Search Results (31)

Melanins are multifunctional biopolymers with unique properties, ranging from UV and radiation protection to antioxidant activity and metal chelation, making them highly attractive for biomedical applications. Despite extensive research, the mechanisms underlying melanin formation remain only partially understood, and access to these biopolymers therefore relies on suitable molecular precursors. While most studies have focused on catecholamine-derived eumelanins such as 3,4-dihydroxyphenylalanine (L-DOPA) and dihydroxyindole (DHI), nitrogen-free precursors such as 1,8-dihydroxynaphthalene (1,8-DHN) are emerging as promising routes to allomelanins. To date, however, these two precursor classes have largely been investigated separately, limiting a broader understanding of structure–function relationships. This review aims to compare electrochemical and redox-based pathways to catecholamine- and DHN-derived materials, emphasizing both their common principles and distinctive features. By bridging these parallel research streams, we propose a methodological framework for guiding future research on melanin-inspired materials and bioelectrochemical technologies. Full article

Fungal melanin plays a vital role in the survival, reproduction, infection, and environmental adaptation of plant pathogenic fungi. To develop innovative strategies for managing plant fungal diseases, comprehensive investigations into melanin are imperative. Such research is fundamental to elucidating the mechanistic basis of fungal pathogenesis and holds promise for the design of targeted interventions against melanin-mediated virulence determinants. This review systematically elaborates on the classification of fungal melanin in plant pathogens, provides a detailed analysis of the biosynthetic processes of 3,4-dihydroxyphenylalanine (DOPA) and 1,8-dihydroxynaphthalene melanin (DHN melanins), and reveals the catalytic functions and regulatory mechanisms of key enzymes within these pathways. Melanin modulates fungal virulence by influencing appressorial integrity and turgor pressure formation, thereby participating in the host infection process and the formation of overwintering sclerotia. Melanin provides stress resistance by protecting against extreme environmental factors, including UV radiation and high temperatures. It also has the capacity to absorb heavy metals, which increases pathogen survival under adverse conditions. Furthermore, the review also explores the mechanisms of action of melanin inhibitors that target plant pathogenic fungi, providing a theoretical foundation for developing efficient and environmentally friendly antifungal medications. The complex biosynthesis pathways and diverse biological functions of fungal melanin highlight its significant theoretical and practical importance for elucidating pathogenic mechanisms and formulating scientific control strategies. Full article

While the pandemic is behind us, the world community faces a global threat of bacterial resistance outbreak. One of the key ways to combat the spread of multi-resistant bacteria is infection prevention and control tactics using modern antiseptic and disinfectant compositions. Herein, we continue the path to unravel the structure–activity relationship (SAR) of potent pyridine-derived biocide class bis-quaternary ammonium compounds (QACs). In this study, twenty dihydroxynaphthalene-derivative bis-QACs were subjected to extensive microbiological analysis on planktonic cells and biofilms of the ESKAPE microorganisms. Among them, hit compounds were superior in their bacteriostatic and bactericidal action to commercial mono-QACs and were comparable to the best bis-QAC antiseptic on the market. SAR analysis indicated that the linker conformation does not significantly affect the activity, though structure symmetry and especially lipophilicity had an influence on antibacterial performance. Furthermore, we delve deeper in investigation of the antimicrobial potential of bis-QACs and conducted a variety of assays, including time–kill kinetics, bacterial resistance formation, cell morphology, and cytotoxicity. Studies showed promising results for compounds 5d and 6d, indicating 2 to 3-fold less cytotoxicity and hemotoxicity compared to commercial QACs. Moreover, SEM imaging revealed that bis-QACs can cause severe membrane damage to S. aureus and P. aeruginosa strains, confirming great potential of novel compounds as antiseptic and disinfectant. Full article

Metarhizium robertsii microsclerotia are fungal aggregates composed of compacted, pigmented hyphae. As they are highly tolerant to desiccation and produce infective conidia, they are promising candidates to be formulated as bioinsecticides. Despite this potential, the nature of the pigments within these structures remains unclear. In this study, routine culture media used for the differentiation of M. robertsii microsclerotia were supplemented with four melanin inhibitors, and the resulting propagules were characterized. Inhibitors of the 1,8-dihydroxynaphthalene (DHN)-melanin biosynthetic pathway such as tricyclazole and guaiacol induced significant phenotypic and molecular modifications in the obtained M. robertsii propagules, which exhibited a more spherical shape, reduced size, and increased susceptibility to desiccation, heat, and oxidative stress than microsclerotia obtained without inhibitors. Additionally, genes encoding for a polyketide synthase (Mrpks2) and a putative 1,3,6,8-tetrahydroxynaphthalene reductase (Mrthnr), potentially involved in the DHN-melanin biosynthetic pathway, were upregulated in fungi grown in the inhibitor-added media. In conclusion, M. robertsii microsclerotia contain melanins of type DHN that might play a role in both microsclerotia differentiation and environmental stress tolerance. Full article

