Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)

Permanent URI for this collectionhttps://hdl.handle.net/10347/34291

O Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) foi creado por acordo do Consello de Goberno da Universidade de Santiago de Compostela o 10 de febreiro de 2010.

É o primeiro dunha rede de centros de investigación cun novo modelo de organización e funcionamento, que constitúe o elemento fundamental da estratexia de I+D do proxecto CAMPUS VIDA (Campus de Excelencia Internacional, MEC-MICINN, 2009).

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Total Synthesis of Isoriccardin C and Isoriccardin D Based on a Hydroxyl-Directed Palladium-Catalyzed Intramolecular C–H Alkenylation
(American Chemical Society, 2026-04-06) Losada Castro, Pablo; Mascareñas Cid, José Luis; Gulías Costa, Moisés; Universidade de Santiago de Compostela. Departamento de Química Orgánica; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
A concise, nine-step total synthesis of isoriccardin C and isoriccardin D has been developed. The strategy centers on the sequential installation of the four aromatic rings of the backbone by using three key transformations: Suzuki coupling, Wittig olefination, and Ullmann coupling. The pivotal step is a palladium(II)-catalyzed, intramolecular ortho-alkenylation that forges the 18-membered macrocyclic core. This streamlined route enables the total synthesis with minimal reliance on protecting groups, and its modular nature offers a versatile platform for the construction of structural analogues.
Structural Screening of Short Peptide Amphiphiles with Autocatalytic Self-Replication
(Wiley, 2025-01-09) Turcan, Ion; Insua López, Ignacio; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
There is great interest in developing small synthetic molecules that imitate some of the functions and behaviour of living beings. Here, we describe the structural screening of peptide amphiphiles with autocatalytic self-replication, which mimics the perpetuation mechanisms of living matter. Our design uses two reactive precursors to generate self-assembling peptide amphiphiles, which form micelles that catalyse their own synthesis. A collection of precursors with varying sizes was screened combinatorially, revealing a minimal tripeptide amphiphile required to trigger autocatalytic self-replication. These results contribute to the structural simplification of synthetic supramolecular monomers with life-like behaviour.
Emergent properties of supramolecular peptide assemblies
(Royal Society of Chemistry, 2026) Vila García, Álvaro; González Domínguez, Sela; Insua López, Ignacio; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
The self-assembly of supramolecular monomers can change their chemical properties and produce emergent functions that are absent in their dispersed state. In this review article, we describe structural and functional material properties emerging from the self-assembly of peptides, which are based on interactions between neighbouring monomers and the supramolecular environments they create. The non-covalent cooperativity of peptides is here discussed in terms of emergent properties like catalysis, chiral amplification, hierarchical self-assembly and life-like function. These collective effects are rationalised by the monomer packing structure and reactive group proximity, providing a perspective of self-assembling peptide designs and supramolecular material applications, including our own contribution to this topic.
