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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).

PurposeThe aim of this study was to analyse the relationship between organizational citizenship and commitment in a sample of employees of banking branches in Puerto Rico. The specific objectives were to identify the practices of organizational citizenship and determine the relationship of altruism, awareness, courtesy, tolerance and civil virtue with organizational commitment.Design/methodology/approachThe research design was quantitative, descriptive, correlational and transversal. The research instrument was validated and obtained high coefficients.FindingsThe results confirm a significant statistical relationship between awareness, civil virtue, tolerance and altruism with organizational commitment.Research limitations/implicationsThis research has a positive impact on companies in increasing their finances with intangible strategies, and leadership styles can evolve towards civility. It suggests modifying the university curricula to prepare managers with intangible supervisory and performance management strategies through workshops, seminars and professional conferences.Practical implicationsOrganizations and employees develop their own traits and establish patterns of citizenship behaviour that allow them to create passionate and committed employees.Social implicationsThe research was able to predict that citizenship is related in a positive way to reach operational goals and fostering an atmosphere and image of cordiality as a success strategy. The contribution to the organizational policy can be established in the development processes among partners, in training, regulations and policies. It provides the academic contribution of the model.Originality/valueThis is the first attempt to evaluate citizenship behaviour in the banking industry in Puerto Rico.

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

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).

El COVID-19 ha generado una situación sin precedentes. Para afrontar el embate de esta crisis hace falta liderazgo, visión y colaboración del gobierno central y los GAD para combatir la propagación de la enfermedad en los cantones. El COVID-19 ha sido catalogado por la Organización Mundial de la Salud como una emergencia en salud pública de importancia internacional (ESPII); por lo tanto, en la ciudad de Babahoyo, el Gobierno Municipal necesita garantizar a la población Babahoyense la seguridad ciudadana a través de las instituciones del Sistema Nacional Descentralizado de Gestión de Riesgos (SNDGR) para que apliquen planes de contingencia y medidas de precaución ante la declaratoria de emergencia sanitaria.

Here, we report a short series of six new boron Schiff bases (BOSCHIBAs), four of them bearing anionic boron clusters. The boron complexes (1–2) were synthesized by the multicomponent reaction. The Boron Schiff bases were appropriately functionalized with boron cluster anions [B12H12]2− (3–4) and [3,3’-Co(C2B9H11)2]− (5–6). Remarkably, BOSCHIBAs bearing [B12H12]2− showed fluorescence emission to the NIR and far-red regions (3: 747 nm, 4: 690 nm), while 5 and 6 exhibited emission in the UV region (5: 525 and 6: 475 nm). Notably, complexes 2, 5, and 6 showed the highest photostability, followed by the boron complexes 1 and 3, which suggest that the nature of the boron cluster influences photostability properties. Compounds 3–4 represent the first example of boron Schiff bases bearing boron cluster anions [B12H12]2− exhibiting fluorescence emission in the NIR and far-red regions, make them potential candidates as fluorescence probes for bioimaging., The authors thanks to CONACYT (Grant: 240011) and the PAICYT (Grant: CE-1268-20) for the financial support. M. M. Corona-López thanks to CONACYT for the scholarship. This work was supported in part by MINECO (CTQ2016-75150-R project) and MICINN through the Agencia Estatal de Investigación (PID2019-106832RB−I00 project). People from ICMAB also acknowledge the support of MICINN through the Severo Ochoa Program for Centers of Excellence for the FUNFUTURE (CEX2019-000917-S) project.

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

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).

Four novel transition metal-carborane photosensitisers were prepared by Sonogashira cross-coupling of 1-(4-ethynylbenzyl)-2-methyl-o-carborane (A-CB) with halogenated Ru(II)- or Ir(III)-phenanthroline complexes. The resulting boron-rich complexes with one (RuCB and IrCB) or two carborane cages (RuCB2 and IrCB2) were spectroscopically characterised, and their photophysical properties investigated. RuCB displayed the most attractive photophysical properties in solution (λem 635 nm, τT 2.53 μs, and φp 20.4%). Nanosecond time-resolved transient absorption studies were used to explore the 3MLCT nature of the triplet excited states, and the highest singlet oxygen quantum yields (ΦΔ) were obtained for the mono-carborane-phenanthroline complexes (RuCB: 52% and IrCB: 25%). None of the complexes produce dark toxicity in SKBR-3 cells after incubation under photodynamic therapy (PDT) conditions. Remarkably, mono-carboranes RuCB and IrCB were the best internalised by the SKBR-3 cells, demonstrating the first examples of tris-bidentate transition metal-carborane complexes acting as triplet photosensitisers for PDT with a high photoactivity; RuCB or IrCB killed ∼50% of SKBR-3 cells at 10 μM after irradiation. Therefore, the high-boron content and the photoactive properties of these photosensitisers make them potential candidates as dual anti-cancer agents for PDT and Boron Neutron Capture Therapy (BNCT)., The authors thank Drs J. O'Brien, M. Reuther, and G. Hessman at Trinity College Dublin for spectroscopic and technical assistance, and the staff at the Servei de Microscòpia from Universitat Autònoma de Barcelona. This work was supported by Science Foundation Ireland (15/IA/3046), Spanish Ministerio de Ciencia e Innovación through Agencia Estatal de Investigación MICIIN (MAT2017-86357-C3-3-R and PID2019-106832RB-100/AEI/10.13039/501100011033 projects) and the Generalitat de Cataluña (2017-SGR-503 and 2017-SGR-1720 projects). People from ICMAB acknowledge the support of the Spanish MICINN through the Severo Ochoa Centers of Excellence Program, under grant CEX2019-000917-S. R. C.-K. acknowledges additional funding from the Higher Education Authority (HEA) and the Department of Further and Higher Education, Research, Innovation and Science.

