387 research outputs found

    The Specifics of the State-Business Relations in Modern China

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    For the further development of Russian-Chinese cooperation, it is fundamentally important to understand fully the specific characteristics of the political, economic and social system of this country, which, in particular, is determined by the established system of the state — business relations.Aim. To identify the specifics of the model of relations between government and business, which has developed in the PRC during the period of economic reforms and is one of the most important aspects of the “Chinese miracle”.Tasks. To determine the applicability of Western models of state and business relations to Chinese realities, to characterize the main basic principles and approaches to the regulation of relations between the state and business, to identify problems, contradictions and prospects for their resolution in the conditions of modern China.Methods. System and comparative analysis, scientific generalization, expert assessments.Results. The specific characteristics of the state-business relations model in the country are determined, on the one hand, by the polymorphous nature of the Chinese state, on the other — by the formation of business as a hybrid actor. In this regard, it is, in our opinion, incorrect to see the state-business relations in China as uniform or dominated by a specific form of interaction. In reality, these relations are heterogeneous and vary not only depending on regions and sectors, but also “uneven” across different types of business actors within the same sector and/or region, as a result of which different types of businesses have different degrees of closeness to the state and subnational authorities.Conclusion. The system, historically formed under the influence of decisions and actions of the ruling party at various stages of the development of modern Chinese statehood, despite its complexity and often confusion, nevertheless allows the government to maneuver flexibly in the situations of serious economic and financial shocks caused by both economic and socio-political factors

    Synthesis and Characterization of Pt(II) Complexes with Pyridyl Ligands: Elongated Octahedral Ion Pairs and Other Factors Influencing \u3csup\u3e1\u3c/sup\u3eH NMR Spectra

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    © 2017 American Chemical Society. Our goal is to develop convenient methods for obtaining trans-[PtII(4-Xpy)2Cl2] complexes applicable to 4-substituted pyridines (4-Xpy) with limited volatility and water solubility, properties typical of 4-Xpy, with X being a moiety targeting drug delivery. Treatment of cis-[PtII(DMSO)2Cl2] (DMSO = dimethyl sulfoxide) with 4-Xpy in acetonitrile allowed isolation of a new series of simple trans-[PtII(4-Xpy)2Cl2] complexes. A side product with very downfield H2/6 signals led to our synthesis of a series of new [PtII(4-Xpy)4]Cl2 salts. For both series in CDCl3, the size of the H2/6 δ[coordinated minus free 4-Xpy H2/6 shift] decreased as 4-Xpy donor ability increased from 4-CNpy to 4-Me2Npy. This finding can be attributed to the greater synergistic reduction in the inductive effect of the Pt(II) center with increased 4-Xpy donor ability. The high solubility of [PtII(4-Xpy)4]Cl2 salts in CDCl3 (a solvent with low polarity) and the very downfield shift of the [PtII(4-Xpy)4]Cl2 H2/6 signals for the solutions provide evidence for the presence of strong {[PtII(4-Xpy)4]2+,2Cl-} ion pairs that are stabilized by multiple CH···Cl contacts. This conclusion gains considerable support from [PtII(4-Xpy)4]Cl2 crystal structures revealing that a chloride anion occupies a pseudoaxial position with nonbonding (py)C-H···Cl contacts (2.4-3.0 Å). Evidence for (py)C-H···Y contacts was obtained in NMR studies of [PtII(4-Xpy)4]Y2 salts with Y counterions less capable of forming H-bonds than chloride ion. Our synthetic approaches and spectroscopic analysis are clearly applicable to other nonvolatile ligands

