Monatshefte Fur Chemie最新文献

Abstract: Theoretical quantum mechanical calculations have been carried out to establish the effect of surface vacancies on the adsorption of Pd and Pb atoms on the defective MgO(100) surface. The investigated defects included neutral, singly and doubly charged O and Mg vacancies on the (100) surface of MgO. These vacancies played the role of F_sⁿ⁺ and V_s^n- (n = 0, 1, 2) adsorption centers for a single Pd or Pb atom. From the results of calculations, it is clear that the Pd- and Pb-atom adsorption at the F_sⁿ⁺ and V_s^n- centers shows different characteristics than at the regular O^2- and Mg²⁺ centers. Drastic changes in geometric, energetic, and electronic parameters are evident in Pd/V_s^n- and Pb/V_s^n-. The effect of F_s⁰ and F_s⁺, which in practice are the most important vacancies, is smaller, yet the adsorption of Pd and Pb at these centers is more energetically favorable than at the regular O^2- center. Of the two metals studied, the atom of Pd is bound by the F_s⁰ and F_s⁺ centers with higher adsorption energies.

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Abstract: A commercially available biliverdin sample was analyzed by means of HPLC/ESI-MS and NMR spectroscopy. It was been found that beside the main IXα 5Z,10Z,15Z isomer, the sample contains also the geometric isomer IXα 5Z,10Z,15E. It was also found the isomers behave differentially upon "in-source" fragmentation in negative ion mode (in contrast to the their behavior upon "in-source" fragmentation in positive ion mode and to their behavior upon MS/MS fragmentation in both modes): the relative abundances of deprotonated molecules and fragment ions are significantly different for both isomers, which can be used as an analytical tool to differentiate between the isomers.

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Abstract: X-ray analysis confirmed that in all investigated samples, the active API (acetylsalicylic acid and ascorbic acid) was present. The values of the interplanar distance d_hkl for the studied samples are in good accordance with those presented in the ICDD database. The intensities of the diffraction lines depend on the content of the component in the tested preparation. Therefore, different intensities of lines for the APIs were observed in the obtained diffraction patterns. Thermal analysis of the studied substances showed that during the thermal analysis, the following phenomena might occur: dehydration and (or) melting, crystalline transformation. Moreover, it was found that the chemical structure of the studied compounds affects the process of their thermal decomposition. The data obtained during these investigations can be useful in quick tests of physicochemical discrepancies and abnormalities between potential components of pharmaceutical preparations. The evidence for the interaction can be obtained by comparing DSC and TG curves of the drug and the excipient, as well as those of their physical mixtures. For this reason, the study of characteristics of thermal decomposition of drugs and excipients is necessary. Based on the above investigations, it may be stated that a combination of two methods: XRPD and DSC can be used to distinguish the original drugs from counterfeit products, e.g., by checking for the presence of the correct API or by a comparison of the drugs fingerprint.

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Abstract: To safeguard the consumers' well-being, it is necessary to develop novel methods for determination of carcinogens in food, including volatiles generated during frying. The currently used procedures for analysis of volatile fraction of vegetable oils are not based on real-time measurements and thus do not enable the determination of carcinogenic compounds in frying fumes; instead, only the headspace or liquid fraction is sampled. In this article, described is an approach in which proton transfer reaction mass spectrometry with time-of-flight analyser (PTR-TOFMS) was used for real-time monitoring of carcinogenic compounds generated during thermal degradation of rapeseed oil. Using PTR-MS, it was possible to monitor the concentration of known volatile carcinogens according to the International Agency for Research on Cancer (IARC), alongside BTEX compounds, acrolein, and selected aldehydes. Moreover, the applicability of several supervised data analysis methods for the classification of oil samples according to their degree of thermal degradation was presented, with best results obtained using the k-nearest neighbours algorithm. Proton transfer reaction mass spectrometry is a powerful technique for the determination of carcinogenic compounds generated during thermal degradation of edible oils. Further investigation of the chemical processes which occur during frying can lead to improvement of food safety.

