Spectral Tuning Research Articles

The Mechanism and Fine-Tuning of Chiral Plexcitons in the Strong Coupling Regime.

Chiral plexcitons, produced by the strong interaction between plasmonic nanocavities and chiral molecules, can provide a promising direction for controlling chiroptical responses on the nanoscale. Here, we reveal the chiral origin and electromagnetic hybridization process in chiral strongly coupled systems. The mechanism and unique advantages of chiral plexcitons for fine-tuning circular dichroism (CD) responses are demonstrated, providing a rule for controlling chiral light-matter interactions in complex chiral nanosystems. Furthermore, we experimentally demonstrate the fine-tuning of chiral plexcitons in hybrid systems consisting of plasmonic nanoparticles and chiral J-aggregates. Continuous and precise tuning of the CD resonance positions was successfully achieved in a given structure. Compared with the previous work, the CD spectral tuning accuracy has been improved by an order of magnitude, which can reach the level of 1 nm. Our findings provide a feasible strategy and theoretical basis for accurately controlling chirality in multiple dimensions.

A compendium of photopigment peak sensitivities and visual spectral response curves of terrestrial wildlife to guide design of outdoor nighttime lighting

The presence and proportions of photopigments, which are responsible for the visual and physiological effects of light, vary between taxonomic groups. This leads to differing wavelength sensitivities ranging from ultraviolet (UV; <400 nm) to infrared (IR; >780 nm) and complicates the balancing of spectra used for outdoor lighting to maximize human visual performance while mitigating light pollution effects on wildlife. I developed a database of spectral response information for terrestrial wildlife to create generalized spectral response curves by taxonomic phylum, class, and order. Existing data on species visual sensitivity were collected from previously published research that used behavioral responses, electroretinograms (ERGs), and reflectance within the eye. Resulting summaries of photopigment peak sensitivities (n=968) and sensitivity curves (n=177) allow for general observations. Overall, longer wavelengths provide the highest possibility for supporting human visual performance at night while reducing intrusive overlap with the vision of other species, because many taxonomic groups are sensitive to light in the blue and into the ultraviolet. Comparison of average response curves at the class level and the spectral power distribution of lamps suggests that spectral tuning might reduce the apparency of the lowest correlated color temperature (CCT) lamps to insects, spiders, and non-human mammals the most, with substantial but smaller reductions for reptiles, birds, and amphibians. Spectral tuning, most simply by reducing CCT, should be considered an additional benefit to be used in concert with other mitigation measures such as dimming, shielding, and part-night lighting.

Spectroscopic Validation of Crystallographic Structures of a Protein Active Site by Chiroptical Spectroscopy.

Out-of-plane distortions of a cofactor molecule in a protein active site are functionally important, and in photoreceptors, it has been proposed that they are crucial for spectral tuning and energy storage in photocycle intermediates. However, these subtle structural features are often beyond the grasp of structural biology. This issue is strikingly exemplified by photoactive yellow protein: its 14 independently determined crystal structures exhibit considerable differences in the dihedral angles defining the chromophore geometry, even though most of these are at excellent resolution. Here we developed a strategy to verify cofactor distortions in crystal structures by using quantum chemical calculations and chiroptical spectroscopy, particularly Raman optical activity and electronic circular dichroism spectroscopies. Based on this approach, we identify seven crystal structures with the chromophore geometries inconsistent with the experimentally observed data. The strategy implemented here promises to be widely applicable to uncovering cofactor distortions at active sites and to studies of reaction intermediates.

Spectral Tunability, Luminescence Enhancement, and Temperature Sensitivity of Sb3+-Doped Bismuth-Based Halide Emission Crystals for Anti-Counterfeiting Applications.