A carbon-based hybrid nanocomposite, which consists of monoiodinated boron-cluster derivatives covalently attached to graphene oxide, is hereby introduced. This GO-I-COSAN has been synthesized using a novel boron-rich cobaltabis(dicarbollide) precursor with one iodide group attached to one of the boron atoms of the cluster (I-COSAN) and designed to be subsequently labeled with radioactive 124I for its use in positron emission tomography (PET). In vitro cytotoxicity studies of GO-I-COSAN with HeLa cells at different concentrations up to 48 h proved that the cell mortality was lower than 10%, indicating minimal cytotoxicity of the nanomaterial. Remarkably, internalization of the nanomaterial by cells was confirmed by transmission electron microscopy, which indicated its accumulation in the cytoplasm, without causing changes in either the size or morphology of the cells. Additionally, in vivo tests using Caenorhabditis elegans confirmed that GO-I-COSAN could be ingested by the worms, showing no significant damage and very low toxicity, which supports the results observed in the in vitro studies. Radioisotopic labeling of I-COSAN using a palladium-catalyzed isotopic exchange reaction with Na[124I]I and its subsequent functionalization onto GO was performed successfully, leading to formation of the radioactive nanocomposite GO-[124I]I-COSAN, which was quickly injected in mice. PET images at different times revealed excellent in vivo stability of the developed nanomaterial. No activity in thyroid and stomach was observed even at long times, proving that iodide did not detach from the material. GO-[124I]I-COSAN presented a favorable biodistribution profile, being mainly accumulated in the liver and slightly in the lung, with a long residence time on blood and progressive elimination via the gastrointestinal tract. It is noteworthy that the high boron content of this material paves the way toward theranostics because it benefits of a traceable boron delivery for boron neutron capture therapy., This work was supported by the Spanish Ministry of Science and Innovation MICINN, through the Severo Ochoa Program for Centers of Excellence FUNFUTURE (CEX2019-000917- S), for funding with an internal Severo Ochoa FIP project. J.L. thanks the Spanish Ministry of Economy and Competitiveness for funding through Grant CTQ2017-87637-R. Part of the work was conducted under the Maria de Maeztu Units of Excellence Programme (Grant MDM-2017-0720). A.M.-J. and A.L. are thankful for financial support from the Spanish Ministry of Science and Innovation through Project RTI2018- 096273-B-I00 and a Ph.D. scholarship for A.M.J. (FPU18/ 05190) and the Generalitat de Catalunya with Projects 2017SGR765 and 2017SGR581. A.M.-J. and A.L. participated in the MICINN, “Research Networks” nanoCARE (RED2018- 102469-T). This work has been conducted within the Biotechnology Doctoral Program of the Autonomous University of Barcelona (A.M.J). The authors thank the staff from the Servei de Cultius Cel·lulars and Servei de Microscopia, ̀ both at the UAB, for performing the cytotoxicity studies, cellular uptake analysis, and HRTEM.

Icosahedral metallacarboranes are θ‐shaped anionic molecules in which two icosahedra share one vertex that is a metal center. The most remarkable of these compounds is the anionic cobalt‐based metallacarborane [Co(C2B9H11)2]‐ , whose oxidation‐reduction processes occur via an outer sphere electron process. This, along with its low density negative charge, makes [Co(C2B9H11)2]‐ very appealing to participate in electron‐transfer processes. In this work, [Co(C2B9H11)2]‐ is tethered to a perylenediimide dye to produce the first examples of switchable luminescent molecules and materials based on metallacarboranes. In particular, the electronic communication of [Co(C2B9H11)2]‐ with the appended chromophore unit in these compounds can be regulated upon application of redox stimuli, which allows the reversible modulation of the emitted fluorescence. As such, they behave as electrochemically‐controlled fluorescent molecular switches in solution, which surpass the performance of previous systems based on conjugates of perylendiimides with ferrocene. Remarkably, they can form gels by treatment with appropriate mixtures of organic solvents, which result from the self‐assembly of the cobaltabisdicarbollide‐perylendiimide conjugates into 1D nanostructures. The interplay between dye π‐stacking and metallacarborane electronic and steric interactions ultimately governs the supramolecular arrangement in these materials, which for one of the compounds prepared allows preserving the luminescent behavior in the gel state., This work was supported by MINECO/FEDER (CTQ2015-65439-R and CTQ2016-75150-R projects) and Generalitat de Catalunya (2017 SGR00465 and 2017SGR1720projects). ICMAB acknowledges the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program, under grant SEV-2015-0496.L. P.thanksthe Universitat Autònoma de Barcelona for herpredoctoral PIF fellowship.

