MetBioCat
ERC Advanced Grant Project

News

Please find below all relevant news regarding our Group.
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One of our last publications at ACIE is getting plenty of attention

09/29/2020
This VIP (Very Important Paper) at Angew. Chem. Int. Ed. shows a very complex chemical reaction run at the living cell for the very first time

This work, published by the beginning of July at Angew. Chem. Int. Ed. and authored by Joan Miguel, María Tomás and José Luis Mascareñas, has been considered as a Very Important Paper by the reviewers.


See some news at:


External link: https://onlinelibrary.wiley.com/toc/15213773/2020/59/40

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Our last review at 'Chemical Society Reviews' is available as accepted manuscript

09/14/2020
So glad to share our revision article is available as Advance Article at Chem. Soc. Rev.

We are starting 2020-2021 academic course and we have good news... our revision publication at Chemical Society Revies journal, entitled "Catalytic addition of C–H bonds across C–C unsaturated systems promoted by iridium(i) and its group IX congeners" and authored by D. Fernández, J. L. Mascareñas and F. López is already on-line.

Abstract:  Transition metal-catalyzed hydrocarbonations of unsaturated substrates have emerged as powerful synthetic tools for increasing molecular complexity in an atom-economical manner. Although this field was traditionally dominated by low valent rhodium and ruthenium catalysts, in recent years, there have been many reports based on the use of iridium complexes. In many cases, these reactions have a different course from those of their rhodium homologs, and even allow performing otherwise inviable transformations. In this review we aim to provide an informative journey, from the early pioneering examples in the field, most of them based on other metals than iridium, to the most recent transformations catalyzed by designed Ir(I) complexes. The review is organized by the type of C–H bond that is activated (with C sp2, sp or sp3), as well as by the C–C unsaturated partner that is used as a hydrocarbonation partner (alkyne, allene or alkene). Importantly, we discuss the mechanistic foundations of the methods highlighting the differences from those previously proposed for processes catalyzed by related metals, particularly those of the same group (Co and Rh).



External link: https://pubs.rsc.org/en/content/articlelanding/2020/CS/D0CS00359J#!divAbstract

Our last paper at 'The Journal of Physical Chemistry Letters' is available as accepted manuscript

08/10/2020
Pleased to announce our most recent J. Phys. Chem. Lett. manuscript has been accepted, and it's already on-line

We are very happy to share here that our research article at J. Phys. Chem. Lett., entitled "Surface-enhanced Raman Scattering Detection of Nucleic Acids exhibiting Sterically Accessible Guanines using Ruthenium-polypyridyl Reagents" and authored by and M. Martínez-Calvo, L. Guerrini, J. Rodríguez, R. A. Álvarez-Puebla and J. L. Mascarenas, has been accepted and it's already available through the journal website.

Abstract: Here, we report the application of surface-enhanced Raman scattering (SERS) spectroscopy as a rapid and practical tool for assessing the formation of coordinative adducts between nucleic acid guanines and ruthenium polypyridyl reagents. The technology provides a practical approach for the wash-free and quick identification of nucleic acid structures exhibiting sterically accessible guanines. This is demonstrated for the detection of a quadruplex-forming sequence present in the promoter region of the c-myc oncogene, which exhibits a non-paired, reactive guanine at a flanking position of the G-quartets.




External link: https://pubs.acs.org/doi/abs/10.1021/acs.jpclett.0c02148

Our last communication to Chem. Eur. J. is already a hot paper

07/16/2020
So glad to share our publication is available as Early view, and also getting lots of attention

We are really happy to annouce our recent accepted article at Chemistry, a European Journal has been highlighted as Hot Paper.
This is entitled "Assembly of a Ternary Metallopeptide Complex at Specific DNA Sites Mediated by an AT‐Hook Adaptor" and authored by S. Learte‐Aymamí, J. Rodríguez, M. E. Vázquez and J. L. Mascareñas.

In this manuscript, we present a nickel(II)‐mediated self‐assembly of a multimeric DNA binder composed of two metal‐chelating peptides derived from a bZIP transcription factor and one short AT‐hook domain equipped with two bipyridine ligands.



...see also: https://chemistry-europe.onlinelibrary.wiley.com/toc/15213765/0/0 (Early view, section Communications/Chemical Biology)



External link: https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.202001277

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Congrats to Felipe, on his successful PhD defense

06/25/2020
Felipe Verdugo was great today at his online PhD defense!

Felipe I. Verdugo Leal is our brand new Doctor in the group, after defending his PhD entitled "Transition metal promoted transformations of alkylidenecyclopropanes".

This PhD work, supervised by Prof. Mascareñas and Dr. López, has received the highest qualification by the jury committee.

Congrats Felipe!!!


