CINQUIMA - Artículos de revista https://uvadoc.uva.es/handle/10324/28543 2026-04-06T07:00:09Z 2026-04-06T07:00:09Z De La Fuente Ballesteros, Adrián Obaydo, Reem H. Elagamy, Samar H. Ares Sacristán, Ana María Bernal del Nozal, José https://uvadoc.uva.es/handle/10324/83789 2026-03-24T20:07:22Z 2026-01-01T00:00:00Z

The analysis of plastics and related chemical compounds, such as plasticizers, flame retardants, and micro- or nanoplastics, often requires working at trace levels, where even minimal contamination can significantly affect results. However, many of these target analytes are also present in common laboratory materials and environ- ments, increasing the risk of cross-contamination. We identified six major cross-contamination pathways frequently found in analytical workflows: (I) laboratory materials, (II) environmental contamination, (III) human handling and manipulation, (IV) solvents and reagents, (V) cleaning and sample preparation, and (VI) instru- mental and system-related contamination. For each of these, preventive measures and good laboratory practices are suggested based on both experimental experience and examples in the literature. As a general recommen- dation, procedural blanks should be included throughout the analytical process, and contamination risks should be anticipated as early as the experimental design stage. This work provides a structured reference to support more reliable and reproducible data generation in the analysis of plastic-related contaminants. Researchers are further encouraged to evaluate contamination risks throughout the workflow and to report them transparently in their publications.

2026-01-01T00:00:00Z Chico Robles, Rubén Baena Alonso, María Jesús Cuerva, Cristián Schmidt, Rainer Donnio, Bertrand Coco Cea, Silverio https://uvadoc.uva.es/handle/10324/83784 2026-03-24T20:07:21Z 2026-01-01T00:00:00Z

Ionic liquid crystals (iLCs) constitute an emerging materials type that combines the properties of an ionic liquid, such as ionic mobility, with the supramolecular organization of a liquid crystal. This makes them suitable candidates for applications such as anisotropic ion conductor and next-generation energy storage systems. In this work, we report ion conducting columnar mesophases based on bis(triphenylene-isocyanide) metal complexes of the type [M(CNR)2]Y (CNR = 2-(6-(4- isocyanophenoxy)hexyloxy)hexyloxy)-3,6,7,10,11-pentakisdodecyloxy-triphenylene; M = Ag(I), Au(I); Y = NO3 -, BF4 -). All the gold and silver complexes display enantiotropic mesomorphism in the temperature range 35-80 °C. They self-assemble into rectangular columnar mesophases, whose X-ray diffraction profiles reveal the simultaneous stacking of triphenylene disks into one-dimensional columns and the aggregation of metallic fragments assembled into filaments that are arranged parallel between the triphenylene columns. The ionic conductivity of these mesophases is based on the counterion mobility and increases regularly as the molecular slice thickness increases along the columns, ranging from 1.70 10-9 to 1.64 10-8 S/cm. Although these conductivity values obtained so far are lower than those required for commercial displays, our results demonstrate the key role of packaging efficiency in ion transport in soft materials, and the potential of organic/inorganic nanosegregated mesophases to develop tailored and advanced ion-conducting materials. The gold and silver complexes display fluorescent behavior related to the triphenylene core in solution.

2026-01-01T00:00:00Z De La Fuente Ballesteros, Adrián Smerkol, Maj Gradišek, Anton Sarmento, Artur Fourrier, Julie Arapcheska, Mila Hajrulai Musliu, Zehra Franeta, Filip Milovac, Željko Gvozdenac, Sonja İçli, Nesrin Kurtagić, Harun Pasho, Ina Zioga, Elena Vázquez, Beatriz I. Pavliček, Damir Busquets, Rosa Ciric, Jelena Esenbuga, Nurinisa Cavaco, Miriam Rodrigues, Helena Ferreira, Rosa Leite, Marta Lace, Zane Ares Sacristán, Ana María Bernal del Nozal, José Pugajeva, Iveta https://uvadoc.uva.es/handle/10324/82830 2026-02-17T20:02:39Z 2026-01-01T00:00:00Z