Objective: this study analyses long-term results of sublobar resection in daily clinical activity versus the standard procedure (lobectomy). Method: From a prospective database, patients treated with sublobar resection for NSCLC were identified (2007-2017). None of them had malignant disease in the 5 previous years nor induction treatment. Log-rank test was used to compare overall survival and disease free survival. One-to-one propensity score matching was performed for age, sex, stage, and comorbities to reduce bias selection. Results: 1214 patients were surgically treated for lung cancer in that period of time. Finally, 52 patients were included in sublobar group with following resections: pulmonary wedge 37(71.2%) cases; anatomic segmentectomy 15(28.8%) cases. Women 4(7.7%); Men 48(92.3%). Mean age: 68.6 y.o. (range 42-86). Pulmonary function test (FEV1 64.9% vs 77.3% p=0.004) and tumoral size (1.9cm vs 3.0cm p

A set of BODIPY‐carboranyl dyads synthesized by a Sonogashira cross‐coupling reaction, where different C‐substituted ortho‐ and meta‐carboranyl fragments have been linked to a BODIPY fluorophore is described. Chemical, photophysical and physicochemical analyses are presented, including NMR and SXRD experiments, optical absorption/emission studies and log P measurements. These studies, supported by DFT computations (M06‐2X/6‐31G**) provide an explanation to the largely divergent cell income that these fluorescent carboranyl‐based fluorophores display, for which a structural or physicochemical explanation remains elusive. By studying the cell uptake efficiency and subcellular localization for our set of dyads on living HeLa cells, we tracked the origins of these differences to significant variations in their static dipole moments and partition coefficients, which tune their ability to interact with lipophilic microenvironments in cells. Remarkably, m‐carboranyl‐BODIPY derivatives with a higher lipophilicity are much better internalised by cells than their homologous with o‐carborane, suggesting that m‐isomers are potentially better theranostic agents for in vitro bioimaging and boron carriers for BNCT., The work has been performed within the framework of the French-Mexican International Laboratory (LIA-LCMMC). Authors acknowledge support from PAPIIT (IN222819) and CONACyT. The work was supported by Spanish Ministerio de Economía y Competitividad, MINECO (CTQ2016-75150-R) and Generalitat de Catalunya (2017/SGR/1720). Doctoral scholarships were granted by CONACyT to P.L.-V (337958) and R. F.-C. (576635). We thank María E. Ochoa (CINVESTAV-IPN), Marco A. Leyva (CINVESTAV-IPN) and Flor R. Vega (FQ-UNAM) for NMR/HRMS experiments, SXRD experiments and technical support, correspondingly.

Two anthracenyl-styrenyl-m-carborane triads (one non-iodinated on B, 3, and one iodinated, 4) were synthesized and characterized to be further linked to octavinylsilsesquioxane (OVS) via cross-metathesis, giving rise to the corresponding hybrid materials 5 and 6. The crystal structure of the non-iodinated heterosubstituted-m-carborane 3 was analyzed by X-ray diffraction. Transmission electron microscopy images of pristine OVS and hybrids 5-6 show important differences in the morphology of the particles; whereas OVS forms cubic-like particles, 5-6 have a spherical shape with a broad particle-size distribution. All compounds showed similar vibronic emission spectra in solution, with maxima around 415 nm, assigned to the locally excited state (LE) emission of the anthracene moiety. The similarity with the spectra of the free anthracene (λem = 420 nm) suggested that only small electronic interactions between the anthracene units have taken place, and there is no influence of the iodo or styrene groups on the absorption properties. This is in agreement with the DFT calculations, where calculated oscillator strength corresponding to the transitions from iodo orbitals to the LUMO are weak and could not be observed experimentally. Noticeable, triads 3-4 exhibited exceptional fluorescence quantum yield values of around 100% in solution, that are comparable to those determined for their precursors 1-2, demonstrating that the influence of the styrene group is negligible. Linking these m-carborane derivatives to the OVS led to a significant decrease of quantum yields to 34-45% for 5-6 in solution. Moreover, the PL behavior in the aggregate state was investigated and the spectra of all compounds were very similar, showing emission red-shift with maxima around 455-459 nm. Remarkably, quite high fluorescence quantum yields were determined for 3-4 ((ϕF = 26-31%) and 5-6 (ϕF = 27-36%) in the aggregated state. These data confirm that the m-carborane platform enhances the quantum efficiency of the anthracene in solution, without losing the emission properties in the aggregate state. If this affirmation is associated to other scattered examples on other fluorophores also linked to m-carborane existing in the literature, the former conclusion is reinforced. m-Carborane enhances the fluorescence quantum yield of the free fluorophore, but does not alter the energy of the participating states in the photoluminescence in solution., The work was supported by Spanish Ministerio de Economía y Competitividad, MINEICO (CTQ2016-75150-R and “Severo Ochoa” Program for Centers of Excellence in R&D SEV-2015-0496) and Generalitat de Catalunya (2017/SGR/1720). Z. K. is grateful for the general support of the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement MSCA-IF-2016-751587. D. Ch.-L. acknowledges funding by project No. PGC2018-102047-B-I00 (MCIU/AEI/FEDER, UE). Theoretical calculations have been achieved using computers from the Supercomputing Centre of Catalonia (CESCA).

