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Lipid membranes are notorious for their ability to maintain ionic concentration gradients, acting as efficient barriers to ions. However, the validity of this statement for nano-ions (ions of nanometric size which are in fact small charged molecules) is not obvious. Experimental results show that the presence of a concentration gradient of certain nano- ions (most notably cobaltabisdicarbollide ([o-COSAN] − an- ions), induce a current across intact artificial phospholipid bilayers. The mechanism underlying this observed translo- cation of nano-anions across membranes is unknown. Here we show, using molecular dynamics simulations, that the permeation of [o-COSAN] − anions across a lipid bilayer pro- ceeds in a cooperative manner. Single nano-ions can enter the bilayer but they cannot cross it due to a free energy barrier of about 8k B T . The interaction between these nano- ions inside a leaflet induces a flip-flop translocation mech- anism with the formation of transient, elongated structure inside the membrane. This cooperative flip-flop allows an efficient distribution of [o-COSAN] − anions in both bilay- ers of the membrane. These results suggest the existence of a new mechanism for permeation of nano-ions across lipid membranes, relevant for those that have the appropriate self-assembly character.

Glioblastoma (GBM), as the most central nervous system (CNS) intractable disease, has spoiled millions of lives due to its high mortality. Even though several efforts have been made, the existing treatments have had limited success. In this sense, we studied a lead compound, the boron-rich selective epidermal growth factor receptor (EGFR)-inhibitor hybrid 1, as a potential drug for GBM treatment. For this end, we analyzed the in vitro activity of hybrid 1 in a glioma/primary astrocytes coculture, studying cellular death types triggered by treatment with this compound and its cellular localizations. Additionally, hybrid 1 concentrated boron in glioma cells selectively and more effectively than the boron neutron capture therapy (BNCT)-clinical agent 10B-l-boronophenylalanine and thus displayed a better in vitro-BNCT effect. This encouraged us to analyze hybrid 1 in vivo. Therefore, immunosuppressed mice bearing U87 MG human GBM were treated with both 1 and 1 encapsulated in a modified liposome (recognized by brain-blood barrier peptide transporters), and we observed a potent in vivo per se antitumor activity (tumor size decrease and animal survival increase). These data demonstrate that 1 could be a promising new targeted therapy for GBM., This research was funded by Agencia Nacional de Investigación e Innovación (ANII, Uruguay), grant numbers FCE_3_2018_1_148288 and POS_NAC_2015_1_110068, Institut Pasteur de Montevideo─FOCEM, and Comisión Sectorial de Investigación Científica-Universidad de la República (Uruguay). M.F.G., E.T., R.F., H.C., and M.C. are Sistema Nacional de Investigadores-ANII researchers., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

This work was financially supported by MICINN (PID2019-106832RB-I00), MICINN through the Severo Ochoa Program for Centers of Excellence for the FUNFUTURE (CEX2019-000917-S project) and the Generalitat de Catalunya (2017/SGR/1720). D. Ch.-L. acknowledges funding by project no. PGC2018-102047-B-I00 (MCIU/AEI/FEDER, UE). Zhen Li is enrolled in the UAB PhD program and acknowledges the China Scholarship Council (CSC) for his PhD grant (201808310071)., A new unsymmetric carborane-based dicarboxylic linker provided a 1D Cu2-paddle wheel coordination polymer (2) with much higher hydrolytic stability than the corresponding 2D Cu2-paddle wheel polymer (1), obtained from a related more symmetrical carborane-based linker. Both 1 and 2 were used as efficient heterogeneous catalysts for a model aza-Michael reaction but only 2 can be reused several times without significant degradation in catalytic activity., Spanish Government, European Commission PID2019-106832RB-I00, MICINN through the Severo Ochoa Program for Centers of Excellence for the FUNFUTURE CEX2019-000917-S, Generalitat de Catalunya, General Electric 2017/SGR/1720, MCIU/AEI/FEDER, UE PGC2018-102047-B-I00, China Scholarship Council 201808310071

Although a variety of cancers are initially susceptible to chemotherapy, they eventually develop multi-drug resistance. To overcome this situation, more effective and selective treatments are necessary using anti-tumour agents that act in two or more ways and offer greater therapeutic benefits over single-mechanism entities. In this study, we report on treating cancer with Na[3,3′-57Fe(1,2-C2B9H11)2], which offers the possibility of dual action (radiation-drug combinations) to improve the clinical benefits and reduce healthy tissue toxicity. An approach to evaluating the potential of [o-57FESAN]− to treat glioblastoma using the Mössbauer effect is presented. As the therapeutic outcomes rely on the amount and distribution of [o-57FESAN]− inside the cells, several studies, using magnetization, Mössbauer spectroscopy and nuclear microscopy techniques, were performed to ascertain the uptake of [o-57FESAN]− in U87 glioblastoma cells. [o-57FESAN]− was found to be within the cells; 29% of its uptake was in the nuclear fraction, which is a particularly desirable target, because the nucleus is the cell's control centre where DNA and the transcription machinery reside. Irradiation studies with 2D and 3D cellular models of U87 cells showed that the growth inhibition effect observed was more pronounced when [o-57FESAN]− was used in combination with the Mössbauer effect in low total dose regimens, suggesting that this procedure either alone or as adjuvant may be useful for glioblastoma treatment., This work was supported by the Spanish Ministerio de Economía y Competitividad (PID2019-106832RB-100) and the Generalitat de Catalunya (2017SGR1720) and by the Fundação para a Ciência e Tecnologia (FCT/MEC) for projects UID/MULTI/04349/2020, PTDC/BTM-TEC/29256/2017, UIDB/04565/2020, UIDP/04565/2020 (iBB/IST), LA/P/0140/2020 (Associate Laboratory Institute for Health and Bioeconomy – i4HB), PTDC/QUI-QIN/32240/2017, LISBOA-01-0145-FEDER-022096 (National Infrastructure Roadmap, LTHMFL-NECL) and GCT grant to A. C. Cerdeira (BL156/2019_IST-ID). A. B. Buades was enrolled in the PhD program of the UAB. C. I. G. Pinto is enrolled in the PhD scholarship 689 DFA/BD/07119/2020. The authors thank Dr Moulay Sougrati, Charles Gerhardt Institute, ICGM UMR 5253, Montpellier, France for a kind gift of 57FeCl2. The LMRI (Metrology Laboratory of Ionizing Radiation) team is acknowledged for their support in the X-ray irradiation setup., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

