ICN2 Publications

2017

  • A statistical analysis of nanocavities replication applied to injection moulding

    Pina-Estany J., Colominas C., Fraxedas J., Llobet J., Perez-Murano F., Puigoriol-Forcada J.M., Ruso D., Garcia-Granada A.A. International Communications in Heat and Mass Transfer; 81: 131 - 140. 2017. 10.1016/j.icheatmasstransfer.2016.11.003.

    Force Probe Microscopy and Surface Nanoengineering

    The purpose of this paper is to investigate both theoretically and experimentally how nanocavities are replicated in the injection moulding manufacturing process. The objective is to obtain a methodology for efficiently replicate nanocavities. From the theoretical point of view, simulations are carried out using a submodeling approach combining Solidworks Plastics for a first macrosimulation and Fluent solver for a subsequent nanosimulation. The effect of the four main factors (melt temperature, mould temperature, filling time and cavity geometry) are quantified using an statistical 24 factorial experiment. It is found that the main effects are the cavity length, the mould temperature and the polymer temperature, with standardized effects of 5, 3 and 2.6, respectively. Filling time has a negative 1.3 standardized effect. From the experimental point of view, Focused Ion Beam technique is used for mechanizing nanocavities in a steel mould. The replication achieved in polycarbonate injection is quantified using an Atomic Force Microscope. It is observed how both the geometry and the position of the cavities in the mould affect its replication. © 2016 Elsevier Ltd


  • A universal strategy for metal oxide anchored and binder-free carbon matrix electrode: A supercapacitor case with superior rate performance and high mass loading

    Zhang X., Luo J., Tang P., Ye X., Peng X., Tang H., Sun S.-G., Fransaer J. Nano Energy; 31: 311 - 321. 2017. 10.1016/j.nanoen.2016.11.024.

    Despite the significant advances in preparing carbon-metal oxide composite electrodes, strategies for seamless interconnecting of these two materials without using binders are still scarce. Herein we design a novel method for in situ synthesis of porous 2D-layered carbon–metal oxide composite electrode. Firstly, 2D-layered Ni-Co mixed metal-organic frameworks (MOFs) are deposited directly on nickel foam by anodic electrodeposition. Subsequent pyrolysis and activation procedure lead to the formation of carbon–metal oxides composite electrodes. Even with an ultrahigh mass loading of 13.4 mg cm−2, the as-prepared electrodes exhibit a superior rate performance of 93% (from 1 to 20 mA cm−2), high capacitance (2098 mF cm−2 at a current density of 1 mA cm−2), low resistance and excellent cycling stability, making them promising candidates for practical supercapacitor application. As a proof of concept, several MOF derived electrodes with different metal sources have also been prepared successfully via the same route, demonstrating the versatility of the proposed method for the preparation of binder-free carbon–metal oxide composite electrodes for electrochemical devices. © 2016 Elsevier Ltd


  • Analysis of alternative splicing events for cancer diagnosis using a multiplexing nanophotonic biosensor

    Huertas C.S., Domínguez-Zotes S., Lechuga L.M. Scientific Reports; 7 ( 41368) 2017. 10.1038/srep41368.

    NanoBiosensors and Bioanalytical Applications

    Personalized medicine is a promising tool not only for prevention, screening and development of more efficient treatment strategies, but also for diminishing the side effects caused by current therapies. Deciphering gene regulation pathways provides a reliable prognostic analysis to elucidate the origin of grave diseases and facilitate the selection of the most adequate treatment for each individual. Alternative splicing of mRNA precursors is one of these gene regulation pathways and enables cells to generate different protein outputs from the same gene depending on their developmental or homeostatic status. Its deregulation is strongly linked to disease onset and progression constituting a relevant and innovative class of biomarker. Herein we report a highly selective and sensitive nanophotonic biosensor based on the direct monitoring of the aberrant alternative splicing of Fas gene. Unlike conventional methods, the nanobiosensor performs a real-time detection of the specific isoforms in the fM-pM range without any cDNA synthesis or PCR amplification requirements. The nanobiosensor has been proven isoform-specific with no crosshybridization, greatly minimizing detection biases. The demonstrated high sensitivity and specificity make our nanobiosensor ideal for examining significant tumor-associated expression shifts of alternatively spliced isoforms for the early and accurate theranostics of cancer.


  • Analysis of C9orf72 repeat expansions in a large international cohort of dementia with Lewy bodies

    Kun-Rodrigues C., Ross O.A., Orme T., Shepherd C., Parkkinen L., Darwent L., Hernandez D., Ansorge O., Clark L.N., Honig L.S., Marder K., Lemstra A., Scheltens P., van der Flier W., Louwersheimer E., Holstege H., Rogaeva E., St. George-Hyslop P., Londos E., Zetterberg H., Barber I., Braae A., Brown K., Morgan K., Maetzler W., Berg D., Troakes C., Al-Sarraj S., Lashley T., Holton J., Compta Y., Van Deerlin V., Trojanowski J.Q., Serrano G.E., Beach T.G., Clarimon J., Lleó A., Morenas-Rodríguez E., Lesage S., Galasko D., Masliah E., Santana I., Diez M., Pastor P., Tienari P.J., Myllykangas L., Oinas M., Revesz T., Lees A., Boeve B.F., Petersen R.C., Ferman T.J., Escott-Price V., Graff-Radford N., Cairns N.J., Morris J.C., Stone D.J., Pickering-Brown S., Mann D., Dickson D.W., Halliday G.M., Singleton A., Guerreiro R., Bras J. Neurobiology of Aging; 49: 214.e13 - 214.e15. 2017. 10.1016/j.neurobiolaging.2016.08.023.

    C9orf72 repeat expansions are a common cause of amyotrophic lateral sclerosis and frontotemporal dementia. To date, no large-scale study of dementia with Lewy bodies (DLB) has been undertaken to assess the role of C9orf72 repeat expansions in the disease. Here, we investigated the prevalence of C9orf72 repeat expansions in a large cohort of DLB cases and identified no pathogenic repeat expansions in neuropathologically or clinically defined cases, showing that C9orf72 repeat expansions are not causally associated with DLB. © 2016 Elsevier Inc.


  • Biosensors for plant pathogen detection

    Khater M., de la Escosura-Muñiz A., Merkoçi A. Biosensors and Bioelectronics; 93: 72 - 86. 2017. 10.1016/j.bios.2016.09.091.

    Nanobioelectronics and Biosensors

    Infectious plant diseases are caused by pathogenic microorganisms such as fungi, bacteria, viruses, viroids, phytoplasma and nematodes. Worldwide, plant pathogen infections are among main factors limiting crop productivity and increasing economic losses. Plant pathogen detection is important as first step to manage a plant disease in greenhouses, field conditions and at the country boarders. Current immunological techniques used to detect pathogens in plant include enzyme-linked immunosorbent assays (ELISA) and direct tissue blot immunoassays (DTBIA). DNA-based techniques such as polymerase chain reaction (PCR), real time PCR (RT-PCR) and dot blot hybridization have also been proposed for pathogen identification and detection. However these methodologies are time-consuming and require complex instruments, being not suitable for in-situ analysis. Consequently, there is strong interest for developing new biosensing systems for early detection of plant diseases with high sensitivity and specificity at the point-of-care. In this context, we revise here the recent advancement in the development of advantageous biosensing systems for plant pathogen detection based on both antibody and DNA receptors. The use of different nanomaterials such as nanochannels and metallic nanoparticles for the development of innovative and sensitive biosensing systems for the detection of pathogens (i.e. bacteria and viruses) at the point-of-care is also shown. Plastic and paper-based platforms have been used for this purpose, offering cheap and easy-to-use really integrated sensing systems for rapid on-site detection. Beside devices developed at research and development level a brief revision of commercially available kits is also included in this review. © 2016 Elsevier B.V.


  • Capacitive vs Faradaic Energy Storage in a Hybrid Cell with LiFePO4/RGO Positive Electrode and Nanocarbon Negative Electrode

    Cabán-Huertas Z., Dubal D.P., Ayyad O., Gómez-Romero P. Journal of the Electrochemical Society; 164 (1): A6140 - A6146. 2017. 10.1149/2.0211701jes.

    Novel Energy-Oriented Materials

    We report an advanced device based on a Nitrogen-doped Carbon Nanopipes (N-CNP) negative electrode and a lithium iron phosphate (LiFePO4) positive electrode. We carefully balanced the cell composition (charge balance) and suppressed the initial irreversible capacity of the anode in the round of few cycles.We demonstrated an optimal performance in terms of specific capacity 170 mAh/g of LiFePO4 with energy density of about 203 Wh kg-1 and a stable operation for over 100 charge-discharge cycles. The components of this device (combining capacitive and faradaic electrodes) are low cost and easily scalable. This device has a performance comparable to those offered by the present technology of LIBs with the potential for faster charging; hence, we believe that the results disclosed in this work may open up new opportunities for energy storage devices. © The Author(s) 2016. Published by ECS.


  • Carborane bis-pyridylalcohols as linkers for coordination polymers: Synthesis, crystal structures, and guest-framework dependent mechanical properties

    Tsang M.Y., Rodríguez-Hermida S., Stylianou K.C., Tan F., Negi D., Teixidor F., Viñas C., Choquesillo-Lazarte D., Verdugo-Escamilla C., Guerrero M., Sort J., Juanhuix J., Maspoch D., Planas J.G. Crystal Growth and Design; 17 (2): 846 - 857. 2017. 10.1021/acs.cgd.6b01682.

    Supramolecular NanoChemistry and Materials

    We report the synthesis and characterization of six novel coordination polymers (CPs) based on M(II) (M: Zn and Co), di-, tri-, and tetracarboxylate linkers and two novel bis-pyridylalcohol 1,7-bis{(pyridin-n′-yl)methanol}-1,7-dicarba-closo-dodecaboranes (n′ = 3, L1; n′ = 4, L2) ligands. The polycarboxylates are terephthalic acid (H2BDC), 1,3,5-benzenetricarboxylic acid (H3BTB), and 1,2,4,5-Tetrakis(4-carboxyphenyl)benzene (H4TCPB). Structural description of CPs reveals the flexibility of the carborane ligands and their ability to construct extended structures. The CP containing Co(II), BTB, and L2 behaves as a crystalline sponge for a variety of guests, showing a higher affinity for aromatic guest molecules. Single-crystal nanoindentation experiments indicate that a high number of specific interactions between the guests and the CP framework result in a high elastic modulus and hardness values. © 2016 American Chemical Society.


  • Characterization of industrial Coolant Fluids and continuous ageing monitoring by wireless node—Enabled fiber optic sensors

    El Sachat A., Meristoudi A., Markos C., Sakellariou A., Papadopoulos A., Katsikas S., Riziotis C. Sensors (Switzerland); 17 (3, 568) 2017. 10.3390/s17030568.

