Improving inclusion capabilities of permethylated cyclodextrins by appending a cap-like aromatic moiety

Steady-state and time-resolved fluorescence techniques have been employed in the study of the complexation of methyl 2-naphthalenecarboxylate (2MN), a fluorescent probe, with 2^I,3^I-O-(o-Xylylene)-per-O-Me-α-, -β-, and -γ-cyclodextrins (Xmα-, Xmβ-, and XmγCDs, respectively), which have also the capability of self-aggregate. The influence of the xylylene moiety was assessed by comparing the data of 2MN complexation by Xmα-, Xmβ-, and XmγCD with those obtained for their fully permethylated mα-, mβ-, and mγCD counterparts. The 2MN emission spectrum shows two overlapping electronic bands whose ratio of intensities, R, is very sensitive to the polarity of the surrounding medium. The stoichiometry, the complex formation constants and the ΔH⁰ and ΔS⁰ parameters upon inclusion were obtained from the variations in R and 〈τ〉 as a function of CD concentration and temperature. 2MN forms 1:1 stoichiometry complexes with all the CDs. Molecular Mechanics and Molecular Dynamics calculations were performed to simulate the complexation processes in the presence of water, determine their preferred structures, and ascertain the host–guest interactions at play.     

The influence of some triphenylantimony(V) catecholates and o‐amidophenolates on lipid peroxidation in vitro

A number of catecholates (complexes 1–3, 6) and o‐amidophenolates (complexes 4, 5) of triphenylantimony(V) was examined in the process of lipid peroxidation of liver homogenates and sperm of Russian sturgeon (Acipenser gueldenstaedti B.), and human red blood cells. It was shown that the influence of complexes 1–6 on lipid peroxidation process in model systems depends on the nature of redox‐active ligand and varies from weak anti‐ and pro‐oxidant (catecholates 1, 6) to pronounced antioxidant (catecholates and o‐amidophenolates 2–5). It was found that the complexes 2–5 are the more effective inhibitors of lipid peroxidation than standard antioxidant ionol. Copyright © 2012 John Wiley & Sons, Ltd.     

Conformational Dynamics of Sensory Rhodopsin II in Nanolipoprotein and Styrene–Maleic Acid Lipid Particles

Styrene–maleic acid lipid particles (SMALPs) provide stable water‐soluble nanocontainers for lipid‐encased membrane proteins. Possible effects of the SMA‐stabilized lipid environment on the interaction dynamics between functionally coupled membrane proteins remain to be elucidated. The photoreceptor sensory rhodopsin II, NpSRII and its cognate transducer, NpHtrII, of Natronomonas pharaonis form a transmembrane complex, NpSRII₂/NpHtrII₂ that plays a key role in negative phototaxis and provides a unique model system to study the light‐induced transfer of a conformational signal between two integral membrane proteins. Photon absorption induces transient structural changes in NpSRII comprising an outward movement of helix F that cause further conformational alterations in NpHtrII. We applied site‐directed spin labeling and time‐resolved optical and EPR spectroscopy to compare the conformational dynamics of NpSRII₂/NpHtrII₂ reconstituted in SMALPs with that of nanolipoprotein particle and liposome preparations. NpSRII and NpSRII₂/NpHtrII₂ show similar photocycles in liposomes and nanolipoprotein particles. An accelerated decay of the M photointermediate found for SMALPs can be explained by a high local proton concentration provided by the carboxylic groups of the SMA polymer. Light‐induced large‐scale conformational changes of NpSRII₂/NpHtrII₂ observed in liposomes and nanolipoprotein particles are affected in SMALPs, indicating restrictions of the protein's conformational freedom.     

A novel method for purification of biologically active C-terminal fragment of human recombinant anti-mullerian hormone

Anti-mullerian hormone (AMH) is one of the least studied members of transforming growth factor beta superfamily showing pro-apoptotic activity against cells positive for hormone type II receptor overexpressed by malignant cells in many cancer cases. Here, we propose an improved method for isolation of recombinant C-terminal AMH fragment (C-rAMH) to obtain homogeneous preparations of this protein with high biological activity. In contrast to our previously developed C-rAMH purification technology based on reversed-phase HPLC, the key stage of the new approach is hydrophobic interaction chromatography using Toyopearl Butyl-650S resin performed under more benign conditions. This modification of the previously developed method allowed highly purified C-rAMH to be obtained that is characterized by twice the specificity estimated as the ability to bind to the recombinant analog of AMH type II receptor and by significantly higher biological activity, that is, the ability to induce the death of target cells. Thus, we made the purification technology even more cost-effective and suitable for the production of drug forms based on C-rAMH.     

Simultaneous separation of actinides and technetium from large volumes of natural water for their determination

Journal of Radioanalytical and Nuclear Chemistry - Monitoring of radionuclide concentration in natural samples is important for assessing environmental safety. The low concentration of long-lived...     

Investigation of the resonance‐assisted hydrogen bond in model β‐diketones through localized molecular orbital analysis of the spin–spin coupling constants related to the O–H · · · O hydrogen bond

The resonance‐assisted hydrogen bond (HB) phenomenon has been studied theoretically by a localized molecular orbital (LMO) decomposition of the spin–spin coupling constants between atoms either involved or close to the O–H · · · O system of some β‐diketones and their saturated counterparts. The analysis, carried out at the level of the second‐order polarization propagator approximation, shows that the contributions in terms of LMO to the paramagnetic spin orbital and the spin dipolar Ramsey terms proof the importance of the delocalized π‐electron structure supporting the idea of the existence of the resonance‐assisted HB phenomenon phenomenon. The LMO contributions to the Fermi contact term indicate mainly the presence of the HB that may or not be linked to the π‐electrons. Copyright © 2014 John Wiley & Sons, Ltd.     

4-(Boc-amino)-1Н-1,2,3-triazole-5-carboxylic acids –convenient reagents for the synthesis of 1,4,6,7-tetrahydro[1,2,3]- triazolo[4,5-е][1,4]diazepine-5,8-diones

Chemistry of Heterocyclic Compounds - The corresponding ethyl 5-carbonylglycinates were synthesized by condensation of 4-(Boc-amino)-1,2,3-triazole-5-carboxylic acids with ethyl glycinate...     

A New Protonated form of Porphyrins in Solutions

The H-associate as a new protonated form of metalloporphyrins in strong acid media has been obtained and a qualitative reaction for its determination has been found; the properties and structure of a protonated form have been analyzed by spectral methods and quantum-chemical calculations.