Molecular Recognition and Supramolecular Chemistry
A new line of research has been initiated by our research group at the institute, aimed at developing new chiral receptors of cations and peptidomimetics as simple molecular models for the study and understanding of non-covalent interactions.
The Molecular Recognition and Supramolecular Chemistry group profile page on Digital.CSIC.
These weak non-covalent interactions are responsible for the binding between receptor and substrate, and for the folding of organic molecules. This in turn gives rise to the different functions of biological molecules.
The knowledge and scope of these non-covalent interactions are essential for the development of diverse areas of knowledge, such as Biology, Chemistry, Medicine, Materials Science, etc.
New Chiral Cation Receptors
Numerous biological and chemical processes are based on chiral recognition, such as: enzyme-substrate interactions, immune responses, mechanisms of action of drugs, storage and retrieval of genetic information, and asymmetric catalysis are some of the most relevant examples.
Quantification of Non-Covalent Interaction
Using the design of the second generation of chiral cation receptors, we were able to synthesize several receptors that present good levels of chiral discrimination. Specifically, the receptor that incorporates 2,6-dicarbonyl-pyridine as spacer A and oxybis(ethanediil) as spacer B, is capable of...
Chiral Recognition Reinforcement
Co-operation is one of the most fundamental concepts in molecular recognition and supramolecular self-assemblies. It explains how the behaviour of a system as a whole is different from what is expected of each of the individual isolated interactions. This is a fundamental phenomenon in the...
Peptide-Mimetic Design and Synthesis
The main objective of mimetic peptides is to imitate the peptide structure by means of models that have the functional groups spatially arranged in a controlled way. As they have similar characteristics to their natural counterparts, they have been used to replace substrates (peptides) of...
PhD & MSc. Thesis
Receptores Quirales de Cationes y Foldámeros como Modelos para el Estudio del Plegamiento Molecular y sus Consecuencias
Diseño y Síntesis de Nuevas Unidades de Aminoácidos no Naturales con Aplicación en la Formación de Péptidos Miméticos (DEA)
Uso de la Reacción de Nicholas Intermolecular y Metátesis de Cierre de Anillos en la Formación de Éteres Cíclicos con Alto Grado de Sustitución
Uso de la Reacción de Nicholas Intermolecular y Metátesis de Cierre de Anillos en la Formación de Éteres Cíclicos con Alto Grado de Sustitución (DEA)
Aplicación de la Reacción de Nicholas en la Síntesis de Éteres Cíclicos
Diseño, Síntesis y Estudio de Nuevos Receptores Quirales de Cationes (DEA)
Nuevos Receptores Quirales de Cationes: Diseño y Síntesis (TFM)
Reacción de Nicholas Intramolecular Estereoselectiva empleando Epóxidos como Nucleófilos (DEA)
Del Reconocimiento Molecular a la Organocatálisis: La unidad de Tetrahidropirano como Motivo Estructural Privilegiado
Síntesis de Éteres Cíclicos a Través de Ciclaciones en Cascada de Epóxidos (DEA)
MAC-INTERREG MIMAR+ "Seguimiento, control y mitigación de proliferaciones de organismos marinos asociadas a perturbaciones humanas y cambio climático en la Región Macaronésica"
Con MIMAR+ se consolidan y expanden los avances en el conocimiento de MIMAR, pretendiendo agrupar a los agentes interesados en toda la región bajo la cobertura de un…
Valorization of a marine natural product from the Canary Islands. Preformulation and in vivo proof of concept of the norzoanthamine potential for the treatment of cartilage disorders
Asignación Estereoquímica de Moléculas Orgánicas Utilizando Métodos Computacionales y RMN
Dr. Antonio Hernández Daranas
- 19 January 2021
- 17 July 2020
- 22 June 2020
- 20 December 2018
- 20 September 2018
Efficient synthesis of benzocyclotrimer analogues by Negishi cross-coupling and intramolecular nucleophilic substitution
We report a new and efficient synthetic strategy that allows access to flexible and functionalized benzocyclotrimers under mild conditions and in few steps. The Negishi cross-coupling reaction was used for the C-C bond formation, whereas intramolecular O-alkylations provided the oxepane rings.
