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Thioether polymers are fundamental for a variety of applications. Their synthesis is, however, more challenging than that of other metal-catalyzed reactions due to the reported detachment of the S atom during thermal activation. In this study, it has been demonstrated unambiguously that thermal annealing results in the thioetherification of the 4-bromo-4-mercaptobiphenyl molecule (Br-MBP) adsorbed on the surface of Au(111). Through complementary techniques, such as scanning tunneling microscopy, spectroscopy, and first-principle calculations, we have identified four reaction steps, involving sulfhydryl or bromine molecular functional groups and leading to the formation of intermolecular C–S bonds. To form the thioether polymer and to overcome the competitive formation of C–C bonds, two reaction steps, the dehalogenation, and dissociation of the S–Au bond, must occur simultaneously. We detail the electronic properties of the phenyl–sulfur bond and the polymer as a function of the ligand length. This result suggests a wider perspective of this chemical synthesis., L.V. acknowledges the funding of Diputación Foral de Guipuzcoa (Red/Sarea 2021-CIEN-000032-01, Red/Sarea 2022-CIEN-000017-01), the Basque Government (Proyectos de Investigación Básica y/o Aplicada grant number PIBA-2021-0026, and Grupo consolidado IT1453-22. R.R. and N.L. acknowledge financial support from the Spanish State Research Agency Grant PID2021-127917NB-I00 funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe”; from the European Union project ESiM 101046364; and they are grateful for the computer resources at Finisterrae II, and the technical support provided by CESGA.

Strain is an effective strategy to modulate the optoelectronic properties of 2D materials, but it has been almost unexplored in layered hybrid organic–inorganic metal halide perovskites (HOIPs) due to their complex band structure and mechanical properties. Here, we investigate the temperature-dependent microphotoluminescence (PL) of 2D (C6H5CH2CH2NH3)2Cs3Pb4Br13 HOIP subject to biaxial strain induced by a SiO2 ring platform on which flakes are placed by viscoelastic stamping. At 80 K, we found that a strain of, This work is supported by the Spanish MICINN under Project PID2019-108153GA-I00 and under the María de Maeztu Units of Excellence Programme (MDM-2016-0618). B.M-G. thanks Gipuzkoa Council (Spain) in the frame of Gipuzkoa Fellows Program and to Prof. A. Mateo-Alonso (Molecular and Supramolecular Materials Group - POLYMAT) for the access to the Chemistry Lab to grow the crystals. M.G. acknowledges support from la Caixa Foundation (ID 0010434) for a Junior Leader fellowship (Grant No. LCF/BQ/PI19/11690017).

Non-covalent bonds are fundamental for designing self-assembled organic structures with potentially high responsiveness to mechanical, light, and thermal stimuli. The weak intermolecular interaction allows triggering charge-transport, energy-conversion, enzymatic, and catalytic activity, to name a few. Here, we discuss the synergistic action that multiple highly-directional and purely electrostatic bonds have in assembling one molecular specie, namely 4,7-dibromobenzo[c]-1,2,5-thiadiazole (2Br-BTD), in two different patterns on the Au(111) surface. We find, using scanning tunneling microscopy (STM) and density functional theory (DFT), that multiple secondary-interactions strengthen the electrostatic attraction between the pnicogen and chalcogen atoms forming [S–N]2 heterocycles, the building block of the two networks. Among these interactions, there are halogen–halogen bonds that form characteristic supra-molecular synthons of 3, 4, or 6 molecules. However, not all these nodal structures contribute to the cohesion of the system. In such cases, other secondary bonds involving hydrogen or nitrogen compensate for the eventual deficiency., We acknowledge the funding of Diputación Foral de Guipuzcoa (Red/Sarea 2021-CIEN-000032-01, Red/Sarea 2022-CIEN-000017-01), the Basque Government (Proyectos de Investigación Básica y/o Aplicada grant number PIBA-2021-0026 and Grupo consolidado IT1453-22.) and the Spanish State Research Agency PID2019-107338RB-C66).

The condensed phases of the carbon-based nanobowl corannulene are herein investigated in the temperature range 200–573 K, combining differential scanning calorimetry, synchrotron X-ray diffraction, and quasielastic neutron-scattering. For the first time, we identify the presence of a well-defined thermal event at 382 K, a figure well below a melting point of 540 K. Contrary to naïve expectation, detailed analysis of the neutron-scattering data below and above this pre-melting transition signals the emergence of correlated stochastic dynamics within both thermodynamically stable solid phases of the material. We find that these are progressively responsible for the suppression of molecular and supramolecular order over mesoscopic length scales, and are associated with the formation of high-symmetry rotor-like states exhibiting localized stochastic motions. Upon cooling from the melt, we have also discovered a robust hysteresis associated with the existence of hitherto-unknown metastable liquid (deep-supercooled) and disordered-solid phases. This behaviour is markedly different from that observed in the quintessential Buckminsterfullerene C60 or other chemically substituted fullerene adducts studied to date at this level of detail. These results evince new and yet-to-tapped opportunities for the use of the stable and metastable phases of carbon-based nanobowls in novel applications exploiting the emergence of dynamical disorder at the nanoscale., This work has received support from the Gipuzkoako Foru Aldundia and the Spanish Ministry of Science and Innovation under Grant Numbers 2020-CIEN-000009-01 and PID2020-114506 GB-I00, respectively.

[Background and Aims] Cholangiocarcinoma (CCA) includes a heterogeneous group of biliary cancers with a dismal prognosis. We investigated if lipid metabolism is disrupted in CCA and its role in tumor proliferation., [Approach and Results] The in vitro and in vivo tumorigenic capacity of five human CCA cell lines was analyzed. Proteome, lipid content, and metabolic fluxes were evaluated in CCA cells and compared with normal human cholangiocytes (NHC). The Akt1/NOTCH1 intracellular cytoplasmic domain (Nicd1)-driven CCA mouse model was also evaluated. The proteome of CCA cells was enriched in pathways involved in lipid and lipoprotein metabolism. The EGI1 CCA cell line presented the highest tumorigenic capacity. Metabolic studies in high (EGI1) versus low (HUCCT1) proliferative CCA cells in vitro showed that both EGI1 and HUCCT1 incorporated more fatty acids (FA) than NHC, leading to increased triglyceride storage, also observed in Akt1/Nicd1-driven CCA mouse model. The highly proliferative EGI1 CCA cells showed greater uptake of very-low-density and HDLs than NHC and HUCCT1 CCA cells and increased cholesteryl ester content. The FA oxidation (FAO) and related proteome enrichment were specifically up-regulated in EGI1, and consequently, pharmacological blockade of FAO induced more pronounced inhibition of their tumorigenic capacity compared with HUCCT1. The expression of acyl-CoA dehydrogenase ACADM, the first enzyme involved in FAO, was increased in human CCA tissues and correlated with the proliferation marker PCNA., [Conclusions] Highly proliferative human CCA cells rely on lipid and lipoprotein uptake to fuel FA catabolism, suggesting that inhibition of FAO and/or lipid uptake could represent a therapeutic strategy for this CCA subclass., This work was supported by “Ayudas para apoyar grupos de investigación del sistema Universitario Vasco” (IT971‐16 to PA), MCIU/AEI/FEDER, UE (2018‐095134‐B‐100 to PA and by the University of Basque Country COLAB20/01 to PA; Spanish Carlos III Health Institute (ISCIII) (FIS PI15/01132, PI18/01075, PI21/00922, and Miguel Servet Program CON14/00129 and CPII19/00008 to JMB; FIS PI14/00399, PI17/00022 and PI20/00186 to MJP; Sara Borrell [CD19/00254 to PMR]) cofinanced by “Fondo Europeo de Desarrollo Regional” (FEDER); CIBERehd (ISCIII) to JMB, MJP, PMR, PA and LB); “Diputación Foral Gipuzkoa” (DFG15/010, DFG16/004 to JMB and 2020‐CIEN‐000067‐01 to PMR), Department of Health of the Basque Country (2019111024 to MJP, 2017111010 to JMB, and 2020111077 to JMB and PA), “Euskadi RIS3” (2016222001, 2017222014, 2018222029, 2019222054, 2020333010 to JMB), BIOEF (Basque Foundation for Innovation and Health Research: EiTB Maratoia BIO15/CA/016/BD to JMB) and Department of Industry of the Basque Country (Elkartek: KK‐2020/00008 to JMB); La Caixa Scientific Foundation (HR17‐00601 to JMB). “Fundación Científica de la Asociación Española Contra el Cáncer” (AECC Scientific Foundation, to JMB). AMMF‐The Cholangiocarcinoma Charity (EU/2019/AMMFt/001, to JMB and PMR). MRDG was funded by “Fundación Científica de la Asociación Española Contra el Cáncer” (AECC de Bizkaia), MJP was funded by the Spanish Ministry of Economy and Competitiveness (MINECO: “Ramón y Cajal” Program RYC‐2015‐17755), IL, AL and FG‐R by the Basque Government (PRE_2016_1_0152, PRE_2018_2_0195 and PRE 2020 2 02500, respectively), AN‐Z and BG‐S by the UPV/EHU, AB‐V by “Programa de especialización de Personal Investigador Doctor” at the UPV/EHU (2019‐2020) and MA by the MCIU/AEI/FEDER.