A small library of carborane-BODIPY/aza-BODIPY dyads were efficiently synthesized by means of a novel convergent synthetic approach, the key step of which is a Pd-catalyzed Heck coupling reaction. The structural characterization and photoluminescence properties of the newly synthesized dyads were evaluated. The presence of the carborane did not significantly alter the photophysical patterns of the BODIPY or aza-BODIPY in the final fluorophores, but it produced a decrease of the emission fluorescent quantum yields that was in the range from 1.4 % for aza-BODIPY to 48 % for BODIPY-dyads. The carborane-BODIPY dyads were successfully incorporated into cells, especially compounds 2, 4 and 13, demonstrating their cytoplasmic localization. The fluorescent and biocompatibility properties make these compounds good candidates for in vitro cell tracking.

Cross-linking of magnetic nanoparticles with proteins plays a significant role in the preparation of new materials for biotechnological applications. The aim was the maximization of the magnetic mass attracted and protein loading of magnetic iron oxide nanoparticles coated with chitosan, synthesized in a single step by alkaline precipitation. Chitosan-coated magnetite particles (Fe3O4@Chitosan) were cross-linked to a xylanase and a cellulase (Fe3O4@Chitosan@Proteins), showing a 93% of the magnetic saturation of the magnetite. X-ray diffraction pattern in composites corresponds to magnetite. Thermogravimetry and differential scanning calorimetry showed that 162 mg of chitosan was coating one gram of composite and 12 mg of protein was cross-linked to each gram of magnetic support. Cross-linking between enzymes and Fe3O4@Chitosan was confirmed by infrared spectroscopy with Fourier transform, X-ray energy, and X-ray photoelectron spectroscopy dispersion analysis. From dynamic light scattering, transmission and electron microscopy the average particle size distribution was 230 nm and 430 nm for Fe3O4@Chitosan and Fe3O4@Chitosan@Proteins, showing agglomerates of individual spherical particles, with an average diameter of 8.5 nm and 10.8 nm, respectively. The preparation method plays a key role in determining the particle size and shape, size distribution, surface chemistry, and, therefore, the applications of the superparamagnetic nanoparticles.

A set of distyrylbenzene, distyrylbiphenyl and distyrylanthracene end-substituted with carborane clusters is introduced herein. All these compounds have been prepared from the corresponding styrene-containing carborane derivatives via Heck coupling reaction. High regioselectivity has been achieved yielding exclusively E isomers. All compounds have been fully characterized and the crystal structure of the distyrylbiphenyl end-substituted with Methyl-o-carborane was analyzed by X-ray diffraction. The absorption properties of compounds were elucidated by TD-DFT calculations, highlighting the importance of the aromatic core and π-conjugation. It is worth noting that the luminescence properties of these systems depend on the aromatic core; in solution, benzene and biphenyl derivatives showed higher fluorescence emission than the anthracene ones and the presence of the carborane clusters does not induce any major change in fluorescence as compared to the pristine non-carborane containing partners. Nevertheless, all compounds exhibited low fluorescence quantum yields in aggregation state, which gives clear evidence of considerable intermolecular interactions between aggregates that could be the reason of the fluorescence quenching.

A series of novel fluorescent BODIPY-anionic boron cluster conjugates bearing [B12H12]2– (5, 6), [3,3′-Co(1,2-C2B9H11)2]− (7, 8), and [3,3′-Fe(1,2-C2B9H11)2]− (9) anions have been readily synthesized from meso-(4-hydroxyphenyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY 4), and their structure and photoluminescence properties have been assessed. Linking anionic boron clusters to the BODIPY (4) does not alter significantly the luminescent properties of the final fluorophores, showing all of them similar emission fluorescent quantum yields (3–6%). Moreover, the cytotoxicity and cellular uptake of compounds 5–9 have been analyzed in vitro at different concentrations of B (5, 50, and 100 μg B/mL) using HeLa cells. At the lowest concentration, none of the compounds shows cytotoxicity and they are successfully internalized by the cells, especially compounds 7 and 8, which exhibit a strong cytoplasmic stain indicating an excellent internalization efficiency. To the best of our knowledge, these are the fi...