Borges-González, Jorge; Martín, Tomás
Tetrahydropyran-based hybrid dipeptides as asymmetric catalysts for michael addition of Aldehydes to ß-Nitrostyrenes
A new series of hybrid dipeptide‐like organocatalysts based on pyranoid ϵ‐ or ζ‐amino acids and proline have been prepared for the asymmetric Michael addition of aldehydes to β‐nitrostyrenes. The reaction proceeds under mild conditions to afford a wide range of γ‐nitroaldehydes with up to 98% yield and up to 96% ee. These dipeptides are bifunctional organocatalysts, with a proline at the N‐terminus and a carboxylic acid at the C‐terminus. The tetrahydropyran unit embedded in the ϵ‐ or ζ‐amino acid induces a well‐defined conformation that is responsible for the catalysis. These dipeptides represent a new type of organocatalyst with a large number of possibilities to modulate their reactivity and selectivity.
Borges-González, Jorge; Feher Voelger, Andrés; Pinacho Crisóstomo, Fernando R.; Quintana Morales, Ezequiel; Martín, Tomás
Epoxide-opening cascades triggered by a Nicholas reaction: Total synthesis of teurilene
Natural inspiration: Based on the biosynthesis of squalene‐derived polyethers, a total synthesis of teurilene is described. The carbocation formation in the Nicholas reaction serves to control the initiation of a polyepoxide ring‐opening cascade. The three furan rings present in teurilene were obtained in excellent yield in one step. Boc=tert‐butoxycarbonyl, TMS=trimethylsilyl.
Rodríguez-López, Julio; Pinacho Crisóstomo, Fernando R.; Ortega, Nuria; López Rodríguez, Matías; Martín, Víctor S.; Martín, Tomás
Application of isothermal titration calorimetry as a tool to study natural product interactions
Over the past twenty-five years, isothermal titration calorimetry (ITC) has become a potent tool for the study a great variety of molecular interactions. This technique is able to provide a complete thermodynamic profile of an interaction process in a single experiment, with a series of advantages in comparison to other comparable techniques, such as less amount of sample or no need of chemical modification or labelling. It is thus not surprising that ITC has been applied to study the manifold types of interactions of natural products to get new insights into the molecular key factors implied in the complexation process of this type of compounds. This review provides an overview over the applications of ITC as a potent tool to investigate interactions of natural products with proteins, nucleic acids, oligosaccharides, and other types of receptors. The examples have been selected depending on the impact that this technique had during the investigation and revision of the interactions involved in the bioactivity of a compound, lead optimization or technical applications.
Callies, Oliver; Hernández Daranas, Antonio
Towards a Structural Basis for the Relationship Between Blood Group and the Severity of El Tor Cholera
It has long been known that people with blood group O are more severely affected by El Tor cholera than those with blood groups A or B. Microcalorimetry and NMR spectroscopy are used to evaluate the ability of the B‐subunits of cholera toxin and E. coli heat‐labile toxin to bind to selected blood group oligosaccharides.
Mandal, Pintu K.; Branson, Thomas R.; Hayes, Edward D.; Ross, James F.; Gavín, José A.; Hernández Daranas, Antonio; Turnbull, W. Bruce
Combining the Power of J Coupling and DP4 Analysis on Stereochemical Assignments: The J-DP4 Methods
A systematic study to include J couplings into DP4 formalism (J-DP4) led to the development of three alternative strategies. The dJ-DP4 (direct) approach involves a new DP4-like equation including an additional probability term given by J. The iJ-DP4 (indirect) approach explores the original DP4 method with a restricted conformational search. Despite both strategies performing better than DP4, their combined use (iJ/dJ-DP4) provided the best results, with a 2.5-fold performance improvement at similar or lower computational cost.
Grimblat, Nicolás; Gavín, José A.; Hernández Daranas, Antonio; Sarotti, Ariel M.