The colloidal stability of metal nanoparticles is tremendously dependent on the thermal behavior of polymer brushes. Neat polyethylene glycol (PEG) presents an unconventional upper critical solution temperature in ethanol, where phase segregation and crystallization coexist. This thermal behavior translated to a PEG brush has serious consequences on the colloidal stability in ethanol of gold nanoparticles (AuNPs) modified with PEG brushes upon cooling. We observed that AuNPs (13 nm diameter) stabilized with conventional linear PEG brushes (Mn = 6 and 11 kg mol−1) in ethanol suffer from reversible phase separation upon a temperature drop over the course of a few hours. However, the use of a polymer brush with cyclic topology as a stabilizer prevents sedimentation, ensuring the colloidal stability in ethanol at −25 °C for, at least, four months. We postulate that temperature-driven collapse of chain brushes promotes the interpenetration of linear chains, causing progressive AuNP sedimentation, a process that is unfavorable for cyclic polymer brushes whose topology prevents chain interpenetration. This study reinforces the notion about the importance of polymer topology on the colloidal stability of AuNPs., We gratefully acknowledge support from the Spanish Ministry “Ministerio de Ciencia, Innovación y Universidades” (PGC2018-094548-B-I00, MICINN/FEDER, UE, and PID2019-111772RB-I00), Basque Government (IT-1175-19 and PIBA 2018-34) and Diputación Foral de Guipúzcoa (RED 2018).

The computational study of DNA and its interaction with ligands is a highly relevant area of research, with significant consequences for developing new therapeutic strategies. However, the computational description of such large and complex systems requires considering interactions of different types simultaneously in a balanced way, such as non-covalent weak interactions (namely hydrogen bonds and stacking), metal–ligand interactions, polarisation and charge transfer effects. All these considerations imply a real challenge for computational chemistry. The possibility of studying large biological systems using quantum methods for the entire system requires significant computational resources, with improvements in parallelisation and optimisation of theoretical strategies. Computational methods, such as Linear-Scaling Density Functional Theory (LS-DFT) and DLPNO-CCSD(T), may allow performing ab initio quantum mechanics calculations, including the electronic structure for large biological systems, in a reasonable computing time. In this work, we study the interaction of small molecules and cations with DNA (both duplex DNA and G-quadruplexes), comparing different computational methods: a LS-DFT method at the LMKLL/DZDP level of theory, semi-empirical methods (PM6-DH2 and PM7), mixed QM/MM, and DLPNO-CCSD(T). Our goal is to demonstrate the adequacy of LS-DFT to treat the different types of interactions present in DNA-dependent systems. We show that LMKLL/DZDP using SIESTA can yield very accurate geometries and energetics in all the different systems considered in this work: duplex DNA (dDNA), phenanthroline intercalating dDNA, G-quadruplexes, and metal-G-tetrads considering alkaline metals of different sizes. As far as we know, this is the first time that full G-quadruplex geometry optimisations have been carried out using a DFT method thanks to its linear-scaling capabilities. Moreover, we show that LS-DFT provides high-quality structures, and some semi-empirical Hamiltonians can also yield suitable geometries. However, DLPNO-CCSD(T) and LS-DFT are the only methods that accurately describe interaction energies for all the systems considered in our study., This research was financially supported by Diputación Foral de Gipuzkoa through the Gipuzkoa Fellows Program to A. G. This research was also financially supported by the Fundação para a Ciência e a Tecnologia (FCT) by means of Projects PTDC/QUI-QFI/29236/2017, UIDB/04046/2020, and UIDP/04046/2020 and by the Spanish Ministry of Economy, Industry and Competitiveness under the Maria de Maeztu Units of Excellence Program/MDM-2016-0618). A. G. is thankful to ARAID – Fundación Agencia Aragonesa para la Investigación y el Desarrollo for current funding in the frame of ARAID researchers. The authors also thank for technical and human support provided by IZO-SGI (SGIker) of UPV/EHU and European funding (ERDF and ESF). Financial support comes also from Eusko Jaurlaritza (Basque Government) through the project IT1254-19 and IT1584-22, from Spanish MICINN through Grant No. PID2019-107338RB-C61/AEI/10.13039/501100011033, and grant PGC2018-099321-B-100 from the Ministry of Science, Innovation and Universities through the Office of Science Research (MINECO/FEDER). Pseudopotentials and Numerical Atomic Orbitals Basis Dataset for SIESTA were provided by Simune Atomistics S. L. (www.simuneatomistics.com). S. E. thanks the Ministry of Higher Education and Scientific Research of Tunisia for the funding of intership carried out in Portugal and Spain. I. O. D. L. is also very grateful to CICnanoGUNE BRTA for his PhD grant.

Single-chain nanoparticles (SCNPs) result from the folding of isolated polymer chains via intramolecular interactions. Currently, there is no theory able to rationalize the astonishing conformational behaviour of SCNPs under severe crowding conditions (e.g., highly concentrated solutions, all-polymer nanocomposites) and, specifically, the significant size reduction observed in highly crowded solutions of covalent-bonded SCNPs and all-polymer nanocomposites containing SCNPs. Herein, we propose a valuable method to estimate the size of SCNPs under crowding. The method – which is based on combining MD simulations results with scaling concepts – is also useful for ring polymers and nanostructured Janus-shaped SCNPs., Financial support by MCIN/AEI/10.13039/501100011033 and “ERDF – A way of making Europe” (PGC2018-094548-B-I00), Eusko Jaurlaritza – Basque Government (IT-1175-19), and Gipuzkoako Foru Aldundia, Programa Red Gipuzkoana de Ciencia, Tecnología e Innovación (2021-CIEN-000010-01) is gratefully acknowledged.

This article belongs to the Special Issue Advances in Molecular Biosensors., Even with the widespread uptake of vaccines, the SARS-CoV-2-induced COVID-19 pandemic continues to overwhelm many healthcare systems worldwide. Consequently, massive scale molecular diagnostic testing remains a key strategy to control the ongoing pandemic, and the need for instrument-free, economic and easy-to-use molecular diagnostic alternatives to PCR remains a goal of many healthcare providers, including WHO. We developed a test (Repvit) based on gold nanoparticles that can detect SARS-CoV-2 RNA directly from nasopharyngeal swab or saliva samples with a limit of detection (LOD) of 2.1 × 105 copies mL−1 by the naked eye (or 8 × 104 copies mL−1 by spectrophotometer) in less than 20 min, without the need for any instrumentation, and with a manufacturing price of, This research was funded by EITB Maratoia (BIO21/COV/032/BD) and Iniciativa Medtech (BIO21/COV/032/BD) grants. C.H.L. and his research were supported by grants from the IKERBASQUE Foundation for Science, the Starmer–Smith Memorial Fund, Ministerio de Economía y Competitividad (MINECO) of the Spanish Central Government, the ISCIII and FEDER funds (PI12/00663, PIE13/00048, DTS14/00109, PI15/00275, PI18/01710), Departamento de Desarrollo Económico y Competitividad y Departamento de Sanidad of the Basque government, Asociación Española Contra el Cancer (AECC), Diputación Foral de Guipuzcoa (DFG) and Gobierno Vasco, Departamento de Industria (ELKARTEK project code: KK-2018/00038). The involvement of B.K. in this project was supported by Project EVAgoEAST, funded by the European Regional Development Fund, Operational program Integrated Infrastructure, ITMS code: 313011ASU8.

Atomically thin van der Waals magnetic crystals are characterized by tunable magnetic properties related to their low dimensionality. While electrostatic gating has been used to tailor their magnetic response, chemical approaches like intercalation remain largely unexplored. Here, we demonstrate the manipulation of the magnetism in the van der Waals antiferromagnet NiPS3 through the intercalation of different organic cations, inserted using an engineered two-step process. First, the electrochemical intercalation of tetrabutylammonium cations (TBA+) results in a ferrimagnetic hybrid compound displaying a transition temperature of 78 K, and characterized by a hysteretic behavior with finite remanence and coercivity. Then, TBA+ cations are replaced by cobaltocenium via an ion-exchange process, yielding a ferrimagnetic phase with higher transition temperature (98 K) and higher remanent magnetization. Importantly, we demonstrate that the intercalation and cation exchange processes can be carried out in bulk crystals and few-layer flakes, opening the way to the integration of intercalated magnetic materials in devices., The authors acknowledge R. Llopis and A. Eleta for technical support. This work is supported by “la Caixa” Foundation (ID 100010434), under the agreement LCF/BQ/PI19/11690017, by the Spanish MICINN under Project PID2019-108153GA-I00, RTI2018-094861-B-100 and under the María de Maeztu Units of Excellence Program (MDM-2016-0618). B. M.-G. thanks Gipuzkoa Council (Spain) in the frame of Gipuzkoa Fellows Program.