Cobaltabis(dicarbollide) anion ([o-COSAN]- ) is a well-known metallacarborane with multiple applications in a variety of fields. In aqueous solution, the cisoid rotamer is the most stable disposition in the ground state. The present work provides theoretical evidence on the possibility to photoinduce the rotation from the cisoid to the transoid rotamer, a conversion that can be reverted when the ground state is repopulated. The non-radiative decay mechanisms proposed in this work are coherent with the lack of fluorescence observed in 3D fluorescence mapping experiments performed on [o-COSAN]- and its derivatives. This phenomenon induced by light has the potential to destruct the vesicles and micelles cisoid [o-COSAN]- typically forms in aqueous solution, which could lead to promising applications, particularly in the field of nanomedicine., This work was supported by the Generalitat Valenciana (GV, project GV/2020/226), Generalitat de Catalunya (2017 SGR 1720), and the Spanish Ministerio de Ciencia e Innovación (MICINN, projects CTQ2017-87054-C2-2–304-P and PID2019-106832RB-I00). A.M.A.A. is grateful to the Erasmus+ Programme of the European Comission for his Erasmus Mundus TCCM scholarship. A.F.-M. is grateful to the GV and the European Social Fund for the postdoctoral contract APOSTD/2019/149 and to the MICINN for the Juan de la Cierva contract IJC2019-039297-I. D.R.-S. is grateful to the MICINN for the “Ramón y Cajal” grant (RYC-2015–19234). “Severo Ochoa” Program for Centers of Excellence in R&D 234 (SEV-2015-0496) is appreciated. J. A. M. Xavier acknowledges DOC-FAM programme under the Marie Sklodowska-Curie grant agreement No. 754397 and is enrolled in the PhD program of the UAB. Computations have been conducted at the local QCEXVAL and the LluisVives and Tirant III clusters of the Servei d'Informàtica (University of Valencia). We thank Dr. Jordi Faraudo (ICMAB-CSIC) for the scientific discussions., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

This proceeding article compiles current research on the development of boron delivery drugs for boron neutron capture therapy that was presented and discussed at the National Cancer Institute (NCI) Workshop on Neutron Capture Therapy that took place on April 20-22, 2022. The most used boron sources are icosahedral boron clusters attached to peptides, proteins (such as albumin), porphyrin derivatives, dendrimers, polymers, and nanoparticles, or encapsulated into liposomes. These boron clusters and/or carriers can be labeled with contrast agents allowing for the use of imaging techniques, such as PET, SPECT, and fluorescence, that enable quantification of tumor-localized boron and their use as theranostic agents., C.V. thanks the Spanish Ministerio de Economiay Competitividad (PID2019-106832RB-100) and the Generalitat de Catalunya (2017SGR1720). H.N. received a Grant-in-Aid for Scientific Research (B) (No. 21H02066) from MEXT, Japan. M.G.H.V. thanks the National Institutes of Health grant number T34 GM136452. R.P. thanks the National Institutes of Health, grant number R21 CA259911 and the Department of Neurosurgery, Cedars Sinai MedicalCenter, Los Angeles., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

Over the years, extensive research has been carried out to optimize the oxygen evolution reaction (OER) by adopting different techniques as well as catalysts. Conducting organic polymers such as PEDOT have been employed to study the reaction but have failed to lower the over-potential for the reaction. Here we show electrochemically made, intimately blended, dual redox reversible materials incorporating PEDOT and metallacarboranes. The metallacarboranes act as doping agents but with tunable E1/2 potentials. The tunability of E1/2 allows the overlapping of the two redox potentials which subsequently leads to their synergy. The physico-chemical properties of the metallacarboranes fade and become integrated with PEDOT to form a dual redox reversible system. Therefore, the properties of the dopant are modified by the polymer. Thus, due to its high E1/2, the Co4+/3+ couple would not be an efficient electrocatalyst for water oxidation but when it is immersed in the PEDOT matrix the Co4+/3+ potential is more accessible so that very low overpotential values are obtained, which justifies the title of the work, How to switch from a poor PEDOT:X oxygen evolution reaction (OER) to a good one. The dual redox reversible system has been extensively characterized and has been shown to be a promising candidate for the water oxidation reaction., Jewel A. M. Xavier and Isabel Fuentes have contributed equally to this work. We gratefully acknowledge the Spanish Ministerio de Economía y Competitividad (PID2019-106832RB-I00) and Generalitat de Catalunya (2017SGR1720). Jewel A. M. Xavier acknowledges the DOC-FAM programme under the Marie Sklodowska-Curie grant agreement no. 754397. This work was also funded by the Spanish Ministry of Science, through the “Severo Ochoa” Programme for Centers of Excellence in R&D (CEX2019-000917-S). Jewel A. M. Xavier and Miquel N. M are enrolled in the PhD program of UAB., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

Post-synthetic modification of a dynamic carborane-based soft porous crystal (1 * DMF) by in situ polymerization of pyrrole to polypyrrole (PPy) provided a permanently porous MOF/polypyrrole hybrid composite material that did not show the dynamic behavior of the mother MOF. Apart from stability, the introduction of conductive PPy in the composite material brings new properties to the otherwise non-conductive MOF., This work was financially supported by MINECO (CTQ2016-75150-R, PID2019-106832RB-I00) and the Generalitat de Catalunya (2017/SGR/1720). ICMAB acknowledges the support of the Spanish MINECO (Grant SEV-2015-0496). Z. Li is enrolled in the UAB PhD program and acknowledges the China Scholarship Council (CSC) for his PhD grants (201808310071). Z. Li thanks Fangchang Tan and Lei Gan for their assistance with the synthesis of 1 ⊃ DMF. The present publication is dedicated to Prof. Alan Welch on the occasion of his retirement from Heriot-Watt University.

