University of Pardubice

Property tuning in selected examples of D–π–A molecules has been discussed and summarized in this review article. The tuning and structure–property relationships have been demonstrated on the particular A, π and D parts of the push–pull molecule. Special emphasis has been put on the tuning of the FMO levels and optical properties. Further prospective applications of the given chromophore have also been considered.

BACKGROUND: Olfactory dysfunction is an increasingly recognised condition, associated with reduced quality of life and major health outcomes such as neurodegeneration and death. However, translational research in this field is limited by heterogeneity in methodological approach, including definitions of impairment, improvement and appropriate assessment techniques. Accordingly, effective treatments for smell loss are limited. In an effort to encourage high quality and comparable work in this field, among others, we propose the following ideas and recommendations. Whilst the full set of recommendations are outlined in the main document, points include the following: - Patients with suspected olfactory loss should undergo a full examination of the head and neck, including rigid nasal endoscopy with small diameter endoscopes. - Subjective olfactory assessment should not be undertaken in isolation, given its poor reliability. - Psychophysical assessment tools used in clinical and research settings should include reliable and validated tests of odour threshold, and/or one of odour identification or discrimination. - Comprehensive chemosensory assessment should include gustatory screening. - Smell training can be helpful in patients with olfactory loss of several aetiologies. CONCLUSIONS: We hope the current manuscript will encourage clinicians and researchers to adopt a common language, and in so doing, increase the methodological quality, consistency and generalisability of work in this field.

Abstract This article reviews the electrochemistry and electroanalytical applications of carbon paste‐based electrodes, sensors, and detectors on the occasion of the half‐of‐century anniversary since the discovery of carbon paste. The review (with 333 references) has been prepared in the form of a retrospective compilation presenting the field by means of various facts, notes, data, surveys, and summaries, including numerous rarities or curiosities that illustrate the individual achievements and milestones. Carbon paste‐based electrodes are discussed in their entirety by covering all important areas of the field, starting from basic characterization of carbon paste as the electrode material, via its typical physicochemical and electrochemical properties or specific features, up to a representative documentation of their applicability in electrochemical and electroanalytical measurements.

Master plot methods based on the integral and/or the differential forms of the kinetic equation describing solid-state reactions have been redefined by using the concept of the generalized time, θ, introduced by Ozawa. This redefinition permits the application of these master plots to the kinetic analysis of solid-state reactions, whatever the type of temperature program used for recording the experimental data. In isothermal conditions, a single curve is enough to construct the experimental master plots. In nonisothermal conditions, the knowledge of both α as a function of temperature and activation energy is required for calculating the master plot curves from the experimental data. Practical usefulness of the present master plot methods is examined, and exemplified by being applied to the thermal decomposition of ZnCO3 under isothermal, linear nonisothermal, and nonlinear nonisothermal conditions.

Abstract A review is presented dealing with the use of carbon paste as an electrode maaterial for electrochemical sensors (311 references). It covers mainly publications which appeared during the period 1990–1993; numerous applications demonstrate the widespread applicability of carbon paste in the field of electrochemical analysis, such as voltammetry, amperometry, and potentiometry, but also as an electrode for electrochemical detectors in flow systems.

Recent trends and advances in the electrochemistry with both unmodified and modified carbon paste electrodes are reviewed (247 refs.). Present day knowledge of their basic physico-chemical properties and characteristics is surveyed, including some specifics important in electrochemical measurements. Special attention is paid to the possibilities of carbon paste-based electrodes in electrochemical investigations and in modern electroanalysis of inorganic ions or molecules, organic substances, biologically important compounds, and pharmaceuticals.