Understanding the structural and magnetic properties in layered hybrid organic-inorganic metal halide perovskites (HOIPs) is key for their design and integration in spin-electronic devices. Here, a systematic study is conducted on ten compounds to understand the effect of the transition metal (Cu2+, Mn2+, Co2+), organic spacer (alkyl- and aryl-ammonium), and perovskite phase (Ruddlesden-Popper and Dion-Jacobson) on the properties of these materials. Temperature-dependent Raman measurements show that the crystals’ structural phase transitions are triggered by the motional freedom of the organic cations as well as by the flexibility of the inorganic metal-halide lattice. In the case of Cu2+ HOIPs, an increase of the in-plane anisotropy and a reduction of the octahedra interlayer distance is found to change the behavior of the HOIP from that of a 2D ferromagnet to that of a quasi-3D antiferromagnet. Mn2+ HOIPs show inherent antiferromagnetic octahedra intralayer interactions and a phenomenologically rich magnetism, presenting spin-canting, spin-flop transitions, and metamagnetism controlled by the crystal anisotropy. Co2+ crystals with non-linked tetrahedra show a dominant paramagnetic behavior irrespective of the organic spacer and the perovskite phase. This study demonstrates that the chemical flexibility of HOIPs can be exploited to develop novel layered magnetic materials with tailored magnetic properties., This work was supported by the Spanish MCIN/AEI under Projects PID2019-108153GA-I00, RTI2018-094861-B-I00, PID2021-128004NB-C21, and under the María de Maeztu Units of Excellence Programme (Grant CEX2020-001038-M & CEX2020-001067-M). This work was also supported by the FLAG-ERA grant MULTISPIN, by the Spanish MCIN/AEI with grant number PCI2021-122038-2A. This project received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (Grant Agreement No. 722951). Additionally, this work was carried out with support from the Basque Science Foundation for Science (IKERBASQUE), POLYMAT, EHU/UPV, Gipuzkoa Council, and Basque Government (BERC program). Technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF) is also acknowledged. B.M-G. thanks Gipuzkoa Council (Spain) in the frame of Gipuzkoa Fellows Program. M.G. acknowledges support from la Caixa Foundation (ID 0010434) for a Junior Leader fellowship (Grant No. LCF/BQ/PI19/11690017).

Chiral materials are an ideal playground for exploring the relation between symmetry, relativistic effects and electronic transport. For instance, chiral organic molecules have been intensively studied to electrically generate spin-polarized currents in the last decade, but their poor electronic conductivity limits their potential for applications. Conversely, chiral inorganic materials such as tellurium have excellent electrical conductivity, but their potential for enabling the electrical control of spin polarization in devices remains unclear. Here, we demonstrate the all-electrical generation, manipulation and detection of spin polarization in chiral single-crystalline tellurium nanowires. By recording a large (up to 7%) and chirality-dependent unidirectional magnetoresistance, we show that the orientation of the electrically generated spin polarization is determined by the nanowire handedness and uniquely follows the current direction, while its magnitude can be manipulated by an electrostatic gate. Our results pave the way for the development of magnet-free chirality-based spintronic devices., This work is supported by the Spanish Ministerio de Ciencia e Innovación (MICINN) under projects RTI2018-094861-B-100 and PID2019-108153GA-I00 and under the Maria de Maeztu Units of Excellence Programme (MDM-2016-0618); by the European Union Horizon 2020 under the Marie Slodowska-Curie Actions (0766025-QuESTech and 892983-SPECTER); and by Intel Corporation under ‘FEINMAN’ and ‘VALLEYTRONICS’ Intel Science Technology Centers. B.M.-G. acknowledges support from the Gipuzkoa Council (Spain) in the frame of the Gipuzkoa Fellows Program. M.S.-R. acknowledges support from La Caixa Foundation (no. 100010434) with code LCF/BQ/DR21/11880030. M.G. acknowledges support from La Caixa Foundation (no. 100010434) for a Junior Leader fellowship (grant no. LCF/BQ/PI19/11690017). A.J. acknowledges support from CRC/TRR 227 of Deutsche Forschungsgemeinschaft.

Essential tremor (ET) is a highly prevalent neurological disorder characterized by action-induced tremors involving the hand, voice, head, and/or face. Importantly, hand tremor is present in nearly all forms of ET, resulting in impaired fine motor skills and diminished quality of life. To advance early diagnostic approaches for ET, automated handwriting tasks and magnetic resonance imaging (MRI) offer an opportunity to develop early essential clinical biomarkers. In this study, we present a novel approach for the early clinical diagnosis and monitoring of ET based on integrating handwriting and neuroimaging analysis. We demonstrate how the analysis of fine motor skills, as measured by an automated Archimedes’ spiral task, is correlated with neuroimaging biomarkers for ET. Together, we present a novel modeling approach that can serve as a complementary and promising support tool for the clinical diagnosis of ET and a large range of tremors., This work was supported in part by the Universidad del País Vasco/Euskal Herriko Unibertsitatea, the University of Cambridge, PPG 17/51 and GIU 092/19, the Basque government (Saiotek SA-2010/00028, ELEKIN, Engineering and Society and Bioengineering Research Groups, GIC18/136, and ELKARTEK 18/99, 20/81), ‘‘Ministerio de Ciencia e Innovación’’ (SAF201677758R), FEDER funds, DomusVi Foundation (FP18/76), and the government of Gipuzkoa (HELENA, SABRINA, DG18/14-23, DG19/29, DG20/25 projects). This work is also based upon the work from COST Actions CA18106 and CA15225, supported by COST (European Cooperation in Science and Technology).

The vibrational dynamics of pure and methylammonium-doped formamidinium lead iodide perovskites (FAPbI3) has been investigated by high-resolution neutron spectroscopy. For the first time, we provide an exhaustive and accurate analysis of the cation vibrations and underlying local structure around the organic moiety in these materials using first-principles electronic-structure calculations validated by the neutron data. Inelastic neutron scattering experiments on FAPbI3 provide direct evidence of the formation of a low-temperature orientational glass, unveiling the physicochemical origin of phase metastability in the tetragonal structure. Further analysis of these data provides a suitable starting point to explore and understand the stabilization of the perovskite framework via doping with small amounts of organic cations. In particular, we find that the hydrogen-bonding interactions around the formamidinium cations are strengthened as a result of cage deformation. This synergistic effect across perovskite cages is accompanied by a concomitant weakening of the methylammonium interactions with the surrounding framework., K.D. and F.F.A. gratefully acknowledge financial support from the Gipuzkoako Foru Aldundia under grant no. 2020-CIEN-000009-01. This work has been supported by PL-Grid Infrastructure and the PROMETHEUS facility. M.K. is grateful for financial support from the Swedish Research Council (2016-06258).

This article belongs to the Special Issue Single-Chain Polymer Nanotechnology., The folding of certain proteins (e.g., enzymes) into perfectly defined 3D conformations via multi-orthogonal interactions is critical to their function. Concerning synthetic polymers chains, the “folding” of individual polymer chains at high dilution via intra-chain interactions leads to so-called single-chain nanoparticles (SCNPs). This review article describes the advances carried out in recent years in the folding of single polymer chains into discrete SCNPs via multi-orthogonal interactions using different reactive chemical species where intra-chain bonding only occurs between groups of the same species. First, we summarize results from computer simulations of multi-orthogonally folded SCNPs. Next, we comprehensively review multi-orthogonally folded SCNPs synthesized via either non-covalent bonds or covalent interactions. Finally, we conclude by summarizing recent research about multi-orthogonally folded SCNPs prepared through both reversible (dynamic) and permanent bonds., This research was funded by Gipuzkoako Foru Aldundia -Programa Red Gipuzkoana de Ciencia, Tecnología e Innovación 2019-, grant number 2019-CIEN-000050-01; Basque Government, grant number IT-1175-19; and MCIU/AEI/FEDER, UE, grant number PGC2018-094548-B-I00.

Time Reversal Symmetry (TRS) broken topological phases provide gapless surface states protected by topology, regardless of additional internal symmetries, spin or valley degrees of freedom. Despite the numerous demonstrations of 2D topological phases, few examples of 3D topological systems with TRS breaking exist. In this article, we devise a general strategy to design 3D Chern insulating (3D CI) cubic photonic crystals in a weakly TRS broken environment with orientable and arbitrarily large Chern vectors. The designs display topologically protected chiral and unidirectional surface states with disjoint equifrequency loops. The resulting crystals present the following characteristics: First, by increasing the Chern number, multiple surface states channels can be supported. Second, the Chern vector can be oriented along any direction simply changing the magnetization axis, opening up larger 3D CI/3D CI interfacing possibilities as compared to 2D. Third, by lowering the TRS breaking requirements, the system is ideal for realistic photonic applications where the magnetic response is weak., A.G.E., C.D. and M.B.P. acknowledge support from the Spanish Ministerio de Ciencia e Innovación (PID2019-109905GA-C2) and from Eusko Jaurlaritza (IT1164-19, KK-2019/00101 and KK-2021/00082). M.G.D., I.R. and M.G.V. acknowledge the Spanish Ministerio de Ciencia e Innovacion (grant PID2019-109905GB-C21). J.L.A. acknowledges support from the Spanish Ministerio de Ciencia e Innovación (PID2019-109905GA-C2). The work of B.B. is supported by the Air Force Office of Scientific Research under award number FA9550-21-1-0131. C.D. acknowledges financial support from the MICIU through the FPI PhD Fellowship CEX2018-000867-S-19-1. The work of J.L.M. has been supported by Spanish Science Ministry grant PGC2018-094626-BC21 (MCIU/AEI/FEDER, EU) and Basque Government grant IT979-16. A.G.E. and M. G. V. acknowledge funding from Programa Red Guipuzcoana de Ciencia, Tecnología e Innovación 2021 (Grant Nr. 2021-CIEN-000070-01. Gipuzkoa Next).

