https://hdl.handle.net/10259/3597 2026-04-28T11:52:40Z https://hdl.handle.net/10259/11151 New approach using alternative proteolytic enzymes to the conventional enzyme pronase for the isolation of bread melanoidins Cavia Saiz, Mónica; Gerardi, Gisela; Muñiz Rodríguez, Pilar; García Tojal, Javier; Salazar Mardones, Gonzalo Bread melanoidins are melanoproteins classically extracted with the proteolytic enzyme pronase E (S. griserus). In this study, the structure and functionality of melanoidins extracted with the proteolytic enzymes papain (PE) and enzymes from B. subtillus (SP) and a mixture from B. subtillus and A. oryzae (MP) were evaluated. PE extracted melanoidins have the highest nitrogen (4.3 %) and protein (29 %) content. FTIR showed that PE had a higher protein content and pronase had higher in carbohydrates. The K420 and K345 values and antioxidant capacities of the PE extract were similar to pronase and higher than the other microbial enzymes. After in vitro digestion, the increased in the antioxidant capacity was most pronounced in the PE extract. No neurotoxicity was observed, as evidenced by no neuronal cell death or changes in neuronal ROS levels. These results indicate that the PE enzyme may be a good alternative to pronase for extraction of melanoidins. 2025-06-01T00:00:00Z https://hdl.handle.net/10259/9807 Tridentate acylhydrazone copper(II) complexes with heterocyclic bases as coligands. Synthesis, spectroscopic studies, crystal structure and cytotoxicity assays Burgos López, Y.; Balsa, Lucía M.; Piro, Oscar Enrique; León, Ignacio E.; García Tojal, Javier; Echeverría, Gustavo A.; González Baró, Ana C.; Parajón Costa, Beatriz S. Two new penta-coordinated copper(II) hydrazone coordination compounds with 2,2́ bipyridine (I) or 1,10 phenanthroline (II) as coligands are synthesized and characterized in the solid state and in solution by spectroscopic methods (FTIR, Raman, UV–vis, EPR). Single crystal X-ray studies show that they have closely related molecular structures with the copper center in a distorted square pyramidal O2N3 environment. The N-acylhydrazone, 4-hydroxy-NŃ-(E)2-hydroxy-3-methoxybenzylidene]benzohydrazide, H2L, coordinates tridentate through its ONO donor atoms as monoanion (HL-) in the cationic complex (I), [Cu(HL)(bipy)](NO3). During the period that takes the synthesis reaction of compound (II), [Cu(L)(o-phen)] to complete, keto-amine to enol-imine tautomerization of H2L occurs and the hydrazone coordinates tridentate as dianionic ligand (L2-). The fivefold coordination sphere of the complexes is completed with the nitrogen atoms of the respective coligands. Cytotoxicity studies against bone (MG-63, IC50(I) = 5.6 ± 1.0 , IC50(II) = 3.5 ± 0.3), breast (MCF7, IC50(I) = 10.8 ± 1.9, IC50(II) = 4.0 ± 1.3), (MDA-MB-231, IC50(I) = 11.4 ± 0.6, IC50(II) = 5.3 ± 0.2) and lung cancer cells (A549, IC50(I) = 7.7 ± 0.7, IC50(II) = 7.0 ± 0.4) reveals increased effectiveness of both complexes compared with the free ligand, the copper nitrate salt and the reference metallodrug cisplatin (CDDP). 2022-02-01T00:00:00Z https://hdl.handle.net/10259/9784 Transforming the ancestors: early evidence of fire-induced manipulation on human bones in the Near East from the Pre-Pottery Neolithic B of Kharaysin (Jordan) Santana Cabrera, Jonathan Alberto; Iriarte Avilés, Eneko; Teira, Luis .; García Tojal, Javier; Muñiz Álvarez, Juan Ramón; Ibáñez, Juan José . Cremation is an unusual burial practice in the Neolithic of the Near East. At Kharaysin, a Pre-Pottery Neolithic site in Jordan, we found a secondary burial with evidence of burnt human bones. This paper assesses (1) the intentionality of fire-induced alterations on human bones, (2) the pre-burning condition of the human remains, and (3) their significance within the burial customs of the Pre-Pottery Neolithic in the Near East. Burial SU-815 was a secondary multiple burial with burnt and unburnt human remains from at least three adult individuals. Directly dated at 8010 ± 30 BP (7058–6825 cal BC), it corresponds to the Late Pre-Potttery Neolithic B (LPPNB). Macroscopic changes in human remains were analysed to investigate the circumstances of burning. Some bones were selected for mineralogical and compositional analysis through X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Colour changes, fractures, cracking, and chemical changes on bones were identified as resulting from fire-induced alterations. Our results show that the bones were intentionally burnt when they were already skeletonised or almost dry. This intentional manipulation using fire happened after other burial practices took place. After burning, the bones were collected and transported to this burial during a final episode. Fire-induced manipulation or cremation was not a significant development of the habitual burial practice, but evidence from Kharaysin shows an innovation in handling the human remains. Therefore, this case provides new insight into the complexity and variability of burial customs within the Late Pre-Pottery Neolithic B in Southern Levant. 2020-05-01T00:00:00Z https://hdl.handle.net/10259/9778 Synthesis, Crystal Structure, Spectroscopic Characterization, DFT Calculations and Cytotoxicity Assays of a New Cu(II) Complex with an Acylhydrazone Ligand Derived from Thiophene Rodríguez, María R.; Balsa, Lucía M.; Piro, Oscar Enrique; Echeverría, Gustavo A.; García Tojal, Javier; Pis Diez, Reinaldo; León, Ignacio E.; Parajón Costa, Beatriz S.; González Baró, Ana C. A new Cu(II) complex is synthetized by the reaction of copper nitrate and a N-acylhydrazone ligand obtained from the condensation of o-vanillin and 2-thiophecarbohydrazide (H2L). The solid-state structure of [Cu(HL)(H2O)](NO3)·H2O, or CuHL for simplicity, was determined by X-ray diffraction. In the cationic complex, the copper center is in a nearly squared planar environment with the nitrate interacting as a counterion. CuHL was characterized by spectroscopic techniques, including solid-state FTIR, Raman, electron paramagnetic resonance (EPR) and diffuse reflectance and solution UV-Vis electronic spectroscopy. Calculations based on the density functional theory (DFT) assisted the interpretation and assignment of the spectroscopic data. The complex does not show relevant antioxidant activity evaluated by the radical cation of 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) method, being even less active than the free ligand as a radical quencher. Cytotoxicity assays of CuHL against three human tumor cell lines, namely MG-63, A549 and HT-29, revealed an important enhancement of the effectiveness as compared with both the ligand and the free metal ion. Moreover, its cytotoxic effect was remarkably stronger than that of the reference metallodrug cisplatin in all cancer cell lines tested, a promissory result in the search for new metallodrugs of essential transition metals. 2021-01-01T00:00:00Z