The synthesis of sustainable luminescent materials with simplicity, low energy consumption, and nontoxicity is of great importance in the field of chemistry and materials science. In this study, a room temperature evaporation method was employed to synthesize Sb3+-doped bismuth-based halide emission crystals, allowing for investigation of spectral tuning, luminescence enhancement, and temperature sensitivity. By substitution of Rb+ with varying concentrations of Cs+ in Rb3BiCl6 (RBC), the luminescent color of the crystals can be tuned from orange to yellow. The resulting alloyed yellow-emitting crystals were identified as Rb2CsBiCl6 (RCBC). Remarkably, when one-third of the Rb+ ions were replaced by Cs+ in the RBC, the crystals exhibited improved thermal stability and a 20-fold increase in luminescence intensity. The temperature-sensitive behavior was observed for RBC:Sb, with emission shifting from 590 to 574 nm upon heating while the yellow emission of RCBC:Sb exhibited no significant peak shift with temperature. Notably, the yellow emission of RBC:Sb could be reversibly converted back to orange light upon cooling to room temperature. In contrast, RCBC:Sb exhibited no significant peak shift with temperature. The differential temperature sensitivity between RBC:Sb and RCBC:Sb offers potential applications in anti-counterfeiting measures.

Selection on Visual Opsin Genes in Diurnal Neotropical Frogs and Loss of the SWS2 Opsin in Poison Frogs.

Amphibians are ideal for studying visual system evolution because their biphasic (aquatic and terrestrial) life history and ecological diversity expose them to a broad range of visual conditions. Here, we evaluate signatures of selection on visual opsin genes across Neotropical anurans and focus on three diurnal clades that are well-known for the concurrence of conspicuous colors and chemical defense (i.e., aposematism): poison frogs (Dendrobatidae), Harlequin toads (Bufonidae: Atelopus), and pumpkin toadlets (Brachycephalidae: Brachycephalus). We found evidence of positive selection on 44 amino acid sites in LWS, SWS1, SWS2, and RH1 opsin genes, of which one in LWS and two in RH1 have been previously identified as spectral tuning sites in other vertebrates. Given that anurans have mostly nocturnal habits, the patterns of selection revealed new sites that might be important in spectral tuning for frogs, potentially for adaptation to diurnal habits and for color-based intraspecific communication. Furthermore, we provide evidence that SWS2, normally expressed in rod cells in frogs and some salamanders, has likely been lost in the ancestor of Dendrobatidae, suggesting that under low-light levels, dendrobatids have inferior wavelength discrimination compared to other frogs. This loss might follow the origin of diurnal activity in dendrobatids and could have implications for their behavior. Our analyses show that assessments of opsin diversification in across taxa could expand our understanding of the role of sensory system evolution in ecological adaptation.

Bi-channel compressive hyperspectral imager based on polarization conversion metasurface

Metasurfaces have demonstrated remarkable capabilities in manipulating light fields and reducing the size of conventional optical elements to ultrathin devices, and compressive hyperspectral imaging systems can effectively utilize the spectral modulations of metasurfaces through spectral transmission tuning. In this paper, a bi-channel compressive hyperspectral imager based on polarization conversion metasurfaces is proposed. The metasurface layer of this device is able to modulate and convert the polarized incidence into two outputs of different transmission spectra with orthogonal polarizations, providing two channels of hyperspectral information that can be detected by a polarization image sensor in one snapshot. Additionally, this design offers a compact size, high speed, and accurate reconstruction through the utilization of a macro-pixel segmentation method for compressive sensing algorithms, and it is firmly demonstrated that the proposed hyperspectral imaging technology surpasses other traditional compressive hyperspectral image recovery methods in terms of improved reconstruction quality. Therefore, it is envisioned that this technology will find significant applications in various fields, including food safety, biomedical imaging, precision agriculture, object detection and so on.

Optical heating-induced spectral tuning of supercontinuum generation in liquid core fibers using multiwall carbon nanotubes.

In this work, we demonstrate the optical heating modulation of soliton-based supercontinuum generation through the employment of multi-walled carbon nanotubes (MW-CNTs) acting as fast and efficient heat generators. By utilizing highly dispersion-sensitive liquid-core fibers in combination with MW-CNTs coated to the outer wall of the fiber, spectral tuning of dispersive waves with response times below one second via exploiting the strong thermo-optic response of the core liquid was achieved. Local illumination of the MW-CNTs coated fiber at selected points allowed modulation of the waveguide dispersion, thus controlling the soliton fission process. Experimentally, a spectral shift of the two dispersive waves towards the region of anomalous dispersion was observed at increasing temperatures. The presented tuning concept shows great potential in the context of nonlinear photonics, as complex and dynamically reconfigurable dispersion profiles can be generated by using structured light fields. This allows investigating nonlinear frequency conversion processes under unconventional conditions, and realizing nonlinear light sources that are reconfigurable quickly.