Apoptosis has been recognized as a type of programmed cell death connected with characteristic morphological and biochemical changes in cells. This programmed cell death plays an important role in the genesis of a number of physiological and pathological processes. Thus, it can be very important to detect the signs of apoptosis in a study of cellular metabolism. The present paper provides an overview of methods often being used for detecting DNA fragmentation as one of the most specific findings in apoptosis. To date, three routine assays have been developed for detecting DNA fragmentation: DNA ladder assay, TUNEL assay, and comet assay. All these methods differ in their principles for detecting DNA fragmentation. DNA ladder assay detects the characteristic "DNA ladder" pattern formed during internucleosomal cleavage of DNA. Terminal deoxynUcleotidyl transferase Nick-End Labeling (TUNEL) assay detects DNA strand breaks using terminal deoxynucleotidyl transferase catalyzing attachment of modified deoxynucleotides on the DNA strand breaks. Comet assay can be used for detecting nucleus breakdown producing single/double-strand DNA breaks. The aim of this review is to describe the present knowledge on these three methods, including optimized approaches, techniques, and limitations.

The worldwide prevalence of obesity more than doubled between 1980 and 2014. The obesity pandemic is tightly linked to an increase in energy availability, sedentariness and greater control of ambient temperature that have paralleled the socioeconomic development of the past decades. The most frequent cause which leads to the obesity development is a dysbalance between energy intake and energy expenditure. The gut microbiota as an environmental factor which influence whole-body metabolism by affecting energy balance but also inflammation and gut barrier function, integrate peripheral and central food intake regulatory signals and thereby increase body weight. Probiotics have physiologic functions that contribute to the health of gut microbiota, can affect food intake and appetite, body weight and composition and metabolic functions through gastrointestinal pathways and modulation of the gut bacterial community.

Abstract In this article, the decade of electroanalysis with bismuth‐based electrodes is reviewed (with 222 refs.). Emphasis is put on the environmentally friendly (“green”) character of bismuth electrodes, their versatility and variability in use, as well as the actual classification of the individual types of electrodes, sensors, and detectors that utilize the unique properties of metallic bismuth. Of particular interest is the genesis of the field, when the respective activities and achievements are monitored year by year over the whole period of 2000–2009, including the circumstances of the introduction of bismuth‐coated electrodes into electrochemical stripping analysis. The review highlights all the significant milestones and break‐points that had directed the experimental work around the globe, outlining the present day's position of this lively, inspiring, and still highly prospective area. Finally, it provides a special insight into electroanalysis with bismuth electrodes through numerous surveys, summaries, and detailed statistical data obtained by analyzing the accessible literature database.

Abstract This paper provides an overview of the main developments over the past nine years in the study of the sensitivity of energetic materials (EM) to impact, shock, friction, electric spark, laser beams, and heat. Attention is also paid to performance and to its calculation methods. Summaries are provided of the relationships between sensitivity and performance, the best representations for the calculation methods of performance being the volume heat of explosion or the product of crystal density and the square of detonation velocity. On the basis of current knowledge, it is possible to state that a single universal relationship between molecular structure and initiation reactivity does not yet exist. It is confirmed that increasing the explosive strength is usually accompanied by an increase in the sensitivity. In the case of nitramines this rule is totally valid for friction sensitivity, but for impact sensitivity there are exceptions to the rule, and with 1,3,5‐trinitro‐1,3,5‐triazepane, 1,3,5‐trinitro‐1,3,5‐triazinane, β‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane, and the α‐, β‐ and ε‐polymorphs of 2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane the relationship works in the opposite direction. With respect to the QSPR approach there might be reasonably good predictions but it provides little insight into the physics and chemistry involved in the process of initiation.