2D/2D fusion of aromatic halves leading to a global aromatic is found in many polycyclic aromatic hydrocarbons. 3D/3D aromaticity is also found in fused boranes that follow the Jemmis’ mno rule, but 2D/3D aromaticity is difficult or impossible to achieve.

This article is part of the themed collection: Boron Chemistry in the 21st Century: From Synthetic Curiosities to Functional Molecules, A set of o-carborane-appended π-conjugated fluorophores and their light-emitting properties in the solid state are reported. The aggregation-induced emission enhancement (AIEE) exhibited for one of the fluorenyl derivatives paved the way to successfully preparing o-carborane-containing organic nanoparticles (NPs) homogeneously dispersed in aqueous media that maintain their luminescence properties. Notably, NPs processed as thin films also show high fluorescence efficiency, suggesting potential optical and optoelectronic applications., This work was financially supported by MICINN (PID2019-106832RB-I00, PID2019-105622RB-I00 and the Severo Ochoa Program for Centers of Excellence for the FUNFUTURE CEX2019-000917-S project). S. S. acknowledges financial support from DOC-FAM, the European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 754397. Z. K. is grateful for the general support of the Premium Postdoctoral Research Program 2019. We thank Dr Claudio Roscini from ICN2 for his kind help with the solid state luminescence measurements. Sohini Sinha is enrolled in the UAB PhD Program., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

Ferrocene and its derivatives have been extensively used as an internal reference in electrochemical processes. Yet, they possess limitations such as solvent restrictions that require chemical modifications. In this regard, we have studied the use of metallacarboranes [3,3'-M(1,2-C2B9H11)2]- (M = Co, Fe) as general internal reference systems and have proven their suitability by thoroughly investigating their electrochemical properties in both aqueous and organic electrolytes without any derivatization., This work was funded by the Spanish Ministry of Science, through the ‘‘Severo Ochoa’’ Programme for Centres of Excellence in R&D (CEX2019-000917-S) as well as the Ministerio de Economia y Competitividad (PID2019-106832RB-I00), (PID2020- 116728RB-I00, CTQ2015-71955-RED ELECTROBIONET) and Generalitat de Catalunya (2017SGR1720) are appreciated. J. A. M. Xavier acknowledges DOC-FAM programme under the Marie Sklodowska-Curie grant agreement no. 754397 and is enrolled in the PhD programme in UAB. Support from the Community of Madrid (TRANSNANOAVANSENS S2018/NMT-4349), is acknowledged., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

Luminescent lanthanide metal-organic frameworks (Ln-MOFs) have been shown to exhibit relevant optical properties of interest for practical applications, though their implementation still remains a challenge. To be suitable for practical applications, Ln-MOFs must be not only water stable but also printable, easy to prepare, and produced in high yields. Herein, we design and synthesize a series of

Benzene and pyrene can be synthetically linked to [o-COSAN]

Luminescent lanthanide metal-organic frameworks (Ln-MOFs) have been shown to exhibit relevant optical properties of interest for practical applications, though their implementation still remains a challenge. To be suitable for practical applications, Ln-MOFs must be not only water stable but also printable, easy to prepare, and produced in high yields. Herein, we design and synthesize a series of m CB-Eu y Tb 1-y (y = 0-1) MOFs using a highly hydrophobic ligand mCBL1: 1,7-di(4-carboxyphenyl)-1,7-dicarba-closo-dodecaborane. The new materials are stable in water and at high temperature. Tunable emission from green to red, energy transfer (ET) from Tb3+ to Eu3+, and time-dependent emission of the series of mixed-metal m CB-Eu y Tb 1-y MOFs are reported. An outstanding increase in the quantum yield (QY) of 239% of mCB-Eu (20.5%) in the mixed mCB-Eu0.1Tb0.9 (69.2%) is achieved, along with an increased and tunable lifetime luminescence (from about 0.5 to 10 000 μs), all of these promoted by a highly effective ET process. The observed time-dependent emission (and color), in addition to the high QY, provides a simple method for designing high-security anticounterfeiting materials. We report a convenient method to prepare mixed-metal Eu/Tb coordination polymers (CPs) that are printable from water inks for potential applications, among which anticounterfeiting and bar-coding have been selected as a proof-of-concept., This work was financially supported by the MINECO (PID2019-106832RB-I00), MICINN through the Severo Ochoa Program for Centers of Excellence for the FUNFUTURE (CEX2019-000917-S, MDM-2017-0767, and SEV-2017-0706 projects), grant RTI2018-098027-B-C21 funded by MCIN/AEI/10.13039/501100011033 and by ERDF A way of making Europe and the Generalitat de Catalunya (2017/SGR/1720 and SGR2017-1289). Z.L. is enrolled in the UAB Ph.D. program and acknowledges the China Scholarship Council (CSC) for his Ph.D. grant (201808310071)., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