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Abstract: Limited drinking water resources and water pollution are one of the main worldwide problems. To reduce the consumption of fresh water resources, the use of treated wastewater has been proposed. The farmlands have been irrigated with wastewater for centuries, but the composition of used sewage has changed over the years. Recent research has revealed the presence of hundreds of new organic contaminants in many environmental waters, including wastewaters and their receivers. For this reason, wastewater profiling and monitoring are of high importance and urgent need. In this study, the HPLC-Q-TOF-MS has been used for the profiling of wastewater composition and evaluation of the water pollution markers belonging to emerging contaminants. Three different solid-phase extraction approaches were applied to obtain the best results. Compounds such as acesulfame-K, caffeine, carbamazepine, cyclamate, ibuprofen, methyl paraben, paracetamol, or saccharin were detected in raw wastewater samples, whereas only acesulfame-K, carbamazepine, and sucralose were found in effluent samples. It seems that these particular compounds might be chosen as water pollution marker specific to Polish communal sewages.

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Abstract: In this contribution, we present new insights and a critical discussion in the optical detection of saxitoxin using fluorophores with crown ethers. Fluorescence enhancement is caused by the reduction of photoinduced electron transfer upon complexation with the analyte. Our attempts to improve this detection method neither did yield a functioning sensor nor were the attempts to reproduce published data in this area successful. Due to the fact that only low concentrations of saxitoxin are available, multiple surrogates were investigated at high concentrations. However, no turn on response was observed. Moreover, a fluorescent decomposition product of saxitoxin that forms under UV light was discovered which was in our opinion misinterpreted as a sensor response by previous publications.

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Abstract: This article presents the most popular methods of sewage sludge management and analytical techniques which could be a powerful tool in designing new sewage sludge management methods. Chemical analysis is also described as a vital point at the subsequent stages of technological processes control and sewage sludge quality assessment. It is also an instrument essential to maintaining control of processed sewage sludge introduced to the environment as ready-to-use materials. The sludge management method is conditioned by the compliance with legal acts concerning sludge management. The most important of these contain information regarding allowable concentrations of pollutants which can be released into the environment, and the most important declarations concerning sewage sludge management. Various analytical techniques and preparation methods that can be used during the monitoring of the managed and processed sewage sludge are described. The most important are chromatographic techniques, methods based on inductively coupled plasma, and mass spectrometry based methods.

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Abstract: The food authenticity assessment is an increasingly important issue in food quality and safety. The application of an electronic nose based on ultra-fast gas chromatography technique enables rapid analysis of the volatile compounds from food samples. Due to the fact that this technique provides chemical profiling of natural products, it can be a powerful tool for authentication in combination with chemometrics. In this article, a methodology for classification of Not From Concentrate (NFC) juices was presented. During research samples of 100% orange juice, 100% apple juice, as well as mixtures of these juices with known percentage of base juices were tested. Classification of juice samples was carried out using unsupervised and supervised statistical methods. As chemometric methods, Hierarchical Cluster Analysis, Classification Tree, Naïve Bayes, Neural Network, and Random Forest classifiers were used. The ultra-fast GC technique coupled with supervised statistical methods allowed to distinguish juice samples containing only 1.0% of impurities. The developed methodology is a promising analytical tool to ensure the authenticity and good quality of juices.

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Abstract: Cyclobutane thymine dimerization is the most prominent DNA photoinduced damage. While the ultrafast mechanism that proceeds in the singlet manifold is nowadays well established, the triplet-state pathway is not completely understood. Here we report the underlying mechanism of the photosensitized dimerization process in the triplet state. Quantum chemical calculations, combined with wavefunction analysis, and nonadiabatic molecular dynamics simulations demonstrate that this is a stepwise reaction, traversing a long-lived triplet biradical intermediate, which is characterized as a Frenkel exciton with very small charge-transfer character. The low yield of the reaction is regulated by two factors: (i) a relatively large energy barrier that needs to be overcome to form the exciton intermediate, and (ii) a bifurcation of the ground-state potential-energy surface that mostly leads back to the Franck-Condon region because dimerization requires a very restricted combination of coordinates and velocities at the event of non-radiative decay to the ground state.

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Abstract: Malodorous odors, by definition, are unpleasant, irritating smells being a mixture of volatile chemical compounds that can be sensed at low concentrations. Due to the increasing problem of odor nuisance associated with odor sensations, and thus the need to remove them from the air, deodorization techniques are commonly used. Biofiltration is one of the methods of reducing odorants in the air stream. In the paper, the possibility of using an electronic nose as an alternative method to gas chromatography for the online monitoring and evaluation of efficiency of the n-butanol vapors biofiltration process in a transient state was investigated. Three calibration models were used in the research, i.e., multiple linear regression, principal component regression, and partial least-square regression. The obtained results were compared with the theoretical values.

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