Potentiometric ion sensors represent a significant subgroup of electrochemical sensors. In this study, we have developed a potentiometric sensor using an electrically conductive copolymer of 2,2'-bithiophene (BT) and 1,2-bis(o-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid (BAPTA) for the selective detection of Ca2+ ions in extracellular interstitial fluids. The integration of BAPTA with its highly selective calcium chelating properties into a polymer matrix via electrochemical polymerization results in a sensitive conductive polymer layer that effectively detects the presence of calcium ions. This sensor aims at the early detection of inflammation or infection around implants because local calcium concentration is strongly elevated in interstitial fluid in such pathologies. The potentiometric study proves the incorporation of BAPTA into the polymer matrix was successful and its potential decreased upon calcium binding demonstrating the Nernstian behavior with a slope of approximately 20 ± 0.3 mV per decade in the concentration range from 0.1 mM to 1 mM. Moreover, the selectivity coefficient of -0.4 was measured by SSM and calculated from the Nicolsky-Eisenmann equation, which indicates selectivity towards Ca2+ ions with respect to Mg2+ ions.
Raman micro-spectroscopy technique offers a combination of relatively high spatial resolution with identification of components or mixtures of components in different sample areas, e.g. on the surface or the cross-section of a sample. This study is focused on the analysis of the tablets from pharmaceutical development with different technological parameters: (1) the manufacturing technology, (2) the particle size of the input API (active pharmaceutical ingredient) and (3) the quantitative composition of the individual excipients. These three mentioned parameters represent the most frequently solved problems in the field of reverse engineering in pharmacy. The investigation aims to distinguish tablets with the above-described technological parameters with limited subjective steps by Raman microscopy. Furthermore, non-subjective methods of Raman data analysis using advanced statistical analysis have been proposed, namely Principal Component Analysis, Soft Independent Modelling of Class Analogy and Linear Discriminant Analysis. The methods successfully distinguished and identified even very small differences in the analysed tablets within our study and provided objective statistic evaluation of Raman maps. The information on component and particle size distribution including their small differences, which is the critical parameter in the development of the original and generic products, was obtained due to combination of these methods. Even though each of these chemometric methods evaluates the data set from a different perspective, their mutual application on the problem of Raman maps evaluation confirmed and specified results on level that would be unattainable with the use of only one them.
- Klíčová slova
- Linear Discriminant Analysis, Multivariate analysis, Principal Component Analysis, Raman mapping, Soft Independent Modelling of Class Analogy, Tablets,
- MeSH
- chemometrika MeSH
- farmacie * MeSH
- léčivé přípravky * MeSH
- pomocné látky MeSH
- Ramanova spektroskopie MeSH
- tablety MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- léčivé přípravky * MeSH
- pomocné látky MeSH
- tablety MeSH
An efficient methodology for the synthesis of two groups of silicon-containing alkenes is reported. It includes a highly regioselective functionalization of 1,5-hexadiene through hydrosilylation and dehydrogenative silylation with organofunctional silanes and siloxanes. The established conditions enable selective monofunctionalization of 1,5-hexadiene regardless of the organosilicon modifier used as well as the type of functional group bonded to the silicon-based compound. All products were isolated and fully characterized by NMR spectroscopy and MS techniques.
- Publikační typ
- časopisecké články MeSH
Automobile friction brakes generate, in addition to coarse particles generated by mechanical processes, highly variable amount of nanoparticles from high temperature processes. The effects of braking conditions - speed, deceleration rate, brake rotor temperatures - on nanoparticle production were investigated here, aiming to provide practical guidance for reducing emissions through driving style and traffic management. Typical brake pads and a rotor from a common passenger car were subjected, on a brake dynamometer, to three runs of the WLTP brake cycle developed for brake wear particle measurements. Additionally, four sets of common brake pads were subjected to those parts of standardized brake performance tests believed to be reasonably realistic for common driving. Particle size distributions (5.6-560 nm electric mobility diameter, without removal of volatiles) show a dominant peak at 10 nm commensurate to the severity of braking and a non-linear increase of the total particle number at higher braking powers and higher total energy dissipated. The average emissions for three runs of the WLTP brake cycle were 3.3 × 1010 particles/km, while the harshest deceleration, 175-100 km/h at 5.28 m·s-2, has produced 8.4 to 38 × 1013 particles, corresponding to 2.5-11.5 thousands of km of WLTP-like driving. While previous studies have correlated higher PN production with higher average brake rotor temperature, a more complex relationship between nanoparticle emissions and a combination of initial rotor temperature, total energy dissipated and braking power has been observed here. From a driver behavior and regulatory perspective, it appears limiting harsh braking and braking from high speeds, possibly through improved driving practices, road design and traffic management, may potentially reduce brake wear nanoparticles. From the measurement perspective, it appears that "off-cycle" braking, even if relatively infrequent, may be associated with exponentially higher emissions and non-negligible share of the total emissions, and therefore should not be neglected.