    Phononic and Photonic Nanostructures

    Environmentally robust chemical sensors for monitoring industrial processes or infrastructures are lately becoming important devices in industry. Low complexity and wireless enabled characteristics can offer the required flexibility for sensor deployment in adaptable sensing networks for continuous monitoring and management of industrial assets. Here are presented the design, development and operation of a class of low cost photonic sensors for monitoring the ageing process and the operational characteristics of coolant fluids used in an industrial heavy machinery infrastructure. The chemical, physical and spectroscopic characteristics of specific industrial-grade coolant fluids were analyzed along their entire life cycle range, and proper parameters for their efficient monitoring were identified. Based on multimode polymer or silica optical fibers, wide range (3–11) pH sensors were developed by employing sol-gel derived pH sensitive coatings. The performances of the developed sensors were characterized and compared, towards their coolants’ ageing monitoring capability, proving their efficiency in such a demanding application scenario and harsh industrial environment. The operating characteristics of this type of sensors allowed their integration in an autonomous wireless sensing node, thus enabling the future use of the demonstrated platform in wireless sensor networks for a variety of industrial and environmental monitoring applications. © 2017 by the authors. Licensee MDPI, Basel, Switzerland.


  • Design of Hierarchical Surfaces for Tuning Wetting Characteristics

    Fernández A., Francone A., Thamdrup L.H., Johansson A., Bilenberg B., Nielsen T., Guttmann M., Sotomayor Torres C.M., Kehagias N. ACS Applied Materials and Interfaces; 9 (8): 7701 - 7709. 2017. 10.1021/acsami.6b13615.

    Phononic and Photonic Nanostructures

    Patterned surfaces with tunable wetting properties are described. A hybrid hierarchical surface realized by combining two different materials exhibits different wetting states, depending on the speed of impingement of the water droplets. Both "lotus" (high contact angle and low adhesion) and "petal" (high contact angle and high adhesion) states were observed on the same surface without the need of any modification of the surface. The great difference between the capillary pressures exerted by the microstructures and nanostructures was the key factor that allowed us to tailor effectively the adhesiveness of the water droplets. Having a low capillary pressure for the microstructures and a high capillary pressure for the nanostructures, we allow to the surface the possibility of being in a lotus state or in a petal state. © 2017 American Chemical Society.


  • Direct and label-free detection of the human growth hormone in urine by an ultrasensitive bimodal waveguide biosensor

    González-Guerrero A.B., Maldonado J., Dante S., Grajales D., Lechuga L.M. Journal of Biophotonics; 10 (1): 61 - 67. 2017. 10.1002/jbio.201600154.

    NanoBiosensors and Bioanalytical Applications

    A label-free interferometric transducer showing a theoretical detection limit for homogeneous sensing of 5 × 10–8 RIU, being equivalent to a protein mass coverage resolution of 2.8 fg mm–2, is used to develop a high sensitive biosensor for protein detection. The extreme sensitivity of this transducer combined with a selective bioreceptor layer enables the direct evaluation of the human growth hormone (hGH) in undiluted urine matrix in the 10 pg mL–1 range. (Figure presented.). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim


  • Directional elastic wave propagation in high-aspect-ratio photoresist gratings: Liquid infiltration and aging

    Alonso-Redondo E., Gueddida A., Li J., Graczykowski B., Sotomayor Torres C.M., Pennec Y., Yang S., Djafari-Rouhani B., Fytas G. Nanoscale; 9 (8): 2739 - 2747. 2017. 10.1039/c6nr08312a.

    Phononic and Photonic Nanostructures

    Determination of the mechanical properties of nanostructured soft materials and their composites in a quantitative manner is of great importance to improve the fidelity in their fabrication and to enable the subsequent reliable utility. Here, we report on the characterization of the elastic and photoelastic parameters of a periodic array of nanowalls (grating) by the non-invasive Brillouin light scattering technique and finite element calculations. The resolved elastic vibrational modes in high and low aspect ratio nanowalls reveal quantitative and qualitative differences related to the two-beam interference lithography fabrication and subsequent aging under ambient conditions. The phononic properties, namely the dispersion relations, can be drastically altered by changing the surrounding material of the nanowalls. Here we demonstrate that liquid infiltration turns the phononic function from a single-direction phonon-guiding to an anisotropic propagation along the two orthogonal directions. The susceptibility of the phononic behavior to the infiltrating liquid can be of unusual benefits, such as sensing and alteration of the materials under confinement. © The Royal Society of Chemistry 2017.


  • Effect of the annealing on the power factor of un-doped cold-pressed SnSe

    Morales Ferreiro J.O., Diaz-Droguett D.E., Celentano D., Reparaz J.S., Sotomayor Torres C.M., Ganguli S., Luo T. Applied Thermal Engineering; 111: 1426 - 1432. 2017. 10.1016/j.applthermaleng.2016.07.198.

    Phononic and Photonic Nanostructures

    Tin Selenide (SnSe), a thermoelectric material of the chalcogenide family, has attracted tremendous interest in the past few years due to its unprecedented thermoelectric figure-of-merit, ZT, of 2.6. In this work we have carried out an experimental study of the impact of annealing on the thermoelectric properties of polycrystalline SnSe formed by cold-pressing un-doped SnSe powders with a Hall carrier concentration of 5.37 × 1017 cm−3. The crystalline structure and morphology of the samples are characterized and properties, including electrical conductivity, Seebeck coefficient and thermal conductivity, are measured. It is found that thermal annealing has a large impact on both the microstructure and the thermoelectric properties. Notably, annealing leads to re-alignment of crystalline domains, increase in Seebeck coefficient by a factor of as much as 3, and increase in the electrical conductivity. A peak ZT of 0.11 was achieved at 772 K which is smaller than un-doped polycrystalline SnSe. © 2016 Elsevier Ltd


  • Electrical and Thermal Transport in Coplanar Polycrystalline Graphene-hBN Heterostructures

    Barrios-Vargas J.E., Mortazavi B., Cummings A.W., Martinez-Gordillo R., Pruneda M., Colombo L., Rabczuk T., Roche S. Nano Letters; 17 (3): 1660 - 1664. 2017. 10.1021/acs.nanolett.6b04936.

    Theoretical and Computational Nanoscience

    We present a theoretical study of electronic and thermal transport in polycrystalline heterostructures combining graphene (G) and hexagonal boron nitride (hBN) grains of varying size and distribution. By increasing the hBN grain density from a few percent to 100%, the system evolves from a good conductor to an insulator, with the mobility dropping by orders of magnitude and the sheet resistance reaching the MΩ regime. The Seebeck coefficient is suppressed above 40% mixing, while the thermal conductivity of polycrystalline hBN is found to be on the order of 30-120 Wm-1 K-1. These results, agreeing with available experimental data, provide guidelines for tuning G-hBN properties in the context of two-dimensional materials engineering. In particular, while we proved that both electrical and thermal properties are largely affected by morphological features (e.g., by the grain size and composition), we find in all cases that nanometer-sized polycrystalline G-hBN heterostructures are not good thermoelectric materials. © 2017 American Chemical Society.


  • Electrochemically reduced graphene and iridium oxide nanoparticles for inhibition-based angiotensin-converting enzyme inhibitor detection

    Kurbanoglu S., Rivas L., Ozkan S.A., Merkoçi A. Biosensors and Bioelectronics; 88: 122 - 129. 2017. 10.1016/j.bios.2016.07.109.

    Nanobioelectronics and Biosensors

    In this work, a novel biosensor based on electrochemically reduced graphene oxide and iridium oxide nanoparticles for the detection of angiotensin-converting enzyme inhibitor drug, captopril, is presented. For the preparation of the biosensor, tyrosinase is immobilized onto screen printed electrode by using 1-Ethyl-3-(3-dimethylaminopropyl)-carbodiimide and N-Hydroxysuccinimide coupling reagents, in electrochemically reduced graphene oxide and iridium oxide nanoparticles matrix. Biosensor response is characterized towards catechol, in terms of graphene oxide concentration, number of cycles to reduce graphene oxide, volume of iridium oxide nanoparticles and tyrosinase solution. The designed biosensor is used to inhibit tyrosinase activity by Captopril, which is generally used to treat congestive heart failure. It is an angiotensin-converting enzyme inhibitor that operates via chelating copper at the active site of tyrosinase and thioquinone formation. The captopril detections using both inhibition ways are very sensitive with low limits of detection: 0.019 µM and 0.008 µM for chelating copper at the active site of tyrosinase and thioquinone formation, respectively. The proposed methods have been successfully applied in captopril determination in spiked human serum and pharmaceutical dosage forms with acceptable recovery values. © 2016 Elsevier B.V.


  • Enhanced photoelectrochemical properties of nanoflower-like hexagonal CdSe0.6Te0.4: Effect of electron beam irradiation

    Shinde S.K., Ghodake G.S., Dubal D.P., Dhaygude H.D., Kim D.-Y., Fulari V.J. Journal of Industrial and Engineering Chemistry; 45: 92 - 98. 2017. 10.1016/j.jiec.2016.09.007.

    Novel Energy-Oriented Materials

    Present investigation deals with the effect of electron beam irradiation on the photoelectrochemical properties of cadmium selenium telluride (CdSe0.6Te0.4) thin films. Initially, CdSe0.6Te0.4 thin films were electrodeposited on fluorine doped tin oxide (FTO) coated glass and stainless steel substrates. Later, these CdSe0.6Te0.4 thin films were irradiated with high energy electron beam (10 MeV) of different doses from 10 to 30 kilograys (kGy). The effect of electron beam irradiation on different physico-chemical properties of CdSe0.6Te0.4 thin films such as morphological, structural, optical and photoelectrochemical has been investigated. It is observed that, the electron beam irradiation treatment considerably affects the properties of CdSe0.6Te0.4 thin films. The surface morphology of CdSe0.6Te0.4 thin films was changed from cauliflowers to nanoflowers, nanoroses and interconnected nanoflakes with doses of electron beams. Furthermore, the effect of electron beam irradiation on photoelectrochemical properties of CdSe0.6Te0.4 films was investigated. It is interesting to note that, the photoelectrochemical (PEC) properties of CdSe0.6Te0.4 thin films are extensively affected by electron beam irradiation. The photoconversion efficiency values of CdSe0.6Te0.4 films for different doses of electron beam are found to be 0.9%, 1.1%, 2.0% and 1.5%, respectively. © 2016


  • Epitaxial Growth of SrTiO3 Films on Cube-Textured Cu-Clad Substrates by PLD at Low Temperature Under Reducing Atmosphere

    Padilla J.A., Xuriguera E., Rodríguez L., Vannozzi A., Segarra M., Celentano G., Varela M. Nanoscale Research Letters; 12 (1, 226) 2017. 10.1186/s11671-017-1997-9.

