Search

Orbital Battleship, published in 2016 in this "Journal," is a hands-on competitive exercise which has been shown to be an efficient tool to reinforce the knowledge of the atomic structure. We decided to give it a more futuristic look and are presenting VR Orbital Battleship, a completely immersive collaborative experience which, in contrast to the pen-and-paper version, guarantees that students are unable to fill in an erroneous electron configuration thanks to the special control elements of the game. Hence, they are motivated to do their best in order to apply Madelung's rule and Hund's rule right to be able to start the game. The game design makes full use of what the immersive virtual reality has to offer: the headset completely immerses the player in the process of the game, resulting in less distraction compared to the classic version. Furthermore, the game's design is user-friendly and intuitive, and thus, it adds to the overall immersive experience. The game is recommended for use as an interactive addition to school and university classes that are dedicated to the atomic structure. VR Orbital Battleship is available for free worldwide in both a portable mobile platform (Oculus Go) and a PC version by downloading the game (see the Supporting Information of this paper).

Objectives. To study the possibility of using nitrogen-containing organosilicon compounds in the creation of heat-resistant and fireresistant casting compositions to seal high-voltage high-frequency equipment.Methods. Nitrogen-containing organosilicon compounds were obtained using the N-siloxycarbonylation, formylation, and silylation methods. The methods used in the work were infrared spectroscopy, elemental analysis, viscometry, and differential scanning calorimetry. The mechanical and dielectric properties of the samples were determined.Results. Previously unknown substances and compounds containing nitrogen-containing organosilicon products as components of the curing composition were obtained. Their physicomechanical and operational properties were examined, including the possibility of using them as filling heat-resistant and fire-resistant compositions for sealing high-voltage and high-frequency equipment.Conclusions. It was shown that nitrogen-containing organosilicon compounds — 3-(diethylamino)-2-[(triethoxysilyl)oxy]propyl-2-methacrylate and triethoxysilyl ester of γ-triethoxysilylpropyl-carbamic acid — can be used as part of a curing system together with bromine-containing fillers, in order to obtain compounds used for filling high-voltage high-frequency transformers, throttle valves, and other electronic equipment elements with non-combustible properties and increased heat resistance.

A new method for assessing the quality of fibre coating based on a combination of fluorescence microscopy and electron paramagnetic resonance is presented in this work. An influence of the carboxymethylcellulose/polyvinylamine gel preparation method on the mobility of the spin label was established. The mobility of the spin label changes from 3.5 ns in the case of a polyvinylamine solution to 12.8 ns in the case of a cross-linked gel on the surface of the glass fibre. A qualitative relationship was found between the mobility of the spin label in the gel applied to the glass fibre and the rate of spreading of crude oil over its surface. This method can be used to make membranes for the separation of water-in-oil emulsions.

Currently, increasing the efficiency of glioblastoma treatment is still an unsolved problem. In this study, a combination of promising approaches was proposed: (i) an application of nanotechnology approach to create a new terpene-modified lipid system (7% w/w), using soybean L-α-phosphatidylcholine, N-carbonyl-methoxypolyethylene glycol-2000)-1,2-distearoyl-sn-glycero-3-phosphoethanolamine for delivery of the chemotherapy drug, temozolomide (TMZ, 1 mg/mL); (ii) use of TMZ associated with natural compounds—terpenes (1% w/w) abietic acid and Abies sibirica Ledeb. resin (A. sibirica). Different concentrations and combinations of terpene–lipid systems were employed to treat human cancer cell lines T 98G (glioblastoma), M-Hela (carcinoma of the cervix) and human liver cell lines (Chang liver). The terpene–lipid systems appeared to be unilamellar and of spherical shape under transmission electron microscopy (TEM). The creation of a TMZ-loaded terpene–lipid nanosystem was about 100 nm in diameter with a negative surface charge found by dynamic light scattering. The 74% encapsulation efficiency allowed the release time of TMZ to be prolonged. The modification by terpenes of TMZ-loaded lipid nanoparticles improved by four times the cytotoxicity against human cancer T 98G cells and decreased the cytotoxicity against human normal liver cells. Terpene-modified delivery lipid systems are of potential interest as a combination therapy.

