Removal of <Superscript>90</Superscript>Sr from nitric acid solutions with sorbents based on di-<Emphasis Type="Italic">tert</Emphasis>-butyldicyclohexyl-18-crown-6

A series of impregnated sorbents based on di-tert-butyldicyclohexyl-18-crown-6 (DTBDCH18C6), various diluents (1-octanol, nitrobenzene, telomeric alcohol n3), and supports (Porolas-Т, LPS-500, hydrophobized silica gel) for removing tracer and weighable amounts of Sr ions from nitric acid solutions were prepared. The distribution coefficient of tracer amounts of ⁹⁰Sr on all the synthesized sorbents increases with an increase in the HNO₃ concentration in the range 1–7 M. The most pronounced increase in the sorption occurs with an increase in the HNO₃ concentration to 3 M. The maximal distribution coefficient of ⁹⁰Sr (K _d = 158 cm³ g^–1) is reached for the sorbent based on DTBDCH18C6 and 1-octanol in 7 M HNO₃. Experiments on sorption of weighable amounts of Sr²⁺ ions show that the static capacity of all the prepared sorbents for Sr in nitric acid solutions amounts to 4.3, 9.2, and 8.4 mg g^–1 for the sorbents based on 1-octanol, nitrobenzene, and telomeric alcohol n3, respectively. The synthesized sorbents are suitable for radioanalytical determination of Sr radionuclides in liquid radioactive waste and in radioactively contaminated natural objects.     

Magnesium octa[(4′-benzo-15-crown-5)oxy]phthalocyaninate in water micellar solutions of sodium deoxycholate

Aggregation of magnesium octa-[(4′-benzo-15-crown-5)oxy]phthalocyaninate (Mgcr₈Pc) in solutions of biocompatible anionic surfactant, sodium deoxycholate (SDC), was studied. It was shown using the electron absorption spectra that formation of Mgcr₈Pc monomers in micellar solutions of SDC is affected by both increased surfactant concentration and by changes in the ionic strength of solution after sodium chloride is added. The effect of the chemical structure of biocompatible anionic surfactant on monomerization of crown-containing phthalocyanines was identified; this fact opens new possibilities for using this family of compounds for fluorescent diagnosis and photodynamic therapy.     

Extraction of U(VI) and Th(IV) from nitric acid solutions with tetraaryl-substituted (<Emphasis Type="Italic">o</Emphasis>-phenyleneoxymethylene)diphosphine dioxides

Extraction of U(VI) and Th(IV) from HNO₃ solutions in the form of complexes with tetraarylsubstituted (o-phenyleneoxymethylene)diphosphine dioxides is studied. The effect of substituents at the P atoms in the extractant molecule on its extraction ability and selectivity is considered. The stoichiometry of the extractable complexes is determined. The possibility of U(VI) and Th(IV) preconcentration with a complexing sorbent prepared by noncovalent immobilization of tetra-p-tolyl-substituted (o-phenyleneoxymethylene)-diphosphine dioxide on a polymeric matrix is demonstrated.     

New tetra- and octa-functionalized phthalocyanines: Methods of synthesis and physicochemical properties in aqueous solutions and on solid substrates. Review

Methods of synthesis of a number of new functionalized phthalocyanines, as well as Mg^II, Co^II, Cu^II, Zn^II, and Ni^II phthalocyaninates, that involve benzo-15-crown-5-, phosphoryl-, or pyridine-containing fragments as peripheral substituents, which were developed and tested in IPCE RAS in the last five years, are reviewed and systematized. Methods of synthesis of the original phthalogens, which involve substituents of diverse composition, are considered. Results of an investigation of the aggregate states of the compounds in water and aqueous solutions of salts are generalized. The possibilities of electrostatic immobilization of the synthesized phthalocyanines in the form of self-assembled systems composed of ultrathin ionic layers on quartz and conductive glasses are considered. Based on the spectral, electrochemical, and electrocatalytic properties, the role of noncovalent interactions in the synthesis and operation of the composite systems is clarified.     

