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Annual Report 2022

Research Groups

Researchers at ICMAB in 2022 are organized in 17 Research Groups, that are grouped forming 9 Research Units. At the same time, each researcher can belong to one or two reserach lines (of the five there are). Discover in this site the main achievements and highlights of each research group.

  • ACNM

    The activity of the group during 2022 has been focus of different aspects of the application of transition Metal oxides (TMOs) in spintronics.
    On one side we have continued our work in the preparation and optimization of TMOs thin films and heterostructures aimed to spintronic applications. On the other hand, we have deepened our studies of interfaces with local techniques and spin to charge conversion processes in TMOs/normal metal (NM) heterostructures, that are fundamental for the advancement of spintronics.

    HIGHLIGHTS
    • Suppression of spin rectification effects in spin pumping experiments
      Sergi Martin‐Rio, Carlos Frontera, Alberto Pomar, Lluis Balcells & Benjamin Martinez
      Sci Rep 12, 224 (2022)
      DOI: https://doi.org/10.1038/s41598-021-04319-z
    • Spin to charge conversion in chemically deposited epitaxial La0.9MnO3 thin films capped with Pt
      Sergi Martin-Rio, Alberto Pomar, Carlos Frontera, Hailin Wang, Ramón Manzorro, César Magén, Lluis Balcells, Narcis Mestres and Benjamin Martinez
      J. Mater. Chem. C 10, 5914 (2022)
      DOI: 10.1039/d2tc00048b
    • Optimization of the Growth Process of Double Perovskite Pr2−δNi1−xMn1+xO6−y Epitaxial Thin Films by RF Sputtering
      Monica Bernal-Salamanca, Lluis Balcells, Zorica Konstantinovic ́, Alberto Pomar, Benjamín Martínez and Carlos Frontera
      Materials 15. 5046 (2022)
      DOI: https://doi.org/10.3390/ma15145046
    • Interfacial Magnetic Features of La2CoMnO6/Pt Bilayers Studied by Using Spin Hall Magnetoresistance.
      Sergi Martín-Rio, Carlos Frontera, Juan M. Gómez-Pérez, Montserrat X. Aguilar-Pujol, Sara Catalano, Jaume Gázquez, Fèlix Casanova, Lluis Balcells, Alberto Pomar and Benjamin Martinez
      Adv. Mater. Interfaces. 9, 2201171 (2022)
      DOI: 10.1002/admi.202201171
    • X-ray Absorption Spectroscopy Study of Thickness Effects on the Structural and Magnetic Properties of Pr2−δNi1−xMn1+xO6−y Double Perovskite Thin Films
      Mónica Bernal-Salamanca, Javier Herrero-Martín, Zorica Konstantinović, Lluis Balcells, Alberto Pomar, Benjamín Martínez, and Carlos Frontera
      Nanomaterials 12 (23), 4337 (2022)
      DOI: https://doi.org/10.3390/nano12234337
  • Crystallography and X-Ray Diffraction

    The aim of the group is to explore, understand and develop new strongly correlated materials of interest in fundamental science, such as studies of intermolecular interactions, and in the improvement of methods for crystal structure determination from electron diffraction data. The group has developed the new through-the-substrate (tts) X-ray microdiffraction technique, integrated now at ALBA Synchrotron, and has a great expertise in nanocomposite porous materials, applied to different catalysis reactions.

  • Crystallography of Magnetic and Electronic Oxides and Surfaces (CMEOS)

    In 2022 our activities principally focused on non-conventional frustrated and quantum magnetic oxides, pivoting around three main axes: (a) chiral magnets and spin-driven potential magnetoelectrics and multiferroics; (b) the investigation of symmetry related mechanisms in improper multiferroics, and (c) frustrated magnets with strong magnetostructural coupling. Most of the magnetic materials investigated were fabricated in our group, typically in polycrystalline and single-crystal forms.

    Spiral (chiral) insulating magnets (with broken time and space inversion symmetries) are being profusely investigated as excellent candidates for magnetoelectric applications. They are rare and mostly are geometrically frustrated magnets with too low transition temperatures, typically below 50 K. The exceptional stability and tunability of the spiral magnetic order in the layered structure of YBaCuFeO5 (YBCFO) requires a non-conventional mechanism. Using neutron and synchrotron beams we have investigated and described the influence of tuning frustration in YBaCuFeO5 through B-site cation disorder, covering the full magnetic phase diagram and comparing our experimental results to theoretical models. Our research has confirmed a radically new mechanism for stabilization of spiral and cycloidal orders: “Spiral order by disorder”, in which frustration has no geometrical or electronic origins but it is based on chemical disorder. The relationship between disorder (Cu/Fe), stability (from 0-to-370 K) and features of the chiral magnetic phase unveiled in YBCFO-like systems illustrate the opportunities of the new avenue to supply chiral functional magnets at normal working temperatures. Lattice effects driven by chemical pressure and changes in the spin-orbit coupling were also explored in (R,A)Ba(Cu,M)FeO5 layered perovskites. Several strategies were identified that allow the manipulation of the chiral vector orientation and the thermal stability of the spiral phase.

    In addition to oxides with chiral magnetic orders, other experiments in neutron and synchrotron sources were performed to investigate symmetry related mechanisms, the magnetic structures and the interplay between the emergence of noncollinear spin ordering and the magnetoelectric and multiferroic properties in several oxide families such as RCrTiO5, RNiO3 or ε-(Fe1-xMx)2O3. The ground state, magnetic properties and charge-orbital order (COO) transitions in other A-site ordered layered perovskites of the type RBaMn2O6 and RBaMn2O5 were also investigated in powders and single crystals in collaboration with external groups. The combination of layered cationic order and cooperative tilts of the octahedra generates in some compositions improper ferroelectricity and multiferroic phases.