2-(((2,7-Dihydroxynaphthalen-1-yl)methylene)amino)-3′,6′-bis(ethylamino)-2′,7′-dimethylspiro[isoindoline-1,9′-xanthen]-3-one was synthesized using Rhodamine 6G hydrazide (prepared using literature methods) and commercially available 2,7-dihydroxynaphthalene-1-carbaldehyde via imine condensation. Structural characterization was performed using FT-IR, ¹H-NMR, ¹³C-NMR, X-ray, and HRMS. This Schiff base shows promise as a ligand for the colorimetric analysis of uranium in water. Full article

Penicillium roqueforti is a fungal starter culture used for the production of blue-veined cheeses, such as Roquefort, Gorgonzola, Stilton, Cabrales, and Danablue. During ripening, this species grows in the veins of the cheese, forming the emblematic blue-green color and establishing the characteristic flavor owin to its biochemical activities. P. roqueforti synthesizes a diverse array of secondary metabolites, including the well-known compounds roquefortine C, clavine alkaloids, such as isofumigaclavine A and B, mycophenolic acid, andrastin A, and PR-toxin. This review provides an in-depth exploration of P. roqueforti’s secondary metabolites, focusing on their biosynthetic pathways, the gene clusters responsible for their production, and their bioactivities. The presence of these compounds in blue cheeses is also reviewed. Furthermore, the silent clusters and the potential of P. roqueforti for producing secondary metabolites were discussed. The review highlights recently identified metabolites, including sesterterpenoids; tetrapeptides, D-Phe-L-Val-D-Val-L-Tyr, and D-Phe-L-Val-D-Val-L-Phe; cis-bis(methylthio)silvatin; and the 1,8-dihydroxynaphthalene (DHN)-melanin precursor, scytalone. Additionally, a gene cluster for DHN–melanin biosynthesis is presented. Finally, a revised cluster for roquefortine C biosynthesis comprising three rather than four genes is proposed. Full article

As the most abundant catecholamine neurotransmitter in the brain, dopamine plays an important role in the normal physiological process, and its level in urine also changes during human pathological processes. In clinic, the detection of dopamine in urine is a potential marker for the diagnosis and the treatment of endocrine-related diseases. In this work, a copper metal organic framework with catecholase-like activity was prepared via the precipitation of Cu²⁺ and imidazole, simulating the N-Cu coordination environment in the active site of catecholase. Cu-MOF (the copper–metal organic framework) can catalyze the oxidation of DA (dopamine) to dopaquinone using O₂ in the air. The oxidation product can further react with 1,3-dihydroxynaphthalene to produce a fluorophore product. Based on the above reaction, a multimodal sensing platform with three signal outputs, including ratio-metric fluorescence, absorbance and digital information extracted from smartphone images for simple and sensitive determination of DA, was proposed, with detection limits of 0.0679, 0.3206, and 0.3718 μM, respectively. This multimodal sensing platform was able to detect DA in body fluid in a self-correcting way, as demonstrated by the successful determination of DA in normal human urine samples, and samples with a high level of interference. Full article

Melanins are stable and non-toxic pigments with great potential as chemopreventive agents against oxidative stress for medical and cosmetic applications. Allomelanin is a class of nitrogen-free melanin often found in fungi. The artificial allomelanin obtained by the polymerization of 1,8-dihydroxynaphthalene (DHN), poly-DHN (PDHN), has been recently indicated as a better radical quencher than polydopamine (PDA), a melanin model obtained by the polymerization of dopamine (DA); however, the chemical mechanisms underlying this difference are unclear. Here we investigate, by experimental and theoretical methods, the ability of PDHN nanoparticles (PDHN-NP), in comparison to PDA-NP, to trap alkylperoxyl (ROO^•) and hydroperoxyl (HOO^•) radicals that are involved in the propagation of peroxidation in real conditions. Our results demonstrate that PDHN-NP present a higher antioxidant efficiency with respect to PDA-NP against ROO^• in water at pH 7.4 and against mixed ROO^• and HOO^• in acetonitrile, showing catalytic cross-termination activity. The antioxidant capacity of PDHN-NP in water is 0.8 mmol/g (ROO^• radicals quenched by 1 g of PDHN-NP), with a rate constant of 3 × 10⁵ M⁻¹ s⁻¹ for each reactive moiety. Quantum-mechanical calculations revealed that, thanks to the formation of a H-bond network, the quinones in PDHN-NP have a high affinity for H-atoms, thus justifying the high reactivity of PDHN-NP with HOO^• observed experimentally. Full article