The creation of mitochondria-targeted vector systems is a new tool for the treatment of socially significant diseases. Phosphonium groups provide targeted delivery of drugs through biological barriers to organelles. For this purpose, a new class of alkyl(diethylAmino)(Phenyl) Phosphonium halides (APPs) containing one, two, or three diethylamino groups was obtained by the reaction of alkyl iodides (bromides) with (diethylamino)(phenyl)phosphines under mild conditions (20 °C) and high yields (93–98%). The structure of APP was established by NMR and XRD. A high in vitro cytotoxicity of APPs against M-HeLa, HuTu 80, PC3, DU-145, PANC-1, and MCF-7 lines was found. The selectivity index is in the range of 0.06–4.0 μM (SI 17-277) for the most active APPs. The effect of APPs on cancer cells is characterized by hyperproduction of ROS and depolarization of the mitochondrial membrane. APPs induce apoptosis, proceeding along the mitochondrial pathway. Incorporation of APPs into lipid systems (liposomes and solid lipid nanoparticles) improves cytotoxicity toward tumor cells and decrease toxicity against normal cell lines. The IC50s of lipid systems are lower than for the reference drug DOX, with a high SI (30–56) toward MCF-7 and DU-145. APPs exhibit high selective activity against Gram-positive bacteria S. aureus 209P and B. segeus 8035, including methicillin-resistant S. aureus (MRSA-1, MRSA-2), comparable to the activity of the fluoroquinolone antibiotic norfloxacin. A moderate in vivo toxicity in CD-1 mice was established for the lead APP.

Materials with high optical constants are of paramount importance for efficient light manipulation in nanophotonics applications. Recent advances in materials science have revealed that van der Waals (vdW) materials have large optical responses owing to strong in-plane covalent bonding and weak out-of-plane vdW interactions. However, the optical constants of vdW materials depend on numerous factors, e.g., synthesis and transfer method. Here, we demonstrate that in a broad spectral range (290–3300 nm) the refractive index n and the extinction coefficient k of Bi2Se3 are almost independent of synthesis technology, with only a ~10% difference in n and k between synthesis approaches, unlike other vdW materials, such as MoS2, which has a ~60% difference between synthesis approaches. As a practical demonstration, we showed, using the examples of biosensors and therapeutic nanoparticles, that this slight difference in optical constants results in reproducible efficiency in Bi2Se3-based photonic devices.

Natural and synthetic hydrogel scaffolds containing bioactive components are increasingly used in solving various tissue engineering problems. The encapsulation of DNA-encoding osteogenic growth factors with transfecting agents (e.g., polyplexes) into such scaffold structures is one of the promising approaches to delivering the corresponding genes to the area of the bone defect to be replaced, providing the prolonged expression of the required proteins. Herein, a comparative assessment of both in vitro and in vivo osteogenic properties of 3D printed sodium alginate (SA) hydrogel scaffolds impregnated with model EGFP and therapeutic BMP-2 plasmids was demonstrated for the first time. The expression levels of mesenchymal stem cell (MSC) osteogenic differentiation markers Runx2, Alpl, and Bglap were evaluated by real-time PCR. Osteogenesis in vivo was studied on a model of a critical-sized cranial defect in Wistar rats using micro-CT and histomorphology. The incorporation of polyplexes comprising pEGFP and pBMP-2 plasmids into the SA solution followed by 3D cryoprinting does not affect their transfecting ability compared to the initial compounds. Histomorphometry and micro-CT analysis 8 weeks after scaffold implantation manifested a significant (up to 46%) increase in new bone volume formation for the SA/pBMP-2 scaffolds compared to the SA/pEGFP ones.

Ultrathin metal films are an essential platform for two-dimensional (2D) material compatible and flexible optoelectronics. Characterization of thin and ultrathin film-based devices requires a thorough consideration of the crystalline structure and local optical and electrical properties of the metal-2D material interface since they could be dramatically different from the bulk material. Recently, it was demonstrated that the growth of gold on the chemical vapor deposited monolayer MoS2 leads to a continuous metal film that preserves plasmonic optical response and conductivity even at thicknesses below 10 nm. Here, we examined the optical response and morphology of ultrathin gold films deposited on exfoliated MoS2 crystal flakes on the SiO2/Si substrate via scattering-type scanning near-field optical microscopy (s-SNOM). We demonstrate a direct relationship between the ability of thin film to support guided surface plasmon polaritons (SPP) and the s-SNOM signal intensity with a very high spatial resolution. Using this relationship, we observed the evolution of the structure of gold films grown on SiO2 and MoS2 with an increase in thickness. The continuous morphology and superior ability with respect to supporting SPPs of the ultrathin (≤10 nm) gold on MoS2 is further confirmed with scanning electron microscopy and direct observation of SPP fringes via s-SNOM. Our results establish s-SNOM as a tool for testing plasmonic films and motivate further theoretical research on the impact of the interplay between the guided modes and the local optical properties on the s-SNOM signal.

