole chromophore phycocyanobilin. Our calculations reveal that the effective conjugation length in the chromophore becomes shorter upon conversion from the red to the green form. This is related to the planarity of the entire chromophore. A large distortion was found for the terminal pyrrole rings A and D; however, the D ring contributes more strongly to the photoproduct tuning, despite a larger change in the twist of the A ring. Our findings implicate that the D ring twist can be exploited to regulate the absorption of the photoproduct. Hence, mutations that affect the D ring twist can lead to rational tuning of the photoproduct absorption, allowing the tailoring of cyanobacteriochromes for biotechnological applications such as optogenetics and bioimaging.

Resonant-antiresonant coupled cavity VCSELs.

The wavelength tuning range of a tunable vertical-cavity surface-emitting laser (VCSEL) is strongly influenced by the design of the interface between the semiconductor cavity and the air cavity. A simplified model is used to investigate the origin of the dramatic differences in free spectral range (FSR) and tuning slope observed in semiconductor cavity dominant, extended cavity, and air cavity dominant VCSELs. The differences arise from the positioning of the resonant and antiresonant wavelengths of the semiconductor cavity with respect to the center wavelength. The air cavity dominant design is realized by designing an antiresonant semiconductor cavity, resulting in a larger tuning slope near the center of the tuning range and a wider FSR toward the edges of the tuning range. The findings from the simplified model are confirmed with the simulation of a full VCSEL structure. Using an air cavity dominant design, an electrically pumped laser with a tuning range of 68.38 nm centered at 1056.7 nm at a 550 kHz sweep rate is demonstrated with continuous wave emission at room temperature. This epitaxial design rule can be used to increase the tuning range of tunable VCSELs, making them more applicable in swept-source optical coherence tomography and frequency-modulated continuous-wave LIDAR systems.

STRFs in primary auditory cortex emerge from masking-based statistics of natural sounds.

We investigate how the neural processing in auditory cortex is shaped by the statistics of natural sounds. Hypothesising that auditory cortex (A1) represents the structural primitives out of which sounds are composed, we employ a statistical model to extract such components. The input to the model are cochleagrams which approximate the non-linear transformations a sound undergoes from the outer ear, through the cochlea to the auditory nerve. Cochleagram components do not superimpose linearly, but rather according to a rule which can be approximated using the max function. This is a consequence of the compression inherent in the cochleagram and the sparsity of natural sounds. Furthermore, cochleagrams do not have negative values. Cochleagrams are therefore not matched well by the assumptions of standard linear approaches such as sparse coding or ICA. We therefore consider a new encoding approach for natural sounds, which combines a model of early auditory processing with maximal causes analysis (MCA), a sparse coding model which captures both the non-linear combination rule and non-negativity of the data. An efficient truncated EM algorithm is used to fit the MCA model to cochleagram data. We characterize the generative fields (GFs) inferred by MCA with respect to in vivo neural responses in A1 by applying reverse correlation to estimate spectro-temporal receptive fields (STRFs) implied by the learned GFs. Despite the GFs being non-negative, the STRF estimates are found to contain both positive and negative subfields, where the negative subfields can be attributed to explaining away effects as captured by the applied inference method. A direct comparison with ferret A1 shows many similar forms, and the spectral and temporal modulation tuning of both ferret and model STRFs show similar ranges over the population. In summary, our model represents an alternative to linear approaches for biological auditory encoding while it captures salient data properties and links inhibitory subfields to explaining away effects.

Femtosecond 78-nm Tunable Er:Fibre Laser Based on Drop-Shaped Resonator Topology

We report for the first time on study of a passively mode-locked Er-doped fibre laser with ultra-wide tuning (from 1524 to 1602 nm) of the central wavelength of its femtosecond output (503–940 fs). The recently proposed drop-shaped cavity topology for fibre lasers enabled a compact widely tuneable femtosecond laser with a single discrete element, a reflective diffraction grating used for wavelength tuning of the output radiation. The key features of the proposed laser are: spectral tuning does not require adjustment of any other cavity elements; stable generation with a single pulse per round trip is provided over the entire wavelength tuning range; and the output pulses are close to transform limited and feature relatively high (>58 dB) signal-to-noise ratio of laser inter-mode beats indicating high quality of mode locking across the entire wavelength tuning range. The proposed laser configuration relying on the new drop-shaped cavity topology simultaneously delivers stability and reliability of mode locking, possibility of broad-range wavelength tunability, and adjustability of the output pulse repetition rate of the laser (which is important in various metrological and other applications).