A small library of 2,6- and 3,5-distyrenyl-substituted carborane-BODIPY dyes was efficiently synthesized by means of a Pd-catalyzed Heck coupling reaction. Styrenyl-carborane derivatives were exploited as molecular tools to insert two carborane clusters into the fluorophore core and to extend the π-conjugation of the final molecule in a single synthetic step. The synthetic approach allows to increase the molecular diversity of this class of fluorescent dyes by the synthesis of symmetric or asymmetric units with enhanced boron content. The structural characterization and the photoluminescence (PL) properties of synthesized dyes were evaluated, and the structure/properties relationships have been investigated by theoretical calculations. The developed compounds exhibit a significant bathochromic shift compared to their parent fluorophore scaffolds, and absorption and emission patterns were practically unaffected by the different substituents (Me or Ph) on the Ccluster atom (Cc) of the carborane cage or the cluster isomer (ortho- or meta-carborane). Remarkably, the presence of carborane units at 2,6-positions of the fluorophore produced a significant increase of the emission fluorescent quantum yields, which could be slightly tuned by changing the Cc-substituent and the carborane isomer, as well as introducing ethylene glycol groups at the meso-position of the BODIPY., We would like to acknowledge Dr. Emanuele Priola (UniTO) and Dr. Francesco Marra (UniTO) for technical support, and Prof. Claudio Medana (UniTO) for HRMS measurements. We acknowledge the italian MIUR, Huvepharma Italia srl, Regione Piemonte and Cassa di Risparmio di Torino for financial support. This research was funded by MINECO ((CTQ2016-75150-R) Agencia Estatal de Investigación AEI from MICINN (PID2019-106832RB-100/AEI/10.13039/501100011033) and Generalitat de Catalunya (2017 SGR1720). The work was also supported by the MICINN through the Severo Ochoa Program for Centers of Excellence FUNFUTURE (CEX2019-000917-S). Sohini Sinha was enrolled in the PhD Program of UAB. S. S. acknowledges financial support from DOC-FAM, European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 754397., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).

El experimento se realizó en tres etapas. La etapa 0 (caudal 4.2 L/hr, TRH 24 hs, sin metanol); etapa 1 (caudal 6.6 L/hr, TRH 15 hs con metanol) y etapa 2 (caudal 10.8 L/hr, TRH 9 hs con metanol). Las eficiencias de remoción de nitratos fueron del 6%, 91% y 92% en cada etapa. La fuente de carbono suplementaria fue un factor decisivo para incrementar la capacidad de desnitrificación del sistema. Entre la etapa 1 y la 2 se incrementó un 64% el caudal y por ende, la tasa de carga de nitratos. En cada una se verificó una remoción de 85,7 y 140,6 gNO3/m3.día o 14,8 y 24,3 gNO3/m2.día respectivamente. No se determinó la tasa máxima de eliminación pero se estima muy por encima de lo reportado. Se concluye que esta tecnología puede ser una herramienta práctica y económica para mejorar la calidad del agua contaminada con nitratos., Tesis co-dirigida por el Dr. Alejandro Mariñelarena y el Lic. Hugo Di Giorgi., Facultad de Ciencias Naturales y Museo

Amphiphilic triblock terpolymers have attractive applications in the preparation of nanoparticles with controlled morphology. An additional level of morphology control can be provided by reactive blocks, whose interactions with the solvent vary under different stimuli. In this work, we synthesized a triblock terpolymer (poly(acrylic acid)-b-poly(4-hydroxystyrene)-b-poly{1-[4-(1-methyl-1,2-dicarba-closo-dodecaborane-2-yl methyl)-phenyl]ethylene}) (PAA-b-PHS-b-PSC) containing carboranes as pendant groups by reversible addition fragmentation chain transfer (RAFT) polymerization and subsequently studied its behavior in aqueous solution. Once the nanoparticles were formed, the solubility of the second and third blocks was changed via pH and CsF reactions, respectively. The resulting micelles work as an ON/OFF system, using changes in fluorescence intensity at different pH values., The authors acknowledge the financial support from the Czech Science Foundation Grant No. 17-00289Y. The authors would like to thank Prof. Miroslav Štěpánek for his counseling in SAXS fitting and interpretation, Prof. Jiří Vohlídal for his assistance in polymer nomenclature, Dr Jiří Brus for solid state NMR measurements, and Dr Carlos V. Melo for editing the manuscript. The group from ICMAB thanks the Spanish Ministerio de Economía y Competitividad, MINEICO (CTQ2016-75150-R9) and Generalitat de Catalunya (2017/SGR/1720) for financial support.

