Oxygen Atom from Carbonyl Group as an Important Binding Agent to the G-Quadruplex - Study Case of Flavonoids.

In the field of anticancer therapy study it is of great interest to find effective G-quadruplex ligands which may be of potential use in medical treatment or cancer prevention. Since among the compounds of natural origin, flavonoids have attracted notable attention because of their unique properties and promising therapeutic applications, an interesting question was to identify the flavonoid structural features that could provide effective binding properties toward G-quadruplex. By using electrospray ionization mass spectrometry, followed by the survival yield method, it has been shown that the flavonoid molecules which contain an available C4=O carbonyl group form more stable adducts with G-tetrads than the other ones. Molecular docking has shown that C4=O carbonyl group can be a source of hydrogen bonds and/or π-stacking interactions. Therefore, the flavonoid molecules which contain an available C4=O carbonyl group can be regarded as good binders of G-quadruplexes.

Comment on the "Does saponin in quinoa really embody the source of its bitterness?"

Saponins are considered the main source of the bitter taste of quinoa, however, it has not been confirmed by Song et al. (2024). These authors suggested that saponin extracts contribute to the umami taste, however, the stronger source of the bitter taste may be the flavonoids contained in the extracts. It is an interesting finding in view of the flavonoids role in the field of food sciences. The UPLC-MS results showed that besides saponins, also polyphenols were present in the analyzed samples. However, the presented results of UPLC-MS analysis should be substantially improved, mainly with respect to the reported accurate masses and retention times, as described in details in this comment.

New Ceramics Precursors Containing Si and Ge Atoms-Cubic Germasilsesquioxanes-Synthesis, Thermal Decomposition and Spectroscopic Analysis.

Compounds of the silsesquioxane type are attractive material precursors. High molecular weights and well-defined structures predestine them to create ceramics with a controlled composition at the molecular level. New molecular precursors of ceramic materials with the ratio of Si:Ge = 7:1 atoms were obtained. The influence of organic substituents on the thermal decomposition processes of germasilsesquioxanes was investigated. Some of the structures obtained are characterized by a high non-volatile residue after the thermal decomposition process. The introduction of the germanium atom to the structure of the silsesquioxane molecular cage reduces the thermal stability of the obtained structures.

High energy radiation - Induced cooperative reductive/oxidative mechanism of perfluorooctanoate anion (PFOA) decomposition in aqueous solution.

The mechanism of high-energy radiation induced degradation of perfluorooctanoate anion (PFOA, C7F15COO-) was investigated in aqueous solutions. Identification and quantification of transient species was performed by pulse radiolysis and of final products by gas and ion chromatography, electrochemical method using fluoride ion-selective electrode and ESI-MS after γ-radiolysis. Experimental data were further supported by kinetic simulations and quantum mechanical calculations. Radiation induced degradation of PFOA includes as a primary step one-electron reduction of PFOA by hydrated electrons (e-aq) resulting in formation of [C7F15COO-]●-. The rate constants of this reaction were found to be in the range 7.7 × 107-1.3 × 108 M-1s-1 for ionic strength of the solutions in the range 0.01-0.1 M and were independent of pH of the solutions. At pH > 11 [C7F15COO-]●- tends to defluorination whereas at lower pH undergoes protonation forming [C7F15COOH]•-. A sequence of consecutive reactions involving [C7F15COOH]•- leads to PFOA regeneration what explains a high radiation resistance of PFOA at moderately acidic solutions. A simultaneous presence of oxidizing transient species (●OH) in the irradiated system enhanced decomposition of (C7F14)·COO- as well as [C7F15COOH]•-. The key steps in this complex radical mechanism are the reactions of both these radical anions with ●OH leading to semi-stable products which further undergo consecutive thermal reactions. On the other hand, direct reactions of PFOA with ●OH and ●H were found to be relatively slow (7 × 103 and <4 × 107 M-1s-1, respectively) and do not play relevant role in PFOA degradation. Collected for the first time results, such as dependence of selected reaction rate constants and selected products radiation chemical yields on pH as well as finding of several semi-stable products, missing in previous studies, indicate incompleteness of published earlier reaction pathways of PFOA degradation. The presented overall mechanism explains experimental results and verifies previously suggested mechanisms found in the literature.

Laser Desorption/Ionization Mass Spectrometry as a Potential Tool for Evaluation of Hydroxylation Degree of Various Types of Titanium Dioxide Materials.

For many applications, TiO2 must have a unique surface structure responsible for its desirable physicochemical properties. Therefore the fast and easy methods of TiO2 surface characterization are of great interest. Heated TiO2 samples and dye-modified TiO2 samples were analyzed by laser desorption/ionization mass spectrometry. In the negative ion mode, two types of ions were detected, namely (TiO2)n- and (TiO2)nOH-. It has been established that the samples can be differentiated based on the relative ion abundances, especially with respect to the free hydroxyl group population. It indicates that laser desorption ionization mass spectrometry has the potential for the investigation of the surface properties of various TiO2 materials.

Ethoxylated Butoxyethanol-BADGE Adducts-New Potential Migrants from Epoxy Resin Can Coating Material.

