Background: There are two main approaches for nasal septal perforation (NSP) surgery-bilateral and unilateral repair. There are advantages and disadvantages to each of these techniques. At the same time, there is a lack of comparative studies on the effectiveness of these approaches.
View Article and Find Full Text PDFCombinatorial post-translational modifications (PTMs), such as those forming the so-called "histone code", have been linked to cell differentiation, embryonic development, cellular reprogramming, aging, cancers, neurodegenerative disorders, . Nevertheless, a reliable mass spectral analysis of the combinatorial isomers represents a considerable challenge. The difficulty stems from the incompleteness of information that could be generated by the standard MS to differentiate cofragmented isomeric sequences in their naturally occurring mixtures based on the fragment mass-to-charge ratio and relative abundance information only.
View Article and Find Full Text PDFIn the present contribution, we use x-rays to monitor charge-induced chemical dynamics in the photoionized amino acid glycine with femtosecond time resolution. The outgoing photoelectron leaves behind the cation in a coherent superposition of quantum mechanical eigenstates. Delayed x-ray pulses track the induced coherence through resonant x-ray absorption that induces Auger decay.
View Article and Find Full Text PDFThe study of onset and decay, as well as control of ultrafast quantum coherence in many-electron systems is in the focus of interest of attosecond physics. Interpretation of attosecond experiments detecting the ultrafast quantum coherence requires application of advanced theoretical and computational tools combining many-electron theory, description of the electronic continuum, including in the strong laser field scenario, as well as nuclear dynamics theory. This perspective reviews the recent theoretical advances in understanding the attosecond dynamics of quantum coherence in photoionized molecular systems and outlines possible future directions of theoretical and experimental study of coherence and entanglement in the attosecond regime.
View Article and Find Full Text PDFIt has recently been shown that an interferometric approach can be used to obtain Auger lifetimes in molecules in certain point groups. Here, we extend this concept to those molecular states for which Auger decay is energetically forbidden and which exhibit initial quasi-exponential decay followed by quantum revivals. We demonstrate that this allows us to extract the quasi-exponential decay rate and the revival timescale.
View Article and Find Full Text PDFHere, we use x-rays to create and probe quantum coherence in the photoionized amino acid glycine. The outgoing photoelectron leaves behind the cation in a coherent superposition of quantum mechanical eigenstates. Delayed x-ray pulses track the induced coherence through resonant x-ray absorption that induces Auger decay and by photoelectron emission from sequential double photoionization.
View Article and Find Full Text PDFIn quantum systems, coherent superpositions of electronic states evolve on ultrafast time scales (few femtoseconds to attoseconds; 1 attosecond = 0.001 femtoseconds = 10 seconds), leading to a time-dependent charge density. Here we performed time-resolved measurements using attosecond soft x-ray pulses produced by a free-electron laser, to track the evolution of a coherent core-hole excitation in nitric oxide.
View Article and Find Full Text PDFObjective: To describe the technique and determine the indications for sleep endoscopy in children.
Material And Methods: This study included 35 children, the average age of 5 years 1 month ± 3 years 4 months (from 1 year 6 months to 14 years 5 months). All children underwent standard polysomnography and sleep endoscopy.
We present a protein database search engine for the automatic identification of peptide and protein sequences using the recently introduced method of two-dimensional partial covariance mass spectrometry (2D-PC-MS). Because the 2D-PC-MS measurement reveals correlations between fragments stemming from the same or consecutive decomposition processes, the first-of-its-kind 2D-PC-MS search engine is based entirely on the direct matching of the pairs of theoretical and the experimentally detected correlating fragments, rather than of individual fragment signals or their series. We demonstrate that the high structural specificity afforded by 2D-PC-MS fragment correlations enables our search engine to reliably identify the correct peptide sequence, even from a spectrum with a large proportion of contaminant signals.
View Article and Find Full Text PDFTwo-dimensional partial covariance mass spectrometry (2D-PC-MS) exploits the inherent fluctuations of fragment ion abundances across a series of tandem mass spectra, to identify correlated pairs of fragment ions produced along the same fragmentation pathway of the same parent (e.g., peptide) ion.
View Article and Find Full Text PDFThe rate of successful identification of peptide sequences by tandem mass spectrometry (MS/MS) is adversely affected by the common occurrence of co-isolation and co-fragmentation of two or more isobaric or isomeric parent ions. This results in so-called `chimera spectra', which feature peaks of the fragment ions from more than a single precursor ion. The totality of the fragment ion peaks in chimera spectra cannot be assigned to a single peptide sequence, which contradicts a fundamental assumption of the standard automated MS/MS spectra analysis tools, such as protein database search engines.
View Article and Find Full Text PDFAttosecond pump-attosecond probe spectroscopy is becoming possible due the development of sub-femtosecond free electron laser (FEL) pulses as well as intense high-order harmonic generation-based attosecond sources. Here we investigate theoretically whether these developments can provide access to direct time-resolved measurement of Auger decay through detection of the total yield of an ionic decay product, in analogy to the photodissociation product detection in femtochemistry. We show that the ion yield based measurement is generally possible and in the case of the inner-valence hole decay can be background-free.
