Search

The development of (bio)catalysts capable of selectively activating strong C-H bonds is a continuing challenge in modern chemistry. In both metalloenzymes and synthetic systems capable of activating C-H bonds, transition metal-oxido intermediates serve as the active species for reactivity whose thermodynamic properties influence the bond strengths they are capable of activating. In this Frontier article, we present current ideas of how the basicity of transition metal-oxidos impacts their reactivity with C-H bonds and present new opportunities within this field. We highlight recent insights into the role basicity plays in the activation process and its influence on mechanism, as well as the important role that secondary coordination sphere effects, such as hydrogen bonds, in tuning the basicity of the metal-oxido species is discussed.

of the DissertationPreparation and Properties of Mono- and Bimetallic Paramagnetic Co Complexes Supported by Tripodal Ligand Frameworks by Meghen E. Goulet Doctor of Philosophy in Chemistry University of California, Irvine, 2022 Distinguished Professor Andrew S. Borovik, Chair Many important and synthetically challenging chemical reactions are carried out by metalloenzymes, including water oxidation, nitrogen fixation, O2 reduction, and oxidation of C–H bonds in substrates such as methane, fatty acids, and pharmaceutical products. Metalloenzymes are able to catalyze these reactions in part due to their ability to access reactive intermediates which is facilitated by the protein host. To replicate these effects synthetically, the Borovik lab designs organic ligands that incorporate both primary and secondary coordination sphere interactions to control the local environment within metal complexes. This dissertation presents research that employs these ligand frameworks in both mono- and bimetallic small molecule Co complexes. Chapter 1 provides a brief introduction to key features of metalloenzyme active sites that support their reactivity. A concise overview of relevant synthetic ligand designs is given, in addition to summaries of the following chapters. Chapter 2 describes the preparation of mononuclear CoII– and CoIII–OH complexes within an unsymmetric, hybrid tripodal ligand framework: [H2pout]3–. The characterization of these complexes is discussed, including the molecular structure of K[CoIIIH2pout(OH)]. xx K[CoIIIH2pout(OH)] is paramagnetic, an unusual trait for a CoIII center. The reactivity of K[CoIIIH2pout(OH)] towards substrates with an O–H bonds is also examined. This work is the first reactivity study of a CoIII–OH complex. Chapter 3 describes the preparation of a trigonal monopyramidal, four-coordinate Co complex supported by the C3 symmetric [poat]3– ligand framework. This complex, K[CoIIpoat] is used in Chapter 3 – 5 to prepare unsymmetric bi

Non-heme Fe monooxygenases activate C-H bonds using intermediates with high-spin FeIV-oxido centers. To mimic these sites, a new tripodal ligand [pop]3- was prepared that contains three phosphoryl amido groups that are capable of stabilizing metal centers in high oxidation states. The ligand was used to generate [FeIVpop(O)]-, a new FeIV-oxido complex with an S = 2 spin ground state. Spectroscopic measurements, which included low-temperature absorption and electron paramagnetic resonance spectroscopy, supported the assignment of a high-spin FeIV center. The complex showed reactivity with benzyl alcohol as the external substrate but not with related compounds (e.g., ethyl benzene and benzyl methyl ether), suggesting the possibility that hydrogen bonding interaction(s) between the substrate and [FeIVpop(O)]- was necessary for reactivity. These results exemplify the potential role of the secondary coordination sphere in metal-mediated processes.

The Parameter Continuation Theorem is the theoretical foundation for polynomial homotopy continuation, which is one of the main tools in computational algebraic geometry. In this note, we give a short proof using Gr\"obner bases. Our approach gives a method for computing discriminants.

Artificial metalloproteins (ArMs) have recently gained significant interest due to their potential to address issues in a broad scope of applications, including biocatalysis, biotechnology, protein assembly, and model chemistry. ArMs are assembled by the incorporation of a non-native metallocofactor into a protein scaffold. This can be achieved by a number of methods that apply tools of chemical biology, computational de novo design, and synthetic chemistry. In this Perspective, we highlight select systems in the hope of demonstrating the breadth of ArM design strategies and applications and emphasize how these systems address problems that are otherwise difficult to do so with strictly biochemical or synthetic approaches.