Objectives. This study aims to obtain the amino acid derivatives of chlorophyll a and bacteriochlorophyll a for the targeted delivery of pigments to tumor foci. This will increase biocompatibility and, as a result, reduce toxic side effects. In addition to photodynamic efficiency, an additional cytotoxic effect is expected for the obtained conjugates of photosensitizers (PSs) with amino acids. This is owing to the participation of the latter in intracellular biochemical processes, including interaction with the components of the glutathione antioxidant system, leading to the vulnerability of tumor cells to oxidative stress.Methods. In this work, we have implemented the optimization of the structure of a highly efficient infrared PS based on O-propyloxim-N-propoxybacteriopurpurinimide (DPBP), absorbing at 800 nm and showing photodynamic efficacy for the treatment of deep-seated and pigmented tumors, by introducing L-lysine, L-arginine, methionine sulfoximine (MSO), and buthionine sulfoximine (BSO) methyl esters. The structure of the obtained compounds was proved by mass spectrometry and nuclear magnetic resonance spectroscopy, and the photoinduced cytotoxicity was studied in vitro on the HeLa cell line.Results. Conjugates of DPBP with amino acids and their derivatives, such as lysine, arginine, MSO, and BSO have been prepared. The chelating ability of DPBP conjugate with lysine was shown, and its Sn(IV) complex was obtained.Conclusions. Biological testing of DPBP with MSO and BSO showed a 5–6-fold increase in photoinduced cytotoxicity compared to the parent DPBP PS. Additionally, a high internalization of pigments by tumor cells was found, and the dark cytotoxicity (in the absence of irradiation) of DPBP-MSO and DPBP-BSO increased fourfold compared to the initial DPBP compound. This can be explained by the participation of methionine derivatives in the biochemical processes of the tumor cell.

In this work, we implemented different models for predicting adsorption separation of a dye from aqueous solution using porous materials. The equilibrium data of solute concentrations were collected from resources and used in the models for training and verification purposes to develop the models. For prediction of the equilibrium solute concentrations (Ce), we used tree models: Multi-layer Perceptron (MLP), Passive aggressive regression, and Decision Tree (DT) Regressor. In the modeling, we considered the adsorbent dosage as well as solution pH as the input parameters to the model, and the model was able to generate the output values, i.e., equilibrium concentrations based on the input variables. The evaluation of the models’ performances revelated that the final R2 scores are 0.99, 0.98, 0.93 for DT, MLP and Passive-Aggressive, respectively and a very low RMSE of 0.055 for decision tree that shows this model is the best among models used in this study. Indeed, decision tree model is recommended among the other three models to be employed for correlation of adsorption equilibrium data.

Improving the efficiency of spin generation, injection, and detection remains a key challenge for semiconductor spintronics. Electrical injection and optical orientation are two methods of creating spin polarization in semiconductors, which traditionally require specially tailored p-n junctions, tunnel or Schottky barriers. Alternatively, we introduce here a novel concept for spin-polarized electron emission/injection combining the optocoupler principle based on vacuum spin-polarized light-emitting diode (spin VLED) making it possible to measure the free electron beam polarization injected into the III-V heterostructure with quantum wells (QWs) based on the detection of polarized cathodoluminescence (CL). To study the spin-dependent emission/injection, we developed spin VLEDs, which consist of a compact proximity-focused vacuum tube with a spin-polarized electron source (p-GaAs(Cs,O) or Na2KSb) and the spin detector (III-V heterostructure), both activated to a negative electron affinity (NEA) state. The coupling between the photon helicity and the spin angular momentum of the electrons in the photoemission and injection/detection processes is realized without using either magnetic material or a magnetic field. Spin-current detection efficiency in spin VLED is found to be 27% at room temperature. The created vacuum spin LED paves the way for optical generation and spin manipulation in the developing vacuum semiconductor spintronics.

