Savostina, Liudmila Ivanovna

Logacheva K.A., Belushkin A.V., Gergelezhiu P.A., Eresko A.B., Malakhov S.N., Raksha E.V., Savostina L.I., Chudoba D.M.

Logacheva K., Gergelezhiu P., Raksha E., Savostina L., Arzumanyan G., Eresko A., Malakhov S., Mamatkulov K., Ponomareva O., Belushkin A., Chudoba D.

Vibrational spectroscopic features of ibuprofen and ketoprofen (non-steroidal anti-inflammatory drugs) were determined as a result of joint analysis of experimental and DFT-calculated data. There is a good agreement between the experimental (IR, Raman) and calculated (BP86/def2-SVP) vibrational frequencies of ibuprofen and ketoprofen.

Batueva E.E., Sharipova A.R., Frolova E.N., Savostina L.I., Bazan L.V., Cherosov M.A., Batulin R.G., Turanova O.A., Turanov A.N.

New heptanuclear mixed-valence iron complexes with pentadentate ligands are synthesized, and their magnetic properties are analyzed. Magnetometry and EPR show that thiocyanate anions promote spin-crossover properties. Introducing long alkoxy chains into a molecule gives it thermotropic liquid crystalline properties and enhances its cooperative magnetic properties.

Volkov M.Y., Sharipova A.R., Turanova O.A., Gubaidullin A.T., Shaidullina A.F., Savostina L.I., Turanov A.N.

Abstract1‐phenyl‐3‐(quinolin‐8‐ylamino)prop‐2‐en‐1‐one was obtained by a two‐step synthesis. From X‐ray crystallography, NMR and UV‐vis spectra it follows that in the crystalline state and in solutions, regardless of the polarity of the solvent, 1‐phenyl‐3‐(quinolin‐8‐ylamino)prop‐2‐en‐1‐one exists in the ketone form of the cis‐isomer. DFT calculations confirmed that the cis‐isomer is the most energetically favorable among all its isomers.

Zinnatullin A.L., Zagidullin A.A., Savostina L.I., Bezkishko I.A., Petrov A.V., Dulov E.N., Zairov R.R., Miluykov V.A., Vagizov F.G.

Shaidullina A.F., Sharipova A.R., Volkov M.Y., Savostina L.I., Gafiyatullin L.G., Turanova O.A., Turanov A.N.

Morozova A.S., Ziganshina S.A., Kudryavtseva E.O., Kurbatova N.V., Savostina L.I., Bukharaev A.A., Ziganshin M.A.

The formation of dipeptide micro- and nanostructures in the solid state or in solutions usually occurs in the presence of water in the ambient air or in the organic media used. This factor should be taken into account since the results of the self-assembly of dipeptides are very sensitive to external conditions and may depend on the water content. In this work, the study of the mutual effect of water and organic vapors on the self-assembly of the glycyl-glycine (GlyGly) dipeptide in the solid state was carried out for the first time using atomic force microscopy. The crystallization of an amorphous GlyGly film upon interaction with vapors of organic compounds such as dichloromethane, chloroform, tetrachloromethane, and benzene occurs only in the presence of water vapors. The rate of dipeptide crystallization was found also depends on the organic compound used. The solubility of GlyGly in organic media and the solubility of organic solvent in water are the main factors that affect the dipeptide self-assembly. Using the Raman spectroscopy and quantum chemical calculations a possible mechanism of the combined effect of water and organic compounds on the GlyGly self-assembly has been proposed. • The mechanism of glycyl-glycine self-assembly in thin film under organic and water vapors was studied by AFM technique. • The key role of water in self-assembly of glycyl-glycine in the solid state revealed. • The amorphous film consists mostly of a molecular form of dipeptide. • The dualism of water effect on the glycyl-glycine self-assembly was demonstrated. • The atomic force microscopy technique was used for qualitative estimation of dipeptide solubility for the first time.

Sukhanov A.A., Savostina L.I., Voronkova V.K., Mikhalitsyna E.A., S Tyurin V.

