Kinetics of self-condensation of acetone over heterogeneous Ba(OH)2 and Sr(OH)2 catalysts

Catalytic performance of Ba(OH)₂ and Sr(OH)₂ in self-condensation of acetone was examined in the temperature range from 273 to 303 K. A kinetic model of second order with respect to acetone was used for interpretation of the results obtained for the diacetone alcohol formation.This revised version was published online in December 2005 with corrections to the Cover Date.     

In Vitro Inhibitory Effects of Viburnum opulus Bark and Flower Extracts on Digestion of Potato Starch and Carbohydrate Hydrolases Activity

One of the effective treatments for diabetes is to reduce and delay the absorption of glucose by inhibition of α-amylase and α-glucosidase in the digestive tract. Currently, there is a great interest in natural inhibitors from various part of plants. In the present study, the phenolic compounds composition of V. opulus bark and flower, and their inhibitory effects on in vitro potato starch digestion as well as on α-amylase and α-glucosidase, have been studied. Bark and flower phenolic extracts reduced the amount of glucose released from potato starch during tree-stage simulated digestion, with IC₅₀ value equal to 87.77 µg/mL and 148.87 µg/mL, respectively. Phenolic bark extract showed 34.9% and 38.4% more potent inhibitory activity against α-amylase and α-glucosidase, respectively, but the activity of plant extracts was lower than that of acarbose. Chlorogenic acid (27.26% of total phenolics) and (+)-catechin (30.48% of total phenolics) were the most prominent phenolics in the flower and bark extracts, respectively. Procyanidins may be responsible for the strongest V. opulus bark inhibitory activity against α-amylase, while (+)-catechin relative to α-glucosidase. This preliminary study provides the basis of further examination of the suitability of V. opulus bark compounds as components of nutraceuticals and functional foods with antidiabetic activity.     

Cornelian Cherry (Cornus mas L.) Extracts Exert Cytotoxicity in Two Selected Melanoma Cell Lines—A Factorial Analysis of Time-Dependent Alterations in Values Obtained with SRB and MTT Assays

Despite the fact that phytochemicals of Cornaceae species have long been discussed as possible auxiliary agents in contemporary treatment, the insights on their properties remain relatively scarce. This study focuses on Cornus mas L. (Cornelian cherry), the extracts of which are reported to exert a pleiotropic effect shown in both in vivo and in vitro studies. This study aimed to explore the cytotoxic effect of extracts from fruits of red (Cornus mas L. ‘Podolski’) and yellow (Cornus mas L. ‘Yantarnyi’ and ‘Flava’) Cornelian cherries on two melanoma cell lines (A375 and MeWo). The extracts were characterized in the context of the concentration of bioactive compounds of antioxidative properties. Cytotoxicity was investigated with the use of the following two assays: SRB and MTT. An additional, alternative protocol for the SRB assay was used in this study so as to account for possible bias. Cytotoxicity was assessed as a difference in the whole time series of cell viability, instead of analyzing differences in raw values (often found in the literature). Both extracts from Cornus mas L. induced cytotoxicity in both A375 and MeWo cell lines, although the response of these cells was different. Moreover, based on this study, there is no evidence for claiming a different magnitude of cytotoxicity between these two extracts.     

Morphology and molecular organisation of liquid-crystalline perylene-3,4,9,10-tetra-(n-hexylester) deposited on a solid substrate

Liquid-crystalline perylene-3,4,9,10-tetra-(n-hexylester) forms characteristic dendritic or flower-like structures at room temperature when it is deposited on a hydrophilic glass substrate using the zone-casting technique. It was found that such unique structures were not possible to be created simply by recrystallisation of this dye from a liquid-crystalline columnar phase. On the basis of the observations using a confocal microscope and the study of wide angle X-ray scattering (WAXS) as well as the analysis of the absorption and fluorescence spectra, some conclusions, concerning the molecular organisation in the dendritic structure, are drawn. Based on the research, one can assume that the dendrites are formed by columnar molecular aggregates with the column axes parallel to the substrate. Such an organisation of the molecules can be interesting from the point of view of organic electronics.     

Heptametallic,Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

New complexes with six ferrocenyl (Fc) groups connected to Zn^II or Cd^II tris(2,2′‐bipyridyl) cores are described. A thorough characterisation of their BPh₄^? salts includes two single‐crystal X‐ray structures, highly unusual for such species with multiple, extended substituents. Intense, visible d(Fe^II)→π* metal‐to‐ligand charge‐transfer (MLCT) bands accompany the π→π* intraligand charge‐transfer absorptions in the near UV region. Each complex shows a single, fully reversible Fe^III/II wave when probed electrochemically. Molecular quadratic nonlinear optical (NLO) responses are determined by using hyper‐Rayleigh scattering and Stark spectroscopy. The latter gives static first hyperpolarisabilities β₀ reaching as high as approximately 10^?27 esu and generally increasing with π‐conjugation extension. Z‐scan cubic NLO measurements reveal high two‐photon absorption cross‐sections σ₂ of up to 5400 GM in one case. DFT calculations reproduce the π‐conjugation dependence of β₀, and TD‐DFT predicts three transitions close in energy contributing to the MLCT bands. The lowest energy transition has octupolar character, whereas the other two are degenerate and dipolar in nature.     