The Ural Population Project (URAPP) is built from individual level data transcriptions of 19th- to early 20th-century parish records and mid-19th-century census-like tax revisions manuscripts. This article discusses the source material, the contents, the history of creation and the strategy of the URAPP database and the outcome of the main research topics so far, including historical demography, Jewish studies, indigenous studies and studies of religious minorities in the Urals and Siberia. Our studies of the ethno-religious cultural landscape of the Urals and northwestern Siberia as well as participation in population history projects was more vital backgrounds than the traditional focus on aggregates. The over 65,000 vital events transcribed from parish records of Russian Orthodox Churches and minority religions in and around Ekaterinburg have been the basis for studies of mortality, nuptiality, religion and other characteristics. We found that the Jewish population kept their traditions and connections with relatives in the Pale of Settlement. Prisoners of WWI usually marrying within their own religious group. Infant mortality in Ekaterinburg was lower among Jews and the Catholics, minorities with higher education and western background, while the Orthodox majority exposed their newborn to extremely tough baptism. The burial records show cases of the Spanish flu in 1918–1919, but on a lower level than in the West, supporting recent theories that estimates of flu mortality may be too high. Based on the tax revisions, polygyny was officially recognized among the indigenous Siberian people. The strategy of the URAPP project has evolved from transcribing microdata about minorities towards covering the whole population.

Artificial metalloproteins (ArMs) have recently gained significant interest due to their potential to address issues in a broad scope of applications, including biocatalysis, biotechnology, protein assembly, and model chemistry. ArMs are assembled by the incorporation of a non-native metallocofactor into a protein scaffold. This can be achieved by a number of methods that apply tools of chemical biology, computational de novo design, and synthetic chemistry. In this Perspective, we highlight select systems in the hope of demonstrating the breadth of ArM design strategies and applications and emphasize how these systems address problems that are otherwise difficult to do so with strictly biochemical or synthetic approaches.

Нравственные категории, хорошо и плохо, как добро и зло, можно и нельзя, целесообразно формировать своим собственным примером, а также с помощью народных сказок. Именно сказки утверждают ребёнка в правильных отношениях к миру.

In nature, metalloproteins can perform difficult transformations with high selectivity and efficiency through precise control of the primary and secondary coordination sphere. Synthetic chemists have developed biomimetic ligand scaffolds to better understand the coordination environments in the active sites of metalloproteins. However, besides the ligands covalently bound to the metal center, secondary coordination sphere that is comprised of non-covalent interactions also has significant influence in complex properties. This dissertation describes how modulation of the secondary coordination sphere by incorporating different H-bond donors or acceptors affects the chemistry of metal complexes. Chapter 2 describes a series of MnIII-oxido complexes within the hybrid tripodal framework, [H3bpuea-R]3‒, which one of the ligand arms contains a para-substituted phenyl ring. Varying the R-groups on the phenyl ring allowed modulation on the strength of one single H-bond donor in the secondary coordination sphere without perturbing the primary coordination sphere. This modulation showed influences on basicity and reactivity of the MnIII-oxido complexes. Chapter 3 describes newly synthesized FeII/III-NH3 and FeIII-amido complexes in C3-symmetric tripodal phosphinic amido ligand framework, [poat]3–. Comparing the FeII/III-NH3 complexes in the [poat]3– ligand framework and analogous complexes in [MST]3– ligand framework showed significant differences in their structural and redox properties, suggesting [poat]3– can serve as a stronger donor ligand and provide stronger H-bonding interactions. Chapter 4 describes the reactivity of a high spin FeIV-oxido complex, [FeIVPOP(O)]–, in C3-symmetric tripodal phosphoryl amido ligand framework. Taking inspiration from TauD having substrate anchored in close proximity of the metal center, benzyl alcohol was used as a substrate that can participate in possible H-bond interaction with the P=O in phosphoryl amido arms of the complex. Reactivit

In nature, metalloproteins can perform difficult transformations with high selectivity and efficiency through precise control of the primary and secondary coordination sphere. Synthetic chemists have developed biomimetic ligand scaffolds to better understand the coordination environments in the active sites of metalloproteins. However, besides the ligands covalently bound to the metal center, secondary coordination sphere that is comprised of non-covalent interactions also has significant influence in complex properties. This dissertation describes how modulation of the secondary coordination sphere by incorporating different H-bond donors or acceptors affects the chemistry of metal complexes. Chapter 2 describes a series of MnIII-oxido complexes within the hybrid tripodal framework, [H3bpuea-R]3‒, which one of the ligand arms contains a para-substituted phenyl ring. Varying the R-groups on the phenyl ring allowed modulation on the strength of one single H-bond donor in the secondary coordination sphere without perturbing the primary coordination sphere. This modulation showed influences on basicity and reactivity of the MnIII-oxido complexes. Chapter 3 describes newly synthesized FeII/III-NH3 and FeIII-amido complexes in C3-symmetric tripodal phosphinic amido ligand framework, [poat]3–. Comparing the FeII/III-NH3 complexes in the [poat]3– ligand framework and analogous complexes in [MST]3– ligand framework showed significant differences in their structural and redox properties, suggesting [poat]3– can serve as a stronger donor ligand and provide stronger H-bonding interactions. Chapter 4 describes the reactivity of a high spin FeIV-oxido complex, [FeIVPOP(O)]–, in C3-symmetric tripodal phosphoryl amido ligand framework. Taking inspiration from TauD having substrate anchored in close proximity of the metal center, benzyl alcohol was used as a substrate that can participate in possible H-bond interaction with the P=O in phosphoryl amido arms of the complex. Reactivit