Inverted perovskite solar cells with a p-i-n configuration have attracted considerable attention from the research community because of their simple design, insignificant hysteresis, improved operational stability, and low-temperature fabrication technology. However, this type of device is still lagging behind the classical n-i-p perovskite solar cells in terms of its power conversion efficiency. The performance of p-i-n perovskite solar cells can be increased using appropriate charge transport and buffer interlayers inserted between the main electron transport layer and top metal electrode. In this study, we addressed this challenge by designing a series of tin and germanium coordination complexes with redox-active ligands as promising interlayers for perovskite solar cells. The obtained compounds were characterized by X-ray single-crystal diffraction and/or NMR spectroscopy, and their optical and electrochemical properties were thoroughly studied. The efficiency of perovskite solar cells was improved from a reference value of 16.4% to 18.0–18.6%, using optimized interlayers of the tin complexes with salicylimine (1) or 2,3-dihydroxynaphthalene (2) ligands, and the germanium complex with the 2,3-dihydroxyphenazine ligand (4). The IR s-SNOM mapping revealed that the best-performing interlayers form uniform and pinhole-free coatings atop the PC₆₁BM electron-transport layer, which improves the charge extraction to the top metal electrode. The obtained results feature the potential of using tin and germanium complexes as prospective materials for improving the performance of perovskite solar cells. Full article

Aspergillus fumigatus is an opportunistic fungal pathogen that causes serious lung diseases in immunocompromised patients. The lung surfactant produced by alveolar type II and Clara cells in the lungs is an important line of defense against A. fumigatus. The surfactant consists of phospholipids and surfactant proteins (SP-A, SP-B, SP-C and SP-D). The binding to SP-A and SP-D proteins leads to the agglutination and neutralization of lung pathogens as well as the modulation of immune responses. SP-B and SP-C proteins are essential for surfactant metabolism and can modulate the local immune response; however, the molecular mechanisms remain unclear. We investigated changes in the SP gene expression in human lung NCI-H441 cells infected with conidia or treated with culture filtrates obtained from A. fumigatus. To further identify fungal cell wall components that may affect the expression of SP genes, we examined the effect of different A. fumigatus mutant strains, including dihydroxynaphthalene (DHN)-melanin-deficient ΔpksP, galactomannan (GM)-deficient Δugm1 and galactosaminogalactan (GAG)-deficient Δgt4bc strains. Our results show that the tested strains alter the mRNA expression of SP, with the most prominent and consistent downregulation of the lung-specific SP-C. Our findings also suggest that secondary metabolites rather than the membrane composition of conidia/hyphae inhibit SP-C mRNA expression in NCI-H441 cells. Full article

Monilinia is the causal agent of brown rot in stone fruit. The three main species that cause this disease are Monilinia laxa, M. fructicola, and M. fructigena, and their infection capacity is influenced by environmental factors (i.e., light, temperature, and humidity). To tolerate stressful environmental conditions, fungi can produce secondary metabolites. Particularly, melanin-like pigments can contribute to survival in unfavorable conditions. In many fungi, this pigment is due to the accumulation of 1,8-dihydroxynaphthalene melanin (DHN). In this study, we have identified for the first time the genes involved in the DHN pathway in the three main Monilinia spp. and we have proved their capacity to synthetize melanin-like pigments, both in synthetic medium and in nectarines at three stages of brown rot development. The expression of all the biosynthetic and regulatory genes of the DHN-melanin pathway has also been determined under both in vitro and in vivo conditions. Finally, we have analyzed the role of three genes involved in fungi survival and detoxification, and we have proved that there exists a close relationship between the synthesis of these pigments and the activation of the SSP1 gene. Overall, these results deeply describe the importance of DHN-melanin in the three main species of Monilinia: M. laxa, M. fructicola, and M. fructigena. Full article