    HIGHLIGHTS

    (1) Disclosing the new avenue “Spiral order by disorder” in frustrated magnetic oxides
    “Helimagnets by disorder: Its role on the high-temperature magnetic spiral in the YBaCuFeO5 perovskite”
    Arnau Romaguera, Xiaodong Zhang, Oscar Fabelo, Francois Fauth, Javier Blasco and José Luis García-Muñoz
    Phys. Rev. Research 4, 043188 (2022) [18pp]
    doi.org/10.1103/PhysRevResearch.4.043188

    (2) Participation of CMEOS in specialized panels and boards of scientific associations (2022): (i) Review Panel of the EU Research Infrastructure Project ReMade@ARI (REcyclable MAterials DEvelopment at Analytical Research Infrastructures: trans-national access to instrumentation at 48 facilities all over Europe to advance the development of materials for a Circular Economy), (ii) Chemistry&Materials Science Panel of ALBA synchrotron; Advisory Boards of (iii) SETN, (iv) AUSE and (v) ESUO (the European Synchrotron and FEL User Organisation).

    (3) A new project started in October 2022: Magnetic multifunctional ferroics for a sustainable data-driven society [MAGMUF]. Funding: MINCIU PGC-2021, 223 k€. 2022-2025.

  • Functional Nanomaterials & Surfaces (FunNanoSurf)

    Our FunNanoSurf group focuses its work on the molecular design, with the creation of functional units of curcuminoid (CCMoid) and porphyrazinic type, which together with methodologies for the control of their deposition on different substrates, give rise to responsive molecular-based devices, applicable in the fields of electronics, sensors and therapy-diagnostics.

    This approach is perfectly reflected in the publications in iScience, Inorganic Chemistry and ACS Applied Nano Materials, this year, where CCMoids systems have been (ii) directly deposited and measured in FET-type devices by means of a sublimation system that is being patented in the group, (ii) fluorescence molecular systems have been deposited by means of the micro-contact printing technique and (iii) hydrogels have been created with different CCMoid systems for their testing as anti-inflammatory agents, respectively.

    HIGHLIGHTS
    • Participation as a keynote speaker of Prof. Núria Aliaga-Alcalde in the SMS Conference and Exhibition (SMS 2022) in Athens, Greece and in Physics in 2D Nanoarchitectonics, Mini-Colloquium within the CMD29 conference of the European Physical Society – Manchester, UK.
    • SYNERY project: IP Arántzazu González-Campo, “Synthetic blood cells as an alternative to blood products” The SynEry project has received funding from the Horizon Europe programme under grant agreement No 101046894.
  • Inorganic Materials & Catalysis Laboratory (LMI)

    The group's outstanding contributions lie in advancing 3D aromaticity, notably with boron clusters. They made a major breakthrough, revealing that while combining 2D/2D and 3D/3D aromatic systems forms a new aromatic system, the 3D/2D hybrid combination is not possible, leaving only one system aromatic.[1] In this category, it was shown that clustered polyaromatic hydrocarbons, like pyrene or perylene, are more stable than linear polyaromatic hydrocarbons like anthracene or pentacene. This stability is demonstrated when they fuse with q-metallacarboranes, in accordance with Clar's rules.[2] In nanomedicine, the group investigated the therapeutic potential of [o-57FESAN], either as a standalone treatment or as an adjuvant, using nontoxic concentrations for glioblastoma treatment, leveraging the Mössbauer effect. The findings strongly advocate the use of metallacarboranes as novel platforms to explore innovative low-dose regimens for brain cancer treatment.2  

    Moreover, ferrabis(dicarbollides) were employed as radiosensitizers for the pioneering use of proton therapy (PBFR), revealing promising potential for multimodal (chemo/radio/PBFR) therapy of glioblastoma and reshaping the future of cancer treatment.[3] Our research group has also achieved remarkable breakthroughs in carborane-based Metal Organic Frameworks (MOFs) research. We successfully synthesized new water-stable materials with tunable emission and time-dependent emission. These properties have great potential for developing high-security anticounterfeiting and bar-coding materials.[4] Additionally, we pioneered the development of o-carborane appended π-conjugated fluorophores, which exhibit exceptional light-emitting properties in both solid state and thin films. By processing water-dispersible nanoparticles (NPs) from these systems into thin films with high fluorescence efficiency, we have opened up exciting opportunities for optical and optoelectronic applications.[5]

    HIGHLIGHTS
    • The group also contributed to the Book “Advanced in Catalysis. Advances in the synthesis and catalytic applications of boron clusters: A tribute to the works or Professors Francesc Teixidor and Clara Viñas”, Vol 71, 2022, Ed. R Núñez and M. Diéguez.
    • Our group successfully hosted Euroboron9, a prestigious European boron conference, gathering global scientists who showcased cutting-edge advancements in boron chemistry.
    • Boron clusters (ferrabisdicarbollides) shaping the future as radiosensitizers for multimodal (chemo/radio/PBFR) therapy of glioblastoma. M. Nuez-Martínez, M. Queralt-Martín, A. Muñoz-Juan, V. M. Aguilella, A. Laromaine, F. Teixidor, C. Viñas, C. G. Pinto, T. Pinheiro, J. F. Guerreiro, F. Mendes, C. Roma-Rodrigues, P. V. Baptista, A. R. Fernandes, S. Valic and F. Marques. J. Mater. Chem. B, 2022, 10, 9794–9815.