The present work demonstrates the optimization of the ligand structure in the series of bis(phosphine oxide) and β-ketophosphine oxide representatives for efficient coordination of Tb3+ and Eu3+ ions with the formation of the complexes exhibiting high Tb3+- and Eu3+-centered luminescence. The analysis of the stoichiometry and structure of the lanthanide complexes obtained using the XRD method reveals the great impact of the bridging group nature between two phosphine oxide moieties on the coordination mode of the ligands with Tb3+ and Eu3+ ions. The bridging imido-group facilitates the deprotonation of the imido- bis(phosphine oxide) ligand followed by the formation of tris-complexes. The spectral and PXRD analysis of the separated colloids indicates that the high stability of the tris-complexes provides their safe conversion into polystyrenesulfonate-stabilized colloids using the solvent exchange method. The red Eu3+-centered luminescence of the tris-complex exhibits the same specificity in the solutions and the colloids. The pronounced luminescent response on the antibiotic ceftriaxone allows for sensing the latter in aqueous solutions with an LOD value equal to 0.974 μM.

Objectives. Chlorin and bacteriochlorin photosensitizers are effective agents for cancer photodynamic therapy and fluorescence imaging. They are also excellent chelators forming stable metal complexes. Besides, 64Cu and 109Pd isotopes can serve as emitters for nuclear medicine. Chelation of these metals with cyclen conjugates with chlorin and bacteriochlorin photosensitizers can become a simple and universal strategy for the synthesis of diagnostic and therapeutic radiopharmaceuticals for nuclear medicine. This article reports on the synthesis of similar Cu and Pd complexes of cyclen conjugates with pheophorbide and bacteriopheophorbide and the study of their photophysical properties.Methods. Metalation of cyclen conjugates was carried out with palladium and copper acetates. For bacteriochlorins, 6-O-palmitoyl-L-ascorbic acid was additionally used as a reducing agent. MALDI mass spectrometry, which was carried out on a time-of-flight mass spectrometer Bruker Ultraflex TPF/TOF and a Bruker Daltonics Autoflex II confirmed the structure of the compounds obtained Electronic absorption spectra were obtained on a Shimadzu 3101 spectrophotometer. Fluorescence and phosphorescence spectra were obtained on a FluoTime 300 PicoQuant spectrofluorometer.Results. Photophysical studies of metal complexes showed that the introduction of palladium cations quenches fluorescence and increases the quantum yield of singlet oxygen generation to 0.98 for the chlorin conjugate. Besides, it decreases the quantum yield of fluorescence to 0.10 and increases the quantum yield of singlet oxygen generation to 0.72 for the bacteriochlorin conjugate. Introducing a copper cation to cyclen conjugates with pheophorbide and bacteriopheophorbide leads to photophysical characteristics quenching.Conclusions. Due to the stability of the synthesized metal complexes in acidic media, as well as the short metalation time (5, 20, 10, and 15 minutes) it is reasonable to expect the successful development of effective imaging agents for positron emission tomography and radionuclide therapy. In addition, the residual fluorescence of bacteriochlorins makes it possible to use fluorescence diagnostics in combination with these methods.

A series of 2-aminosubstituted (5Z)-3-phenyl-5-(pyridine-2-ylmethylene)-3,5-dihydro-4H-imidazole-4-ones (L) was prepared by the reaction of the corresponding 2-alkylthio-3,5-dihydro-4H-imidazole-4-ones with morpholine or piperidine in the presence of ytterbium(III) triflate. The resulting ligands were subsequently reacted with CuCl2·2H2O and CoCl2·6H2O to give the corresponding copper(II) and cobalt(II) complexes, respectively. Analysis revealed that the complexes were formed with an LMCl2 (M = Cu, Co)-type composition in all cases. The structures of the three cobalt complexes prepared in this way were determined by X-ray crystallography. The results revealed that the cobalt ions in these complexes were tetrahedrally coordinated to two chloride anions and two nitrogen atoms from the pyridine and imidazole moieties of the ligand. The electrochemical properties of the ligands and their complexes were evaluated by cyclic voltammetry, and the results revealed that the first stage in the reduction of the Co(II) and Cu(II) complexes involved the reversible formation of the corresponding Co(I) and Cu(I) complexes, respectively. The cytotoxicity activities of the organic ligands and their complexes were evaluated against several cancer cell lines, including MCF-7, A549 and HEK293 cells. The copper complexes of the organic ligands bearing a phenyl or allyl moiety at their N(3) position together with a piperidine substituent at the 2-position of their imidazolone ring exhibited the greatest cytotoxicity of all of the compounds tested in the current study. Keywords: Cobalt(II) complexes, Copper(II) complexes, 2-Aminoimidazole-4-ones, Cytotoxicity

