Monatshefte Fur Chemie最新文献

Abstract: Citrus fruits are very popular food products. There are many species and varieties of them. There are also documented cases of some citrus fruits causing a severe allergic reaction. Some species of the citrus fruits, especially hybrid ones show a reduced allergenic effect due to the lack of seeds. There is a need for rapid methods for evaluation of citrus' botanical origin. During research, the headspace of three citrus fruits Citrus Aurantifolia, Citrus japonica, and Citrus × floridana was analysed using electronic nose based on ultrafast gas chromatography and gas chromatography with mass spectrometry. In the paper, two approaches were compared. The usefulness of an electronic nose to control the quality of hybrids was demonstrated. The results obtained during ultrafast gas chromatography analyses were subjected to statistical analysis. Four chemometric methods namely: principal component analysis (PCA), discriminant function analysis (DFA), soft independent modeling of class analogies (SIMCA), statistical quality control (SQC) were used to distinguish between limequat and its parent fruits. Electronic nose combined with chemometrics is a novel analytical tool for hybrid fruits' classification due to their botanical origin. It can supplement established techniques by providing results in a short time and at a low cost.

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Abstract: The quality of the fruit is affected by several main ingredients and the aroma plays a fundamental role during the selection of fruit by consumers. In the case where several fruit have similar aromas and only one of them has specific health properties, it is very important to find the differences in the volatile organic compounds (VOCs) composition to distinguish these samples. Such situations are often found for hybrid fruit. Sweetie is a hybrid of grapefruit and pummelo. Sweetie fruit is characterized by high antioxidant potential and a positive effect on human health. The aim of this study was to verify the unique volatile compositional traits of three species of citrus fruit. Proton transfer reaction Time-of-Flight mass spectrometry (PTR-TOF-MS) was utilized to obtain the mass-resolved fingerprints of VOCs. The chemical formula of these VOC masses was tentatively identified. Principal component analysis was performed to evaluate the differences between the groups.

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Abstract: Thermodynamic data of various crystalline solids are assessed from low temperature heat capacity measurements, i.e., from almost absolute zero to 300 K by means of semi-empirical models. Previous studies frequently present fit functions with a large amount of coefficients resulting in almost perfect agreement with experimental data. It is, however, pointed out in this work that special care is required to avoid overfitting. Apart from anomalies like phase transformations, it is likely that data from calorimetric measurements can be fitted by a relatively simple Debye-Einstein integral with sufficient precision. Thereby, reliable values for the heat capacities, standard enthalpies, and standard entropies at T = 298.15 K are obtained. Standard thermodynamic functions of various compounds strongly differing in the number of atoms in the formula unit can be derived from this fitting procedure and are compared to the results of previous fitting procedures. The residuals are of course larger when the Debye-Einstein integral is applied instead of using a high number of fit coefficients or connected splines, but the semi-empiric fit coefficients keep their meaning with respect to physics. It is suggested to use the Debye-Einstein integral fit as a standard method to describe heat capacities in the range between 0 and 300 K so that the derived thermodynamic functions are obtained on the same theory-related semi-empiric basis. Additional fitting is recommended when a precise description for data at ultra-low temperatures (0-20 K) is requested.

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Abstract: The series of new hydrazide derivatives were synthesized in reactions of N³-substituted amidrazones with cyclic anhydrides as potential anti-inflammatory and antibacterial agents. The compounds were characterized by ¹H-¹³C two-dimensional NMR techniques, which revealed the presence of two tautomeric forms in DMSO-d₆ solutions, while the molecular structure of one species was confirmed by single-crystal X-ray diffraction. The anti-inflammatory effects of hydrazides on peripheral blood mononuclear cells were experimentally evaluated. Three compounds showed antiproliferative activity comparable to ibuprofen. One derivative demonstrated strong reduction of lymphocyte proliferation stimulated by anti-CD3 antibody (by 90%) and PHA, as well as low cell toxicity. The obtained compounds exhibited relatively weak antibacterial activity; they were more effective against Gram-positive bacterial strains.