    [1] J. Poater, C. Viñas, M. Solà and F. Teixidor, Nat. Commun., 2022, 13, 3844.
    [2] J. Poater, C. Viñas, D. Olid, M. Solà and F. Teixidor, Angew. Chem. Int. Ed., 2022, e202200672.
    [3] M. Nuez-Martínez, M. Queralt-Martín, A. Muñoz-Juan, V. M. Aguilella, A. Laromaine, F. Teixidor, C. Viñas, C. G. Pinto, T. Pinheiro, J. F. Guerreiro, F. Mendes, C. Roma-Rodrigues, P. V. Baptista, A. R.          Fernandes, S. Valic and F. Marques. J. Mater. Chem. B, 2022, 10, 9794–9815.
    [4] Z. Li, R. Núñez, M. E. Light, E. Ruiz, F. Teixidor, C. Viñas, D. Ruiz-Molina, C. Roscini and J. G. Planas, Chem. Mater., 2022, 34, 4795–. 808.
    [5] S. Sinha, Z. Kelemen, E. Hümpfner, I. Ratera, J.-P. Malval, J. P. Jurado, C. Viñas, F. Teixidor and R. Núñez, Chem. Commun., 2022, 58, 4016–4019.

  • Laboratory of Electronic Structure of Materials (LEEM)

    The group has made fundamental contributions to our understanding of materials properties, and has continued to push the methodological frontier in first-principles simulations.

    Dynamical tuning of the thermal conductivity in crystals is critical for thermal management applications, including energy harvesting and phononic logical devices. Building on our previous work on electrophonnic effects, we have studied the dual case of magnetophononic effects, i.e., the use of magnetic field in magnetic material to control the thermal conductivity.

    We have continued our work on the charge density wave (CDW) instability in metallic systems. For quasi-1D systems, weak coupling theories work appropriately and the CDW is primarily due to a Fermi nesting mechanism. However, for materials with higher dimensionality, intermediate and strong coupling regimes are generally at work and the modification of the chemical bonding network by the PLD is at the heart of the instability. We have also argued that the momentum dependent electron-phonon coupling plays a key role in linking electronic and structural degrees of freedom.

    The interaction of spin and curvature has fundamental and practical implications for controlling chirality and topological order in two-dimensional magnets. We have demonstrated how noncollinear-spin polarized density-functional theory can be used to determine the flexomagnetic coupling coefficients in real systems. In monolayer CrI3 we have found a crossover as a function of curvature between a magnetization normal to the surface to a cycloidal state.

    Born effective charges (BECs) govern the coupling between optical phonona and macroscopic electric fields in insulators. We have found, contrary to the conventional wisdom, that in the nonadiabatic regime BECs are well defined also in conductors, and established a sum rule that relates them to the Drude weight, a characterizing fundamental property of the metallic state.

    Building on the electrostatic formalism developed recently, we have demonstrated the crucial importance of the quadrupolar long-range effects in the first-principles calculation of electronic mobilities in two-dimensional (2D) crystals.

    By including the contributions from the lattice degrees of freedom we have achieved our long-standing goal of computing the flexoelectric tensor of any crystalline insulator from first-principles. The whole formalism has been implemented in ABINIT, an open-source electronic-structure package with thousands of users between academia and industry.

    We have continued the development of the Siesta materials-simulation program, which is one of the flagship codes of the MaX (Materials at the eXascale) EU Center of Excellence.

    HIGHLIGHTS
    • Accurate Prediction of Hall Mobilities in Two-Dimensional Materials through Gauge-Covariant Quadrupolar Contributions
      Samuel Poncé, Miquel Royo, Marco Gibertini, Nicola Marzari and Massimiliano Stengel
      Physical Review Letters 130 (16), 166301, 2023. (Published in 2023, although first submission was July 2022)
      https://doi.org/10.1103/PhysRevLett.130.166301
    • Nonadiabatic Born Effective Charges in Metals and the Drude Weight
      Dreyer, CE; Coh, S; Stengel, M.
      Physical Review Letters, 128, 095901, 2022 (Editorial Suggestion)
      https://doi.org/10.1103/PhysRevLett.128.095901
    • Curved magnetism in CrI3
      Edström, A; Amoroso, D; Picozzi, S.; Barone, P.; Stengel, M.
      Physical Review Letters, 128, 177202, 2022 (Editoral Suggestion)
      https://doi.org/10.1103/PhysRevLett.128.177202
    • Competition between Ta-Ta and Te-Te Bonding Leading to the Commensurate Charge Density Wave in TaTe4
      Guster, Bogdan, Miguel Pruneda, Pablo Ordejón, and Enric Canadell
      Physical Review B 105 (6): 064107, 2022
      https://doi.org/10.1103/PhysRevB.105.064107
  • Laser Processing Research

    The activities of the group were mainly dedicated to the fabrication of hybrid electrodes constituted by nanostructured carbon-metal oxides for supercapacitors. The objective of the research was to develop different types of carbon electrodes with increased energy density by crystallizing pseudocapacitive metal-oxide nanoparticles on the surface of the carbon nanostructures through advanced laser technologies. Two main approaches were developed:

    1. Laser deposition of hybrid electrodes by the Reactive Inverse Matrix Assisted Pulsed Laser Evaporation (RIMAPLE) method:  Frozen targets composed of aqueous dispersions of graphene oxide (GO), carbon nanotubes (CNT), nickel oxide (NiO) nanoparticles and nitrogen containing precursors were irradiated in vacuum conditions in order to induce the simultaneous chemical transformation of the reactants and the deposition of electrochemically active nitrogen-doped reduced GO-CNT-NiO composites. The mechanisms responsible for the charge storage were thoroughly studied by advanced characterization techniques.

