slavicek

Spatial neglect (SN) impedes functional recovery after stroke, leading to reduced rehabilitation gains and slowed recovery. The objective of the present study was to investigate whether integrating prism adaptation treatment (PAT) into a highly intensive rehabilitation program eliminates the negative impact of spatial neglect on functional and motor recovery. We examined clinical data of the 355 consecutive first-time stroke patients admitted to a sub-acute inpatient neurorehabilitation program that integrated PAT...

Disasters involving radioactive materials are one of the most dangerous accidents a living organism can be exposed to. Individuals and first responders are in risk during accidents or interventions, due to radioactive debris impact, due to the use of depleted uranium ammunition or a malevolent act against individuals. Moreover, radioactive contamination of wounds causes internal exposure in the body and standard decontamination procedures cannot be applied. In order to deal with such situations, we are developing a measurement system consisting of a robotic arm, an array of various detectors and a corresponding methodology, which allows quantifying timely the spatial distribution of contamination and the radiation dose for the adequate medical response...

We report the first nitrogen 1s Auger-Meitner electron spectrum from a liquid ammonia microjet at a temperature of ∼223 K (-50 °C) and compare it with the simultaneously measured spectrum for gas-phase ammonia. The spectra from both phases are interpreted with the assistance of high-level electronic structure and ab initio molecular dynamics calculations. In addition to the regular Auger-Meitner-electron features, we observe electron emission at kinetic energies of 374-388 eV, above the leading Auger-Meitner peak (3a1 2 )...

Directly contrasting ultrafast excited-state dynamics in the gas and liquid phases is crucial to understanding the influence of complex environments. Previous studies have often relied on different spectroscopic observables, rendering direct comparisons challenging. Here, we apply extreme-ultraviolet time-resolved photoelectron spectroscopy to both gaseous and liquid cis-stilbene, revealing the coupled electronic and nuclear dynamics that underlie its isomerization. Our measurements track the excited-state wave packets from excitation along the complete reaction path to the final products...

Photoremovable protecting groups (PPGs) represent one of the main contemporary implementations of photochemistry in diverse fields of research and practical applications. For the past half century, organic and metal-complex PPGs were considered mutually exclusive classes, each of which provided unique sets of physical and chemical properties thanks to their distinctive structures. Here, we introduce the meso-methylporphyrin group as a prototype hybrid-class PPG that unites traditionally exclusive elements of organic and metal-complex PPGs within a single structure...

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The transport of free electrons in a water environment is still poorly understood. We show that additional insight can be brought about by investigating fragmentation patterns of finite-size particles upon electron impact ionization. We have developed a composite protocol aiming to simulate fragmentation of water clusters by electrons with kinetic energies in the range of up to 100 eV. The ionization events for atomistically described molecular clusters are identified by a kinetic Monte Carlo procedure. We subsequently model the fragmentation with classical molecular dynamics simulations, calibrated by non-adiabatic quantum mechanics/molecular mechanics simulations of the ionization process...

Non-local analogues of Auger decay are increasingly recognized as important relaxation processes in the condensed phase. Here, we explore non-local autoionization, specifically Intermolecular Coulombic Decay (ICD), of a series of aqueous-phase isoelectronic cations following 1s core-level ionization. In particular, we focus on Na+ , Mg2+ , and Al3+ ions. We unambiguously identify the ICD contribution to the K-edge Auger spectrum. The different strength of the ion-water interactions is manifested by varying intensities of the respective signals: the ICD signal intensity is greatest for the Al3+ case, weaker for Mg2+ , and absent for weakly-solvent-bound Na+ ...

Nanoparticles can serve as an efficient reaction environment for bimolecular reactions as the reactants concentrate either inside the nanoparticle or on the surface of the nanoparticle. The reaction rate is then controlled by the rate of formation of the reaction pairs. We demonstrate this concept on the example of electron-induced reactions in hydrogen peroxide. We consider two types of nanoparticle environments: solid argon particles, only weakly interacting with the hydrogen peroxide reactant, and ice particles with a much stronger interaction...

Characterizing the photochemical reactivity of transient volatile organic compounds (VOCs) in our atmosphere begins with a proper understanding of their abilities to absorb sunlight. Unfortunately, the photoabsorption cross-sections for a large number of transient VOCs remain unavailable experimentally due to their short lifetime or high reactivity. While structure-activity relationships (SARs) have been successfully employed to estimate the unknown photoabsorption cross-sections of VOCs, computational photochemistry offers another promising strategy to predict not only the vertical electronic transitions of a given molecule but also the width and shape of the bands forming its absorption spectrum...