Design of a Tunable Snapshot Multispectral Imaging System through Ray Tracing Simulation

Research on snapshot multispectral imaging has been popular in the remote sensing community due to the high demands of video-rate remote sensing system for various applications. Existing snapshot multispectral imaging techniques are mainly of a fixed wavelength type, which limits their practical usefulness. This paper describes a tunable multispectral snapshot system by using a dual prism assembly as the dispersion element of the coded aperture snapshot spectral imagers (CASSI). Spectral tuning is achieved by adjusting the air gap displacement of the dual prism assembly. Typical spectral shifts of about 1 nm at 400 nm and 12 nm at 700 nm wavelength have been achieved in the present design when the air-gap of the dual prism is changed from 4.24 mm to 5.04 mm. The paper outlines the optical designs, the performance, and the pros and cons of the dual-prism CASSI (DP-CASSI) system. The performance of the system is illustrated by TraceProTM ray tracing, to allow researchers in the field to repeat or to validate the results presented in this paper.

The retinal pigments of the whale shark (Rhincodon typus) and their role in visual foraging ecology.

The spectral tuning properties of the whale shark (Rhincodon typus) rod (rhodopsin or Rh1) and long-wavelength-sensitive (LWS) cone visual pigments were examined to determine whether these retinal pigments have adapted to the broadband light spectrum available for surface foraging or to the narrowband blue-shifted light spectrum available at depth. Recently published whale shark genomes have identified orthologous genes for both the whale shark Rh1 and LWS cone opsins suggesting a duplex retina. Here, the whale shark Rh1 and LWS cone opsin sequences were examined to identify amino acid residues critical for spectral tuning. Surprisingly, the predicted absorbance maximum (λmax) for both the whale shark Rh1 and LWS visual pigments is near 500 nm. Although Rh1 λmax values near 500 nm are typical of terrestrial vertebrates, as well as surface foraging fish, it is uncommon for a vertebrate LWS cone pigment to be so greatly blue-shifted. We propose that the spectral tuning properties of both the whale shark Rh1 and LWS cone pigments are most likely adaptations to the broadband light spectrum available at the surface. Whale shark melanopsin (Opn4) deactivation kinetics was examined to better understand the underlying molecular mechanisms of the pupillary light reflex. Results show that the deactivation rate of whale shark Opn4 is similar to the Opn4 deactivation rate from vertebrates possessing duplex retinae and is significantly faster than the Opn4 deactivation rate from an aquatic rod monochromat lacking functional cone photoreceptors. The rapid deactivation rate of whale shark Opn4 is consistent with a functional cone class and would provide the animal with an exponential increase in the number of photons required for photoreceptor signaling when transitioning from photopic to scotopic light conditions, as is the case when diving.

Temperature-controlled spectral tuning of full-color carbon dots and their strongly fluorescent solid-state polymer composites for light-emitting diodes.

The development of full-color/white carbon-dot-based light-emitting diodes (LEDs) has been achieved, which show promising applications in full-color and flexible displays, backlights, and novel lighting sources. The gram-level synthesis of these full-color carbon dots (CDs) from citric acid by controlling the temperature has been achieved. By increasing the temperature from 120 to 180 °C, two, four, and six light-emitting CDs can be obtained, for which the emission wavelength shifts from 440 to 585 nm. This result reveals that temperature has a huge impact on the evolution of surface states, that is, increasing the temperature brings about enhanced surface functionalization and passivation, resulting in a red shift of the emission wavelength and enhancement of quantum yield. Then, full-color CDs/polymer composite phosphors are fabricated for efficient phosphor-based LED devices with quench-resistant solid-state fluorescence. By regulating the proportion of various CDs/polymer phosphors, white LEDs are realized with Commission Internationale de L'Eclairage coordinates of (0.32, 0.33) and a color rendering index of 82.7. The as-prepared CD-based full/white color LEDs can prove to be promising candidates for alternative light sources.