Gene therapy is one of the most promising approaches in regenerative medicine to restore damaged tissues of various types. However, the ability to control the dose of bioactive molecules in the injection site can be challenging. The combination of genetic constructs, bioresorbable material, and the 3D printing technique can help to overcome these difficulties and not only serve as a microenvironment for cell infiltration but also provide localized gene release in a more sustainable way to induce effective cell differentiation. Herein, the cell transfection with plasmid DNA directly incorporated into sodium alginate prior to 3D printing was investigated both in vitro and in vivo. The 3D cryoprinting ensures pDNA structure integrity and safety. 3D printed gene-activated scaffolds (GAS) mediated HEK293 transfection in vitro and effective synthesis of model EGFP protein in vivo, thereby allowing the implementation of the developed GAS in future tissue engineering applications.

The separation and discrete detection of isomeric sequence peptides with similar properties are important tasks for analytical science. Three different peptide isomers of 12 amino-acid residues long, containing direct and reverse regions of the alanine-valine-proline-isoleucine (AVPI) motif, were partially separated and discretely detected from their mixture using two approaches. Capillary electrophoresis enabled the separation and optical detection of the peptide sequence isomers close to the baseline. The ability to separate these sequence isomers from the mixture and discretely identify them from mass spectra has also been demonstrated by ion-mobility tandem mass spectrometry. Moreover, for the first time, capillary electrophoresis and ion-mobility mass spectrometry connected online have shown their ability for a discrete detection of the multidirectional sequence isomers.

This work is dedicated to the synthesis of porphyrin metal complexes for creation of dyesensitized solar cells (DSSC). Three different dyes were synthesized - zinc complexes of porphyrins containing alkoxyl substituents: with symmetric structure (Zn-P1), as well as asymmetric (type A3B) with the introduction of a donor (Zn-P2) or an acceptor (Zn-P3) substituents via the 1,3,5-triazine fragment. The spectral characteristics of the synthesized substances are compared. For all the obtained dyes, geometry optimization and visualization of the electron density distribution were carried out using computational methods based on the density functional theory (DFT). The location of the frontier unbound molecular orbitals is more optimal when an acceptor substituent containing anchor groups is introduced via the triazine moiety. However, the use of ligands containing an anchor group simplifies the synthesis of the dye and opens up more possibilities for varying both the ligand and the introduced donor substituents. As a result, it was concluded that the spatial distribution of the dye, when applied to the electrode and, consequently, the number of its molecules per unit area of the semiconductor, can have the greatest effect on the efficiency of a cell using t he described compounds.

Bismuth and its compounds have been known since ancient times and now are widely used in practice in various fields. Bismuth use in medicine can be traced back to the Middle Ages, and its wide application is due to its very low toxicity - for most bismuth compounds it is less than for sodium chloride. Bismuth and its compounds, in particular salts, are used in medical practice in the treatment of diseases such as spirochetosis, gastric and duodenal ulcer, leishmaniasis and coronaviral infection, as well as in cancer therapy. In addition to solid preparations liquid peroral pharmaceutical forms have been developed for the treatment of diarrhea, colitis, ulcers etc. Bismuth preparations are used in stomatology for the treatment of inflammatory diseases of paradontium. The review considers the syntheses and properties of bismuth complexes with natural and synthetic porphyrins, which are used in medicine and other fields of science and technology. Considerable attention is paid to the structure features of bismuth porphyrins complexes, their dimeric structures, and the influence of various extra ligands. The counterion nature and structure make a substantial contribution in solving the problem of complexes stability. The central bismuth atom in these complexes extends far above the plane of the macrocycle due to the large ionic radius. Thus, the counterions action on the conformation, physicochemical properties and stability of metal porphyrins complexes is shown. A separate section is devoted to unique and interesting properties of bismuth porphyrins complexes, such as fluorescence and color variation of crystals.

