Nitric oxide is an important molecule that plays a crucial role in regulating physiological processes in mammals. To develop a sensitive method for detecting NO, new heterostructures based on cobalt phthalocyanine (CoPc) films decorated with Ir-IrO2 nanoparticles were considered as active layers of chemiresistive sensors for the direct NO detection. Within deposition conditions, Ir-IrO2 nanoparticles with an Ir concentration of 0.48-1.5 mu g/cm2, a fraction of IrO2 phase of 10-20 %, and particles sizes from 1 to 3 to 14 nm were obtained on the surface of CoPc films. The influence of these parameters of Ir-IrO2 particles on the sensor response of Ir-IrO2/CoPc heterostructures to NO was investigated using theoretical and practical approaches. Based on DFT calculations, an electronic sensitization mechanism of NO detection by Ir-IrO2/CoPc heterostructures was proposed. These heterostructures are able to detect of NO gas at the ppb level and show the selectively to NOx in the presense of other gases.

Film heterostructures of compositions Ag/Au/Ti and Ag/Au/CFR-PEEK are obtained by thermal evaporation with subsequent deposition of metallic gold sublayers and silver nanostructures on modern biomaterials (Ti-6Al-4V alloy, polyether ether ketone CFR-PEEK). Silver concentration is varied within 2.1-20.8 µg/cm2 by changing the initial metal portion (1.2-5 mg) and the number of successive depositions (1–3). According to SEM data, Ag nanofilms with a thickness up to 10-15 nm are formed on the surface of gold sublayers. According to XPS results, gold is present in the metallic state on the surface of biomaterials whereas along with metal, the Ag2O oxide phase is detected for silver. The dynamics of silver dissolution from the Ag/Au surface is analyzed by ICP-AES (2-48 h). It is found that regardless of the silver concentration, the samples demonstrate moderate dynamics of releasing metal ions; some amount of gold is detected together with silver in the solution. The absence of cytotoxicity of the synthesized film heterostructures in vitro (L-929 cells, viability >95-98

Методом термического испарения получены пленочные гетероструктуры составов Ag/Au/Ti, Ag/Au/CFR-PEEK при последовательном осаждении подслоев металлического золота и наноструктур серебра на современные биоматериалы (сплав Ti-6Al-4V, полиэфирэфиркетон CFR-PEEK). Содержание серебра варьировали в интервале 2.1-20.8 мкг/см2 путем изменения исходной навески металла (1.2-5 мг) и количества последовательных нанесений (1-3). По данным СЭМ, на поверхности золотых подслоев формируются нанопленки Ag толщиной до 10-15 нм. По данным РФЭС на поверхности биоматериалов золото присутствует в металлическом состоянии, тогда как для серебра наряду с металлом регистрируется таже наличие оксидной фазы Ag2О. Методом ИСП-АЭС исследована динамика (2-48 ч) растворения серебра с поверхности Ag/Au. Обнаружено, что, независимо от концентрации серебра, образцы демонстрируют умеренную динамику выделения ионов металла, наряду с серебром в растворе также регистрируется небольшое количество золота. Показано отсутствие цитотоксичности синтезированных пленочных гетероструктур in vitro (клетки L-929, жизнеспособность >95-98%). Гетероструктуры полностью подавляют рост колоний грамотрицательных (P. аeruginosa) и грамположительных (S. аureus) бактерий через 6 и 24 часа воздействия, соответственно.

В работе исследована нуклеация гидрата метана из чистой воды и 2 мас. % раствора малоновой кислоты. Эксперименты проводились в стеклянных ампулах с обычной либо увеличенной гидрофильностью поверхности. Для увеличения гидрофильности поверхности использовались обработка хромовой смесью с последующим кипячением в воде. Показано, что более быстрая нуклеация (меньшие индукционные периоды) имеют место на более гидрофобных стенках. Если вместо чистой воды берется 2 мас. % раствор малоновой кислоты, индукционные периоды для большей части образцов существенно увеличиваются, причем этот эффект более выражен для гидрофилизированных стенок ампул. В работе обсуждаются возможные причины этих изменений. Визуальные наблюдения показали, что как минимум в большинстве случаев нуклеация гидрата в стеклянных ячейках в растворах малоновой кислоты происходит на поверхности контакта раствор — стекло, а не на трехфазной линии контакта раствор — стекло — газ.

