Instituto de Nanociencia y Materiales de Aragón

Metals such as silver support surface plasmons: electromagnetic surface excitations localized near the surface that originate from the free electrons of the metal. Surface modes are also observed on highly conducting surfaces perforated by holes. We establish a close connection between the two, showing that electromagnetic waves in both materials are governed by an effective permittivity of the same plasma form. The size and spacing of holes can readily be controlled on all relevant length scales, which allows the creation of designer surface plasmons with almost arbitrary dispersion in frequency and in space, opening new vistas in surface plasmon optics.

The interrogation of genetic markers in environmental meta-barcoding studies is currently seriously hindered by the lack of taxonomically curated reference data sets for the targeted genes. The Protist Ribosomal Reference database (PR(2), http://ssu-rrna.org/) provides a unique access to eukaryotic small sub-unit (SSU) ribosomal RNA and DNA sequences, with curated taxonomy. The database mainly consists of nuclear-encoded protistan sequences. However, metazoans, land plants, macrosporic fungi and eukaryotic organelles (mitochondrion, plastid and others) are also included because they are useful for the analysis of high-troughput sequencing data sets. Introns and putative chimeric sequences have been also carefully checked. Taxonomic assignation of sequences consists of eight unique taxonomic fields. In total, 136 866 sequences are nuclear encoded, 45 708 (36 501 mitochondrial and 9657 chloroplastic) are from organelles, the remaining being putative chimeric sequences. The website allows the users to download sequences from the entire and partial databases (including representative sequences after clustering at a given level of similarity). Different web tools also allow searches by sequence similarity. The presence of both rRNA and rDNA sequences, taking into account introns (crucial for eukaryotic sequences), a normalized eight terms ranked-taxonomy and updates of new GenBank releases were made possible by a long-term collaboration between experts in taxonomy and computer scientists.

Light usually diffracts in all directions when it emerges from a subwavelength aperture, which puts a lower limit on the size of features that can be used in photonics. This limitation can be overcome by creating a periodic texture on the exit side of a single aperture in a metal film. The transmitted light emerges from the aperture as a beam with a small angular divergence (approximately +/-3 degrees ) whose directionality can be controlled. This finding is especially surprising, considering that the radiating region is mainly confined to an area with lateral dimensions comparable to the wavelength of the light. The device occupies no more than one cubic micrometer and, when combined with enhanced transmission, suggests that a wide range of photonic applications is possible.

Non-invasive precise thermometers working at the nanoscale with high spatial resolution, where the conventional methods are ineffective, have emerged over the last couple of years as a very active field of research. This has been strongly stimulated by the numerous challenging requests arising from nanotechnology and biomedicine. This critical review offers a general overview of recent examples of luminescent and non-luminescent thermometers working at nanometric scale. Luminescent thermometers encompass organic dyes, QDs and Ln(3+)ions as thermal probes, as well as more complex thermometric systems formed by polymer and organic-inorganic hybrid matrices encapsulating these emitting centres. Non-luminescent thermometers comprise of scanning thermal microscopy, nanolithography thermometry, carbon nanotube thermometry and biomaterials thermometry. Emphasis has been put on ratiometric examples reporting spatial resolution lower than 1 micron, as, for instance, intracellular thermometers based on organic dyes, thermoresponsive polymers, mesoporous silica NPs, QDs, and Ln(3+)-based up-converting NPs and β-diketonate complexes. Finally, we discuss the challenges and opportunities in the development for highly sensitive ratiometric thermometers operating at the physiological temperature range with submicron spatial resolution.

This review provides a perspective on the recent developments in the transmission of light through subwavelength apertures in metal films. The main focus is on the phenomenon of extraordinary optical transmission in periodic hole arrays, discovered over a decade ago. It is shown that surface electromagnetic modes play a key role in the emergence of the resonant transmission. These modes are also shown to be at the root of both the enhanced transmission and beaming of light found in single apertures surrounded by periodic corrugations. This review describes both the theoretical and experimental aspects of the subject. For clarity, the physical mechanisms operating in the different structures considered are analyzed within a common theoretical framework. Several applications based on the transmission properties of subwavelength apertures are also addressed.

