The paper presents data that testify in favor of the participation of the cytochrome P450 system in the light emission of higher fungi. Extracts from mycelia of different species of luminous basidiomycetes containing fungal luminescent systems that provide luminescence in vitro were obtained. Applied conditions for the isolation of luminescent systems (sonication, centrifugation at 40000g) indicate the presence of membrane structures in the extracts, in particular, microsomes formed as a result of ultrasonic disintegration of the endoplasmic reticulum (ER). Differential spectral analysis of the extracts revealed the presence of two absorption peaks at 410 nm and 450 nm, which indicates the presence of cytochromes b5 and P450. The luminescence of the extracts is stimulated by reduced pyridine nucleotides, however, the addition of NADPH causes a higher level of luminescence compared with NADH. The addition of hydrogen peroxide significantly (from several times to 1-2 orders of magnitude) increases the luminescence intensity of extracts activated by NAD(P)H. The addition of fluconazole significantly inhibits the light emission of extracts. The data obtained indicates that the cytochrome P450 system associated with ER membranes may participate in the mechanism of light emission of higher fungi with the involvement in the process of electron transport enzyme systems: NADPH-dependent reductase of cytochrome P450 - cytochrome P450 and NADH-dependent reductase of cytochrome b5 - cytochrome b5 - cytochrome P450. In this case, cytochrome P450 may hydroxylate hispidin (precursor of the luminescent reaction substrate) to form luciferin and catalyze its oxidation in the presence of ROS with light emission.

This paper presents the preliminary results of the separation of the Chaetopterus variopedatus bioluminescent system into luciferin and luciferase and a brief description of some of their properties.

Bioluminescence is found across the entire tree of life, conferring a spectacular set of visually oriented functions from attracting mates to scaring off predators. Half a dozen different luciferins, molecules that emit light when enzymatically oxidized, are known. However, just one biochemical pathway for luciferin biosynthesis has been described in full, which is found only in bacteria. Here, we report identification of the fungal luciferase and three other key enzymes that together form the biosynthetic cycle of the fungal luciferin from caffeic acid, a simple and widespread metabolite. Introduction of the identified genes into the genome of the yeast Pichia pastoris along with caffeic acid biosynthesis genes resulted in a strain that is autoluminescent in standard media. We analyzed evolution of the enzymes of the luciferin biosynthesis cycle and found that fungal bioluminescence emerged through a series of events that included two independent gene duplications. The retention of the duplicated enzymes of the luciferin pathway in nonluminescent fungi shows that the gene duplication was followed by functional sequence divergence of enzymes of at least one gene in the biosynthetic pathway and suggests that the evolution of fungal bioluminescence proceeded through several closely related stepping stone nonluminescent biochemical reactions with adaptive roles. The availability of a complete eukaryotic luciferin biosynthesis pathway provides several applications in biomedicine and bioengineering.

This is the first study to obtain a high-purity luciferase from the fungus Neonothopanus nambi biomass that is suitable for subsequent sequencing.

By determining the components involved in the bioluminescence process in luminous and nonluminous organs of the honey fungus Armillaria mellea, we have established causes of partial luminescence of this fungus. The complete set of enzymes and substrates required for bioluminescence is formed only in the mycelium and only under the conditions of free oxygen access. Since the synthesis of luciferin precursor (hispidin) and 3-hydroxyhispidin hydroxylase in the fruiting bodies is blocked, the formation of luciferin-the key component of fungal bioluminescent system-was not observed. That is why the fruiting body of Armillaria mellea is nonluminous despite the presence of luciferase, the enzyme that catalyzes the oxidation of luciferin with a photon emission.

The structure of fungal oxyluciferin was determined, the enzymatic bioluminescence reaction under substrate saturation conditions with discrete monitoring of formed products was conducted, and the structures of the end products of the reaction were established. On the basis of these studies, the scheme of oxyluciferin degradation to the end products was developed. The structure of fungal oxyluciferin was confirmed by counter synthesis.