External link: https://www.usc.es/ciqus/en/news/ciqus-theses-transition-metal-promoted-transformations-alkylidenecyclopropanes

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One further publication for June, this time in collaboration with P. Del Pino group

06/24/2020
We are very glad to announce our first Cell Rep. Phys. Sci. paper is already published. Take also a look to our cover for this issue no. 6

It's almost middle of 2020 year and we are very happy to share our first publication at the brand-new Cell Reports Physical Science journal, entitled "Core-Shell Palladium/MOF Platforms as Diffusion-Controlled Nanoreactors in Living Cells and Tissue Models" and authored by R. Martínez, C. Carrillo-Carrión, P. Destito, A. Álvarez, M. Tomás , B. Peláz, F. López, J. L. Mascareñas and P. Del Pino.

Summary:
Translating the potential of transition metal catalysis to biological and living environments promises to have a profound impact in chemical biology and biomedicine. A major challenge in the field is the creation of metal-based catalysts that remain active over time. Here, we demonstrate that embedding a reactive metallic core within a microporous metal-organic framework-based cloak preserves the catalytic site from passivation and deactivation, while allowing a suitable diffusion of the reactants. Specifically, we report the fabrication of nanoreactors composed of a palladium nanocube core and a nanometric imidazolate framework, which behave as robust, long-lasting nanoreactors capable of removing propargylic groups from phenol-derived pro-fluorophores in biological milieu and inside living cells. These heterogeneous catalysts can be reused within the same cells, promoting the chemical transformation of recurrent batches of reactants. We also report the assembly of tissue-like 3D spheroids containing the nanoreactors and demonstrate that they can perform the reactions in a repeated manner.




External link: https://www.cell.com/cell-reports-physical-science/fulltext/S2666-3864(20)30071-0#%20

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Another 2020 publication from the group at ACS Catalysis is on-line

06/12/2020
So glad to announce our second ACS Catal. paper for 2020 is already available on-line.

We are very happy to share our last publication at ACS Catalysis journal, entitled "Pd–Catalyzed (3 + 2) Heterocycloadditions between Alkylidenecyclopropanes and Carbonyls: Straightforward Assembly of Highly Substituted Tetrahydrofurans" and authored by F. Verdugo, E. da Concepción, R. Rodiño, M. Calvelo, J. L. Mascareñas and F. López

Abstract:
A Pd catalyst made from a Pd(0) source and a bulky biaryl phosphine ligand promotes highly efficient intramolecular (3 + 2) heterocycloadditions between alkylidenecyclopropanes (ACPs) and carbonyls. The annulations provide a straightfor-ward access to fused polycyclic systems featuring β-methylene tetrahydrofuran moieties. DFT data support a pallada-ene process and shed light on the critical role of hemilabile interactions between the Pd center and the bulky biaryl phosphine. Significantly, these Pd(0) catalysts are also effective for promoting intermolecular formal cycloadditions between ACPs and trifluoromethyl ketones, thus providing for a direct entry to chiral THFs bearing trifluoromethyl–substituted carbons



External link: https://pubs.acs.org/doi/10.1021/acscatal.0c01827

A brand new chembio field paper is on-line, available at Chem. Eur. J.

04/01/2020
Glad to announce another S. Learte's first author publication (two in a row) has been accepted at "Chemistry, a European Journal"

Continuing with the nice results coming out during the beginning of 2020, we are very pleased to share our last publication at Chem. Eur. J., entitled "Assembly of a ternary metallopeptide complex at specific DNA sites mediated by an AT‐Hook adaptor" and authored by S. Learte-Aymamí, J. Rodríguez, E. Vázquez and J. L. Mascareñas.

Abstract:
We describe the nickel(II)‐mediated self‐assembly of a multimeric DNA binder composed by two metal‐chelating peptides derived from a bZIP transcription factor ( brHis 2 ) and one short AT‐hook domain equipped with two bipyridine ligands ( HkBpy 2 ). These peptides reversibly assemble in the presence of Ni(II) ions at selected DNA sequences of 13 base pairs.




External link: https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.202001277

Our last paper at Angew. Chem. Int. Ed. is available as accepted article

03/11/2020
Pleased to announce our most recent ACIE manuscript has been accepted, and it's already on-line

We are very happy to share here that our research article at Angew. Chem. Int. Ed., entitled "Intracellular reactions promoted by bis‐histidine miniproteins stapled with Pd(II) complexes" and authored by J. L. Mascarenas, S. Learte-Aymamí, C. Vidal and A. Gutiérrez-González, has been accepted and it's already available through the journal website.

Abstract: The generation of catalytically active metalloproteins inside living mammalian cells is a major research challenge at the interface between catalysis and cell biology. Herein we demonstrate that basic domains of bZIP transcription factors, mutated to include two histidine residues at i, i+4 positions, react with palladium (II) sources to generate catalytically active, stapled pallado‐miniproteins. The resulting constrained peptides are efficiently internalized into living mammalian cells, where they can perform palladium‐promoted depropargylation reactions, without cellular fixation. Control experiments confirm the requirement of the peptide scaffolding and the palladium staple for attaining the intracellular reactivity.



External link: https://onlinelibrary.wiley.com/doi/10.1002/anie.202002032