Single-Bubble Sonoluminescence of Colloidal Suspensions of Europium(II) Salt Nanoparticles.

Colloidal suspensions of EuCl2, EuBr2, and EuSO4 nanoparticles (<50 nm) in dodecane and EuSO4 in 70% H2SO4 were synthesized. Moving single-bubble sonoluminescence (m-SBSL) spectra were obtained for a bubble performing radial oscillations in these suspensions and translational motions at the antinode of a standing ultrasonic wave with a frequency of about 27 kHz. In these spectra (at a spectral resolution of 10 nm), the sono-excited luminescence bands of the Eu2+ ion were detected for the first time, coinciding in the shape and position of the maxima (404, 413, and 377 nm for EuCl2, EuBr2, and EuSO4, respectively) with the bands of Eu2+ located in a crystalline environment in the photoluminescence spectra of nanoparticles of europium salts in suspensions. The detected sonoluminescence of Eu2+ arises due to the injection of nanoparticles into a bubble deformed during motion and excitation of a lanthanide ion at the periphery of the bubble volume during collisions of nanoparticles with charged particles, mainly electrons, coming from a hot nonequilibrium plasma, which periodically arises during bubble compression. Evidence for the excitation of the europium ion in the bubble is the absence of its luminescence bands in the SBSL spectra of the translationally immobile bubble, in which nanoparticles are unlikely to enter. The nanoparticles that enter the bubble also undergo decomposition in the plasma into fragments, in particular, with the formation of Eu, Eu+ in the excited state. The atomic lines of these fragments were recorded for the first time in the m-SBSL spectrum with a resolution of 1 nm for a suspension of EuSO4 nanoparticles in 70% H2SO4. The resulting m-SBSL spectra will add to the library of characteristic spectra of objects of sonoluminescent spectroscopic analysis and will make it possible to identify and determine the content of Eu or Eu2+ in these objects.

Application of Sonotriboluminescence to Determine Arene Molecules in Hydrocarbons.

The sonotriboluminescence of suspensions of terbium(III) and europium(III) sulfates in decane without and in the presence of benzene, toluene and p-xylene was studied. The choice of crystals of these lanthanides is due to the fact that they have intense luminescence during mechanical action, and also do not dissolve in hydrocarbon solvents. During ultrasonic exposure to suspensions in pure alkanes, bands of Ln3+ ions and N2 in the UV region are recorded in the luminescence spectrum. When aromatic hydrocarbon molecules are added, bands of benzene, toluene and p-xylene molecules, coinciding with their photoluminescence spectra, are recorded in the sonotriboluminescence spectra in the UV region. The high sensitivity of the luminescence of suspensions to arene additives made it possible to obtain the dependence of the characteristic fluorescence of arene molecules in the sonotriboluminescence spectra on their concentration in suspensions. The limits of detection of benzene, toluene and p-xylene in the composition of this suspension were established. The lower limits of detection from the sonotriboluminescence spectra for xylene, toluene and benzene are 0.1, 3 and 50 ppmv, respectively. Fluorescence bands of these molecules were also recorded in the sonotriboluminescence spectra of suspensions in commercial dodecane and heptane with additives of commercial gasoline (up to 1%). The results obtained can be used for luminescent detection of aromatic compounds in saturated hydrocarbons.

Assessment of soil development during rapid urbanization using the carbon and nitrogen stable isotope composition.

The proposed paper is devoted to the analysis of the urbanization effects on soil cover using physico-chemical parameters and stable isotopic signatures on the example of Tyumen. The study methods included analysis of C and N elemental and isotope (δ13C and δ15N) composition, analysis of soil physico-chemical properties and major oxides content. The results of the survey have shown that soil properties within the city limits vary significantly depending on both anthropogenic activities and geomorphological context. The urban soils of Tyumen differ from very strongly acidic with pH values down to 4.8 to strongly alkaline with pH values reaching 8.9, and from sandy loams to silty loams by texture. The study results have shown that δ13C values varied from - 33.86 to - 25.14‰ and δ15N values varied in range, especially, from - 1.66 to 13.38‰. The range of these signatures was smaller than those reported for urbanized areas in Europe and USA. The δ13C values in our case were more related to the geological and landscape parameters of the study area, rather than with urban disturbances and development of urban ecosystems. At the same time, the δ15N values probably indicate zones with increased atmospheric N deposition in the case of Tyumen. The application δ13C and δ15N is a promising tool for analysis of urban soil disturbances and functions, though the regional context should be taken into account.