Чрезмерная занятость родителей, разрыв поколений, изолированность ребёнка в семье, отсутствие «дворовой» культуры и другие тенденции негативно отражаются на социализации современных детей. Нарастание негативных тенденций в подростковой среде выдвигает на первый план задачу социализации детей, начиная с дошкольного возраста. В статье описывается опыт реализации в дошкольном образовательном учреждении социальных акций, основная цель которых – формирование эмоционально-ценностного отношения к миру, окружающим людям и самому себе на основе нравственного содержания.

This article compares interethnic and interreligious marriages in Russia and Norway during the decades around 1900. State churches dominated religious life in both countries with over 90 percent of the population but both were losing influence during the period we focus on—rapidly in Russia after the 1917 Revolution. The part on Norway employs nominative and aggregate census material which from 1865 asked questions about religious affiliation, while the Russian case study utilizes the database of church microdata being built for Ekaterinburg—a railway hub and an industrial city in the Middle Urals, in Asia—in addition to census aggregates. Our main conclusion is that religion was a stronger regulator of intermarriage than ethnicity. Religious intermarriage was unusual in Ekaterinburg, even if official regulations were softened by the State over time—the exception is during World War I, when there was a deficit of young, Russian men at home and influx of refugees and Austro-Hungarian Prisoners of War (mostly Catholics and Lutherans). The situation was also affected by the 1917 Revolution creating equal rights for all religious denominations. The relatively few religious intermarriages in Norway were mostly between members of different Protestant congregations—nonmembers being the only group who often outmarried. We conclude that representatives of ethnic minorities and new religions seldom outmarry when religion was important for maintaining their identity. © 2020 The Author(s).

In nature, metalloproteins can perform difficult transformations with high selectivity and efficiency through precise control of the primary and secondary coordination sphere. Synthetic chemists have developed biomimetic ligand scaffolds to better understand the coordination environments in the active sites of metalloproteins. However, besides the ligands covalently bound to the metal center, secondary coordination sphere that is comprised of non-covalent interactions also has significant influence in complex properties. This dissertation describes how modulation of the secondary coordination sphere by incorporating different H-bond donors or acceptors affects the chemistry of metal complexes. Chapter 2 describes a series of MnIII-oxido complexes within the hybrid tripodal framework, [H3bpuea-R]3‒, which one of the ligand arms contains a para-substituted phenyl ring. Varying the R-groups on the phenyl ring allowed modulation on the strength of one single H-bond donor in the secondary coordination sphere without perturbing the primary coordination sphere. This modulation showed influences on basicity and reactivity of the MnIII-oxido complexes. Chapter 3 describes newly synthesized FeII/III-NH3 and FeIII-amido complexes in C3-symmetric tripodal phosphinic amido ligand framework, [poat]3–. Comparing the FeII/III-NH3 complexes in the [poat]3– ligand framework and analogous complexes in [MST]3– ligand framework showed significant differences in their structural and redox properties, suggesting [poat]3– can serve as a stronger donor ligand and provide stronger H-bonding interactions. Chapter 4 describes the reactivity of a high spin FeIV-oxido complex, [FeIVPOP(O)]–, in C3-symmetric tripodal phosphoryl amido ligand framework. Taking inspiration from TauD having substrate anchored in close proximity of the metal center, benzyl alcohol was used as a substrate that can participate in possible H-bond interaction with the P=O in phosphoryl amido arms of the complex. Reactivit