Here we have investigated the effect of enshrouding polymer-coated nanoparticles (NPs) with polyethylene glycol (PEG) on the adsorption of proteins and uptake by cultured cells. PEG was covalently linked to the polymer surface to the maximal grafting density achievable under our experimental conditions. Changes in the effective hydrodynamic radius of the NPs upon adsorption of human serum albumin (HSA) and fibrinogen (FIB) were measured in situ using fluorescence correlation spectroscopy. For NPs without a PEG shell, a thickness increase of around 3 nm, corresponding to HSA monolayer adsorption, was measured at high HSA concentration. Only 50% of this value was found for NPs with PEGylated surfaces. While the size increase clearly reveals formation of a protein corona also for PEGylated NPs, fluorescence lifetime measurements and quenching experiments suggest that the adsorbed HSA molecules are buried within the PEG shell. For FIB adsorption onto PEGylated NPs, even less change in NP diameter was observed. In vitro uptake of the NPs by 3T3 fibroblasts was reduced to around 10% upon PEGylation with PEG chains of 10 kDa. Thus, even though the PEG coatings did not completely prevent protein adsorption, the PEGylated NPs still displayed a pronounced reduction of cellular uptake with respect to bare NPs, which is to be expected if the adsorbed proteins are not exposed on the NP surface.

The field of metal-organic framework based mixed matrix membranes (M(4)s) is critically reviewed, with special emphasis on their application in CO2 capture during energy generation. After introducing the most relevant parameters affecting membrane performance, we define targets in terms of selectivity and productivity based on existing literature on process design for pre- and post-combustion CO2 capture. Subsequently, the state of the art in M(4)s is reviewed against these targets. Because final application of these membranes will only be possible if thin separation layers can be produced, the latest advances in the manufacture of M(4) hollow fibers are discussed. Finally, the recent efforts in understanding the separation performance of these complex composite materials and future research directions are outlined.

In the past few years, cancer immunotherapy has emerged as a safe and effective alternative for treatment of cancers that do not respond to classical treatments, including those types with high aggressiveness. New immune modulators, such as cytokines, blockers of CTLA-4 (cytotoxic T-lymphocyte-associated protein 4) and PD-1(programmed cell death protein 1)/PD-L1 (programmed death-ligand 1), and interaction or adoptive cell therapy, have been developed and approved to treat solid and hematologic carcinomas. In these scenarios, cytotoxic lymphocytes (CL), mainly cytotoxic T cells (Tc) and natural killer (NK) cells, are ultimately responsible for killing the cancer cells and eradicating the tumor. Extensive studies have been conducted to assess how Tc and NK cells get activated and recognize the cancer cell. In contrast, few studies have focused on the effector molecules used by CLs to kill cancer cells during cancer immunosurveillance and immunotherapy. In this article, the two main pathways involved in CL-mediated tumor cell death, granule exocytosis (perforin and granzymes) and death ligands, are briefly introduced, followed by a critical discussion of the molecules involved in cell death during cancer immunosurveillance and immunotherapy. This discussion also covers unexpected consequences of proinflammatory and survival effects of granzymes and death ligands and recent experimental evidence indicating that perforin and granzymes of CLs can activate nonapoptotic pathways of cell death, overcoming apoptosis defects and chemoresistance. The consequences of apoptosis versus other modalities of cell death for an effective treatment of cancer by modulating the patient immune system are also briefly discussed. See all articles in this CCR Focus section, "Cell Death and Cancer Therapy."

The stochastic Landau-Lifshitz-Gilbert equation of motion for a classical magnetic moment is numerically solved (properly observing the customary interpretation of it as a Stratonovich stochastic differential equation), in order to study the dynamics of magnetic nanoparticles. The corresponding Langevin-dynamics approach allows for the study of the fluctuating trajectories of individual magnetic moments, where we have encountered remarkable phenomena in the overbarrier rotation process, such as crossing-back or multiple crossing of the potential barrier, rooted in the gyromagnetic nature of the system. Concerning averaged quantities, we study the linear dynamic response of the archetypal ensemble of noninteracting classical magnetic moments with axially symmetric magnetic anisotropy. The results are compared with different analytical expressions used to model the relaxation of nanoparticle ensembles, assessing their accuracy. It has been found that, among a number of heuristic expressions for the linear dynamic susceptibility, only the simple formula proposed by Shliomis and Stepanov matches the coarse features of the susceptibility reasonably. By comparing the numerical results with the asymptotic formula of Storonkin {Sov. Phys. Crystallogr. 30, 489 (1985) [Kristallografiya 30, 841 (1985)]}, the effects of the intra-potential-well relaxation modes on the low-temperature longitudinal dynamic response have been assessed, showing their relatively small reflection in the susceptibility curves but their dramatic influence on the phase shifts. Comparison of the numerical results with the exact zero-damping expression for the transverse susceptibility by Garanin, Ishchenko, and Panina {Theor. Math. Phys. (USSR) 82, 169 (1990) [Teor. Mat. Fiz. 82, 242 (1990)]}, reveals a sizable contribution of the spread of the precession frequencies of the magnetic moment in the anisotropy field to the dynamic response at intermediate-to-high temperatures.

