Unexpected Colloidal Stability of Fullerenes in Dimethyl Sulfoxide and Related Systems.

It is known that fullerenes are poorly soluble in polar solvents, but readily form colloidal solutions in such media. These solutions are typically solvophobic (hydrophobic when prepared in water), that is, thermodynamically unstable colloidal systems with negatively charged particles. To understand the stability factors of a colloidal system, the thresholds for coagulation of a sol or suspension by electrolytes are of key importance. While hydrosols and aqueous suspensions coagulate at concentrations of 1:1 inorganic electrolytes about 0.1-0.2 M, in acetonitrile and methanol, the corresponding critical concentrations of coagulation are ca. 3 orders of magnitude lower. Given the wide variety of properties of organic solvents, it seemed important to complete the picture to study solvents with more basic properties. This is all the more reasonable since electrophilic fullerenes are in fact Lewis acids. Our choice was dimethyl sulfoxide, DMSO, and related solvent systems. The colloidal solutions of fullerenes C60 and C70 in DMSO and N,N-dimethyl formamide, DMF, are unexpectedly easy to prepare by mechanical methods, and addition of water leads to formation of relatively stable organo-hydrosols. UV-visible spectra and dynamic light scattering were used to characterize the solutions of C60 and C70 in DMSO, benzene-DMSO, acetonitrile-DMSO, and benzene-acetonitrile-DMSO systems, as well as in DMF. Our present study demonstrated that, in contrast to organosols in methanol and acetonitrile, colloids of C70 and C60 fullerenes in DMSO and DMF are surprisingly as stable with respect to electrolytes as the corresponding hydrosols are. Such high stability is caused by the non-DLVO interactions, or, in terms proposed by Churaev and Derjaguin, by the so-called structural effect. These results shed light on the nature of the solvation of colloidal fullerene particles in solvents of various chemical natures.

Young «oil site¼ of the Uzon Caldera as a habitat for unique microbial life.

BACKGROUND: The Uzon Caldera is one of the places on our planet with unique geological, ecological, and microbiological characteristics. Uzon oil is the youngest on Earth. Uzon oil has unique composition, with low proportion of heavy fractions and relatively high content of saturated hydrocarbons. Microbial communities of the «oil site¼ have a diverse composition and live at high temperatures (up to 97 °C), significant oscillations of Eh and pH, and high content of sulfur, sulfides, arsenic, antimony, and mercury in water and rocks. RESULTS: The study analyzed the composition, structure and unique genetics characteristics of the microbial communities of the oil site, analyzed the metabolic pathways in the communities. Metabolic pathways of hydrocarbon degradation by microorganisms have been found. The study found statistically significant relationships between geochemical parameters, taxonomic composition and the completeness of metabolic pathways. It was demonstrated that geochemical parameters determine the structure and metabolic potential of microbial communities. CONCLUSIONS: There were statistically significant relationships between geochemical parameters, taxonomic composition, and the completeness of metabolic pathways. It was demonstrated that geochemical parameters define the structure and metabolic potential of microbial communities. Metabolic pathways of hydrocarbon oxidation was found to prevail in the studied communities, which corroborates the hypothesis on abiogenic synthesis of Uzon hydrothermal petroleum.

Aminofluoresceins Versus Fluorescein: Ascertained New Unusual Features of Tautomerism and Dissociation of Hydroxyxanthene Dyes in Solution.

Within the course of this spectroscopic research, we revealed novel features of the protolytic behavior, which extend the knowledge of the chemistry of xanthene dyes and rationalize the utilization of these compounds. In addition to the well-known tautomerism of the molecular form, H2R, of fluorescein dyes, new aspects of tautomeric transformation of anions are disclosed. First, for the dyes bearing the substituents in the phthalic acid residue, 4'- and 5'-aminofluoresceins and 4'-fluorescein isothiocyanate, the monoanion HR- exists in non-hydrogen-bond donor solvents not only as a tautomer with the ionized carboxylic and nonionized OH group but also as a "phenolate" ion with a nonionized COOH group. Such state of HR- ions is typical for dyes bearing halogen atoms or NO2 groups in the xanthene moiety but was not observed until now in the case of substitution in the phthalic residue. Second, the possibility of the existence of the HR- species in DMSO in the form of colorless lactone is deduced for the 5'-aminofluorescein using the visible and infrared spectra. This results in a dramatic difference in medium effects. For instance, whereas for fluorescein in DMSO, the inversion of the stepwise ionization constants takes place and the Ka1/Ka2 value equals 0.08, the same ratio for 5'-aminofluorescein is as high as ∼800. In addition, the pKa values of sulfonefluorescein, erythrosin, methyl ether of fluorescein, and phenol red were obtained to verify the acidity scale in DMSO and to support the detailed scheme of protolytic equilibria of fluorescein dyes.

Aminofluoresceins Versus Fluorescein: Peculiarity of Fluorescence.