This work was supported by the Spanish Ministerio de Economia y Competitividad (PID2019-106832RB-100, and SAF2017-82261-P grant cofounded by the European Regional Development Fund) and the Generalitat de Catalunya (2017SGR1720). J. A. M. Xavier acknowledges DOC-FAM program under the Marie Sklodowska-Curie grant agreement N degrees 754397. A. B. Buades, M. Nuez and J. A. M. Xavier are enrolled in the PhD program of the UAB., The Na[3,3’-Fe(8-I-1,2-C2B9H10)2] and Na[2,2’-M(1,7-C2B9H11)] (M = Co3+, Fe3+) small molecules are synthesized and the X-ray structures of [(H3O)(H2O)5][2,2’-Co(1,7-C2B9H11)2] and [Cs(MeCN)][8,8’-I2-Fe(1,2 C2B9H10)2], both displaying a transoid conformation of the [M(C2B9)2]− framework, are reported. Importantly, the supramolecular structure of [(H3O)(H2O)5][2,2’-Co(1,7-C2B9H11)2] presents 2D layers leading to a lamellar arrangement of the anions while the cation layers form polymeric water rings made of six- and fourmembered rings of water molecules connected via OH⋯H hydrogen bonds; B–H⋯O contacts connect the cationic and anionic layers. Herein, we highlight the influence of the ligand isomers (ortho-/meta-), the metal effect (Co3+/Fe3+) on the same isomer, as well as the influence of the presence of the iodine atoms on the physical–chemical and biological properties of these molecules as antimicrobial agents to tackle antibioticresistant bacteria, which were tested with four Gram-positive bacteria, five Gram-negative bacteria, and three Candida albicans strains that have been responsible for human infections. We have demonstrated an antimicrobial effect against Candida species (MIC of 2 and 3 nM for Na[3,3’-Co(8-I-1,2-C2B9H10)2] and Na[2,2’-Co (1,7-C2B9H11)2], respectively), and against Gram-positive and Gram-negative bacteria, including multiresistant MRSA strains (MIC of 6 nM for Na[3,3’-Co(8-I-1,2-C2B9H10)2]). The selectivity index for antimicrobial activity of Na[3,3’-Co(1,2-C2B9H11)2] and Na[3,3’-Co(8-I-1,2-C2B9H10)2] compounds is very high (165 and 1180, respectively), which reveals that these small anionic metallacarborane molecules may be useful to tackle antibioticresistant bacteria. Moreover, we have demonstrated that the outer membrane of Gram-negative bacteria constitutes an impermeable barrier for the majority of these compounds. Nonetheless, the addition of two iodine groups in the structure of the parent Na[3,3’-Co(1,2-C2B9H11)2] had an improved effect (3–7 times) against Gram-negative bacteria. Possibly the changes in their physical–chemical properties make the meta-isomers and the ortho-di-iodinated small molecules more permeable for crossing this barrier. It should be emphasized that the most active metallabis(dicarbollide) small molecules are both transoid conformers in contrast to the ortho- [3,3’-Co(1,2-C2B9H11)2]− that is cisoid. The fact that these small molecules cross the mammalian membrane and have antimicrobial properties but low toxicity for mammalian cells (high selectivity index, SI) represents a promising tool to treat infectious intracellular bacteria. Since there is an urgent need for antibiotic discovery and development, this study represents a relevant advance in the field., Spanish Government PID2019-106832RB-100 SAF2017-82261-P, Generalitat de Catalunya, General Electric 2017SGR1720, DOC-FAM program under the Marie Sklodowska-Curie grant 754397

Benzene and pyrene can be synthetically linked to [o-COSAN]- keeping their aromaticity. In contrast, naphthalene and anthracene are extruded in the same reaction. We have proven that extrusion is only favorable if the number of Clar's π-sextets remains constant. Thus, Clar has the answer to whether an attached polycyclic aromatic hydrocarbon to [o-COSAN]- is extruded or not., This work has been supported by the Ministerio de Ciencia e Innovación of Spain (Projects PID2020-113711GB-I00, PID2019-106832RB-I00, PID2019-106830GB-I00, and MDM-2017-0767) and the Catalan Conselleria de Recerca i Universitats (projects 2017SGR39, 2017SGR1720, and 2017SGR348). Excellent service by the Supercomputer center of the Consorci de Serveis Universitaris de Catalunya (CSUC) is gratefully acknowledged. Open Access funding provided thanks to the CRUE-CSIC agreement with Wiley., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

Glioblastoma multiforme (GBM) is the most common and fatal primary brain tumor, and is highly resistant to conventional radiotherapy and chemotherapy. Therefore, the development of multidrug resistance and tumor recurrence are frequent. Given the poor survival with the current treatments, new therapeutic strategies are urgently needed. Radiotherapy (RT) is a common cancer treatment modality for GBM. However, there is still a need to improve RT efficiency, while reducing the severe side effects. Radiosensitizers can enhance the killing effect on tumor cells with less side effects on healthy tissues. Herein, we present our pioneering study on the highly stable and amphiphilic metallacarboranes, ferrabis(dicarbollides) ([o-FESAN]- and [8,8'-I2-o-FESAN]-), as potential radiosensitizers for GBM radiotherapy. We propose radiation methodologies that utilize secondary radiation emissions from iodine and iron, using ferrabis(dicarbollides) as iodine/iron donors, aiming to achieve a greater therapeutic effect than that of a conventional radiotherapy. As a proof-of-concept, we show that using 2D and 3D models of U87 cells, the cellular viability and survival were reduced using this treatment approach. We also tested for the first time the proton boron fusion reaction (PBFR) with ferrabis(dicarbollides), taking advantage of their high boron (11B) content. The results from the cellular damage response obtained suggest that proton boron fusion radiation therapy, when combined with boron-rich compounds, is a promising modality to fight against resistant tumors. Although these results are encouraging, more developments are needed to further explore ferrabis(dicarbollides) as radiosensitizers towards a positive impact on the therapeutic strategies for GBM., The authors received support from the Spanish Ministerio de Economía y Competitividad (PID2019-106832RB-100), the Generalitat de Catalunya (2017SGR1720), FCT - Fundação para a Ciência e a Tecnologia, in the scope of the project UID/Multi/04349/2019 and the projects LISBOA-01-0247-FEDER-045904 and UTAP-EXPL/FMT/0020/2021 of Centro de Ciências e Tecnologias Nucleares/IST, PTDC/BTM-TEC/29256/2017, UIDP/04565/2020 of iBB/IST, UIDP/04378/2020 and UIDB/04378/2020 of the Research Unit on Applied Molecular Biosciences – UCIBIO and the project LA/P/0140/2020 of the Associate Laboratory Institute for Health and Bioeconomy – i4HB. The Metrology Laboratory of Ionizing Radiation team of Centro Tecnológico e Nuclear, Instituto Superior Técnico (CTN/IST) is acknowledged for their support in the irradiation setups. Miquel Nuez-Martínez is enrolled in the PhD program of the UAB. MQM and VMA acknowledge financial support by the Spanish Government MCIN/AEI/10.13039/501100011033 (project 2019-108434GB-I00 to VMA and project IJC2018-035283-I to MQM), and Universitat Jaume I (project UJI-B2018-53 to V. M. A. and project UJI-A2020-21 to MQM). SV thanks Croatian Science Foundation (project IP-2018-01-3168). Catarina I.G. Pinto is enrolled in the PhD scholarship 689 DFA/BD/07119/2020., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