Photoredox Unmasking of Aromatic CH Bonds in Living Environments Enabled by Thianthrenium Salts
(American Chemical Society, 2026-02-07) Mato, Mauro; Rivas Saborido, Adrián; Casas Pais, Alba; Tomás Gamasa, María; Mascareñas Cid, José Luis; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
Prodrug strategies traditionally rely on masking polar functional groups of bioactive molecules with protecting units that can be removed by specific stimuli in biological settings. Here, we introduce an alternative uncaging approach that bypasses the need for heteroatom handles, based on reversible masking of aromatic C–H bonds with thianthrenium groups. Unmasking is triggered by low-energy photoredox activation, which generates aryl radicals that are rapidly reduced by endogenous bioreductants to restore the native C–H bond. Beyond establishing the feasibility of photoredox radical chemistry in living cells, we demonstrate a proof-of-concept application of this strategy for the modulation of activity of antifungal agents
Photolysis of CO₂ carbamate for hydrocarboxylation reactions
(American Chemical Society, 2026-01-12) Azzi, Emanuele; Rodríguez Martínez, Manuel; Kolusu, Sai Rohini Narayanan; Scarfiello, Jacopo; Varela Carrete, Jesús Ángel; Nappi, Manuel; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
The conversion of carbon dioxide into value-added products has emerged as an alternative method to achieve net-zero emissions. While technologies that transform CO2 into fuels and chemical feedstocks have made great strides, the direct use of CO2 as a C1 synthon for the formation of new carbon–carbon bonds remains a critical challenge. Herein, we present a new catalytic CO2 activation mode for hydrocarboxylation reactions. Key to this methodology is the formation of a CO2 carbamate with a phenothiazine catalyst, which sets the required trigonal geometry for the release of CO2•– via photolysis upon absorption of visible light. The polarity-reversed CO2•– is employed in the hydrocarboxylation reactions of alkenes and heterocycles. This protocol is distinguished by its mild reaction conditions, wide substrate scope and broad applicability, even in the context of pharmaceutical cores. Our chemistry can also be utilized for the synthesis of carbon-13 labeled spirolactones using 13CO2. Mechanistic experiments support the photolysis of the CO2 carbamate as the main productive pathway under our optimized reaction conditions
Multi-omics reveals wastewater sludge bacteria with genomic potential to degrade poly(ethylene terephthalate)
(Elsevier, 2026-03) Vijande, Carlota; Balboa Méndez, Sabela; Lazzari, Massimo; Lema Rodicio, Juan Manuel; Pabst, Martin; Universidade de Santiago de Compostela. Departamento de Enxeñaría Química; Universidade de Santiago de Compostela. Departamento de Microbioloxía e Parasitoloxía; Universidade de Santiago de Compostela. Departamento de Química Física; Universidade de Santiago de Compostela. Centro Interdisciplinar de Investigación en Tecnoloxías Ambientais (CRETUS); Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
Plastic pollution is a growing concern, especially poly(ethylene terephthalate) (PET), one of the most produced plastic polymers. Although several microorganisms capable of degrading PET have been identified, little is known about those present in wastewater treatment plants (WWTPs). This study explores their ability to degrade PET and the enzymes involved. Activated sludge from two facilities—one urban WWTP and one industrial WWTP—was cultivated with PET of different crystallinities. The inoculum source primarily determined differences in microbial community composition. Metagenomics revealed more than 300 genes homologous to PET-degrading enzymes in all biofilms; however, metaproteomics confirmed expression of only a few of these enzymes in industrial WWTP-derived biofilms. This inoculum demonstrated the ability to degrade PET breakdown products within 24 h. In addition, FTIR analysis revealed initial signs of surface alteration. In conclusion, this study reveals the presence of microorganisms in industrial wastewater treatment sludge that possess the genetic potential to degrade PET.
Enantioselective synthesis of allylic boronates bearing a stereodefined (E)-alkenyl chloride by Cu-catalyzed borylation of allylic gem-dichlorides
(Royal Society of Chemistry, 2026-02-24) Chaves Pouso, Andrea; Álvarez Constantino, Andrés Manuel; Gómez Roibás, Patricia; Fañanás-Mastral, Martín; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
Chiral α,γ-substituted allyl boron reagents are valuable tools in organic synthesis. However, asymmetric catalytic strategies for synthesising this type of compound bearing a stereodefined alkenyl chloride are underdeveloped. Here we report a copper-catalyzed enantioselective borylation of allylic gem-dichlorides that provides optically active allylic boronates bearing an (E)-configured alkenyl chloride with high levels of enantioselectivity and E-selectivity. These enantioenriched allyl boronates serve as versatile building blocks for different stereospecific reactions, including their conversion into chiral propargyl alcohols and the diastereoselective addition to ketones to afford enantioenriched allylic chlorohydrins. DFT calculations provide mechanistic insight, revealing key noncovalent interactions that rationalize the observed stereocontrol. This study expands the synthetic utility of allylic boronates and offers a mechanistically informed approach to asymmetric catalysis involving gem-dichloride substrates.