The aim of study is to conduct in vivo biological testing of titanium nickelide samples modifed with Ag/Pt or AuAg/Pt flm heterostructures in comparison with the bare carrier.Material and Methods. Titanium nickelide plates modifed with flm heterostructures made of noble metals and the laboratory mini-pigs used for in vivo tests were the objects of the study. To form flm structures on titanium nickelide samples, the physical gasphase deposition methods: ion plasma deposition (IPD) and thermal (PVD) sputtering were used. The Ag/ Pt or AuAg/Pt heterostructures were characterized by X-ray diffraction and scanning microscopy methods.Results. The biocompatibility of implants before (TiNi, control) and after (Ag/Pt/TiNi and AuAg/Pt/TiNi) modifcation with flm heterostructures was tested in in-vivo experiments on a laboratory animal (mini-pig). General toxic reactions of the body to the injected samples were absent. A comparative macroscopic and histological analysis of the condition of peri-implant tissues after 39 days of implantation was performed. The connective tissue capsule around the TiNi sample revealed the presence of a certain number of lymphocytes, eosinophils and macrophages, but these indicators decrease in the order of TiNi > AuAg/Pt/TiNi > Ag/Pt/TiNi.Conclusion. The positive effect of modifying the titanium nickelide surfaces with noble metal heterostructures on the biocompatibility of metal implants was demonstrated in an in vivo experiment.

In this work crystal structures of octa- and hexadecafluoro-substituted tin(II) and tin(IV) phthalocyanines are shown. Complexes were obtained by fusing of fluorinated phthalonitriles with SnCl2 (Method 1) and refluxing the initial reagents in 1-chloronaphthalene (Method 2). In the case of octafluorosubstituted tin complexes it has been shown that during synthesis by the Method 1, Sn(II)PcF8 complexes are formed. At the same time, during the synthesis by the Method 2, Sn(IV)Cl2PcF8 complexes are obtained. It was demonstrated that not only the synthesis method but also the number of fluorine substituents affects the composition and structure of the obtained complexes. Unlike octasubstituted derivatives, only tin(IV) complexes are formed during the synthesis of hexadecafluorosubstituted phthalocyanines using both methods. Thus, when fusing tetrafluorophthalonitrile with SnCl2, halogen atoms are exchanged and a mixture of monomeric SnF2(PcF15Cl) and dimeric Sn2F3(PcF15Cl)2 complexes is formed. The synthesis in solution leads to the formation of SnCl2PcF16, which crystallizes together with 1-chloronapthalene solvate molecules. The effect of heating and vacuum sublimation on the transformation of Sn(IV) phthalocyanines is also studied.

The work investigated the nucleation of methane hydrate from pure water and a 2 wt

В данной работе проводится сравнительное исследование кристаллической структуры, а также структурных особенностей пленок фталоцианинов свинца с хлор-заместителями в периферийных (PbPcCl4-p) и непериферийных положениях фталоцианинового кольца (PbPcCl4-np), полученных методом термической сублимации в вакууме. Показано, что, как в случае незамещенного фталоцианина свинца, в молекулах PbPcCl4-p и PbPcCl4-np катион свинца выходит из плоскости макрокольца. PbPcCl4-p кристаллизуется в пр. гр. I4/m и молекулы PbPcCl4-p упаковываются в вертикальные стопки вдоль оси 4. Введение Cl-заместителей в непериферийные положения фталоцианинового кольца приводит к изменению кристаллической структуры. PbPcCl4-np кристаллизуется в пр. гр. P21/n, при этом молекулы PbPcCl4-np упаковываются в слои вдоль оси b, внутри одного слоя молекулы упакованы в цепочки, с чередующейся ориентацией молекул с атомами свинца «вверх» и «вниз». Изучено влияние положения хлор-заместителя на микроструктурные особенности пленок PbPcСl4-p и PbPcCl4-np методами рентгенофазового анализа и электронной спектроскопии поглощения.

In this review, we generalize the research results obtained by Russian scientists in the last 10-15 years for porphyrins, related compounds, and their metal complexes with a pronounced application potential. The main attention is paid to the analysis of relationships between the spectral, catalytic, and sensor properties of tetrapyrrole compounds and the structure of peripheral substituents and axial ligands and the nature of the coordinating metal atom.