Black phosphorus exhibits a high degree of band anisotropy. However, we find that its in-plane static screening remains relatively isotropic for momenta relevant to elastic long-range scattering processes. On the other hand, the collective electronic excitations in the system exhibit a strong anisotropy. Band nonparabolicity, due to interband couplings, leads to a plasmon frequency which scales as nβ, where n is the carrier concentration, and β<1/2. Screening and charge distribution in the out-of-plane direction are also studied using a nonlinear Thomas-Fermi model.

BACKGROUND: Valvular heart disease (VHD) is an important cause of mortality and morbidity and has been subject to important changes in management. The VHD II survey was designed by the EURObservational Research Programme of the European Society of Cardiology to analyze actual management of VHD and to compare practice with guidelines. METHODS: Patients with severe native VHD or previous valvular intervention were enrolled prospectively across 28 countries over a 3-month period in 2017. Indications for intervention were considered concordant if the intervention was performed or scheduled in symptomatic patients, corresponding to Class I recommendations specified in the 2012 European Society of Cardiology and in the 2014 American Heart Association/American College of Cardiology VHD guidelines. RESULTS: A total of 7247 patients (4483 hospitalized, 2764 outpatients) were included in 222 centers. Median age was 71 years (interquartile range, 62-80 years); 1917 patients (26.5%) were ≥80 years; and 3416 were female (47.1%). Severe native VHD was present in 5219 patients (72.0%): aortic stenosis in 2152 (41.2% of native VHD), aortic regurgitation in 279 (5.3%), mitral stenosis in 234 (4.5%), mitral regurgitation in 1114 (21.3%; primary in 746 and secondary in 368), multiple left-sided VHD in 1297 (24.9%), and right-sided VHD in 143 (2.7%). Two thousand twenty-eight patients (28.0%) had undergone previous valvular intervention. Intervention was performed in 37.0% and scheduled in 26.8% of patients with native VHD. The decision for intervention was concordant with Class I recommendations in symptomatic patients with severe single left-sided native VHD in 79.4% (95% CI, 77.1-81.6) for aortic stenosis, 77.6% (95% CI, 69.9-84.0) for aortic regurgitation, 68.5% (95% CI, 60.8-75.4) for mitral stenosis, and 71.0% (95% CI, 66.4-75.3) for primary mitral regurgitation. Valvular interventions were performed in 2150 patients during the survey; of them, 47.8% of patients with single left-sided native VHD were in New York Heart Association class III or IV. Transcatheter procedures were performed in 38.7% of patients with aortic stenosis and 16.7% of those with mitral regurgitation. CONCLUSIONS: Despite good concordance between Class I recommendations and practice in patients with aortic VHD, the suboptimal number in mitral VHD and late referral for valvular interventions suggest the need to improve further guideline implementation.

A very exciting prospect in coordination chemistry is to manipulate spins within magnetic complexes for the realization of quantum logic operations. An introduction to the requirements for a paramagnetic molecule to act as a 2-qubit quantum gate is provided in this tutorial review. We propose synthetic methods aimed at accessing such type of functional molecules, based on ligand design and inorganic synthesis. Two strategies are presented: (i) the first consists in targeting molecules containing a pair of well-defined and weakly coupled paramagnetic metal aggregates, each acting as a carrier of one potential qubit, (ii) the second is the design of dinuclear complexes of anisotropic metal ions, exhibiting dissimilar environments and feeble magnetic coupling. The first systems obtained from this synthetic program are presented here and their properties are discussed.

We investigate qubit-qubit entanglement mediated by plasmons supported by one-dimensional waveguides. We explore both the situation of spontaneous formation of entanglement from an unentangled state and the emergence of driven steady-state entanglement under continuous pumping. In both cases, we show that large values for the concurrence are attainable for qubit-qubit distances larger than the operating wavelength by using plasmonic waveguides that are currently available.