The successive self-nucleation and annealing (SSA) thermal fractionation technique has been applied for the first time to thermoplastic polyurethanes (TPUs). The changes in structure and morphology before and after SSA fractionation were monitored by Differential Scanning Calorimetry (DSC), in situ real-time Small and Wide-angle X-ray scattering synchrotron experiments (SAXS/WAXS) and Atomic Force Microscopy (AFM). SSA applies a series of successive cooling and heating runs to a self-nucleated sample that promotes the creation of a series of thermal fractions in the TPUs with a specific lamellar thicknesses and melting point distribution thanks to the multi-block structure of TPUs. The SSA fractionated samples experienced a general increase in lamellar thickness that has been revealed by both AFM and SAXS and a distribution of lamellar thickness estimated by DSC and AFM. The average lamellar thickness of SSA fractionated samples has been estimated by SAXS, AFM, and DSC. The values obtained are in quantitative agreement (within the errors involved in the techniques) when considering that phase segregation in the TPU samples has been promoted by crystallization. The refined crystalline structure obtained after SSA produced a number of clear WAXS reflections, as compared to the unfractionated materials, facilitating the determination of the TPUs crystallinity degree by WAXS., The authors would like to acknowledge BASF for project funding. This study has also received funding from the Eusko Jaurlaritza through grant IT1309-19. We acknowledge funding by the Spanish ALBA Synchrotron of the Proposal 2015091420-“Self-nucleation, thermal fractionation, and confined crystallization studies of semicrystalline polymers by in-situ synchrotron WAXS and SAXS thermal analysis” (2016). We would also like to acknowledge the staff from the BL11 beamline at the ALBA synchrotron, as well as the travel funding by Spanish “Ministerio de Economía y Competitividad” and “Generalidad de Cataluña.” J.M. acknowledges support from the Provincial Council of Gipuzkoa under the program Fellow Gipuzkoa and “Fomento San Sebastián” in the frame work program “Retorno del Talento Local” Donostia up! 2016. R.A.P.-C. is supported by PIFI of the Chinese Academy of Science for international postdoctoral researchers (2019PE0004).

Large conjugated rings with persistent currents are novel promising structures in molecular-scale electronics. A six-porphyrin nanoring structure that allegedly sustained an aromatic ring current involving 78π electrons was recently synthesized. We provide here compelling evidence that this molecule is not aromatic, contrary to what was inferred from the analysis of 1H-NMR data and computational calculations that suffer from large delocalization errors. The main reason behind the absence of an aromatic ring current in these nanorings is the low delocalization in the transition from the porphyrins to the bridging butadiyne linkers, which disrupts the overall conjugated circuit. These results highlight the importance of choosing a suitable computational method to study large conjugated molecules and the appropriate aromaticity descriptors to identify the part of the molecule responsible for the loss of aromaticity., This work has been supported by grants from the Spanish government MICINN (PGC2018-098212-B-C21, PID2019-104772GB-I00, EUR2019-103825, PID2019-105488GB-I00, and PCI2019-103657), Diputación Foral de Gipuzkoa (2019-CIEN-000092-01), and Gobierno Vasco (IT1346-19, IT1254-19, PRE_2016_1_0159, and PIBA19-0004). E.R.C. acknowledges funding from the Juan de la Cierva program IJCI-2017-34658.

The exfoliation of layered magnetic materials generates atomically thin flakes characterized by an ultrahigh surface sensitivity, which makes their magnetic properties tunable via external stimuli, such as electrostatic gating and proximity effects. Another powerful approach to engineer magnetic materials is molecular functionalization, generating hybrid interfaces with tailored magnetic interactions, called spinterfaces. However, spinterface effects have not yet been explored on layered magnetic materials. Here, the emergence of spinterface effects is demonstrated at the interface between flakes of the prototypical layered magnetic metal Fe3GeTe2 and thin films of Co-phthalocyanine. Magnetotransport measurements show that the molecular layer induces a magnetic exchange bias in Fe3GeTe2, indicating that the unpaired spins in Co-phthalocyanine develop antiferromagnetic ordering and pin the magnetization reversal of Fe3GeTe2 via magnetic proximity. The effect is strongest for a Fe3GeTe2 thickness of 20 nm, for which the exchange bias field reaches −840 Oe at 10 K and is measurable up to ≈110 K. This value compares very favorably with previous exchange bias fields reported for Fe3GeTe2 in all-inorganic van der Waals heterostructures, demonstrating the potential of molecular functionalization to tailor the magnetism of van der Waals layered materials., This work was supported by “la Caixa” Foundation (ID 100010434), under the agreement LCF/BQ/PI19/11690017, by the Spanish MICINN under Project PID2019-108153GA-I00, RTI2018-094861-B-100 and under the María de Maeztu Units of Excellence Program (MDM-2016-0618). This work was also supported by the FLAG-ERA grant MULTISPIN, by the Spanish MCIN/AEI with grant number PCI2021-122038-2A. B.M.-G. thanks Gipuzkoa Council (Spain) in the frame of Gipuzkoa Fellows Program. J.J. acknowledges the support of Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2020R1A6A3A03039086).

Over the past decades, polymer mechanochemistry has focused on the development and application of advanced force application methods to better understand the mechanochemical response of mechanophores. In this regard, techniques such as ultrasonication and single-molecule force spectroscopy (SMFS) are used to activate and detect up to thousands of chemical events within a polymer single chain, allowing the researchers to probe the mechanochemical reactivity of these stress-responsive motifs. Here, the most recent contributions of the single-molecule force spectroscopy technique to this field are presented, putting emphasis on the fundamental parameters of the technique for triggering specific force responses and on the description of force–extension curves measured for single- and multi-mechanophore polymers. Moreover, new contributions of microscopy-based techniques in the field of polymer mechanochemistry, as well as the potential application of single-chain nanoparticles as mechanoresponsive materials, are highlighted., J.A.P and E.V.-S gratefully acknowledge funding by Gipuzkoako Foru Aldundia-Programa Red Gipuzkoana de Ciencia, Tecnología e Innovación 2019 (Grant No. 2019-CIEN-000050-01); Basque Government (Grant No. IT-1175-19); and MCIU/AEI/FEDER, UE (Grant No. PGC2018-094548-B-I00). E.V.-S acknowledges the Materials Physics Center-MPC for her postdoctoral grant. D.E.M.-T. acknowledges the financial support obtained by the MCIU fellowship “Juan de la Cierva—Incorporación” (IJCI-2017-31600).

Self‐reporting fluorescence methods for monitoring folding and aggregation of proteins have a long history in biochemistry. Placing orthogonal luminophores within individual synthetic polymer chains for self‐reporting both folding (i.e., its intramolecular compaction to isolated single‐chain nanoparticles, SCNPs) and unbidden aggregation (i.e., the intermolecular association of SCNPs) remains a great challenge. Herein, a simple and efficient platform to identify both single‐chain compaction and intermolecular aggregation phenomena via photoluminescence is presented based on simultaneous synthesis through Hantzsch ester formation of orthogonal luminophores within the same polymer chain. Starting from non‐luminescent β‐ketoester‐decorated chains, intramolecular compaction is visually detected through fluorescence arising from Hantzsch fluorophores generated as intra‐chain connectors during folding. Complementary, intermolecular association is identified via aggregation‐induced emission (AIE) from orthogonal luminophores displaying intense photoluminescence at redshifted wavelengths after formation of multi‐SCNPs assemblies., We gratefully acknowledge funding by Gipuzkoako Foru Aldundia—Programa Red Gipuzkoana de Ciencia, Tecnología e Innovación 2019‐, grant number 2019‐CIEN‐000050‐01; Basque Government, grant number IT‐1175‐19; and MCIU/ EI/FEDER, UE, grant number PGC2018‐094548‐B‐I00.

Cyclic polymers behave different than linear polymers due to the lack of end groups and smaller coil dimensions. Herein, we demonstrate that cyclic polyethylene glycol (PEG) can be used as an alternative of classical linear PEG ligands for gold nanoparticle (AuNP) stabilization. We observed that the brush height of cyclic PEG on AuNPs of diameter 4.4 and 13.2 nm increases identically as that of linear brushes with (Nσ1/2)0.7 (N, number of monomers in a chain and σ, grafting density) and that cyclic brushes are more stretched than their linear analogues when compared to their unperturbed dimensions. Such structural effect and the reduced footprint diameter in cyclic brushes with the entire chain in a concentrated polymer brush regime explains the distinct response of NPs to ionic strength and temperature, respectively, compared to linear analogues. These experiments are an important step in understanding the effect of polymer brush topology on colloidal properties., We gratefully acknowledge support from the Spanish Ministry “Ministerio de Ciencia, Innovación y Universidades” (PGC2018-094548-B-I00, MICIU/AEI/FEDER, UE), Basque Government (IT-1175-19 and PIBA 2018-34) and Diputación Foral de Guipúzcoa (RED 2018).