    The growth of epitaxial {001}<100> SrTiO3 (STO) on low-cost cube-textured Cu-based clad substrate at low temperature was carried out by means of pulsed laser deposition (PLD). STO film was deposited in one step under a reducing atmosphere (5% H2 and 95% Ar mixture) to prevent the oxidation of the metal surface. The optimization of PLD parameters leads to a sharpest biaxial texture at a temperature as low as 500 °C and a thickness of 500 nm with a (100) STO layer. The upper limit of highly textured STO thickness was also investigated. The maximum thickness which retains the best quality {001}<100> texture is 800 nm, since the texture is preserved not only through the layer but also on the surface. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) measurements showed that STO films are continuous, dense, and smooth with very low roughness (between 5 and 7 nm). This paper describes the development of STO layer by means of PLD in absence of oxygen throughout the process, suggesting an alternative and effective method for growing highly {001}<100> textured STO layer on low-cost metal substrates. © 2017, The Author(s).


  • Evaluation of the immunological profile of antibody-functionalized metal-filled single-walled carbon nanocapsules for targeted radiotherapy

    Perez Ruiz De Garibay A., Spinato C., Klippstein R., Bourgognon M., Martincic M., Pach E., Ballesteros B., Ménard-Moyon C., Al-Jamal K.T., Tobias G., Bianco A. Scientific Reports; 7 ( 42605) 2017. 10.1038/srep42605.

    Force Probe Microscopy and Surface Nanoengineering | Electron Microscopy Division

    This study investigates the immune responses induced by metal-filled single-walled carbon nanotubes (SWCNT) under in vitro, ex vivo and in vivo settings. Either empty amino-functionalized CNTs [SWCNT-NH 2 (1)] or samarium chloride-filled amino-functionalized CNTs with [SmCl 3 @SWCNT-mAb (3)] or without [SmCl 3 @SWCNT-NH 2 (2)] Cetuximab functionalization were tested. Conjugates were added to RAW 264.7 or PBMC cells in a range of 1 μg/ml to 100 μg/ml for 24 h. Cell viability and IL-6/TNFα production were determined by flow cytometry and ELISA. Additionally, the effect of SWCNTs on the number of T lymphocytes, B lymphocytes and monocytes within the PBMC subpopulations was evaluated by immunostaining and flow cytometry. The effect on monocyte number in living mice was assessed after tail vein injection (150 μg of each conjugate per mouse) at 1, 7 and 13 days post-injection. Overall, our study showed that all the conjugates had no significant effect on cell viability of RAW 264.7 but conjugates 1 and 3 led to a slight increase in IL-6/TNFα. All the conjugates resulted in significant reduction in monocyte/macrophage cell numbers within PBMCs in a dose-dependent manner. Interestingly, monocyte depletion was not observed in vivo, suggesting their suitability for future testing in the field of targeted radiotherapy in mice. © The Author(s) 2017.


  • Field Effect in Graphene-Based van der Waals Heterostructures: Stacking Sequence Matters

    Stradi D., Papior N.R., Hansen O., Brandbyge M. Nano Letters; 17 (4): 2660 - 2666. 2017. 10.1021/acs.nanolett.7b00473.

    Stacked van der Waals (vdW) heterostructures where semiconducting two-dimensional (2D) materials are contacted by overlaid graphene electrodes enable atomically thin, flexible electronics. We use first-principles quantum transport simulations of graphene-contacted MoS2 devices to show how the transistor effect critically depends on the stacking configuration relative to the gate electrode. We can trace this behavior to the stacking-dependent response of the contact region to the capacitive electric field induced by the gate. The contact resistance is a central parameter and our observation establishes an important design rule for ultrathin devices based on 2D atomic crystals. © 2017 American Chemical Society.


  • Filling Single-Walled Carbon Nanotubes with Lutetium Chloride: A Sustainable Production of Nanocapsules Free of Nonencapsulated Material

    Kierkowicz M., González-Domínguez J.M., Pach E., Sandoval S., Ballesteros B., Da Ros T., Tobias G. ACS Sustainable Chemistry and Engineering; 5 (3): 2501 - 2508. 2017. 10.1021/acssuschemeng.6b02850.

    Force Probe Microscopy and Surface Nanoengineering | Electron Microscopy Division

    Filled carbon nanotubes are of interest for a wide variety of applications ranging from sensors to magnetoelectronic devices and going through the development of smart contrast and therapeutic agents in the biomedical field. In general, regardless of the method employed, bulk filling of carbon nanotubes results in the presence of a large amount of external nonencapsulated material. Therefore, further processing is needed to achieve a sample in which the selected payload is present only in the inner cavities of the nanotubes. Here, we report on a straightforward approach that allows the removal of nonencapsulated compounds in a time efficient and environmentally friendly manner, using water as a "green" solvent, while minimizing the residual waste. The results presented herein pave the way toward the production of large amounts of high-quality closed-ended filled nanotubes, also referred to as carbon nanocapsules, readily utilizable in the foreseen applications. © 2017 American Chemical Society.


  • Frequency response of electrolyte-gated graphene electrodes and transistors

    Drieschner S., Guimerà A., Cortadella R.G., Viana D., Makrygiannis E., Blaschke B.M., Vieten J., Garrido J.A. Journal of Physics D: Applied Physics; 50 (9, 095304) 2017. 10.1088/1361-6463/aa5443.

    Advanced Electronic Materials and Devices

    The interface between graphene and aqueous electrolytes is of high importance for applications of graphene in the field of biosensors and bioelectronics. The graphene/electrolyte interface is governed by the low density of states of graphene that limits the capacitance near the Dirac point in graphene and the sheet resistance. While several reports have focused on studying the capacitance of graphene as a function of the gate voltage, the frequency response of graphene electrodes and electrolyte-gated transistors has not been discussed so far. Here, we report on the impedance characterization of single layer graphene electrodes and transistors, showing that due to the relatively high sheet resistance of graphene, the frequency response is governed by the distribution of resistive and capacitive circuit elements along the graphene/electrolyte interface. Based on an analytical solution for the impedance of the distributed circuit elements, we model the graphene/electrolyte interface both for the electrode and the transistor configurations. Using this model, we can extract the relevant material and device parameters such as the voltage-dependent intrinsic sheet and series resistances as well as the interfacial capacitance. The model also provides information about the frequency threshold of electrolyte-gated graphene transistors, above which the device exhibits a non-resistive response, offering an important insight into the suitable frequency range of operation of electrolyte-gated graphene devices. © 2017 IOP Publishing Ltd.


  • Functional dependence of resonant harmonics on nanomechanical parameters in dynamic mode atomic force microscopy

    Gramazio F., Lorenzoni M., Pérez-Murano F., Trinidad E.R., Staufer U., Fraxedas J. Beilstein Journal of Nanotechnology; 8 (1, 90) 2017. 10.3762/bjnano.8.90.

    Force Probe Microscopy and Surface Nanoengineering

    We present a combined theoretical and experimental study of the dependence of resonant higher harmonics of rectangular cantilevers of an atomic force microscope (AFM) as a function of relevant parameters such as the cantilever force constant, tip radius and free oscillation amplitude as well as the stiffness of the sample's surface. The simulations reveal a universal functional dependence of the amplitude of the 6th harmonic (in resonance with the 2nd flexural mode) on these parameters, which can be expressed in terms of a gun-shaped function. This analytical expression can be regarded as a practical tool for extracting qualitative information from AFM measurements and it can be extended to any resonant harmonics. The experiments confirm the predicted dependence in the explored 3-45 N/m force constant range and 2-345 GPa sample's stiffness range. For force constants around 25 N/m, the amplitude of the 6th harmonic exhibits the largest sensitivity for ultrasharp tips (tip radius below 10 nm) and polymers (Young's modulus below 20 GPa). © 2017 Gramazio et al.


  • Functionalization of Polypyrrole Nanopipes with Redox-Active Polyoxometalates for High Energy Density Supercapacitors

    Dubal D.P., Ballesteros B., Mohite A.A., Gómez-Romero P. ChemSusChem; 10 (4): 731 - 737. 2017. 10.1002/cssc.201601610.

    Novel Energy-Oriented Materials | Electron Microscopy Division

    Hybrid materials are very attractive for the fabrication of high-performance supercapacitors. Here, we have explored organic–inorganic hybrid materials based on open-end porous 1 D polypyrrole nanopipes (PPy-NPipes) and heteropolyoxometalates (phosphotungstate ([PW12O40]3−, PW12) or phosphomolybdate ([PMo12O40]3−, PMo12)) that display excellent areal capacitances. Two different hybrid materials (PMo12@PPy and PW12@PPy) were effectively synthesized and used for symmetric supercapacitors. The anchoring of the inorganic nanoclusters onto the conducting polymer nanopipes led to electrodes that stood up to our best expectations exhibiting outstanding areal capacitances that are almost 1.5 to 2 fold higher than that of pristine PPy-NPipes. In addition, symmetric cells based on PMo12@PPy and PW12@PPy hybrid electrodes were fabricated and showed significant improvement in cell performance with very high volumetric capacitances in the range of 6.3–6.8 F cm−3 (considering the volume of whole device). Indeed, they provide extended potential windows in acidic electrolytes (up to 1.5 V) which led to ultrahigh energy densities of 1.5 and 2.2 mWh cm−3 for PMo12@PPy and PW12@PPy cells, respectively. Thus, these unique organic-inorganic hybrid symmetric cells displayed extraordinary electrochemical performances far exceeding those of more complex asymmetric systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


  • GaN surface states investigated by electrochemical studies

    Winnerl A., Garrido J.A., Stutzmann M. Applied Physics Letters; 110 (10, 101602) 2017. 10.1063/1.4977947.

    Advanced Electronic Materials and Devices

    We present a systematic study of electrochemically active surface states on MOCVD-grown n-type GaN in aqueous electrolytes using cyclic voltammetry and impedance spectroscopy over a wide range of potentials and frequencies. In order to alter the surface states, the GaN samples are either etched or oxidized, and the influence of the surface treatment on the defect-mediated charge transfer to the electrolyte is investigated. Etching in HCl removes substoichiometric GaOx, and leads to a pronounced density of electrochemically active surface states. Oxidation effectively removes these surface states. © 2017 Author(s).


  • Graphene Field-Effect Transistors for In Vitro and Ex Vivo Recordings

    Kireev D., Zadorozhnyi I., Qiu T., Sarik D., Brings F., Wu T., Seyock S., Maybeck V., Lottner M., Blaschke B.M., Garrido J., Xie X., Vitusevich S., Wolfrum B., Offenhäusser A. IEEE Transactions on Nanotechnology; 16 (1, 7782310): 140 - 147. 2017. 10.1109/TNANO.2016.2639028.