The short-lived states of the photoexcited conjuncted porphyrin trimer, in which two side zinc porphyrin fragments differ from the central fragment, have been studied by time-resolved continuous-wave and pulse electron paramagnetic resonance (EPR) in X- and Q-bands. It was shown that the observed spectra are the sum of the spectra of two types of porphyrin components. This was particularly evident in the echo-detected spectra at the relatively large time delay between echo-forming microwave pulses when not all the signals were detected due to the anisotropy of phase relaxation times of porphyrin systems. The parameters of the excited triplet states were determined and it was shown that the two types of excited triplet states were characterized by the same values of the g-factors but different values of the zero-field splitting. The anisotropy of the g-tensors of triplet states was estimated from the frequency dependence of the EPR spectra.

Gafiyatullin L.G., Savostina L.I., Gnezdilov O.I., Turanova O.A., Ovchinnikov I.V., Turanov A.N.

Photoisomerization of 4-styrylpyridine at different irradiation wavelengths (λ 365 and 254 nm) and in different solvents was studied by UV and 1H NMR spectroscopy. A procedure for recording the UV spectra of 4-styrylpyridine dissolved in liquid crystalline films freely suspended within a frame. The results of quantum-chemical calculations of the geometry and UV spectra of 4-styrylpyridine isomers are presented.

Sorokin I.D., Pergushov V.I., Savostina L.I., Melnikov M.Y.

It has been established that transformations of azetidine radical cations observed in freonic matrices under the action of light with λ = 436 nm (T = 77 K) are associated with C-N bond cleavage which corresponds to the cyclic form yielding a mixture of open distonic C-centered radical cations of the following structure: ·CH2CH2CH=NH 2 +

Aminova R.M., Savostina L.I.

The most probable mechanisms of bimolecular interactions between a complex heterocyclic salicylic acid derivative, “phosphite,“ and chloral were for the first time studied by the density functional theory method. It was found theoretically that the reaction could develop in three different channels, (a) with six-membered heteroring opening and the formation of a seven-membered product and (b, c) as a Perkov-type reaction leading to (b) acyclic or (c) cyclic vinyl phosphates. The structures of the reagents, products, intermediates, and transition states were calculated with complete geometry optimization. All stationary points were identified by calculations of force constant matrices. For all transition states, intrinsic reaction coordinates were calculated. A comparison with the experimental data was performed.

Savostina L.I., Aminova R.M., Mironov V.F.

The Perkov reaction mechanism on an example of 2-methoxybenzo[d]-1,3,2-dioxaphosphorin-4-one reaction with chloral was investigated by means of quantumchemical calculations [PM3, DFT (PBE functional, “Triple z” basis, “Priroda” program)]. The primary reaction step is shown to include [1+2]-cycloaddition to form an intermediate with pentacoordinated phosphorus atom (oxaphosphirane-containing spirophosphorane) which transforms further to vinyl phosphate. Structure of the transition state on the pathway to vinyl phosphate is close to dichlorovinyloxyquasiphosphonium cation with the chloride counterion. Thermodynamic parameters of the starting compounds and reaction products as well as activation energies of the processes are evaluated.

Aminova R.M., Shamov G.A., Savostina L.I., Mironov V.F.

Quantum-chemical calculations of various stereoisomers, intermediates, and transition states of the reaction of 2-methoxybenzo[d][1,3,2]dioxaphosphinin-4-one with chloral, leading to formation of 2-methoxy-3-(trichloromethyl)benzo[e[1,4,2 5]dioxaphosphepin-2,5-dione, were carried out by the density functional theory (DFT) method with the PBE functional and Triple z basis, using the Priroda program. The first step of the reaction is [1+2] cycloaddition of phosphorus to the chloral C=O bond to form an intermediate with a five-coordinate phosphorus atom via a transition state in which the positive and negative charges are strongly localized on phosphorus and chloral oxygen, respectively. Calculations of the internal reaction coordinate from all transition states were carried out.

Uraev A.I., Milenković M.R., Vlasenko V.G., Lyssenko K.A., Demidov O.P., Shiryaeva A.A., Bubnov M.P., Knyazev P.A., Garnovskii D.A., Burlov A.S., Zubenko A.A.