Contributed Session I: Spectral, Spatial and Temporal Response Properties of Foveal Ganglion Cells.

While the fovea is best known for its high spatial acuity mediated by a high density of midget ganglion cells (RGCs), anatomy and transcriptomics show ~15 rarer RGC types are also present. However, our understanding of the visual information these RGCs convey to the brain is limited as both the fovea and rarer RGC types have been difficult to address with standard physiology techniques. We addressed this gap in knowledge in vivo, with two macaques expressing GCaMP6s in the foveal ganglion cell layer. Using a fluorescence adaptive optics scanning light ophthalmoscope, we presented stimuli to the cones while measuring the responses of hundreds of distinct cells. We classified cells with stimuli assessing polarity, spectral tuning, receptive field size, temporal tuning and motion sensitivity. 21% of cells had response properties inconsistent with midget RGCs, including ON-OFF responses, non-canonical spatial receptive fields, direction selectivity and suppressed-by-contrast responses. Our classification enables in vivo functional identification of the rarest foveal RGCs, laying the foundation for future experiments targeting these elusive cells to determine their roles in vision. While the dominance of midget RGCs observed is consistent with the fovea's specialization for acuity, the unappreciated functional diversity we observed indicates that far more visual processing occurs within the primate fovea than classically thought.

Nanoscale modeling of dynamically tunable planar optical absorbers utilizing InAs and InSb in metal-oxide-semiconductor–metal configurations

The attainment of dynamic tunability in spectrally selective optical absorption has been a longstanding objective in modern optics. Typically, Fabry–Perot resonators comprising metal and semiconductor thin films have been employed for spectrally selective light absorption. In such resonators, the resonance wavelength can be altered via structural modifications. The research has progressed further with the advent of specialized patterning of thin films and the utilization of metasurfaces. Nonetheless, achieving dynamic tuning of the absorption wavelength without altering the geometry of the thin film or without resorting to lithographic fabrication still poses a challenge. In this study, the incorporation of a metal-oxide-semiconductor (MOS) architecture into the Fabry–Perot nanocavity is shown to yield dynamic spectral tuning in a perfect narrowband light absorber within the visible range. Such spectral tuning is achieved using n-type-doped indium antimonide and n-type-doped indium arsenide as semiconductors in a MOS-type structure. These semiconductors offer significant tuning of their optical properties via electrically induced carrier accumulation. The planar structure of the absorber models presented facilitates simple thin-film fabrication. With judicious material selection and appropriate bias voltage, a spectral shift of 47 nm can be achieved within the visible range, thus producing a discernible color change.

Sex-linked gene traffic underlies the acquisition of sexually dimorphic UV color vision in Heliconius butterflies

The acquisition of novel sexually dimorphic traits poses an evolutionary puzzle: How do new traits arise and become sex-limited? Recently acquired color vision, sexually dimorphic in animals like primates and butterflies, presents a compelling model for understanding how traits become sex-biased. For example, some Heliconius butterflies uniquely possess UV (ultraviolet) color vision, which correlates with the expression of two differentially tuned UV-sensitive rhodopsins, UVRh1 and UVRh2. To discover how such traits become sexually dimorphic, we studied Heliconius charithonia, which exhibits female-specific UVRh1 expression. We demonstrate that females, but not males, discriminate different UV wavelengths. Through whole-genome shotgun sequencing and assembly of the H. charithonia genome, we discovered that UVRh1 is present on the W chromosome, making it obligately female-specific. By knocking out UVRh1, we show that UVRh1 protein expression is absent in mutant female eye tissue, as in wild-type male eyes. A PCR survey of UVRh1 sex-linkage across the genus shows that species with female-specific UVRh1 expression lack UVRh1 gDNA in males. Thus, acquisition of sex linkage is sufficient to achieve female-specific expression of UVRh1, though this does not preclude other mechanisms, like cis-regulatory evolution from also contributing. Moreover, both this event, and mutations leading to differential UV opsin sensitivity, occurred early in the history of Heliconius. These results suggest a path for acquiring sexual dimorphism distinct from existing mechanistic models. We propose a model where gene traffic to heterosomes (the W or the Y) genetically partitions a trait by sex before a phenotype shifts (spectral tuning of UV sensitivity).