View Article and Find Full Text PDFFano-ADC is a family of ab initio methods for the prediction of electronic decay widths in excited, singly and doubly ionized systems. It has been particularly successful in elucidating the geometry dependence of the inter-atomic decay widths in clusters and facilitated the prediction of new electronic decay phenomena. However, the available Fano-ADC schemes are limited to the second-order treatment of the initial state and the first-order treatment of the final states of the decay.
View Article and Find Full Text PDFThe recent demonstration of isolated attosecond pulses from an X-ray free-electron laser (XFEL) opens the possibility for probing ultrafast electron dynamics at X-ray wavelengths. An established experimental method for probing ultrafast dynamics is X-ray transient absorption spectroscopy, where the X-ray absorption spectrum is measured by scanning the central photon energy and recording the resultant photoproducts. The spectral bandwidth inherent to attosecond pulses is wide compared to the resonant features typically probed, which generally precludes the application of this technique in the attosecond regime.
View Article and Find Full Text PDFWe introduce and present a theory of interferometric measurement of a normal Auger decay lifetime in molecules. Molecular Auger interferometry is based on the coherent phase control of Auger dynamics in a two-color (ω/2ω) laser field. We show that, in contrast to atoms, in oriented molecules of certain point groups the relative ω/2ω phase modulates the total ionization yield.
View Article and Find Full Text PDFJ Chem Theory Comput
October 2018
Here, we present an ab initio approach to full simulation of an attosecond molecular pump-probe experiment. Sequential molecular double ionization by the pump and probe laser pulses with controlled delay is described from first-principles with a full account of the continuum dynamics of the photoelectrons. Many-electron bound-continuum dynamics is simulated using the time-dependent (TD) molecular B-spline algebraic diagrammatic construction (ADC) method.
View Article and Find Full Text PDFWe present an ab initio theory and computational method for Penning ionization widths. Our method is based on the Fano theory of resonances, algebraic diagrammatic construction (ADC) scheme for many-electron systems, and Stieltjes imaging procedure. It includes an extension of the Fano-ADC scheme [V.
View Article and Find Full Text PDFHere we present a fully ab initio study of the high-order harmonic generation (HHG) spectrum of aligned CO molecules. The calculations have been performed by using the molecular time-dependent (TD) B-spline algebraic diagrammatic construction (ADC) method. We quantitatively study how the sub-cycle laser-driven multi-channel dynamics, as reflected in the position of the dynamical minimum in the HHG spectrum, is affected by the full inclusion of both correlation-driven and laser-driven dipole interchannel couplings.
View Article and Find Full Text PDFWe demonstrate the use of dataflow technology in the computation of the correlation energy in molecules at the Møller-Plesset perturbation theory (MP2) level. Specifically, we benchmark density fitting (DF)-MP2 for as many as 168 atoms (in valinomycin) and show that speed-ups between 3 and 3.8 times can be achieved when compared to the MOLPRO package run on a single CPU.
View Article and Find Full Text PDFWe investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al.
View Article and Find Full Text PDFThe excited state non-adiabatic dynamics of polyatomic molecules, leading to the coupling of structural and electronic dynamics, is a fundamentally important yet challenging problem for both experiment and theory. Ongoing developments in ultrafast extreme vacuum ultraviolet (XUV) and soft X-ray sources present new probes of coupled electronic-structural dynamics because of their novel and desirable characteristics. As one example, inner-shell spectroscopy offers localized, atom-specific probes of evolving electronic structure and bonding (via chemical shifts).
View Article and Find Full Text PDFThree-electron Auger decay is an exotic and elusive process, in which two outer-shell electrons simultaneously refill an inner-shell double vacancy with emission of a single Auger electron. Such transitions are forbidden by the many-electron selection rules, normally making their decay lifetimes orders of magnitude longer than the few-femtosecond lifetimes of normal (two-electron) Auger decay. Here we present theoretical predictions and direct experimental evidence for a few-femtosecond three-electron Auger decay of a double inner-valence-hole state in CH_{3}F.
View Article and Find Full Text PDFThe role of internal molecular degrees of freedom, such as rotation, has scarcely been explored experimentally in low-energy collisions despite their significance to cold and ultracold chemistry. Particularly important to astrochemistry is the case of the most abundant molecule in interstellar space, hydrogen, for which two spin isomers have been detected, one of which exists in its rotational ground state whereas the other is rotationally excited. Here we demonstrate that quantization of molecular rotation plays a key role in cold reaction dynamics, where rotationally excited ortho-hydrogen reacts faster due to a stronger long-range attraction.
View Article and Find Full Text PDFVestn Otorinolaringol
March 2016
This article is focused on the analysis of the literature publications pertaining to the problem of bleeding in otorhinolaryngology. It reports the epidemiological data on the structure of bleeding and the main methods used to arrest it. Special attention is given to the possibilities of application of tranexamic acid as an effective hemostatic agent not only for systemic but also for topical administration.
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