    2. Chemical transformation of carbon electrodes: The laser surface treatment of nanocarbon (graphene derivatives, carbon nanotubes, activated carbon)-metal organic precursor films were carried out for inducing the crystallization of the metal-oxide nanoparticles on the nanocarbons’ surface. The obtained hybrid electrodes revealed increased capacitance as compared to their counterpart electrodes composed of “only” carbon. Thorough work for functional properties optimization and escalation of the electrodes fabrication to large areas was initiated with the aim to get this technology closer to the industry standards.
    HIGHLIGHTS
    • Article: “Unravelling the origin of the capacitance in nanostructured nitrogen-doped carbon - NiO hybrid electrodes deposited with laser”, Pablo García Lebière, Enikó Gyórgy, Constantin Logofatu, Denys Naumenko, Heinz Amenitsch, Piu Rajak, Regina Ciancio, Ángel Pérez del Pino, Ceramics International 48 (2022) 15877–15888
    • The proposal “Fabrication of nanocarbon supercapacitors using laser technology” was granted in the COMTE-EBT 2022 program (FGCSIC) for the acceleration of the developed laser technologies to the Market.
    • The proposal “Laser assisted synthesis of multicomponent photocatalysts for solar hydrogen production” was granted with an Ecologic and Digital Transition (TED) project (Spanish Science and Innovation Ministry). The goal is to synthesize photocatalysts for water-splitting hydrogen generation by means of laser technologies.
  • Molecular Materials for Electronic Devices (eMolMat)

    The e-MolMat group has been working on the preparation of organic semiconducting films using low cost solution shearing techniques compatible with roll-to-roll manufacturing processes. In particular, the group has proved that modifying the ink formulation and the experimental parameters it is possible to process thin films from solution using challenging and promising materials, such the low-solubility DNTT semiconductors and charge transfer salts. The performance of the fabricated organic field-effect transistors (OFETs) has also been optimised by adding in the formulation fluorinated polymers to enhance the devices time and shelf stability. Further, a doping methodology has been developed, which reduces the devices contact resistance and, hence, the field-effect mobility is improved.

    The OFETs fabricated in the group have been applied for the development of detectors for X-ray radiation, achieving an unprecedented sensitivity. The potential of these devices for medical imaging has been demonstrated.

    In addition, the preparation of self-assembled monolayers (SAMs) of electroactive molecules has been pursued. In particular, a methodology has been successfully developed to graft on gold surface urazol radicals, which are not stable in solution. Finally, optically switchable ferrocene SAMs on gold were prepared. Charge transport measurements across these monolayers revealed that upon chemical linkage to the gold substrate there is an alteration of the isomerization pathway, which favours the trans to cis conversion, which is not observed in solution.

    HIGHLIGHTS
    • Chemical doping of the organic semiconductor C8-BTBT-C8 using an aqueous iodine solution for device mobility enhancement
      Li, A. Babuji, I. Temiño, T. Salzillo, F. D’Amico, R. Pfattner, C. Ocal, E. Barrena, M. Mas-Torrent
      Advanced Materials Technologies 2022, 2101535.
    • X-ray detectors with ultrahigh sensitivity employing high performance transistors based on a fully organic small molecule semiconductor/polymer blend active layer
      Tamayo, I. Fratelli, A. Ciavatti, C. Martinez-Domingo, P. Branchini, E. Colantoni, S. De Rosa, L. Tortora, A. Contillo, R. Santiago, S. T. Bromley, B. Fraboni, M. Mas-Torrent, L. Basirico
      Adv. Electr. Mater. 2022, 8, 2200293.
      These results formed the basis of the proof-of-concept awarded project: FLEMING: "X-ray detectors based on flexible organic field-effect transistors for medical imaging " (1/12/2022-30/11/2024). Prueba de Concepto. Agencia Estatal de Investigación, Ministerio de Ciencia e Innovación-Next Generation EU; ref. PDC2022-133750-I00; 149.500 €. IP: Marta Mas-Torrent.
  • Multifunctional Thin Films and Complex Structures (MULFOX)

    MULFOX has continued a fruitful research on ferroelectric materials, mostly focused on the stabilization of the ferroelectric phase of HfO2 by growing thin films by PLD in a variety of conditions and doping levels and disclosing their role. The exploitation of these materials is mainly centered on the electroresistance of tunnel barriers and it has been demonstrated that suitable capping of Hf0.5Zr0.5O2 nanometric films allows to enhance the electroresistance and endurance of tunnel barriers.

    The interaction of light-matter is an emerging activity encompassing the exploration of the photo-response of Jahn-Teller polarons, including detailed quantum-mechanical modeling of their spin orbit-related spectral response, as well a detailed understanding of the photoresponse of non-centrosymmetric materials (Bulk Photovoltaic Effect) and the complex interplay among different contributions to the light-polarization dependence of their photoresponse. Dedicated experiments have permitted to conclude that earlier observations of light induced polarization reversal in suitable ferroelectric films is due to photocarriers rather than thermal effects and the reversing capability of light is directly related to the presence of imprint fields in the ferroelectric layers.

    Within the context of magnetism and spintronics, we have disclosed that earlier 3d transition metals, in spite of having a negligible spin-orbit coupling, may display an unexpected spin absorbing capability, which suggest new avenues for spintronics, probably related to orbital currents rather than spin currents. The development of technologies for the growth of insulating ferro(ferri)magnets and integration in novel spintronic device concepts and caloritronics devices is progressing rapidly, and results are expected in the near future.

    Last, we have largely collaborated with other groups within ICMAB-RL3 to understand the beautiful response of strongly frustrated magnetic spinels, that may open a new strategy in the quest for spin liquids and eventually, quantum materials.