The structure of trimethylplatinum(IV) iodide [(CH 3 ) 3 PtI] 4 ( I ) (CIF file CCDC no. 22330007) is refined. The structure of the synthesized for the first time trimethylplatinum(IV) complex with tridentate N , N , O -iminoketonate [(CH 3 ) 3 Pt(C 9 H 17 N 2 O)] ( II ) is determined by X-ray diffraction (XRD) (CIF file CCDC no. 22330008). The purity of the isolated phases is confirmed by elemental analysis and IR and NMR spectroscopy. The thermal behavior of complex II is studied by thermogravimetry. The energies of ionization and fragmentation of the molecules of complex II leading to the formation of the most stable fragment [(CH 3 ) 3 Pt] + are estimated by quantum-chemical calculations. Complex II is tested in the MOCVD processes. The Pt films with the pronounced (111) texture and particle sizes about 100 nm are prepared on Si plates in the presence of oxygen.

β-Iminoketones H(i-thd) ( t -BuCOCH 2 NH t -Bu) and H(i-zis) ( t -BuCOCH 2 NHC(CH 3 ) 2 (OCH 3 )) and the corresponding platinum(II) complexes Pt(i-thd) 2 ( 1 ) and Pt(i-zis) 2 ( 2 ) are prepared and first characterized by the elemental analysis, IR, and NMR spectroscopy methods. The crystal lattice parameters of H(i-zis) and complexes 1 and 2 are determined by XRD. For 1 , C 22 H 40 N 2 O 2 Pt: a = 9.9059(3) Å, b = 11.9889(3) Å, c = 11.2522(3) Å, β = 110.031(1)°, P 2 1 / n space group, Z = 2, R = 0.014; for 2 , C 22 H 40 N 2 O 4 Pt: a = 9.8340(3) Å, b = 12.4814(4) Å, c = 10.5993(4) Å, β = 104.784(1)°, P 2 1 / n space group, Z = 2, R = 0.022. The platinum atom has a square-planar coordination in both structures; the differences between the lengths of Pt–O and Pt–N bonds are minimal. The thermal behavior of the complexes is studied by thermogravimetry and is compared with that of their Pt(acac) 2 analog.

This work is devoted to the study of the effect of the position of fluorine substituents in the molecules of tetrafluorosubstituted zinc phthalocyanines on their saturated vapor pressure. For this purpose, the temperature dependence of the saturated vapor pressure of zinc phthalocyanines with fluorine substituents in the peripheral (ZnPcF 4 -p) and non-peripheral (ZnPcF 4 -np) positions of the phthalocyanine ring has been studied by the Knudsen method with mass spectrometric recording of the composition of the gas phase and the thermodynamic parameters of vaporization were calculated. The data obtained for ZnPcF 4 -p and ZnPcF 4 -np with unsubstituted and hexadecafluorosubstituted zinc phthalocyanines are compared in terms of analysis of intermolecular interactions in the crystals of these compounds. It has been shown that tetrafluorosubstituted phthalocyanines have a higher vapor pressure than their unsubstituted (ZnPc) and hexadecafluorosubstituted (ZnPcF 16 ) derivatives. In this case, the enthalpy of sublimation increases in the series ZnPcF 4 -p < ZnPcF 4 -np < ZnPc < ZnPcF 16 .

Получены β-иминокетоны H(i-thd) – tBuCOCH2NHtBu, H(i-zis) – tBuCOCH2NHC(CH3)2(OCH3) и, соответствующие комплексы платины(II) Pt(i-thd)2 (1) и Pt(i-zis)2 (2). Комплексы платины(II) с β-иминокетонами впервые охарактеризованы методами элементного анализа и ИК, ЯМР спектроскопии комплексы. Методом РСА определены параметры кристаллической решётки для H(i-zis) и комплексов 1 и 2. Для 1 – C22H40N2O2Pt: a = 9.9059(3), b = 11.9889(3), c = 11.2522(3) Å, b =110.031(1)°, пр. гр. P21/n, Z = 2, R = 0.014; для 2 – C22H40N2O4Pt: a = 9.8340(3), b = 12.4814(4), c = 10.5993(4) Å, b =104.784(1)°, пр. гр. P21/n, Z = 2, R = 0.022. В обеих структурах атом платины имеет плоско-квадратную координацию, а различия в длинах связей Pt-O и Pt-N минимальны. Термическое поведение комплексов исследовано методом термогравиметрии в сравнении с их аналогом Pt(acac)2.