    Advanced Electronic Materials and Devices

    Recording extracellular potentials from electrogenic cells (especially neurons) is the hallmark destination of modern bioelectronics. While fabrication of flexible and biocompatible in vivo devices via silicon technology is complicated and time-consuming, graphene field-effect transistors (GFETs), instead, can easily be fabricated on flexible and biocompatible substrates. In this work, we compare GFETs fabricated on rigid (SiO2/Si and sapphire) and flexible (polyimide) substrates. The GFETs, fabricated on the polyimide, exhibit extremely large transconductance values, up to 11 mS·V-1, and mobility over 1750 cm2·V-1·s-1. In vitro recordings from cardiomyocyte-like cell culture are performed by GFETs on a rigid transparent substrate (sapphire). Via multichannel measurement, we are able to record and analyze both: difference in action potentials as well as their spatial propagation over the chip. Furthermore, the controllably flexible polyimide-on-steel (PIonS) substrates are able to ex vivo record electrical signals from primary embryonic rat heart tissue. Considering the flexibility of PIonS chips, together with the excellent sensitivity, we open up a new road into graphene-based in vivo biosensing. © 2016 IEEE.


  • Graphene-Based Biosensors: Going Simple

    Morales-Narváez E., Baptista-Pires L., Zamora-Gálvez A., Merkoçi A. Advanced Materials; 29 (7, 1604905) 2017. 10.1002/adma.201604905.

    Nanobioelectronics and Biosensors

    The main properties of graphene derivatives facilitating optical and electrical biosensing platforms are discussed, along with how the integration of graphene derivatives, plastic, and paper can lead to innovative devices in order to simplify biosensing technology and manufacture easy-to-use, yet powerful electrical or optical biosensors. Some crucial issues to be overcome in order to bring graphene-based biosensors to the market are also underscored. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim


  • Graphene-based hybrid for enantioselective sensing applications

    Zor E., Morales-Narváez E., Alpaydin S., Bingol H., Ersoz M., Merkoçi A. Biosensors and Bioelectronics; 87: 410 - 416. 2017. 10.1016/j.bios.2016.08.074.

    Nanobioelectronics and Biosensors

    Chirality is a major field of research of chemical biology and is essential in pharmacology. Accordingly, approaches for distinguishing between different chiral forms of a compound are of great interest. We report on an efficient and generic enantioselective sensor that is achieved by coupling reduced graphene oxide with γ-cyclodextrin (rGO/γ-CD). The enantioselective sensing capability of the resulting structure was operated in both electrical and optical mode for of tryptophan enantiomers (D-/L-Trp). In this sense, voltammetric and photoluminescence measurements were conducted and the experimental results were compared to molecular docking method. We gain insight into the occurring recognition mechanism with selectivity toward D- and L-Trp as shown in voltammetric, photoluminescence and molecular docking responses. As an enantioselective solid phase on an electrochemical transducer, thanks to the different dimensional interaction of enantiomers with hybrid material, a discrepancy occurs in the Gibbs free energy leading to a difference in oxidation peak potential as observed in electrochemical measurements. The optical sensing principle is based on the energy transfer phenomenon that occurs between photoexcited D-/L-Trp enantiomers and rGO/γ-CD giving rise to an enantioselective photoluminescence quenching due to the tendency of chiral enantiomers to form complexes with γ-CD in different molecular orientations as demonstrated by molecular docking studies. The approach, which is the first demonstration of applicability of molecular docking to show both enantioselective electrochemical and photoluminescence quenching capabilities of a graphene-related hybrid material, is truly new and may have broad interest in combination of experimental and computational methods for enantiosensing of chiral molecules. © 2016 Elsevier B.V.


  • Hierarchical surfaces for enhanced self-cleaning applications

    Fernández A., Francone A., Thamdrup L.H., Johansson A., Bilenberg B., Nielsen T., Guttmann M., Sotomayor Torres C.M., Kehagias N. Journal of Micromechanics and Microengineering; 27 (4, 045020) 2017. 10.1088/1361-6439/aa62bb.

    Phononic and Photonic Nanostructures

    In this study we present a flexible and adaptable fabrication method to create complex hierarchical structures over inherently hydrophobic resist materials. We have tested these surfaces for their superhydrophobic behaviour and successfully verified their self-cleaning properties. The followed approach allow us to design and produce superhydrophobic surfaces in a reproducible manner. We have analysed different combination of hierarchical micro-nanostructures for their application to self-cleaning surfaces. A static contact angle value of 170 with a hysteresis of 4 was achieved without the need of any additional chemical treatment on the fabricated hierarchical structures. Dynamic effects were analysed on these surfaces, obtaining a remarkable self-cleaning effect as well as a good robustness over impacting droplets. © 2017 IOP Publishing Ltd.


  • Hurdles to organic quinone flow cells. Electrode passivation by quinone reduction in acetonitrile Li electrolytes

    Rueda-García D., Dubal D.P., Hugenin F., Gómez-Romero P. Journal of Power Sources; 350: 9 - 17. 2017. 10.1016/j.jpowsour.2017.03.048.

    Novel Energy-Oriented Materials

    The uses of quinones in Redox Flow Batteries (RFBs) has been mainly circumscribed to aqueous solutions (of derivatives with polar groups) despite a larger solubility and wider electrochemical window provided by organic media. The redox mechanism of quinones in protic media is simpler and better known than in aprotic media, where radical species are involved. This paper reports the behaviour of methyl-p-benzoquinone (MBQ) under electrochemical reduction conditions in a LiClO4[sbnd]CH3CN electrolyte and various working electrodes. We detected the reversible generation of a bright green coating on the working electrode and the subsequent formation of a polymer (the nature of which depends on the presence or absence of oxygen). These coatings prevent the regular redox process of methyl-p-benzoquinone from taking place on the surface of the electrode and is generated regardless of the electrode material used or the presence of O2 in solution. In addition to MBQ, the green passivating layer was also found for less sterically hindered quinones such as p-benzoquinone or 1,4-naphthoquinone, but not for anthraquinone. We have also shown the central role of Li+ in the formation of this green layer. This work provides important guidelines for the final use of quinones in RFBs with organic electrolytes. © 2017


  • Inductively coupled remote plasma-enhanced chemical vapor deposition (rPE-CVD) as a versatile route for the deposition of graphene micro- and nanostructures

    Cuxart M.G., Šics I., Goñi A.R., Pach E., Sauthier G., Paradinas M., Foerster M., Aballe L., Fernandez H.M., Carlino V., Pellegrin E. Carbon; 117: 331 - 342. 2017. 10.1016/j.carbon.2017.02.067.

    Force Probe Microscopy and Surface Nanoengineering | Atomic Manipulation and Spectroscopy

    Multiple layers of graphene thin films with micro-crystalline orientation and vertical graphene nano-sheets were grown on different substrates (i.e., polycrystalline nickel foil, Ni(111), highly oriented pyrolytic graphite) using a single-step process based on low-pressure remote Plasma-Enhanced Chemical Vapor Deposition (rPE-CVD). In contrast to previous studies, a novel basic approach to this technique including a new remote inductively coupled RF plasma source has been used to (i) minimize the orientational effect of the plasma electrical fields during the catalyst-free growth of graphene nano-sheets, (ii) warrant for a low graphene defect density via low plasma kinetics, (iii) decouple the dissociation process of the gas from the growth process of graphene on the substrate, (iv) tune the feedstock gas chemistry in view of improving the graphene growth, and (v) reduce the growth temperature as compared to conventional chemical vapor deposition (CVD). In order to study the various aspects of the rPE-CVD graphene growth modes and to assess the characteristics of the resulting graphene layers, Raman spectroscopy, XPS, SEM, and STM were used. The results give evidence for the successful performance of this new rPE-CVD plasma deposition source, that can be combined with in situ UHV-based processess for the production of, e. g., hybrid metal ferromagnet/graphene systems. © 2017 Elsevier Ltd


  • Influence of texture in hybrid carbon-phosphomolybdic acid materials on their performance as electrodes in supercapacitors

    Palomino P., Suarez-Guevara J., Olivares-Marín M., Ruiz V., Dubal D.P., Gómez-Romero P., Tonti D., Enciso E. Carbon; 111: 74 - 82. 2017. 10.1016/j.carbon.2016.09.054.

    Novel Energy-Oriented Materials

    In this paper, phosphomolybdic acid H3PMo12O40 (PMo12) was anchored to four synthetic micro-mesoporous carbons and a commercial one to analyse the relationship between the porous texture of the support, the PMo12 adsorption and the performance of the resulting hybrid materials as electrodes in supercapacitors. The uptake of PMo12 on carbon supports follows a clear correlation with the micropore volume, which implies that PMo12 is mainly adsorbed in microporosity as a consequence of a greater confinement in this kind of pores instead of mesopores. Transmission electron microscopy indicates that the PMo12 adsorbed is homogeneously dispersed in the carbon texture. Finally, the addition of PMo12 to the original carbon electrodes provided capacitances up to 293 F per gram of electrode, substantially larger than the 206–240 F g−1 of the unmodified activated carbon. This result represented an increase of up to 35% in terms of gravimetric energy density and 160% in terms of volumetric energy density, after PMo12 integration into the carbon matrix. © 2016 Elsevier Ltd


  • Inorganic photocatalytic enhancement: Activated RhB Photodegradation by surface modification of SnO2 Nanocrystals with V2 O5-like species

    Epifani M., Kaciulis S., Mezzi A., Altamura D., Giannini C., Díaz R., Force C., Genç A., Arbiol J., Siciliano P., Comini E., Concina I. Scientific Reports; 7 ( 44763) 2017. 10.1038/srep44763.

    Advanced Electron Nanoscopy

    SnO2 nanocrystals were prepared by precipitation in dodecylamine at 100 °C, then they were reacted with vanadium chloromethoxide in oleic acid at 250 °C. The resulting materials were heat-treated at various temperatures up to 650 °C for thermal stabilization, chemical purification and for studying the overall structural transformations. From the crossed use of various characterization techniques, it emerged that the as-prepared materials were constituted by cassiterite SnO2 nanocrystals with a surface modified by isolated V(IV) oxide species. After heat-treatment at 400 °C, the SnO2 nanocrystals were wrapped by layers composed of vanadium oxide (IV-V mixed oxidation state) and carbon residuals. After heating at 500 °C, only SnO2 cassiterite nanocrystals were obtained, with a mean size of 2.8 nm and wrapped by only V2 O5-like species. The samples heat-treated at 500 °C were tested as RhB photodegradation catalysts. At 10-7 M concentration, all RhB was degraded within 1 h of reaction, at a much faster rate than all pure SnO2 materials reported until now. © The Author(s) 2017.