Noble transition metal dichalcogenides (TMDCs) such as PtS2 and PtSe2 show significant potential in a wide range of optoelectronic and photonic applications. Noble TMDCs, unlike standard TMDCs such as MoS2 and WS2, operate in the ultrawide spectral range from ultraviolet to mid-infrared wavelengths; however, their properties remain largely unexplored. Here, we measured the broadband (245–3300 nm) optical constants of ultrathin PtS2 and PtSe2 films to eliminate this gap and provide a foundation for optoelectronic device simulation. We discovered their broadband absorption and high refractive index both theoretically and experimentally. Based on first-principle calculations, we also predicted their giant out-of-plane optical anisotropy for monocrystals. As a practical illustration of the obtained optical properties, we demonstrated surface plasmon resonance biosensors with PtS2 or PtSe2 functional layers, which dramatically improves sensor sensitivity by 60 and 30%, respectively.

We present long-term (5-year) measurements of particulate matter with an upper diameter limit of ∼ 10 µm (PM10), elemental carbon (EC), organic carbon (OC), and water-soluble organic carbon (WSOC) in aerosol filter samples collected at the Zotino Tall Tower Observatory in the middle-taiga subzone (Siberia). The data are complemented with carbon monoxide (CO) measurements. Air mass back trajectory analysis and satellite image analysis were used to characterise potential source regions and the transport pathway of haze plumes. Polluted and background periods were selected using a non-parametric statistical approach and analysed separately. In addition, near-pristine air masses were selected based on their EC concentrations being below the detection limit of our thermal–optical instrument. Over the entire sampling campaign, 75 and 48 % of air masses in winter and in summer, respectively, and 42 % in spring and fall are classified as polluted. The observed background concentrations of CO and EC showed a sine-like behaviour with a period of 365 ± 4 days, mostly due to different degrees of dilution and the removal of polluted air masses arriving at the Zotino Tall Tower Observatory (ZOTTO) from remote sources. Our analysis of the near-pristine conditions shows that the longest periods with clean air masses were observed in summer, with a frequency of 17 %, while in wintertime only 1 % can be classified as a clean. Against a background of low concentrations of CO, EC, and OC in the near-pristine summertime, it was possible to identify pollution plumes that most likely came from crude-oil production sites located in the oil-rich regions of Western Siberia. Overall, our analysis indicates that most of the time the Siberian region is impacted by atmospheric pollution arising from biomass burning and anthropogenic emissions. A relatively clean atmosphere can be observed mainly in summer, when polluted species are removed by precipitation and the aerosol burden returns to near-pristine conditions.

The development of efficient plasmonic nanostructures with controlled and reproducible surface-enhanced Raman spectroscopy (SERS) signals is an important task for the evolution of ultrasensitive sensor-related methods. One of the methods to improving the characteristics of nanostructures is the development of hybrid structures that include several types of materials. Here, we experimentally investigate ultrathin gold films (3–9 nm) near the percolation threshold on Si/Au/SiO2 and Si/Au/SiO2/graphene multilayer structures. The occurring field enhanced (FE) effects were characterized by a recording of SERS signal from Crystal Violet dye. In this geometry, the overall FE principally benefits from the combination of two mechanisms. The first one is associated with plasmon excitation in Au clusters located closest to each other. The second is due to the gap plasmons’ excitation in a thin dielectric layer between the mirror and corrugated gold layers. Experimentally obtained SERS signals from sandwiched structures fabricated with Au film of 100 nm as a reflector, dielectric SiO2 spacer of 50 nm and ultrathin gold atop could reach SERS enhancements of up to around seven times relative to gold films near the percolation threshold deposited on a standard glass substrate. The close contiguity of the analyte to graphene and nanostructured Au efficiently quenches the fluorescent background of the model compound. The obtained result shows that the strategy of combining ultrathin nano-island gold films near the percolation threshold with gap plasmon resonances is promising for the design of highly efficient SERS substrates for potential applications in ultrasensitive Raman detection.