The primary and secondary coordination spheres can have large regulatory effects on the properties of metal complexes. To examine their influences on the properties of monomeric Fe complexes, the tripodal ligand containing phosphinic amido groups, N,N',N''-[nitrilotris(ethane-2,1-diyl)]tris(P,P-diphenylphosphinic amido) ([poat]3-), was used to prepare [FeII/IIIpoat]-/0 complexes. The FeII complex was four-coordinate with 4 N-atom donors comprising the primary coordination sphere. The FeIII complex was six-coordinate with two additional ligands coming from coordination of O-atom donors on two of the phosphinic amido groups in [poat]3-. In the crystalline phase, each complex was part of a cluster containing potassium ions in which KO[double bond, length as m-dash]P interactions served to connect two metal complexes. The [FeII/IIIpoat]-/0 complexes bound an NH3 molecule to form trigonal bipyramidal structures that also formed three intramolecular hydrogen bonds between the ammine ligand and the O[double bond, length as m-dash]P units of [poat]3-. The relatively negative one-electron redox potential of -1.21 V vs. [FeIII/IICp2]+/0 is attributed to the phosphinic amido group of the [poat]3- ligand. Attempts to form the FeIII-amido complex via deprotonation were not conclusive but isolation of [FeIIIpoat(NHtol)]- using the p-toluidine anion was successful, allowing for the full characterization of this complex.

The oxidation of substrates via the cleavage of thermodynamically strong C-H bonds is an essential part of mammalian metabolism. These reactions are predominantly carried out by enzymes that produce high-valent metal-oxido species, which are directly responsible for cleaving the C-H bonds. While much is known about the identity of these transient intermediates, the mechanistic factors that enable metal-oxido species to accomplish such difficult reactions are still incomplete. For synthetic metal-oxido species, C-H bond cleavage is often mechanistically described as synchronous, proton-coupled electron transfer (PCET). However, data have emerged that suggest that the basicity of the M-oxido unit is the key determinant in achieving enzymatic function, thus requiring alternative mechanisms whereby proton transfer (PT) has a more dominant role than electron transfer (ET). To bridge this knowledge gap, the reactivity of a monomeric MnIV-oxido complex with a series of external substrates was studied, resulting in a spread of over 104 in their second-order rate constants that tracked with the acidity of the C-H bonds. Mechanisms that included either synchronous PCET or rate-limiting PT, followed by ET, did not explain our results, which led to a proposed PCET mechanism with asynchronous transition states that are dominated by PT. To support this premise, we report a semiempirical free energy analysis that can predict the relative contributions of PT and ET for a given set of substrates. These findings underscore why the basicity of M-oxido units needs to be considered in C-H functionalization.

The functionalization of C-H bonds is one of the most challenging transformations in synthetic chemistry. In biology, these processes are well-known and are achieved with a variety of metalloenzymes, many of which contain a single metal center within their active sites. The most well studied are those with Fe centers, and the emerging experimental data show that high-valent iron oxido species are the intermediates responsible for cleaving the C-H bond. This Forum Article describes the state of this field with an emphasis on nonheme Fe enzymes and current experimental results that provide insights into the properties that make these species capable of C-H bond cleavage. These parameters are also briefly considered in regard to manganese oxido complexes and Cu-containing metalloenzymes. Synthetic iron oxido complexes are discussed to highlight their utility as spectroscopic and mechanistic probes and reagents for C-H bond functionalization. Avenues for future research are also examined.

The article deals with fiscal policy in the decentralized space of the financial system of Ukraine. The methodology of complex, systematic assessment of fiscal policy in the decentralized space of the financial system of the state is grounded. It is proved that effective methodological approach to assessing fiscal policy in the decentralized space of the financial system of the state is a vector auto regression (VAR), which provides dynamic correlation of time series with simultaneous determination of each exogenous and endogenous variable in the system, in case of fiscal impulses (shocks) in economy. The production-institutional function is used which, when adapting to the relationship between GDP and tax burden with specific statistics, changes the type of trend of tax revenue. A method for evaluating the effectiveness of financing targeted programs for decentralized territory has been developed. The dynamics of direct and indirect taxes to the state and local budgets are analyzed and the fiscal significance of VAT in GDP, the state budget and tax revenues of Ukraine is determined. The amount of tax debt and the state budget deficit has been estimated and the structure of tax benefits in terms of taxes and fees in Ukraine is presented. The projected values of real tax revenues per capita are substantiated and the forecast parameters of the level of subsidization of local budgets of decentralized territories are given.