A new N,O-rich covalent organic framework (COF_DHNDA-BTH) was synthesized by an amine-aldehyde condensation reaction between 2,6-dialdehyde-1,5-dihydroxynaphthalene (DHNDA) and 1,3,5-phenyltriformylhydrazine (BTH) for carbaryl detection. The free NH, OH, and C=O groups of COF_DHNDA-BTH not only covalently couples with acetylcholinesterase (AChE) into the pores of COF_DHNDA-BTH, but also greatly improves the catalytic activity of AChE in the constrained environment of COF_DHNDA-BTH’s pore. Under the catalysis of AChE, the acetylthiocholine (ATCl) was decomposed into positively charged thiocholine (TCl), which was captured on the COF_DHNDA-BTH modified electrode. The positive charges of TCl can attract anionic probe [Fe(CN)₆]^3−/4− on the COF_DHNDA-BTH-modified electrode to show a good oxidation peak at 0.25 V (versus a saturated calomel electrode). The carbaryl detection can inhibit the activity of AChE, resulting in the decrease in the oxidation peak. Therefore, a turn-off electrochemical carbaryl biosensor based on a flexible carbon paper electrode loaded with COF_DHNDA-BTH and AChE was constructed using the oxidation peak of an anionic probe [Fe(CN)₆]^3−/4− as the detection signal. The detection limit was 0.16 μM (S/N = 3), and the linear range was 0.48~35.0 μM. The sensor has good selectivity, repeatability, and stability, and has a good application prospect in pesticide detection. Full article

Covalent organic frameworks (COFs) have attracted significant interest because of their heteroatom-containing architectures, high porous networks, large surface areas, and capacity to include redox-active units, which can provide good electrochemical efficiency in energy applications. In this research, we synthesized two novel hydroxy-functionalized COFs—TAPT-2,3-NA(OH)_2, TAPT-2,6-NA(OH)₂ COFs—through Schiff-base [3 + 2] polycondensations of 1,3,5-tris-(4-aminophenyl)triazine (TAPT-3NH₂) with 2,3-dihydroxynaphthalene-1,4-dicarbaldehyde (2,3-NADC) and 2,6-dihydroxynaphthalene-1,5-dicarbaldehyde (2,6-NADC), respectively. The resultant hydroxy-functionalized COFs featured high BET-specific surface areas up to 1089 m² g^–1, excellent crystallinity, and superior thermal stability up to 60.44% char yield. When used as supercapacitor electrodes, the hydroxy-functionalized COFs exhibited electrochemical redox activity due to the presence of redox-active 2,3-dihydroxynaphthalene and 2,6-dihydroxynaphthalene in their COF skeletons. The hydroxy-functionalized COFs showed specific capacitance of 271 F g⁻¹ at a current density of 0.5 A g⁻¹ with excellent stability after 2000 cycles of 86.5% capacitance retention. Well-known pore features and high surface areas of such COFs, together with their superior supercapacitor performance, make them suitable electrode materials for use in practical applications. Full article

Sclerotium cepivorum Berk is the etiological agent of white rot disease that affects plants of the genus Allium. This fungus produces resistance structures called sclerotia that are formed by a rolled mycelium with a thick layer of melanin and it can remain dormant for many years in the soil. Current interest in S. cepivorum has arisen from economic losses in Allium crops in the agricultural sector. Melanin is a component that protects the sclerotia from adverse environmental conditions In many organisms, it plays an important role in the infectious process; in S. cepivorum, the pathway by which this component is synthetized is not fully described. By using infrared spectrophotometric assays applied direct to the sclerotia and a melanin extract followed by an NMR analysis and a tricyclazole melanin inhibition experiment, it allowed us to determine the dihydroxynaphthalene (DHN)-melanin pathway by which S. cepivorum performs its melanin synthesis. Moreover, we focused on studying scytalone dehydratase (SDH) as a key enzyme of the DHN-melanin synthesis. We obtained the recombinant SDH enzyme and tested its activity by a zymogram assay. Thereby, the S. cepivorum melanogenic route was established as a DHN pathway. Full article

Fungi are well-known for their abundant supply of metabolites with unrivaled structure and promising bioactivities. Naphthalenones are among these fungal metabolites, that are biosynthesized through the 1,8-dihydroxy-naphthalene polyketide pathway. They revealed a wide spectrum of bioactivities, including phytotoxic, neuro-protective, cytotoxic, antiviral, nematocidal, antimycobacterial, antimalarial, antimicrobial, and anti-inflammatory. The current review emphasizes the reported naphthalenone derivatives produced by various fungal species, including their sources, structures, biosynthesis, and bioactivities in the period from 1972 to 2021. Overall, more than 167 references with 159 metabolites are listed. Full article