Spectral Tuning of a Nanoparticle-on-Mirror System by Graphene Doping and Gap Control with Nitric Acid.

Nanoparticle-on-mirror systems are a stable, robust, and reproducible method of squeezing light into sub-nanometer volumes. Graphene is a particularly interesting material to use as a spacer in such systems as it is the thinnest possible 2D material and can be doped both chemically and electrically to modulate the plasmonic modes. We investigate a simple nanoparticle-on-mirror system, consisting of a Au nanosphere on top of an Au mirror, separated by a monolayer of graphene. With this system, we demonstrate, with both experiments and numerical simulations, how the doping of the graphene and the control of the gap size can be controlled to tune the plasmonic response of the coupled nanosphere using nitric acid. The coupling of the Au nanosphere and Au thin film reveals multipolar modes which can be tuned by adjusting the gap size or doping an intermediate graphene monolayer. At high doping levels, the interaction between the charge-transfer plasmon and gap plasmon leads to splitting of the plasmon energies. The study provides evidence for the unification of theories proposed by previous works investigating similar systems.

Introduction of reversible cysteine ligation ability to the biliverdin-binding cyanobacteriochrome photoreceptor.

Cyanobacteriochrome (CBCR) photoreceptors are distantly related to the canonical red/far-red reversible phytochrome photoreceptors. In the case of the CBCRs, only the GAF domain is required for chromophore incorporation and photoconversion. The GAF domains of CBCR are highly diversified into many lineages to sense various colors of light. These CBCR GAF domains are divided into two types: those possessing only the canonical Cys residue and those with both canonical and second Cys residues. The canonical Cys residue stably ligates to the chromophore in both cases. The second Cys residue mostly shows reversible adduct formation with the chromophore during photoconversion for spectral tuning. In this study, we focused on the CBCR GAF domain AnPixJg2_BV4, which possesses only the canonical Cys residue. AnPixJg2_BV4 covalently ligates to the biliverdin (BV) chromophore and shows far-red/orange reversible photoconversion. Because BV is a mammalian intrinsic chromophore, BV-binding molecules are advantageous for in vivo optogenetic and bioimaging tool development. To obtain a better developmental platform molecule, we performed site-saturation random mutagenesis and serendipitously obtained a unique variant molecule that showed far-red/blue reversible photoconversion, in which the Cys residue was introduced near the chromophore. This introduced Cys residue functioned as the second Cys residue that reversibly ligated with the chromophore. Because the position of the introduced Cys residue is distinct from the known second Cys residues, the variant molecule obtained in this study would expand our knowledge about the spectral tuning mechanism of CBCRs and contribute to tool development.

Precise modulation of multiple resonance emitters toward efficient electroluminescence with pure-red gamut for high-definition displays.

Multiple resonance (MR) compounds have garnered substantial attention for their prospective utility in wide color gamut displays. Nevertheless, developing red MR emitters with both high efficiency and saturated emission color remains demanding. We herein introduce a comprehensive strategy for spectral tuning in the red region by simultaneously regulating the π-conjugation and electron-donating strengths of a double boron-embedded MR skeleton while preserving narrowband characteristics. The proof-of-concept materials manifested emissions from orange-red to deep red, with bandwidths below 0.12 eV. The pure-red device based on CzIDBNO displayed superior color purity with CIE coordinates of (0.701, 0.298), approaching the Broadcast Television 2020 standard. In concert with high photoluminescence quantum yield and strong horizontal dipole orientation, CzIDBNO also achieved a maximum external quantum efficiency of 32.5% and a current efficiency of 20.2 cd A-1, outstripping prior reported organic light-emitting diodes (OLEDs) with CIEx exceeding 0.68. These findings offer a roadmap for designing high-performance emitters with exceptional color purity for future OLED material research advancements.

A Unipolar Quantum Dot Diode Structure for Advanced Quantum Light Sources.