  • Interfacing neurons on carbon nanotubes covered with diamond

    Seyock S., Maybeck V., Scorsone E., Rousseau L., Hébert C., Lissorgues G., Bergonzo P., Offenhäusser A. RSC Advances; 7 (1): 153 - 160. 2017. 10.1039/c6ra20207a.

    Advanced Electronic Materials and Devices

    A recently discovered material, carbon nanotubes covered with diamond (DCNTs) was tested for its suitability in bioelectronics applications. Diamond shows advantages for bioelectronics applications (wide electro chemical window and bioinertness). This study investigates the effect of electrode surface shape (flat or three dimensional) on cell growth and behavior. For comparison, flat nanocrystalline diamond substrates were used. Primary embryonic neurons were grown on top of the structures and neither incorporated the structures nor did they grow in between the single structures. The interface was closely examined using focused ion beam (FIB) and scanning electron microscopy. Of special interest was the interface between cell and substrate. 5% to 25% of the cell membrane adhered to the substrate, which fits the theoretical estimated value. While investigating the conformity of the neurons, it could be observed that the cell membrane attaches to different heights of the tips of the 3D structure. However, the aspect ratio of the structures had no effect on the cell viability. These results let us assume that not more than 25% of cell attachment is needed for the survival of a functional neuronal cell. © The Royal Society of Chemistry.


  • Kondo screening of the spin and orbital magnetic moments of Fe impurities in Cu

    Joly L., Kappler J.-P., Ohresser P., Sainctavit P., Henry Y., Gautier F., Schmerber G., Kim D.J., Goyhenex C., Bulou H., Bengone O., Kavich J., Gambardella P., Scheurer F. Physical Review B - Condensed Matter and Materials Physics; 95 (4, 041108) 2017. 10.1103/PhysRevB.95.041108.

    We use x-ray magnetic circular dichroism to evidence the effect of correlations on the local impurity magnetic moment in an archetypal Kondo system, namely, a dilute Cu:Fe alloy. Applying the sum rules on the Fe L2,3 absorption edges, the evolution of the spin and orbital moments across the Kondo temperature are determined separately. The spin moment presents a crossover from a nearly temperature-independent regime below the Kondo temperature to a paramagneticlike regime above. Conversely, the weak orbital moment shows a temperature-independent behavior in the whole temperature range, suggesting different Kondo screening temperature scales for the spin and orbital moments. © 2017 American Physical Society.


  • Large edge magnetism in oxidized few-layer black phosphorus nanomeshes

    Nakanishi Y., Ishi A., Ohata C., Soriano D., Iwaki R., Nomura K., Hasegawa M., Nakamura T., Katsumoto S., Roche S., Haruyama J. Nano Research; 10 (2): 718 - 728. 2017. 10.1007/s12274-016-1355-8.

    Theoretical and Computational Nanoscience

    The formation and control of a room-temperature magnetic order in two-dimensional (2D) materials is a challenging quest for the advent of innovative magnetic- and spintronic-based technologies. To date, edge magnetism in 2D materials has been experimentally observed in hydrogen (H)-terminated graphene nanoribbons (GNRs) and graphene nanomeshes (GNMs), but the measured magnetization remains far too small to allow envisioning practical applications. Herein, we report experimental evidences of large room-temperature edge ferromagnetism (FM) obtained from oxygen (O)-terminated zigzag pore edges of few-layer black phosphorus (P) nanomeshes (BPNMs). The magnetization values per unit area are ~100 times larger than those reported for H-terminated GNMs, while the magnetism is absent for H-terminated BPNMs. The magnetization measurements and the first-principles simulations suggest that the origin of such a magnetic order could stem from ferromagnetic spin coupling between edge P with O atoms, resulting in a strong spin localization at the edge valence band, and from uniform oxidation of full pore edges over a large area and interlayer spin interaction. Our findings pave the way for realizing high-efficiency 2D flexible magnetic and spintronic devices without the use of rare magnetic elements. [Figure not available: see fulltext.] © 2017, Tsinghua University Press and Springer-Verlag Berlin Heidelberg.


  • Lateral Magnetically Modulated Multilayers by Combining Ion Implantation and Lithography

    Menéndez E., Modarresi H., Petermann C., Nogués J., Domingo N., Liu H., Kirby B.J., Mohd A.S., Salhi Z., Babcock E., Mattauch S., Van Haesendonck C., Vantomme A., Temst K. Small; 13 (11, 1603465) 2017. 10.1002/smll.201603465.

    Oxide Nanophysics | Magnetic Nanostructures

    The combination of lithography and ion implantation is demonstrated to be a suitable method to prepare lateral multilayers. A laterally, compositionally, and magnetically modulated microscale pattern consisting of alternating Co (1.6 µm wide) and Co-CoO (2.4 µm wide) lines has been obtained by oxygen ion implantation into a lithographically masked Au-sandwiched Co thin film. Magnetoresistance along the lines (i.e., current and applied magnetic field are parallel to the lines) reveals an effective positive giant magnetoresistance (GMR) behavior at room temperature. Conversely, anisotropic magnetoresistance and GMR contributions are distinguished at low temperature (i.e., 10 K) since the O-implanted areas become exchange coupled. This planar GMR is principally ascribed to the spatial modulation of coercivity in a spring-magnet-type configuration, which results in 180° Néel extrinsic domain walls at the Co/Co-CoO interfaces. The versatility, in terms of pattern size, morphology, and composition adjustment, of this method offers a unique route to fabricate planar systems for, among others, spintronic research and applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim


  • Ligand and solvent effects in the formation and self-assembly of a metallosupramolecular cage

    Adarsh N.N., Chakraborty A., Tarrés M., Dey S., Novio F., Chattopadhyay B., Ribas X., Ruiz-Molina D. New Journal of Chemistry; 41 (3): 1179 - 1185. 2017. 10.1039/C6NJ03456J.

    Nanostructured Functional Materials

    Two bis-pyridyl-bis-urea ligands namely N,N′-bis-(3-pyridyl)diphenylmethylene-bis-urea (L1) and N,N′-bis-(3-picolyl)diphenylmethylene-bis-urea (L2) have been reacted with a Cu(ii) salt resulting in the formation of a metallosupramolecular cage [{Cu2(μ-L1)4(DMSO)2(H2O)2}·SO4·X] (1) and a one-dimensional coordination polymer [{Cu(1)(μ-L2)2(H2O)2}{Cu(2)(μ-L2)2(H2O)2}·2SO4·9H2O·X]n (2) (where DMSO = dimethylsulfoxide, and X = disordered lattice included solvent molecules), respectively. The single crystal structures of 1 and 2 are discussed in the context of the effect of the ligands, particularly the hydrogen bonding functionality of the ligand, on the supramolecular structural diversities observed in these metal organic compounds. The supramolecular packing of 1 is clearly influenced by the nature of the solvent and ligand used; mixtures of DMSO/MeOH or DMSO/H2O lead to the formation of blue crystals or a hydrogel, respectively. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.


  • Metamirrors Based on Arrays of Silicon Nanowires with Height Gradients

    Otte M.A., Garcia-Martin A., Borrise X., Sepulveda B. Advanced Optical Materials; 5 (4, 1600933) 2017. 10.1002/adom.201600933.

    Magnetic Nanostructures

    [No abstract available]


  • Microencapsulation with alginate/CaCO 3: A strategy for improved phage therapy

    Colom J., Cano-Sarabia M., Otero J., Aríñez-Soriano J., Cortés P., Maspoch D., Llagostera M. Scientific Reports; 7 ( 41441) 2017. 10.1038/srep41441.

    Supramolecular NanoChemistry and Materials

    Bacteriophages are promising therapeutic agents that can be applied to different stages of the commercial food chain. In this sense, bacteriophages can be orally administered to farm animals to protect them against intestinal pathogens. However, the low pH of the stomach, the activities of bile and intestinal tract enzymes limit the efficacy of the phages. This study demonstrates the utility of an alginate/CaCO3 encapsulation method suitable for bacteriophages with different morphologies and to yield encapsulation efficacies of ∼100%. For the first time, a cocktail of three alginate/CaCO3-encapsulated bacteriophages was administered as oral therapy to commercial broilers infected with Salmonella under farm-like conditions. Encapsulation protects the bacteriophages against their destruction by the gastric juice. Phage release from capsules incubated in simulated intestinal fluid was also demonstrated, whereas encapsulation ensured sufficient intestinal retention of the phages. Moreover, the small size of the capsules (125-150 μm) enables their use in oral therapy and other applications in phage therapy. This study evidenced that a cocktail of the three alginate/CaCO3-encapsulated bacteriophages had a greater and more durable efficacy than a cocktail of the corresponding non-encapsulated phages in as therapy in broilers against Salmonella, one of the most common foodborne pathogen. © 2017 The Author(s).


  • Mimics of microstructures of Ni substituted Mn1−xNixCo2O4 for high energy density asymmetric capacitors

    Tamboli M.S., Dubal D.P., Patil S.S., Shaikh A.F., Deonikar V.G., Kulkarni M.V., Maldar N.N., Inamuddin, Asiri A.M., Gomez-Romero P., Kale B.B., Patil D.R. Chemical Engineering Journal; 307: 300 - 310. 2017. 10.1016/j.cej.2016.08.086.

    Novel Energy-Oriented Materials

    The preparation of nanostructured hierarchical Mn1−xNixCo2O4 metal oxides as efficient supercapacitors of different structures and configurations especially for the miniaturized electronics is still a challenge. In this context, we report template free facile hydrothermal synthesis of hierarchical nanostructured Mn1−xNixCo2O4 with excellent supercapacitive performance. Significantly, the morphology of pure MnCo2O4 transformed from 3D microcubes to 1D nanowires with incorporation of Ni. The electrochemical study shows highest specific capacitance i.e. 1762 F/g for Mn0.4Ni0.6Co2O4 with high cycling stability of 89.2% which is much higher than pristine MnCo2O4 and NiCo2O4. Later, asymmetric capacitor has been fabricated successfully using Mn0.4Ni0.6Co2O4 nanowires as positive electrode and activated carbon (AC) as negative electrode in a KOH aqueous electrolyte. An asymmetric cell could be cycled reversibly in the high-voltage range of 0–1.5 V and displays intriguing performances with a specific capacitance of 112.8 F/g (6.87 F/cm3) and high energy density of 35.2 Wh/kg (2.1 mWh/cm3). Importantly, this asymmetric capacitor device exhibits an excellent long cycle life along with 83.2% specific capacitance retained after 2000 cycles. © 2016 Elsevier B.V.


  • Modeling the Optical Responses of Noble Metal Nanoparticles Subjected to Physicochemical Transformations in Physiological Environments: Aggregation, Dissolution and Oxidation

    Piella J., Bastús N.G., Puntes V. Zeitschrift fur Physikalische Chemie; 231 (1): 33 - 50. 2017. 10.1515/zpch-2016-0874.

