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A V Eliseev

Publications and source records attributed to A V Eliseev.

11 recordsLinked to original sources

Chloroform-soluble schiff-base Zn(II) or Cd(II) complexes from a dynamic combinatorial library.

A dynamic combinatorial library of metal ion Schiff-base complexes have been studied for the extraction of Zn(II) or Cd(II) from aqueous solution into chloroform. Library components consist of different aminophenols and 2-pyridinecarboxaldehyde. Extraction of both Zn(II) and Cd(II) into chloroform was observed from aqueous solutions containing 0.0500 mM M(NO3)2, 0.100 M aminophenol, 0.100 M 2-pyridinecarboxaldehyde, 0.100 M NaCl, and 5.00 mM buffer at pH 8.5. Extraction was dependent on pH but not on counterions including Cl-, Br-, or NO3-. Studies showed that equilibrium was attained between the Schiff-base complexes across the two-phase chloroform-water system after 24 h of stirring. Analysis of the extracted species by use of 1H NMR spectroscopy and mass spectrometry as well as solubility studies on characterized complexes suggested that the major extracted species is the neutral bis-Schiff-base metal ion complex. In libraries containing mixtures of two different aminophenols and 2-pyridinecarboxaldehyde, an enhanced extent of extraction of Zn(II) into chloroform is observed. Studies suggest that a Zn(II) complex, which is likely the mixed Schiff-base complex, has superior extraction properties compared to simple libraries with a single aminophenol component. The structures of two bis-Schiff-base complexes of Zn(II) and one of Cd(II) have been determined by X-ray crystallography. The geometries of the two Zn(II) complexes, which differ only by a methyl substituent on the Schiff-base ligand, are markedly different, supporting the use of combinatorial methods in coordination chemistry. Zn(SB14)2 crystallized as the sesquihydrate (C24H18N4O2Zn.1.5 H2O) in the space group C2/c, with cell dimensions a = 23.219(15) A, b = 11.299(7) A, c = 16.822(11) A, beta = 102.91(5) degrees, V = 4302(5) A3, and Z = 8. Zn(SB15)2 crystallized as a 1:1 methanol solvate (C26H22N4O2Zn.CH3OH) in the space group P2(1)/c with cell dimensions a = 13.981(5) A, b = 7.978(3) A, c = 22.568(8) A, beta = 104.53(3) degrees, V = 2436.8(15) A3, and Z = 4. Cd(SB14)2 crystallized as a 1:1 ethanol solvate (C24H18N4O2Cd.CH3CH2OH) in the space group R3 with unit cell dimensions of a = 36.423(2) A, c = 9.2930(10) A, V = 10678(2) A3, and Z = 18.

Journal Article↗

Double-level "orthogonal" dynamic combinatorial libraries on transition metal template.

Dynamic combinatorial libraries are mixtures of compounds that exist in a dynamic equilibrium and can be driven to compositional self adaptation via selective binding of a specific assembly of certain components to a molecular target. We present here an extension of this initial concept to dynamic libraries that consists of two levels, the first formed by the coordination of terpyridine-based ligands to the transition metal template, and the second, by the imine formation with the aldehyde substituents on the terpyridine moieties. Dialdehyde 7 has been synthesized, converted into a variety of ligands, oxime ethers L(11)-L(33) and acyl hydrazones L(44)-L(77), and subsequently into corresponding cobalt complexes. A typical complex, Co(L(22))(2)(2+) is shown to engage in rapid exchange with a competing ligand L(11) and with another complex, Co(L(22))(2)(2+) in 30% acetonitrile/water at pH 7.0 and 25 degrees C. The exchange in the corresponding Co(III) complexes is shown to be much slower. Imine exchange in the acyl hydrazone complexes (L(44)-L(77)) is strongly controlled by pH and temperature. The two types of exchange, ligand and imine, can thus be used as independent equilibrium processes controlled by different types of external intervention, i.e., via oxidation/reduction of the metal template and/or change in the pH/temperature of the medium. The resulting double-level dynamic libraries are therefore named orthogonal, in similarity with the orthogonal protecting groups in organic synthesis. Sample libraries of this type have been synthesized and showed the complete expected set of components in electrospray ionization MS.

Aldehydes↗

Phosphatase-triggered guest release from a cyclodextrin complex.

[reaction: see text] A synthetic supramolecular system is described that models the effect of phosphoryl transfer in molecular recognition. beta-Cyclodextrin-6A-phosphate (pCD), which is shown to be a substrate of alkaline phosphatase, binds cationic aromatic guests, including anticancer agents, up to 100-fold better than native beta-CD. The above observations demonstrate that pCD is capable of releasing the guests from its cavity upon hydrolysis with the phosphatase, as also confirmed by monitoring the hydrolysis in the presence of a guest.