Triggered, indistinguishable single photons are crucial in various quantum photonic implementations. Here, we realize a novel n+-i-n++ diode structure embedding semiconductor quantum dots: the gated device enables spectral tuning of the transitions and deterministic control of the charged states. Blinking-free single-photon emission and high two-photon indistinguishability are observed. The line width's temporal evolution is investigated across over 6 orders of magnitude time scales, combining photon-correlation Fourier spectroscopy, high-resolution photoluminescence spectroscopy, and two-photon interference (visibility of VTPI,2ns = (85.8 ± 2.2)% and VTPI,9ns = (78.3 ± 3.0)%). Most of the dots show no spectral broadening beyond ∼9 ns time scales, and the photons' line width ((420 ± 30) MHz) deviates from the Fourier-transform limit by a factor of 1.68. The combined techniques verify that most dephasing mechanisms occur at time scales ≤2 ns, despite their modest impact. The presence of n-doping implies higher carrier mobility, enhancing the device's appeal for high-speed tunable, high-performance quantum light sources.

Mixed-Halide Perovskites with Halogen Bond Induced Interlayer Locking Structure for Stable Pure-Red PeLEDs.

Mixed-halide perovskites enable precise spectral tuning across the entire spectral range through composition engineering. However, mixed halide perovskites are susceptible to ion migration under continuous illumination or electric field, which significantly impedes the actual application of perovskite light-emitting diodes (PeLEDs). Here, we demonstrate a novel approach to introduce strong and homogeneous halogen bonds within the quasi-two-dimensional perovskite lattices by means of an interlayer locking structure, which effectively suppresses ion migration by increasing the corresponding activation energy. Various characterizations confirmed that intralattice halogen bonds enhance the stability of quasi-2D mixed-halide perovskite films. Here, we report that the PeLEDs exhibit an impressive 18.3% EQE with pure red emission with CIE color coordinate of (0.67, 0.33) matching Rec. 2100 standards and demonstrate an operational half-life of ∼540 min at an initial luminance of 100 cd m-2, representing one of the most stable mixed-halide pure red PeLEDs reported to date.

Enhancing LED spectral output with perylene dye-based remote phosphor

LEDs offer a wide range of spectral output with high efficiencies. However, the efficiencies of solid-state LEDs with green and yellow wavelengths are rather low due to the lack of suitable direct bandgap materials. Here, we introduce and develop perylene-enhanced green LEDs that produce a higher wall-plug efficiency of 48% compared to 38% for a solid-state green LED. While the wall-plug efficiency of the perylene-enhanced red LED is still lower than that of a solid-state red LED, we demonstrate that remote phosphor colour converters are effective solutions for targeted spectral tuning across the visible spectrum for horticultural lighting. In this work, we retrofit existing white LEDs and augment photosynthesis via spectral output tuning to achieve a higher red-to-blue ratio. Our results show a significant improvement in plant growth by up to 39%, after a 4-month growth cycle. We observe no visible degradation of the colour converter even under continuous illumination with a current of 400 mA. This opens up new opportunities for using perylene-based colour converters for tuneable illumination with high brightness.

Functional Duplication of the Short-Wavelength-Sensitive Opsin in Sea Snakes: Evidence for Reexpanded Color Sensitivity Following Ancestral Regression

Abstract Color vision is mediated by ancient and spectrally distinct cone opsins. Yet, while there have been multiple losses of opsin genes during the evolution of tetrapods, evidence for opsin gains via functional duplication is extremely scarce. Previous studies have shown that some secondarily marine elapid snakes have acquired expanded “UV–blue” sensitivity via changes at key spectral tuning amino acid sites of the Short-Wavelength Opsin 1 (SWS1) gene. Here, we use elapid reference genomes to show that the molecular origin of this adaptation involved repeated, proximal duplications of the SWS1 gene in the fully marine Hydrophis cyanocinctus. This species possesses four intact SWS1 genes; two of these genes have the ancestral UV sensitivity, and two have a derived sensitivity to the longer wavelengths that dominate marine habitats. We suggest that this remarkable expansion of the opsin repertoire of sea snakes functionally compensates for the ancestral losses of two middle-wavelength opsins in the earliest (dim-light adapted) snakes. This provides a striking contrast to the evolution of opsins during ecological transitions in mammals. Like snakes, early mammals lost two cone photopigments; however, lineages such as bats and cetaceans underwent further opsin losses during their adaptation to dim-light environments.