Sharipova A.R., Batueva E.E., Gubaidullin A.T., Turanova O.A., Savostina L.I., Frolova E.N., Zaripov R.B., Turanov A.N.

Morozova A.S., Kudryavtseva E.O., Ziganshina S.A., Kurbatova N.V., Ziganshin M.A., Bukharaev A.A.

Li T., Xiao W., Ren S., Xue R., Chen F.

Amorphous solid dispersions are good candidates for improving solubility in water and the oral bioavailability of poorly water-soluble active pharmaceutical ingredients (APIs). Amorphous solids become supercooled liquids when the temperature reaches the glass transition temperature (Tg). For APIs with low melting points, Tg can be below room temperature, which makes it difficult to prepare long-term stable amorphous solids. Studies on the physicochemical properties of supercooled liquids shed light on the design of ASDs for APIs with low melting points. Racemic ibuprofen (IBU) supercooled liquid has been detected using differential scanning calorimetry and powder X-ray diffraction during the melt-quenching of IBU at a low temperature (0 °C). In this work, gram-scaled IBU supercooled liquid was prepared using the melt-quenching method, maintaining a liquid state for minutes at room temperature and for hours at 10 °C, as confirmed by visual observation. The Raman spectra, IR spectra, and UV-vis spectra results indicate that the structure of the IBU supercooled liquid is similar to that of an IBU solution instead of IBU Form I. The rate of recrystallization into Form I can be adjusted by controlling the temperature and additives, as confirmed by visual observation. Moreover, long-term stable IBU dispersions, with improved aqueous solubility, were inspired by the IBU supercooled liquid. The IBU supercooled liquid model can guide the preparation of ASDs for low melting point drugs.

Volkov M.Y., Sharipova A.R., Turanova O.A.

β-Enaminone 1-[4-(4-pentylcyclohexyl)-phenyl]-3-(quinolin-8-ylamino)prop-2-en-1-one was first synthesized and studied by NMR and UV spectroscopy. It was established that the molecules of this substance exist in the ketone form of the cis-isomer in both polar acetone and weakly polar chloroform. Exposing the solutions of this enaminone daylight at room temperature leads to the formation of small amounts of trans-isomer in them. 365 nm UV irradiation of the solution in chloroform leads to reversible cis–trans isomerization of the dissolved molecules of 1-[4-(4-pentylcyclohexyl)phenyl]-3-(quinolin-8-ylamino)prop-2-en-1-one.

Wang Y., Luo Q., Zheng Y.

AbstractLanthanide (Ln) based mononuclear single‐molecule magnets (SMMs) provide probably the finest ligand regulation model for magnetic property. Recently, the development of such SMMs has witnessed a fast transition from coordination to organometallic complexes because the latter provides a fertile, yet not fully excavated soil for the development of SMMs. Especially those SMMs with heterocyclic ligands have shown the potential to reach higher blocking temperature. In this minireview, we give an overview of the design principle of SMMs and highlight those “shining stars” of heterocyclic organolanthanide SMMs based on the ring sizes of ligands, analysing how the electronic structures of those ligands and the stiffness of subsequently formed molecules affect the dynamic magnetism of SMMs. Finally, we envisaged the future development of heterocyclic Ln‐SMMs.

Wang Y., Luo Q., Zheng Y.

AbstractLanthanide (Ln) based mononuclear single‐molecule magnets (SMMs) provide probably the finest ligand regulation model for magnetic property. Recently, the development of such SMMs has witnessed a fast transition from coordination to organometallic complexes because the latter provides a fertile, yet not fully excavated soil for the development of SMMs. Especially those SMMs with heterocyclic ligands have shown the potential to reach higher blocking temperature. In this minireview, we give an overview of the design principle of SMMs and highlight those “shining stars” of heterocyclic organolanthanide SMMs based on the ring sizes of ligands, analysing how the electronic structures of those ligands and the stiffness of subsequently formed molecules affect the dynamic magnetism of SMMs. Finally, we envisaged the future development of heterocyclic Ln‐SMMs.