3D self-assembly of cyclic peptides into multilayered nanosheets
(Royal Society of Chemistry, 2026-02-26) Díaz Arias, Sandra Natalia; Sánchez Fernández, Adrián; Granja Guillán, Juan Ramón; Insua López, Ignacio; Montenegro García, Javier; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS); Universidade de Santiago de Compostela. Departamento de Enxeñaría Química; Universidade de Santiago de Compostela. Departamento de Farmacoloxía, Farmacia e Tecnoloxía Farmacéutica
The hierarchical self-assembly of three-dimensional (3D) supramolecular materials presents a significant challenge in molecular design. This process requires monomers with specific packing geometries and orthogonal contacts to enable multidimensional elongation. Here, we describe a new cyclic peptide design that allows hierarchical self-assembly in all three spatial dimensions to produce nanosheets composed of ordered nanotube layers. The uniformity of the nanosheet aspect ratio and thickness is consistent with the high packing order of the monomers observed in this 3D assembly.
Combined In-Solution and On-Surface Synthesis of a Fully Fused Cross-Shaped Phthalocyanine Pentamer
(Wiley, 2026-03-09) Mateo de Doni, Luis Manuel; Hung, Tzu-Chao; Rank, Andreas; Spachtholz, Raffael; Giselbrecht, Felix; Schön, Jonas; Gross, Leo; Repp, Jascha; Peña Gil, Diego; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
Phthalocyanines (Pcs) are a class of technologically relevant tetrapyrrolic macrocycles that offer rich photophysical properties as well as excellent tunability by means of chemical functionalization. Among such functionalization strategies, the synthesis of multinuclear, fully fused Pcs – adjacent macrocycles seamlessly fused through a shared aromatic ring into a continuous π-system – is particularly appealing for the preparation of new, exotic, atomically precise carbon frameworks. However, the notoriously low solubility of Pcs typically impedes the synthesis of oligomers beyond trimers. In addition, the positional control for specific units in large low-symmetry frameworks is particularly challenging. In this work, taking advantage of the benefits of on-surface synthesis under ultra-high vacuum (UHV) conditions, we present a strategy that allows the on-surface synthesis of cross-shaped Pc pentamers. This pentamer, which bears two different metal ions with pre-defined positional control, shows a small transport gap of 1.15 eV on Au(111).
Accessing molecular complexity from methane and other GaseousAlkanes via photocatalytic cascade cyclization
(Wiley, 2026-01-28) Nair, Akshay M.; Malga Díaz, José Manuel; Martínez Acevedo, Nicolás; Fañanás-Mastral, Martín; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
The direct transformation of simple and abun-dant feedstocks into structurally complex moleculesremains a central challenge in modern organic synthesis.Herein, we report a method for the oxidative cascadecyclization of N-aryl and N-benzoyl acrylamide deriva-tives, promoted by methane and other gaseous alkanes.This transformation is enabled by a readily available ironcatalyst in combination with N-ﬂuorobenzenesulfonimide(NFSI) as the oxidant, proceeding under mild conditionsto afford a diverse array of N-heterocyclic frameworks inhigh yields. Late-stage functionalization studies highlightthe utility of methane in the synthesis of biologicallyrelevant scaffolds. Moreover, the Fe/NFSI system facili-tates a radical sampling regime that enables the selectivefunctionalization of less reactive primary C─H bonds.Overall, this work establishes a sustainable and versatileplatform for constructing molecular complexity directlyfrom gaseous alkanes.