Three systems of gold(III) complexes in an aqueous solution (I = 0.05 M, 25[degrees]C) with slow equilibration were studied by capillary electrophoresis. It was shown on an example of mixed chloride-hydroxide complexes Au[(OH).sub.i][Cl.sup.-.sub.4-i] that, despite close sizes and identical charges of the forms, the mixed forms can be separated if they are kinetically inert. For the equilibria Au[Cl.sup.-.sub.4] + am = Auam[Cl.sup.+.sub.2] + 2[Cl.sup.-] and Auam[Cl.sup.+.sub.2] + am = [Auam.sup.3+.sub.2] + 2[Cl.sup.-], where am is ethylenediamine (en) and 1,3- diaminopropane (tn), the logarithmic constants were log [K.sub.2] = 10.4 for en, and log [K.sub.1] = 16.1 and log [K.sub.2] = 12.0 for tn, which satisfactorily agrees with the spectrophotometric data. There was a considerable effect of side processes, insignificant under normal conditions. Keywords: capillary electrophoresis, gold(III) complexes, 1,3-diaminopropane DOI: 10.1134/S1061934818060084, Capillary zone electrophoresis (CZE) based on the separation of ionic species of a solution in a narrow fused-silica capillary on exposure to an electric field is mainly used to determine [...]

Malignant tumors are the second most frequent cause of death after cardiovascular diseases. The photodynamic therapy based on the interaction of laser light with different photosensitizers was discovered in the 20th century as one of treatment methods. When using photosensitizers, the process of singlet oxygen and other active forms generation is observed in both malignant and healthy body tissues, which leads to a number of adverse reactions. More promising diagnostic compounds that do not have these disadvantages are ytterbium porphyrin complexes. These compounds slightly generate singlet oxygen under light irradiation, while maintaining a high level of tumorotropic agents as for therapeutic photosensitizers. This work continues a series of studies devoted to the analysis of physicochemical properties of Yb-complex 2,4-dimetoxyhematoporphyrin IX as a promising marker for fluorescent diagnostics of various tumors. Pharmaceutical compositions based on Yb3+-dimetoxyhematoporphyrin IX dipotassium salt were created. These compositions are capable of accumulating in the sites of inflammation and proliferation in diseases of mucosal membranes and cancer lesions. Toxicological and pharmacokinetic studies were carried out with the use of laboratory animals and volunteers. The analysis results showed that the pharmaceutical compositions are perspective for use in clinical practice.

A series of five neutral mononuclear lanthanide complexes [Ln(HL)(L)] (Ln = Dy3+, Ho3+ Er3+ and Tb3+) with rigid pentadentate N3O2-type Schiff base ligands, H2LH (1-Dy, 3-Ho, 4-Er and 6-Tb complexes) or H2LOCH3, (2-Dy complex) has been synthesized by reaction of two equivalents of 1,1′-(pyridine-2,6-diyl)bis(ethan-1-yl-1-ylidene))dibenzohydrazine (H2LH, [H2DAPBH]) or 1,1′-(pyridine-2,6-diyl)bis(ethan-1-yl-1-ylidene))di-4-methoxybenzohydrazine (H2LOCH3, [H2DAPMBH]) with common lanthanide salts. The terbium complex [Tb(LH)(NO3)(H2O)2](DME)2 (5-Tb) with one ligand H2LH was also obtained and characterized. Single crystal X-ray analysis shows that complexes 1–4 have the composition {[Ln3+(HL)−(L)2−] solv} and similar molecular structures. In all the compounds, the central Ln3+ ion is chelated by two interlocked pentadentate ligands resulting in the coordination number of ten. Each lanthanide ion is coordinated by six nitrogen atoms and four oxygen atoms of the two N3O2 chelating groups forming together a distorted bicapped square antiprismatic polyhedron N6O4 with two capping pyridyl N atoms in the apical positions. The ac magnetic measurements reveal field-induced single-molecule magnet (SMM) behavior of the two dysprosium complexes (with barriers of Ueff = 29 K at 800 Oe in 1-Dy and Ueff = 70 K at 300 Oe in 2-Dy) and erbium complex (Ueff = 87 K at 1500 Oe in 4-Er); complex 3-Ho with a non-Kramers Ho3+ ion is SMM-silent. Although 2-Dy differs from 1-Dy only by a distant methoxy-group in the phenyl ring of the ligand, their dynamic magnetic properties are markedly different. This feature can be due to the difference in long-range contributions (beyond the first coordination sphere) to the crystal-field (CF) potential of 4f electrons of Dy3+ ion that affects magnetic characteristics of the ground and excited CF states. Magnetic behavior and the electronic structure of Ln3+ ions of 1–4 complexes are analyzed in terms of CF calculations.

