S. N. Dmitrieva

Oxidative stress-induced autophagy in plants: the role of mitochondria.

The strictly regulated removal of oxidized structures is a universal stress response of eukaryotic cells that targets damaged or toxic components for vacuolar or lysosomal degradation. Autophagy stands at the crossroad between cell survival and death. It promotes survival by degrading proteins and organelles damaged during oxidative stress, but it is also activated as a part of death programs, when the damage cannot be overcome. Evidence is accumulating that the cellular sites of ROS production and signaling may be primary targets of autophagy. Therefore, autophagosomal targeting of mitochondria (mitophagy) is of particular importance. Mitophagy is a selective process that can specifically target dysfunctional mitochondria, but also mitophagy may play a role in controlling the number and quality of mitochondria during stress. Here we review the mechanisms of both non-specific autophagy and mitochondrial targeting in plants, drawing analogies and emphasizing differences with yeast and mammalian systems.

Macrocyclic Complexes of Palladium(II) with Benzothiacrown Ethers: Synthesis, Characterization, and Structure of cis and trans Isomers

A series of palladium(II) complexes with nitro- and formylbenzothiacrown-ether derivatives was synthesized. The spatial structure of the complexes was studied by NMR, X-ray diffraction analysis, and quantum chemical calculations (density functional theory). The cavity size and the ligand denticity were found to be crucial factors determining the geometric configuration of the thiacrown-ether complexes. Palladium(II) complexes with benzodithia-12(18)-crown-4(6) ethers were demonstrated to have a cis-configured S(2)PdY(2) fragment (Y = Cl, OAc). In the case of Pd(II) and benzodithia-21-crown-7 ethers, only complexes with a trans configuration of the S(2)PdY(2) fragment form. In the case of Pd(II) and nitrobenzomonothia-15-crown-5 ether, only 2(ligand):1(Pd) complex with trans configuration of the core fragment forms.

Synthesis, structure, and characterization of chromo(fluoro)ionophores with cation-triggered emission based on N-methylaza-crown-ether styryl dyes.

Novel 2-benzothiazole-, 4-pyridine-, and 2- and 4-quinoline-based styryl dyes containing an N-methylbenzoaza-15(18)-crown-5(6)-ether moiety were synthesized. A detailed electronic spectroscopy study revealed high performance of these compounds as optical molecular sensors for alkali and alkaline-earth metal cations. They were shown to considerably surpass analogous chromoionophores based on N-phenylaza-crown ethers regarding both the ionochromism and the cation-binding ability. In addition, they act as fluorescent sensors for the metal cations by demonstrating cation-triggered emission. Upon complexation with Ba(2+), the fluorescence enhancement factor reaches 61. The structural features of dyes and their metal complexes were studied by NMR spectroscopy and X-ray diffraction. The high degree of macrocycle preorganization was found to be one of the factors determining the high cation-binding ability of the sensor molecules based on N-methylbenzoaza-crown ethers.

Supramolecular Dimerization and [2 + 2] Photocycloaddition Reactions of Crown Ether Styryl Dyes Containing a Tethered Ammonium Group: Structure–Property Relationships

Molecular self-assembly is an effective strategy for controlling the [2 + 2] photocycloaddition reaction of olefins. The geometrical properties of supramolecular assemblies are proven to have a critical effect on the efficiency and selectivity of this photoreaction both in the solid state and in solution, but the role of other factors remains poorly understood. Convenient supramolecular systems to study the structure-property relationships are pseudocyclic dimers spontaneously formed by styryl dyes containing a crown ether moiety and a remote ammonium group. New dyes of this type were synthesized to investigate the effects of structural and electronic factors on the quantitative characteristics of supramolecular dimerization and [2 + 2] photocycloaddition in solution. Variable structural parameters for the styryl dyes were the size and structure of macrocyclic moiety, the nature of heteroaromatic residue, and the length of the ammonioalkyl group attached to this residue. Quantum chemical calculations of the pseudocyclic dimers were performed in order to interpret the relationships between the structure of the ammonium dyes and the efficiency of the supramolecular photoreaction. One of the dimeric complexes was obtained in the crystalline state and studied by X-ray diffraction. The results obtained demonstrate that the photocycloaddition in the pseudocyclic dimers can be dramatically affected by the electronic structure of the styryl moieties, as dependent on the electron-donating ability of the substituents on the benzene ring, and by the conformational flexibility of the pseudocycle, which determines the mobility of the olefinic bonds. The significance of electronic factors is highlighted by the fact that the photocycloaddition quantum yield in geometrically similar dimeric structures varies from ≤10(-4) to 0.38. The latter value is unusually high for olefins in solution.