    Inorganic Nanoparticles

    Herein, we study how optical properties of colloidal dispersions of noble metal nanoparticles (Au and Ag) are affected by processes such as aggregation and oxidative dissolution. The optical contributions of these processes to the extinction spectra in the UV-vis region are often overlapped, making difficult its interpretation. In this regard, modeling the UV-vis spectra (in particular absorbance curve, peaks position, intensity and full width at half maximum-FWHM) of each process separately offers a powerful tool to identify the transformation of NPs under relevant and complex scenarios, such as in biological media. The proper identification of these transformations is crucial to understand the biological effects of the NPs. © 2017 Walter de Gruyter GmbH, Berlin/Boston.


  • Morphological modification of CdSe0.6Te0.4 nanostructures by electron irradiation and the effect on photoelectrochemical cells

    Shinde S.K., Ghodake G.S., Dubal D.P., Dhaygude H.D., Kim D.-Y., Rath M.C., Fulari V.J. Journal of Materials Science: Materials in Electronics; 28 (2): 1976 - 1984. 2017. 10.1007/s10854-016-5754-0.

    Novel Energy-Oriented Materials

    Morphologically well-ordered synthesis of nanomaterials by modification simple and cost effective. Electron irradiation is a promising pathway to develop various nanostructured materials. We report on the successful fabrication of hierarchical CdSe0.6Te0.4 nanostructures (nanonests, nanobrick-like small spheres with hybrid nanostructure, marigold, and nanoflowers) by electron beam irradiation in electrodeposition. These CdSe0.6Te0.4 nanostructures were employed as electrode material in solar cells, and the relationship between photoelectrochemical properties and CdSe0.6Te0.4 nanostructures was investigated, and showed that the photoelectrochemical properties strongly depend on CdSe0.6Te0.4 nanostructure morphology. The power conversion efficiency for nanonests, nanobrick-like small spheres with hybrid nanostructure, marigold, and nanoflowers of CdSe0.6Te0.4 were 0.88, 0.71, 1.03, and 0.94 %, respectively. © 2016, Springer Science+Business Media New York.


  • Multi-scale analysis of the diffusion barrier layer of gadolinia-doped ceria in a solid oxide fuel cell operated in a stack for 3000 h

    Morales M., Miguel-Pérez V., Tarancón A., Slodczyk A., Torrell M., Ballesteros B., Ouweltjes J.P., Bassat J.M., Montinaro D., Morata A. Journal of Power Sources; 344: 141 - 151. 2017. 10.1016/j.jpowsour.2017.01.109.

    Electron Microscopy Division

    The state-of-the-art materials for SOFCs are yttria-stabilized zirconia as electrolyte and lanthanum strontium cobalt ferrite as cathode. However, the formation of insulating phases between them requires the use of diffusion barriers, typically made of gadolinia doped ceria. The study of the stability of this layer during the fabrication and in operando is currently one of the major goals of the SOFC industry. In this work, the cation inter-diffusion at the cathode/barrier layer/electrolyte region is analysed for an anode-supported cell industrially fabricated by conventional techniques, assembled in a short-stack and tested under real operation conditions for 3000 h. A comprehensive study of this cell, and an equivalent non-operated one, is performed in order to understand the inter-diffusion mechanisms with possible effects on the final performance. The analyses evidence that the cation diffusion is occurring during the fabrication process. Despite the significant diffusion of Ce,Gd, Zr, Y and Sr cations, the formation of typically reported CGO-YSZ solid solution is not observed while the presence of isolated grains of SrZrO3 is proved. All in all, this study presents new insights into the stability of the typically employed diffusion barriers for solid oxide cells that will guide future strategies to improve their performance and durability. © 2017 Elsevier B.V.


  • Nanosecond Laser-Assisted Nitrogen Doping of Graphene Oxide Dispersions

    Kepić D., Sandoval S., Pino Á.P.D., György E., Cabana L., Ballesteros B., Tobias G. ChemPhysChem; 18 (8): 935 - 941. 2017. 10.1002/cphc.201601256.

    Electron Microscopy Division

    N-doped reduced graphene oxide (RGO) has been prepared in bulk form by laser irradiation of graphene oxide (GO) dispersed in an aqueous solution of ammonia. A pulsed Nd:YAG laser with emission wavelengths in the infrared (IR) 1064 nm, visible (Vis) 532 nm, and ultraviolet (UV) 266 nm spectral regions was employed for the preparation of the N-doped RGO samples. Regardless of the laser energy employed, the resulting material presents a higher fraction of pyrrolic nitrogen compared to nitrogen atoms in pyridinic and graphitic coordination. Noticeably, whereas increasing the laser fluence of UV and Vis wavelengths results in an increase in the total amount of nitrogen, up to 4.9 at. % (UV wavelength at 60 mJ cm−2 fluence), the opposite trend is observed when the GO is irradiated in ammonia solution through IR processing. The proposed laser-based methodology allows the bulk synthesis of N-doped reduced graphene oxide in a simple, fast, and cost efficient manner. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


  • Nanostructured graphene for spintronics

    Gregersen Sø.S., Power S.R., Jauho A.-P. Physical Review B - Condensed Matter and Materials Physics; 95 (12, 121406) 2017. 10.1103/PhysRevB.95.121406.

    Zigzag edges of the honeycomb structure of graphene exhibit magnetic polarization, making them attractive as building blocks for spintronic devices. Here, we show that devices with zigzag-edged triangular antidots perform essential spintronic functionalities, such as spatial spin splitting or spin filtering of unpolarized incoming currents. Near-perfect performance can be obtained with optimized structures. The device performance is robust against substantial disorder. The gate-voltage dependence of transverse resistance is qualitatively different for spin-polarized and spin-unpolarized devices, and can be used as a diagnostic tool. Importantly, the suggested devices are feasible within current technologies. © 2017 American Physical Society.


  • Nanostructured mixed transition metal oxides for high performance asymmetric supercapacitors: Facile synthetic strategy

    Tajik S., Dubal D.P., Gomez-Romero P., Yadegari A., Rashidi A., Nasernejad B., Inamuddin X., Asiri A.M. International Journal of Hydrogen Energy; 2017. 10.1016/j.ijhydene.2017.03.117.

    Novel Energy-Oriented Materials

    Exceptionally simple and cost-effective solid-state method is reported for the synthesis of different mixed transition metal oxides (MTMOs) including FeCo2O4, MnCo2O4 and ZnCo2O4 with unique nanostructures. The morphological analysis show that MTMOs possess distinct nanostructures such as tetragonal, spherical nanoparticles and hexagonal nanosheets. Furthermore, these MTMOs showed excellent supercapacitive properties with specific capacitances of 660-1263 F/g at current density of 2 A/g. Asymmetric capacitor was fabricated with FeCo2O4 as positive and activated carbon as negative electrode which exhibits a specific capacitance of 88 F/g with energy density of 24 Wh/kg (1.1 mWh/cm3) and cycle life (93%) over 5000 cycles. © 2017 Hydrogen Energy Publications LLC.


  • Nonlinear dynamics and chaos in an optomechanical beam

    Navarro-Urrios D., Capuj N.E., Colombano M.F., Garciá P.D., Sledzinska M., Alzina F., Griol A., Martínez A., Sotomayor-Torres C.M. Nature Communications; 8 ( 14965) 2017. 10.1038/ncomms14965.

    Phononic and Photonic Nanostructures

    Optical nonlinearities, such as thermo-optic mechanisms and free-carrier dispersion, are often considered unwelcome effects in silicon-based resonators and, more specifically, optomechanical cavities, since they affect, for instance, the relative detuning between an optical resonance and the excitation laser. Here, we exploit these nonlinearities and their intercoupling with the mechanical degrees of freedom of a silicon optomechanical nanobeam to unveil a rich set of fundamentally different complex dynamics. By smoothly changing the parameters of the excitation laser we demonstrate accurate control to activate two- A nd four-dimensional limit cycles, a period-doubling route and a six-dimensional chaos. In addition, by scanning the laser parameters in opposite senses we demonstrate bistability and hysteresis between two- A nd four-dimensional limit cycles, between different coherent mechanical states and between four-dimensional limit cycles and chaos. Our findings open new routes towards exploiting silicon-based optomechanical photonic crystals as a versatile building block to be used in neurocomputational networks and for chaos-based applications. © 2017 The Author(s).


  • One-Pot Synthesis of Cationic Gold Nanoparticles by Differential Reduction

    Sperling R.A., Garciá-Fernández L., Ojea-Jiménez I., Piella J., Bastús N.G., Puntes V. Zeitschrift fur Physikalische Chemie; 231 (1): 7 - 18. 2017. 10.1515/zpch-2016-0864.

    Inorganic Nanoparticles

    The size-controlled synthesis of cationic particles by differential reduction of HAuCl4 precursor in the presence of NaBH4 and 1-aminoundecane-12-thiol (AUT) is reported. The number of seed particles is determined by the fraction of the initially Au precursor reduced by NaBH4 present in the reaction mixture, which are then grown larger by the AUT, acting as both weak reducing agent and stabilizing surfactant. By this methodology, size controlled synthesis is achieved in a two-step one-pot synthesis at room temperature. © 2017 Walter de Gruyter GmbH, Berlin/Boston.


  • Optomechanical coupling in the Anderson-localization regime

    García P.D., Bericat-Vadell R., Arregui G., Navarro-Urrios D., Colombano M., Alzina F., Sotomayor-Torres C.M. Physical Review B - Condensed Matter and Materials Physics; 95 (11, 115129) 2017. 10.1103/PhysRevB.95.115129.

    Phononic and Photonic Nanostructures

    Optomechanical crystals, purposely designed and fabricated semiconductor nanostructures, are used to enhance the coupling between the electromagnetic field and the mechanical vibrations of matter at the nanoscale. However, in real optomechanical crystals, imperfections open extra channels where the transfer of energy is lost, reducing the optomechanical coupling efficiency. Here, we quantify the role of disorder in a paradigmatic one-dimensional optomechanical crystal with full phononic and photonic band gaps. We show how disorder can be exploited as a resource to enhance the optomechanical coupling beyond engineered structures, thus providing a new tool set for optomechanics. © 2017 American Physical Society.


  • Partial oxidation in a dense phase sub-monolayer of Fe-phthalocyanine on Ag(110)

    Bartolomé E., Bartolomé J., Sedona F., Herrero-Albillos J., Lobo J., Piantek M., García L.M., Panighel M., Mugarza A., Sambi M., Bartolomé F. Solid State Phenomena; 257: 219 - 222. 2017. 10.4028/www.scientific.net/SSP.257.219.