Honeybees and their products integrate landscape-level chemical exposure, making apicultural matrices valuable bioindicators for both food safety and environmental monitoring. This review summarizes current knowledge on pesticide residues in honey, pollen, beebread, beeswax, royal jelly, and propolis from 2019 to 2024, with an overview of analytical methodologies used in their determination. Multi-residue methods remain dominated by Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction combined with liquid and gas chromatography coupled to tandem mass spectrometry, while high-resolution MS enables broader screening. Highly polar pesticides, particularly glyphosate and its metabolites, require specialised single-residue approaches, such as the Quick Polar Pesticides (QuPPe) method and ion chromatography–high-resolution mass spectrometry (IC-HRMS). Co-occurrence patterns frequently involve mixtures of neonicotinoids, acaricides, and fungicides, reflecting combined agricultural and in-hive treatments. Regarding matrices, honey typically shows insecticide and acaricide residues, pollen concentrates fungicides and insecticides as the main exposure route, and beeswax acts as a long-term sink for lipophilic compounds; royal jelly generally exhibits the lowest contamination levels. Although exceedances of Maximum Residue Limits in honey remain uncommon in European monitoring programs, the presence of pesticide mixtures and limited residue data for bee-related products beyond honey raise concern. Future research should prioritize harmonized residue limits for all beekeeping matrices, standardized quality control and reporting practices, targeted mixture-toxicity assessment under realistic co-exposure scenarios, and the broader adoption of green, miniaturized, and matrix-tailored sample preparation strategies to enhance sensitivity, sustainability, and comparability across studies.

2026-01-01T00:00:00Z Heras Elvira, Domingo Li, Wenqin Alkorta, Ibon Pinacho Gómez, Ruth Enríquez Giraudo, María Lourdes Rubio García, José Emiliano Pérez Cuadrado, Cristobal Lesarri Gómez, Alberto Eugenio https://uvadoc.uva.es/handle/10324/82710 2026-02-12T20:02:38Z 2026-01-01T00:00:00Z

We used jet-cooled broadband rotational spectroscopy and quantum mechanical calculations to study the po- tential energy surface, molecular structure and intra- and intermolecular interactions of the biarylic thienyl pyridines of 2-(2-thienyl)pyridine and 2-(2-pyridyl)benzothiophene and their monohydrates. Two isomers of the bare molecules were identified in the gas phase, characterized by planar structures and zusammen (Z) or entgegen (E) orientations around the ring junction. A single Z-isomer was observed for both monohydrates, primary stabilized by a hydroxyl-to-nitrogen (O-H⋅⋅⋅N) hydrogen bond and secondary C-H⋅⋅⋅O interactions. The compu- tational study included D3 dispersion-corrected hybrid (B3LYP) and double hybrid (B2PLYP) density functional methods, with additional calculations at the RI-MP2 and DLPNO-CCSD(T) levels. NBO calculations examined the donor-acceptor hyperconjugative effects involving the nitrogen and sulfur atoms, suggesting that their partici- pation in the larger stability of the Z form is not decisive and may involve other intramolecular interactions. In particular, examination of the electronic density shifts (EDS) further suggests that non-covalent N⋅⋅⋅S chalcogen interactions partially contribute to the preference for the Z conformation

2026-01-01T00:00:00Z Prieto Diez, Estela Ares Sacristán, Ana María Bernal Yagüe, José Luis Valverde Bastardo, Silvia https://uvadoc.uva.es/handle/10324/82488 2026-02-03T20:01:31Z 2026-01-01T00:00:00Z