    Laser pulse effects on plasma-sprayed and bulk tungsten

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    Tungsten (W) is considered a promising plasma-facing material for protecting the divertor of the ITER (International Thermonuclear Experimental Reactor). The effects on W of transient thermal loads of high energy occurring in a tokamak under operative conditions have been simulated through a single laser pulse delivered by an Nd:YAG laser. Bulk and plasma-sprayed (PS) samples have been submitted to tests and successively examined via SEM (scanning electron microscopy) observations. In both types of materials, the laser pulse induces similar effects: (i) a crater forms in the spot central area; (ii) all around the area, the ejection and the movement of molten metal give rise to a ridge; (iii) in a more external area, the surface shows plates with jagged boundaries and cracks induced by thermal stresses; (iv) the pores present in the original material become preferred ablation sites. However, the affected surface area in PS samples is larger and asymmetric if compared to that of bulk material. Such a difference has been explained by considering how microstructural characteristics influence heat propagation from the irradiated spot, and it was found that grain size and shape play a decisive role

    Integrated hardening of the heavily loaded gear surfaces

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    В работе проведено исследование режимов деформационного упрочнения поверхностей зубчатых колес из высокопрочных сталей с целью повышения их работоспособности и надежности. Исследованы закономерности изменения характеристик качества цементованного слоя, тонкой структуры его фаз и их взаимосвязь с контактной выносливостью.The deformation hardening, widely use for the increase of operability of carburized gear wheels. The plastic deformation strengthens the weak sites of the structure and complicates the microplastic deformation development in them. The efficiency of deformation hardening depends on initial structural condition of carburized layer

    A Very Rare Example of a Structurally Characterized 3′-GMP Metal Complex. NMR and Synthetic Assessment of Adducts Formed by Guanine Derivatives with [Pt(L\u3csup\u3etri\u3c/sup\u3e)Cl]Cl Complexes with an N,N′,N″ Tridentate Ligand (L\u3csup\u3etri\u3c/sup\u3e) Terminated by Imidazole Rings

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    © 2017 American Chemical Society. [Pt(N(R)-1,1′-Me2dma)Cl]Cl complexes with tridentate ligands (bis(1-methyl-2-methylimidazolyl)amine, R = H; N-(methyl)bis(1-methyl-2-methylimidazolyl)amine, R = Me) were prepared in order to investigate Pt(N(R)-1,1′-Me2dma)G adducts (G = monodentate N9-substituted guanine or hypoxanthine derivative). Solution NMR spectroscopy is the primary tool for studying metal complexes of nucleosides and nucleotides because such adducts rarely crystallize. However, [Pt(N(H)-1,1′-Me2dma)(3′-GMPH)]NO3·5H2O (5) was crystallized, allowing, to our knowledge, the first crystallographic molecular structure determination for a 3′-GMP platinum complex. The structure is one of only a very few structures of a 3′-GMP complex with any metal. Complex 5 has the syn rotamer conformation, with 3′-GMP bound by N7. All Pt(N(R)-1,1′-Me2dma)G adducts exhibit two new downfield-shifted G H8 signals, consistent with G bound to platinum by N7 and a syn/anti rotamer mixture. Anticancer-active monofunctional platinum(II) complexes have bulky carrier ligands that cause DNA adducts to be distorted. Hence, understanding carrier-ligand steric effects is key in designing new platinum drugs. Ligand bulk can be correlated with the degree of impeded rotation of the G nucleobase about the Pt-N7 bond, as assessed by the observation of rotamers. The signals of syn and anti rotamers are connected by EXSY cross-peaks in 2D ROESY spectra of Pt(N(H)-1,1′-Me2dma)G adducts but not in spectra of Pt(N(H)dpa)G adducts (N(H)dpa = bis(2-picolyl)amine), indicating that rotamer interchange is more facile and carrier-ligand bulk is lower in Pt(N(H)-1,1′-Me2dma)G than in Pt(N(H)dpa)G adducts. The lower steric hindrance is a direct consequence of the greater distance of the G nucleobase from the H4/4′ protons in the N(R)-1,1′-Me2dma carrier ligand in comparison to that from the H6/6′ protons in the N(H)dpa carrier ligand. Although in 5 the nucleotide is 3′-GMP (not the usual 5′-GMP) and the N(H)-1,1′-Me2dma carrier ligand is very different from those typically present in structurally characterized Pt(II) G complexes, the rocking and canting angles in 5 adhere to long-recognized trends