Tuning the Twist by Molecular Design: A New Strategy for Hexabenzocoronene‐Containing Helical Twistacene
(Wiley, 2026-02-15) Mora Fuentes, Juan Pedro; Villar Castro, Daniel; Barbosa de Bessa, J. Francisco; Aranda Ruiz, Daniel; Hampel, Frank; Pérez Meirás, María Dolores; Pérez Ojeda, M. Eugenia; Peña Gil, Diego; Hirsch, Andreas; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS); Universidade de Santiago de Compostela. Departamento de Química Orgánica
In this work, we present an efficient synthetic methodology that allows precise and selective control on the C–C bonds during the Scholl reaction. The first ever described hexabenzocoronene (HBC)-containing helical twistacene NG2 has been obtained with very high yield and practically no need for purification, starting from a helical-twisted hexacene NG1. X-ray analysis reveals an end-to-end twist angle, from approximately 145° in NG1 to 132° in NG2. This approach has provided access to nanographenes (NGs) with improved properties compared to their planar analogues, in particular, enhanced solubility and high stability. In addition, they exhibit interesting redox properties, which, together with their high molar absorbance and optimal energy levels, highlight their potential as new organic semiconductor materials for emerging photovoltaic and electronic technologies.
Correlation between Microstructural and Magnetic Properties of Epitaxial YIG Films by Pulsed Laser Deposition
(ACS Publications, 2026-02-10) Costa, José Diogo; Adelmann, Christoph; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
In this study, we investigate the relationships among film growth conditions, crystalline microstructure, and magnetic properties of epitaxial yttrium iron garnet (Y3Fe5O12, YIG) thin films, deposited on gallium gadolinium garnet (Ga3Gd5O12, GGG). A direct correlation was observed between the residual epitaxial strain, bulk magnetic properties like effective magnetization and magnetic damping, and the performance of spin-wave transmission devices based on these films. This correlation offers a pathway for a simplified, rapid assessment of YIG film quality, avoiding the need for complex time-consuming characterization techniques. In addition, we report a comprehensive investigation into the influence of pulsed-laser deposition parameters, including deposition temperature, pressure, laser fluence, frequency, and annealing conditions. Through systematic deposition optimization, state-of-the-art YIG films exhibiting ultralow magnetic damping could be obtained, which is critical for high-performance spintronic applications
Novel antimicrobial self-assembled cyclic peptide nanotubes containing (1R,3S,4R,5R)-3-amino-4,5-dihydroxycyclohexane-1-carboxylic acid, a new building block for developing mimetics of saccharide–peptide hybrids
(Royal Society of Chemistry, 2026) González Freire, Eva; Vilela Picos, Marcos; Prado López, Verónica; Pérez Estévez, Antonio; Seoane Prado, Rafael; Amorín López, Manuel; González Bello, Concepción; Granja Guillán, Juan Ramón; Universidade de Santiago de Compostela. Departamento de Química Orgánica; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS); Universidade de Santiago de Compostela. Departamento de Microbioloxía e Parasitoloxía
A new class of supramolecular antimicrobials based on D,L-cyclic peptides containing a dihydroxylated-γ-residue, which was designed to mimic the saccharide component present in certain carbohydrate–peptide hybrids, is described. The fully protected amino acid was prepared from shikimic acid and incorporated into clickable amphipathic cyclic peptides. The resulting peptides self-assemble into nanotubes that interact with bacterial membranes, ultimately causing cell death. Notably, the incorporation of this new residue not only retains antimicrobial activity but also significantly reduces toxicity in mammalian cells, thereby broadening the therapeutic window of these peptides.
Inverse Conformational Selection in Lipid–Protein Binding
(American Chemical Society, 2021-08-16) Bacle, Amélie; García Fandiño, Rebeca; Ferreira, Tiago M.; Piñeiro Guillén, Ángel; Virtanen, Salla I.; Universidade de Santiago de Compostela. Departamento de Química Física; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS); Universidade de Santiago de Compostela. Departamento de Física Aplicada
Interest in lipid interactions with proteins and other biomolecules is emerging not only in fundamental biochemistry but also in the field of nanobiotechnology where lipids are commonly used, for example, in carriers of mRNA vaccines. The outward-facing components of cellular membranes and lipid nanoparticles, the lipid headgroups, regulate membrane interactions with approaching substances, such as proteins, drugs, RNA, or viruses. Because lipid headgroup conformational ensembles have not been experimentally determined in physiologically relevant conditions, an essential question about their interactions with other biomolecules remains unanswered: Do headgroups exchange between a few rigid structures, or fluctuate freely across a practically continuous spectrum of conformations? Here, we combine solid-state NMR experiments and molecular dynamics simulations from the NMRlipids Project to resolve the conformational ensembles of headgroups of four key lipid types in various biologically relevant conditions. We find that lipid headgroups sample a wide range of overlapping conformations in both neutral and charged cellular membranes, and that differences in the headgroup chemistry manifest only in probability distributions of conformations. Furthermore, the analysis of 894 protein-bound lipid structures from the Protein Data Bank suggests that lipids can bind to proteins in a wide range of conformations, which are not limited by the headgroup chemistry. We propose that lipids can select a suitable headgroup conformation from the wide range available to them to fit the various binding sites in proteins. The proposed inverse conformational selection model will extend also to lipid binding to targets other than proteins, such as drugs, RNA, and viruses.