Bee pollen is a natural food supplement collected by honeybees that has significant nutritional value and ther- apeutic qualities, including antioxidant, antibacterial, and anticarcinogenic properties. Due to its hygroscopic nature, bee pollen readily promotes microbial growth; however, there is no specific legislation for bee pollen in the European Union. Microbiological contamination therefore stands out as a crucial factor in determining its quality. To address this, the study focused on isolating bacterial and fungal colonies from bee pollen using various culture media, followed by a protein extraction based on a lysis process. Identification was achieved through the Biotyper-MALDI-TOF (Matrix-Assisted Laser Desorption/Ionization coupled to Time-of-Flight de- tector) system. The greenness and blueness of the methods were assessed using different tools, which classified them as environmentally friendly and practical. Thirty-two samples were analyzed using proposed sample treatment approaches. Data were processed using chemometric techniques based on linear models. The results revealed the presence of both beneficial and potentially pathogenic species, including key representatives such as Bacillus licheniformis, Micrococcus luteus, and Aspergillus fumigatus. These findings highlight the importance of microbiota characterization in bee pollen and demonstrate that MALDI-TOF is a rapid and effective tool for profiling culturable microbial communities in this matrix.

2026-01-01T00:00:00Z Gil Ordóñez, Marta Pérez Aragón, Miriam Martín Maroto, Laura Maestro Fernández, Alicia Andrés García, José María https://uvadoc.uva.es/handle/10324/81354 2026-01-12T20:04:03Z 2025-01-01T00:00:00Z

Quinine-derived bifunctional squaramide catalyzed the asymmetric addition of different alcohols to pyrazolone-derived Boc-ketimines, providing chiral pyrazolones containing a tetrasubstituted stereocenter bearing a new N,O-acetal motif. The products were isolated in satisfactory yields (up to 91%) and with moderate levels of enantioselectivity (up to 79:21 er) by using 5 mol% of the chiral squaramide catalyst across a broad substrate scope. Importantly, enantioenriched N,O-aminals can be efficiently recovered from the mother liquors by a simple recrystallization. The reaction was extended to other nucleophiles, thiophenol and N-methylaniline, providing the corresponding N,S- and N,N-acetals in moderate to good yield but low enantioselectivity.

2025-01-01T00:00:00Z Jano, Ana De La Fuente Ballesteros, Adrián Tapia García, Jesús Alberto Valverde Bastardo, Silvia Ares Sacristán, Ana María Bernal del Nozal, José https://uvadoc.uva.es/handle/10324/80763 2025-12-18T20:06:27Z 2025-01-01T00:00:00Z

The increasing demand for bee-derived products such as honey and bee pollen has led to a rise in adulteration and mislabeling, making it essential to develop reliable tools for authentication. Lipids, which are found in both matrices, are potential biomarkers for tracing their origin and may be used for detecting fraud. In this work, a solid–liquid extraction using hexane:isopropanol (10:1, v/v) followed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) was optimized. The method was applied for tentative lipid screening of 15 honeys and 13 bee pollens showing a total number of lipids above 700, including fatty acyls, glycerolipids, glycerophospholipids, sphingolipids, and sterol lipids. For the first time, a principal component analysis was carried out for botanical and geographical origin, classifying most of the samples correctly. Additionally, the method was categorized as green (environmentally friendly) and blue (practical).

2025-01-01T00:00:00Z Steber, Amanda Hussain, Farha S. Lesarri Gómez, Alberto Eugenio Zwier, Timothy S. Pate, Brooks H. Evangelisti, Luca Pérez Cuadrado, Cristobal https://uvadoc.uva.es/handle/10324/80758 2025-12-18T20:06:29Z 2025-01-01T00:00:00Z