Solubilization and Photochemical Stability of Octa[(4′-Benzo-15-Crown-5)Oxy]-Phthalocyanines in Aqueous Micellar Solutions

Protection of Metals and Physical Chemistry of Surfaces - Methods of absorption and fluorescence spectroscopy and, in some cases, small angle X-ray scattering, are used to study solubilization and...     

Extraction of Lanthanides(III) with N,N′-Bis(Diphenylphosphinyl-Methylcarbonyl)Diaza-18-Crown-6 in the Presence of Ionic Liquids

The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from nitric acid solutions into an organic phase containing N,N′-bis(diphenylphosphinyl-methylcarbonyl)diaza-18-crown-6 and ionic liquid (IL) 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (BMImTf₂N) has been studied. The effect of HNO₃ concentration in the aqueous phase and that of the extractant and IL concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. A considerable synergistic effect was observed in the presence of IL in the organic phase containing a neutral organophosphorus ligand. This effect is connected with the hydrophobic nature of the IL anion. The partition of IL between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of lanthanide (III) ions in the extraction system. The potentialities of polymeric resin impregnated with compound I and BMImTf₂N for the preconcentration of lanthanides(III) from nitric acid solutions are demonstrated.     

Octa- and tetra-(benzo-15-crown-5)phthalocyanines in surfactant-containing solutions

The behavior of octa-(benzo-15-crown-5)phthalocyanine (H₂cr₈Pc), as well as cobalt octa- and tetra-(benzo-15-crown-5)phthalocyaninates (Cocr₈Pc and Cocr₄Pc), in aqueous solutions containing cationic or anionic surfactants, such as cetyl trimethylammonium bromide (CTAB), sodium carboxymethyl cellulose (Na-CMC), and sodium dodecyl sulfate (SDS), is studied using electronic spectroscopy. The presence of eight benzo-15-crown-5 ether fragments on the periphery of the phthalocyanine ring is shown to facilitate the dissolution of Pc in an aqueous environment. The interactions between CTAB and crown-containing Pc promotes the dissolution of H₂cr₈Pc; Cocr₈Pc; and, to a lesser degree, Cocr₄Pc, which is accompanied by the appearance of molecular aggregates, including heteronuclear cofacial dimers. The presence of a metal in the ring is not the necessary condition of the process. In microscopically heterogeneous medium, such as an aqueous SDS-containing solution, H₂cr₈Pc is present in monomeric form at SDS concentrations close to C _cr and in dimeric form at SDS content below C _cr. Under similar conditions (environment, surfactant), Cocr₄Pc can exist in monomeric form at SDS concentrations much high than C _cr. The effect of the size of cation on the form of the crown-containing Pc in an aqueous solution is illustrated by an example of H₂cr₈Pc. Na-CMC promotes the dissolution of Pc and enables one to produce K⁺/Mcr₈Pc-modified films from aqueous solutions.     

Solubilization of Crown-Substituted Magnesium Phthalocyaninates in Solutions of Salts of Bile Acids

Crown-containing Pc Mg[(B15C5O)₈Pc], Mg[(B15C5O)₄Pc], and Mg[(15C5)₄Pc] are in the monomolecular state in solutions of synthetic anionic surfactants: sodium dodecylsulfate and sodium dodecylbenzenesulfonate. In micellar solutions of bile-acid salts, molecular organization of crown-substituted Pc with different methods of introduction of crown groups into the macrocycle and their different numbers changes their state from predominantly monomeric for Mg[(B15C5O)₈Pc] in the presence of NaCl to the aggregated one in the case of Mg[(15C₅)₄Pc)]. Magnesium phthalocyaninate with annulated (15-crown-5)-fragments, Mg[(15C₅)₄Pc], is characterized by the highest sensitivity to the structure of the micelle-forming biocompatible surfactant.