Dynamic Covalent Boronate Chemistry for In Situ Formation, Interfacial Stabilization, and Cytomimetic Optimization of Coacervates
(American Chemical Society, 2026-02-27) Delgado González, Bruno; García Abuin, Lucas; Jiménez López, Celia; Fernández Megía, Eduardo; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
Bioinspired synthetic cells are rapidly transforming the way we interrogate the principles of cellular life and the development of bioengineering and medical applications. However, despite significant progress in modeling cell-like behavior, material engineering remains a time-consuming and often behind-the-scenes endeavor when optimizing cytomimetic functions. Here, we describe how dynamic covalent chemistry can be used to bypass this bottleneck using membranized coacervate microdroplets (MCM) as synthetic cell models. Specifically, the potential of dynamic covalent boronate chemistry for the in situ formation, interfacial stabilization, and adaptive cytomimetic optimization of MCM is presented. Simultaneous addition of cationic and anionic catechols to a polymeric boronic acid (BA) generates dynamic zwitterionic polyboronates that spontaneously phase separate into microdroplets, which can then be interfacially stabilized as MCM with a BA-functionalized block copolymer. The cytomimetic properties, membranization, internal dynamics, and enzymatic activity within the MCM can be modulated in situ using dynamic covalent libraries to fine-tune material properties (either by adjusting the charge ratio between oppositely charged catechols, varying the catechol-to-BA ratio, or introducing auxiliary catechol dopants) without the need to synthesize, isolate, purify, and characterize new polymeric materials. Application of this technology to other catechols, multivalent BA, and synthetic cell architectures holds promise for optimizing diverse biomimetic functions and providing programmable synthetic cells with emerging properties
Computational insights into the chemical reaction networks of C3H6O3, C3H7O3 and C2H5O2: implications for the interstellar medium
(Royal Society of Chemistry, 2025-09-17) Lema Saavedra, Anxo; Fernández Ramos, Antonio; Martínez Núñez, Emilio; Universidade de Santiago de Compostela. Departamento de Química Física; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
The formation of complex organic molecules (COMs) in the interstellar medium (ISM) is central to astrochemistry and prebiotic chemistry, as these species may act as precursors to biomolecules essential for life. Among COMs, glyceraldehyde (HOCH2CH(OH)C(O)H, GCA) has attracted attention as a potential building block in early biochemical pathways. Although GCA has not yet been detected in the ISM, the presence of structurally related compounds in various astronomical environments suggests that it may form under interstellar conditions. In this study, we employed the automated reaction discovery tool AutoMeKin to systematically explore the gas-phase chemical reaction networks (CRNs) of C3H6O3 (GCA), C3H7O3 (a hydrogenated analog), and C2H5O2. Reaction pathways were characterized at the oB97XD/Def2-TZVPP level of theory, and rate coefficients for key processes were computed using the competitive canonical unified statistical (CCUS) model, which accounts for multiple dynamic bottlenecks. Our analysis revealed several barrierless pathways leading to GCA or to GCA and a leaving group. Notably, the reaction between glyoxal (HCOHCO) and the HOCHCH2OH radical, though neither has yet been detected in the ISM, was found to efficiently produce GCA and a formyl radical, with rate coefficients on the order of 5.4–7.9 10 10 cm3 molecule 1 s 1 across the 10–100 K temperature range. However, aside from the aforementioned exception, most GCA formation channels result in highly vibrationally excited intermediates that are more likely to undergo rapid unimolecular decomposition than to be stabilized by radiative emission under typical ISM conditions. These results suggest that while gas-phase GCA formation is chemically feasible, it is likely transient and difficult to detect directly. In contrast, alternative products such as formaldehyde, glycolaldehyde, and (Z)-ethene-1,2-diol dominate many pathways and align better with current astronomical observations. This work provides detailed mechanistic and kinetic insights that enhance astrochemical modeling and advance our understanding of molecular complexity in star-forming environments. Furthermore, it highlights the utility of automated CRN exploration for uncovering viable synthetic routes to prebiotic molecules in space