Context. In border security uses a system of optical-electronic observation, which presents a set of towers that have radar, thermal imaging and video surveillance. The efficiency of detecting trespassers with the use of this system significantly depends on its functional and structural construction. The functional structure of system of optical-electronic observation is determined by the selection of technical means of surveillance (TCS) based on their functionality. Structure of the system depends on the choice of the locations of observation towers with the physical and geographical conditions of the terrain and technical characteristics of the TCS. The imperfection of the scientific methodological apparatus in the field of structural optimization of building of system of optical-electronic observation was determined by the relevance of the study.Objective. The aim of this work is to develop a method of structural optimization of the placement of the system of optical-electronic observation towers.Method. In work the task of optimizing the placement of the towers of system of optical-electronic observation and the proposed method of its solution, which involves the maximization of efficiency of functioning of the system. The peculiarity of this method is the use of geomodel to reduce the number of accommodation of the towers of the system, the use of the author’s approach to sampling of spatial data and high-speed algorithm for calculation of efficiency of functioning of system of optical-electronic observation.Results. The paper shows the advantages of the proposed method compared to previously proposed approaches for the choice of rational placement of towers on the basis of cluster analysis. In this work the proposed software-algorithmic implementation of the method to structural optimization of the system of optical-electronic observation. The authors describe the description of algorithmic and software implementation of this method. Using the developed soft

In this article methods and means of ensuring electromagnetic compatibility were considered, which can be used to reduce the effect of crosstalk between conductors on the device board. We analyzed the causes and mechanism of crosstalk, which can disrupt the correct operation of the device due to a change in the logic level of the signal on the victim conductor due to the effect of crosstalk pickup on it. The simulation of the influence of interference on the signal in the passive line was automated depending with the distance between conductors, the length of the adjacent section of conductors, and conductor materials. For the study, a logical circuit of an electronic device, in particular encoder, and a printed circuit board were built. Experiments were carried out using the following data: conductor thickness of 5, 6 and 1.2 mils, conductor spacing of 5 and 6 mils, adjacent conductor lengths of 4340. 2020, 1620, 1050, 630, 320 and 300 mils, and materials conductors that have different values of specific electrical conductivity: silver (62,500,000 S/m), copper (5950,000 S/m), platinum (10,000,000 S/m), gold (43,000,000 S/m), nickel (15,000,000 S/m), aluminum (35*106 S/m), steel (1400000 S/m). The data on the values of crosstalk were obtained. Research performed at the designed logic circuit electronic device and its circuit board. The data on the values of crosstalk were obtained according to the constructed reports. In the course of these studies, the dependences of an increase in the value of crosstalk on an increase in the length of adjacent sections, a decrease in the distance between conductors.

Статья посвящена технологии Н.А. Коротковой «Путешествие по реке времени», которая способствует развитию познавательно-исследовательской деятельности у детей с тяжелым нарушением речи. В своей работе авторы доказывают, что использование этой технологии создаёт у детей положительную мотивацию в различных видах деятельности, способствует повышению уровня самооценки, позволяет варьировать методы и приемы обучения с учетом индивидуальных особенностей детей с ТНР, обеспечивает успешность формирования речевой и познавательной активности у детей.

Присутствие большого количества старообрядцев является одной из черт конфессионального своеобразия Уральского региона. Главным городским центром местного старообрядчества начиная с XVIII в. был Екатеринбург. По численности сторонники «древлего благочестия» уступали лишь православному населению и были в конце XIX в. самым крупным религиозным меньшинством города. Однако по городам Урала и всему региону в целом, где старообрядческая составляющая также была очень весомой, почти нет регулярных данных о событиях жизненного цикла. Исключением являлся Екатеринбург, где все объединения старообрядцев имели с 1907 г. статус официально признанных религиозных общин и вели собственные метрические книги. Сохранившийся комплекс этих уникальных документов за 1907–1926 гг. является источником по истории отдельных семей и локального религиозного сообщества, но также может привлекаться к изучению широкого спектра исторических процессов, выявлению их региональной и локальной специфики. Ценность выявленных документов в том, что на территории Среднего Урала это единственный на данный момент комплекс метрик городского старообрядческого сообщества, охватывающий все имевшиеся в населенном пункте направления за максимально возможный для этого источника период. Из-за сомнений часовенных в пользе от регистрации общин по Указу 17 октября 1906 г. в их приходах ведение собственных метрик было редкостью. Метрики остальных согласий, прежде всего белокриницкого, встречаются чаще, но охватывают незначительную часть старообрядческого населения и за более короткий период. В данной статье рассматриваются проблемы и перспективы использования данных старообрядческих метрик, степень их надежности и полноты для исследования младенческой и детской смертности., A large number of Old Believers is a feature of the confessional diversity of the Urals. Starting from the 18th century, Yekaterinburg was the main urban centre of Old Believers. There were fewer Old Believers than Orthodox Christians, but they were the largest religious minority of the city. However, there is no information about their everyday life routines in other Ural cities and parts of the region on the whole that had considerable Old Believer communities. Yekaterinburg was an exception where all Old Believer communities had official status from 1907 and kept their own metric books. The extant complex of unique documents from the period between 1907 and 1926 is a valuable source on the history of families and the local religious community, but it is also important for studying the local specifics of historical processes. The Old Believer metrics of Yekaterinburg are particularly valuable because the complex covers all the available directions in the village for the maximum period possible for this source. Because of the doubts Chasovennye had concerning the use of registering communities under the Edict of October 17, 1906, in their parishes, metric records were a rare thing. Metric books of the other concords, such as, most importantly, those of Belaya Krinitsa, can be found more often but they only cover a minor part of the Old Believer population and over a shorter period. This article discusses the problems and prospects of using data from Old Believer metrics, the degree of their reliability and completeness for the study of infant and child mortality.

