1,720,972 research outputs found
Ultrafast Soft X-ray Photoelectron Spectroscopy at Liquid Water Microjets
No full textSince the pioneering work of Kai Siegbahn, electron spectroscopy for chemical analysis (ESCA) has been developed into an indispensable analytical technique for surface science. The value of this powerful method of photoelectron spectroscopy (PES, also termed photoemission spectroscopy) and Siegbahn's contributions were recognized in the 1981 Nobel Prize in Physics. The need for high vacuum, however, originally prohibited PES of , volatile liquids, and only allowed for investigation of low-vapor-pressure molecules attached to a surface (or dose to a surface) or liquid films of low volatility. Only with the invention of liquid beams of volatile liquids compatible with high-vacuum conditions was PES from liquid surfaces under vacuum made feasible. Because of the ubiquity of water interfaces in nature, the liquid water vacuum interface became a most attractive research topic, particularly over the past 10 years. PES studies of these important aqueous interfaces remained significantly challenging because of the need to develop high-pressure PES methods. For decades, ESCA or PES (termed XPS, for X-ray photoelectron spectroscopy, in the case of soft X-ray photons) was restricted to conventional laboratory X-ray sources or beamlines in synchrotron facilities. This approach enabled frequency domain measurements, but with poor time resolution. Indirect access to time-resolved processes in the condensed phase was only achieved if line-widths could be analyzed or if processes could be related to a fast clock, that is, reference processes that are fast enough and are also well understood in the condensed phase. Just recently, the emergence of high harmonic light sources, providing short-wavelength radiation in ultrashort light pulses, added the dimension of time to the classical ESCA or XPS technique and opened the door to (soft) X-ray photoelectron spectroscopy with ultrahigh time resolution. The combination of high harmonic light sources (providing radiation with laserlike beam qualities) and liquid microjet technology recently enabled the first liquid interface PES experiments in the IR/UV-pump and extreme ultraviolet-probe (EUV-probe) configuration. In this Account, we highlight features of the technology and a number of recent applications, including extreme states of matter and the discovery and detection of short-lived transients of the solvated electron in water. Properties of the EUV radiation, such as its controllable polarization and features of the liquid microjet, will enable unique experiments in the near future. PES measures electron binding energies and angular distributions of photoelectrons, which comprise unique information about electron orbitals and their involvement in chemical bonding. One of the future goals is to use this information to trace molecular orbitals, over time, in chemical reactions or biological transformations.Graduate School 782 of the DFG; [SPP1134]; [SFB 755
New design for a time-of-flight mass spectrometer with a liquid beam laser desorption ion source for the analysis of biomolecules
Get PDFWe describe a novel liquid beam mass spectrometer, based on a recently discovered nanosecond laser desorption phenomenon, [W. Kleinekofort, J. Avdiev, and B. Brutschy, Int. J. Mass Ion. Processes 152, 135 (1996)] which allows the liquid-to-vacuum transfer, and subsequent mass analysis of pre-existing ions and ionic associates from liquid, microjets of aqueous solutions. The goal of our novel technical approach is to establish a system with good mass resolution that implements improvements on critical components that make the system more reliable and easier to operate. For laser desorption pulsed dye-laser difference frequency mixing is used that provides tunable infrared light near the absorption maximum of liquid water around 3 gm. Different types of liquid beam glass nozzles (convergent capillary and aperture plate nozzles) are investigated and characterized. Starting from theoretical considerations of hydrodynamic drag forces on micrometer size droplets in supersonic rarefied gas flows we succeeded in capturing efficiently the liquid beam in a liquid beam recycling trap operating at the vapor pressure of liquid water. For improving the pollution resistance, the liquid jet high vacuum ion source region is spatially separated from the reflectron time-of-flight mass spectrometer (TOF-MS) working behind a gate valve in an ultrahigh vacuum environment. A simple (simulation optimized) ion optics is employed for the ion transfer from the source to the high vacuum region. This new feature is also mostly responsible for the improved mass resolution. With the present tandem-TOF MS setup a resolution of m/Deltam approximate to 1800 for the low and m/Deltam approximate to 700 in the high mass region has been obtained for several biomolecules of different mass and complexity (amino acids, insulin, and cytochrome c). 0 2004 American Institute of Physics
EUV and fast ion emission from cryogenic liquid jet target laser-generated plasma
No full textA liquid jet of either nitrogen or argon of 20 mum diameter was exposed to intense laser fields with pulse durations between 70 fs and 250 ps, leading to intensities of 10(16) W cm(-2) and 10(13) W cm(-2), respectively. The emission of extreme UV light and soft X-rays shows the characteristic lines of hydrogen-like nitrogen and carbon-like argon. For nitrogen the emitted photon flux at 250 ps was about two orders of magnitude higher than for 70 fs pulses. A weak dependence on the laser polarization with respect to the liquid jet axis was found. The kinetic energy of the emitted ions easily exceeded 100 keV for nitrogen and 200 keV for argon for a pulse duration close to 2 ps
Ultrafast electronic spectroscopy for chemical analysis near liquid water interfaces: concepts and applications
No full textElectron spectroscopy for chemical analysis (ESCA) being conceptually a photoelectron spectroscopy is established as a chemically specific probe mostly for surface analysis. Liquid phase ESCA for volatile liquids has become possible through the development of the liquid microjet technique in vacuum enabling the measurement of liquid interface photoelectron emission at the high vapor pressure of volatile liquids. Recently we have been able to add the dimension of time to the liquid interface ESCA technique employing high-harmonics soft X-ray and UV/near IR femtosecond pulses in combination with liquid water micro beams in vacuum. The concepts as well as technical details are outlined and several characteristic applications are highlighted
Applications, features, and mechanistic aspects of liquid water beam desorption mass spectrometry
No full textIn the present study we highlight recent applications of liquid beam desorption mass spectrometry for the analysis of biomolecules. The protonated. macromolecules are desorbed from a 10 mu m thick liquid jet in vacuum with an IR laser pulse tuned in resonance with the OH stretch vibration of water. Cytochrome c, viscotoxin A3, synthetic analogues of DNA and nucleobase substituted P-peptides (PNA like oligomers), bovine serum albumin (BSA), as well as specifically designed pharmaceutical macromolecules have been investigated. The salt and buffer tolerance has been measured for the desorption of cytochrome c. For the PNA oligomers it has been shown that a mixture can be desorbed and that the relative intensity of the mass peaks reflects relative concentrations in solution. With diluted BSA water solutions it has been demonstrated that the desorption technique provides a quantitative measure of BSA in solution. The gas phase signal of singly protonated BSA desorbed from a series of well defined solution concentrations has been found to be linear over at least three orders of magnitude. This feature appears to be promising for quantitative online monitoring applications of this technique. Beyond applications of this technique mechanistic aspects of the poorly characterized desorption mechanism are discussed. With a field-free-drift time-of-flight approach we were able to monitor features of the desorption process by selecting fractions of the broad velocity distribution of desorbed species using an ion optics acting as an ion gate. The observed features were discussed within a "desorption/ionization" model featuring the interplay of an explosive thermal and a shock wave dispersion of the microfilament controlling the ejection of hot nano-droplets and microsolvated molecules as well as their desolvation. (c) 2005 Elsevier B.V. All rights reserved
Going Beyond Counting First Authors in Author Co-citation Analysis
Get PDFThe 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
Get PDF“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
Get PDFWe 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
Get PDFWe 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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