Bioluminescence - The Vibrant Glow of Nature and its Chemical Mechanisms.

Bioluminescence, the mesmerizing natural phenomenon where living organisms produce light through chemical reactions, has long captivated scientists and laypersons alike, offering a rich tapestry of insights into biological function, ecology, evolution as well as the underlying chemistry. This comprehensive introductory review systematically explores the phenomenon of bioluminescence, addressing its historical context, geographic dispersion, and ecological significance with a focus on their chemical mechanisms. Our examination begins with terrestrial bioluminescence, discussing organisms from different habitats. We analyze thefireflies of Central Europe's meadows and the fungi in the Atlantic rainforest of Brazil. Additionally, we inspect bioluminescent species in New Zealand, specifically river-dwelling snails and mosquito larvae found in Waitomo Caves. Our exploration concludes in the Siberian Steppes, highlighting the area's luminescent insects and annelids. Transitioning to the marine realm, the second part of this review examines marine bioluminescent organisms. We explore this phenomenon in deep-sea jellyfish and their role in the ecosystem. We then move to Toyama Bay, Japan, where seasonal bioluminescence of dinoflagellates and ostracods present a unique case study. We also delve into the bacterial world, discussing how bioluminescent bacteria contribute to symbiotic relationships. For each organism, we contextualize its bioluminescence, providing details about its discovery, ecological function, and geographical distribution. A special focus lies on the examination of the underlying chemical mechanisms that enables these biological light displays. Concluding this review, we present a series of practical bioluminescence and chemiluminescence experiments, providing a resource for educational demonstrations and student research projects. Our goal with this review is to provide a summary of bioluminescence across the diverse ecological contexts, contributing to the broader understanding of this unique biological phenomenon and its chemical mechanisms serving researchers new to the field, educators and students alike.

Natural Product Isolation of the Extract of Cleome rupicola Fruits Exhibiting Antioxidant Activity.

Cataracts are the leading cause of blindness worldwide, however, there is currently no drug-based treatment. Plants that exhibit antioxidant properties have shown promising anticataract effects, likely because they supplement the activity of glutathione, the major antioxidant in lens cells. An extract of Cleome rupicola, a desert plant found in the United Arab Emirates, has traditionally been used to treat cataracts. Phytochemical screening of the aqueous extract established the presence of flavonoids, tannins, steroid derivatives, and reducing sugars. Fractioning of extracts from the fruits using high-performance liquid chromatography (HPLC) yielded the isolation of the anthelmintic compound cleomin, and its structure was confirmed using mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectroscopy.

Three-Dimensional Light Field Fundus Imaging: Automatic Determination of Diagnostically Relevant Optic Nerve Head Parameters.

Purpose: Morphological changes to the optic nerve head (ONH) can be detected at the early stages of glaucoma. Three-dimensional imaging and analysis may aid in the diagnosis. Light field (LF) fundus cameras can generate three-dimensional (3D) images of optic disc topography from a single shot and are less susceptible to motion artifacts. Here, we introduce a processing method to determine diagnostically relevant ONH parameters automatically and present the results of a subject study performed to validate this method. Methods: The ONHs of 17 healthy subjects were examined and images were acquired with both an LF fundus camera and by optical coherence tomography (OCT). The LF data were analyzed with a novel algorithm and compared with the results of the OCT study. Depth information was reconstructed, and a model with radial basis functions was used for processing of the 3D point cloud and to provide a finite surface. The peripapillary rising and falling edges were evaluated to determine optic disc and cup contours and finally calculate the parameters. Results: Nine of the 17 subjects exhibited prominent optic cups. The contours and ONH parameters determined by an analysis of LF 3D imaging largely agreed with the data obtained from OCT. The median disc areas, cup areas, and cup depths differed by 0.17 mm², -0.04 mm², and -0.07 mm, respectively. Conclusions: The findings presented here suggest the possibility of using LF data to evaluate the ONH. Translational Relevance: LF data can be used to determine geometric parameters of the ONH and thus may be suitable for future use in glaucoma diagnostics.

Spectrochemistry of Firefly Bioluminescence.