Charushin Valery N., Verbitskiy Egor V., Chupakhin Oleg N., Vorobyeva Daria V., Gribanov Pavel S., Osipov Sergey N., Ivanov Andrey V., Martynovskaya Svetlana V., Sagitova Elena F., Dyachenko Vladimir D., Dyachenko Ivan V., Krivokolysko Sergey G., Dotsenko Viktor V., Aksenov Aleksandr V., Aksenov Dmitrii A., et. al.

The chemistry of heterocyclic compounds has traditionally been and remains a bright area of chemical science in Russia. This is due to the fact that many heterocycles find the widest application. These compounds are the key structural fragments of most drugs, plant protection agents. Many natural compounds are also derivatives of heterocycles. At present, more than half of the hundreds of millions of known chemical compounds are heterocycles. This collective review is devoted to the achievements of Russian chemists in this field over the last 15–20 years. The review presents the achievements of leading heterocyclists representing both RAS institutes and university science. It is worth noting the wide scope of the review, both in terms of the geography of author teams, covering the whole of our large country, and in terms of the diversity of research areas. Practically all major types of heterocycles are represented in the review. The special attention is focused on the practical applications of heterocycles in the design of new drugs and biologically active compounds, high-energy molecules, materials for organic electronics and photovoltaics, new ligands for coordination chemistry, and many other rapidly developing areas. These practical advances would not be possible without the development of new fundamental transformations in heterocyclic chemistry.The bibliography includes 2237 references.

Frolova E.N., Turanova O.A., Bazan L.V., Ovchinnikov I.V., Turanov A.N.

Schiff bases allow the creation of compounds with a wide variety of architectures and properties and have been of interest to researchers for many years. This mini-review describes some of the possibilities of the EPR method, which we use to study Fe(III) complexes with polydentate Schiff bases, many of which have been synthesized for the first time. Obtaining information at the local level using EPR spectroscopy allows us to grasp the molecular structure–property relationship and to adjust the synthesis strategy to create multifunctional substances with predetermined properties.

Bezkishko I.A., Zagidullin A.A., Fayzullin R.R., Samorodnova A.P., Khrizanforov M.N., Zinnatullin A.L., Vagizov F.G., Miluykov V.A.

A new representative of 1,2-diphosphaferrocenes containing p-fluorophenyl substituents on the 1,2-diphosphacyclopentadienyl ring was synthesized. Its structure was confirmed by multinuclear NMR, IR, and Mössbauer spectroscopy, and its electrochemical properties were studied.

Kusumoto S., Wakabayashi K., Rakumitsu K., Harrowfield J., Kim Y., Koide Y.

AbstractWe report on the elastic and photodynamic properties of (E)‐1,2‐bis(pyridinium‐4‐yl)ethene dinitrate [H2Ebpe](NO3)2, whose needle‐like crystals can be reversibly deformed by applying external mechanical stress. The macro‐scale mechanical properties of [H2Ebpe](NO3)2 crystals were quantified by a three‐point bending test, which gave a stress‐strain curve with an elastic modulus of 1.18 GPa, and its values are lower than those of other flexible elastic organic crystals. It can also be reversibly bent through the [2+2] cycloaddition reaction of the olefin moiety, depending on the direction of UV irradiation.

Zagidullin A.A., Lakomkina A.R., Gerasimova T.P., Samorodnova A.P., Khrizanforov M.N., Bezkishko I.A., Miluykov V.A.

The synthesis of tetraaryl-substituted 1-monophospholes and 1-monophosphaferrocenes, bearing 4-bromophenyl and 2-thienyl substituents at the PCα carbon atoms are described. It was shown that the reaction of n-octyl chloride with a mixture of sodium 1,2,3-tri- and 1-monophospholides results in the exclusive formation of new luminescent 1-n-octyl-1-monophospholes. All novel compounds have been fully characterized by NMR spectroscopy and mass-spectrometry, their optical and electrochemical behaviors have been elucidated. Phosphaferrocene-based compounds exhibit higher oxidation stability and higher HOMO-LUMO separation compared to the corresponding 1-monophosphole units.