[EN] Two different depositional phases can be identified in the Urumea estuarine infill. They werechronologically separated by a long period without sedimentological evidence. The first one, Pleistocene in age (> 43500 BP), is composed of a marsh facies overlaid by fluvio-estuarine facies.This could indicate that the sea level at the time was similar or slightly lower than the present parameter. The later information rules out the coldest stages of the Pleistocene as their origin. On top of the uppermost Pleistocene layer, a Holocene sequence developed which extends from 7040 ± 30 BP (7565–7390 cal. BP) to modern times. In this part of the infill, 3 transgressive pulses can be identified, separated or followed by phases of sea level stabilization or even regression. The first pulse began before 7040 ± 30 BP (7565–7390 cal. BP) and extended to 5200 ± 30 BP (5995–5910 cal. BP). The first regressive pulse took place around the last date, placing the shoreline a few meters below its present position. After 5200 ± 30 BP (5995–5910 cal. BP), afast sea level rise can be recorded, followed by a stabilisation phase first. Also, a minor regression happened afterwards, which was used by local communities to build two ramps of unknown utility. This regressive pulse was dated 4710 ± 30 BP (4945–4650 cal. BP). A new transgressive pulse took place after 3000 BP extending through a gentle sea level rise to 1240 ± 30 BP (1190–1065 cal. BP). From this date, sea level stabilisation (and maybe a new transgression in historical times) favoured the total infilling of the estuary, which, together with the development of a tombolo on the left bank, induced the formation of a semi-enclosed estuary which can still be observed nowadays., [ES] El análisis y caracterización del relleno sedimentario del estuario del Urumea permite diferenciar 2 sucesiones deposicionales distintas, separadas por un largo período cronológico sin registro sedimentario. La primera de estas sucesiones, de edad Pleistocena (> 43500 BP), está formada por una facies palustre sobre la que se desarrollan facies fluvio-estuarinas, señalando un nivel marino similar o algo más bajo que el actual, lo que permite descartar las fases más frías del Pleistoceno. Sobre esta sucesión se desarrolla otra de edad Holocena que abarca el período comprendido entre el 7040 ± 30 BP (7565–7390 cal. BP) y la época actual. Se reconocen 3 pulsos transgresivos separados o seguidos por fases de estabilización o de regresión. La primera fase transgresiva se inició con anterioridad al 7040 ± 30 BP (7565–7390 cal. BP) y ya había concluido en el 5200 ± 30 BP (5995–5910 cal. BP). Alrededor de esta última fecha tiene lugar una breve pulsación regresiva que sitúa el nivel del mar varios metros por debajo de su posición actual. A partir del 5200 ± 30 BP (5995-5910 cal. BP) se constata un rápido ascenso del nivel del mar, seguido de una fase de estabilización primero y de discreta regresión después, que es aprovechada por grupos humanos para construir 2 rampas de uso desconocido. La cronología de esta fase regresiva se sitúa en torno al 4710 ± 30 BP (4945-4650 cal. BP). Una nueva pulsación transgresiva tiene lugar a partir del 3000 BP prolongándose mediante una suave elevación hasta el 1240 ± 30 BP (1190–1065 cal. BP). La estabilización (y quizás una nueva oscilación en época histórica) del nivel del mar a partir de esta fecha favorece la colmatación del estuario, lo que unido a la formación de un tómbolo en la margen izquierda determina el desarrollo de un estuario semi-cerrado que pervive hasta la actualidad, Este manuscrito ha sido mejorado gracias a las sugerencias y aportaciones de dos revisores. Extendemos nuestro más sincero agradecimiento alExcmo. Ayuntamiento de Donostia – San Sebastián y al consorcio de empresas (UTE Intermodal Donosti) por la disponibilidad y comprensión demostrada a la hora de acceder a la obra a pesar de las inevitables molestias generadas, así como a la Diputación de Gipuzkoa por la financiación de algunas de las dataciones aquí presentadas. El estudio se ha desarrollado en el marco del Proyecto HAR2011-26956 (Ministerio de Ciencia y Competitividad) y del Grupo de Investigación del Sistema Universitario Vasco IT-622-13 quehan financiado algunas de las dataciones aquí presentadas.

Clean use of photons from light to activate chemical reactions offers many possibilities in different fields, from chemistry and biology to materials science and medicine. This review article describes the advances carried out in last decades toward the phototriggered synthesis of single-chain polymer nanoparticles (SCNPs) as soft nanomaterials with promising applications in enzyme-mimicking catalysis and nanomedicine, among other different uses. First, wesummarize some different strategies developed to synthesize SCNPs based on photoactivated intrachain homocoupling, phototriggered intrachain heterocoupling and photogenerated collapse induced by an external cross-linker. Next, we comprehensively review the emergent topic of photoactivated multifolding applied to SCNP construction. Finally, we conclude by summarizing recent strategies towards phototriggered disassembly of SCNPs., This research was funded by Gipuzkoako Foru Aldundia -Programa Red Gipuzkoana de Ciencia, Tecnología e Innovación 2019-, grant number 2019-CIEN-000050-01; Basque Government, grant number IT-1175-19; and MCIU/AEI/FEDER, UE, grant number PGC2018-094548-B-I00.

This article belongs to the Special Issue Polymers and Soft Matter: From Synthesis to Structure & Dynamics., This work provides an up-to-date overview of recent developments in neutron spectroscopic techniques and associated computational tools to interrogate the structural properties and dynamical behavior of complex and disordered materials, with a focus on those of a soft and polymeric nature. These have and continue to pave the way for new scientific opportunities simply thought unthinkable not so long ago, and have particularly benefited from advances in high-resolution, broadband techniques spanning energy transfers from the meV to the eV. Topical areas include the identification and robust assignment of low-energy modes underpinning functionality in soft solids and supramolecular frameworks, or the quantification in the laboratory of hitherto unexplored nuclear quantum effects dictating thermodynamic properties. In addition to novel classes of materials, we also discuss recent discoveries around water and its phase diagram, which continue to surprise us. All throughout, emphasis is placed on linking these ongoing and exciting experimental and computational developments to specific scientific questions in the context of the discovery of new materials for sustainable technologies., This research was funded by the Gipuzkoako Foru Aldundia under Grant Number 2020-CIEN-000009-01.

Metallic structures with nanogap features have proven highly effective as building blocks for plasmonic systems, as they can provide a wide tuning range of operating frequencies and large near-field enhancements. Recent work has shown that quantum mechanical effects such as electron tunnelling and nonlocal screening become important as the gap distances approach the subnanometre length-scale. Such quantum effects challenge the classical picture of nanogap plasmons and have stimulated a number of theoretical and experimental studies. This review outlines the findings of many groups into quantum mechanical effects in nanogap plasmons, and discusses outstanding challenges and future directions., W.Z. acknowledges support under the Cooperative Research Agreement between the University of Maryland and the National Institute of Standards and Technology Center for Nanoscale Science and Technology, award no. 70NANB10H193, through the University of Maryland. K.B.C. acknowledges funding from the Australian Research Council’s Discovery Projects (project number DP150103736) and Future Fellowship (project number FT140100577) funding schemes and from the Victorian Endowment for Science, Knowledge and Innovation (VESKI). R.E. acknowledges the Fellow Gipuzkoa of the Gipuzkoako Foru Aldundia through FEDER funds of the European Union ‘Una manera de hacer Europa’. R.E. and J.A. acknowledge Project FIS2013-41184-P of the Spanish Ministry of Economy and Competitiveness and federal grant 70NANB15H321 from the National Institute of Standards and Technology (NIST). A.G.B. acknowledges warm hospitality of Donostia International Physics Center. J.J.B. acknowledges support from UK EPSRC grants EP/G060649/1, EP/L027151/1, EP/G037221/1, EPSRC NanoDTC and ERC grant LINASS 320503. P.N. acknowledges support from the Robert A. Welch foundation under grant C-1222 and the Air Force Office of Science and Research under grant FA9550-15-1-0022.