The interactions between water and aromatic rings are pervasive across various scientific and technological disciplines, including biochemistry, materials science, and environmental chemistry. In this study, we combine broadband rotational spectroscopy and quantum-chemical calculations to reveal detailed structural and binding motifs in the aggregation of benzene, as the prototypical aromatic molecule, in the presence of a few water molecules. The benzene dimer and trimer structures with up to two water molecules are conclusively identified through isotopic substitution. We observe that the π-stacking interactions are substituted by more favorable CH···π contacts, allowing the insertion of water molecules acting as bridges between aromatic rings. This induces a shortening of the O···O distances for the complexes with two water molecules compared to that of the isolated water dimer. A many-body decomposition analysis of the interaction energy reveals the interactions of water with the aromatic partners through three-body contributions. While in the prototypical hydrogen-bonded pure water clusters this contribution amounts to 20–25% of the total interaction energy, we observe a significant contribution on the order of 10% in the interactions with the benzene rings. These results experimentally rationalize the binding strength of π-systems with water.

2025-01-01T00:00:00Z Steber, Amanda Evangelisti, Luca Lobsiger, Simon Kisiel, Zbigniew Pate, Brooks H. Lesarri Gómez, Alberto Eugenio Pérez Cuadrado, Cristobal https://uvadoc.uva.es/handle/10324/80757 2025-12-18T20:06:30Z 2025-01-01T00:00:00Z

Characterizing the interactions between water and volatile anesthetics at a molecular level is crucial for understanding their mechanisms of action. We employed broadband molecular rotational spectroscopy (CP-FTMW) and extensive isotopic substitution experiments to generate and characterize the stepwise addition of up to four water molecules to the volatile anesthetic sevoflurane, a flexible molecule with multiple binding sites. The substantial amount of isotopic data enabled the conclusive derivation of accurate structural information. The observed structures contain the most stable conformer of the previously identified monomer, with water clusters favorably interacting with the molecule to form an open chain with up to three water molecules. Notably, two isomers were detected for the tetrahydrate, which exhibit a cyclic structure with either a clockwise or anticlockwise orientation, resembling that of the pure water tetramer. The four-water marks a transition where water–water interactions dominate over direct sevoflurane–water interactions driving the assembly of the water network.

2025-01-01T00:00:00Z Jano, Ana De La Fuente Ballesteros, Adrián Martín Gómez, María Teresa Ares Sacristán, Ana María Bernal del Nozal, José https://uvadoc.uva.es/handle/10324/80669 2025-12-16T20:07:42Z 2025-01-01T00:00:00Z

Background: Lipids play essential roles in food systems, and their study through lipidomics offers insights into biochemical processes and issues such as food fraud and adulteration. Among lipid classes, glycerolipids (GLs), particularly triacylglycerols (TAGs), are the most frequently analysed in food-related studies. Results: Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and MALDI mass spec- trometry imaging (MSI) have emerged as powerful tools for lipidomic investigations. While traditionally applied in biological research, their use in food science is expanding to diverse matrices, including oils, dairy, cereals, algae, and meat. In terms of MALDI matrices, 2,5-dihydroxybenzoic acid (DHB) is most commonly used in positive ion mode, whereas 9-aminoacridine (9-AA) is typically employed in negative mode. MALDI-MS has advanced lipid characterization, and MALDI-MSI now enables mapping of lipid spatial distributions, revealing processes such as lipid degradation. Significance: This review underscores the growing utility of MALDI-MS and MALDI-MSI for lipid analysis in food science. We highlight their analytical capabilities, workflows, and limitations, it demonstrates how these tech- niques can enhance understanding of food composition, quality, and authenticity.

2025-01-01T00:00:00Z García Moreno, Gregorio José Coco Cea, Silverio https://uvadoc.uva.es/handle/10324/80445 2025-12-10T20:02:53Z 2025-01-01T00:00:00Z

We investigated the modulation of UV–Vis absorption features and perceived color in hybrid organic/inorganic columnar mesophases obtained by blending a metal-organic triphenylene metallomesogen with bipyridine or phenanthroline metal complexes. This blending results in complementary π-electron donor-acceptor interactions between triphenylene groups and metal-bipyridine/phenanthroline acceptor units through charge-transfer in- teractions. Our approach involved tuning the LUMO energy level of the acceptor molecule, covering a total of 140 acceptor molecules, by varying the metal (Pt or Pd), the aromatic nature of the ligand (bipyridine or phe- nanthroline) and the functionalization of the ligand with common electron-donor or electron-withdrawing functional groups. We employed a combined methodology based on extended tight-binding methods (xTB) and Time-Dependent Density Functional Theory (TD-DFT) to characterize UV–Vis absorption features and perceived color of hybrid organic/inorganic columnar mesophases as influenced by the chemical structure of the acceptor unit.