A new unsymmetric carborane-based dicarboxylic linker provided a 1D Cu

The relatively low symmetry of [3,3'-Co(1,2-C2B9H11)2]- ([1]-), along with the high number of available substitution sites, 18 on the boron atoms and 4 on the carbon atoms, allows a fairly regioselective and stepwise chlorination of the platform and therefore a very controlled tuning of the electrochemical potential tuning. This is not so easily found in other systems, e.g., ferrocene. In this work, we show how a single platform with boron and carbon in the ligand, and only cobalt can produce a tuning of potentials in a stepwise manner in the 1.3 V range. The platform used is made of two icosahedra sharing one vertex. The E1/2 tuning has been achieved from [1]- by sequential chlorination, which has given potentials whose values increase sequentially and linearly with the number of chloro groups in the platform. [Cl8-1]-, [Cl10-1]-, and [Cl12-1]- have been obtained, which are added to the existing [Cl-1]-, [Cl2-1]-, [Cl4-1]-, and [Cl6-1]- described earlier to give the 1.3 V range. It is envisaged to extend this range also sequentially by changing the metal from cobalt to iron. The last successful synthesis of the highest chlorinated derivatives of cobaltabis(dicarbollide) dates back to 1982, and since then, no more advances have occurred toward more substituted metallacarborane chlorinated compounds. [Cl8-1]-, [Cl10-1]-, and [Cl12-1]- are made with an easy and fast method. The key point of the reaction is the use of the protonated form of [Co(C2B9H11)2]-, as a starting material, and the use of sulfuryl chloride, a less hazardous and easier to use chlorinating agent. In addition, we present a complete, spectroscopic, crystallographic, and electrochemical characterization, together with a study of the influence of the chlorination position in the electrochemical properties., We gratefully acknowledge the Spanish Ministerio de Economía y Competitividad (Grant PID2019-106832RB-I00) and Generalitat de Catalunya (Grant 2017SGR1720). A.B.B. was enrolled in the Ph.D. program of UAB., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

Monovalent cations, Cs+, and alkylammonium ([NR4]+) salts have traditionally been used to precipitate the anions of boranes, carborane and metallocarborane clusters. In contrast, in the body and in living organisms in general, divalent cations have a special relevance. In this work, we isolate for the first time the cobaltabis(dicarbollide) salts of the biocompatible divalent cations of biological importance that can have application both in biology and in materials science. The preparation of Ca2+, Mg2+ and Fe2+ salts of anionic iodinated nido-[C2B9H12]− and cobaltabis(dicarbollide) as well as its di-, tetra- and octa-iodinated derivatives are reported. Ca2+ and Mg2+ are hard Lewis acids and thus forms aqua ions if water is present in the synthetic process. All solid Ca2+ and Mg2+ salts studied in this work contained water molecules coordinated that have been detected by IR and TGA/DSC. Fe2+ is a medium hard Lewis acid and Fe3+ is a hard one. In acetone they do not coordinate to cobaltabis(dicarbollide) anion, but are solvated by acetone. The studied Ca2+ salts of iodinated cobaltabis(dicarbollide) are basically inorganic small molecules that provide at once the biocompatible divalent Ca2+ cation and and iodinated anions thus simultaneously providing an X-ray contrast agent and/or bone defect repairing agent in regenerative medicine., This work has been supported by the Spanish Ministerio de Economía y Competitividad (CTQ2016-75150-R) and the Generalitat de Catalunya (2017SGR1720). Miquel Nuez is enrolled in the PhD program of the UAB.

An inorganic sandwich molecule, Na[Co(C2B9H11)2], able to produce vesicles through self‐assembly and known to produce strong dihydrogen‐bond interactions with amine groups is capable of interacting with proteins. This dual non‐bonding ability of Na[Co(C2B9H11)2] is what makes this molecule unique: it can be firmly anchored to a protein surface and is capable of extending over it. To prove this, the widely available bovine serum albumin (BSA), which has many pendant amino groups in its structure, has been taken as the model protein. It has been found that around 100 molecules of Na[Co(C2B9H11)2] preserve the native structure of BSA, while endorsing it with a significantly increased stability with respect to chemical‐ and thermal‐induced denaturation due to efficient encapsulation. The advantages of this encapsulation technique are two‐fold; the first is its simplicity as it relies on the anchoring capacity of Na[Co(C2B9H11)2] to the surface of the protein through the amine‐containing residues and the second is its self‐assembling capacity allowing it to spread across the surface. The dense shield of protection offered by Na[Co(C2B9H11)2] has been demonstrated by the inhibition of BSA pseudo‐esterase activity, which indicates that the inorganic corset around BSA protects its reactive surface residues, thereby preventing their acetylation.