    HIGHLIGHTS
    • Synergetic contributions of chemical doping and epitaxial stress to polarization in ferroelectric HfO2 films
      Song, H. Tan, A.C. Robert, S. Estandía, J. Gàzquez, F. Sánchez, I. Fina
      Applied Materials Today 29, 101621 (2022)
    • Jahn-Teller states mixed by spin-orbit coupling in an electromagnetic field
      S. Miñarro and G. Herranz
      Phys. Rev. B 106,165108 (2022)
    • Bulk photovoltaic effect modulated by ferroelectric polarization back-switching”, Y Sheng, I Fina, M Gospodinov, J Fontcuberta
      Applied Physics Letters 120 (24) (2022)
  • NANOMOL-BIO

    NANOMOL-BIO is devoted to the synthesis, physico-chemical characterization and development, up to pre-clinical regulatory phases, of molecular and polymeric (nano)materials for biomedical applications. The metal-free materials that we develop, are always validated in the frame of collaborations with research groups allocated in hospitals or in biomedical research centers. We belong to CIBER network (https://www.ciberisciii.es/), as many of our collaborators.

    Our activity within 2022 was principally focused on:

    1)  The advancement towards the clinics of two nanovesicle based nanopharmaceuticals in the frame of the European initiative PHOENIX-OITB (https://www.phoenix-oitb.eu/): (i) peptide targeted nanoliposomes for the intravenous treatment of Fabry lysosomal disorder; (ii) antimicrobial nanovesicles for topical administration.  We described part of this achievements in a review (DOI:10.1016/j.addr.2022.114531) published in the special-issue “Lysosomal Therapies and Drug Delivery Strategies” at Advanced Drug Delivery Reviews.

    2) Development of surface coating strategies using multifunctional biomaterials to prevent infections in the framework of the project “FUNCATH: Prevention of vascular catheter-related infections by the functionalization of catheters with hydrogels with antimicrobial agents of broad spectrum” in collaboration with Hospital Clinic (Barcelona); Hospital Taulí and IRTA, and financed by La Marató TV3. We published two book chapters related to this project: “Methods for the Characterization of Protein Aggregates” (DOI: 10.1007/978-1-0716-1859-2_29) and “Methods for Processing Protein Aggregates into Surfaces” (DOI: 10.1007/978-1-0716-1859-2_31) at Methods in Molecular Biology; Springer

    3) Development of metal-free contrast agents as an alternative to those based on metals such as gadolinium complexes that present toxicity concerns. We work with different systems based on organic radicals such as radical dendrimers, nanovesicles or nanoparticles, all within the framework the projects MOL4BIO, financed by the Spanish Agency AEI (Agencia Estatal de Investigación) and “VIRADEN: In vivo Studies of Radical Dendrimers as Contrast Agents for Magnetic Resonance Imaging”, a Frontier Interdisciplinary Project financed by FUNFUTURE Severo Ochoa. These results are described in “Metal-free Radical Dendrimers as MRI Contrast Agents for Glioblastoma Diagnosis: Ex vivo and In vivo Approaches” (DOI: 10.1021/acs.biomac.2c00088) published by Biomacromolecules; ACS.

    4) The synthesis and fabrication of healthy and malignant artificial tissues based on 3D biohybrid hydrogels to be used for the development of novel cancer therapies in the framework of the projects “IMMUNYS: Mimicking the Immune System against Cancer”,  financed by the Spanish Agency AEI and “LYNOID: Development of Patient-Derived Organoids based on Lymph Node-inspired 3D Hydrogels as Hematological Cancer Models”,  a Frontier Interdisciplinary Project financed by FUNFUTURE Severo Ochoa. Some of these results are described in the paper “Enhanced human T cell expansion with inverse opal hydrogels” (DOI: 10.1039/d2bm00486k) published by Biomaterials Science; RSC.  

    HIGHLIGHTS

    1. Synthesis of new multifunctional nanoparticles for molecular spintronics, with high interest to the development of more efficient technologies for data storage and transfer.

    Multifunctional Switch Based on Spin-Labeled Gold Nanoparticles
    Vega Lloveras, Pilar Elías-Rodríguez, Luca Bursi, Ehsan Shirdel, Alejandro R. Goñi, Arrigo Calzolari, and José Vidal-Gancedo; Nano Letters 2022, 22, 768-774 DOI: 10.1021/acs.nanolett.1c04294

    2. Quatsomes, non-liposomal nanovesicles, with well-defined physico-chemical characteristics and infinite shelf life, for the development of metal-free pharmaceutical liquid nanoformulations.

    (i) “Stable nanovesicles formed by intrinsically planar bilayers” Mariana Kober; Silvia Illa-Tuset, Lidia Ferrer-Tasies, Evelyn Moreno-Calvo, Witold Tatkiewicz, Natascia Grimaldi, David Piñaa, Alejandro Perez, Vega Lloveras, José Vidal-Gancedo, Donatella Bulone, Imma Ratera, Jan Skov Pedersen, Dganit Danino, Dganit; Jaume Veciana, Jordi Faraudo, Nora Ventosa; Journal of Colloid and Interface Science 2022, 631, 202 - 211 DOI: 10.1016/j.jcis.2022.10.104  (ii) “Engineering pH-Sensitive Stable Nanovesicles for Delivery of MicroRNA Therapeutics” Ariadna Boloix, Natalia Feiner-Gracia,  Mariana Kober, Rosa Pascarella, Aroa Soriano, Marc Masanas, Nathaly Segovia, Guillem Vargas-Nadal, Josep Merlo-Mas, Dganit Danino, Inbal Abutbul-Ionita, Laia Foradada, Josep Roma, Alba Córdoba, Santi Sala, Josep Sánchez de Toledo, Soledad Gallego, Jaume Veciana, Lorenzo Albertazzi, Miguel F. Segura, Nora Ventosa 2022, Small, 18, 2101959 DOI: 10.1002/smll.202101959. This article also appears in: Celebrating Excellence in the Advanced Materials Family: Women in Materials Science.