Bioluminescent fungi are spread throughout the globe, but details on their mechanism of light emission are still scarce. Usually, the process involves three key components: an oxidizable luciferin substrate, a luciferase enzyme, and a light emitter, typically oxidized luciferin, and called oxyluciferin. We report the structure of fungal oxyluciferin, investigate the mechanism of fungal bioluminescence, and describe the use of simple synthetic α-pyrones as luciferins to produce multicolor enzymatic chemiluminescence. A high-energy endoperoxide is proposed as an intermediate of the oxidation of the native luciferin to the oxyluciferin, which is a pyruvic acid adduct of caffeic acid. Luciferase promiscuity allows the use of simple α-pyrones as chemiluminescent substrates.

The suggested model of plastic garbage degradation allows us to obtain an estimate of the stationary density of their distribution over the surface of the World Ocean with account for the temperature dependence on the degradation rate. The model also allows us to estimate the characteristic time periods of degradation of plastic garbage and the dynamics of the mean density variation as the mean rate of plastic garbage entry into the ocean varies.

Leuchtende Pilze wurden von Aristoteles bereits im 4. Jahrhundert v. Chr. beschrieben. I. V. Yampolsky, J. I. Gitelson et al. decken in ihrer Zuschrift auf S. 8242 ff. die Struktur von Pilz-Luciferin auf, einer Verbindung, die für die Biolumineszenz von Pilzen verantwortlich ist. Leuchtende Pilze wurden von Aristoteles bereits im 4. Jahrhundert v. Chr. beschrieben. I. V. Yampolsky, J. I. Gitelson et al. decken in ihrer Zuschrift auf S. 8242 ff. die Struktur von Pilz-Luciferin auf, einer Verbindung, die für die Biolumineszenz von Pilzen verantwortlich ist. Krebsdiagnostik Ein Hypoxie erkennender Sauerstoffsensor für die Diagnose von Krebsmetastasierungen wird von X. Q. Jiang et al. auf S. 8212 ff. beschrieben. Nach systemischer Verabreichung des Sensors wird die Metastase von Krebszellen in die Lunge oder in Lymphknoten durch optische Ganzkörperbildgebung nachgewiesen.1 Elektroreduktion von NO Die entscheidende Rolle von Wasser für den Mechanismus der NO-Elektroreduktion auf Pt(111) untersuchen J. Greeley et al. in der Zuschrift auf S. 8373 ff. Wasser erleichtert den Elektronentransfer zu adsorbierten Oberflächenintermediaten mit sehr niedrigen kinetischen Barrieren.1 Porphyrinoide M. Bröring et al. präsentieren in ihrer Zuschrift auf S. 8331 ff. die erste radikalische freie Corrolbase. Der Verlust eines inneren H-Atoms des luftstabilen, leicht handhabbaren Porphyrinoids ergibt ein planares Molekül, das z. B. Zn2+ binden kann.1

Glowing fungi were described by Aristotle as early as the fourth century B.C. In their Communication on page 8124 ff., I. V. Yampolsky, J. I. Gitelson, and co-workers unveil the structure of fungal luciferin, a compound that is responsible for fungal biolumescence. Glowing fungi were described by Aristotle as early as the fourth century B.C. In their Communication on page 8124 ff., I. V. Yampolsky, J. I. Gitelson, and co-workers unveil the structure of fungal luciferin, a compound that is responsible for fungal biolumescence. Cancer Diagnostics A hypoxia-sensitive sensor for tracking cancer metastasis is reported by X. Q. Jiang et al. on page 8094 ff. After systemic administration of the sensor, cancer cells metastasizing to the lungs or to the lymph nodes are detected by whole-body optical imaging.1 NO Electroreduction The crucial role of water in determining the mechanism of NO electroreduction to ammonia on Pt(111) surfaces is investigated by J. Greeley et al. in their Communication on page 8255 ff. Water facilitates proton transfer to adsorbed surface intermediates with very low kinetic barriers.1 Porphyrinoids M. Bröring et al. present the first free-base corrole radical in their Communication on page 8213 ff. Loss of an inner hydrogen atom from the air-stable, easy-to-handle porphyrinoid gives a planar molecule that can, for example, bind Zn2+.1