Los adolescentes viven inmersos en un universo virtual en el que han construido un modelo propio de entretenimiento, aprendizaje y comunicación. El objetivo de este trabajo es definir los patrones de consumo, creación y difusión de contenidos audiovisuales de Internet en los ámbitos del ocio y las fuentes de información complementarias para uso escolar de los jóvenes guipuzcoanos, atendiendo a las variables de género, curso y tipo de centro. La metodología partió del diseño de un cuestionario autorrellenable que cumplimentaron 2.426 adolescentes (de 12 a 16 años), estudiantes de los cuatro cursos de ESO. La muestra es una selección aleatoria de 60 centros de Guipúzcoa y un total de 120 grupos, 30 por cada curso. Los resultados corroboran que los patrones de consumo, creación y difusión de contenidos de ocio masculinos y femeninos son monolíticos y opuestos entre sí. Los videojuegos son el eje vertebrador del consumo y creación masculino, mientras que la toma y difusión de fotografías y vídeos de sí mismas es el de las chicas. Estas prácticas repiten los estereotipos de género, por lo que la formación en igualdad se perfila como un aspecto relevante. Por último, las fuentes de información complementarias a la educación reglada, principalmente Wiki - pedia, se imponen como referencia entre los adolescentes, por lo que es imprescindible garantizar su solvencia para una adecuada adquisición de conocimientos Teenagers inhabit a virtual universe with their own model of entertainment, learning and communication. This research work defines the consumption, creation and dissemination patterns of online audiovisual content young students of Guipuzcoa have acquired in the fields of leisure and complementary information resources for school use, attending to three different variables: gender, grade (age) and type of educational institution (public or private). The research methodology focuses on a self-administered questionnaire filled out by 2,426 adolescents of secondary school (12 to 16 years old). The sample consists of a random selection of 120 student groups, which are distributed in 60 schools and 30 groups each course. The results verify the existence of monolithic and opposed male/female patterns in the way young people consume, create and diffuse leisure content. Video games are the central backbone of male consumption and creation, as long as girls prefer to take pictures and videos of themselves using smar tphones and to share them on social networks. These practices repeat gender stereotypes, transforming the education in equality into a relevant issue. Finally, sources of information that are complementary to formal education, especially Wikipedia, are the main references among adolescents. Consequently, it seems essential to guarantee their solvency for appropriate knowledge acquisition

XXXIV Jornadas de Paleontología y IV Congreso Ibérico de Paleontología (Vila Real, Portugal. Sep 2018) p 391-398, La necesidad de preservar este Patrimonio Paleontológico tan excepcional, como amenazado por los agentes geológicos externos, justifica la necesidad de preservar su morfología a largo plazo, que de otra forma no se podría garantizar. En este sentido la situación de la placa en una ubicación afectada por la acción de las mareas, junto al gran tamaño, la verticalidad y un ligero extraplomo, obligan a generar una infraestructura de cierta envergadura para la realización del molde. Sin embargo, y debido a la superficie plana de la placa la dificultad de la fabricación de la réplica se reduce enormemente ya que no es necesario el uso de una carcasa. La utilización para la realización de esta réplica de otros materiales (de uso reciente) más ligeros, como la celulosa, el nylon y la madera en sustitución de otros clásicos como el tejido y las varillas de fibra de vidrio y el gel de sílice micronizado proporciona una resistencia similar y una importante reducción de peso, además de evitar el contacto con productos nocivos por su toxicidad. La ubicación en un centro de visitantes de la pieza hace que pueda ser observada por cualquier persona y en unas condiciones adecuadas, mientras que su observación in situ está limitada para personas con movilidad reducida, además de lo complicado de su observación debido a las mareas y a la luz, adecuada o no, según la hora del día., Museo Geominero, Instituto Geológico y Minero de España, Geoparque Mundial de la UNESCO de Costa Vasca, Facultad de Bellas Artes, Universidad del País Vasco, Baleike kultur elkartea

SOX2 (Sex-determining region Y box 2) is a transcription factor expressed in several foetal and adult tissues and its deregulated activity has been linked to chronic diseases associated with ageing. Nevertheless, the level of SOX2 expression in aged individuals at the tissue level has not previously been examined. In this work, we show that SOX2 expression decreases significantly in the brain with ageing, in both humans and rodents. The administration of resveratrol for 6 months in mice partly attenuated this reduction. We also identified an age-related decline in SOX2 mRNA and protein expression in several other organs, namely, the lung, heart, kidney, spleen and liver. Moreover, peripheral blood mononuclear cells (PBMCs) from elderly expressed lower levels of SOX2 than those from young individuals. Mechanistically, SOX2 expression inversely correlates with p16Ink4a levels. Together, these data show a widespread decrease in SOX2 with age, suggesting that the decline in SOX2 expression might be used as a biomarker of ageing., This work is supported by grants from the Carlos III Health Institute (PI13/02277, CP16/00039, PI16/01580, DTS16/0184), Diputacion Foral Gipuzkoa, and the Departments of Industry and Health of the Basque Government, as well as from the European Union (Marie Curie CIG 2012/712404 and REFBIO13/BIOD/009) and European Regional Development Fund to Ander Matheu.

Published with the permission of Cambridge Scholars Publishing., Basagain is an Iron Age fortified site located on the north-eastern side of the Basque Country (Spain). As is common in other Iron Age sites of the region, evidence has been found of the coexistence and complementarity of two types of pottery production, which can be differentiated by their ownmodes of production and use, even though both were made with the same basic raw materials but with different preparation processes. This contribution presents the results derived from an archaeometric study carried out to determine the clay sediments and the tempers probably used in the making of mainly hand-made pottery from Basagain. A representative set of raw materials from the surroundings of the Basagain site was prepared in the laboratory, with the aim of comparing them with the archaeological material. The same characterization techniques used with archaeological items were applied: petrographic analysis by thin section and X-ray diffraction (XRD). The resulting data suggest that the clays used by Basagain potters were quite similar to clay sediments sampled in this study, as the main characteristics of these clay sediments are shared with archaeological ceramic potsherds previously analysed., The authors are grateful for the financial support given by the Heritage Program of the Provincial Council of Gipuzkoa (Spain) to J. López de Heredia. The authors would also like to acknowledge the project Geomateriales 2 (Ref. S2013/MIT-2914, Regional Government of Madrid and EU structural funds). J. Peña Poza acknowledges a job contract from this project. They are also indebted to the TechnoHeritage network on Science and Technology for the Conservation of Cultural Heritage for its professional support.

A comparative study of the electronic and optical properties of Mn-Bi-Te layered compounds was carried out using spectroscopic ellipsometry (SE) over a photon energy range of 0.7-6.5 eV at room temperature and density functional theory (DFT)-based first-principle calculations within the general gradient approximation with Hubbard like correction (GGA+U) and allowance for a spin-orbital coupling. The total energies of the above compounds in ferromagnetic (FM) and antiferromagnetic (AFM) spin configurations are obtained by taking the long-range van der Waals interaction into account. The stability of the AFM state of MnBiTe and MnBiTe over the corresponding FM counterpart is disclosed. The SE-based and calculated dielectric functions are compared. It is shown that interband optical transitions in the accessed photon energy range mainly occur between Mn 3d + Te 5p states of the valence band and Bi 6p + Te 5p with a small admixture of Mn 3d states of the conduction band., We acknowledge the support by the Science Development Foundation under the President of the Republic of Azerbaijan (Grant No. EI F-BGM-4-RFTF1/2017-21/04/1-M-02), Russian Foundation for Basic Research (Grant No. 18-52-06009), the Basque Departamento de Educación, UPV/EHU (Grant No. IT-756-13), Spanish Ministerio de Economia y Competitividad (MINECO Grant No. FIS2016-75862-P), the Saint Petersburg State University grant for scientific investigations (Grant No.15.61.202.2015). M.M.O. acknowledges support by the Diputación Foral de Gipuzkoa (SAREA 2018 - RED 2018*, *Project No. 2018-CIEN-000025-01).

International audience; Analyzing protein ubiquitylation changes during physiological or pathological processes is challenging due to its high reversibility and dynamic turnover of modified targets. We have developed a protein microarray to assess endogenous ubiquitylation levels from cell cultures, employing tandem ubiquitin-binding entities (TUBEs) with three or four ubiquitin-associated (UBA) domains as capture probes. Adriamycin (ADR)-stimulated MCF7 cells were used to differentiate protein ubiquitylation levels between cells that are sensitive or resistant to ADR treatment. We show that TUBEs-based microarrays can be used for the analysis of cellular processes regulated by ubiquitylation and for the detection of pathologies with aberrant ubiquitylation levels.

Microfluidic microdroplets have increasingly found application in biomolecular sensing as well as nanomaterials growth. More recently the synthesis of plasmonic nanostructures in microdroplets has led to surface-enhanced Raman spectroscopy (SERS)-based sensing applications. However, the study of nanoassembly in microdroplets has previously been hindered by the lack of on-chip characterization tools, particularly at early timescales. Enabled by a refractive index matching microdroplet formulation, dark-field spectroscopy is exploited to directly track the formation of nanometer-spaced gold nanoparticle assemblies in microdroplets. Measurements in flow provide millisecond time resolution through the assembly process, allowing identification of a regime where dimer formation dominates the dark-field scattering and SERS. Furthurmore, it is shown that small numbers of nanoparticles can be isolated in microdroplets, paving the way for simple high-yield assembly, isolation, and sorting of few nanoparticle structures., J.J.B. and A.S. acknowledge the support of the European Research Council (LINASS 320503), the UK Engineering and Physical Sciences Research Council EP/K028510/1, EP/G037221/1, EP/G060649/1, EP/L027151/1, and the Nano Science and Technology Doctoral Training Centre (NanoDTC) of the University of Cambridge. J.A. and R.E. acknowledge the Spanish Ministry of Economy and Competitiveness (FIS2013-41184-P). R.E. acknowledges the Fellow Gipuzkoa Program of the Gipuzkoako Foru Aldundia through FEDER “Una Manera de hacer Europa.”