The acetonitrile extracts of can-coating materials have been analyzed by using high-pressure liquid chromatography/electrospray ionization-mass spectrometry (HPLC/ESI-MS). On the basis of detected ions [M + H]+, [M + NH4]+, [M + Na]+ and product ions, the ethoxylated butoxyethanol-bisphenol A diglycidyl ether adducts were identified in two of the analyzed extracts. Although the oxyethylene unit-containing compounds are widely used for the production of different kinds of materials, the ethoxylated species have not been earlier detected in epoxy resin can-coatings.

Gas-phase generation of dinuclear Au(I)-Au(II) complexes by laser desorption ionization mass spectrometry.

Alkali metal chloroaurates(III) were analysed by laser desorption ionization mass spectrometry. Among a number of generated gas-phase ionic clusters, the unusual ions [MAu2Cl5]- (were M stands for Na, K, Rb, Cs) were detected. The spectra of metastable ions and quantum mechanics calculations show the presence of unprecedented Au(I)-Au(II) interactions in the clusters.

Differentiation of bisphenol F diglycidyl ether isomers and their derivatives by HPLC-MS and GC-MS-comment on the published data.

Positional isomers of bisphenol F diglycidyl ether (BFDGE) have been analyzed by high-pressure liquid chromatography-mass spectrometry and by gas chromatography-mass spectrometry (HPLC-MS, GC-MS). Positional isomers of BFDGE derivatives (BFDGEx2H2O, BFDGExH2OxHCl) have been analyzed by HPLC-MS. On the basis of the obtained fragmentation patterns, the elution order of the isomers has been unequivocally determined, in standard solutions and in the sample of liquid obtained after rinsing an empty mackerel fish can with acetonitrile. Under HPLC condition, para,para isomers are eluted first, then ortho,para isomers' elution follows, and ortho,ortho isomers are eluted last. Under GC condition, the reverse elution order has been obtained. For the first time, two ortho,para isomers of BFDGExH2OxHCl have been detected and their elution order has been determined. The obtained results are of key importance for determination of the isomer distribution of BFDGE and its derivatives in food samples.

Comment on the published data concerning the identification of biochanin A and prunetin by LC/ESI-MS.

Biochanin A is one of the most common phytoestrogens, occurring in high concentrations in soy and red clover, for instance, which shows a wide spectrum of biological activity. Prunetin is an isomer of biochanin A, and even though it is not very common, its structural relationship to the latter makes it interesting, regarding its biological activity. Nowadays, LC/ESI-MS methods are widely used for identification of natural compounds, including biochanin A and prunetin. However, we found that the published data concerning the identification of biochanin A and prunetin are sometimes disputable. Namely, the identification is based on the product ions which cannot be regarded as characteristic of biochanin A or prunetin. The reported retention times sometimes may be also disputable.

Differentiation of isomeric heptylamines by in-source collision-induced dissociation of [M + H]+ ions.

RATIONALE: 1,3-Dimethylamylamine (1,3-DMAA), 1,4-dimethylamylamine (1,4-DMAA) and 2-aminoheptane are isomeric heptylamines commonly used as stimulants. The fragmentations of their [M + H]+ ions (m/z 116) are almost identical and consist of the formation of a fragment ion C4 H9 + at m/z 57. It is interesting to check if analysis of electrospray ionization (ESI) mass spectra of these three amines enables their differentiation. In order to better understand the fragmentation of isomeric heptylamines, 1-, 3- and 4-aminoheptane were also included in the study. METHODS: ESI in-source collision-induced dissociation (CID) mass spectra were obtained with a Waters/Micromass ZQ2000 mass spectrometer (single quadrupole-type instrument) at a cone voltage of 12-34 V. The influence of three commonly used solvents on the fragmentation of [M + H]+ ions was tested, namely methanol, methanol/water (1/1) and acetonitrile/water (1/1). RESULTS: Only one quantitative difference was observed in the mass spectra of 1,3-DMAA, 1,4-DMAA and 2-aminoheptane, namely formation of a product ion at m/z 57 from the [M + H]+ ion of 1,3-DMAA is more efficient than the formation of this ion from [M + H]+ ions of 2-aminoheptane and 1,4-DMAA. In-source CID of 3- and 4-aminoheptane consists of (besides the formation of ion C4 H9 + ) the formation of a low-abundance, but clearly seen, fragment ion at m/z 114 (loss of H2 ). CONCLUSIONS: Differentiation of 1,3-DMAA from 1,4-DMAA and 2-aminoheptane seems to be possible by in-source CID of their [M + H]+ ions. However, comparison of the mass spectrum obtained for the analysed sample with that of a standard seems to be necessary. Only 3- and 4-aminoheptane may be easily differentiated from the other heptylamines by the presence of fragment ions at m/z 114.

Identification of a biliverdin geometric isomer by means of HPLC/ESI-MS and NMR spectroscopy. Differentiation of the isomers by using fragmentation "in-source".

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.

Influence of relative humidity on the properties of examined materials by means of inverse gas chromatography.

Inverse gas chromatography (IGC) at infinite dilution was applied to evaluate the surface properties of sorbents and the effect of different carrier gas humidity. They were stored in different environmental humidity - 29%, 40%, and 80%. The dispersive components of the surface free energy of the zeolites and perlite were determined by Schulz-Lavielle method, whereas their tendency to undergo specific interactions was estimated basing on the electron donor-acceptor approach presented by Flour and Papirer. Surface parameters were used to monitor the changes of the properties caused by the humidity of the storage environment as well as of RH of carrier gas. The increase of humidity of storage environment caused a decrease of sorbents surface activity and increase the ability to specific interaction.