    Atomic Manipulation and Spectroscopy

    In this contribution we report on the structural and magnetic changes along a catalytic cycle of a new dense, “quasi-squared” FePc submonolayer phase (R3) evaporated on Ag(110). X-ray magnetic circular dichroism (XMCD) experiments at the Fe L2,3 edge were performed on four samples: the as-evaporated phase (R3), two differently oxygenated samples (OX1 and OX2) and the annealed phase (ANN). It is concluded that all characterized phases display planar anisotropy, and the values of mseff/nh are one order of magnitude larger than mL/nh. By oxidation, the isotropic moment increases from 7.2 x 10-2 μB/hole to 1.8 x 10-1 μB/hole, which is about a factor of 2 smaller than the increase achieved for the low-density phase. © 2017 Trans Tech Publications, Switzerland.


  • Potassium disorder in the defect pyrochlore KSbTeO6: A neutron diffraction study

    Alonso J.A., Mayer S., Falcón H., Turrillas X., Fernández-Díaz M.T. Crystals; 7 (1, 24) 2017. 10.3390/cryst7010024.

    KSbTeO6 defect pyrochlore has been prepared from K2C2O4, Sb2O3, and 15% excess TeO2 by solid-state reaction at 850 °C. Direct methods implemented in the software EXPO2013 allowed establishing the basic structural framework. This was followed by a combined Rietveld refinement from X-ray powder diffraction (XRD) and neutron powder diffraction (NPD) data, which unveiled additional structural features. KSbTeO6 is cubic, a = 10.1226(7) Å, space group Fd3m, Z = 8 and it is made of a mainly covalent framework of corner-sharing (Sb,Te)O6 octahedra, with weakly bonded K+ ions located within large cages. The large K-O distances, 3.05(3)–3.07(3) Å, and quite large anisotropic atomic displacement parameters account for the easiness of K+ exchange for other cations of technological importance. © 2016 by the authors; licensee MDPI, Basel, Switzerland.


  • Rapid on-chip apoptosis assay on human carcinoma cells based on annexin-V/quantum dot probes

    Montón H., Medina-Sánchez M., Soler J.A., Chałupniak A., Nogués C., Merkoçi A. Biosensors and Bioelectronics; 94: 408 - 414. 2017. 10.1016/j.bios.2017.03.034.

    Nanobioelectronics and Biosensors

    Despite all the efforts made over years to study the cancer expression and the metastasis event, there is not a clear understanding of its origins and effective treatment. Therefore, more specialized and rapid techniques are required for studying cell behaviour under different drug-based treatments. Here we present a quantum dot signalling-based cell assay carried out in a segmental microfluidic device that allows studying the effect of anti-cancer drugs in cultured cell lines by monitoring phosphatidylserine translocation that occurs in early apoptosis. The developed platform combines the automatic generation of a drug gradient concentration, allowing exposure of cancer cells to different doses, and the immunolabeling of the apoptotic cells using quantum dot reporters. Thereby a complete cell-based assay for efficient drug screening is performed showing a clear correlation between drug dose and amount of cells undergoing apoptosis. © 2017 Elsevier B.V.


  • Solution-based synthesis and processing of Sn- and Bi-doped Cu3SbSe4 nanocrystals, nanomaterials and ring-shaped thermoelectric generators

    Liu Y., García G., Ortega S., Cadavid D., Palacios P., Lu J., Ibáñez M., Xi L., De Roo J., López A.M., Martí-Sánchez S., Cabezas I., Mata M.D.L., Luo Z., Dun C., Dobrozhan O., Carroll D.L., Zhang W., Martins J., Kovalenko M.V., Arbiol J., Noriega G., Song J., Wahnón P., Cabot A. Journal of Materials Chemistry A; 5 (6): 2592 - 2602. 2017. 10.1039/c6ta08467b.

    Advanced Electron Nanoscopy

    Copper-based chalcogenides that comprise abundant, low-cost, and environmental friendly elements are excellent materials for a number of energy conversion applications, including photovoltaics, photocatalysis, and thermoelectrics (TE). In such applications, the use of solution-processed nanocrystals (NCs) to produce thin films or bulk nanomaterials has associated several potential advantages, such as high material yield and throughput, and composition control with unmatched spatial resolution and cost. Here we report on the production of Cu3SbSe4 (CASe) NCs with tuned amounts of Sn and Bi dopants. After proper ligand removal, as monitored by nuclear magnetic resonance and infrared spectroscopy, these NCs were used to produce dense CASe bulk nanomaterials for solid state TE energy conversion. By adjusting the amount of extrinsic dopants, dimensionless TE figures of merit (ZT) up to 1.26 at 673 K were reached. Such high ZT values are related to an optimized carrier concentration by Sn doping, a minimized lattice thermal conductivity due to efficient phonon scattering at point defects and grain boundaries, and to an increase of the Seebeck coefficient obtained by a modification of the electronic band structure with Bi doping. Nanomaterials were further employed to fabricate ring-shaped TE generators to be coupled to hot pipes, which provided 20 mV and 1 mW per TE element when exposed to a 160 °C temperature gradient. The simple design and good thermal contact associated with the ring geometry and the potential low cost of the material solution processing may allow the fabrication of TE generators with short payback times. © The Royal Society of Chemistry.


  • Sonochemical synthesis, characterization, and effects of temperature, power ultrasound and reaction time on the morphological properties of two new nanostructured mercury(II) coordination supramolecule compounds

    Hayati P., Rezvani A.R., Morsali A., Molina D.R., Geravand S., Suarez-Garcia S., Villaecija M.A.M., García-Granda S., Mendoza-Meroño R., Retailleau P. Ultrasonics Sonochemistry; 37: 382 - 393. 2017. 10.1016/j.ultsonch.2017.01.021.

    Two new mercury(II) coordination supramolecular compounds (CSCs) (1D and 0D), [Hg(L)(I)2]n (1) and [Hg2(L′)2(SCN)2]·2H2O (2) (L = 2-amino-4-methylpyridine and L′ = 2,6-pyridinedicarboxlic acid), have been synthesized under different experimental conditions. Micrometric crystals (bulk) or nano-sized materials have been obtained depending on using the branch tube method or sonochemical irradiation. All materials have been characterized by field emission scanning electron microscope (FESEM), scanning electron microscopy (SEM), powder X-ray diffraction (PXRD) and FT-IR spectroscopy. Single crystal X-ray analyses on compounds 1 and 2 show that Hg2+ ions are 4-coordinated and 5-coordinated, respectively. Topological analysis shows that the compound 1 and 2 have 2C1, sql net. The thermal stability of compounds 1 and 2 in bulk and nano-size has been studied by thermal gravimetric (TG), differential thermal analyses (DTA) for 1 and differential scanning calorimetry (DSC) for 2, respectively. Also, by changing counter ions were obtained various structures 1 and 2 (1D and 0D, respectively). The role of different parameters like power of ultrasound irradiation, reaction time and temperature on the growth and morphology of the nano-structures are studied. Results suggest that increasing power ultrasound irradiation and temperature together with reducing reaction time and concentration of initial reagents leads to a decrease in particle size. © 2017 The Authors


  • Spin precession in anisotropic media

    Raes B., Cummings A.W., Bonell F., Costache M.V., Sierra J.F., Roche S., Valenzuela S.O. Physical Review B - Condensed Matter and Materials Physics; 95 (8, 085403) 2017. 10.1103/PhysRevB.95.085403.

    Theoretical and Computational Nanoscience | Physics and Engineering of Nanodevices

    We generalize the diffusive model for spin injection and detection in nonlocal spin structures to account for spin precession under an applied magnetic field in an anisotropic medium, for which the spin lifetime is not unique and depends on the spin orientation. We demonstrate that the spin precession (Hanle) line shape is strongly dependent on the degree of anisotropy and on the orientation of the magnetic field. In particular, we show that the anisotropy of the spin lifetime can be extracted from the measured spin signal, after dephasing in an oblique magnetic field, by using an analytical formula with a single fitting parameter. Alternatively, after identifying the fingerprints associated with the anisotropy, we propose a simple scaling of the Hanle line shapes at specific magnetic field orientations that results in a universal curve only in the isotropic case. The deviation from the universal curve can be used as a complementary means of quantifying the anisotropy by direct comparison with the solution of our generalized model. Finally, we applied our model to graphene devices and find that the spin relaxation for graphene on silicon oxide is isotropic within our experimental resolution. © 2017 American Physical Society.


  • Structural, optical, and photoelectrochemical properties of nanosphere-like CdXZn1-XS synthesized by electrochemical route

    Dhaygude H.D., Shinde S.K., Dubal D.P., Velhal N.B., Kim D.-Y., Fulari V.J. Ionics; 23 (1): 223 - 231. 2017. 10.1007/s11581-016-1797-8.

    Novel Energy-Oriented Materials

    Here, we present the effect of different Zn contents on the structural, morphological, and optical properties of CdXZn1-XS thin films deposited by electrodeposition method on stainless steel and indium-doped tin oxide (ITO) glass substrates. Electrosynthesized CdXZn1-XS thin films are characterized by using X-ray diffraction (XRD), UV-Vis spectrophotometer, field emission scanning electron microscope (FE-SEM), and surface wettability analysis. XRD pattern reveals that the CdXZn1-XS thin films are polycrystalline in nature with hexagonal crystal structure. FE-SEM micrograph displays that these CdXZn1-XS thin films exhibit the different sizes of sphere-like nanostructures by varying the X value. The optical absorption study indicates that drastic variation in band gap energy of CdXZn1-XS thin films. In advance photovoltaic measurements, CdXZn1-XS thin films are to be studied by forming the photoelectrochemical (PEC) cell having CdXZn1-XS/0.5 M (Na2SO3)/C configuration. The efficiency values of CdXZn1-XS are found to be 0.2, 0.35, 0.32, 0.25, and 0.23 % respectively at X content. © 2016, Springer-Verlag Berlin Heidelberg.


  • Synthesis and characterization of a new nano lead(II) 0-D coordination supramolecular compound: A precursor to produce pure phase nano-sized lead(II) oxide

    Fard M.J.S., Hayati P., Naraghi H.S., Tabeie S.A. Ultrasonics Sonochemistry; 39: 129 - 136. 2017. 10.1016/j.ultsonch.2017.04.023.

    Nano-structure of a new 0D Pb(II) coordination supramolecular compound, [Pb4(8-Quin)6](ClO4)2(1), L = 8-HQuin = 8-hydroxyquinolin ligand has been synthesized by use of a sonochemical process and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), Fourier transform infrared spectroscopy (FTIR) and elemental analyses. The structure of compound 1 was determined by single-crystal X-ray diffraction. The single crystal X-ray data of compound 1 implies that the Pb+2 ions are five coordinated. Each lead atom is coordinated to nitrogen and oxygen atoms of 8-hydroxyquinolin ligand. Topological analysis shows that the compound 1 is 1,2,3,4,4M12-1net. Nanoparticles of lead(II) oxide have been prepared by calcination of lead(II) coordination polymer at 500 °C that were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD) and IR spectroscopy. © 2017 Elsevier B.V.


