Catalyst-Controlled Transannular Polyketide Cyclization Cascades: Selective Folding of Macrocyclic Polyketides

The biomimetic synthesis of aromatic polyketides from macrocyclic substrates by means of catalyst-controlled transannular cyclization cascades is described. The macrocyclic substrates, which feature increased stability and fewer conformational states, were thereby transformed into several distinct polyketide scaffolds. The catalyst-controlled transannular cyclizations selectively led to aromatic polyketides with a defined folding and oxygenation pattern, thus emulating β-keto-processing steps of polyketide biosynthesis

Atroposelective synthesis of tetra-ortho-substituted biaryls by catalyst-controlled non-canonical polyketide cyclizations

The cyclization of poly-β-carbonyl-substrates controlled by polyketide synthases intricately governs the biosynthesis of a wide range of aromatic polyketides. Analogous small-molecule-catalysed processes would conceivably induce selective cyclizations of non-canonical polycarbonyl substrates to provide products distinct from natural polyketides. Here, we report a secondary amine-catalysed twofold cyclization of non-canonical hexacarbonyl substrates, furnishing enantioenriched tetra-ortho-substituted binaphthalenes. The substrates were prepared by a fourfold ozonolysis of dicinnamyl biindenes and converted under catalyst control with high atroposelectivity. Privileged catalysts, helicenes and ligands are readily accessible from the binaphthalene products stemming from the non-canonical polyketide cyclizations

Methodology of assessment of population satisfaction with the quality of medical service based on the adaptive polling technologyn

This article covers the problem of assessment of patient satisfaction as a parameter of the quality of medical service. The existing methods of assessment of patients' attitude to a medical institution, their benefits and disadvantages are considered. The methodology for the calculation of the satisfaction coefficient is proposed, which can be the basis for the application of the technology (depending on the type and amount of medical care received by the patient) of adaptive polling and analysis of the information received

The effects of introducing sterically demanding aryl substituents in [Cu(N^N)(P^P)]+ complexes

The syntheses and characterizations of six [Cu(N^N)(POP)][PF 6 ] and [Cu(N^N)(xantphos)][PF 6 ] compounds (POP = bis(2-(diphenylphosphino)phenyl)ether, xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene), in which N^N is a bpy ligand (1-Naphbpy, 2-Naphbpy, 1-Pyrbpy) bearing a sterically hindered 1-naphthyl, 2-naphthyl or 1-pyrenyl substituent in the 6-position, are reported. Single-crystal structure determinations of five complexes confirm a distorted tetrahedral environment for copper( I ) and a preference for the N^N ligand to be oriented with the sterically-demanding aryl group being remote from the (C 6 H 4 ) 2 O unit of POP or the xanthene ‘bowl’ of xantphos. The angle between the ring planes of the bpy range from 5.8 to 26.0° and this is associated with interactions between the aryl unit and the phenyl substituents of the P^P ligand. In solution at room temperature, the complexes undergo dynamic behaviour which has been investigated using variable temperature 2D NMR spectroscopy. The [Cu(N^N)(xantphos)] + complexes exist as a mixture of conformers which interconvert through inversion of the xanthene bowl-shaped unit; the preference for one conformer over the other is significantly changed on going from N^N = Phbpy to 1-Pyrbpy (Phbpy = 6-phenyl-2,2’-bipyridine). The electrochemical and photophysical properties of the [Cu(N^N)(POP)][PF 6 ] and [Cu(N^N)(xantphos)][PF 6 ] compounds are presented; the compounds are orange emitters but the introduction of the 1-naphthyl, 2-naphthyl or 1-pyrenyl substituents result in poor photoluminescence quantum yields

Corporate Culture of Contemporary Research University in Search of Complementarity of Humanitarian and Commercial Principles in Education (Russian Context)

Background: In the paper the formation of world-class research universities is analysed. The paper studies the history of the research university, prerequisites of its appearance, formation and its development toward modern research university. The modern research university is being cautiously viewed nowadays. The crisis of the university is its reality. The question of the corporate culture formation is now considered to be a topical matter in connection with globalization process, Methods: The authors implemented comparative analysis by comparing Humboldt's model of the research university and the modern one. Results: The comparison is made in regard to the idea of university, its criteria and mission. Special emphasis is laid on the analysis and comparison of corporate culture systems. Conclusions: Corporate culture is a novel criterion of the classical university that has recently arisen in the information society and now characterizes the university in a complementary way: on the one hand, as a competitive market entity, and on the other hand, as a guardian of its traditional, historically formed humanitarian criteria, ideas and mission. The following conclusion has been reached: the updated parameters have the identical form to those found by W. von Humboldt, only essence has changed

Simulation of the furnace of the boiler P-49 in the package of applied programs fire 3D