Fuente TESIUNAM

Efficient monosubstitution of the non-iodinated, mono-iodinated and di-iodinated m-carborane cluster at one Ccluster has led to the preparation of three single organic molecule-carborane dyads (4–6), which exhibited exceptional fluorescence properties with quantum yield values of 100% in solution, for all of them, with maxima around 415 nm, which correspond to the locally excited state (LE) emission. These results suggest that simply linking the m-carborane fragment to one anthracene unit through a CH2 spacer produces a significant enhancement of the fluorescence in the final fluorophore, probably due to the free rotation of the anthracene linked to the Ccluster. Besides, the presence of one or two iodine atoms linked to boron atoms does not cause any influence on the photophysical properties of the dyads, as it is confirmed by TD-DFT calculations. Notably, the three conjugates show good fluorescence efficiency in the aggregate state with quantum yields in the range of 19–23%, which could be ascribed to the presence of CH2, particularly for 4, and the iodine atoms in 5 and 6, which prevent π–π stacking. All these results indicate that our dyads are extremely good emitters in solution while maintaining the emission properties in the aggregate state. Crystal packing, fingerprint plot analysis, and TD-DFT calculations for the three compounds support these results. Confocal microscopy studies show that 6 is the best-internalized compound by HeLa cells via endocytosis, although 4 and 5 also presented a high fluorescence intensity emission. Moreover, due to the blue emission, this compound is an excellent candidate to be applied as a fluorescent dye in bioimaging studies., The work was supported by the Spanish Ministerio de Economía y Competitividad, MINECO (CTQ2016-75150-R, MAT2017-86357-C3-3-R and “Severo Ochoa” Program for Centers of Excellence in R&D SEV-2015-0496) and Generalitat de Catalunya (2017/SGR/1720, 2017/SGR/503). Z. K. is grateful for the general support of the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement MSCA-IF-2016-751587. D. Ch.-L. acknowledges funding from the Intramural CSIC (201730I019) project. Theoretical calculations have been achieved using computers from the Supercomputing Centre of Catalonia (CESCA). The authors would like to thank the staff at the Servei de Microscòpia de la Universitat Autònoma de Barcelona., We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI).

A set of triads in which o- and m-carborane clusters are bonded to two stilbene units through Ccluster -CH2 bonds was synthesized, and their structures were confirmed by X-ray diffraction. A study on the influence of the o- and m- isomers on the absorption and photoluminescence properties of the stilbene units in solution revealed no charge-transfer contributions in the lowest excited state, as confirmed by (TD)DFT calculations. The presence of one or two B-I groups in m-carborane derivatives does not affect the emission properties of the stilbenes in solution, probably due to the rather large distance between the iodo substituents and the fluorophore. Nevertheless, a significant redshift of the photoluminescence (PL) emission maximum in the solid state (thin films and powder samples) compared to solution was observed; this can be traced back to PL sensitization, most probably due to more densely packed stilbene moieties. Remarkably, the PL absolute quantum yields of powder samples are significantly higher than those in solution, and this was attributed to the restricted environment and the aforementioned sensitization. Thus, the bonding of the carborane clusters to two stilbene units preserves their PL behavior in solution, but produces significant changes in the solid state. Furthermore, iodinated species can be considered to be promising precursors for theranostic agents in which both imaging and therapeutic functions could possibly be combined.

High boron content systems were prepared by the peripheral functionalisation of 1,3,5-triphenylbenzene (TPB) and octavinylsilsesquioxane (OVS) with two different anionic boron clusters: closo-dodecaborate (B12) and cobaltabisdicarbollide (COSAN). TPB was successfully decorated with three cluster units by an oxonium ring-opening reaction, while OVS was bonded to eight clusters by catalysed metathesis cross-coupling. The resulting compounds were spectroscopically characterised, and their solution-state photophysical properties analysed. For TPB, the presence of COSAN dramatically quenches the fluorescence emission (&lambda, em = 369 nm, &Phi, F = 0.8%), while B12-substituted TPB shows an appreciable emission efficiency (&lambda, em = 394 nm, F = 12.8%). For octasilsesquioxanes, the presence of either COSAN or B12 seems to be responsible for &sim, 80 nm bathochromic shift with respect to the core emission, but both cases show low emission fluorescence (&Phi, F = 1.4&ndash, 1.8%). In addition, a remarkable improvement of the thermal stability of OVS was observed after its functionalisation with these boron clusters.

A mini-review based on radial growing macromolecules and core initiated Borane periphery decorated with o-carboranes and metallacarboranes that has been developed in the authors laboratories is reported. The review is divided into four sections; three of them are related to the design and synthesis of these large boron-containing molecules and the fourth deals with the unique properties of anionic metallacarborane molecules that provide a glimpse of their potential for their promising use in medicinal applications. Their unique stability along with their geometrical and electronic properties, as well as the precise steric structure of 1,2-closo-C2B10H12 (o-carborane) that has the potential for the incorporation of many substituents: at the carbon (Cc), at the boron and at both carbon and boron vertices, suggests this cluster as an innovative building block or platform for novel applications that cannot be achieved with organic hydrocarbon compounds. Poly(aryl-ether) dendrimers grown from fluorescent cores, such as 1,3,5-triarylbenzene or meso-porphyrins, have been decorated with boron clusters to attain rich boron containing dendrimers. Octasilsesquioxane cubes have been used as a core for its radial growth to get boron-rich large molecules. The unique properties of cobaltabisdicarbollide cluster, which include: i) self-assembly in water to produce monolayer nano-vesicles, ii) crossing lipid bilayer membranes, iii) interacting with membrane cells, iv) facilitating its visualization within cells by Raman and fluorescence techniques and v) their use as molecular platform for “in vivo” imaging are discussed in detail., This work has been supported by the Spanish Ministerio de Economía y Competitividad (MINECO, project CTQ2016-75150-R) and Generalitat de Catalunya (2017 SGR 1720).