Background: Carboranylanilinoquinazoline-hybrids, developed for boron neutron capture therapy, have demonstrated cytotoxicity against murine-glioma cells with EGFR-inhibition ability. In addition, their adequate aqueous/metabolic stabilities and ability to cross blood–brain barrier make them good leads as to become antiglioma drugs. Aim: Analyze drug-like properties of representative carboranylanilinoquinazolines. Materials & methods: To expand carboranylanilinoquinazolines therapeutic spectrum, we studied their ability to act against glioma-mammal cells, U-87 MG and other tyrosine kinase-overexpress cells, HT-29. Additionally, we predicted theoretically and studied experimentally drug-like properties, in other words, organization for economic cooperation and development-recommended toxicity-studies and, due to some aqueous-solubility problems, and vehicularization for oral and intravenous administrations. Conclusion: We have identified a promising drug-candidate with broad activity spectrum, appropriate drug-like properties, adequate toxicological behavior and able ability to be loaded in suitable vehicles.

The detection of a drug belonging to the Sulfonamide class of compounds, namely Sulfapyridine, is reported in this work using an in-situ and fast potentiometric method. The strategy employed for this detection is based on the novel ion pair complex, [Sulfapyridine-H]+[Co(C2B9H11)2]- acting as the active site for highly selective recognition of Sulfapyridine. This enables the sensor's selectivity to be improved by incorporating the target molecule to the selective membrane. In this work, all solid state Sulfapyridine selective microelectrodes based on PVC-type membranes were prepared using three different plasticizers and the aforementioned ion pair complex. The sensors developed have provided quick and accurate response within the range of 10−6 mol/dm3 to 10−3 mol/dm3 of Sulfapyridine concentration and showed a Nernstian slope between 47 and 61 depending upon the type of plasticizer used. The lowest limit of detection achieved was 4 μmol/dm3. The potentiometric coefficient of selectivity, KA,Bpot, has shown that the Sulfapyridine-selective microsensors were highly selective towards Sulfapyridine even when compared to other members of the Sulfonamides class of compounds. In addition, from the Reilley diagram it can be observed that the sensor signal is stable for a working pH interval between 6.00 and 8.00.

Four-fold aryl substituted o-carborane derivatives with defined patterns of substitution at the antipodal region of the cluster carbon atoms have been achieved. It is proven that this region is congested but lacks steric hindrance. Also, the two antipodal sites Cc–Cc and B9–B12 are affected very distinctly by electron donor substituents., This work has been supported by the Spanish Ministerio de Economı´a y Competitividad (CTQ2016-75150-R), the Generalitat de Catalunya (2017SGR1720) and European Union’s Horizon 2020 Marie Skłodowska-Curie grant agreement MSCA-IF-2016- 751587., We acknowledge support of the publication fee by the CSIC Open Access Support Initiative through its Unit of Information Resources for Research (URICI

Does the use of Internet for professional purposes foster employees' job satisfaction? We focus on six main work characteristics – income, education, occupation type, autonomy, time pressure and social interactions – and we develop new hypotheses on how Internet use moderates the effects of these factors. We use data from the European Working Conditions Survey, and estimate a bivariate ordered probit model, and a hierarchical ordered probit model. The results point out that Internet technologies enhance job satisfaction by improving access to data and information, creating new activities, and facilitating communication and social interactions. However, these positive effects are skewed. Workers in some occupations, and with higher income and education levels, benefit relatively more from the Internet vis-a-vis workers in occupations that are more weakly related to ICTs activities.

This work was financially supported by MICINN (PID2019-106832RB-I00, PGC2018-093863-B-C21), MICINN through the Severo Ochoa Program for Centers of Excellence for the FUNFUTURE (CEX2019-000917-S and MDM-2017-0767 projects) and the Generalitat de Catalunya (2017/SGR/1720 and SGR2017-1289). D. Ch.-L. acknowledges funding by project no. PGC2018-102047-B-I00 (MCIU/AEI/FEDER, UE). J. Soldevila-Sanmartin is enrolled in the UAB PhD program and acknowledges the PIF pre-doctoral Fellowship from the UAB for his pre-doctoral grant (no. 19032/2). E. R. acknowledges computer resources, technical expertise and assistance provided by the CSUC. We thank Prof. D. Ruiz and Dr C. Roscini for the quantum yield measurements. The present publication is dedicated to Prof. Elena Shubina on the occasion of her 70th birthday., Incorporation of one or two o-carborane moieties at the backbone of the pyrazole ring was achieved by lithiation and nucleophilic addition onto the corresponding 3,5-dimethyl-1-(2-toluene-p-sulfonyloxyethyl)pyrazole. Two monosubstituted carboranyl pyrazoles (L2 and L3) and one disubstituted carboranyl pyrazole (L4) were synthesized and fully characterized. All new compounds, and the corresponding monosubstituted phenylderivative (L1) behave as N-type ligands upon coordination with CuI to afford different polynuclear Cu(I) compounds 1-4. Compounds 1-4 were fully characterized and their molecular structures were determined by X-ray diffraction. It is noteworthy that whereas the pyrazolylphenyl ligand L1, without o-carborane, provides a 1D coordination polymer (1), ligands containing carborane, L2-L3, affords 0D coordination compounds 2 and 3, and disubstituted carboranyl pyrazole ligand L4 gives rise to a 3D coordination polymer. The photoluminescence behaviour of compounds 1-4 has been investigated in the solid state and by TDDFT calculations for molecular compounds 2 and 3. Complex 2 exhibits blue emission with a maximum at 483 nm and a high fluorescence quantum yield of 66.5%. According to TDDFT calculations the emission occurs from LUMO to HOMO-1 and HOMO-2 and deexcitation could be described as cluster-centred excited state of d-s transition in origin. This result contradicts previous studies of scarce tri-coordinated rhombohedral Cu(I) clusters, where it was assumed the origin of their emissions is (X + M)LCT in nature by analogy with tetra-coordinated rhombohedral Cu(I) clusters. Complex 3 exhibits very weak emission (Phi(F) of 5%) in the green region with a maximum at 517 nm, which according to TDDFT is through a (CC)-C-3 state. Calculations also show that, upon excitation, 3 suffers a notable distortion resulting in the total cleavage of the Cu4I4 framework. This cleavage could be the cause of the relatively large Stokes shift observed for 3. To the best of our knowledge, this is the first time that such behaviour is observed for this type of octahedral compounds. Additionally, the 1D polymer 1 exhibits weak fluorescence emission in the orange range with a maximum at 609 nm and a remarkable Stokes shift, whereas the 3D polymer 4 exhibits a similar emission to compound 2, with a moderate quantum yield (FF of 13.7%)., Spanish Government European Commission PID2019-106832RB-I00 PGC2018-093863-B-C21, MICINN through the Severo Ochoa Program for Centers of Excellence for the FUNFUTURE CEX2019-000917-S MDM-2017-0767, Generalitat de Catalunya 2017/SGR/1720 SGR2017-1289, MCIU/AEI/FEDER, UE PGC2018-102047-B-I00, UAB 19032/2