Alkaline Phosphatase↗

[Interhemispheric EEG coherence in men with abnormal sexual behavior].

Interhemispheric interactions were examined in individuals with abnormal sexual behaviour by means of method of evaluation of coherent EEG properties in symmetric points of two hemispheres in different levels of awakening and in elaboration of cognitive tests related with preferential activation of one of two hemispheres. It was determined that EEG of the individuals who had committed sexual deliquency and had the signs of paraphilia was characterized by diffuse elevation of the degree of interhemispheric coherence in alpha-activity in the state of both passive and active awakening and by its local elevation in theta-activity. The results obtained might testify to the disorders either in cortical-subcortical interactions and in the cortical processes and permitted to suppose the decrease of degree of functional hemispheric lateralization in persons with paraphilias.

Adult↗

[Comparative catamnestic studies of newly hospitalized patients with schizophrenia associated with alcoholism].

The authors analyze the destiny of 289 patients with associated schizophrenia and alcoholism. For the first time they were admitted to the psychiatric hospital in 1948-1951 (period I); 1959-1961 (period II); 1969-1971 (period III), and in 1979-1981 (period IV). The five-year catamnesis has demonstrated that schizophrenic patients abusing alcohol are often admitted to the hospital with paranoid symptomatology, retaining, however, a high enough level of social and labour adaptation, emotions, communicability for a long time. In the course of transition from the first to the fourth period, this group patients demonstrated an increase of the crime rate.

Adult↗

[Epidemiological characteristics associated with alcoholism in schizophrenics].

Schizophrenic patients residents of the city of Tomsk and Tomsk Province were studied at first admittance to the Tomsk Psychiatric Clinic in 1948 to 1951 (1st period), 1959 to 1961 (2nd period), 1969 to 1971 (3rd period), 1979 to 1981 (4th period). In each of the 4 periods cases were detected with apparent alcoholization preceding or coinciding with the onset of schizophrenic signs. Intensive indices (per 10,000 population) of the 1st hospitalization of patients with schizophrenic signs. Intensive indices (per 10,000 population) of the 1st hospitalization of patients with schizophrenia and alcoholism were significantly different for the 1st and 4th periods (0.026 and 0.51 respectively). Clinical analysis revealed the hallucinatory-paranoid symptoms to be most common for these patients.

Adult↗

Molecular recognition by natural macrocycles. I. d-tubocurarine as a host molecule for organic anions.

The binding of 8-anilino-1-naphthalenesulfonate and 15 anions of substituted benzoic, aliphatic dicarboxylic, and N-acetyl-alpha-amino acids to a macrocyclic alkaloid d-tubocurarine in aqueous solution has been studied by fluorometry, conductometry, and 1H NMR. The binding constants vary from ca. 50 to 3300 M-1 depending on the guest structure, charge and hydrophobicity. The results of fluorescence and NMR studies show that the host-guest complexation of the anions of aromatic acids involves the formation of a salt bridge between the quaternary nitrogen of the alkaloid and the anionic group of the guest as well as hydrophobic/Van der Waals interactions between the guest and host aromatic moieties. The binding of dianions of aliphatic dicarboxylic acids most probably is purely electrostatic. In general, d-tubocurarine possesses binding ability comparable to that of synthetic cyclophanes. It binds enantiospecifically anions of N-acetyl-alpha-amino acids and discriminates between positional isomers of anions of hydroxy and carboxy substituted benzoic acids.

Anions↗

[The current concepts of the mechanisms of the interaction of the CNS and the hypophyseal-adrenal system under the ordinary conditions of the activities of living].

Elucidation of mechanisms of hormonal influence on the CNS function is one of the primary concerns of neuroendocrinology. The study of the action of hormones on nervous centres is hampered by extraordinary complexity of morphological and functional organization of the CNS. Inquiry into the influence of hormones on separate structures of the hypothalamo-reticulo-limbic complex regulating emotional state and motivated behavior, allows to approach the task. Consideration is given to the present knowledge about effects of adrenal cortex steroids and peptides (delta-sleep, etc.) on functional state of various brain structures and their role in integrative processes in the central nervous system. Special attention is attributed to discussions of current understanding of the CNS-hypophysial/adrenal interactions in normal environments, and to formation of inter-central interactions with assistance of hormones and neuropeptides.

Activities of Daily Living↗

[A neurophysiological analysis of the mechanisms of neuroendocrine regulation in stress and under the antistress action of the delta sleep-inducing peptide].

In the article one can find analysis of modern theories about mechanisms of neuroendocrine regulation under stress, influence of steroid hormones and neuropeptides (delta-sleep-inducing peptide) on the functional state of hypothalamic reticular limbic structures of the brain. Special attention is paid to the analysis of mechanisms of creation of integrative processes under aggressive-defensive behaviour and roles of biologically active factors in the regulation of the processes.

Amygdala↗