1,720,975 research outputs found

    Nanoparticle-assisted NMR spectroscopy: A chemosensing perspective

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    Sensing methodologies for the detection of target compounds in mixtures are important in many different contexts, ranging from medical diagnosis to environmental analysis and quality assessment. Ideally, such detection methods should allow for both identification and quantification of the targets, minimizing the possibility of false positives. With very few exceptions, most of the available sensing techniques rely on the selective interaction of the analyte with some detector, which in turn produces a signal as a result of the interaction. This approach hence provides indirect information on the targets, whose identity is generally ensured by comparison with known standards, if available, or by the selectivity of the sensor system itself. Pursuing a different approach, NMR chemosensing aims at generating signals directly from the analytes, in the form of a (complete) NMR spectrum. In this way, not only are the targets unequivocally identified, but it also becomes possible to identify and assign the structures of unknown species. In this review we show how relaxation- and diffusion-based NMR techniques, assisted by appropriate nanoparticles, can be used to edit the 1H NMR spectrum of a mixture and extract the signals of specific target compounds. Monolayer-protected nanoparticles, in particular those made from gold, are well suited to this task because they provide a versatile, protein-size support to build or incorporate supramolecular receptors. Remarkably, the self-organized and multifunctional nature of the nanoparticle coating allows exploitation of different kinds of non-covalent interactions, to provide tailored binding sites for virtually any class of molecules. From the NMR standpoint, the reduced translational and rotational diffusion rates of bulky nanoparticles offer a way to manipulate the states of the monolayer spins and build a reservoir of magnetization that can be selectively transferred to the interacting analytes. In addition, the low correlation time and the enhanced rigidity of the coating molecules (due to their grafting and crowding on the particle surface) promote efficient spin diffusion, useful in saturation transfer experiments. The optimized combination of NMR experiments and nanoreceptors can ultimately allow the detection of relevant analytes in the micromolar concentration range, paving the way to applications in the diagnostic field and beyond

    Hybrid nanoreceptors for high sensitivity detection of small molecules by NMR chemosensing

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    “Nanoparticle-assisted NMR chemosensing” combines magnetization transfer NMR techniques with the recognition abilities of gold nanoparticles (AuNPs) to isolate the NMR spectrum of relevant organic species in mixtures. The efficiency of the magnetization transfer is crucial to set the detection limit of the technique. To this aim, a second generation of nanoreceptors obtained by the self-organization of 2 nm AuNPs onto the surface of bigger silica nanoparticles shows better magnetization transfer performances, allowing the detection of analytes in water down to 10 μM concentration using standard instrumentation

    Imaging agents based on lanthanide doped nanoparticles

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    Nanotechnology has recently allowed us to design and prepare nanoplatforms with the potential to face currently unresolved problems. Among these platforms, nanoparticles in particular are versatile objects that find applications in many different areas. In the vast ensemble of materials that have been explored to obtain nanoparticles with improved performances, we here focus our attention on lanthanide-based nanocrystals. These recently developed species are extremely interesting and well known particularly for their ability to emit anti-Stokes shifted light (upconversion) with relatively high brightness. Many advantageous characteristics of such materials are emerging, and their use as multimodal imaging agents is rapidly growing. We here survey some recent examples on this subject, mainly focusing on systems having NIR-to-NIR emission properties for in vivo applications

    Monolayer-protected gold nanoparticles for molecular sensing and catalysis

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    This chapter shows how monolayer-protected gold nanoparticles (AuNPs), which are nanometer-sized gold colloids coated with a monolayer of organic molecules, are rapidly emerging as a class of molecular systems with a true potential to behave as artificial proteins. It starts with a short discussion of the analytical techniques that are commonly used to study molecular recognition processes at the monolayer. The chapter then illustrates how the monolayer can be equipped with recognition elements for the selective interaction with guests, and shows how such systems can be applied for chemosensing applications. It also discusses catalytic AuNPs, which display enzyme-like reaction kinetics. These so-called nanozymes rely on the selective recognition of small molecules followed by a chemical conversion assisted by catalytic centers embedded in the monolayer. Finally, the chapter focuses on the introduction of regulatory elements that permit spatiotemporal control to be gained over the molecular recognition processes occurring at the monolayer by means of external triggers

    Going Beyond Counting First Authors in Author Co-citation Analysis

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    The present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed

    Variations on the Author

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    “Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship

    Appropriate Similarity Measures for Author Cocitation Analysis

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    We provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis

    Dispelling the Myths Behind First-author Citation Counts

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    We conducted a full-scale evaluative citation analysis study of scholars in the XML research field to explore just how different from each other author rankings resulting from different citation counting methods actually are, and to demonstrate the capability of emerging data and tools on the Web in supporting more realistic citation counting methods. Our results contest some common arguments for the continued use of first-author citation counts in the evaluation of scholars, such as high correlations between author rankings by first-author citation counts and other citation counting methods, and high costs of using more realistic citation counting methods that are not well-supported by the ISI databases. It is argued that increasingly available digital full text research papers make it possible for citation analysis studies to go beyond what the ISI databases have directly supported and to employ more sophisticated methods

    Author Index

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