Electronic spectra of flavin in different redox and protonation states: a computational perspective on the effect of the electrostatic environment.

Flavins are versatile molecules due to their ability to exist in multiple redox and protonation states. At physiological conditions, they are usually encountered either as oxidized quinones, neutral semiquinones, anionic semiquinones, neutral hydroquinones, or anionic hydroquinones. We compute the electronic near-UV/vis spectra for flavin in each of these five states. Specifically, we compute vertical, adiabatic, and vibronic excitations for all excited states that have wavelengths longer than 300 nm. We employ the calculations to assign the peaks in the corresponding experimental UV/vis spectra from literature. We also compare the effect of polar and non-polar solvents on the spectra using a polarizable continuum model. Finally, we construct "electrostatic spectral tuning maps" for prominent peaks in each of the five states. These maps qualitatively describe how the flavin electronic spectra will be shifted by an anisotropic electrostatic environment such as a protein. Understanding how flavin's UV/vis absorption spectrum is modulated by its environment can aid in experiments employing flavin as a probe of internal electrostatics of a protein and in engineering new color variants of flavoproteins.

Subwavelength Plasmonic Color Tuning of Quantum Dot Emission

The need to develop new patterning techniques for high-resolution microdisplays becomes paramount with the rapidly emerging popularity of augmented/virtual reality. Localized surface plasmon resonance (LSPR) can be precisely designed for wide spectral tuning of external broadband sources with subwavelength resolution. However, emission shifting of chromophores with LSPR is limited in range due to their narrowband emission. We report an alternative method of producing full-color tunability, by modulating the intensity of red, green, and blue peaks of gradient alloy cadmium–zinc chalcogenide core/shell quantum dots (QDs) using LSPR of Ag nanopillar arrays. Photoluminescence enhancement is largely dependent on the Purcell effect and radiative scattering and is found to be highest when emission coincides with the resonance wavelength. Red, green, and blue subpixels with dimensions of 480, 312, and 225 nm, respectively, can be generated in a single patterning step (equivalent to 24 500 ppi), which far exceeds ...

Free spectral range electrical tuning of a high quality on-chip microcavity.

Reconfigurable photonic circuits have applications ranging from next-generation computer architectures to quantum networks, coherent radar and optical metamaterials. Here, we demonstrate an on-chip high quality microcavity with resonances that can be electrically tuned across a full free spectral range (FSR). FSR tuning allows resonance with any source or emitter, or between any number of networked microcavities. We achieve it by integrating nanoelectronic actuation with strong optomechanical interactions that create a highly geometry-dependent effective refractive index. This allows low voltages and sub-nanowatt power consumption. We demonstrate a basic reconfigurable photonic network, bringing the microcavity into resonance with an arbitrary mode of a microtoroidal optical cavity across a telecommunications fibre link. Our results have applications beyond photonic circuits, including widely tuneable integrated lasers, reconfigurable optical filters for telecommunications and astronomy, and on-chip sensor networks.

Flexible Filtering Element on SOI With Wide Bandwidth Tunability and Full FSR tuning

We demonstrate a silicon-on-insulator flexible filtering element, relying on two serially coupled micro-ring resonators equipped with three thermo-optically tuned Mach–Zehnder interferometers, acting as variable optical couplers. A single electrode configuration is adopted, enabling the low-complexity thermo-optical control of the filtering element for bandwidth and wavelength tunability. The module's performance has been studied in detail via simulation analysis, and the obtained results were verified through experimental evaluation. Wide bandwidth tunability from 9 GHz to 103 GHz is achieved with a power efficiency of 0.284 mW/GHz, while full free spectral range wavelength tuning is achieved with an efficiency of 0.297 mW/GHz. Module's insertion loss lays below 3 dB.