Background About 30–50% of Primary Care (PC) users in Spain suffer mental health problems, mostly mild to moderate anxious and depressive symptoms, which account for 2% of Spain's total Gross domestic product and 50% of the costs associated to all mental disorders. Mobile health tools have demonstrated to cost-effectively reduce anxious and depressive symptoms while machine learning (ML) techniques have shown to accurately detect severe cases. The main aim of this project is to develop a comprehensive ML digital support platform (PRESTO) to cost-effectively screen, assess, triage, and provide personalized treatments for anxious and depressive symptoms in PC. Methods The project will be carried out in 3 complementary phases: First, a ML predictive severity model will be built based on all the cases referred to the PC mental health support programme during the last 5 years in Catalonia. Simultaneously, a smartphone app to monitor and deliver psychological interventions for anxiety and depressive symptoms will be developed and tested in a clinical trial. Finally, the ML models and the app will be integrated in a comprehensive decision-support platform (PRESTO) which will triage and assign to each patient a specific intervention based on individual personal and clinical characteristics. The effectiveness of PRESTO to reduce waiting times in receiving mental healthcare will be tested in a stepped-wedge cluster randomized controlled trial in 5 PC centres. Discussion PRESTO will offer timely and personalized cost-effective mental health treatment to people with mild to moderate anxious and depressive symptoms. This will result in a reduction of the burden of mental health problems in PC and on society as a whole. Trial registration The project and their clinical trials were registered in Clinical Trials.gov: NCT04559360 (September 2020).

A set of mesomorphic materials in which the o-carborane cluster is covalently bonded to a cholesteryl benzoate moiety (mesogen group) through a suitably designed linker is described. The olefin cross-metathesis between appropriately functionalized styrenyl-o-carborane derivatives and a terminal alkenyl cholesteryl benzoate mesogen (all type I terminal olefins) leads to the desired trans-regioisomer, which is the best-suited configuration to obtain mesomorphic properties in the final materials. The introduction of different substituents (R = H (M2), Me (M3), or Ph (M4)) to one of the carbon atoms of the o-carborane cluster (Ccluster) enables the tailoring of liquid crystalline properties. Compounds M2 and M3 show the chiral nematic (N*) phase, whereas M4 do not show liquid crystal behavior. Weaker intermolecular interactions in the solid M3 with respect to those in M2 may allow the liquid crystallinity in M3 to be expressed as enantiotropic behavior, whereas breaking the stronger intermolecular interaction in the solid state of M2 leads directly to the isotropic state, resulting in monotropic behavior. Remarkably, M3 also displays the blue phase, which was observed neither in the chiral nematic precursor nor in the styrenyl-cholesterol model (M5) without an o-carborane cluster, which suggests that the presence of the cluster plays a role in stabilizing this highly twisted chiral phase. In the carborane-containing mesogens (M2 and M3), the o-carborane cluster can be incorporated without destroying the helical organization of the mesophase., This research was funded by MICINN grants (PID2019-106832RB-100 and CEX2019-000917-S) and Generalitat de Catalunya (2017/SGR/1720).