2025-01-01T00:00:00Z Haque, Shaikh Manirul Kabir, Abuzar Rafatullah, Mohd. Sadique, Zakariya De La Fuente Ballesteros, Adrián https://uvadoc.uva.es/handle/10324/79691 2025-12-18T07:32:06Z 2025-01-01T00:00:00Z

The development of sustainable pharmaceutical analysis is essential to ensure drug safety, efficacy, and envi- ronmental responsibility. Amlodipine (AML) and valsartan (VAL) are widely prescribed antihypertensive agents often used in combination due to their synergistic effects on cardiovascular and renal health. This review pre- sents a comparison of recent analytical methodologies developed for the quantification of AML and VAL in active pharmaceutical ingredients, dosage forms, and biological fluids. The techniques evaluated include ultraviolet- visible (UV–Vis) spectrophotometry, spectrofluorimetry, high-performance liquid chromatography (HPLC), micellar electrokinetic chromatography (MEKC), and ultra-high-performance liquid chromatography (UHPLC). Each method is critically assessed in terms of analytical performance and environmental sustainability, following the twelve principles of green analytical chemistry (GAC). To evaluate the environmental impact and practical applicability of the methods, three complementary assessment tools were applied: the analytical Eco-Scale, the analytical GREEnness metric (AGREE), and the blue applicability grade index (BAGI). The results indicate that while all reviewed techniques are capable of accurately quantifying AML and VAL, simpler methods such as UV–Vis and MEKC show higher green scores, whereas spectrofluorimetry and UHPLC offer greater sensitivity and speed. This work aims to guide researchers in selecting or developing analytical methods that balance perfor- mance, sustainability, and practical implementation in pharmaceutical analysis.

2025-01-01T00:00:00Z De La Fuente Ballesteros, Adrián Ciulu, Marco Haque, Shaikh Manirul Syrgabek, Yerkanat Basaran, Burhan https://uvadoc.uva.es/handle/10324/79690 2025-12-18T08:12:09Z 2025-01-01T00:00:00Z

Honeybee (Apis mellifera) has emerged as a valuable bioindicator for environmental pollution due to its morphological and behavioural traits, wide distribution, short life cycle, high reproductive rate, and ease of domestication. Through their extensive foraging activity, bees interact with multiple environmental compartments. They are increasingly exposed to a wide range of contaminants, including plastic-related compounds. In this work, we examine the potential of honeybees as active samplers of plastic pollution and identify the main exposure pathways. A brief overview of current sampling approaches, sample preparation techniques, and analytical strategies for detecting plastic contaminants is also presented. This study offers practical insights for beekeepers and policymakers to promote more sustainable hive management practices that reduce plastic exposure. Finally, we emphasize the need for harmonized methodologies, expanded geographic monitoring, and interdisciplinary collaboration, alongside the adoption of greener and standardized analytical techniques to improve detection accuracy and mitigate environmental impact.