Plasmonic multinanoparticle systems exhibit collective electric and magnetic resonances that are fundamental for the development of state-of-the-art optical nanoantennas, metamaterials, and surface-enhanced spectroscopy substrates. While electric dipolar modes have been investigated in both the classical and quantum realm, little attention has been given to magnetic and other “dark” modes at the smallest dimensions. Here, we study the collective electric, magnetic, and dark modes of colloidally synthesized silver nanosphere trimers with varying interparticle separation using scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS). This technique enables direct visualization and spatially selective excitation of individual trimers, as well as manipulation of the interparticle distance into the subnanometer regime with the electron beam. Our experiments reveal that bonding electric and magnetic modes are significantly impacted by quantum effects, exhibiting a relative blueshift and reduced EELS amplitude compared to classical predictions. In contrast, the trimer’s electric dark mode is not affected by quantum tunneling for even Ångström-scale interparticle separations. We employ a quantum-corrected model to simulate the effect of electron tunneling in the trimer which shows excellent agreement with experimental results. This understanding of classical and quantum-influenced hybridized modes may impact the development of future quantum plasmonic materials and devices, including Fano-like molecular sensors and quantum metamaterials., A.G.-E., G.A., R.E., and J.A acknowledge project FIS2013-41184-P of the Spanish Ministry of Economy and Competitiveness. J.A.S. and J.A.D. acknowledge funding from a Presidential Early Career Award administered through the Air Force Office of Scientific Research (FA9550-15-1-0006), as well as funding from a National Science Foundation CAREER Award (DMR-1151231). Electron spectroscopy was partially supported by the DOE ‘Light-Material Interactions in Energy Conversion’ Energy Frontier Research Center under Grant DESC0001293. A.G.-E. and R.E. received funding from the Fellows Gipuzkoa fellowship of the Gipuzkoako Foru Aldundia through the FEDER “Una Manera de hacer Europa”.

Elucidating the connection between shape and properties is a challenging but essential task for a rational design of nanoparticles at the atomic level. As a paradigmatic example we investigate how geometry can influence the magnetic properties of nanoparticles, focusing in particular on platinum clusters of 1–2 nm in size. Through first-principle calculations, we have found that the total magnetization depends strongly on the local atomic arrangements. This is due to a contraction of the nearest neighbor distance together with an elongation of the second nearest neighbor distance, resulting in an interatomic partial charge transfer from the atoms lying on the subsurface layer (donors) toward the vertexes (acceptors)., C.D.P. and F.B. have been supported by the U.K. research council EPSRC, under Grant No. EP/GO03146/1. R.D’A. acknowledges support by DYN-XC-TRANS (Grant No. FIS2013-43130-P) and NANOTherm (CSD2010-00044) of the Spanish Ministerio de Economia y Competitividad, the Grupo Consolidado UPV/EHU del Gobierno Vasco (Grant No. IT578-13), and Grant No. MV-2015-1-17 of the Diputacion Foral de Guipuzkoa.

We have recently developed an ab initio scheme for the calculation of the electronic structure of surfaces. The method is based on the combination of density functional calculations using finite slabs and the use of recursive methods to obtain the Green’s function of the surface. The slab calculations are performed using a linear combination of atomic orbitals as a basis set. From such calculation we directly obtain the surface Hamiltonian in a tight-binding form. Combining this information with that from a bulk calculation of the substrate, we gather all the pieces to construct the Hamiltonian of the semi-infinite system. The surface Green’s function is then computed using the transfer-matrix method and projected onto a wavepacket localized in the surface region. The width and energy of the surface electronic features are obtained from the analysis of such projection. With this approach we get rid of the finite size effects associated with the slab calculations. We have applied this method to the calculation of resonant charge transfer times from adsorbates to metallic substrates. We have focused in the case of core-excited Ar and S on Ru(0 0 0 1) to compare with core-hole clock spectroscopy experiments. We have also used our method to reveal the role of the elastic width in the scanning tunneling spectroscopy measurements of the quasi two-dimensional quantum well state appearing in p(2 × 2) ordered overlayers of Na and Cs on Cu(1 1 1). Here we present a new application of the method to study a more diluted alkali overlayer, the Cu(1 1 1)–(4 × 4)-Na surface. We present results for the relaxed geometries, binding energies, work function change and the position and width of the 3s Na resonance., This work was supported by the Basque Departamento de Educación, Universidades e Investigación, the Basque Departamento de Industria, Comercio y Turismo and the Diputación Foral de Gipuzkoa through the Etortek programme (Grants NANOMATERIALES and NANOTRON), the University of the Basque Country UPV/EHU (Grant No. 9/UPV 00206.215-13639/2001), the Spanish Ministerio de Educación y Ciencia (Grant No. FIS2004-06490-C03-00), and the EU Network of Excellence NANOQUANTA (Grant No. NMP4-CT-2004-500198).

Carbon nanotubes, gold nanorods, and silver nanoparticles can be transferred from water to organic solvents and back to water again by using polymeric ionic liquids (PILs) as vehicles (see scheme). The PILs are able to trap several nano-objects during their anion-exchange-induced precipitation in water. This reversible process provides a PIL/nano-object composite that is fully redispersible in organic solvents., This work was funded by the Diputación of Gipuzkoa and the Basque Government.

We present an investigation carried out with adolescents from different cultural contexts and sex in order to analyze the similarities and differences in the profile of television consumption (television preferences, permanence, alternative activities) and the family context (parental mediation and family climate). These aspects have their relevance from the point of view of educational intervention related to the development of media competence. Diputación Foral de Gipuzkoa (Basque Country, Spain)

Se presenta una investigación llevada a cabo con adolescentes de diferentes contextos culturales y sexo con objeto de analizar las similitudes y diferencias en el perfil de consumo televisivo (preferencias televisivas, permanencia, actividades alternativas) y el contexto familiar (mediación parental y clima familiar). Estos aspectos tienen su relevancia desde el punto de vista de la intervención educativa relacionada con el desarrollo de la competencia mediática. Diputación Foral de Gipuzkoa

Surface plasmon energies of single and oxidized spheres half-embedded on a planar support are calculated in the framework of the classical dielectric theory. Simple analytic expressions are obtained. New resonances appear related to the coupling between both media. The main difference between a supported sphere and an isolated sphere is the splitting of the multipolar energy modes, according to their parity. The support effect on EELS spectra is analyzed for some cases of experimental interest in electron microscopy., The authors thank Gipuzkoako Foru Aldundia for financial support.

Using density-functional theory we found that, depending on coverage, coadsorbed oxygen can act both as a promoter and as an inhibitor of the dissociation of water on Ru(0001), the transition between these two behaviors occurring at ∼0.2 ML. The key factor that determines this transition is the adsorption energy of the reaction products, OH in particular. The chemistry of this coadsorbed system is dictated by the effective coordination of the Ru atoms that participate in the bonding of the different species. In particular, we observed that a low coverage of oxygen increases the adsorption energy of the OH fraction on the Ru surface. This surprising extra stabilization of the OH with the coadsorption of oxygen can be understood in the context of the metallic bonding and could well correspond to a general trend for the coadsorption of electronegative species on metallic surfaces., We acknowledge support from the Basque Departamento de Educación, UPV/EHU Grant No. IT-366-07, the Spanish Ministerio de Educación y Ciencia Grant No. FIS2007-66711-C02-02, and ETORTEK research contracts funded by the Basque Departamento de Industria and the Diputación Foral de Guipuzcoa. The work at the Berkeley Lab was supported by the Director, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The work of A.M. was financed by the Marie Curie Outgoing International Fellowship, Project No. 514412.

The quasi-one-dimensional Si(557)-Au reconstruction has attracted a lot of attention in recent years. We study here the interplay between the electronic and structural degrees of freedom in this system. Our calculations are in good agreement with recent experimental data obtained using scanning tunneling microscopy and spectroscopy both at room and low temperatures. Together with the quite successful description of the experimental band structure, these results give further support to the current structural model of the Si(557)-Au surface. We consider in detail the energetics and variation of the band structure as a function of the buckling of the step edge and its implications to explain the observed metal-insulator transition. Finally, we present the results of a first-principles molecular dynamics simulation of several picoseconds performed at room temperature. As expected, we find a strong oscillation of the step-edge atoms. The dynamics associated with other vibrational modes is also observed. Particularly apparent are the oscillations of the height of the restatoms and adatoms and the associated fluctuation of the Si–Au–Si bond angles along the gold chain. This mode, together with step-edge buckling, has a strong influence on the insulating and/or metallic character of the surface., This work was supported by the Basque Departamento de Educación and the UPV/EHU Grant No. 9/UPV 00206.215-13639/2001, the Spanish Ministerio de Educacón y Ciencia Grant No. FIS2004-06490-C3-02, the European Network of Excellence FP6-NoE “NANOQUANTA” Grant No. 500198-2, and the research contracts “Nanomateriales” and “Nanotron” funded by the Basque Departamento de Industria, Comercio y Turismo within the ETORTEK program and the Departamento para la Innovación y la Sociedad del Conocimiento from the Diputación Foral de Guipuzcoa.