Pollen data from bottom sediments of a tundra lake in the Yerkuta River basin on the Yamal Peninsula.

This article extends the findings of our previous research "Preliminary reconstruction of climate changes and vegetation cover inferred from pollen study of the arctic lake bottom sediments from the southwestern part of the Yamal Peninsula" (G.R. Nigamatzyanova, N.M. Nigmatullin, B.I. Gareev, O.N. Tumanov, L.A. Frolova, 21st International Multidisciplinary Scientific GeoConference SGEM. 4 (2021) 415-421. https://doi.org/10.5593/sgem2021/4.1/s19.53) [1]. The Late Holocene vegetation history of the southern part of the Yamal Peninsula was reconstructed using the pollen data obtained from bottom sediments of the tundra lake K1 (68°15.320' N, 69°07.675' E) near the Yerkuta research station in the Yerkuta River basin. A 30-cm-long sediment core was drilled during the expedition to the lake in 2014. A total of 15 samples were taken at 1-cm intervals for palynological analysis. To extract pollen grains, prior chemical treatment of the samples by the standard methods. The palynological dataset was exported in Excel sheets, one listing the raw pollen counts and the other containing the pollen percentages determined with respect to the total pollen counts for all taxa. The palynodiagram illustrating the variations in pollen and spore percentages with depth is given. These palynological records yield insight into the vegetation dynamics on the Yamal Peninsula in response to the climate forcing and may be of practical importance in regional syntheses of the vegetation history in the region.

Single-Bubble Sonoluminescence of Colloidal Suspensions as a New Technique for Sonoluminescent Spectroscopic Analysis.

This is a brief research review on the new method of development for element luminescence determination, namely, sonoluminescent spectroscopy. The advantages and disadvantages of the technique of multibubble sonoluminescence (MBSL) in solutions used to apply this method are discussed. It has been shown that the use of a new technique moving single-bubble sonoluminescence (m-SBSL) in colloidal suspensions of nanoparticles (<50 nm) containing the elements analyzed seems preferable for this purpose. This makes it possible to determine elements not only at lower concentrations than when using MBSL in solutions but also to find elements that are unavailable for determination through previous techniques. Thus, this new technique expands the range of elements that can be determined using sonoluminescent spectroscopy. The article provides a detailed description of the standard procedure for the preparation and recording of m-SBSL in colloidal suspensions, as well as examples of characteristic spectra of some elements obtained and recorded for the first time according to this new technique (Al, K, Mn, Cd, Pt, Ni, and Ti), including those not previously found using the MBSL in solutions (Al, Cd, Pt, Ni, and Ti). An example of the analytical line at 396 nm in the Al spectrum obtained through this new technique on the basis of an AlCl3 initial aqueous solution, the region of the linear dependence of the intensity on the AlCl3 concentration was registered, and the lower limit of the spectroscopic determination of the Al content in this solution was estimated as 8.3·10-3 M. Using the analysis of the obtained Cd spectrum as an example, we carried out a spectroscopic measurement of the electronic temperature achieved at m-SBSL in bubble plasma at the moment of greatest compression of a bubble with light emission during its acoustic oscillations in dodecane, Te = 7900 ± 500 K.

Dithiophosphate-Induced Redox Conversions of Reduced and Oxidized Glutathione.