The combustion of solid low-grade fuel in LTV-boiler furnaces is a pressing research questions currently. The aim of this work is the creation of a computational grid model LTV-furnace to calculate the package of applied programs FIRE 3D. The study created a model LTV-furnace. The model tested on brown coal from the Nazarovo Deposit. The resulting distribution of temperatures and velocities has proved the performance of the model

ИССЛЕДОВАНИЕ ВОЗДЕЙСТВИЯ АПОЛЯРНЫХ РЕАГЕНТОВ НА ТЕКУЧЕСТЬ ВОДОУГОЛЬНЫХ СУСПЕНЗИЙ

В последнее время возник интерес к поведению водоугольных суспензий в связи с поиском альтернативных видов энергоресурсов [1-4]. Повышенный интерес к водо угольному топливу вызван ростом цен на нефть и нефтепродукты и ограниченностью запасов этого сырья. Водоугольные смеси широко изучаются в различных странах мира, так как они могут заменить и традиционное пылевидное топливо, перед которым имеют ряд существенных преимуществ. Особенности горения водоугольного топлива позволяют относить его к разряду экологически чистых видов топлива. При сжигании угля в виде водоугольной суспензии увеличивается скорость выгорания углерода, снижаются выбросы вредных веществ в атмосферу и образование оксидов азота

[Cu(POP)(N^S)][PF6] and [Cu(xantphos)(N^S)][PF6] compounds with 2-(thiophen-2-yl)pyridines

A series of [Cu(POP)(N^S)][PF 6 ] and [Cu(xantphos)(N^S)][PF 6 ] compounds (POP = bis(2-(diphenylphosphino)phenyl)ether, xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) in which the N^S ligand is a 2-(thiophen-2-yl)pyridine ( 1 ), 2-(thiophen-2-yl)-6-methylpyridine ( 2 ), 2-(5-methylthiophen-2-yl)pyridine ( 3 ) or 2-(5-methylthiophen-2-yl)-6-methylpyridine ( 4 ) have been prepared and characterized in solution and the solid state. Single crystal structures of [Cu(POP)( 1 )][PF 6 ], [Cu(xantphos)( 1 )][PF 6 ], [Cu(xantphos)( 2 )][PF 6 ], [Cu(POP)( 3 )][PF 6 ] . CH 2 Cl 2 , and [Cu(xantphos)( 4 )][PF 6 ] confirm chelating N^S and P^P ligands, and distorted tetrahedral copper(I) centres. There is close cation...anion association, particularly in [Cu(xantphos)( 1 )][PF 6 ]. Although the compounds are stable over days in CH 2 Cl 2 solution, they are susceptible to the effects of competing ligands such as chloride ion and MeCN. Analysis of the NMR spectroscopic data a solution of [Cu(POP)( 3 )][PF 6 ] in with addded Cl - gives a K d value of 0.14 ± 0.03 mM, indicative of ion-pairing. [Cu(POP)(N^S)][PF 6 ] and [Cu(xantphos)(N^S)][PF 6 ] exhibit quasi-reversible or irreversible Cu + /Cu 2+ oxidations. They are blue emitters in solution, and the presence of the 5-methyl group in the thiophene ring in 3 and 4 leads to a red-shift in the emission. The highest photoluminescence quantum yields are for [Cu(POP)( 2 )][PF 6 ] (30.8%) and [Cu(POP)( 4 )][PF 6 ] (33.2%), both of which have a 6-methyl-substituted pyridine ring in the N^S ligand. Excited-state lifetimes are <5ns. On going from solution to powder samples, red-shifts of 133 to 163 nm are observed leading to yellow emitters. The brightest emitter, [Cu(xantphos)( 1 )][PF 6 ], was tested in a LEC device but showed poor electroluminsecence and poor charge transporting characteristic

Sunitinib induced pyoderma gangrenosum-like ulcerations

Pyoderma gangrenosum is a non-infectious neutrophilic skin disease commonly associated with underlying systemic diseases. Histopathological and laboratory diagnostics are unspecific in the majority of the cases and the diagnosis is made in accordance with the clinical picture. Here, we report the case of a 69-year old man with progredient pyoderma gangrenosum-like ulcerations under treatment with sunitinib due to hepatocellular carcinoma. A conventional ulcer therapy did not lead to a regression of the lesions. Solely cessation of sunitinib therapy resulted in an improvement of the ulcerations. Sunitinib is a multikinase inhibitor that targets the PDGF-α - and -β-, VEGF-1-3-, KIT-, FLT3-, CSF-1- and RET-receptor, thereby impairing tumour proliferation, pathological angiogenesis and metastasation. Here, we demonstrate that pyoderma gangrenosum-like ulcers may represent a serious side effect of sunitinib-based anti-cancer treatment