New hybrids synthesized by linking two anthracenyl units to the Ccluster atoms of a non- (4), a mono- (5) and a di-iodinated (6) m-carborane fragment through CH2 spacers, along with their full characterization, are reported. Noticeably, bonding the m-carborane fragment to the anthracene moieties produces a significant increase of more than two-fold in the intrinsic fluorescence quantum yield (ϕF) of the anthracene itself, with values of ϕF > 60% in THF and ϕF > 48% in toluene, although it does not alter the absorption and emission patterns of the fluorophore in solution. A red-shift of the emission maximum with respect to the solution is observed in the aggregate state (THF/H2O, 1 : 99 v/v), along with moderate quantum yields; compounds 4 and 5 show ϕF = 22 and 19%, respectively, whereas 6 has a lower value (ϕF = 8%). The difference between the ϕF values in the aggregate state has been attributed to the arrangement of dimers for each compound in the solid state structures. X-ray crystal structures of compounds 4 and 5 show the anthracene units to be roughly parallel, whereas such an arrangement is clearly disrupted in compound 6. Such differences have been analyzed by Hirshfeld surfaces, decomposed fingerprint plots for the three compounds and DFT calculations. The combined results from the supramolecular analyses and DFT studies support the idea that a less delocalized system in the case of 6 can be explained by the different packing in the aggregate or solid state for this di-iodo derivative. The observed arrangement of molecules of 6 seems to be related to a larger number of H⋯I contacts, with respect to the non-iodinated or mono-iodinated compounds, 4 or 5. According to this assumption, there is a direct relationship between the structure in the solid state and the PL properties; in the m-carborane derivatives, small changes in their structures have caused variations in the photophysical properties, especially in the quantum efficiency., The work was supported by the Spanish Ministerio de Economı´a y Competitividad, MINEICO (CTQ2016-75150-R and ‘‘Severo Ochoa’’ Program for Centers of Excellence in R&D SEV-2015-0496) and the Generalitat de Catalunya (2017/SGR/1720). ZK is grateful for the general support of the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement MSCA-IF-2016-751587. Theoretical calculations have been achieved using computers from the Supercomputing Centre of Catalonia (CESCA).

El presente trabajo tiene como objetivo profundizar en la importancia que tiene la expresión y la comunicación emocional como factores que enriquecen el desarrollo integraldel individuo. Especialmente, pone el foco atencional en las pedagogías alternativas, en particularla educación libre,y cómo benefician consu dinámica diaria la adquisición de competencias socioemocionales.Situando la investigaciónen dos escuelas alternativas de la provincia de Sevilla, Criança y Tambora, se haceuso de la metodología de estudio de casosa fin de comprender su realidad a fondo, y entender cómo potencian la educación emocional en las niñas y niños. El recorrido aquí plasmado corresponde a una primera fase de aproximación teórica y dedesarrollo de entrevistas, junto al análisis de datos ysutriangulación. A través de esta, se visibilizanlas oportunidades que ofrecen estos espacios de crianza, el respeto que muestran hacia la infancia y las emociones, y todo ello desde la voz de quienes conforman esta realidad.Estos resultadoshacen posible entrever la relaciónde interdependenciaexistente entre las metodologías empleadas en las escuelas, y un mayor desarrollo emocional de los más pequeños. Universidad de Sevilla. Grado en Educación Primaria

Within the cell nucleus, in the nucleoli, ribosomal RNAs are synthesized and participate in several biological processes. To better understand nucleoli-related processes, their visualization is often required, for which specific markers are needed. Herein, we report the design of novel fluorescent organotin compounds derived from 4-hydroxy-N'-((2-hydroxynaphthalen-1-yl)methylene)benzohydrazide and their cytoplasm and nucleoli staining of B16F10 cells in vitro. Tin compounds bearing an aliphatic carbon chain (-C12 H25 ) and an electron-donating group (-OH) were prepared, and the latter could be derivatized to bear the boron cluster anions [B12 H12 ]2- and [3,3'-Co(1,2-C2 B9 H11 )2 ]- (COSAN). All of the conjugates have been fully characterized and their luminescence properties have been assessed. In general, they show good quantum yields in solution (24-49 %), those for the COSAN derivatives being lower. Remarkably, the linking of [B12 H12 ]2- and COSAN to the complexes made them more soluble, without being detrimental to their luminescence properties. Living B16F10 cells were treated with all of the compounds to determine their fluorescence staining properties; the compounds bearing the aliphatic chain showed a reduced staining capacity due to the formation of aggregates. Notably, the complexes bearing different boron clusters showed different staining effects; those bearing [B12 H12 ]2- showed extraordinary staining of the nucleoli and cytoplasm, whereas those bearing COSAN were only detected in the cytoplasm. The remarkable fluorescence staining properties shown by these organotin compounds make them excellent candidates for fluorescence bioimaging in vitro.