Influence of Extraction Solvent on the Phenolic Profile and Bioactivity of Two Achillea Species

The phenolic composition, as well as the antioxidant and antimicrobial activities of two poorly investigated Achillea species, Achillea lingulata Waldst. and the endemic Achillea abrotanoides Vis., were studied. To obtain a more detailed phytochemical profile, four solvents with different polarities were used for the preparation of the plant extracts whose phenolic composition was analyzed using UHPLC-MS/MS (ultra-high performance liquid chromatography-tandem mass spectrometry). The results indicate that both of the investigated Achillea species are very rich in both phenolic acids and flavonoids, but that their profiles differ significantly. Chloroform extracts from both species had the highest yields and were the most chemically versatile. The majority of the examined extracts showed antimicrobial activity, while ethanolic extracts from both species were potent against all tested microorganisms. Furthermore, the antioxidant activity of the extracts was evaluated. It was found that the ethanolic extracts possessed the strongest antioxidant activities, although these extracts did not contain the highest amounts of detected phenolic compounds. In addition, several representatives of phenolic compounds were also assayed for these biological activities. Results suggest that ethanol is a sufficient solvent for the isolation of biologically active compounds from both Achillea species. Moreover, it was shown that the flavonoids naringenin and morin are mainly responsible for these antimicrobial activities, while caffeic, salicylic, chlorogenic, p-coumaric, p-hydroxybenzoic, and rosmarinic acid are responsible for the antioxidant activities of the Achillea extracts.     

Copper and Zinc as Potential Biomarkers of Mood Disorders and Pandemic Syndrome

The diagnosis of affective disorders has been the subject of constant research by clinicians from all over the world for many years. Making an appropriate diagnosis among patients suffering from mood disorders is sometimes problematic due to the personality-changing nature of patients and the similarity in the clinical picture of episodes in affective disorders. For this reason, there is a need to develop rapid and effective methods of determining biological markers that differentiate these diseases. The research was carried out with blood taken from 15 patients and 15 volunteers. The analysis of biological material for trace concentrations of zinc and copper was carried out with the use of ultrasensitive triple-quadrupole inductively coupled plasma mass spectrometry (TQ ICP-MS). The obtained results prove that the concentration of copper in the test group was lower than in the control group. For the zinc concentrations, the inverse relationship was observed. The group of patients was characterized by a higher concentration of this element than the group of healthy volunteers. Summarizing the obtained results and comparing them with the results of studies by other authors, it was found that zinc and copper may be potential biomarkers of affective disorders and pandemic syndrome.     

The Current Directions of Searching for Antiparasitic Drugs

Parasitic diseases are still a huge problem for mankind. They are becoming the main cause of chronic diseases in the world. Migration of the population, pollution of the natural environment, and climate changes cause the rapid spread of diseases. Additionally, a growing resistance of parasites to drugs is observed. Many research groups are looking for effective antiparasitic drugs with low side effects. In this work, we present the current trends in the search for antiparasitic drugs. We report known drugs used in other disease entities with proven antiparasitic activity and research on new chemical structures that may be potential drugs in parasitic diseases. The described investigations of antiparasitic compounds can be helpful for further drug development.     

Fine Tuning of Chlorophyll Spectra by Protein‐Induced Ring Deformation

The ability to tune the light‐absorption properties of chlorophylls by their protein environment is the key to the robustness and high efficiency of photosynthetic light‐harvesting proteins. Unfortunately, the intricacy of the natural complexes makes it very difficult to identify and isolate specific protein–pigment interactions that underlie the spectral‐tuning mechanisms. Herein we identify and demonstrate the tuning mechanism of chlorophyll spectra in type II water‐soluble chlorophyll binding proteins from Brassicaceae (WSCPs). By comparing the molecular structures of two natural WSCPs we correlate a shift in the chlorophyll red absorption band with deformation of its tetrapyrrole macrocycle that is induced by changing the position of a nearby tryptophan residue. We show by a set of reciprocal point mutations that this change accounts for up to 2/3 of the observed spectral shift between the two natural variants.     

Synthesis of oligosaccharides corresponding to Vibrio cholerae O139 polysaccharide structures containing dideoxy sugars and a cyclic phosphate

A spacer-equipped tetrasaccharide, p-aminocyclohexylethyl alpha-l-Colp-(1-->2)-beta-d-Galp-(1-->3)-[alpha-l-Colp-(1-->4)]-beta-D-GlcpNAc, containing a 4,6-cyclic phosphate in the galactose residue, has been synthesised. The structure corresponds to a part of the repeating unit of the capsular (and lipo-) polysaccharide of the endemic bacteria Vibrio cholerae type O139 synonym Bengal. The synthetic strategy allows continuous syntheses of the complete O139 hexasaccharide repeating unit as well as of the structurally related repeating unit of serotype O22. Starting from ethyl 2-azido-4,6-O-benzylidene-2-deoxy-1-thio-beta-D-glucopyranoside, a thioglycoside tetrasaccharide donor block was constructed through two orthogonal glycosylations with glycosyl bromide donors. First, a properly protected galactose moiety was introduced using silver triflate as promoter and subsequently the two colitose residues, carrying electron-withdrawing protecting groups for stability reasons, under halide-assisted conditions. The tetrasaccharide block was then linked to the spacer in a NIS-TMSOTf-promoted coupling. Transformation of the azido group into an acetamido group using H2S followed by removal of temporary protecting acetyl groups gave a 4',6'-diol, which was next phosphorylated with methyl dichlorophosphate and deprotected to yield the 4,6-cyclic phosphate tetrasaccharide target structure.