The applicability of AM1 and PM3 semi-empirical methods for the study of N-H bond dissociation enthalpies and ionisation potentials of amine type antioxidants

A study of 40 para-substituted anilines is presented. These serve as model structures of amine type antioxidants. Molecules and their radical structures were studied using the AM1 and PM3 quantum chemical methods in order to calculate the N-H bond dissociation enthalpies (BDEs) and ionisation potentials (IPs) which are among the most important characteristics of antioxidants. Calculated BDEs were compared with available experimental values and the results of DFT calculations to ascertain the suitability of AM1 and PM3 methods for amine BDEs calculation. The results show that both methods reproduce experimental BDEs and DFT data satisfactorily. Comparison with experimental data shows that AM1 and PM3 methods overestimate the IP values. The results also indicate that dependences of N-H bond BDEs and IPs on Hammett constants of the substituents are linear.     

Thermal study of zinc(II) 4-chlorosalicylate complex compounds with bioactive ligands

Three new complex compounds of general formula Zn{4-ClC₆H₃-2-(OH)COO}₂⋅L₂⋅nH₂O (where L=thiourea (tu), nicotinamide (nam), caffeine (caf), n=2,3), were prepared and characterized by chemical analysis, IR spectroscopy and their thermal properties were studied by TG/DTG, DTA methods. It was found that the thermal decomposition of hydrated compounds starts with the release of water molecules. During the thermal decomposition of anhydrous compounds the release of organic ligands take place followed by the decomposition of salicylate anion. Zinc oxide was found as the final product of the thermal decomposition performed up to 650°C. RTG powder diffraction method, IR spectra and chemical analysis were used for the determination of products of the thermal decomposition.     

Use of MALDI-TOF MS to Discriminate between Aflatoxin B1-Producing and Non-Producing Strains of Aspergillus flavus

Aflatoxin B₁ (AFB₁) is one of the most toxic mycotoxins. One of the producers of AFB₁ is Aspergillus flavus. Therefore, its rapid identification plays a key role in various sectors of the food and feed industry. MALDI-TOF mass spectrometry is one of the fastest and most accurate methods today. Therefore, the aim of this research was to develop the rapid identification of producing and non-producing strains of A. flavus based on the entire mass spectrum. To accomplish the main goal a different confirmatory MALDI-TOF MS and TLC procedures such as direct AFB₁ identification by scraping from TLC plates, A. flavus mycelium, nutrient media around A. flavus growth, and finally direct AFB₁ identification from infected wheat and barley grains had to be conducted. In this experiment, MALDI-TOF mass spectrometry with various modifications was the main supporting technology. All confirmatory methods confirmed the presence of AFB₁ in the samples of aflatoxin-producing strains of A. flavus and vice versa; AFB₁ was not detected in the case of non-producing strains. Entire mass spectra (from 2 to 20 kDa) of aflatoxin-producing and non-producing A. flavus strains were collected, statistically analyzed and clustered. An in-depth analysis of the obtained entire mass spectra showed differences between AFB₁-producing and non-producing strains of A. flavus. Statistical and cluster analysis divided AFB₁-producing and non-producing strains of A. flavus into two monasteries. The results indicate that it is possible to distinguish between AFB₁ producers and non-producers by comparing the entire mass spectra using MALDI-TOF MS. Finally, we demonstrated that if there are established local AFB₁-producing and non-producing strains of A. flavus, the entire mass spectrum database identification of aflatoxigenic A. flavus strains can be even faster and cheaper, without the need to identify the toxin itself.     

Formation of poly(ethylene glycol) inclusion complexes in aqueous solutions of mixed cyclodextrins

Even though the addition of modified cyclodextrins (modified CDs) accelerates the precipitation in aqueous solutions of poly(ethylene glycol) (PEG) and α-cyclodextrin (α-CD) the final amount of formed solid complex remains unchanged, with no significant presence of modified CDs detected by MALDI-TOF mass spectrometry. Thus unsuitability of kinetic turbidity measurements for determination of binding parameters was confirmed. On the other hand, theoretical calculations based on a model of a chain of freely accessible binding sites demonstrated that the results do not necessarily contradict the finding that individual modified CD molecules can thread onto PEG chains with the efficiency comparable to that of natural (unmodified) α-CD.     

Mechanical properties of crosslinked polyolefin-based materials

The effect of crosslinking on mechanical properties of various polyethylene-based materials is compared. In virgin polyethylene, higher strength results from formation of spatial network, especially at increased temperatures. On the other hand, decreased crystalline portion leads to lower Young's modulus values compared with the uncrosslinked polymer. Crosslinking of LDPE/PP blends leads to a dramatic increase in elongation at break and impact resistance. The reason is seen in an in situ formation of very efficient compatibilizers via co-crosslinking on the phase boundary. In LDPE filled with silica, the main effect consists in higher elongation at break and increased toughness, although the effect is lower than that in LDPE/PP blends. Increased resistance to the crack growth rate was demonstrated to be a reason for the observed behaviour. In LDPE filled with organic fillers, formation of direct covalent bonds on the interface and a significant increase in adhesion is suggested to be the reason for the enormous increase in Young's modulus and tensile strength observed.