The cobalt bis(dicarbollide) complex, Na[3,3′-Co(η5-1,2-C2B9H11) (Na[1]), is an effective photoredox catalyst for the oxidation of alkenes to epoxides in water. Advantageous features of Na[1] include its lack of photoluminescence, high solubility and surfactant behavior in aqueous media, as well as the donor ability of the carborane ligand and high oxidizing power of the Co4+/3+ couple. These features differentiate it from the well-known and widely used photosensitizer tris (2,2′-bipyridine) ruthenium(ii) ([Ru(bpy)3]2+), which also participates in electron transfer through an outer sphere mechanism. A comparison of the catalytic performance of [Ru(bpy)3]2+ with Na[1] for alkene photo-oxidation is fully in favor of Na[1], as the former shows very low or null efficiency. With a catalyst loading of 0.1 mol% conversions between 65-97% have been obtained in short reaction times, 15 minutes, with moderate selectivity for the corresponding epoxide, due to the formation of side products as diols. But when the catalyst loading is reduced to 0.01 mol%, the selectivity for the corresponding epoxide increased considerably, being the only compound formed after 15 minutes of reaction (selectivity >99%). High TON values have been obtained (TON = 8500) for the epoxidation of aromatic and aliphatic alkenes in water. We have verified that Na[3,3′-Co(η5-1,2-C2B9H11)2] acts as a photocatalyst in both the epoxidation of alkenes and in their hydroxylation in aqueous medium with a higher rate for epoxidation than for hydroxylation. Preliminary photooxidation tests using methyl oleate as the substrate led to the selective epoxidation of the double bond. These results represent a promising starting point for the development of practical methods for the processing of unsaturated fatty acids, such as the valorisation of animal fat waste using this sustainable photoredox catalyst. This journal is, This research has been financed by MINECO (PID2019-106832RB-I00 CTQ2015-66143-P), Generalitat de Catalunya (2017 SGR 1720) and Universitat de Girona (PONT2020/05). “Severo Ochoa” Program for Centers of Excellence in R&D 234 (SEV-2015-0496) is appreciated. Dedicated to Prof. M. F. Hawthorne that passed away on July 8, 2021 for his great vision and development of boron hydrides, particularly boron clusters and metallacarboranes and their applications, especially in catalysis., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

The aim of our study was to assess if the sodium salt of cobaltabis(dicarbollide) and its di-iodinated derivative (Na[o-COSAN] and Na[8,8′-I2-o-COSAN]) could be promising agents for dual anti-cancer treatment (chemotherapy + BNCT) for GBM. Methods: The biological activities of the small molecules were evaluated in vitro with glioblastoma cells lines U87 and T98G in 2D and 3D cell models and in vivo in the small model animal Caenorhabditis elegans (C. elegans) at the L4-stage and using the eggs. Results: Our studies indicated that only spheroids from the U87 cell line have impaired growth after treatment with both compounds, suggesting an increased resistance from T98G spheroids, contrary to what was observed in the monolayer culture, which highlights the need to employ 3D models for future GBM studies. In vitro tests in U87 and T98G cells conclude that the amount of 10B inside the cells is enough for BNCT irradiation. BNCT becomes more effective on T98G after their incubation with Na[8,8′-I2-o-COSAN], whereas no apparent cell-killing effect was observed for untreated cells. Conclusions: These small molecules, particularly [8,8′-I2-o-COSAN]−, are serious candidates for BNCT now that the facilities of accelerator-based neutron sources are more accessible, providing an alternative treatment for resistant glioblastoma., This work was supported by the Spanish Ministerio de Economía y Competitividad (PID2019-106832RB-I00, RTI2018-096273-B-I00), the Generalitat de Catalunya (2017SGR1720, 2017SGR765) and the ‘Severo Ochoa’ Program for Centers of Excellence in R&D (SEV-2015-0496), S. Geninatti Crich received funding from AIRC (Associazione Italiana per la Ricerca sul Cancro) under IG 2019—ID. 23267 project and by Fundação para a Ciência e Tecnologia (FCT) Portugal for projects UID/MULTI/04349/2019 and PTDC/BTM-TEC/29256/2017 and for the PhD scholarship DFA/BD/ 07119/2020 to C.I.G. Pinto. A.L. and A.M.-J. participate in the networks of EPNOE, Red Nanocare RED2018-102469-T, and CSIC Interdisciplinary Platform for Sustainable Plastics towards a Circular Economy, SUSPLAST). Jewel A.M. Xavier acknowledges the DOC-FAM program under the Marie Sklodowska-Curie grant agreement nº 754397. Miquel Nuez-Martinez, Jewel A.M. Xavier, and Amanda Muñoz-Juan (Ph.D. scholarship FPU18/05190) are enrolled in the Ph.D. program of the UAB., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

The salts Na[ROC(O)Ph], Na[1-ROC(O)-1,12- C2B10H11], K2[1,4-(ROC(O))2-C6H4], and K2[1,12-(ROC(O))2- 1,12-C2B10H10], where R is the cobaltabis(dicarbollide)-diethylene glycol group [3,3′-Co(8-(OCH2CH2OCH2CH2)-1,2-C2B9H10)- (1′,2′-C2B9H11)]−, were synthesized from the corresponding carboxylate salt and the zwitterion [3,3′-Co(8-(CH2CH2O)2-1,2- C2B9H10)(1′,2′-C2B9H11)]. The dianion in K2[1,12-(ROC(O))2- 1,12-C2B10H10] showed at least one K+ cation to be tightly bound to the dianion via K···O and K···H−B interactions with both pcarborane and cobaltabis(dicarbollide) clusters on the basis of NMR and MS data and support of hybrid-DFT computations. An evaluation of the antimicrobial properties of these compounds revealed all of the salts to be highly effective antibacterial agents for four Gram-positive bacteria strains (standard minimum inhibitory concentration, MIC, of 1 mg/L for Na[ROC(O)Ph]; Na[3]) and antifungal agents for three Candida albicans strains (MIC 4 mg/L for the salts K2[4] and K2[6]). One of the four Gram-positive bacteria strains tested was a life-threatening superbug methicillin-resistant Staphylococcus aureus (MRSA) isolate, which is resistant to many commercial antimicrobial drugs. The cobaltabis(dicarbollide) derivative Na[3] has a remarkable inhibitory effect on the MRSA strain with an MIC of only 1 mg/L and a minimum bactericidal concentration (MBC) of 2 mg/L, thus suggesting its potential as an antibacterial agent against MRSA., This research was financed by the MINECO (CTQ2016-75150-R, CTQ2015-66143-P, and SAF2017-82261-P, with the last grant cofunded by the European Regional Development Fund) and the Generalitat de Catalunya (2017 SGR 1720).