Phosphorus species are potent modulators of physicochemical and bioactive properties of peptide compounds. O,O-diorganyl dithiophoshoric acids (DTP) form bioactive salts with nitrogen-containing biomolecules; however, their potential as a peptide modifier is poorly known. We synthesized amphiphilic ammonium salts of O,O-dimenthyl DTP with glutathione, a vital tripeptide with antioxidant, protective and regulatory functions. DTP moiety imparted radical scavenging activity to oxidized glutathione (GSSG), modulated the activity of reduced glutathione (GSH) and profoundly improved adsorption and electrooxidation of both glutathione salts on graphene oxide modified electrode. According to NMR spectroscopy and GC-MS, the dithiophosphates persisted against immediate dissociation in an aqueous solution accompanied by hydrolysis of DTP moiety into phosphoric acid, menthol and hydrogen sulfide as well as in situ thiol-disulfide conversions in peptide moieties due to the oxidation of GSH and reduction of GSSG. The thiol content available in dissolved GSH dithiophosphate was more stable during air oxidation compared with free GSH. GSH and the dithiophosphates, unlike DTP, caused a thiol-dependent reduction of MTS tetrazolium salt. The results for the first time suggest O,O-dimenthyl DTP as a redox modifier for glutathione, which releases hydrogen sulfide and induces biorelevant redox conversions of thiol/disulfide groups.

New sonochemiluminescence involving solvated electron in Ce(III)/Ce(IV) solutions.

The moving single-bubble sonoluminescence of Ce3+ in water and ethylene glycol solutions of CeCl3 and (NH4)2Ce(NO3)6 was studied. As found, a significant part of intensity of the luminescence (100% with cerium concentration less than 10-4 M) is due to the sonochemiluminescence. A key reaction of sonochemiluminescence is the Ce4+ reduction by a solvated (or hydrated in water) electron: Ce4+ + es (eaq) â†’ *Ce3+. Solvated electrons are formed in a solution via electrons ejection from a low-temperature plasma periodically generated in deformable moving bubble at acoustic vibrations. Reactions of heterolytic dissociation of solvents make up the source of electrons in the plasma. In aqueous CeCl3 solutions, the Ce4+ ion is formed at the oxidation of Ce3+ by OH radical. The latter species originates from homolytic dissociation of water in the plasma of the bubble, also penetrating from the moving bubble into the solution. The sonochemiluminescence in cerium trichloride solutions are quenched by the Br- (acceptor of OH) and H+ ions (acceptor of eaq). In water and ethylene glycol solutions of (NH4)2Ce(NO3)6, the sonochemiluminescence also quenched by the H+ ion. The sonochemiluminescence in CeCl3 solutions is registered at [Ce3+] ≥ 10-5 M. Then the sonochemiluminescence intensity increases with the cerium ion concentration and reaches the saturation plateau at 10-2 M. It was shown that sonophotoluminescence (re-emission of light of bubble plasma emitters by cerium ions) also contributes to the luminescence of Ce3+ in solutions with [Ce3+] ≥ 10-4 M. If the cerium concentration is more than 10-2 M, a third source contributes to luminescence, viz., the collisional excitation of Ce3+ ions penetrating into the moving bubble.

Diet and life history reduce interspecific and intraspecific competition among three sympatric Arctic cephalopods.

Trophic niche and diet comparisons among closely sympatric marine species are important to understand complex food webs, particularly in regions most affected by climate change. Using stable isotope analyses, all ontogenetic stages of three sympatric species of Arctic cephalopods (genus Rossia) were studied to assess inter- and intraspecific competition with niche and diet overlap and partitioning in West Greenland and the Barents Sea. Seven traits related to resource and habitat utilization were identified in Rossia: no trait was shared by all three species. High boreal R. megaptera and Arctic endemic R. moelleri shared three traits with each other, while both R. megaptera and R. moelleri shared only two unique traits each with widespread boreal-Arctic R. palpebrosa. Thus all traits formed fully uncrossing pattern with each species having unique strategy of resource and habitat utilization. Predicted climate changes in the Arctic would have an impact on competition among Rossia with one potential 'winner' (R. megaptera in the Barents Sea) but no potential 'losers'.

Supraamphiphilic Systems Based on Metallosurfactant and Calix[4]resorcinol: Self-Assembly and Drug Delivery Potential.