The synthesis and spectroscopic characterization of the first set of tetra(p-dodecacarborane-stilbeno)ethylenes (TDSE), substituted either with a methyl or phenyl group in the 2-position (Ccluster) of the ortho-carborane, are described. The complex absorption properties are elucidated by TD-DFT calculations, stressing the importance of through bond conjugation. Enhanced conjugation and restriction of the conformational space are identified as the main factors for boosted luminescence properties in solution compared to tetraphenylethylene (TPE) core, effectively reducing internal conversion (IC). IC is further reduced when aggregate suspensions of our compounds in water are formed, providing highly luminescent materials of quasi-isolated (very weakly interacting) emitters.

Two sets of o-carborane derivatives incorporating fluorene and anthracene fragments as fluorophore groups have been successfully synthesized and characterized, and their photophysical properties studied. The first set, comprising fluorene-containing carboranes 6-9, was prepared by catalyzed hydrosilylation reactions of ethynylfluorene with appropriate carboranylsilanes. The compound 1-[(9,9-dioctyl-fluorene-2-yl)ethynyl]carborane (11) was synthesized by the reaction of 9,9-dioctyl-2-ethynylfluorene and decaborane (B10H14). Furthermore, reactions of the lithium salt of 11 with 1 equivalent of 4-(chloromethyl)styrene or 9-(chloromethyl)anthracene yielded compounds 12 and 13. Members of the second set of derivatives, comprising anthracene-containing carboranes, were synthesized by reactions of monolithium or dilithium salts of 1-Me-1,2-C2B10H 11, 1-Ph-1,2-C2B10H11, and 1,2-C2B10H12 with 1 or 2 equivalents of 9-(chloromethyl)anthracene, respectively, to produce compounds 14-16. In addition, 2 equivalents of the monolithium salts of 1-Me-1,2-C2B 10H11 (Me-o-carborane) and 1-Ph-1,2-C2B 10H11 (Ph-o-carborane) were reacted with 9,10-bis(chloromethyl)anthracene to produce compounds 17 and 18, respectively. Fluorene derivatives 6-9 exhibit moderate fluorescence quantum yields (32-44 %), whereas 11-13, in which the fluorophore is bonded to the Ccluster (Cc), show very low emission intensity (6 %) or complete fluorescence quenching. The anthracenyl derivatives containing the Me-o-carborane moiety exhibit notably high fluorescence emissions, with φF=82 and 94 %, whereas their Ph-o-carborane analogues are not fluorescent at all. For these compounds, we have observed a correlation between the Cc - C c bond length and the fluorescence intensity in CH2Cl 2 solution, comparable to that observed for previously reported styrene-containing carboranes. Thus, our hypothesis is that for systems of this type the fluorescence may be tuned and even predicted by changing the substituent on the adjacent Cc. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

This review includes a compilation of different types of star-shaped molecules and dendrimers decorated with boron clusters, carboranes or metallacarboranes, at their periphery. Dendrimeric platforms, such as PAMAM, carbosilane, poly(aryl-ether), among others, have been functionalized with a different number of small metallacarboranes, nido-carboranes or cobaltabisdicarbollide clusters following diverse methodologies. In general, all these structures are high-boron content molecules, and for those that carry nido-carboranes and alkaline metals, are also soluble in water. Most of these compounds have been proposed as highly promising boron delivery agents for the BNCT of tumors, particularly for malignant brain tumors. Nevertheless, other applications such as catalysts, optoelectronic devices, drug delivery systems, and others can be envisaged.

Icosahedral boranes, carboranes, and metallacarboranes are extraordinarily robust compounds with desirable properties such as thermal and redox stability, chemical inertness, low nucleophilicity, and high hydrophobicity, making them attractive for several applications such as medicine, nanomaterials, molecular electronics, energy, catalysis, environmental chemistry, and other areas. The hydrogen atoms in these clusters can be replaced by convenient groups that open the way to a chemical alternative to conventional "organic" or "organometallic" realms. Icosahedral boron cluster derivatives have been reviewed from different perspectives; however, there is a need for a review dedicated to the redox and photophysical characteristics of easily accessible borane and carborane derivatives, which are excellent materials for a wide range of applications. This review deals with the redox properties and photoluminescence behavior of this collection of compounds, as well as their influence on the properties of materials and devices whose working principles are related to electron-transfer or electron-promotion phenomena. We hope that this review will be of great value to boron cluster scientists and researchers working in the photoluminescence and electrochemistry fields who are interested in exploring the possibilities of these unique and promising systems.