https://hdl.handle.net/10481/27968 Sat, 11 Apr 2026 17:20:55 GMT 2026-04-11T17:20:55Z https://hdl.handle.net/10481/112459 Isolation and Characterization of Terpenoids with Promising Biopesticide Activity from Dittrichia viscosa (L.) Roots Segura Navarro, María José; Quílez Del Moral, José Francisco; Galisteo, Alberto; López Pérez, José Luis; Molina Inzunza, Diego O.; Andrés, María Fe de; González Coloma, Azucena; Fernández Barrero, Alejandro The natural product composition of the hexane and methyl tert-butyl ether extracts of Dittrichia viscosa roots was examined. Eight terpenoids were identified by nuclear magnetic resonance (NMR) and high resolution mass spectroscometry (HRMS) techniques, four of which (1, 5, 6 and 8) are reported here for the first time as natural products. Of these eight compounds, four are thymol derivatives (1–4), two are guaianolides (5 and 7) and two are himachalanes (6 and 8). Additionally, the occurrence of himachalanes in this species is reported for the first time. Furthermore, a study of the potential plant protection effects of some of these natural products and the chemical derivative 6a was carried out. Promising preliminary results were obtained for compounds 1–3 and 6a as antifeedant agents against Spodoptera littoralis; 1–3 and 5 against Myzus persicae; 1–3 against Rhopalosiphum padi; and 4 as nematicide against Meloidogyne javanica. Finally, the phytotoxic activity of compounds 4, 5 and 6a against the monocotyledonous species Lolium perenne was also proven. https://hdl.handle.net/10481/112459 https://hdl.handle.net/10481/111639 Theoretical design of novel selenium-substituted meso-aryl-BODIPYs as singlet‑oxygen photosensitizers with biomedical applicability Moral, Mónica; Fernández Vargas, Antonio Jesús; Frutos, Luis Manuel; Garzón Ruiz, Andrés This is a DFT study on selenium-substituted meso-aryl-BODIPYs aimed at designing novel singlet‑oxygen photosensitizers with potential biomedical applicability. Three different selenium-containing heterocycles (2,3-dihydro-1,3-selenazole, 1,3-oxaselenole and 1,3-thiaselenole) were combined with diverse types of meso-aryl-BODIPYs. The incorporation of selenium atoms into BODIPYs is a novel strategy to enhance the photosensitizer performance, reducing the toxicity associated with the use of metal atoms. The present study provides new perspectives on the use of these novel agents which have been scarcely developed to date. Diverse electronic descriptors such as the absorption maxima wavelength, singlet-triplet energy gap and spin-orbit coupling were used in subsequent screening steps to select the most suitable candidates as photosensitizers with biomedical applicability. These descriptors are related to the light absorption within the therapeutic window, the triplet-state formation efficiency, the triplet-state lifetime and the energy transfer to the molecular oxygen. https://hdl.handle.net/10481/111639 https://hdl.handle.net/10481/110142 Zirconocene(III) in Organic Synthesis: Does the Ugly Duckling Become a Swan? Rosales, Jennifer; Chahboun Karimi, Rachid; Justicia Ladrón De Guevara, José The development of efficient C-C bond-forming reactions remains an important objective in organic chemistry. These reactions are fundamental tools for building complex molecules for diverse applications. Among the various strategies available, radical processes promoted by group IV metals—particularly Ti and its titanocene-type complexes—have shown remarkable versatility and utility in organic synthesis. However, closely related zirconium analogues have historically received less attention and have shown a more limited reactivity profile. Thus, zirconium and its zirconocene-type derivatives have often been regarded as the “ugly duckling” of group IV metal-promoted radical chemistry. Yet recent advances indicate that this “ugly duckling” is beginning to reveal its synthetic potential. In this review, we highlight the main synthetic applications of zirconocene(III) complexes and compare them with those of titanocene(III). Special attention is placed on the generation of reactive zirconocene(III) species and their impact on reactivity. Overall, these developments show how zirconocene(III) chemistry is emerging as a valuable complement to titanocene(III)-based radical transformations, turning our ugly duckling into a beautiful swan. https://hdl.handle.net/10481/110142 https://hdl.handle.net/10481/109813 Regio- and Diastereoselective Arylation of rosin acids: A practical strategy for bioactive compounds discovery Wahoodi, Farked S.; Fernández Vargas, Antonio Jesús; Sáinz Pérez, Juan; Rodríguez‑Serrano, Fernando; Reyes Zurita, Fernando Jesús; Chahboun, Rachid A mild, sustainable, and cost-effective arylation of rosin-acids is reported. This new approach, based on a regio- and diastereoselective Friedel-crafts alkylation, enabled the synthesis of fourteen new resin acid derivatives. Selected compounds were screened for cytotoxic activity against three human tumor cell lines. Remarkably, quinone 14 exhibited significant activity: Against HL-60 cells (IC₅₀ = 5.94 μM) cell, and phenol 11f displayed selective cytotoxic activity against HT-29 cells (IC₅₀ = 8.90 μM) cells. Flow cytometry confirmed apoptosis as the primary mechanism of cell death, reaching 78% in HL-60 (14) and 72.6% in HT-29 (11 g), with minimal necrosis. Cell-cycle analysis showed S-phase arrest in HL-60 (14) and G0/G1 arrest in HT-29 (11f/11 g). Consistently, ΔΨm assays showed near-complete collapse in HL-60 (14) and significant depolarization in HT-29 (11 g). In addition, the anti-inflammatory activity of some synthesized compounds was assessed in LPS-stimulated RAW 264.7 macrophages. All tested compounds achieved 70–100% NO inhibition at subcytotoxic concentrations. Derivatives 13 and 14 showed the highest activity (IC50 NO = 0.85 μM and 5.43 μM, respectively). Overall, this green arylation approach enables rapid access to 7-aryl methyl ester dehydroabietic acid libraries with significant cytotoxic and anti-inflammatory activities The authors thank Junta de Andalucía-Consejería de Universidad, Investigación e Innovación (Project C-EXP-053-UGR23 and B-FQM-650-UGR-20) and Vicerrectorado de Investigación y Transferencia, Universidad de Granada for financial and institutional support provided to the research groups FQM-348 and BIO-157. Funding for open access charge: Universidad de Granada/CBUA. https://hdl.handle.net/10481/109813 https://hdl.handle.net/10481/108654 Garlicinals A−D: Bioactive Organosulfur α,β-Unsaturated Aldehydes from Garlic (Allium sativum L.) Hydrolate Galisteo, Alberto; Quílez Del Moral, José Francisco; Fernández Barrero, Alejandro; Andrés, María F.; González Coloma, Azucena Four sulfur-derived compounds, garlicinals A–D (1–4), were isolated from the garlic (Allium sativum) bulb hydrolate. The structural elucidation of 1–4 was achieved with the help of HRMS and 1D and 2D NMR. All of these compounds are characterized by an α,β-unsaturated aldehyde in their structure. Noteworthy, this structural motif is unique in garlic-derived compounds, which would convert them into a new family of garlic-derived organosulfur compounds. A synthetic path to these compounds is proposed. Garlicinals A–C showed potent fungicidal activity against plant pathogens (Aspergillus niger and Botrytis cinerea). Furthermore, 1–4 were active against the nematode Meloidogyne javanica. https://hdl.handle.net/10481/108654