Antimicrobial peptides at (lipid) interfaces: Insights from monolayer models
(Elsevier, 2026) Antelo Riveiro, Paula; García Fandiño, Rebeca; Piñeiro Guillén, Ángel; Universidade de Santiago de Compostela. Departamento de Química Orgánica; Universidade de Santiago de Compostela. Departamento de Física Aplicada; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
Antimicrobial peptides (AMPs) are key effectors of innate immunity that, beyond their canonical activity, exhibit promising therapeutic potential against cancer and cellular senescence. Their efficacy relies on selective membrane disruption driven by specific lipid signatures, yet quantifying these interactions in complex bilayer systems remains challenging. Lipid monolayers serve as powerful reductionist models to isolate the physicochemical determinants of this selectivity, effectively mimicking the outer leaflet of bacterial, cancerous, or senescent membranes. This review provides a critical analysis of how lipid composition, packing density, and phase behavior modulate AMP adsorption and insertion. We systematically integrate thermodynamic profiling (surface pressure, compressibility, mixing energy) with advanced structural and morphological characterization. Special emphasis is placed on how spectroscopic techniques (IRRAS, GIXD, SFG) and real-time microscopy (BAM, fluorescence, AFM) resolve peptide orientation, secondary structure induction, and lipid domain remodeling at the mesoscale. These experimental observables are bridged with Molecular Dynamics (MD) simulations, establishing a feedback loop between macroscopic measurements and atomistic resolution. By defining the advantages and limitations of monolayer models relative to vesicles and bilayers, we outline a rational framework for leveraging interfacial insights in the design of next-generation peptide therapeutics and nanobiotechnological applications.
Gallic Acid–Triethylene Glycol Aptadendrimers Synthesis, Biophysical Characterization and Cellular Evaluation
(MDPI, 2022-11-14) Miranda, André; López-Blanco, Roi; Fernández Megía, Eduardo; Cruz, Carla; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
Herein, we describe the synthesis of an aptadendrimer by covalent bioconjugation of a gallic acid–triethylene glycol (GATG) dendrimer with the G-quadruplex (G4) AT11 aptamer (a modified Academic Editor: Wouter L. J. Hinrichs Received: 28 September 2022 Accepted: 11 November 2022 Published: 14 November 2022 Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. Copyright: © 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). version of AS1411) at the surface. We evaluated the loading and interaction of an acridine orange ligand, termed C8, that acts as an anticancer drug and binder/stabilizer of the G4 structure of AT11. Dynamic light scattering experiments demonstrated that the aptadendrimer was approximately 3.1 nm in diameter. Both steady-state and time-resolved fluorescence anisotropy evidenced the interaction between the aptadendrimer and C8. Additionally, we demonstrated that the iodine atom of the C8 ligand acts as an effective intramolecular quencher in solution, while upon complexation with the aptadendrimer, it adopts a more extended conformation. Docking studies support this conclusion. Release experiments show a delivery of C8 after 4 h. The aptadendrimers tend to localize in the cytoplasm of various cell lines studied as demonstrated by confocal microscopy. The internalization of the aptadendrimers is not nucleolin-mediated or by passive diffusion, but via endocytosis. MTT studies with prostate cancer cells and non-malignant cells evidenced high cytotoxicity mainly due to the C8 ligand. The rapid internalization of the aptadendrimers and the f luorescence properties make them attractive for the development of potential nanocarriers.