В работе проведено исследование влияния магнитного поля на структурную организацию и сенсорные свойства тонких слоев фталоцианина титанила (TiOPc) нанесенных методом термического испарения в вакууме. Показано, что наличие магнитного поля (направлено перпендикулярно к поверхности подложки) не влияет на фазовый состав слоев - в обоих случаях они представлены двумя кристаллическими модификациями - II-триклинной и I-моноклинной. Кристаллиты обеих фаз преимущественно ориентированы, углы между плоскостями молекул и подложкой составляют 62.53 и 5.30° соответственно. Исследование в схеме 2D GIXD, показало, что наличие магнитного поля, существенно улучшило кристалличность полученных тонких слоев, при этом проводимость увеличилась в ~10 раз, но величина сенсорного отклика на аммиак не изменилась. Облучение слоя, полученного в магнитном поле, быстрыми нейтронами (флюенс 3´1014 см-2) привело к уменьшению проводимости на два порядка, в параллельном эксперименте без магнитного поля, эффект не проявился.

The comparative study of the crystal structure and structural features of thermally sublimed films with lead phthalocyanines with chlorine substituents at peripheral (PbPcCl 4 -p) and non-peripheral positions of the phthalocyanine ring (PbPcCl 4 -np) is reported. It is shown that as for non-substituted phthalocyanine lead, in PbPcCl 4 -p and PbPcCl 4 -np molecules, the lead cation is out of the plane of the macrocycle. PbPcCl 4 -p crystallizes in the tetragonal crystal system (space group I 4/ m ), and the PbPcCl 4 -p molecules are packed into vertical stacks along axis 4. The introduction of chlorine substituents into non-peripheral positions of the phthalocyanine ring causes a change in the crystal structure. PbPcCl 4 -np crystallizes in the space group P 2 1 / n , with PbPcCl 4 -np molecules being packed in layers along the b axis; inside one layer - in chains with alternating up and down orientations of lead atoms. The effect of the position of chlorine substituents on the microstructural features of PbPcСl 4 -p and PbPcCl 4 -np films is studied by powder X-ray diffraction and electronic absorption spectroscopy.

The iron phthalocyanine derivatives (FePc) are regarded as active layers of sensors. The films of iron phthalo-cyanines, viz. FePc, FePcF4, and FePcCl4 were deposited onto glassy carbon electrodes. Annealed film (a-FePc) were decorated with platinum nanoparticles (PtNPs) and carbon rods using facile metal organic chemical vapor deposition (MOCVD), resulting in a series of Pt/a-FePc heterostructures. The composition, distribution and sizes of PtNPs and carbon rods in the heterostructures were investigated. The electrochemical characteristics of the series of FePc, FePcF4, and FePcCl4 and Pt/a-FePc samples were determined in 0.1 M PBS solution using cyclic voltammetry (CV, 0.25-2.00 mM), amperometry (CA 0.5-30 & mu;M), and impedance spectroscopy. The Pt/a-FePc heterostructures with a Pt content of 21-63 & mu;M/cm2, which consisted of uniformly distributed PtNPs with a size of 9-12 nm and carbon rods up to 1 & mu;m in length, demonstrated the excellent electron transfer characteristics Synergetic combination of the properties of 3 components (a-FePc, PtNPs or carbon rods) resulted in the improvement of the performance of Pt/a-FePc sensors. The Pt/a-FePc electrode demonstrated the lowest detection limit of 0.06 & mu;M and high sensitivity to NO2 . This sensor had good selectivity in the presence of interfering analytes, repeatability and stability.

В данном обзоре обобщены результаты исследований в области порфиринов, родственных соединений и их металлокомплексов с явно выраженным прикладным потенциалом, выполненных российскими учеными в последние 10-15 лет. Основное внимание сосредоточено на анализе взаимосвязи спектральных, каталитических и сенсорных свойств тетрапиррольных соединений со строением экваториального порфиринового и аксиальных лигандов и природой координирующего атома металла.

We report a study of the effect of magnetic field on the structural organization and sensory properties of thin titanyl phthalocyanine (TiOPc) layers deposited by vacuum thermal evaporation. It is shown that magnetic field (directed perpendicular to the substrate surface) does not affect the phase composition of the layers which are represented by II-triclinic and I-monoclinic crystal modifications in both cases. The crystallites of both phases demonstrate preferential orientations, the angles between molecular planes and the substrate are 62.53° and 5.30°, respectively. The 2D GIXD study shows that magnetic field significantly improves the crystallinity of obtained thin layers; the conductivity increases by ~10 times, but the sensory response to ammonia does not change. Irradiating the layer obtained in magnetic field by fast neutrons (fluence 3·10 14 cm –2 ) decreases the conductivity by two orders of magnitude. This effect is not observed in the parallel experiment without magnetic field.

An Erratum to this paper has been published: https://doi.org/10.1134/S0022476622040205