The chemical reactions underlying the emission of light in fireflies and other bioluminescent beetles are some of the most thoroughly studied processes by scientists worldwide. Despite these remarkable efforts, fierce academic arguments continue around even some of the most fundamental aspects of the reaction mechanism behind the beetle bioluminescence. In an attempt to reach a consensus, we made an exhaustive search of the available literature and compiled the key discoveries on the fluorescence and chemiluminescence spectrochemistry of the emitting molecule, the firefly oxyluciferin, and its chemical analogues reported over the past 50+ years. The factors that affect the light emission, including intermolecular interactions, solvent polarity, and electronic effects, were analyzed in the context of both the reaction mechanism and the different colors of light emitted by different luciferases. The collective data points toward a combined emission of multiple coexistent forms of oxyluciferin as the most probable explanation for the variation in color of the emitted light. We also highlight realistic research directions to eventually address some of the remaining questions related to firefly bioluminescence. It is our hope that this extensive compilation of data and detailed analysis will not only consolidate the existing body of knowledge on this important phenomenon but will also aid in reaching a wider consensus on some of the mechanistic details of firefly bioluminescence.

3D retinal imaging and measurement using light field technology.

SIGNIFICANCE: Light-field fundus photography has the potential to be a new milestone in ophthalmology. Up-to-date publications show only unsatisfactory image quality, preventing the use of depth measurements. We show that good image quality and, consequently, reliable depth measurements are possible, and we investigate the current challenges of this novel technology. AIM: We investigated whether light field (LF) imaging of the retina provides depth information, on which structures the depth is estimated, which illumination wavelength should be used, whether deeper layers are measurable, and what kinds of artifacts occur. APPROACH: The technical setup, a mydriatic fundus camera with an LF imager, and depth estimation were validated by an eye model and in vivo measurements of three healthy subjects and three subjects with suspected glaucoma. Comparisons between subjects and the corresponding optical coherence tomography (OCT) measurements were used for verification of the depth estimation. RESULTS: This LF setup allowed for three-dimensional one-shot imaging and depth estimation of the optic disc with green light. In addition, a linear relationship was found between the depth estimates of the OCT and those of the setup developed here. This result is supported by the eye model study. Deeper layers were not measurable. CONCLUSIONS: If image artifacts can be handled, LF technology has the potential to help diagnose and monitor glaucoma risk at an early stage through a rapid, cost-effective one-shot technology.

The elusive relationship between structure and colour emission in beetle luciferases.

In beetles, luciferase enzymes catalyse the conversion of chemical energy into light through bioluminescence. The principles of this process have become a fundamental biotechnological tool that revolutionized biological research. Different beetle species can emit different colours of light, despite using the same substrate and highly homologous luciferases. The chemical reasons for these different colours are hotly debated yet remain unresolved. This Review summarizes the structural, biochemical and spectrochemical data on beetle bioluminescence reported over the past three decades. We identify the factors that govern what colour is emitted by wild-type and mutant luciferases. This topic is controversial, but, in general, we note that green emission requires cationic residues in a specific position near the benzothiazole fragment of the emitting molecule, oxyluciferin. The commonly emitted green-yellow light can be readily changed to red by introducing a variety of individual and multiple mutations. However, complete switching of the emitted light from red to green has not been accomplished and the synergistic effects of combined mutations remain unexplored. The minor colour shifts produced by most known mutations could be important in establishing a 'mutational catalogue' to fine-tune emission of beetle luciferases, thereby expanding the scope of their applications.

The Influence of the Stimulus Design on the Harmonic Components of the Steady-State Visual Evoked Potential.