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Abstract: A new series of 2-alkylthio-N-(quinazolin-2-yl)benzenesulfonamide derivatives have been synthesized and evaluated in vitro for their antiproliferative activity by MTT assay against cancer cell lines HCT-116, MCF-7, and HeLa as well as the NCI-60 human tumor cell lines screen. In NCI screen, three compounds inhibited approximately 50% growth of RPMI-8226 and A549/ATCC cell lines. The mean of IC₅₀ calculated in MTT assays for three tested cell lines was about 45 μM for four compounds. The QSAR allowed finding statistically significant OPLS models for HeLa cell line. Metabolic stability in vitro studies indicated favorable and unfavorable structural elements. The good metabolic stability, with t_1/2 higher than 40 min, was observed for three derivatives, which together with their antiproliferative activity and good ADMET profile, makes them good leading structures for further research.

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Abstract: We have investigated the photo-induced reduction of Cu²⁺-Cu⁰ using benzil/triethylamine mixtures. The formation of elemental Cu is indicated by the appearance of its characteristic plasmon absorption peaks at 515 nm and 620 nm. Importantly, the nature of the counterion of the Cu²⁺ salt affects the reduction process. In the presence of Cl^-, the reduction proceeds faster than with SO₄^2-. Photo-induced electron transfer between excited benzil and triethylamine leads to the benzil radical anion, which acts as the reducing agent for Cu²⁺ and generates Cu⁰.

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Abstract: We report the chemical synthesis and characterization of the stable 5,15-bis(pentafluorophenyl)-10-(trimethylsilylethynyl)corrole which serves as a precursor for the subsequent in situ sila-Sonogashira-cross-coupling reaction and metalation with copper(II) acetate. Under ambient conditions and a common catalyst system the reaction with 1-iodopyrene occurred within five hours. Due to the direct conjugation of the 18π-electronic system of the corrole macrocycle over the alkynyl group to the pyrene moiety the optical transitions in the Soret (B-) band Q-band region are significantly altered. The copper corrole exhibited complex hyperfine and superhyperfine structure in the EPR spectrum. The assignment of the EPR spectrum reveals the existence of an axial [CuII-cor^∙+] species.

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Abstract: The measurements of double-layer differential capacitance, zero charge potential, and surface tension at that potential allowed us to examine the adsorption properties of adenine on the mercury surface from the neat buffer solution, i.e., the acetate buffer at pH 5 and pH 6. The systems obtained at such pH values were close to physiological fluids in their characteristics. The adsorption energy and interaction constants were determined using Frumkin isotherm and virial isotherm. It was shown that the adenine molecule is adsorbed on the mercury electrode with its negative pole against the electrode surface. Using the cyclic voltammetry technique and measuring Faraday impedance, an increasing effect of adenine on the kinetics of zinc ion electroreduction was found. In both buffer solutions, the neutral adenine molecules can form on the surface of the working electrode, an unstable active complex with depolarizer ions, facilitating electron exchange.

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Abstract: A hydrazone Schiff base ligand was synthesized by the condensation of 3-formyl-4-hydroxycoumarin and oxalyldihydrazide in the molar ratio 2:1. The Schiff base ligand acts as a mono-, bi-, tri- or even tetradentate ligand with metal cations in the molar ratios 1:1 or 2:1 (M:L) to yield either mono- or binuclear complexes as keto or enol isomers, where M = Co(II), Ni(II), Cu(II), VO(IV), and Fe(III). The ligand and its metal complexes were characterized by elemental analyses, IR, ¹H NMR, mass, and UV-Vis spectroscopy. Furthermore, the magnetic moments were calculated from the measured electric conductivities of the complexes. According to the received data, the dihydrazone ligand contains one or two units of ONO domains and can bind to the metal ions via the azomethine nitrogen, the carbonyl oxygen atoms, and/or the phenolic oxygen atoms. Electronic spectra and the magnetic moments of all complexes show that the complexes' geometries are either octahedral, tetrahedral, square planar, or square pyramidal. Cyclic voltammograms of the mononuclear Co(II) and Ni(II) complexes show quasi-reversible peaks. Tests against two pathogenic bacteria as Gram-positive and Gram-negative bacteria for both, the Schiff base ligand and its metal complexes were carried out. In addition, also one kind of fungi was tested. The synthesized complexes demonstrate mild antibacterial and antifungal activities against these organisms.

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