We present an atomic-orbital-based approximate scheme for self-interaction correction (SIC) to the local-density approximation (LDA) of density-functional theory. The method, based on the idea of Filippetti and Spaldin [Phys. Rev. B 67, 125109 (2003)], is implemented in a code using localized numerical atomic-orbital basis sets and is now suitable for both molecules and extended solids. After deriving the fundamental equations as a nonvariational approximation of the self-consistent SIC theory, we present results for a wide range of molecules and insulators. In particular, we investigate the effect of re-scaling the self-interaction correction and we establish a link with the existing atomiclike corrective scheme LDA+U. We find that when no re-scaling is applied, i.e., when we consider the entire atomic correction, the Kohn-Sham highest occupied molecular orbital (HOMO) eigenvalue is a rather good approximation to the experimental ionization potential for molecules. Similarly the HOMO eigenvalues of negatively charged molecules reproduce closely the molecular affinities. In contrast a re-scaling of about 50% is necessary to reproduce insulator band gaps in solids, which otherwise are largely overestimated. The method therefore represents a Kohn-Sham based single-particle theory and offers good prospects for applications where the actual position of the Kohn-Sham eigenvalues is important, such as quantum transport., This work was supported by the Science Foundation of Ireland under Grant No. SFI02/IN1/I175. D.S.P. acknowledges financial support from the University of the Basque Country Grant No. 9/UPV 00206.215-13639/2001, the Spanish Ministerio de Educacion y Ciencia Grant No. FIS2004-06490-C03-00, and the Basque Goverment and Diputacion Foral de Giupuzkoa NANOMATERIALES and NANOTRON grants, ETORTEK program.

The decay rates of electron and hole excitations at metal surfaces as determined by a scanning tunnelling microscope are presented and discussed. Surface-localised electron states as diverse as Shockley-type surface states and quantum well states confined to ultrathin alkali metal adsorption layers are covered. Recent developments in the analysis of the experimental procedures that are used to determine decay rates with the scanning tunnelling microscope, namely the analysis of line shapes and the spatial decay of standing wave patterns, are discussed., Financial support by the Deutsche Forschungsgemeinschaft and the British Council is gratefully acknowledged. This work has been supported by the Basque Departamento de Educación, the UPV/EHU, the Spanish Ministerio de Educación y Ciencia, the European Network of Excellence FP6-NoE NANOQUANTA, and the projects NANOMATERIALES and NANOTRON funded by the Basque Departamento de Industria, Comercio y Turismo within the ETORTEK programme and the Departamento para la Innovación y la Sociedad del Conocimiento from the Diputación Foral de Guipúzcoa.

We calculate the potential induced in a spin-polarized free electron gas by different ions by using density functional theory. By calculating the scattering of the conduction band electrons in this potential, we obtain the number of excited electrons and the polarization of the excitation when a slow ion travels through the system. The calculated spin polarization of the excited electrons shows characteristic oscillations with the atomic number of the projectile., R.V. and J.I.J. acknowledge partial support by the Eusko Jaurlaritza, Gipuzkoako Foru Aldundia, Euskal Herriko Unibertsitatea (project number: 9/UPV00206.215-13639/2001) and by the Spanish MCyT (project number: BFM-2001-0076). I.N. acknowledges partial support by OTKA (Grants No. T046868 and T049571).

Resumen tomado del autor. Este trabajo ha sido parcialmente financiado por la Universidad del País Vasco (UPV00141.226-T-15945/2004), el CICYT (TIC2002-03141) y la Diputación Foral de Gipuzkoa en un programa de la Unión Europea Se presenta una breve introducción al proyecto YADBrowser, el cual incluye un navegador educativo YADBrowser y su lenguaje OPScript. Se exponen algunas características recientemente añadidas al lenguaje; con ellas, el autor de una aplicación educativa puede lograr más funcionalidad y adaptabilidad con menos código. Además, el navegador YADBrowser reduce la interacción con el servidor, disminuyendo de esta forma el tiempo de respuesta de la aplicación. También puede mantener un registro de las acciones y preferencias del usuario durante la sesión. Las nuevas características fueron añadidas para facilitar la creación de aplicaciones dinámicas, adaptables a las habilidades del estudiante. Éstas incluyen comunicación 'verbal' entre objetos, modelos de objetos basados en XML y métodos reutilizables. También se exponen algunas características que pueden ser de importancia en el desarrollo de aplicaciones educativas con un componente matemático. País Vasco Universitat de les Illes Balears. Redined Balears; Edifici Guillem Cifre de Colonya. Ctra. de Valldemossa, Km 7,5; 07122 Palma de Mallorca; +34971172792; +34971173190; redined.balears@uib.es ESP

Energy loss per unit path in grazing collisions with metal surfaces is studied by using the collisional and dielectric formalisms. Within both theories we make use of the band-structure-based (BSB) model to represent the surface interaction. The BSB approach is based on a model potential and provides a precise description of the one-electron states and the surface-induced potential. The method is applied to evaluate the energy lost by 100 keV protons impinging on aluminum surfaces at glancing angles. We found that when the realistic BSB description of the surface is used, the energy loss obtained from the collisional formalism agrees with the dielectric one, which includes not only binary but also plasmon excitations. The distance-dependent stopping power derived from the BSB model is in good agreement with available experimental data. We have also investigated the influence of the surface band structure in collisions with the Al(100) surface. Surface-state contributions to the energy loss and electron emission probability are analyzed., M.N.F. and M.S.G. acknowledge financial support from the ANPCyT Grant No. PICTR 2002-00122, CONICET Grant No. PEI 6417-01, and UBACyT Grant No. X259. M.A., J.I.J, and V.M.S. acknowledge partial support by the Basque Departamento de Educación, Universidades e Investigación, the University of the Basque Country UPV/EHU Grant No. 9/UPV 00206.215-13639/2001, the Spanish MCyT Grants No. BFM2001-0076 and No. FIS2004-06490-CO3-00, and the European FP6 Network of Excellence Grant No. FP6-NoE NANOQUANTA 500198-2. M.A. and V. M. S. acknowledge financial support by the Gipuzkoako Foru Aldundia.

The merging of the main and the secondary dielectric relaxations in a series of six polymers has been investigated by using broadband dielectric spectroscopy (10-2−109 Hz). The data have been analyzed in two different ways. In one case, the whole relaxation process has been modeled by the simple addition of the relaxation functions corresponding to the main and secondary relaxations. In the other case, we have used the approach first proposed by Williams and Watts (Williams, G.; Watts, C.D. In NMR, Basic Principles and Progress; Diehl, P., Fluck, E., Kosfeld R., Eds.; Springer-Verlag, Berlin, 1971; Vol. 4, pp 271−285). This approach can be formally reduced to the addition of two terms, one corresponding to the main relaxation and the other to a combination of the functions corresponding to the main and secondary relaxations extrapolated from low temperatures. Both methods of analysis happen to describe the experimental data successfully in the merging region. In the framework of the Williams and Watts approach, the experimental behavior in the merging range is explained simply as a natural consequence of the extrapolation of the low-temperature relaxation behavior. However, using the simple addition method, this is not possible, which in this framework would be interpreted as due to a change of the secondary relaxation mechanism in the merging region. Therefore, the Williams and Watts approach provides the simplest physical picture for describing the merging of the α and β relaxations. Finally, the results obtained in this framework are interpreted using a free-energy landscape model., This work has been supported by the Spanish Ministry of Education (MEC) (Project PB97-0638), the Government of the Basque Country (Project GV-PI/1998/20), and the University of the Basque Country (Projects 206.215-G20/98). The authors thank Gipuzkoako Foru Aldundia, and Iberdrola S.A. for partial financial support. D.G. is thankful for a grant of the Spanish Ministry of Education. Support from “Donostia International Physics Center” is also acknowledged.

In this work we investigate by means of dielectric relaxation spectroscopy how segmental motions occurring in poly(vinyl chloride) (PVC) are modified by blending of PVC with small amounts of two different homopolymers: crystalline poly(ϵ‐caprolactone) (PCL) and glassy syndiotactic poly(methylmethacrylate) (sPMMA). The dynamics of the α relaxation of PVC is severely changed by blending it with PCL or sPMMA becoming faster or slower, respectively. Simultaneously, the shape of the relaxation function is being importantly altered. It shows a stronger non‐Debye character being broader and strongly temperature‐dependent. This fact leads us to calculate distributions of relaxation times for the blends that are wider in comparison to the one obtained for pure PVC. Complementary X‐ray diffraction measurements have been performed in order to assure the absence of crystallinity in the blends, and some small variations can be deduced at the level of interchain structural correlations of PVC., The authors thank the Spanish Ministry of Education(CICYT project MEC PB94-0468), the Government ofthe Basque Country (projects PI 95/005 and 2EX03/96),the University of the Basque Country (project 206.215RC245/96), and Gipuzkoako Foru Aldundia for financial support.

The role of valence electrons in filling inner-shell vacancies of highly charged ions in metals is studied using self-consistent solid state screened potentials. Explicit results for Ne and N ions in Au and Al targets are presented and discussed in connection to recent experiments. These filling rates are fundamental in understanding the neutralization and relaxation of highly charged ions in solids., The authors gratefully acknowledge help and financial support by Fondo de Cooperacion Euskadi-Aquitania, Ministerio de Educacion y Ciencia, HCM program under Contract No. CHRX-CT93-0103, Euskal Herriko Unibertsitatea, Gipuzkoako Foru Aldundia, and Iberdrola S.A.