    3. Functionalization of SAMs with quatsomes nanovesicles to achieve a tunable hierarchical organization of RGD-peptide and study its impact on cell adhesion processes.

    Hierarchical Quatsome-RGD Nanoarchitectonic Surfaces for Enhanced Integrin-Mediated Cell AdhesionM. Martínez-Miguel, M. Castellote-Borrell, M. Köber, A. R. Kyvik, J. Tomsen-Melero, G. Vargas-Nadal, J. Muñoz, D. Pulido, E. Cristóbal-Lecina, S. Passemard, M. Royo, M.Mas-Torrent, J. Veciana, M. I. Giannotti,¡ J. Guasch, N. Ventosa,* and I. Ratera* ACS Appl. Mat. Interfaces 2022, 14, 48179−48193, DOI: 10.1021/acsami.2c10497

  • Nanoparticles & Nanocomposites (NN)

    The research line co-developed with the CNM on electrochemical sensors for cost-effective on-site analysis of water contaminants has gained momentum. Several studies have been published in 2022 reporting on fluidic electrochemical sensors for online monitoring of the chemical oxygen demand in urban wastewater, the quantification of chemical oxygen demand with an integrated screen-printed sensor, the upcycling of bread waste into Ag-doped carbon to detect halogenated compounds, or new composites of carbon and copper nanoparticles to also sense chemical oxygen demand. Two projects secured funding; UPCYCLING NOW (TED2021-130819B-I00) and CONTASENS (2021 PROD 00116). The technology, which is protected by a patent, has raised the interest of companies and negotiations are on the way towards its commercialization.

    The research line on natural polymers has also received funding through two projects BIOSOFT-REGE (PID2021-122645OB-I00) and HEALTHYCORNEA (2021PROD 00204). This year’s publications were related to the fabrication of a double network hydrogel made by photocurable monomers and bacterial cellulose fibers, attaining aligned bacterial cellulose films during static biosynthesis, and the design of a binder-free electrode for hydrogen evolution reaction made of bacterial cellulose with nickel-phosphorous alloy, this last work in collaboration with D. Tonti. We are also very motivated about the ongoing collaboration with the Ophthalmology Center Barraquer. A joint patent has been filled and the first steps to undertake a clinical study have been completed.

    Interesting results concerning the evaluation of new molecules and nanomaterials in the C. elegans organism have been published in reputed journals and in close collaboration with various groups. Together with P. Horcajada, MOFs were investigated, boron clusters with C. Viñas, and lutein to prevent neuroligin-mediated neurodevelopmental defects with N. Ventura.

    Finally, we kept working on the synthesis of nanoparticles and assessing their potential in nanomedicine by collaborating with expert groups in the field. Some of those works focused on mesoporous silica nanorods and their bioevaluation, PLGA nanocarriers for pulmonary and brain administration or riboflavin–citrate SPIONs with enhanced uptake in breast cancer cells.

    HIGHLIGHTS
    • An EC project has been funded, NextGEM, HORIZON-HLTH-2021-ENVHLTH-02. NextGEM will generate health-relevant knowledge of electromagnetic field exposure in multiple-frequency-band scenarios. Our group will contribute by using the elegans model organism to study such effects.
    • NNGroup has been actively participating in topical roadmaps: EPNOE Research Roadmap 2040, CSIC-Libro Blanco de Nanomedicina and in the organization of schools and Int’l conferences: SURE 2022, Summer School on Sustainable Materials for Renewable Energy Application, the 5th EPNOE Junior Scientist Meeting, the 5th Symposium on Bacterial Cellulose and the Spanish-Portuguese Industry-Academia Aerogel Meeting.
    • Our students keep rocking it! Wenchao Duan defended his Ph.D. and was awarded best oral presentation at the 2nd Int’l Conference on Aerogels for Biomedicine and Environment. Miquel Torras defended his Ph.D. and Anna Solé, Miriam Vidal and Mauricio Echavarria their MSc, all with excellent marks. NN alumni continues to grow!
  • Nanostructured Materials for Optoelectronics and Energy Harvesting (NANOPTO)

    In 2022, our group made significant strides in various research areas. Our accomplishments reflect our commitment to advancing scientific knowledge and also developing technologies with real-world applications.

    We emphasize the critical discussion of the role of ferroelectricity and ferroelasticity in the performance of metal halide Perovskites in an invited perspective article, as well as the in-depth paper of phonon transport in the gigahertz to terahertz range discussing confinement, topology, and second sound.

    We point out our recent patents: Regarding thermal transport, a new contactless approach was developed and patented (ES1641.1660) to study anisotropic thermal transport. Among the awarded projects, patented technology ES1641.1760: “Spectral shaper illumination device” was at the origin of the Proof-of-Concept project PDC2022-134001-I00, Spectrum-on-demand light source for photovoltaic materials characterization (SOLS) from MICINN.

    In Organic Photovoltaics,  research published in Energy & Environmental Science contributed to a general understanding of the relationship between molecular structure and absorption strength in π-conjugated organic molecules, including non-fullerene acceptors (NFAs), while introducing predictive machine-learning models of low computational cost. In Organic Thermoelectrics, design rules for polymer blends with high thermoelectric performance were established by showing the significance of low disorder and a high degree of electrical connectivity between domains, together with similar highest occupied molecular orbital levels for both materials in the blend.

    In the Photonic Architectures for Light Management research line, scalable fabrication using nanoimprinting was employed to greatly enhance outcoupling of light from an emitting layer, offering a seamless fabrication path and an excellent playground for tuning the optical properties of emerging light sources beyond traditional gratings and photonic crystals. We are proud to mention our participation in two Horizon-EIC Pathfinder projects: Dynamic Spatio-Temporal Modulation of Light based on Phononic Architectures (DYNAMO, Pathfinder open) started in 2022, and the newly granted project on Integrated COnversion of NItrate and Carbonate streams (ICONIC, Pathfinder challenges).