Surface plasmon modes supported by graphene ribbon waveguides are studied and classified. The properties of both modes with the field concentration within the ribbon area (waveguiding modes) and on the edges (edge modes) are discussed. The waveguide and edge modes are shown to be separated from each other by a gap in wave numbers. The even-parity hybridized edge mode results to be the fundamental electromagnetic mode of the ribbon, possessing also the lowest losses. All of the plasmonic modes in the ribbons have an optimum frequency, at which the absorption losses are minimum, due to compromise between the plasmon confinement and the decrease of the group velocity close to the modal cutoff. The presented results show that the diffraction limit in graphene ribbons can be surpassed.

We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results.

A unique Eu3+/Tb3+ luminescent self-referencing nanothermometer allowing absolute measurements in the 10–350 K temperature range and sub-micrometer spatial resolution is reported (see Figure). It has up to 4.9%·K−1 temperature sensitivity and high photostability for long-term use. The combination of molecular thermometry, superparamagnetism and luminescence in a nanometric host matrix provides multifunctionality opening the way for new exciting applications. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

BACKGROUND: In recent years, the application of nanotechnology in several fields of bioscience and biomedicine has been studied. The use of nanoparticles for the targeted delivery of substances has been given special attention and is of particular interest in the treatment of plant diseases. In this work both the penetration and the movement of iron-carbon nanoparticles in plant cells have been analyzed in living plants of Cucurbita pepo. RESULTS: The nanoparticles were applied in planta using two different application methods, injection and spraying, and magnets were used to retain the particles in movement in specific areas of the plant. The main experimental approach, using correlative light and electron microscopy provided evidence of intracellular localization of nanoparticles and their displacement from the application point. Long range movement of the particles through the plant body was also detected, particles having been found near the magnets used to immobilize and concentrate them. Furthermore, cell response to the nanoparticle presence was detected. CONCLUSION: Nanoparticles were capable of penetrating living plant tissues and migrating to different regions of the plant, although movements over short distances seemed to be favoured. These findings show that the use of carbon coated magnetic particles for directed delivery of substances into plant cells is a feasible application.

Resonance diffraction in the periodic array of graphene microribbons is theoretically studied following a recent experiment [L. Ju et al., Nature Nanotech. 6, 630 (2011)]. Systematic studies over a wide range of parameters are presented. It is shown that a much richer resonant picture would be observable for higher relaxation times of charge carriers: More resonances appear and transmission can be totally suppressed. The comparison with the absorption cross-section of a single ribbon shows that the resonant features of the periodic array are associated with leaky plasmonic modes. The longest-wavelength resonance provides the highest visibility of the transmission dip and has the strongest spectral shift and broadening with respect to the single-ribbon resonance, due to collective effects.

Conventional separation technologies to separate valuable commodities are energy intensive, consuming 15% of the worldwide energy. Mixed-matrix membranes, combining processable polymers and selective adsorbents, offer the potential to deploy adsorbent distinct separation properties into processable matrix. We report the rational design and construction of a highly efficient, mixed-matrix metal-organic framework membrane based on three interlocked criteria: (i) a fluorinated metal-organic framework, AlFFIVE-1-Ni, as a molecular sieve adsorbent that selectively enhances hydrogen sulfide and carbon dioxide diffusion while excluding methane; (ii) tailoring crystal morphology into nanosheets with maximally exposed (001) facets; and (iii) in-plane alignment of (001) nanosheets in polymer matrix and attainment of [001]-oriented membrane. The membrane demonstrated exceptionally high hydrogen sulfide and carbon dioxide separation from natural gas under practical working conditions. This approach offers great potential to translate other key adsorbents into processable matrix.

The photothermal response of plasmonic nanomaterials can be exploited for a number of biomedical applications in diagnostics (biosensing and optoacoustic imaging) and therapy (drug delivery and photothermal therapy). The most common cellular response to photothermal cancer treatment (ablation of solid tumors) using plasmonic nanomaterials is necrosis, a process that releases intracellular constituents into the extracellular milieu producing detrimental inflammatory responses. Here we report the use of laser-induced photothermal therapy employing gold nanoprisms (NPRs) to specifically induce apoptosis in mouse embryonic fibroblast cells transformed with the SV40 virus. Laser-irradiated "hot" NPRs activate the intrinsic/mitochondrial pathway of apoptosis (programmed cell death), which is mediated by the nuclear-encoded proteins Bak and Bax through the activation of the BH3-only protein Bid. We confirm that an apoptosis mechanism is responsible by showing how the NPR-mediated cell death is dependent on the presence of caspase-9 and caspase-3 proteins. The ability to selectively induce apoptotic cell death and to understand the subsequent mechanisms provides the foundations to predict and optimize NP-based photothermal therapy to treat cancer patients suffering from chemo- and radioresistance.