2025-01-01T00:00:00Z De La Fuente Ballesteros, Adrián Samanidou, Victoria Daryanavard, Seyed Mosayeb Ares Sacristán, Ana María Bernal del Nozal, José https://uvadoc.uva.es/handle/10324/79563 2025-12-17T10:13:10Z 2025-01-01T00:00:00Z

Artificial intelligence (AI) is increasingly present across all phases of analytical chemistry, not only in experimental workflows but also in the way scientific writing is produced, evaluated, and published. This perspective offers a critical reflection on the growing use of AI tools as writing copilots in the field, focusing on novel yet underexplored practices such as literature review support, manuscript drafting, and AI-assisted peer review. While tools like ChatGPT, SciSpace, and Grammarly are becoming commonplace in manuscript preparation, their integration also raises important concerns about authorship transparency, originality, and the homogenization of scientific voice. The article highlights both the opportunities and limitations of these technologies. A comparative analysis is presented to summarize the main strengths, weaknesses, opportunities, and threats associated with AI use in scientific communication. This work advocates for the responsible adoption of these tools, the development of ethical guidelines, and the inclusion of AI training in analytical chemistry curricula. By encouraging the scientific community to reflect on these changes collectively, we expect to ensure that AI enhances, rather than undermines, the critical thinking and creativity that define scientific authorship.

2025-01-01T00:00:00Z Peñas de Frutos, Marconi Nicolás Bartolomé Albistegui, María del Camino García Melchor, Max Espinet Rubio, Pablo https://uvadoc.uva.es/handle/10324/79560 2025-12-17T10:26:03Z 2025-01-01T00:00:00Z

In contrast with the previously reported decelerating effect of added L (L = AsPh3) on the Rf/Pf exchange reaction between [Au(Pf)L] and trans-[Rh(Rf)(CO)L2] (Pf = C6F5; Rf = C6F3Cl2-3,5), the Rf/Cl exchange between [AuClL] and trans-[Rh(Rf)(CO)L2] is accelerated by addition of an excess of L. By combining experimental data and microkinetic modeling, with DFT calculations, the unexpected existence of two cooperative Rf/Cl exchange mechanisms is demonstrated. The opposite kinetic effects of L addition, from negative in the Rf/Pf exchange process, opposing L dissociation in an octahedral rhodium intermediate, to positive in the Rf/Cl exchange, opening an L-catalyzed alternative pathway via tricoordinate gold intermediates, explain the Janus effect of AsPh3. The three transmetalation pathways involve a metal redox-insertion step with accessible activation barrier, producing intermediates with Rh–Au bonds. Whereas our previously reported Rf/Pf exchange implied Rh(I) oxidation by Au(I), the Rf/Cl exchange mechanism involves Au(I) oxidation by Rh(I). Further support is provided by NBO studies, which reveal remarkable electronic donations from the oxidized metal in each case forging the M–M′ covalent interaction in the intermediates yielded by the redox-insertion step.

2025-01-01T00:00:00Z Sánchez Molpeceres, Rodrigo Zhan, Paolo Martín Maroto, Laura Maestro Fernández, Alicia Miguel García, Jesús Ángel Comesaña Gandara, Bibiana Andrés García, José María https://uvadoc.uva.es/handle/10324/79404 2025-12-16T20:01:30Z 2025-01-01T00:00:00Z

We report the design and application of heterogeneous organocatalysts based on polymers of intrinsic microporosity (PIMs) for the asymmetric aza-Henry reaction of N-Boc-protected pyrazolinone ketimines with nitromethane. Two copolymers (PIM-10 and PIM-20) incorporating a flexible isatin-derived monomer were synthesized and postfunctionalized with a quinine-derived thiourea. The resulting materials, PIM-10-TU and PIM-20-TU, exhibited high thermal stability, tailored porosity, and effective enantioselective catalytic performance in batch- and continuous-flow conditions. PIM-10-TU showed superior activity and recyclability, achieving full conversion in 2–4 h and affording β-nitroamine derivatives in up to 87% yield and 85:15 er. Flow experiments enabled gram-scale synthesis with short residence times and a sustained efficiency. The synthetic utility of the chiral aminopyrazolones was demonstrated via derivatization to ureas and thioureas without erosion of the enantiopurity. This study highlights the potential of PIM-supported organocatalysts as robust and recyclable platforms for asymmetric synthesis under sustainable conditions.

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