Steady-state visual evoked potentials (ssVEPs) are commonly used for functional objective diagnostics. In general, the main response at the stimulation frequency is used. However, some studies reported the main response at the second harmonic of the stimulation frequency. The aim of our study was to analyze the influence of the stimulus design on the harmonic components of ssVEPs. We studied 22 subjects (8 males, mean age ± SD = 27 ± 4.8 years) using a circular layout (r 1 = 0-1.6°, r 2 = 1.6-3.5°, r 3 = 3.5-6.4°, r 4 = 6.4-10.9°, and r 5 = 10.9-18°). At a given eccentricity, the stimulus was presented according to a 7.5 Hz square wave with 50% duty cycle. To analyze the influence of the stimulus eccentricity, a background luminance of 30 cd/m2 was added to suppress foveal stray light effects; to analyze the influence of simultaneous foveal and peripheral stimulations, stimulations are performed without stray light suppression. For statistical analysis, medians M of the amplitude ratios for amplitudes at the second harmonic to the first harmonic and the probability of the occurrence of the main response at the second harmonic P(MCSH) are calculated. For stimulations with foveal stray light suppression, the medians were M 0 -1.6^ ∘ = 0.45, M 1.6 -3.5^ ∘ = 0.45, M 3.5 -6.4^ ∘ = 0.76, M 6.4 -10.9^ ∘ = 0.72, and M 10.9 -18^ ∘ = 0.48, and the probabilities were P 0-1.6^ ∘ (MCSH) = 0.05, P 1.6 -3.5^ ∘ (MCSH) = 0.05, P 3.5 -6.4^ ∘ (MCSH) = 0.32, P 6.4 -10.9^ ∘ (MCSH) = 0.29, and P 10.9 -18^ ∘ (MCSH) = 0.30. For stimulations without foveal stray light suppression, the medians M were M 0 -1.6^ ∘ = 0.29, M 1.6 -3.5^ ∘ = 0.37, M 3.5 -6.4^ ∘ = 0.98, M 6.4 -10.9 ^^ ∘ = 1.08, and M 10.9 -18^ ∘ = 1.24, and the probabilities were P 0-1.6^ ∘ (MCSH) = 0.09, P 1.6 -3.5^ ∘ (MCSH) = 0.05, P 3.5 -6.4^ ∘ (MCSH) = 0.50, P 6.4 -10.9^ ∘ (MCSH) = 0.55, and P 10.9 -18^ ∘ (MCSH) = 0.55. In conclusion, the stimulus design has an influence on the harmonic components of ssVEPs. An increase in stimulation eccentricity during extrafoveal stimulation leads to a transition of the main response to the second harmonic. The effect is enhanced by a simultaneous foveal stimulation.

Cracking under Internal Pressure: Photodynamic Behavior of Vinyl Azide Crystals through N2 Release.

When exposed to UV light, single crystals of the vinyl azides 3-azido-1-phenylpropenone (1a), 3-azido-1-(4-methoxyphenyl)propenone (1b), and 3-azido-1-(4-chlorophenyl)propenone (1c) exhibit dramatic mechanical effects by cracking or bending with the release of N2. Mechanistic studies using laser flash photolysis, supported by quantum mechanical calculations, show that each of the vinyl azides degrades through a vinylnitrene intermediate. However, despite having very similar crystal packing motifs, the three compounds exhibit distinct photomechanical responses in bulk crystals. While the crystals of 1a delaminate and release gaseous N2 indiscriminately under paraffin oil, the crystals of 1b and 1c visibly expand, bend, and fracture, mainly along specific crystallographic faces, before releasing N2. The photochemical analysis suggests that the observed expansion is due to internal pressure exerted by the gaseous product in the crystal lattices of these materials. Lattice energy calculations, supported by nanoindentation experiments, show significant differences in the respective lattice energies. The calculations identify critical features in the crystal structures of 1b and 1c where elastic energy accumulates during gas release, which correspond to the direction of the observed cracks. This study highlights the hitherto untapped potential of photochemical gas release to elicit a photomechanical response and motility of photoreactive molecular crystals.

Mechanically Assisted Bioluminescence with Natural Luciferase.

Mechanochemical analogues have recently been established for several enzymatic reactions, but they require periodic interruption of the reaction for sampling, dissolution, and (bio)chemical analysis to monitor their progress. By applying a mechanochemical procedure to induce bioluminescence analogous to that used by the marine ostracod Cypridina (Vargula) hilgendorfii, here we demonstrate that the light emitted by a bioluminescent reaction can be used to directly monitor the progress of a mechanoenzymatic reaction without sampling. Mechanical treatment of Cypridina luciferase with luciferin generates bright blue light which can be readily detected and analyzed spectroscopically. This mechanically assisted bioluminescence proceeds through a mechanism identical to that of bioluminescence in solution, but has higher activation energy due to being diffusion-controlled in the viscous matrix. The results suggest that luciferases could be used as light-emissive reporters of mechanoenzymatic reactions.

Corrigendum: The Influence of the Stimulus Design on the Harmonic Components of the Steady-State Visual Evoked Potential.

[This corrects the article DOI: 10.3389/fnhum.2020.00343.].

Martensitic organic crystals as soft actuators.