Uttendorfer M.K., Hierlmeier G., Balázs G., Wolf R.

The reduction of (tBuCP)2 with alkali metals affords the anion (1,2,3-P3C2tBu2)−. Coordination studies of the anion have yielded organometallic sandwich complexes, while the hexaphosphane tBu4C4P6 was obtained by oxidation.

Volkov M.Y., Sharipova A.R., Turanova O.A., Gubaidullin A.T., Shaidullina A.F., Savostina L.I., Turanov A.N.

Abstract1‐phenyl‐3‐(quinolin‐8‐ylamino)prop‐2‐en‐1‐one was obtained by a two‐step synthesis. From X‐ray crystallography, NMR and UV‐vis spectra it follows that in the crystalline state and in solutions, regardless of the polarity of the solvent, 1‐phenyl‐3‐(quinolin‐8‐ylamino)prop‐2‐en‐1‐one exists in the ketone form of the cis‐isomer. DFT calculations confirmed that the cis‐isomer is the most energetically favorable among all its isomers.

Larionov R.A., Ziganshina S.A., Khayarov K.R., Klimovitskii A.E., Gerasimov A.V., Gorbatchuk V.V., Lantsova N.V., Ziganshin M.A.

Heat treatment of linear dipeptides in the solid state is a good strategy for obtaining their cyclic analogs with a high yield and minimal costs. However, the cyclization of dipeptides under the crystal lattice constraints is still poorly understood. In this work, the thermally induced cyclization of L-phenylalanyl-L-leucine and L-leucyl-L-phenylalanine in the solid state was studied. Kinetic parameters of these reactions were estimated using the approaches of nonisothermal kinetics. For the first time, a possible mechanism of the reaction and rate-determining step is discussed. The effect of the sequence of amino acid residues in the dipeptide molecules on temperature and activation energy of solid-state cyclization was observed. The optical purity of the reaction products was estimated. The effect of temperature on the state of dipeptides films was visualized using atomic force microscopy. The results obtained contribute to the understanding of the mechanisms of solid-state cyclization of dipeptides and can be useful in the development of methods for the synthesis of diketopiperazine derivatives.

Cunha R.S., Cruz P.F., Costa T., Almeida Z.L., Lima M.E., Serpa C., Chaves O.A.

Ketoprofen (KTF) and ketorolac (KTL) are among the most primarily used non-steroidal anti-inflammatory drugs (NSAIDs) in humans to alleviate moderate pain and to treat inflammation. Their binding affinity with albumin (the main globular protein responsible for the biodistribution of drugs in the bloodstream) was previously determined by spectroscopy without considering some conventional pitfalls. Thus, the present work updates the biophysical characterization of the interactions of HSA:KTF and HSA:KTL by 1H saturation-transfer difference nuclear magnetic resonance (1H STD-NMR), ultraviolet (UV) absorption, circular dichroism (CD), steady-state, and time-resolved fluorescence spectroscopies combined with in silico calculations. The binding of HSA:NSAIDs is spontaneous, endothermic, and entropically driven, leading to a conformational rearrangement of HSA with a slight decrease in the α-helix content (7.1% to 7.6%). The predominance of the static quenching mechanism (ground-state association) was identified. Thus, both Stern–Volmer quenching constant (KSV) and binding constant (Kb) values enabled the determination of the binding affinity. In this sense, the KSV and Kb values were found in the order of 104 M−1 at human body temperature, indicating moderate binding affinity with differences in the range of 0.7- and 3.4-fold between KTF and KTL, which agree with the previously reported experimental pharmacokinetic profile. According to 1H STD-NMR data combined with in silico calculations, the aromatic groups in relation to the aliphatic moiety of the drugs interact preferentially with HSA into subdomain IIIA (site II) and are stabilized by interactions via hydrogen bonding and hydrophobic forces. In general, the data obtained in this study have been revised and updated in comparison to those previously reported by other authors who did not account for inner filter corrections, spectral backgrounds, or the identification of the primary mathematical approach for determining the binding affinity of HSA:KTF and HSA:KTL.

