1,723,054 research outputs found
Accessing Excited State Molecular Vibrations by Femtosecond Stimulated Raman Spectroscopy
Full text linkExcited state vibrations are crucial for determining the photophysical and photochemical properties of molecular compounds. Stimulated Raman scattering can coherently stimulate and probe molecular vibrations with optical pulses, but it is generally restricted to ground state properties. Working under resonance conditions enables cross-section enhancement and selective excitation to a targeted electronic level but is hampered by an increased signal complexity due to the presence of overlapping spectral contributions. Here, we show how detailed information about ground and excited state vibrations can be disentangled by exploiting the relative time delay between Raman and probe pulses to control the excited state population, combined with a diagrammatic formalism to dissect the pathways concurring with the signal generation. The proposed method is then exploited to elucidate the vibrational properties of the ground and excited electronic states in the paradigmatic case of cresyl violet. We anticipate that the presented approach holds the potential for selective mapping of the reaction coordinates pertaining to transient electronic stages implied in photoactive compounds
Going Beyond Counting First Authors in Author Co-citation Analysis
Full text linkThe 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
Prognostic factors in primary and iterative surgery of colorectal liver metastases
No full textThe aim of this study was to evaluate the results of surgery of colorectal liver metastases and assess prognostic factors influencing the outcome. A total of 135 hepatic resections performed in 107 patients was reviewed. The following prognostic factors were analyzed: primary tumor localization, Dukes stage, number and presence of metastases in one or two lobes, synchronous or metachronous occurrence, type of resection, use and modality of chemotherapy. The perioperative morbidity rate was 6.5% and mortality was 1.9%. Overall survival was 41.2% and disease-free survival 31.5% at 5 years. Survival at 5 years was better for patients with metachronous than for those with synchronous lesions (60.9% vs 28.1%; p<0.05). There were no significant differences in terms of long-term survival between patients with synchronous metastases that were excised simultaneously or with a delay of 3-6 months (p=n.s.). Site of the primary tumor, Dukes stage, number of metastases and type of resection did not influence survival. A favorable survival trend was observed in those patients who underwent both neoadjuvant and adjuvant chemotherapy. The overall survival rate at 5 years was 45.3% for patients undergoing a second hepatic resection and 50% for those with a third or a fourth hepatic resection. Liver resection remains the "gold standard" for the treatment of patients with colorectal liver metastases, with metachronous type having a better outcome than synchronous. Simultaneous or delayed surgery for synchronous metastases does not influence prognosis. Iterative resection is very encouraging and justifies an aggressive surgical approach. © E.S.I.F.T. srl
Broadband impulsive stimulated Raman scattering based on a chirped detection
No full textIn impulsive stimulated Raman scattering, vibrational oscillations, coherently stimulated by a femtosecond Raman pulse, are monitored in real time and read out as intensity modulations in the transmission of a temporally delayed probe pulse. Critically, in order to retrieve broadband Raman spectra, a fine sampling of the time delays between the Raman and probe pulses is required, making conventional ISRS ineffective for probing irreversible phenomena and/or weak scatterers typically demanding long acquisition times, with signal-to-noise ratios that crucially depend on the pulse fluences and overlap stabilities. To overcome such limitations, here we introduce the chirped-based impulsive stimulated raman scattering (CISRS) technique. Specifically, we show how introducing a chirp in the probe pulse can be exploited for recording the Raman information without the need to scan over the Raman-probe pulse delay. We then experimentally demonstrate with a few examples how to use the introduced scheme to measure Raman spectra
Stimulated Raman lineshapes in the large light–matter interaction limit
No full textStimulated Raman scattering (SRS) represents a powerful tool for accessing the vibrational properties of molecular compounds or solid state systems. From a spectroscopic perspective, SRS is able to capture Raman spectra free from incoherent background processes and typically ensures a signal enhancement of several orders of magnitude with respect to its spontaneous counterpart. Since its discovery in 1962, SRS has been applied to develop technological applications, such as Raman-based lasers, frequency shifters for pulsed sources and Raman amplifiers. For the full exploitation of their potential, however, it is crucial to have an accurate description of the SRS processes under the large gain regime. Here, by taking as an example the stimulated Raman spectrum of a model solvent, namely liquid cyclohexane, we discuss how the spectral profiles and the lineshapes of Raman excitations critically depend on the pump excitation regime. In particular, we show that in the large light–matter interaction limit the Raman gain undergoes an exponential increase (decrease) in the red (blue) side of the spectrum, with the Raman linewidths that appear sharpened (broadened)
Variations on the Author
Full text link“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
Full text linkWe 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
Full text linkWe 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
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