Metalloenzymes are efficient catalysts, operating both stereo- and regioselectively with high reaction rates at ambient temperatures in aqueous conditions. In order to generate synthetic catalysts which operate in similarly efficient pathways, it is useful to study biomimeticcomplexes which incorporate the techniques used by biological systems. In this report, several pincer ligand frameworks are used to incorporate the interplay between primary coordination sphere effects and secondary coordination sphere effects observed in metalloenzyme active sites. H4dippy, which combines appendant dipeptides to create a chiral environment as well as distal hydrogen-bonding groups was prepared and used to generate CuIIH2dippy. Further experiments probed the oxidation of CuIIH2dippy with aqueous H2O2. A new phosphonamide bis(aminophenyl)amine ligand, H3tap, was used to prepare a cobalt(II) complex with opticalfeatures consistent with a [Co2N2] diamond core structure. Reaction with oxidants generated species with spectroscopic characteristics consistent with ligand oxidation and retention of a dinuclear complex. Finally, the redox-active sulfonamide bis(aminophenyl)amine, H3ibaps, as well as H3tap, were used to generate putative iron(III) thiolate complexes. These complexes were studied by reaction with the oxo-transfer reagent isopropyl iodoxybenzoate and subsequent reaction with substrates

Статья посвящена технологии Н.А. Коротковой «Путешествие по реке времени», которая способствует развитию познавательно-исследовательской деятельности у детей с тяжелым нарушением речи. В своей работе авторы доказывают, что использование этой технологии создаёт у детей положительную мотивацию в различных видах деятельности, способствует повышению уровня самооценки, позволяет варьировать методы и приемы обучения с учетом индивидуальных особенностей детей с ТНР, обеспечивает успешность формирования речевой и познавательной активности у детей.

Статья посвящена технологии Н.А. Коротковой «Путешествие по реке времени», которая способствует развитию познавательно-исследовательской деятельности у детей с тяжелым нарушением речи. В своей работе авторы доказывают, что использование этой технологии создаёт у детей положительную мотивацию в различных видах деятельности, способствует повышению уровня самооценки, позволяет варьировать методы и приемы обучения с учетом индивидуальных особенностей детей с ТНР, обеспечивает успешность формирования речевой и познавательной активности у детей.

Metalloenzymes are efficient catalysts, operating both stereo- and regioselectively with high reaction rates at ambient temperatures in aqueous conditions. In order to generate synthetic catalysts which operate in similarly efficient pathways, it is useful to study biomimeticcomplexes which incorporate the techniques used by biological systems. In this report, several pincer ligand frameworks are used to incorporate the interplay between primary coordination sphere effects and secondary coordination sphere effects observed in metalloenzyme active sites. H4dippy, which combines appendant dipeptides to create a chiral environment as well as distal hydrogen-bonding groups was prepared and used to generate CuIIH2dippy. Further experiments probed the oxidation of CuIIH2dippy with aqueous H2O2. A new phosphonamide bis(aminophenyl)amine ligand, H3tap, was used to prepare a cobalt(II) complex with opticalfeatures consistent with a [Co2N2] diamond core structure. Reaction with oxidants generated species with spectroscopic characteristics consistent with ligand oxidation and retention of a dinuclear complex. Finally, the redox-active sulfonamide bis(aminophenyl)amine, H3ibaps, as well as H3tap, were used to generate putative iron(III) thiolate complexes. These complexes were studied by reaction with the oxo-transfer reagent isopropyl iodoxybenzoate and subsequent reaction with substrates

A series of nickel complexes in varying oxidation states were evaluated as precatalysts for the stereospecific cross-coupling of benzylic ethers. These results demonstrate rapid redox reactions of precatalysts, such that the oxidative state of the precatalyst does not dictate the oxidation state of the active catalyst in solution. These data provide the first experimental evidence for a Ni0 -NiII catalytic cycle for a stereospecific alkyl-alkyl cross-coupling reaction, including spectroscopic analysis of the catalyst resting state.