Tsoupras A., Gkika D.A., Siadimas I., Christodoulopoulos I., Efthymiopoulos P., Kyzas G.Z.

Non-steroidal anti-inflammatory drugs (NSAIDs) are among the most widely utilized pharmaceuticals worldwide. Besides their recognized anti-inflammatory effects, these drugs exhibit various other pleiotropic effects in several cells, including platelets. Within this article, the multifaceted properties of NSAIDs on platelet functions, activation and viability, as well as their interaction(s) with established antiplatelet medications, by hindering several platelet agonists’ pathways and receptors, are thoroughly reviewed. The efficacy and safety of NSAIDs as adjunctive therapies for conditions involving inflammation and platelet activation are also discussed. Emphasis is given to the antiplatelet potential of commonly administered NSAIDs medications, such as ibuprofen, diclofenac, naproxen and ketoprofen, alongside non-opioid analgesic and antipyretic medications like paracetamol. This article delves into their mechanisms of action against different pathways of platelet activation, aggregation and overall platelet functions, highlighting additional health-promoting properties of these anti-inflammatory and analgesic agents, without neglecting the induced by these drugs’ side-effects on platelets’ functionality and thrombocytopenia. Environmental issues emerging from the ever-increased subscription of these drugs are also discussed, along with the need for novel water treatment methodologies for their appropriate elimination from water and wastewater samples. Despite being efficiently eliminated during wastewater treatment processes on occasion, NSAIDs remain prevalent and are found at significant concentrations in water bodies that receive effluents from wastewater treatment plants (WWTPs), since there is no one-size-fits-all solution for removing all contaminants from wastewater, depending on the specific characteristics of the wastewater. Several novel methods have been studied, with adsorption being proposed as a cost-effective and environmentally friendly method for wastewater purification from such drugs. This article also presents limitations and future prospects regarding the observed antiplatelet effects of NSAIDs, as well as the potential of novel derivatives of these compounds, with benefits in other important platelet functions.

Khlyustova A.V., Shipko M.N., Stepovich M.A., Agafonov A.V., Sirotkin N.A., Savchenko E.S.

Results are presented from studying nanosized particles of NiFe2O4 and ɛ-Fe2O3, synthesized in low temperature underwater plasma. It is shown that nanocomposites with a fixed ratio of nickel ferrite (which ensures low values of the ferromagnetic resonance linewidth) and ɛ-Fe2O3 (which exhibits high-frequency resonance in the millimeter range of electromagnetic radiation) can be synthesized.

Konieczkowska J., Wasiak A., Sobolewska A., Bartkiewicz S., Małecki J.G., Schab-Balcerzak E.

The paper presents a series of azobenzene and azo pyridine compounds containing hydroxyl or 6-hydroxyhexyloxyl substituents. The nitrogen atom is located at the ortho-, meta- or para-position in the structure of azo pyridine derivatives. The impact of the structural features of azo chromophores on their thermal (DSC, TGA) and optical (UV–Vis) properties was investigated. The dark cis–trans isomerization kinetics was studied in ethanol and chloroform at 298 K. The formation of noncovalent hydrogen bonds between azo molecules and/or chromophore-solvent was monitored using the 1H NMR spectroscopy and estimated by density functional theory (DFT) calculations. Based on experimental and computational studies we proposed the mechanism of the dark cis–trans isomerization for hydroxy-substituted azo compounds.

Kafeeva D.A., Kurshanov D.A., Dubavik A.Y.

The high-temperature organic synthesis of core–shell type Fe3O4/ZnS and Fe3O4/ZnSe hydrophobic superparamagnetic nanocomposites is described. An analysis is performed of the absorption, luminescence, magnetic circular dichroism (MCD), and morphology spectra of hydrophobic magnetoluminescent nanocomposites. It is shown that nanocomposites have luminescent properties, and the growth of shells on the Fe3O4 cores preserves the magnetic properties of the particles. Analysis of the MCD spectra shows the magnetic field induces spin-dependent chiral magneto-optical activity. An estimate of the g-factor’s dependence on the magnitude and sign of the external magnetic field reveals a change in the magnetization of the resulting nanocomposites, relative to Fe3O4.