    Linear Bidentate Ligands (L) with Two Terminal Pyridyl N-Donor Groups Forming Pt(II)LCl\u3csub\u3e2\u3c/sub\u3e Complexes with Rare Eight-Membered Chelate Rings

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    Copyright © 2018 American Chemical Society. NMR and X-ray diffraction studies were conducted on Pt(II)LCl2 complexes prepared with the new N-donor ligands N(SO2R)Mendpa (R = Me, Tol; n = 2, 4). These ligands differ from N(H)dpa (di-2-picolylamine) in having the central N within a tertiary sulfonamide group instead of a secondary amine group and having Me groups at the 6,6′-positions (n = 2) or 3,3′,5,5′-positions (n = 4) of the pyridyl rings. The N(SO2R)3,3′,5,5′-Me4dpa ligands are coordinated in a bidentate fashion in Pt(N(SO2R)3,3′,5,5′-Me4dpa)Cl2 complexes, forming a rare eight-membered chelate ring. The sulfonamide N atom did not bind to Pt(II), consistent with indications in the literature that tertiary sulfonamides are unlikely to anchor two meridionally coordinated five-membered chelate rings in solutions of coordinating solvents. The N(SO2R)6,6′-Me2dpa ligands coordinate in a monodentate fashion to form the binuclear complexes [trans-Pt(DMSO)Cl2]2(N(SO2R)6,6′-Me2dpa). The monodentate instead of bidentate N(SO2R)6,6′-Me2dpa coordination is attributed to 6,6′-Me steric bulk. These binuclear complexes are indefinitely stable in DMF-d7, but in DMSO-d6 the N(SO2R)6,6′-Me2dpa ligands dissociate completely. In DMSO-d6, the bidentate ligands in Pt(N(SO2R)3,3′,5,5′-Me4dpa)Cl2 complexes also dissociate, but incompletely; these complexes provide rare examples of association-dissociation equilibria of N,N bidentate ligands in Pt(II) chemistry. Like typical cis-PtLCl2 complexes, the Pt(N(SO2R)3,3′,5,5′-Me4dpa)Cl2 complexes undergo monosolvolysis in DMSO-d6 to form the [Pt(N(SO2R)3,3′,5,5′-Me4dpa)(DMSO-d6)Cl]+ cations. However, unlike typical cis-PtLCl2 complexes, the Pt(N(SO2R)3,3′,5,5′-Me4dpa)Cl2 complexes surprisingly do not react readily with the excellent N-donor bioligand guanosine. A comparison of the structural features of over 50 known relevant Pt(II) complexes having smaller chelate rings with those of the very few relevant Pt(II) complexes having eight-membered chelate rings indicates that the pyridyl rings in Pt(N(SO2R)3,3′,5,5′-Me4dpa)Cl2 complexes are well positioned to form strong Pt-N bonds. Therefore, the dissociation of the bidentate ligand and the poor biomolecule reactivity of the Pt(N(SO2R)3,3′,5,5′-Me4dpa)Cl2 complexes arise from steric consequences imposed by the -CH2-N(SO2R)-CH2- chain in the eight-membered chelate ring

    Structural and biochemical insights into the mechanism of fosfomycin phosphorylation by fosfomycin resistance kinase FomA

