Solid-phase reagent for molecular spectroscopic determination of heavy metal speciation in natural water

A solid-phase reagent based on 1-(4-adamantyl-2-thiasolylazo)-2-naphthol adsorbed onto silica gel was prepared for Co(II) recovery and preconcentration prior to its sorption-spectroscopic detection. The immobilized reagent was applied to the determination of free cobalt ions in natural water. The solid-phase reagent and chemiluminescent method coupled with membrane filtration, gel-permeation and ion-exchange chromatography were applied to the study of the speciation of iron and cobalt in water from the Dnieper reservoirs and lakes of Kyiv City; their predominant forms were complexes of Fe(III) and Co(II) with dissolved organic matter and fulvic acids play a main role in their complexation.     

Fluctuations of shapes of large areas under paths of random walks

Summary We discuss statistical properties of random walks conditioned by fixing a large area under their paths. We prove the functional central limit theorem (invariance principle) for these conditional distributions. The limiting Gaussian measure coincides with the conditional probability distribution of certain timenonhomogeneous Gaussian random process obtained by an integral transformation of the white noise. From the point of view of statistical mechanics the studied problem is the problem of describing the fluctuations of the phase boundary in the one-dimensional SOS-model.     

Synthesis,structural characterization and anticancer properties of p-cymene Ru(II) complexes with 2-(N-methyl-1H-1,2,4-triazol-3-yl)pyridines

Transition Metal Chemistry - The structures of new p-cymene Ru(II) complexes with 2-(1-methyl-1H-1,2,4-triazol-3-yl)pyridine and 2-(1-methyl-1H-1,2,4-triazol-5-yl)pyridine were established based on...     

Anticancer Aminoferrocene Derivatives Inducing Production of Mitochondrial Reactive Oxygen Species

Elevated levels of reactive oxygen species (ROS) and deficient mitochondria are two weak points of cancer cells. Their simultaneous targeting is a valid therapeutic strategy to design highly potent anticancer drugs. The remaining challenge is to limit the drug effects to cancer cells without affecting normal ones. We have previously developed three aminoferrocene (AF)-based derivatives, which are activated in the presence of elevated levels of ROS present in cancer cells with formation of electron-rich compounds able to generate ROS and reduce mitochondrial membrane potential (MMP). All of them exhibit important drawbacks including either low efficacy or high unspecific toxicity that prevents their application in vivo up to date. Herein we describe unusual AF-derivatives lacking these drawbacks. These compounds act via an alternative mechanism: they are chemically stable in the presence of ROS, generate mitochondrial ROS in cancer cells, but not normal cells and exhibit anticancer effect in vivo.     

Optimization of Pressurized Liquid Extraction of Lycopodiaceae Alkaloids Obtained from Two Lycopodium Species

Alkaloids of the Lycopodiaceae family are of great interest to researchers due to their numerous properties and wide applications in medicine. They play a very important role mainly due to their potent antioxidant, antidepressant effects and a reversible ability to inhibit acetylcholinesterase (AChE) enzyme activity. This property is of immense importance due to the growing problem of an increasing number of patients with neurodegenerative diseases in developed countries and a lack of effective and efficient treatment for them. Numerous studies have shown that Lycopodiaceae alkaloids are a rich source of AChE inhibitors. In the obtaining of new therapeutic phytochemicals from plant material, the extraction process and its efficiency is crucial. Therefore, the aim of this work was to optimize the conditions of modern PLE to obtain bioactive alkaloids from two Lycopodium species: L. clavatum L. and L. annotinum L. Five different solvents of different polarity were used for prepared plant extracts in order to compare the alkaloid content in and thereby effectiveness of the entire extraction. PLE parameters were used based on multiple studies conducted that gave the highest alkaloids recovery. Crude extracts were purified using solid-phase extraction (SPE) on Oasis HLB cartridge and examined by HPLC/ESI-QTOF–MS of the highly abundant alkaloids. To the best of our knowledge, this is the first time such high recoveries have been obtained for known Lycopodiaceae alkaloids. The best extraction results of alkaloid-lycopodine were detected in the dichloromethane extract from L. clavatum, where the yield exceeded 45%. The high recovery of annotinine above 40% presented in L. annotinum was noticed in dichloromethane and ethyl acetate extracts. Moreover, chromatograms were obtained with all isolated alkaloids and the best separation and quality of the bands in methanolic extracts. Interestingly, no alkaloid amounts were detected in cyclohexane extracts belonging to the non-polar solvent. These results could be helpful for understanding and optimizing the best conditions for isolating potent AChE inhibitors.     

Micromorphic Homogenisation of a Porous Medium: Application to Size Effects and Quasi-Brittle Damage

The classical theory of continuum mechanics requires that distances over which gradients occur are much larger than the length scales of the microstructure. This requirement is violated if deformation localizes due to material softening which is why the predictions of classical damage models feature certain unrealistic aspects. In the present contribution, a micromorphic model for quasi-brittle damage, derived through homogenisation, is employed in FEM simulations to overcome this problem. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterizing compact Clifford semigroups that embed into convolution and functor-semigroups

We study algebraic and topological properties of the convolution semigroup of probability measures on a topological groups and show that a compact Clifford topological semigroup S embeds into the convolution semigroup P(G) over some topological group G if and only if S embeds into the semigroup exp(G)\exp(G) of compact subsets of G if and only if S is an inverse semigroup and has zero-dimensional maximal semilattice. We also show that such a Clifford semigroup S embeds into the functor-semigroup F(G) over a suitable compact topological group G for each weakly normal monadic functor F in the category of compacta such that F(G) contains a G-invariant element (which is an analogue of the Haar measure on G).     

Graph-directed systems and self-similar measures on limit spaces of self-similar groups

Let G be a group and ?:H→G be a contracting homomorphism from a subgroup H<G of finite index. V. Nekrashevych (2005) [25] associated with the pair (G,?) the limit dynamical system (JG,s) and the limit G-space XG together with the covering _?g∈GT⋅g by the tile T. We develop the theory of self-similar measures m on these limit spaces. It is shown that (JG,s,m) is conjugated to the one-sided Bernoulli shift. Using sofic subshifts we prove that the tile T has integer measure and we give an algorithmic way to compute it. In addition we give an algorithm to find the measure of the intersection of tiles T∩(T⋅g) for g∈G. We present applications to the invariant measures for the rational functions on the Riemann sphere and to the evaluation of the Lebesgue measure of integral self-affine tiles.     

Fluctuations of the Phase Boundary in the 2D Ising Ferromagnet

We discuss some statistical properties of the phase boundary in the 2D low-temperature Ising ferromagnet in a box with the two-component boundary conditions. We prove the weak convergence in C[0,1] of measures describing the fluctuations of phase boundaries in the canonical ensemble of interfaces with fixed endpoints and area enclosed below them. The limiting Gaussian measure coincides with the conditional distribution of certain Gaussian process obtained by the integral transformation of the white noise. Received: 20 July 1996 / Accepted: 18 February 1997