Because of their simple preparation and low expense, carbon pastes and carbon paste electrodes are widely used in a myriad of instrumental measurements. With an emphasis on practical applications, Electroanalysis with Carbon Paste Electrodes provides a comprehensive overview of carbon paste electrodes. The text offers a comprehensive and unpreceden

Hydrophilic interaction chromatography (HILIC) is becoming increasingly popular for separation of polar samples on polar columns in aqueous-organic mobile phases rich in organic solvents (usually ACN). Silica gel with decreased surface concentration of silanol groups, or with chemically bonded amino-, amido-, cyano-, carbamate-, diol-, polyol-, or zwitterionic sulfobetaine ligands are used as the stationary phases for HILIC separations, in addition to the original poly(2-sulphoethyl aspartamide) strong cation-exchange HILIC material. The type of the stationary and the composition of the mobile phase play important roles in the mixed-mode HILIC retention mechanism and can be flexibly tuned to suit specific separation problems. Because of excellent mobile phase compatibility and complementary selectivity to RP chromatography, HILIC is ideally suited for highly orthogonal 2-D LC-LC separations of complex samples containing polar compounds, such as peptides, proteins, oligosaccharides, drugs, metabolites and natural compounds. This review attempts to present an overview of the HILIC separation systems, possibilities for their characterization and emerging HILIC applications in 2-D off-line and on-line LC-LC separations of various samples, in combination with RP and other separation modes.

The state-of-art in the lipidomic analysis is summarized here to provide the overview of available sample preparation strategies, mass spectrometry (MS)-based methods for the qualitative analysis of lipids, and the quantitative MS approaches for high-throughput clinical workflows. Major challenges in terms of widely accepted best practices for lipidomic analysis, nomenclature, and standards for data reporting are discussed as well.

In this work, an antimony film electrode (SbFE) is reported for the first time as a possible alternative for electrochemical stripping analysis of trace heavy metals. The SbFE was prepared in situ on a glassy carbon substrate electrode and employed in combination with either anodic stripping voltammetry or stripping chronopotentiometry in nondeaerated solutions of 0.01 M hydrochloric acid (pH 2). Several key operational parameters influencing the electroanalytical response of SbFE were examined and optimized, such as deposition potential, deposition time, and composition of the measurement solution. The SbFE exhibited well-defined and separated stripping signals for both model metal ions, Cd(II) and Pb(II), surrounded with low background contribution and a relatively large negative potential range. The electrode revealed good linear behavior in the examined concentration range from 20 to 140 microg L-1 for both test metal ions, with a limit of detection (3sigma) of 0.7 microg L-1 for Cd(II) and 0.9 microg L-1 for Pb(II) obtained after a 120 s deposition step, and good reproducibility, with a relative standard deviation (RSD) of +/-3.6% for Cd(II) and +/-6.2% for Pb(II) (60 microg L-1, n = 12). When comparing the SbFE with the commonly used mercury film electrode and recently introduced bismuth film electrode, the newly proposed electrode offers a remarkable performance in more acidic solutions (pH < or = 2), which can be advantageous in electrochemical analysis of trace heavy metals, hence contributing to the wider applicability of electrochemical stripping techniques in connection with "mercury-free" electrodes.

This paper theoretically and experimentally investigate the spectrum attenuation of free space optical (FSO) communication systems operating at visible and near infrared (NIR) wavelengths (0.6 μm <; λ <; 1.6 μm) under fog and smoke in a controlled laboratory condition. Fog and smoke are generated and controlled homogeneously along a dedicated atmospheric chamber of length 5.5 m. A new wavelength dependent empirical model is proposed to predict the fog and smoke attenuation operating at visible and NIR wavelengths. Comparison of the new proposed model with the measured continuous attenuation spectrum from visible-NIR in the fog and smoke channels shows a close relationship than the semi-empirical Kim and Kruse fog models. The experimental results also show the selection for the possible appropriate wavelengths from visible-NIR for FSO links to achieve the maximum link span in dense fog conditions.