Being capable of rapid and complete structure switching, the martensitic phase transitions in molecular crystals are thought to hold a tremendous potential as thermally driven organic actuators. However, the mechanical engineering parlance in the assessment of their performance is not immediately legible to the chemistry research community that starts to explore these materials, and the unavailability of performance indices has precluded molecular crystals from being considered in the device design process. Here, we demonstrate that an organic martensite, hexamethylbenzene, can be used to perform work that is comparable to that of most actuator classes. Millimeter-size single crystals of this material undergo a transition between two forms by uniaxial expansion at a rate of 6.36(2) mm s-1, exerting force in the range 10-100 mN. The force-to-weight ratio of the crystals is on the order of 104 and is superior to that of some living creatures. An actuator performance chart reveals that the performance of this material is close to that of nanomuscles, electrostatic actuators and voice coils, with a strain higher than that of electro/magnetostrictive actuators and ceramic piezoelectrics and stress higher than that of the electroactive polymers, MEMS devices, nanomuscles, voice coils, and some solenoids. Moreover, the crystals of this material are mechanically compliant and can be reversibly bent and shaped to fit the desired application. Altogether, the results point to the untapped potential of molecular crystals as rapid and efficient soft, organic actuators.

Objective measurement of forward-scattered light in the human eye: An electrophysiological approach.

PURPOSE: Psychophysical measurements are used to examine the perception of ocular stray light, for example, with C-Quant. These measurements are subjective due to their principles. This work aims to determine ocular stray light objectively; thus, a psychophysical method is transferred into an electrophysiological setup. METHODS: Stray light perception was measured using steady-state visual evoked potentials (VEPs) in 10 healthy subjects (7 males, 3 females, mean age ± SD: 29.6 ± 4.1 years). Stray light emulating filters (Tiffen Black Pro Mist 2) were used for simulating the effect of cataracts to validate the results for increased scattered light conditions. Based on the direct compensation method, the stimulus consisted of a central test field (radius = 2°) with a luminance adjustable compensation light and surrounding ring-shaped stray light source (radius = 5 to 10°). Both flickered in the counter phase at a frequency of 7.5 Hz. The stimuli were presented for 15 luminance levels of the compensation light. The recorded steady-state VEPs at Oz channel were transformed by means of Fourier analysis. The magnitudes at the evoked frequency were plotted against the measured brightness levels of the compensation light. By fitting two linear functions to the resulting data points, a robust minimum log(Leq) was determined, which was correlated with the amount of stray light perception. We measured the stray light parameter log(sc) using C-Quant. For comparison, our results were converted into the C-Quant equivalent parameter log(sepm) and paired t-tests were performed for normal distributed results. RESULTS: A significant difference is observed between log(sepm) (without filter) and log(sepm) (with BPM 2 Filter) (p>0.05). No significant difference is observed between log(sepm) (without filter) and log(sc) (without filter) (p > 0.05) and between log(sepm) (with BPM 2 filter) and log(sc) (with BPM 2 filter) (p > 0.05). CONCLUSION: The electrophysiological approach offers the ability to measure stray light perception in an objective manner.

A filled organic crystal as a hybrid large-bandwidth optical waveguide.

A fluorescent hollow crystal of 9,10-dicyanoanthracene was filled with a perylene diimide derivative with complementary emissive features. The obtained crystal-in-crystal hybrid was used as a multiresponsive optical waveguide, which showed passive and active modes of light transduction and a bandwidth that extends from the visible to the infrared region.

Signatures of Quark-Hadron Phase Transitions in General-Relativistic Neutron-Star Mergers.

Merging binaries of neutron-stars are not only strong sources of gravitational waves, but also have the potential of revealing states of matter at densities and temperatures not accessible in laboratories. A crucial and long-standing question in this context is whether quarks are deconfined as a result of the dramatic increase in density and temperature following the merger. We present the first fully general-relativistic simulations of merging neutron-stars including quarks at finite temperatures that can be switched off consistently in the equation of state. Within our approach, we can determine clearly what signatures a quark-hadron phase transition would leave in the gravitational-wave signal. We show that if after the merger the conditions are met for a phase transition to take place at several times nuclear saturation density, they would lead to a postmerger signal considerably different from the one expected from the inspiral, that can only probe the hadronic part of the equations of state, and to an anticipated collapse of the merged object. We also show that the phase transition leads to a very hot and dense quark core that, when it collapses to a black hole, produces a ringdown signal different from the hadronic one. Finally, in analogy with what is done in heavy-ion collisions, we use the evolution of the temperature and density in the merger remnant to illustrate the properties of the phase transition in a QCD phase diagram.