The luminescent system of higher luminous fungi is not fully understood and the enzyme/substrate pair of the light emission reaction has not been isolated. It was suggested that luminescence of fungi involves oxidase-type enzymes, and reactive oxygen species are important for fungal light production. Generation of reactive oxygen species can be stimulated by ionizing irradiation, which has not been studied for luminous fungi. We report the effect of X-irradiation on the luminescence of fungus Neonothopanus nambi. Experiments were performed with mycelium on a home-built setup based on an X-ray tube and monochromator/photomultiplier tube. Application of X-rays does not change the emission spectrum, but after approximately 20 min of continuous irradiation, light production from unsupported mycelium starts growing and increases up to approximately five times. After peaking, its level decreases irrespective of the presence of X-irradiation. After staying at a certain level, light production collapses to zero, which is not related to the drying of the mycelium or thermal impact of radiation. The observed shape of kinetics is characteristic of a multistage and/or chain reaction. The time profile of light production must reflect the current levels of radicals present in the system and/or the activity of enzyme complexes involved in light production.

Many species of fungi naturally produce light, a phenomenon known as bioluminescence, however, the fungal substrates used in the chemical reactions that produce light have not been reported. We identified the fungal compound luciferin 3-hydroxyhispidin, which is biosynthesized by oxidation of the precursor hispidin, a known fungal and plant secondary metabolite. The fungal luciferin does not share structural similarity with the other eight known luciferins. Furthermore, it was shown that 3-hydroxyhispidin leads to bioluminescence in extracts from four diverse genera of luminous fungi, thus suggesting a common biochemical mechanism for fungal bioluminescence.

Bioluminescent assay is one of the most efficient but yet insufficiently used tools of enlightenment and education. The didactic value of bioluminescence is that it can be used to transform many biological processes into light. This provides an opportunity to observe them visually or measure them with photometric instruments. Bioluminescence can be regarded as an attractive educational tool owing to a psycho-physical human feature: we receive more than 80% information through our eyes. Living light has a special emotional attraction-experiments with bioluminescence make a deep impression on students. To realize and use the potential of bioluminescence in education and enlightenment, the luminometer must become as widely used at school and universities as are the microscope and the computer.This assertion is based on the many opportunities provided by the application of bioluminescence in education. Luminous organisms have the methodological advantage (not duly appreciated yet) due to the fact that light is one of the final products of their metabolism. Specific enzymes systems convert the energy of the associated oxidation reactions into the light of visible spectra. For this frequency range, physics has at its disposal extremely sensitive - up to individual quanta - fast acting and relatively simple devices, available for ordinary high schools. Scientists have developed a unique technology which allows bioluminescent organisms and their luciferases to be maintained in containers for a long periods of time.The lecture and practical courses based on bioluminescence have been developed. They have the demonstration methods, experimental and laboratory work, vividly showing by bioluminescence, basic manifestations of life at molecular, biochemical, physiological and ecological levels to be used in the course of teaching in high and higher school. This will afford wide use of visual aids in biology and to allow students to appreciate not only the modern state of research in the world, but also scientific principles and values, and to arouse their interest in the work without assistance.All developed practical courses consist of the following parts: 1. The acquaintance with luminous organisms and bioluminescence. 2. The acquaintance with bioluminescent methods, bioluminescent kits of reagents, bioluminometer and other laboratory techniques. 3. The simple educational experiments with luminous objects according to the Practical Course Manual to show the examples of scientific experiments and prepare the students for their own scientific researches. 4. Every student should make their own scientific experiments using bioluminescent techniques. 5. The scientific conference, where the results of student's research are presented and discussed.Practical courses are usually developed for different levels of education. So there are several variants of one practical course which are suitable for children from 7 to 15, children from 15 to 17, students from 1 to 2 and 3 to 6 years of study and post-graduate students. Special practical courses are intended for the school teachers and for the education of adults.The bioluminescent reactions can be used to demonstrate or measure biological processes in the following fields of biology: human and animal physiology; biochemistry; microbiology; genetics; ecology; toxicology; immunology; cytology; physical chemistry; embryology; plant physiology etc.

The review highlights the results of experimental studies on fungal luminescence carried out during last two centuries. Present concepts on the luminescent system and light emission mechanism in higher fungi are discussed.