In this study we describe the hygroscopic properties of accumulation- and coarse-mode aerosol particles sampled at the Zotino Tall Tower Observatory (ZOTTO) in central Siberia (61° N, 89° E) from 16 to 21 June 2013. The hygroscopic growth measurements were supplemented with chemical analyses of the samples, including inorganic ions and organic/elemental carbon. In addition, the microstructure and chemical compositions of aerosol particles were analyzed by x-ray micro-spectroscopy (STXM-NEXAFS) and transmission electron microscopy (TEM). A mass closure analysis indicates that organic carbon accounted for 61 and 38 % of particulate matter (PM) in the accumulation mode and coarse mode, respectively. The water-soluble fraction of organic matter was estimated to be 52 and 8 % of PM in these modes. Sulfate, predominantly in the form of ammoniated sulfate, was the dominant inorganic component in both size modes: ~ 34 % in the accumulation mode vs. ~ 47 % in the coarse mode. The hygroscopic growth measurements were conducted with a filter-based differential hygroscopicity analyzer (FDHA) over the range of 5–99.4 % RH in the hydration and dehydration operation modes. The FDHA study indicates that both accumulation and coarse modes exhibit pronounced water uptake approximately at the same relative humidity (RH), starting at ~ 70 %, while efflorescence occurred at different humidities, i.e., at ~ 35 % RH for submicron particles vs. ~ 50 % RH for supermicron particles. This ~ 15 % RH difference was attributed to higher content of organic material in the submicron particles, which suppresses water release in the dehydration experiments. The kappa mass interaction model (KIM) was applied to characterize and parameterize non-ideal solution behavior and concentration-dependent water uptake by atmospheric aerosol samples in the 5–99.4 % RH range. Based on KIM, the volume-based hygroscopicity parameter, κv, was calculated. The κv,ws value related to the water-soluble (ws) fraction was estimated to be ~ 0.15 for the accumulation mode and ~ 0.36 for the coarse mode, respectively. The obtained κv,ws for the accumulation mode is in good agreement with earlier data reported for remote sites in the Amazon rain forest (κv ≈ 0.15) and a Colorado mountain forest (κv ≈ 0.16 ). We used the Zdanovskii–Stokes–Robinson (ZSR) mixing rule to predict the chemical composition dependent hygroscopicity, κv,p. The obtained κv,p values overestimate the experimental FDHA-KIM-derived κv,ws by factors of 1.8 and 1.5 for the accumulation and coarse modes, respectively. This divergence can be explained by incomplete dissolution of the hygroscopic inorganic compounds resulting from kinetic limitations due to a sparingly soluble organic coating. The TEM and STXM-NEXAFS results indicate that aged submicron (> 300 nm) and supermicron aerosol particles possess core–shell structures with an inorganic core, and are enriched in organic carbon at the mixed particle surface. The direct FDHA kinetic studies provide a bulk diffusion coefficient of water of ~ 10−12 cm2 s−1 indicating a semi-solid state of the organic-rich phase leading to kinetic limitations of water uptake and release during hydration and dehydration cycles. Overall, the present ZOTTO data set, obtained in the growing season, has revealed a strong influence of organic carbon on the hygroscopic properties of the ambient aerosols. The sparingly soluble organic coating controls hygroscopic growth, phase transitions, and microstructural rearrangement processes. The observed kinetic limitations can strongly influence the outcome of experiments performed on multi-second timescales, such as the commonly applied HTDMA (Hygroscopicity Tandem Differential Mobility Analyzer) and CCNC (Cloud Condensation Nuclei Counter) measurements.

The present article is devoted to the synthesis and investigation of biological and physico-chemical properties of the bacteriopurpurinimide derivative that was used as a photosensitizer. These substances have an ability to accumulate selectively in the malignant tumours. Also this class of photosensitizers is of particular interest because of their strong light absorbtion spectrum in red and NIR-region in the “window of tissue transparency”. This property affords to treat deep-seated tumours at the depth of 2 cm. In this study it was implemented the method of photodynamic therapy of cancer. The photosensitizer for this study was prepared as the nanostructured water-soluble micellar dispersion of O-propyloxime-N-propoxybacteriopurpurinimide methyl ester. The photodynamic therapy using this substance provided the highly effective photoinduced antitumour in vitro and in vivo activity, 100% regression of the tumour and 90% cure of animals.