    HIGHLIGHTS
    • The spin-off Molecular Gate, S.L. was founded by Mariano Campoy-Quiles and Aleksandr Perevedentsev together with BeAble Capital team, to create anti-counterfeit elements for the packaging typically used in the pharmaceutical industry, including bottles and blisters, to ensure that the contained products are authentic.
    • Project Ref. TED2021-132807B-I00, CO2 conversion into chemicals of industrial interest by plasmon-assisted photocatalysis (PLASMOCRACO2) led by Alejandro Goñi and Agustín Mihi was granted by MICINN at the call "Projects Oriented to the Ecological and the Digital Transition".
    • Surface lattice plasmon resonances by direct in situ substrate growth of gold nanoparticles in ordered arrays demonstrated unmatched control over morphology and optical response of individual plasmonic building blocks. The versatility in tuning the array geometry and easy fabrication can be applied to sensors relying on surface-enhanced Raman spectroscopy.
  • Physical Chemistry of Surfaces and Interfaces (SURFACES)

    The consolidated experience of the PCSI group in the study of organic semiconductors for organic electronics, through advanced characterization techniques (particularly those based on local scanning probe microscopies and synchrotron radiation) has allowed us to unravel, in deep detail and sub-nanometric precision, the structure of ultra-thin organic films based on small molecules.

    The objective of this basic research, of low Technology Readiness Level, rather than obtaining materials with champion performances to compete in the market, is to achieve truly extraordinary control of the first molecular layers of the organic semiconductor film, i.e., those layers that govern the properties of the final device.

    We have developed new strategies based on surface and interface engineering, where in situ growth methodologies and annealing treatments allow us to design the formation of new structures and have access, for example, to metastable phases and polymorphs. The combination of donor and acceptor molecules, and/or using novel doping methods, permit us as well to provide the new systems (co-crystals, charge transfer complexes ... ) with a variety of properties that are chosen almost at will.

    The major achievement of our approach is the correlation of the crystallographic quality, mechanical and compositional characteristics of the thin films with their (in-situ) measured macroscopic electronic properties. Our methodology is thought to allow laying the foundations for designing materials with those properties necessary for good performance, durability and stability of organic electronic devices.

    Our group has established collaborations, within the ICMAB and at national and international levels. We highlight next three of the publications resulted from international collaborations that were led by our research group and as part of the activity of the group to visualize the role of women in Science, we also highlight a collaborative and multidisciplinary publication led by three women from ICMAB.

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  • SoftMatter Theory

    During 2021 we have obtained significant advances in different fields: we continued our investigations about the interactions of the SARS-CoV-2 virus with materials and in parallel we have obtained significant simulation results in fields as diverse as MOFs or ionic liquids combining DFT electronic structure calculations and Molecular Dynamics simulations. 

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  • Solid State Chemistry (SSC)

    Batteries based on multivalent ions (e.g. Ca2+, Mg2+) and metal anodes could enable very high energy densities. Bottlenecks to overcome for the study of such new chemistries are not only the development of electrolytes and cathodes enabling efficient cation diffusion, but also careful control of passivation layer on metal anode and interfacial processes such as desolvation. Activities included the screening of new materials as potential cathodes for Ca metal batteries and characterization of the redox mechanism using operando diffraction, the study of the impact of the composition of the passivation layer, and the cation solvation structure on Ca plating kinetics.  A methodology for quantification of charge compensation in lithium-rich cathodes based on X-ray absorption (XAS) has been developed. This allows a better understanding of the irreversible processes that need being hindered for long battery cycle life.

    In the field of carbon nanomaterials, we have shown that nanotubes and carbon nanohorns can be employed for the containment of 6Li, an isotope of interest for neutron capture therapy (NCT). After encapsulation of the active cargo, the external surface of the nanocarrier is modified for improved biocompatibility. The developed 6Li-filled carbon nanomaterials offered the possibility to explore 6Li compounds as active NCT agents by delivering therapeutic doses to cancer cells.

    Neural electrostimulation through direct electric fields modifies cell repair in vitro when using large capacity hybrid electroactive materials. Recently, we have observed this effect in wireless bipolar electrochemistry electrostimulation conditions, and have proven that redox gradients are achieved across the material when cation intercalation is possible. Beyond the redox and ionic gradients in the unwired bipolar electrode where cells grow, a dramatic global impedance has been observed by the same existence of the material which are thought to modify inflammation parameters and cell growth. Oscillatory behaviors in redox state have also been observed and correlated with conductivity, and the global set of factors is being explored in energy storage systems.  

    A collection of new advanced porous materials was produced using conventional and green approaches based on supercritical CO2. In MOFs, we demonstrated how solvents influence the supramolecular polymorphism of compounds with the same stoichiometry. We have prepared composites of graphene-based aerogels with MOFs, polymers, and other fillers for fuel production, specifically for H2 generation from water splitting and methanol production through CO2 hydrogenation. We have developed materials for Hg retention to make polluted water drinkable in affected areas.

    We have designed and developed synthesis methods of new structures of transition metal nitrides and oxynitrides analogous to the oxides. The introduction of nitride in an oxidic compound induces changes in bonding as a consequence of the differences in charge, electronegativity and polarizability between the two anions. An example is the first ternary nitride spinel containing only transition metals MnTa2N4, that shows a strong magnetic frustration induced by the large covalency of metal-nitrogen bonds involved in the superexchange pathways between the Mn2+ spins.