In this article, we examined the fluorescent properties of 4'- and 5'-aminofluorescein, unsubstituted fluorescein, and its 4'-nitro derivative in a set of solvent systems. Fluorescence lifetimes, quantum yields, time-resolved fluorescence spectra, and quantum chemical calculations allowed clarifying the reasons of the emitting properties in this dye series. In water, the dianions R2- of aminofluoresceins are practically nonfluorescent; in alcohols, the quantum yields are low. In dimethylsulfoxide (DMSO), acetonitrile, and other non-hydrogen bond donor solvents, the bright fluorescence of R2- ions is quenched either on adding small amounts of water which hydrate the carboxylate group or under conditions of protonation of this group (COO- → COOH). The last observation is possible owing to the peculiarities of the tautomerism of the 5'-aminofluorescein monoanion, HR-, which exists in DMSO as an equilibrium mixture of a colorless lactone and colored "phenolate" tautomer with an ionized xanthene moiety and unionized carboxylic group. In contrast, the R2- anion of 4'-nitrofluorescein demonstrates spectral behavior different from that of the amino derivatives. It practically does not emit in aprotic solvents; however, in alcohols or water media, its quantum yield increases to some extent. Such changing spectral properties are explained in terms of the excited-state interfragmental charge transfer.

Mechanisms of soil macrofauna community sustainability in temperate rice-growing systems.

Rice growing requires highly destructive and highly invasive field management negatively affecting soil biota and its functions. We aimed to compare taxonomic and functional trait compositions of soil macrofauna at different stages of rice cropping cycles in the three temperate rice-growing regions in Russia. Samples were collected in 2016 at four different biotopes in each region: flooded rice paddies; upland crops planted one year after flooded rice; rice paddy bunds; and relatively undisturbed seminatural control grasslands. Collected soil macrofauna were allocated to different traits according to their feeding preferences, vertical distribution, mobility and flood tolerance. The lowest macrofaunal abundance across all regions was observed in rice paddies. Cultivation of upland crops after paddy flooding consistently decreased the abundance of resident macrofauna, but not that of mobile soil macrofauna. In the upland crops, the abundance of belowground and mobile belowground macrofauna was significantly higher than that in control grasslands. The abundance of aboveground phytophages was significantly lower in the upland crops than in control sites. Flood-associated taxa showed low colonization ability after the paddies were drained. In contrast, representatives of other traits recorded in flooded fields increased their abundance at the next stage of crop rotation, demonstrating high resilience within an entire rice-growing system, including bunds. This finding indicates a high potential of seminatural grasslands and especially bunds as sources of rapid restoration of soil macrofauna functional diversity in rice-growing agroecosystems, thus maintaining the sustainability of soil food webs in the rice paddies.

Towards better understanding of C60 organosols.

It is of common knowledge that fullerenes form colloids in polar solvents. However, the coagulation via electrolytes and the origin of the negative charge of species are still unexplored. Using a 'radical scavenger' and electrospray ionization spectroscopy (ESI), we proved the formation of ion-radical C60˙(-) and its (probable) transformation into C60(2-) or (C60)2(2-). The coagulation of C60 organosols by NaClO4 and other perchlorates and nitrates in acetonitrile and its mixture with benzene obeys the Schulze-Hardy rule. At higher Ca(ClO4)2 and La(ClO4)3 concentrations, instead of coagulation, stable re-charged colloidal particles appeared, up to a zeta-potential of +(20-42) mV, as compared with -(33-35) mV of the initial organosols. The influence of both HClO4 and CF3SO3H was similar. This phenomenon is attributed to poor solvation of inorganic cations in cationo- and protophobic acetonitrile, which was proven using [2.2.2] cryptand. Further increasing the concentration of Ca(ClO4)2 led again to coagulation, thus demonstrating a novel type of 'coagulation zones'.

Ionization and tautomerism of methyl fluorescein and related dyes.

The protolytic equilibrium of methyl ether of fluorescein is studied in water, aqueous ethanol, and in other solvents. The constants of the two-step dissociation are determined by spectrophotometry. In water, the fractions of the zwitterionic, quinonoid, and lactonic tautomes are correspondingly 11%, 6%, and 83%, as deduced from the UV-visible spectra. Corresponding study of the ionization of the methyl ether ester of fluorescein, fluorescein ethyl ester, and sulfonefluorescein allows testing the correction of the attribution of the microscopic dissociation constants of methoxy fluorescein. The results of nuclear magnetic resonance and infrared spectroscopy, as well as the X-ray analysis confirm the predomination of the lactonic structure of the molecular species in solid state and in DMSO. Contrary to it, the spectroscopic studies in both hydrogen-donor bond (HDB) and non-HBD solvents confirm that the presence of lactonic monoanion is atypical for the dye under study and, with high probability, also for the mother compound fluorescein.

Geobacillus icigianus sp. nov., a thermophilic bacterium isolated from a hot spring.

A Gram-reaction-positive, motile, thermophilic spore-forming strain, G1w1(T), was isolated from a hot spring of the Valley of Geysers, Kamchatka (Russia). Based on data from the present polyphasic taxonomic study, including phylogenetic analysis of 16S rRNA and spo0A gene sequences, the strain is considered to represent a novel species of the genus Geobacillus, for which the name Geobacillus icigianus sp. nov. is proposed. The type strain is G1w1(T) ( = VKM B-2853(T) = DSM 28325(T)).