Building up of Macroring in the New Synthesis of Azacrown Ethers. Structure and Complex Formation of Nitrobenzoazacrown Ethers

A cyclization of azapodand haloderivatives into nitrobenzoazacrown ethers under treatment with various bases and in their absence was investigated. The nitrobenzoazacrown ethers obtained and their complexes with metal cations were studied by X-ray diffraction method and by 1H NMR titration. In nitrobenzoaza-15-crown-5 a capability to complex Ca2+ cation was found that significantly exceeded similar ability of nitrobenzocrown ether with the same size of the macroring.

Host-guest complexes of nitro-substituted N-alkylbenzoaza-18-crowns-6

A number of N-alkyl(nitrobenzo)aza-18-crowns-6 in which the nitrogen atom in the macroring is conjugated with the benzene ring were synthesized, and their complexing power was compared with that of model nitro derivatives of benzo-18-crown-6 and N-phenylaza-18-crown-6 using 1H NMR spectroscopy and DFT/PBE quantum-chemical calculations. The stability constants of the complexes formed by crown ethers with NH4/+, EtNH3/+, Li+, Na+, and K+ in CD3CN were determined by 1H NMR titration. The complexing power of N-alkyl(nitrobenzo)aza-18-crowns-6 toward metal and ammonium cation was considerably higher than that of N-(4-nitrophenyl)aza-18-crown-6 and N-alkyl(nitrobenzo)aza-15-crown-5 and was comparable or higher than that of nitrobenzo-18-crown-6.

Complexation of Donor-Acceptor Substituted Aza-Crowns with Alkali and Alkaline Earth Metal Cations. Charge Transfer and Recoordination in Excited State

Complexation between two aza-15-crown-5 ethers bearing electron donor and acceptor fragments and alkali and alkaline earth perchlorates has been studied using absorption, steady-state fluorescence and femtosecond transient absorption spectroscopy. The spectral-luminescent parameters, the stability and dissociation constants of the complexes were calculated. The intramolecular charge transfer reaction takes place both in the excited state of the crowns and their complexes 1:1; the latter is subjected to photorecoordination resulting in a weakening or a complete disruption of coordination bond between nitrogen atom and metal cation, disposed within a cavity of the crown. The compounds investigated can be viewed as novel optical molecular sensors for alkali and alkaline-earth metal cations. The photoejection of a metal cation into the bulk was not observed.

The extraction of noble metals by macrocyclic compounds: II. The extraction by crown compounds

Our review on the extraction of noble metals by macrocyclic compounds, i.e., by crown ethers containing donor atoms O, S, and N, continues. The literary data for the period from 1984 to 2008 are summarized. It is noted that no systematic investigations have been carried out until now. On the whole, the information is incomplete. The solution compositions are far from technological ones, and the chemical state of extracted ions in aqueous solutions is not taken into account. It is emphasized that there is only desultory information on the reextraction in the literature. The problem of selectivity for noble metal extraction by crown compounds is discussed.

Synthesis of nitro and amino derivatives of benzothiacrown ethers

The condensation reaction of 1,2-bis(2-haloethoxy)-4-nitrobenzenes with acyclic α,ω-(oxa)alkanedithiols in the presence of alkali metal carbonates produced a series of nitrobenzodithiacrown ethers with macrocycles of different size. The structures of three ethers were established by X-ray diffraction. A new method was developed for the synthesis of nitrobenzomonothia-15-crown-5 ether. Nitro derivatives of benzodithiacrown ethers were tested as reagents for extraction of palladium(II), platinum(IV), and rhodium(III) from hydrochloric acid solutions. Extraction of PdII salts was found to be highly selective compared to that of PtIV and RhIII salts. Benzodithia-15-crown-5 ether is the most efficient extractant for palladium(II). Reduction of nitrobenzothiacrown ethers with hydrazine hydrate in the presence of a platinum catalyst afforded their amino derivatives.

New methodology for the synthesis of benzoazacrown ethers by transformation of the macrocycle of benzocrown ethers

The review summarizes the results of studies aimed at constructing new promising macrocyclic ligands that bind metal and ammonium ions. A new approach to the synthesis of formyl and nitro derivatives of 1-aza-2,3-benzocrown ethers possessing considerable synthetic potential is described. The review presents a radically new methodology for the synthesis of such benzoazacrown ethers based on stepwise transformations of the macrocycle of readily accessible benzocrown ethers. The main structural factors and necessary conditions enabling stepwise transformations of the macrocycle of crown ethers into azacrown ethers were revealed. For the first time, the ability of N-methylbenzoazacrown ethers to form complexes was found, which is much superior to that of widely used N-phenylazacrown ethers and benzocrown ethers with the same size of the macrocycle.