  • Synthesis and optical characterization of Er-doped bismuth titanate nanoparticles grown by sol–gel hydrothermal method

    Fuentes S., Muñoz P., Llanos J., Vega M., Martin I.R., Chavez-Angel E. Ceramics International; 43 (4): 3623 - 3630. 2017. 10.1016/j.ceramint.2016.11.200.

    The Er3+-doped bismuth titanate (Bi4Ti3O12, BIT) nanoparticles were synthesized by a combined sol–gel and hydrothermal method under a partial oxygen pressure of 30 bar. The composition and morphology were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman scattering. They showed pure and homogeneous spherical BIT nanoparticles with a size below the 30 nm. The incorporation of Er ions showed a strong decrease in the lattice parameters, as well as averaged particle size. The photoluminescence up-conversion (excitation wavelength =1480 nm) showed an enhancement of the infrared emission (980 nm) as Er concentration increased, achieving a maximum for 6% mol, while photoluminescence spectra (excitation wavelength =473 nm) showed a strong green emission (529 and 553 nm) with a maximum at 4% mol. © 2016 Elsevier Ltd and Techna Group S.r.l.


  • Synthesis of Polydopamine-Like Nanocapsules via Removal of a Sacrificial Mesoporous Silica Template with Water

    Nador F., Guisasola E., Baeza A., Villaecija M.A.M., Vallet-Regí M., Ruiz-Molina D. Chemistry - A European Journal; 23 (12): 2753 - 2758. 2017. 10.1002/chem.201604631.

    Nanostructured Functional Materials

    Hollow polymeric polydopamine (PDA) micro-/nanocapsules have been obtained through a very simple, mild, and straightforward method that involves coating of silica mesoporous nanoparticles through an ammonia-triggered polymerization of PDA and the posterior removal of the sacrificial template simply by dispersion in water, without the need of any harsh chemical reagent, either in the presence or absence of active principles, from doxorubicin to iron oxide nanoparticles. To demonstrate the potential of the nanocapsules obtained with this new approach, they have been successfully used as nanocarriers for drug delivery. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


  • Thermal conductivity of epitaxially grown InP: experiment and simulation

    Jaramillo-Fernandez J., Chavez-Angel E., Sanatinia R., Kataria H., Anand S., Lourdudoss S., Sotomayor-Torres C.M. CrystEngComm; 19 (14): 1879 - 1887. 2017. 10.1039/c6ce02642g.

    Phononic and Photonic Nanostructures

    The integration of III-V optoelectronic devices on silicon is confronted with the challenge of heat dissipation for reliable and stable operation. A thorough understanding and characterization of thermal transport is paramount for improved designs of, for example, viable III-V light sources on silicon. In this work, the thermal conductivity of heteroepitaxial laterally overgrown InP layers on silicon is experimentally investigated using microRaman thermometry. By examining InP mesa-like structures grown from trenches defined by a SiO2 mask, we found that the thermal conductivity decreases by about one third, compared to the bulk thermal conductivity of InP, with decreasing width from 400 to 250 nm. The high thermal conductivity of InP grown from 400 nm trenches was attributed to the lower defect density as the InP microcrystal becomes thicker. In this case, the thermal transport is dominated by phonon-phonon interactions as in a low defect-density monocrystalline bulk material, whereas for thinner InP layers grown from narrower trenches, the heat transfer is dominated by phonon scattering at the extended defects and InP/SiO2 interface. In addition to the nominally undoped sample, sulfur-doped (1 × 1018 cm−3) InP grown on Si was also studied. For the narrower doped InP microcrystals, the thermal conductivity decreased by a factor of two compared to the bulk value. Sources of errors in the thermal conductivity measurements are discussed. The experimental temperature rise was successfully simulated by the heat diffusion equation using the FEM. © The Royal Society of Chemistry.


  • Toward integrated detection and graphene-based removal of contaminants in a lab-on-a-chip platform

    Chałupniak A., Merkoçi A. Nano Research; : 1 - 15. 2017. 10.1007/s12274-016-1420-3.

    Nanobioelectronics and Biosensors

    A novel, miniaturized microfluidic platform was developed for the simultaneous detection and removal of polybrominated diphenyl ethers (PBDEs). The platform consists of a polydimethylsiloxane (PDMS) microfluidic chip for an immunoreaction step, a PDMS chip with an integrated screen-printed electrode (SPCE) for detection, and a PDMS-reduced graphene oxide (rGO) chip for physical adsorption and subsequent removal of PBDE residues. The detection was based on competitive immunoassay-linked binding between PBDE and PBDE modified with horseradish peroxidase (HRP-PBDE) followed by the monitoring of enzymatic oxidation of o-aminophenol (o-AP) using square wave anodic stripping voltammetry (SW-ASV). PBDE was detected with good sensitivity and a limit of detection similar to that obtained with a commercial colorimetric test (0.018 ppb), but with the advantage of using lower reagent volumes and a reduced analysis time. The use of microfluidic chips also provides improved linearity and a better reproducibility in comparison to those obtained with batch-based measurements using screen-printed electrodes. In order to design a detection system suitable for toxic compounds such as PBDEs, a reduced graphene oxide–PDMS composite was developed and optimized to obtain increased adsorption (based on both the hydrophobicity and π–π stacking between rGO and PBDE molecules) compared to those of non-modified PDMS. To the best of our knowledge, this is the first demonstration of electrochemical detection of flame retardants and a novel application of the rGO-PDMS composite in a biosensing system. This system can be easily applied to detect any analyte using the appropriate immunoassay and it supports operation in complex matrices such as seawater. [Figure not available: see fulltext.] © 2017 Tsinghua University Press and Springer-Verlag Berlin Heidelberg


  • Ultrathin Mesoporous RuCo2O4 Nanoflakes: An Advanced Electrode for High-Performance Asymmetric Supercapacitors

    Dubal D.P., Chodankar N.R., Holze R., Kim D.-H., Gomez-Romero P. ChemSusChem; 10 (8): 1771 - 1782. 2017. 10.1002/cssc.201700001.

    Novel Energy-Oriented Materials

    A new ruthenium cobalt oxide (RuCo2O4) with a unique marigold-like nanostructure and excellent performance as an advanced electrode material has been successfully prepared by a simple electrodeposition (potentiodynamic mode) method. The RuCo2O4 marigolds consist of numerous clusters of ultrathin mesoporous nanoflakes, leaving a large interspace between them to provide numerous electrochemically active sites. Strikingly, this unique marigold-like nanostructure provided excellent electrochemical performance in terms of high energy-storage capacitance (1469 F g−1 at 6 A g−1) with excellent rate proficiency and long-lasting operating cycling stability (ca. 91.3 % capacitance retention after 3000 cycles), confirming that the mesoporous nanoflakes participate in the ultrafast electrochemical reactions. Furthermore, an asymmetric supercapacitor was assembled using RuCo2O4 (positive electrode) and activated carbon (negative electrode) with aqueous KOH electrolyte. The asymmetric design allowed an upgraded potential range of 1.4 V, which further provided a good energy density of 32.6 Wh kg−1 (1.1 mWh cm−3). More importantly, the cell delivered an energy density of 12.4 Wh kg−1 even at a maximum power density of 3.2 kW kg−1, which is noticeably superior to carbon-based symmetric systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


  • Unveiling the nucleation & coarsening mechanisms of solution-derived self-Assembled epitaxial Ce0.9Gd0.1O2-yNanostructures

    Queralto A., De La Mata M., Arbiol J., Hühne R., Obradors X., Puig T. Crystal Growth and Design; 17 (2): 504 - 516. 2017. 10.1021/acs.cgd.6b01358.

    Advanced Electron Nanoscopy

    Self-Assembling approaches based on chemical solution deposition (CSD) are ideal methods for the cost-effective production of epitaxial nanostructures with high throughput. Therefore, an in-depth investigation of the nucleation and coarsening processes involved in the self-Assembly of nanostructures is mandatory to achieve a good control over nanostructure shape, dimensions, and orientation. Heteroepitaxial Ce0.9Gd0.1O2-y (CGO) is an ideal model system to unveil the underlying nanostructure development mechanisms in addition to their promising properties for catalysis, gas sensors, and ionic conductivity. Rapid thermal annealing furnaces have been used to study separately the thermodynamic and kinetic nucleation and coarsening mechanisms of self-Assembled CGO isotropic and anisotropic nanostructures based on strain-engineering and surface energies control. Different CGO nanoislands are obtained: isotropic (001)CGO nanodots are grown on (001)-oriented Y2O3:ZrO2(YSZ) and LaAlO3 (Lao) substrates, whereas (011)Lao substrates promote the growth of elongated (011)CGO nanowires. HRTEM and RHEED analyses are used to study the early stages of nucleation, as well as the shape and interfacial structure of CGO nanostructures. A systematic study with the heating ramp, annealing temperature and time, and strain in combination with thermally activated theoretical models provides information on the nucleation behavior, nucleation barriers, and atomic diffusion coefficients along in-plane and out-of-plane island orientations. Highly anisotropic atomic diffusion constants have been shown to be at the origin of the high aspect ratios of some of the nanostructures. Overall, our study provides a general method for the evaluation of nucleation and coarsening of multiple CSD-derived oxide nanostructures and understanding the shape development by combining thermodynamic and kinetic approaches. ©2016 American Chemical Society.


  • V2O5 encapsulated MWCNTs in 2D surface architecture: Complete solid-state bendable highly stabilized energy efficient supercapacitor device

    Pandit B., Dubal D.P., Gómez-Romero P., Kale B.B., Sankapal B.R. Scientific Reports; 7 ( 43430) 2017. 10.1038/srep43430.

    Novel Energy-Oriented Materials

    A simple and scalable approach has been reported for 2O5 encapsulation over interconnected multi-walled carbon nanotubes (MWCNTs) network using chemical bath deposition method. Chemically synthesized 2O5/MWCNTs electrode exhibited excellent charge-discharge capability with extraordinary cycling retention of 93% over 4000 cycles in liquid-electrolyte. Electrochemical investigations have been performed to evaluate the origin of capacitive behavior from dual contribution of surface-controlled and diffusion-controlled charge components. Furthermore, a complete flexible solid-state, flexible symmetric supercapacitor (FSS-SSC) device was assembled with 2O5/MWCNTs electrodes which yield remarkable values of specific power and energy densities along with enhanced cyclic stability over liquid configuration. As a practical demonstration, the constructed device was used to lit the 'VNIT' acronym assembled using 21 LED's. © The Author(s) 2017.