Metallic amphiphiles are used as building blocks in the construction of nanoscale superstructures, where the hydrophobic effects induce the self-assembly of the nanoparticles of interest. However, the influence of synergizing multiple chemical interactions on an effective design of these structures mostly remains an open question. In this regard, supraamphiphilic systems based on flexible surfactant molecules and rigid macrocycles are being actively developed, but there are few works on the interaction between metallosurfactants and macrocycles. In the present work, the self-assembly and biological properties of a metallosurfactant with calixarene were studied for the first time. The metallosurfactant, a complex between lanthanum nitrate and two 4-aza-1-hexadecylazoniabicyclo[2.2.2]octane bromide units, and calix[4]resorcinol containing sulfonate groups on the upper rim were used to form a novel supraamphiphilic composition. The system formed was studied using a variety of physicochemical methods, including spectrophotometry, NMR, XRF, and dynamic and electrophoretic light scattering. It was found that the most optimal tetraanionic calix[4]resorcinol to dicationic metallosurfactant molar ratio, leading to mixed aggregation upon ion pair complexation, is 2:3. The mixed aggregates formed in the pentamolar concentration range were able to encapsulate hydrophilic substrates, including the anticancer drug cisplatin, the pure form of which is more cytotoxic toward healthy cells than toward diseased cells. Interestingly, the drug loaded into the macrocycle-metallosurfactant particles was less cytotoxic to a healthy Chang liver cell line and more cytotoxic to tumor M-HeLa cells. This selectivity depends on the amount of cisplatin added. The more drug is added to the macrocycle-metallosurfactant composition, the greater the biological activity against cancer cells. Taking into account that the appearance of resistance of cancer cells to drugs, especially to cisplatin, is one of the most important problems in treatment, the results of this work envisage the potential application of a mixed macrocycle-metallosurfactant system for the design of therapeutic cisplatin compositions.

Counterion Concentration Profiles at the Graphene Oxide/Water Interface.

Despite enormous interest toward graphene oxide (GO) from the research community, surprisingly, little is known about its solutions. In particular, the questions related to the structure of the GO/liquid interface have not been yet properly addressed. In this report, we use a simple but efficient experimental approach to investigate the distribution of the four metal cations Na+, Cs+, Ni2+, and Gd3+ at the GO/water interface. We demonstrate that the concentration of the cations decreases exponentially with the distance from the GO surface. Such distribution for colloid systems was theoretically predicted and commonly accepted for a century but, to the best of our knowledge, has been never proved experimentally. We further demonstrate that the shape of the counterion distribution profiles depends on the pH of solution and on the fine chemical structure of GO. In particular, organic sulfates and vinylogous acids that are ionizable at different pH levels are responsible for the difference in the shapes of the concentration profiles. Unlike classical colloid systems, the diffuse layer in the GO solutions is rather broad (30-55 nm), and the concentration gradient is registered even at distances of >55 nm from the GO surface, which is typically considered as the bulk solution. The latter observation is explained by the immobilized character of the GO flakes in the nematic phase, impeding the flow of liquid and the migration of hydrated metal cations. This helps to establish and maintain the long-range concentration gradient in the space between the two parallel neighboring GO flakes. Based on the new findings and on the previously reported data, we formulate some basic principles of GO solutions.

Transition metal-doped cryogels as bioactive materials for wound healing applications.

Transition metals (TM) are essential microelements with various biological functions demanded in tissue regeneration applications. Little is known about therapeutic potential of TM within soft hydrogel biomaterials. The soluble divalent TM, such as Zn, Cu, Mn and Co, were stably incorporated into gelatin network during cryogelation. TM content in the resultant cryogels varied from 0.1 × 103 to 11.8 × 103 ppm, depending on the TM type and concentration in the reaction solution. Zn component was uniformly complexed with the gelatin scaffold according to elemental imaging, increasing the swelling of polymer walls and the G'/G″ values and also decreasing the size of cryogel macro-pores. Zn-doped cryogels supported migration of human skin fibroblasts (HSF); only upper Zn content of 11.8 × 103 ppm in the scaffold caused c.a. 50% inhibition of cell growth. Zn ions solubilized in culture medium were more active towards HSF (IC50 ≈ 0.3 mM). Treatment of splinted full-skin excisional wounds in rats with the Zn-doped and non-doped cryogels showed that Zn considerably promoted passing inflammatory/proliferation phases of healing process, inducing more intense dermis formation and structuration. The results show the feasibility of development of cryogel based formulations with different TM and support high phase-specific ability of the Zn-gelatin cryogels to repair acute wounds.