An important class of non-heme dioxygenases contains a conserved Fe binding site that consists of a 2-His-1-carboxylate facial triad. Results from structural biology show that, in the resting state, these proteins are six-coordinate with aqua ligands occupying the remaining three coordination sites. We have utilized biotin-streptavidin (Sav) technology to design new artificial Fe proteins (ArMs) that have many of the same structural features found within active sites of these non-heme dioxygenases. An Sav variant was isolated that contains the S112E mutation, which installed a carboxylate side chain in the appropriate position to bind to a synthetic FeII complex confined within Sav. Structural studies using X-ray diffraction (XRD) methods revealed a facial triad binding site that is composed of two N donors from the biotinylated ligand and the monodentate coordination of the carboxylate from S112E. Two aqua ligands complete the primary coordination sphere of the FeII center with both involved in hydrogen bond networks within Sav. The corresponding FeIII protein was also prepared and structurally characterized to show a six-coordinate complex with two exogenous acetato ligands. The FeIII protein was further shown to bind an exogenous azido ligand through replacement of one acetato ligand. Spectroscopic studies of the ArMs in solution support the results found by XRD.

Статья посвящена разнообразию условий, в которых протекает изобразительная деятельность. Авторы полагают, что содержание, формы, методы и приемы работы с детьми, а также материалы, с которыми они действуют, влияют на интенсивность развития самостоятельной творческой деятельности детей.

Данная статья посвящена личным именам, которые давали своим детям старообрядцы крупного административного и торгово-промыслового центра горнозаводского Урала, каковым в начале XX в. являлся Екатеринбург. Целью работы является определение основных характеристик их именника, анализ состава имен, особенностей письменной фиксации. Основу исследования составила база данных о родившихся, созданная на основе метрических книг трех старообрядческих общин Екатеринбурга за 1907–1926 гг. Две общины — Успенская и Никольская — принадлежали к согласию часовенных, не имевших священства, а одна — Троицкая — к белокриницкой старообрядческой иерархии. Анализ записей позволил проследить вариативность каждого из имен, выделить канонические и разговорные формы, определить количество используемых имен, их частотность. После унификации фонетических вариантов имен было получено 178 имен на 929 человек. В статье представлены основные статистические показатели имен старообрядцев, набор самых распространенных имен сопоставлен с антропонимами этой же категории в других регионах. Сделан вывод о том, что в начале XX в. уже почти половина новорожденных обоего пола получала распространенные имена, но в большей степени к ним обращались при наречении мальчиков, которым предстояло более активное взаимодействие с социумом, так что родители при выборе имени, соблюдая в определенной мере внутриконфессиональные традиции, принимали во внимание и общие для городского населения предпочтения. В приложении помещен список всех имен, зафиксированных в разделе о родившихся в старообрядческих храмах Екатеринбурга в 1907–1926 гг., This paper explores the child-naming practices among the Old Believers of Ekaterinburg at the beginning of the 20th century, at that time, a large administrative and trade center of the mining Urals. It aims to outline the main features of their nomenclature and study the composition of names including peculiarities of their writing. The study builds on the database of births, compiled from the metric books of the three Old Believer communities of Ekaterinburg in 1907–1926. Two of these, Uspenskaya and Nikolskaya, belonged to the chasovennye [chapellers] Old Believer hierarchy which did not have a priesthood, whereas the third one, Troitskaya, represented the Belokrinitsky denomination. The records helped to detect each name’s variability, distinguish the canonical and colloquial forms, determine the number of names used, and their frequency. The extraction of phonetic variants brought the author to the final ratio of 178 names per 929 people. The article gives statistical results for the name usage among Old Believers, the set of most common names is compared with the corresponding data sets from other regions. The conclusion holds that in the early 20th century, almost half of the newborns of both sexes received common secular names, particularly it refers to the boys, as they were supposed to be more socially active. Hence, apart from observing religious traditions of their confession, the parents also relied on general preferences of the urban population. The annex contains a list of all the names recorded in the newborns’ section in the Old Believer churches of Ekaterinburg in 1907–1926.