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    We present here the crystal structures of fosfomycin resistance protein (FomA) complexed with MgATP, with ATP and fosfomycin, with MgADP and fosfomycin vanadate, with MgADP and the product of the enzymatic reaction, fosfomycin monophosphate, and with ADP at 1.87, 1.58, 1.85, 1.57, and 1.85 Å resolution, respectively. Structures of these complexes that approximate different reaction steps allowed us to distinguish the catalytically active conformation of ATP and to reconstruct the model of the MgATP•fosfomycin complex. According to the model, the triphosphate tail of the nucleotide is aligned toward the phosphonate moiety of fosfomycin, in contast to the previously published MgAMPPNP complex, with the attacking fosfomycin oxygen positioned 4 Å from the γ-phosphorus of ATP. Site-directed mutagenesis studies and comparison of these structures with that of homologous N-acetyl-l-glutamate and isopentenyl phosphate kinases allowed us to propose a model of phosphorylation of fosfomycin by FomA enzyme. A Mg cation ligates all three phosphate groups of ATP and together with positively charged K216, K9, K18, and H58 participates in the dissipation of negative charge during phosphoryl transfer, indicating that the transferred phosphate group is highly negatively charged, which would be expected for an associative mechanism. K216 polarizes the γ-phosphoryl group of ATP. K9, K18, and H58 participate in stabilization of the transition state. D150 and D208 play organizational roles in catalysis. S148, S149, and T210 participate in fosfomycin binding, with T210 being crucial for catalysis. Hence, it appears that as in the homologous enzymes, FomA-catalyzed phosphoryl transfer takes place by an in-line predominantly associative mechanism. © 2011 American Chemical Society

    Mechanisms of regulation of invasive processes in phytoplankton on the example of the north-eastern part of the Black Sea

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    © 2016, Springer Science+Business Media Dordrecht. In the north-eastern part of the Black Sea, the seasonal complexes of dominant species of phytoplankton were fixed: small-celled diatom (spring), coccolithophores (late spring, early summer) and large diatoms (summer and autumn). In May–June 2005 and 2006, two invasive species of marine diatoms Chaetoceros throndsenii (maximal abundance 1.92 × 105 cells/l) and Chaetoceros minimus (1.6 × 105 cells/l) were recorded. These species have been incorporated in the complex of the late spring and early summer and grew simultaneously with the coccolithophore Emiliania huxleyi. The coccolithophore was dominant species, whose abundance had reached the level of a bloom. C. throndsenii was observed over the entire area from the coast to the centre of the sea; C. minimus were recorded at coastal stations and only at two stations of the open sea. Stratification of the water mass and the low (below the Redfield) ratio of nitrogen to phosphorus were observed at this time. Then, C. throndsenii was not marked even once, and C. minimus has been registered once on a shelf in June 2011. Experimental studies (2005) have shown that intensive growth C. throndsenii requires the simultaneous addition of nitrogen and phosphorus in a ratio close to the Redfield ratio. C. minimus shows the intensive growth only at high concentrations of phosphorus and at low nitrogen-to-phosphorus ratio (the experiment was carried out in June 2011). Mathematical modelling shows that C. throndsenii and Emiliania huxleyi form a stable couple whose growth is limited by different factors: the diatoms by nitrogen and the coccolithophores by phosphorus. C. minimus might not be able to form a stable couple with coccolithophores because they have the same limiting factor, i.e. phosphorus. However, this species could become the dominant one, if low (0.5–1) nitrogen-to-phosphorus ratio conditions were stable for more than 2 months. However, this scenario is improbable in natural circumstances since the existence of this complex seasonal rarely exceeds 1.5 months

    Studies of contribution of metals bonded with organic matter of seawater to the fluxes of total dissolved metals across water-sediment interface at Vistula Lagoon of Baltic Sea

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    © 2004 IEEE. Investigations of fluxes of a dissolved element across the water-sediment interface in Vistula Lagoon (Baltic Sea) were carried out in August 2001 and 2002, using chamber experiments. Oxygen, iron(II), total dissolved iron, manganese, copper and lead fluxes were calculated. For the first time the fluxes of metals bonded with organic matter of sea water were studied. The contribution of metals bonded with organic matter to the total flux was varied depending upon conditions and may reach up to 70 %. It was found that metal fluxes at the coastal zone are larger than at the center of the lagoon by the factor of 2-4
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