We investigate the effect of microhydration on electron attachment to thiophenols with halogen (Br) and nitro (NO2 ) functional groups in the para position. We focus on the formation of anions upon the attachment of low-energy electrons with energies below 8 eV to heterogeneous clusters of the thiophenols with water. For nitro-thiophenol (NTP), the primary reaction channel observed is the associative electron attachment, irrespective of the microhydration. On the other hand, bromothiophenol (BTP) fragments significantly upon the electron attachment, producing Br- and (BTP-H)- anions...

Nuclear densities are frequently represented by an ensemble of nuclear configurations or points in the phase space in various contexts of molecular simulations. The size of the ensemble directly affects the accuracy and computational cost of subsequent calculations of observable quantities. In the present work, we address the question of how many configurations do we need and how to select them most efficiently. We focus on the nuclear ensemble method in the context of electronic spectroscopy, where thousands of sampled configurations are usually needed for sufficiently converged spectra...

Liquid-jet photoelectron spectroscopy was applied to determine the first acid dissociation constant (p K a ) of aqueous-phase glucose while simultaneously identifying the spectroscopic signature of the respective deprotonation site. Valence spectra from solutions at pH values below and above the first p K a reveal a change in glucose's lowest ionization energy upon the deprotonation of neutral glucose and the subsequent emergence of its anionic counterpart. Site-specific insights into the solution-pH-dependent molecular structure changes are also shown to be accessible via C 1s photoelectron spectroscopy...

The distributed long-range sensing system, using the standard telecommunication single-mode optical fiber for the distributed sensing of mechanical vibrations, is described. Various events generating vibrations, such as a walking or running person, moving car, train, and many other vibration sources, can be detected, localized, and classified. The sensor is based on phase-sensitive optical time-domain reflectometry (ϕ-OTDR). Related sensing system components were designed and constructed, and the system was tested both in the laboratory and in the real deployment, with an 88 km telecom optical link, and the results are presented in this paper...

We investigate the photodissociation dynamics of the C-Cl bond in chloroalkanes CH3Cl, n-C3H7Cl, i-C3H7Cl, n-C5H11Cl, combining velocity map imaging (VMI) experiment and direct ab initio dynamical simulations. The Cl fragment kinetic energy distributions (KEDs) from the VMI experiment exhibit a single peak with maximum close to 0.8 eV, irrespective of the alkyl chain length and C-Cl bond position. In contrary to CH3Cl, where less than 10% of the available energy is deposited into the internal excitation of the CH3 fragment, for all higher chloroalkanes around 40% to 60% of the available energy goes into the alkyl fragment excitation...

The combination of supersonic expansions with IR action spectroscopy techniques is the basis of many successful approaches to study cluster structure and dynamics. The effects of temperature and temperature evolution are important with regard to both the cluster synthesis and the cluster dynamics upon IR excitation. In the past the combination of the sodium doping technique with IR excitation enhanced near threshold photoionization has been successfully applied to study neutral, especially water clusters. In this work we follow an overall examination approach for inspecting the interplay of cluster temperature and cluster structure in the initial cooling process and in the IR excitation induced heating of the clusters...

Medical image data plays a critical role in health care today. Whatever the context of image processing (research and educational activities, diagnostic or forensic purposes, etc.), they are supposed to be treated as highly sensitive. Unfortunately, currently available image-processing tools also enable very sophisticated malicious modification of their content.This paper is focused on the assessment of the effectiveness of selected so-called zero watermarking methods (ones that do not cause any modification of an image sample), in the protection of the integrity, and proving authorship, of these medical image studies...

The photochemistry of bilirubin has been extensively studied due to its importance in the phototherapy of hyperbilirubinemia. In the present work, we investigated the ultrafast photodynamics of a bilirubin dipyrrinone subunit, vinylneoxanthobilirubic acid methyl ester. The photoisomerization and photocyclization reactions of its ( E ) and ( Z ) isomers were studied using femtosecond transient absorption spectroscopy and by multireference electronic structure theory, where the nonadiabatic dynamics was modeled with a Landau-Zener surface hopping technique...

Objectives Hyperammonemia in a newborn is a serious condition, which requires prompt intervention as it can lead to severe neurological impairment and death if left untreated. The most common causes of hyperammonemia in a newborn are acute liver failure and inherited metabolic disorders. Several mitochondrial disorders have been described as a cause of severe neonatal hyperammonemia. Case presentation Here we describe a new case of adenosine-triphosphate (ATP) synthase deficiency due to m.8528T>C mutation as a novel cause of severe neonatal hyperammonemia...

Phototherapy is a standard treatment for severe neonatal jaundice to remove toxic bilirubin from the blood. Here, the wavelength-dependent photochemistry of vinylneoxanthobilirubic acid methyl ester, a simplified model of a bilirubin dipyrrinone subunit responsible for a lumirubin-like structural rearrangement, was thoroughly investigated by liquid chromatography and mass and absorption spectroscopies, with the application of a multivariate curve resolution analysis method supplemented with quantum chemical calculations...