Structure, luminescence investigation in Dy3+, Eu3+ and Ce3+, Dy3+ co-activated Sr9MgK(PO4)7 phosphors by energy transfer mechanism

Phosphate based phosphor makes a special impact in the field of luminescent spectroscopy applications from several decades. In the proposed work Dy3+, Eu3+ co-activated and Ce3+, Dy3+ co-activated Sr9MgK(PO4)7 phosphors have been synthesized via solid state reaction method. Phase confirmation and crystal structure determination of proposed sample were confirmed by Rietveld refinement analysis. Crystal structure of the proposed phosphor is in the tetragonal phase with space group R3c. The particle size of the proposed phosphors was in the range of sub-micrometers confirmed by SEM analysis. Photoluminescence study of the proposed sample confirms the spectral tuning from blue to red and blue to white. All these results shows that the Dy3+, Eu3+ co-activated and Ce3+, Dy3+ co-activated Sr9MgK(PO4)7 phosphors are proving their worth as they are might be the potential candidate for color tunable LEDs applications.

Quantum Mechanics/Molecular mechanics calculations predict A1, not A2, is present in melanopsin (Opn4m) of red-eared slider turtles (Trachemys scripta elegans)

Melanopsin is a photopigment that plays a role in non-visual, light-driven, cellular processes such as modulation of circadian rhythms, retinal vascular development, and the pupillary light reflex (PLR). In this study, computational methods were used to understand which chromophore is harbored by melanopsin in red-eared slider turtles (Trachemys scripta elegans). In mammals, the vitamin A derivative 11-cis-retinal (A1) is the chromophore, which provides functionality for melanopsin. However, in red-eared slider turtles, a member of the reptilian class, the identity of the chromophore remains unclear. Red-eared slider turtles, similar to other freshwater vertebrates, possess visual pigments that harbor a different vitamin A derivative, 11-cis-3,4-didehydroretinal (A2), making their pigments more sensitive to red-light than blue-light, therefore, suggesting the chromophore to be the A2 derivative instead of the A1. To help resolve the chromophore identity, in this work, computational homology models of melanopsin in red-eared slider turtles were first constructed. Next, quantum mechanics/molecular mechanics (QM/MM) calculations were carried out to compare how A1 and A2 derivatives bind to melanopsin. Time dependent density functional theory (TDDFT) calculations were then used to determine the excitation energy of the pigments. Lastly, calculated excitation energies were compared to experimental spectral sensitivity data from responses by the irises of red-eared sliders. Contrary to what was expected, our results suggest that melanopsin in red-eared slider turtles is more likely to harbor the A1 chromophore than the A2. Furthermore, a glutamine (Q622.56) and tyrosine (Y853.28) residue in the chromophore binding pocket are shown to play a role in the spectral tuning of the chromophore.

Optimization of polarization parameters for an LCVR polarization spectrometer under non-oversampling.

The spectral polarization measurement can obtain not only the spectral information of the target but also its polarization information, which can improve the detection and identification of the measured target. In the polarization spectrometer based on a liquid crystal variable retarder (LCVR) and acousto-optic tunable filter (AOTF), the LCVR is a core device for achieving fast and high-precision polarization detection. The AOTF is a new, to the best of our knowledge, filter device for spectral tuning. To reduce the sensitivity of an LCVR-based Stokes polarization spectrometer system to errors and Gaussian noise, and to maintain the advantage of fast electrical tuning of the system for spectral polarization detection, the phase retardation and azimuth angle of the polarization device LCVR is calculated and analyzed optimally under the minimum number of samples N=4 of the Stokes vector measurement method in this paper. The optimization algorithm considers the constraints, such as the number of types of LCVR phase retardation and the number of adjustments, and the azimuth and phase retardation to be optimized are searched for optimality step by step. The simulation results show that the number of adjustments of the phase retardation δ of LCVRs is only three times when four Stokes parameters are obtained. The LCVRs' number of species is four kinds (2×2). The condition number of the optimized measurement matrix is 1.742, which converges to the ideal condition number, the optimal azimuth angle (θ 1,θ 2) is (18.9°, 41.9°), and the optimal phase retardation δ is (179.9°, 156.6°, 0.4°, 46.3°). Its corresponding tetrahedral volume is closer to the ideal value. The optimized system is less sensitive to errors and Gaussian noise.