- Klíčová slova
- Brake wear, Friction brakes, Nanoparticles, Non-exhaust emissions, Off-cycle emissions, Operating conditions,
- Publikační typ
- časopisecké články MeSH
The release of soil arsenic (As) in an unsaturated zone under oxidative conditions and at two temperatures simulating the seasonal effect (15 °C and 23 °C) was studied in four cultivated soils from the Elbe River catchment (Czech Republic, Central Europe). The soils with a low geogenic As background contained from 10 to 50 µg.g-1 of As, mostly originating from atmospheric deposition in the past. The temperature effect on the stability of As in soils was studied in connection with the stability of hydrated iron (Fe) oxides and dissolved organic carbon (DOC), as essential binding partners of As in soils. The temperature impact on As release was related to the actual As binding in soil determined by the sequential leaching. With predominant As binding to amorphous and poorly crystalline Fe phases the higher temperature (23 °C) increased As release up to twice compare to 15 °C. In the soils with a low total Fe and the preferential As binding to well-crystallised Fe phases the temperature effect on As release was negligible. Unlike Fe, the release of DOC is strongly temperature dependent, therefore As mobilisation was controlled by the DOC concentration. A higher experimental temperature (23 °C) supported the formation of DOC and the consequent release of As and Fe into the soil solution.
- Klíčová slova
- Arsenic, Mobilisation, Soil, Temperature, Unsaturated zone,
- MeSH
- arsen * analýza MeSH
- látky znečišťující půdu * analýza MeSH
- půda MeSH
- železo MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Geografické názvy
- Česká republika MeSH
- Názvy látek
- arsen * MeSH
- látky znečišťující půdu * MeSH
- půda MeSH
- železo MeSH
Efficient tablet disintegration is a pre-requisite for fast and complete drug dissolution from immediate release formulations. While the overall tablet disintegration time is a routinely measured quality attribute of pharmaceutical products, little attention is usually paid to the analysis of disintegration fragments and the cascade of elementary steps that lead to their formation. In this work, we investigate the disintegration pathways of directly compressed tablets by a unique combination of three methods: (i) magnetic resonance imaging (MRI), to gain insight into structural changes of tablets during disintegration; (ii) texture analysis, to measure the disintegration kinetics; and (iii) static light scattering, to characterise the size distribution of disintegration fragments. By systematically varying the tablet composition (50-90% of ibuprofen as a model active ingredient, 0-4% of croscarmellose sodium disintegrant, 6-50% of lactose monohydrate filler), a relationship between the tablet formulation, the size distribution of the disintegration fragments and the dissolution rate of the active ingredient has been established. To interpret the experimental observations, we analyse the disintegration fragments by Raman mapping and relate their composition and structure to the micro-scale arrangement of individual formulation components inside the tablet.
- Klíčová slova
- Direct compression, Disintegration, Dissolution, Particle size distribution, Wetting,
- MeSH
- farmaceutická chemie * MeSH
- magnetická rezonanční tomografie MeSH
- pomocné látky * MeSH
- rozpustnost MeSH
- tablety MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- pomocné látky * MeSH
- tablety MeSH
Ultrafast measurement using dwell times below 100 μs down to 10 μs is a relatively new feature of single particle analysis using ICP-MS. In this study, we tested the effect of shorter dwell times on the particle size detection limit (Dd.l.). Decreasing dwell times below 100 μs did not lead to a statistically significant decrease in Dd.l. The particle size detection limit (quadrupole ICP-MS) of silver nanoparticles (NP) was estimated to be approx. 10-11 nm. Ag NPs close to Dd.l. were analysed. The 14-nm NPs showed low detection yield; only 5% of number of NPs estimated from transport efficiency was detected. The 20-nm NPs showed 44% detection yield; only in the case of 30-nm NPs did the number of detected NPs correspond to transport efficiency. It is obvious that near Dd.l. estimates of NP concentrations should be made with great caution.