Thermochemiluminescent peroxide crystals.

Chemiluminescence, a process of transduction of energy stored within chemical bonds of ground-state reactants into light via high-energy excited intermediates, is known in solution, but has remained undetected in macroscopic crystalline solids. By detecting thermally induced chemiluminescence from centimeter-size crystals of an organic peroxide here we demonstrate direct transduction of heat into light by thermochemiluminescence of bulk crystals. Heating of crystals of lophine hydroperoxide to ~115 °C results in detectable emission of blue-green light with maximum at 530 nm with low chemiluminescent quantum yield [(2.1 ± 0.1) × 10‒7 E mol‒1]. Spectral comparison of the thermochemiluminescence in the solid state and in solution revealed that the solid-state thermochemiluminescence of lophine peroxide is due to emission from deprotonated lophine. With selected 1,2-dioxetane, endoperoxide and aroyl peroxide we also establish that the thermochemiluminescence is common for crystalline peroxides, with the color of the emitted light varying from blue to green to red.

Intense bone fluorescence reveals hidden patterns in pumpkin toadlets.

The phenomenon of fluorescence can be used by animals to change effective colouration or patterning, potentially to serve functions including intra- and interspecific signalling. Initially believed to be restricted to marine animals, fluorescent colours are now being described in an increasing number of terrestrial species. Here, we describe unique, highly fluorescent patterns in two species of pumpkin toadlets (Brachycephalus ephippium and B. pitanga). We establish that the origin of the fluorescence lies in the dermal bone of the head and back, visible through a particularly thin skin. By comparing them to those of the closely related species Ischnocnema parva, we demonstrate that pumpkin toadlets' bones are exceptionally fluorescent. We characterize the luminescence properties of the toadlets' bones and discuss the potential function of fluorescent patterns in natural lighting conditions.

Reversible Multicolor Photochromism of Dihydroazulene Crystals.

The photochemical conversion of 1,8a-dihydroazulene-1,1-dicarbonitrile (DHA) to vinylheptafulvene (VHF) is a positive T-type photoswitch that is well understood in solution, but has not been explored in the solid state. Upon excitation with UV light, DHA is converted into VHF in the solid state, with a distinct color change from yellow to deep-red, and retention of crystallinity. The structure of the ring-opened product was assigned to syn-VHF using variable-temperature infrared spectroscopy, and determined by X-ray photodiffraction in a crystal enriched with the product by two-photon excitation. A radical pathway becomes an observable photoreaction channel at low temperatures, and includes a strongly colored, short-lived diradical intermediate.

Intense bone fluorescence reveals hidden patterns in pumpkin toadlets

The phenomenon of fluorescence can be used by animals to change effective colouration or patterning, potentially to serve functions including intra- and interspecific signalling. Initially believed to be restricted to marine animals, fluorescent colours are now being described in an increasing number of terrestrial species. Here, we describe unique, highly fluorescent patterns in two species of pumpkin toadlets (Brachycephalus ephippium and B. pitanga). We establish that the origin of the fluorescence lies in the dermal bone of the head and back, visible through a particularly thin skin. By comparing them to those of the closely related species Ischnocnema parva, we demonstrate that pumpkin toadlets' bones are exceptionally fluorescent. We characterize the luminescence properties of the toadlets' bones and discuss the potential function of fluorescent patterns in natural lighting conditions.

Intense bone fluorescence reveals hidden patterns in pumpkin toadlets

The phenomenon of fluorescence can be used by animals to change effective colouration or patterning, potentially to serve functions including intra- and interspecific signalling. Initially believed to be restricted to marine animals, fluorescent colours are now being described in an increasing number of terrestrial species. Here, we describe unique, highly fluorescent patterns in two species of pumpkin toadlets (Brachycephalus ephippium and B. pitanga). We establish that the origin of the fluorescence lies in the dermal bone of the head and back, visible through a particularly thin skin. By comparing them to those of the closely related species Ischnocnema parva, we demonstrate that pumpkin toadlets' bones are exceptionally fluorescent. We characterize the luminescence properties of the toadlets' bones and discuss the potential function of fluorescent patterns in natural lighting conditions.