Magomedov K.E., Omelyanchik A.S., Vorontsov S.A., Čižmár E., Rodionova V.V., Levada E.V.

It is shown that surface-modified magnetic iron oxide nanoparticles with an average size of about 10 nm have a high adsorption capacity for the sorption of pollutants from wastewater. A considerable advantage of using magnetic materials is their ability to extract the sorbent using an external magnetic field, making the purification process more efficient. It is found that anionic sodium dodecyl sulfate increases the electrostatic attraction to the cationic compound Methylene Blue, preventing the aggregation of nanoparticles and increasing the active surface. The sorption capacity of magnetic nanoparticles after surface functionalization grew by a factor of 250, relative to unmodified iron oxide nanoparticles. The mechanism and kinetic parameters of sorption are determined, along with the optimum conditions for increasing the efficiency of the sorption process.

Makeev M.Y., Mamonova M.V.

The energy and magnetic properties of Fe/Cr/Fe and Fe/Pt/Fe systems are studied using the spin density functional theory and the VASP software. Calculated dependences of the total energy on the angle of the magnetic moment of atoms show the advantage of the perpendicular anisotropy of Fe/Cr/Fe for all considered Fe film thicknesses and surface orientations. A more complex dependence is observed for Fe/Pt/Fe, but easy-plane anisotropy predominates upon an increase in the iron film thickness.

Shaidullina A.F., Sharipova A.R., Volkov M.Y., Savostina L.I., Gafiyatullin L.G., Turanova O.A., Turanov A.N.

Shekurov R.P., Khrizanforov M.N., Zagidullin A.A., Zinnatullin A.L., Kholin K.V., Ivshin K.A., Gerasimova T.P., Sirazieva A.R., Kataeva O.N., Vagizov F.G., Miluykov V.A.

A coordination polymer has been synthesized using ferrocene-based ligand-bearing phosphinic groups of 1,1′-ferrocene-diyl-bis(H-phosphinic acid)), and samarium (III). The coordination polymer’s structure was studied by both single-crystal and powder XRD, TG, IR, and Raman analyses. For the first time, the Mössbauer effect studies were performed on ferrocenyl phosphinate and the polymer based on it. Additionally, the obtained polymer was studied by the method of cyclic and differential pulse voltammetry. It is shown that it has the most positive potential known among ferrocenyl phosphinate-based coordination polymers and metal–organic frameworks. Using the values of the oxidation potential, the polymer was oxidized and the ESR method verified the oxidized Fe(III) form in the solid state. Additionally, the effect of the size of the phosphorus atom substituent of the phosphinate group on the dimension of the resulting coordination compounds is shown.

Petrov A., Conrad L., Coles N.T., Weber M., Andrae D., Zagidullin A., Miluykov V., Müller C.

A diglyme solution of Na[cyclo-P5] (1) reacts with alkynes and the isolobal nitriles and phosphaalkynes to afford the otherwise elusive (aza)phospholide anions 2a-c, 4a,b, and 6. The reaction of Na[cyclo-P5] with alkynes and nitriles was studied by means of DFT methods, which suggest a concerted mechanism for the formation of 2a and 4b. The anions 2a-c, 4a,b, and 6 coordinate in an η5-fashion towards Fe(II) to give the sandwich (aza)phosphametallocenes 3a-c, 5a,b and 7 in moderate to good yields. The new compounds were characterized by means of multinuclear NMR spectroscopy, single crystal X-ray diffraction and cyclic voltammetry.

Zagidullin A.A., Akhmatkhanova F.F., Khrizanforov M.N., Fayzullin R.R., Gerasimova T.P., Bezkishko I.A., Miluykov V.A.