New analytical approach for high-throughput and comprehensive lipidomic analysis of biological samples using ultrahigh-performance supercritical fluid chromatography (UHPSFC) with electrospray ionization-mass spectrometry (ESI-MS) is presented in this work as an alternative approach to established shotgun MS or high-performance liquid chromatography-MS. The lipid class separation is performed by UHPSFC method based on 1.7 μm particle-bridged ethylene hybrid silica column with a gradient of methanol-water-ammonium acetate mixture as a modifier. All parameters of UHPSFC conditions are carefully optimized and their influence on the chromatographic behavior of lipids is discussed. The final UHPSFC/ESI-MS method enables a fast separation of 30 nonpolar and polar lipid classes within 6 min analysis covering 6 main lipid categories including fatty acyls, glycerolipids, glycerophospholipids, sphingolipids, sterols, and prenols. Individual lipid species within lipid classes are identified based on positive and negative-ion full-scan and tandem mass spectra measured with high mass accuracy and high resolving power. Developed UHPSFC/ESI-MS method is applied for the analysis of porcine brain extract as a complex lipidomic sample, where 24 lipid classes containing 436 lipid species are identified. The method is validated for the quantitative analysis of lipid species in biological tissues using internal standards for each lipid class. This high-throughput, comprehensive and accurate UHPSFC/ESI-MS method is suitable for the lipidomic analysis of large sample sets in the clinical research.

The main constituents of plant oils are complex mixtures of TGs differing in acyl chain lengths, number and positions of double bonds, and regioisomerism. A non-aqueous reversed-phase HPLC method with acetonitrile-2-propanol gradient and 30 + 15 cm NovaPak C18 columns makes possible an unambiguous identification of the highest number of TGs ever reported for these oils, based on positive-ion APCI mass spectra. A new approach to TG quantitation is based on the use of response factors with three typical detection techniques for that purpose (APCI-MS, evaporative light-scattering detection, and UV at 205 nm). Response factors of 23 single-acid TGs (saturated TGs from C7 to C22, 7 unsaturated TGs), 4 mixed-acid TGs, diolein and monoolein are calculated from their calibration curves and related to OOO. Due to differences between saturated and unsaturated acyl chains, the use of response factors significantly improves the quantitation of TGs. 133 TGs containing 22 fatty acids with 8-25 carbon atoms and 0-3 double bonds are identified and quantified in 9 plant oils (walnut, hazelnut, cashew nut, almond, poppy seed, yellow melon, mango, fig, date) using HPLC/APCI-MS with a response factor approach. Average parameters and relative fatty acid concentrations are calculated with both HPLC/APCI-MS and GC/ FID.

BACKGROUND/OBJECTIVES: Calf muscle hypertonicity following stroke may impair walking rehabilitation. The aim of this study was to assess botulinum toxin (Dysport) in post-stroke calf spasticity. METHODS: A prospective, multicentre, double-blind, placebo-controlled, dose-ranging study was performed to evaluate dysport at 500, 1,000 or 1,500 units in 234 stroke patients. They were assessed at 4-week intervals over 12 weeks. RESULTS: The primary outcome measure, 2-min walking distance and stepping rate increased significantly in each group (p < 0.05, paired test), but there was no significant difference between groups (including placebo). Following dysport treatment, there were small but significant (p = 0.0002-0.0188) improvements in calf spasticity, limb pain, and a reduction in the use of walking aids, compared to placebo. Investigators' and patients' assessments of overall benefit suggested an advantage for dysport over placebo, but this was not significant. Sixty-eight patients reported 130 adverse events, with similar numbers in each group. The few severe events recorded were not considered to be treatment-related. CONCLUSION: Dysport resulted in a significant reduction in muscle tone, limb pain and dependence on walking aids. The greatest benefits were in patients receiving dysport 1,500 units, but 1,000 units also had significant effects. Dysport 500 units resulted in some improvements. Since few adverse events were reported, this therapy is considered safe and may be a useful treatment in post-stroke rehabilitation of the leg. Possible reasons why functional improvements in gait parameters were not observed are also discussed.

One on one: A combination of steric effects and MN interactions of a rigid NCN pincer ligand allows the isolation and characterization of monomeric stibinidene and bismuthinidene compounds. The structure and bonding was confirmed by crystallographic studies (see picture; Sb or Bi yellow, N blue) and calculations. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

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