    HIGHLIGHTS
    • Rosa Palacín has been recipient of the Prix franco-espagnol “Miguel Catalan-Paul Sabatier” Société Chimique de France 2022.
    • Gerard Tobias has been granted with a ERC Proof of Concept - Targeted nanohorns for lithium neutron capture therapy (TARLIT)
    • New patent filed: Lithium filled nanocapsules and use therof. (G. Tobias et al) Ref: 202230271.
    • Dramatic drop in cell resistance through induced dipoles and bipolar electrochemistry. Fuentes-Rodríguez et al, J. Electrochem. Soc., 2022, 169, 016508.
    • Oscillatory Patterns in Redox Gradient Materials through Wireless Bipolar Electrochemistry. The dynamic wave-like case of copper bipolar oxidation. Fuentes-Rodríguez et al, Materials Chemistry Frontiers, 2022, 6, 2284.
    • Supramolecular Isomerism in Cobalt(II) Coordination Polymers Built from 3,5-Bis(trifluorome-thyl)benzoate and 4,4′-Bipyridine. F.Papi et al, Crystal Growth & Design 2022, 22, 4463.
  • Superconducting materials and large scale nanostructures (SUMAN)

    The scientific challenges and achievements of SUMAN comprise the areas of superconducting materials and functional oxide nanocoatings for the fields of energy transition, high energy physics and information -communication technology, as described below.

    Chemical solution deposition (CSD) has enable to demonstrate a novel high throughput TLAG-CSD method for high temperature superconducting film at ultrafast growth rates, with the help of in-situ XRD synchrotron experiments. During 2022 we have also started to evaluate the use of TLAG for fabricating superconducting joints. Furthermore, in combination with compositional gradient inkjet printing, TLAG is being used for fast materials design using machine learning algorithms

    Superconductor Magnetic metasurfaces appears as a promising approach to efficiently control and guide magnetic fields at local scale. On-chip integrated metasurfaces face a very bright future for boosting the sensitivity and efficiency of magnetic sensors, magnetic harvesters and magnetic functional devices. Additionally, electromigration effects have been exploited for electric oxygen doping control of cuprates and manganites. And, we have continued studying other chemical methods like polymer assisted deposition (PAD) for thin films growth with dynamic magnetic and spin pumping properties.

    In addition, we have placed superconducting CC at the scene of future high energy circular accelerators, dark mater detectors for their low surface impedance properties at microwave frequencies, and nanocoated CC with current flow diverter architectures are now seriously considered also to protect high voltage dc grids.

    Furthermore, CSD has demonstrated its versatility to prepare multifunctional complex oxides to be used in an all-oxide photovoltaic devices. The combination of CSD with a homebuilt atomic layer deposition reactor enabled the development of a cost-effective route to prepare free-standing multifunctional complex oxide membranes with atomic control facilitating the transition to crystalline and flexible devices.

    HIGHLIGHTS
    • ICMAB coordinates the European CHIST-ERA project entitled “Magnetic Metasurfaces for sustainable Information and Communication technologies (MetaMagIC)” partnering with UAB, Liège Univ., Bath Univ. and Brno Univ. Techn., to design new magnetic metasurfaces to control low-frequency magnetic fields at the meso/microscale.
    • An ERC-Proof of Concept is awarded to SUMAN to upscale the manufacturing process of colloidal inks for superconducting materials (SMS-INKS project).
    • ICMAB participates at MICIN Complementary Plan of Astrophysics and high energy physics, funded by MRR and CCAA, to explore the universe through advanced superconducting technologies of dark matter detection.
  • Sustainable Molecular Systems (SUSMOSYS)

    The newly formed Sustainable Molecular Systems Laboratory prepares and studies materials capable of capturing sunlight and converting it into useful energy.

    We prepare chiral molecular materials for incorporation into solar energy capturing devices, mainly bulk heterojunction solar cells. Determining the organisation of these molecules in the films is challenging, as most techniques determine surface structure or bulk properties. Synchrotron based circular dichroism has been used in a novel way to observe the arrangement of the molecules in these films.

    Another way to capture sunlight’s energy is in the form of photoswitchable materials that can store heat in their metastable forms.  Triplet energy sensitization of switching has been used to control this process using bioplastics as a medium to ensure controllability and sustainability.

    The stored solar energy can also be converted into electrical power using thermoelectric generators. This achievement was made using two photoswitches in a microelectromechanical chip, it has potential to transfer solar to electrical power without geographical restrictions.


    HIGHLIGHTS
    • Imaging deposition-dependent supramolecular chiral organization
      Elizabeth Killalea, Mario Samperi, Giuliano Siligardi and David B. Amabilino
      Chem. Commun., 2022, 58, 4468-4471
      https://doi.org/10.1039/D1CC06790G
    • Far-red triplet sensitized Z-to-E photoswitching of azobenzene in bioplastics
      Pankaj Bharmoria, Shima Ghasemi, Fredrik Edhborg, Raúl Losantos, Zhihang Wang, Anders Mårtensson, Masa-aki Morikawa, Nobuo Kimizuka, Ümit İşci, Fabienne Dumoulin, Bo Albinsson and Kasper Moth-Poulsen
      Sci., 2022,13, 11904-11911
      https://doi.org/10.1039/D2SC04230D
    • Chip-scale solar thermal electrical power generation
      Zhihang Wang, Zhenhua Wu, Zhiyu Hu, Jessica Orrego-Hernández, Erzhen Mu, Zhao-Yang, Zhang, MartynJevric, Yang Liu, Xuecheng Fu, Fengdan Wang, Tao Li, Kasper Moth-Poulsen
      Cell Reports Physical Science, 3, 3, 2022, 100789
      https://doi.org/10.1016/j.xcrp.2022.100789