POM-Based Water Splitting Catalyst Under Acid Conditions Driven by Its Assembly on Carbon Nanotubes
(Wiley, 2025-11-26) Quirós Díez, Eugenia Pilar; Guillén Soler, Melanie; Herreros Lucas, Carlos; López Moreno, Alejandro; Vila Fungueiriño, José Manuel; Llamas Saiz, Antonio Luis; Strutyński, Karol; Melle Franco, Manuel; Giménez López, María del Carmen; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS); Universidade de Santiago de Compostela. Departamento de Química Física
Development of efficient and stable bifunctional electrocatalysts for water electrolysis under acidic conditions is essential for sustainable hydrogen production. A novel vanadium polyoxometalate (POM)-based material, Na4(H2O)12[(CH2OH)3CNH3]2[V10O28]·4H2O (1) is presented, incorporating non-innocent cations and whose electrocatalytic activity can be switched from the production of oxygen to hydrogen through its assembly on carbon nanotubes (CNT). A physical mixture (1/CNT) shows remarkable oxygen evolution reaction (OER) activity, with an overpotential of 0.34 V at 10 mA cm−2, outperforming commercial IrO2 (0.45 V) and approaching Ir/C (0.31 V), with 80% Faradaic efficiency. In contrast, directed assembly (1@CNT) unlocks TRIS ⁺= [(CH2OH)3CNH3]⁺ groups functionality, enabling high hydrogen evolution reaction (HER) efficiency, with an onset potential of −0.07 V, close to Pt/C, and 94% Faradaic efficiency. Mechanistic studies, strongly supported by in-operando confocal microscopy and theoretical calculations, reveal that the modulation of crystal interactions and the local microenvironment is key to orchestrating the OER/HER tuning. OER is proposed to proceed via an alcohol oxidation reaction (AOR), while HER benefits from TRIS⁺ moieties acting as a “proton sponge”. This work provides a compelling approach for rational design of bifunctional molecular electrocatalysts based on earth-abundant elements and controlled nanoassembly, with clear relevance for advancing green hydrogen production technologies.
2D Assemblies Based on a Tetraphenylethylene D,L-Cyclic Peptide Scaffold
(Wiley and Gesellschaft Deutscher Chemiker, 2025-11-10) Bayón Fernández, Alfonso; Torrón Celada, Alba; Méndez Ardoy, Alejandro; Coste, Maëva; Delgado Gestoso, David; Ulrich, Sébastien; Granja Guillán, Juan Ramón; Montenegro García, Javier; Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS)
Two dimensional (2D) materials and aggregation-induced emission (AIE) fluorophores have recently gained attention due to their unique properties and application potential. However, the combination of AIE probes into 2D self-assembled systems under nanometric control remains elusive due to the sensitivity of supramolecular assemblies to subtle changes in the monomer structure. Herein, we present a new scaffold based on four nanotube-forming cyclic peptide (CP) units attached to a tetraphenylethene (TPE) core whose pH-dependent self-assembly results in light-emitting 2D nanosheets. An oxime bond connection was exploited to synthesize a discrete library of tetrakis-(cyclopeptide) tetraphenylethene monomers that self-assemble into 2D macrotubular nanoarrays under the suitable external stimulus. This new tetrameric CP motif tolerates a broad range of molecular modifications, both on the peptide backbone and TPE core, without compromising the integrity of the 2D self-assembly. We also discovered that adjusting the molecular structure of the TPE aromatic core enabled precise height control of the supramolecular nanosheets. The alignment of the histidine residues within neighboring CPs allowed the application of 2D nanoarchitectures as enzyme mimics with esterase activity. The excellent tolerance to molecular diversity in both the external CP moiety and the internal aromatic AIE core, invites the design of new functional 2D supramolecular materials.

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