- Klíčová slova
- Detection limit, ICP-MS, Nanoparticles, Single particle analysis,
- Publikační typ
- časopisecké články MeSH
Antimony (Sb) and arsenic (As) are elements with similar chemistry, toxicity and binding properties, but different environmental risks and prevailing anthropogenic sources. A significant source of Sb contamination is associated with braking in extremely loaded traffic areas, where the produced abrasion dust contains up to 5% wt. of Sb2S3. In these same exposure areas, As still originates mostly from the combustion of fossil fuels. Heavily loaded crossroads from three different regions of the Czech Republic (Central Europe) were monitored for Sb content in road dusts, topsoils and reference soils during a two-year season (2016-2017). The same samples were also tested for As content to evaluate current contamination trends of both elements in exposed urban areas. The concentration of Sb varied from 5 to 70 µg g-1 in topsoils, and from 20 to 350 µg g-1 in road dusts with the preference for binding to the fine particle fraction (<0.1 mm). The average Sb concentration was up to 60 times the background value and decreased in the order: brake abrasion (103 µg g-1) > road dust (102 µg g-1)> topsoils (101 µg g-1) >> reference soils (<1 µg g-1). The concentration of As in road dust, topsoils and reference soils had about the same level, 101 µg g-1 indicating a more regional character of As pollution. Correlation factors for Sb/As versus iron (Fe)/organic matter (OM) indicated a more robust correlations in soils compared to road dusts and generally better correlations of Sb compared to As. While arsenic contamination has recently decreased thanks to a massive decline of arsenic emissions, antimony contamination indicates a dangerous trend due to growing automotive traffic.
- Klíčová slova
- Antimony, Arsenic, Brake abrasion dust, Contamination gradient, Traffic nodes,
- Publikační typ
- časopisecké články MeSH
This work demonstrates the effect of NaCl and carbon-related interferences on the analysis of arsenic and silver nanoparticles (NPs) by single-particle inductively coupled plasma mass spectrometry. Spectral interference caused by ArCl+ ions disturbing arsenic NPs analysis was eliminated using ammonia as reaction gas in a dynamic reaction cell of inductively coupled plasma mass spectrometer. In comparison to aqueous dispersions, non-spectral interferences caused by sodium lead to under-evaluation of arsenic and silver NPs diameter by about 7% and 15% at NaCl concentration of 450 mg L-1 and about 28% and 41% at NaCl concentration of 4500 mg L-1, respectively. As a consequence of lower transport efficiency, sodium non-spectral interferences also lead to about a 9% lower number of detected NPs for dispersions of both arsenic and silver NPs in 4500 mg L-1 NaCl. On the contrary, measurement of NPs in matrices containing methanol gives results where Ag and As NPs diameter is over-evaluated by about 3% and 15% at a methanol content of 1% (v/v) and about 6% and 20% at a methanol content of 2% (v/v), respectively, in comparison to aqueous dispersions. In addition, the organic carbon species behave as surfactants and increase the transport efficiency; this leads to an increase in the determined number concentration of NPs. In comparison to aqueous dispersions, this is over-evaluated by about 17% for Ag NPs and about 10% for As NPs at a methanol content of 5% (v/v).
- Klíčová slova
- Arsenic nanoparticles, Non-spectral interference, Silver nanoparticles, sp-ICP-MS,
- Publikační typ
- časopisecké články MeSH
The characterisation of inorganic nanoparticles (NPs) by single particle inductively coupled plasma mass spectroscopy is possible only if the spectrometer is capable of measurement with high time-signal resolution. The latest generation of spectrometers allow for measurements with dwell times (dt) shorter than the 100 μs gold standard, i.e. as low as 10 μs. The statistical behaviours of signals obtained with dt values of 10, 20, 50, and 100 μs were tested for 40, 60, and 100 nm silver NPs. Very low measured signals (units of counts) led to the occurrence of zero signal values inside the peaks corresponding to individual NPs. The probability of the occurrence of a zero signal inside the peak increased with decreasing dt and decreasing NP size. The standard approach to the bordering of the beginning and end of the peak by one zero signal point failed here and lead to the false detection of a larger number of smaller peaks. For example, in the case of 40 nm NPs a quadruple number of peaks were detected for a dt value of 10 μs compared to the 100 μs dt value; the mean peak width at 10 μs dt was approximately 220 μs, while at 100 μs dt it was 550 μs. The results tended to be less distorted when dt was longer and the NP size was larger. Low dt values also led to a distortion of the peak area distribution. For 40 nm NPs and 10 μs, the most frequent peak area and the width of the peak area distribution were not evaluated due to a non-Gaussian course; 20 μs dt caused (compared to 100 μs) a decrease in the most frequent peak area by approximately 35% (33 counts for 100 μs dt vs. 22 counts for 20 μs dt) and an increase in the width of the peak area distribution by 70% (10 counts for 100 μs dt vs. 17 counts for 20 μs dt). Therefore, new approaches to bordering peaks were tested, which consisted of searching for an uninterrupted zero signal point sequence with a total length of 50 μs or 100 μs. Only the criterion of a 100 μs delay between the two adjacent peaks resulted in values of the number of detected peaks, the most frequent peak areas, and the width of peak area distribution virtually independent of dt.
- Klíčová slova
- ICP-MS, Nanoparticles, Peak bordering, Single particle analysis,
- Publikační typ
- časopisecké články MeSH