A novel representative of sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienide containing a chloro substituent in the meta-position of the aryl groups was obtained with a high yield based on the reaction of tributyl(1,2,3-triarylcyclopropenyl)phosphonium bromide and sodium polyphosphides. Further reaction of sodium 3,4,5-tris(3-chlorophenyl)-1,2-diphosphacyclopentadienide with [FeCp(η6-C6H5CH3)][PF6] complex gives a new 3,4,5-tris(3-chlorophenyl)-1,2-diphosphaferrocene. The electrochemical properties of 3,4,5-tris(3-chlorophenyl)-1,2-diphosphaferrocene were studied and compared to 3,4,5-tris(4-chlorophenyl)-1,2-diphosphaferrocene. It was found that the position of the chlorine atom on the aryl fragment has an influence on the reduction potential of 1,2-diphosphaferrocenes, while the oxidation potentials do not change.

Liu J., Ji X., Xue J., Hu J., Yao Z., Tao J.

Toledo M.V., Briand L.E., Ferreira M.L.

Lipases are enzymes widely applied in the kinetic resolution of racemic non-steroidal anti-inflammatory drugs (NSAIDs). The esterification of racemic ibuprofen and ketoprofen with glycerol catalyzed by the lipase B of Candida antarctica (CALB) was performed by some of us, achieving very different results for both NSAIDs in terms of enzymatic activity, enantio- and regioselectivity. A molecular modelling investigation allowed to establish the steric energies and the enthalpy variations along the diffusion of glycerol through the enzymatic tunnel towards the active catalytic triad of the lipase along with the interaction with the acyl enzyme species. In this context, it was possible to demonstrate that glycerol approaching the acyl enzyme of the R-ibuprofen possesses lower steric hindrance than the S-ibuprofen acyl enzyme (− 185.3 vs − 188.6 kcal mol−1 for S and R-enantiomers, in average). Although, the steric energy is somehow similar when the acyl enzyme of the R/S-ketoprofen is considered (− 201 kcal mol−1) the proximity of glycerol to the aminoacid residues of the enzymatic tunnel towards the active site plays a key role. In fact, the closer distance of glycerol to the tunnel walls when the acyl enzyme of ketoprofen is present than ibuprofen (2.1 Å vs 2.9 Å) allows multiple H-bonding interactions between the polyol and the aminoacids and also increases the enthalpy of formation of glycerol–acyl enzyme species.

Sun X., Liu Z., Wang Z., Huo M., Zhang H., Liu Y.

The photoisomerization behavior of cyanostilbene molecules is a hotspot in supramolecular configuration transformation research. Here, we reported a cyanostilbene derivative that converted from the Z,Z-isomer to the E,E-isomer under UV light irradiation at 365 nm. This process can be reversibly converted only in the presence of cucurbit[8]uril under the same light source, accompanied by the reversible conversion of fluorescence from green to yellow. No effective configuration transformation occurred with guest molecules only or upon the addition of cucurbit[7]uril. The photoisomerization was fully characterized by UV-vis and fluorescence spectroscopy, NMR, high-resolution mass spectrometry, and transmission electron microscopy. This work provides a new method for the supramolecular macrocyclic-activated configuration transformation.

de Oliveira Junior H., Borges B.A., Barbosa T.W., Batista A., Braga M.T., de Araújo M.B., Bonfilio R.

Ketoprofen (KTP) is an Active Pharmaceutical Ingredient (API) that has low solubility in aqueous solvents. The use of KTP salts has attracted attention due to its improvements in terms of solubility, tolerability, higher rate and extent of absorption, and faster onset of the therapeutic effect. In this work, a crystalline KTP sodium salt (coded as KTP-Na) was successfully obtained and widely characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), solubility and accelerated stability studies. XRD results showed that KTP-Na is not yet reported in the literature. Moreover, FTIR, DSC and TGA were useful for differentiation of KTP-Na from the KTP commercialized form (coded as KTP-R1). The solubility of KTP-Na in water was about 80 times greater than the KTP-R1. However, KTP-Na showed lower physical stability in storage conditions at 40 ± 2°C/ 75% ± 5% RH when compared to KTP-R1, which was shown to be related to a high hygroscopicity of KTP-Na. Therefore, due to its higher solubility, KTP-Na may be a viable alternative for use in solid dosage forms. However, the presence of moisture must be strictly controlled to avoid water absorption and consequent amorphization.