Explaining the main quantitative characteristics of a particular socio-confessional group is necessary for understanding its place and role in society. Edinoverie joined converts from Old Belief to the official Orthodox Church by maintaining the pre-reform liturgical books and rituals whilst also being subordinated to Synodal bishops. The rules of edinoverie were formulated by the joint effort of Old Believers and Platon (Levshin), the metropolitan of Moscow: these were later approved by Emperor Paul I in a decree from 27 October 1880. In practice, however, contradictions appeared rather quickly as a result of the fact that edinoverie was a compromise between two sides that found it difficult to reconcile their differences. The Synodal Church regarded edinoverie as a missionary instrument for converting “schismatics”, while Old Believer organisations strove to receive legalisation and their own independent episcopal hierarchy. The evolution of the composition of parishioners in edinoverie churches took an unexpected turn: at the beginning of the twentieth century, going to edinoverie parishes for the sacraments became attractive to flocks officially counted within the ‘predominant Orthodox confession’. This became possible due to the support edinoverie received from the authorities and the state church: it was gradually becoming recognised as an independent variant of Russian Orthodoxy. In this article, the authors present the results of an analysis of nominative data from marriage registries created between 1901 and 1918 in the Holy Trinity Church of Yekaterinburg, the largest urban edinoverie centre in the Urals. Materials analysed in the paper demonstrate that confessional boundaries between edinoverie and official Orthodoxy in everyday life were becoming blurred, and not only for religious reasons., Выявление принципиальных качественных характеристик отдельной социоконфессиональной группы необходимо для понимания ее места и роли в обществе. Единоверие являлось формой присоединения старообрядцев к государственной православной церкви с сохранением богослужения по книгам и обрядам дореформенного образца, но с подчинением епископам синодальной церкви. Правила единоверия были сформулированы соединенными усилиями старообрядцев и митрополита Московского Платона (Левшина), утверждены императором Павлом I указом 27 октября 1800 г. На практике довольно быстро проявились противоречия, изначально присутствовавшие в единоверии как компромиссе между труднопримиримыми сторонами – синодальной церковью, видевшей в нем миссионерский инструмент для обращения «раскольников», и старообрядческими организациями, стремившимися получить легальный статус с самостоятельной иерархией. Изменение состава прихожан в единоверческих общинах происходило неожиданным образом – в начале XX в. обращение за исполнением таинств в единоверческий приход стало привлекательным для паствы, причисленной к «господствующему православному исповеданию». Этому способствовала эволюция в отношении единоверия со стороны властей, государственной церкви и ее прихожан: направление получало все больше признания в качестве самостоятельного варианта российского православия. Увеличивавшееся присутствие православных среди венчавшихся в единоверческой церкви кардинальным образом меняло состав и облик прихода. В статье представлены результаты анализа метрических записей о браках в 1901–1918 гг. в Свято-Троицкой церкви Екатеринбурга – крупнейшем единоверческом городском центре на Урале. Приведенные материалы свидетельствуют о постепенном размывании конфессиональных границ между официальным православием и единоверием в повседневной жизни, обусловленном комплексом причин не всегда церковно-религиозного свойства.

Photoprocesses of the endohedral fullerene ions Sc3N@C80+ and Sc3N@C80- in the gas phase have been investigated in the photon energy ranges 30-50 eV and 280-420 eV. Single and double ionization as well as single ionization accompanied by the release of a C2 dimer were observed as a function of the photon energy for the positive parent ion and double detachment was measured for the negative parent ion. The emphasis of the experiments was on the specific effects of the encapsulated trimetallic nitride cluster Sc3N on the observed reactions. Clear evidence of photoexcitation near the Sc L edge is obtained with the dominating contributions visible in the one- and two-electron-removal channels. K-vacancy production in the encapsulated central nitrogen atom is seen in the single ionization of Sc3N@C80+ but is much less pronounced in the photoionization-with-fragmentation channel. Comparison of the cross sections near the carbon K edge with the corresponding channels measured previously in the photoionization of Lu3N@C80+ reveal strong similarities. Previously predicted sharp resonance features in the ionization of Sc3N@C80+ ions below the Sc M edge are not confirmed. The experiments are accompanied by quantum-chemistry calculations in the Hartree-Fock approximation and by model calculations employing density functional theory (DFT).

Статья посвящена обследованию звукопроизношения у детей, в результате чего были выявлены «полиформность» нарушения звукопроизношения и нарушение одной группы звуков. В качестве средства коррекционного воздействия были выбраны речевые (логопедические) игры.

Статья посвящена разнообразию условий, в которых протекает изобразительная деятельность. Авторы полагают, что содержание, формы, методы и приемы работы с детьми, а также материалы, с которыми они действуют, влияют на интенсивность развития самостоятельной творческой деятельности детей.

Статья посвящена обследованию звукопроизношения у детей, в результате чего были выявлены «полиформность» нарушения звукопроизношения и нарушение одной группы звуков. В качестве средства коррекционного воздействия были выбраны речевые (логопедические) игры.

Статья посвящена обследованию звукопроизношения у детей, в результате чего были выявлены «полиформность» нарушения звукопроизношения и нарушение одной группы звуков. В качестве средства коррекционного воздействия были выбраны речевые (логопедические) игры.