A covalent organic cage compound acting as a supramolecular shadow mask for the regioselective functionalization of C60

A trigonal-bipyramidal covalent organic cage compound serves as an efficient host to form stable 1 : 1-complexes with C₆₀ and C₇₀. Fullerene encapsulation has been comprehensively studied by NMR and UV/Vis spectroscopy, mass spectrometry as well as single-crystal X-ray diffraction. Exohedral functionalization of encapsulated C₆₀via threefold Prato reaction revealed high selectivity for the symmetry-matched all-trans-3 addition pattern.

The taming of the Prato reaction: a covalent organic cage compound serves as a supramolecular template for the regioselective functionalization of C₆₀.     

Synthesis and Spectroscopic Characterization of Group 6 Pentacarbonyl(4-substituted pyridine)metal(0) Complexes

Carbonyl-metal (M:Cr, Mo, W) derivatives of 4-substituted pyridines [4-methylpyridine (4-mp), 4-tert-butylpyridine (4-tbp) and 4-dimethylaminopyridine (4-dmap)] where the metal center is bonded to the nitrogen atom of the substituted pyridine ring are described. The organometallic complexes, M(CO)₅L, were synthesized by either the direct reaction of the metal hexacarbonyls or by the thermal substitution of M(CO)₅(THF) with the pyridine ligands; 4-methylpyridine (1), 4-tert-butylpyridine (2), 4-dimethylaminopyridine (3). The reported complexes were purified by column chromatography and recrystallization. The complexes were all characterized in solution by elemental analysis, MS, ir , ¹H-nmr and ¹³C-nmr spectroscopies.     

Catalytic mechanism of heme oxygenase through EPR and ENDOR of cryoreduced oxy-heme oxygenase and its Asp 140 mutants

Heme oxygenase (HO) catalyzes the O(2)- and NADPH-cytochrome P450 reductase-dependent conversion of heme to biliverdin, Fe, and CO through a process in which the heme participates both as a prosthetic group and as a substrate. In the present study, we have generated a detailed reaction cycle for the first monooxygenation step of HO catalysis, conversion of the heme to alpha-meso-hydroxyheme. We employed EPR (using both (16)O(2) and (17)O(2)) and (1)H, (14)N ENDOR spectroscopies to characterize the intermediates generated by 77 K radiolytic cryoreduction and subsequent annealing of wild-type oxy-HO and D140A, F mutants. One-electron cryoreduction of oxy-HO yields a hydroperoxoferri-HO with g-tensor, g = [2.37, 2.187, 1.924]. Annealing of this species to 200 K is accompanied by spectroscopic changes that include the appearance of a new (1)H ENDOR signal, reflecting rearrangements in the active site. Kinetic measurements at 214 K reveal that the annealed hydroperoxoferri-HO species, denoted R, generates the ferri-alpha-meso-hydroxyheme product in a first-order reaction. Disruption of the H-bonding network within the distal pocket of HO by the alanine and phenylalanine mutations of residue D140 prevents product formation. The hydroperoxoferri-HO (D140A) instead undergoes heterolytic cleavage of the O-O bond, ultimately yielding an EPR-silent compound II-like species that does not form product. These results, which agree with earlier suggestions, establish that hydroperoxoferri-HO is indeed the reactive species, directly forming the alpha-meso-hydroxyheme product by attack of the distal OH of the hydroperoxo moiety at the heme alpha-carbon.     

Oxidative polymerization of acrylamide in the presence of thioglycolic acid

Chemical polymerization of acrylamide at room temperature was examined by using thioglycolic acid-cerium (IV) sulfate and thioglycolic acid-KMnO₄ redox systems in acid aqueous medium. Water soluble polyacrylamides containing thioglycolic acid end groups were synthesized. The effects of the molar ratio of acrylamide to Ce(IV) n _AAm /n _Ce(IV) , the polymerization time, the temperature, the monomer concentration, the molar ratio of cerium (IV) sulfate to thioglycolic acid and the concentration of sulfuric acid on the yield and molecular weight of polymer were investigated. Lower molar ratios of acrylamide/Ce(IV) at constant monomer concentration resulted in an increase in the yield but a decrease in molecular weight of polymer. The increase of reaction temperature from 20 to 70°C resulted in a decrease in the yield but generally resulted in a constant value for the molecular weight of polymer. With increasing polymerization time, the yield and molecular weight of polymer did not change substantially. Ce(IV) and Mn(VII) ions are reduced to Ce(III) and Mn(II) ions respectively in the polymerization reaction. The existence of Ce(III) ion bound to polymer was investigated by UV-visible spectrophotometry and fluoresce measurements. The amount of Mn(II) incorporated into the polymer was determined using graphite furnace atomic absorption spectrometry. The mechanism of this phenomenon is discussed.     

The orthorhombic polymorph of diammonium trichromate(VI) decaoxide, <Emphasis Type="Italic">α</Emphasis>–(NH<Subscript>4</Subscript>)<Subscript>2</Subscript>Cr<Subscript>3</Subscript>O<Subscript>10</Subscript>

Synthesis and crystal structure of a trichromium(VI) decaoxide compound, α–(NH₄)₂Cr₃O₁₀, is reported. The crystal structure has been determined from three dimensional X-ray data collected at low temperature, 173 K. The structure is isomorphous with its Rb and Cs trichromate analogues, orthorhombic, space group Pbca, with a = 11.2558(3), b = 9.3193(3), c = 18.9819(5) ? and Z = 8. The title compound is composed of discrete [Cr₃O₁₀]^2– chains held together by the counter ion charge and a hydrogen bonding network. The different conformations adopted by trichromate anion within its ammonium, alkali and organic salts are discussed.     

Revealing the Effect of Heat Treatment on the Spectral Pattern of Unifloral Honeys Using Aquaphotomics

In this study we aimed to investigate the effect of heat treatment on the spectral pattern of honey using near infrared spectroscopy (NIRS). For the research, sunflower, bastard indigo, and acacia honeys were collected from entrusted beekeepers. The honeys were not subject to any treatment before. Samples were treated at 40 °C, 60 °C, 80 °C, and 100 °C for 60, 120, 180, and 240 min. This resulted in 17 levels, including the untreated control samples. The 5-hydroxymethylfurfural (HMF) content of the honeys was determined using the Winkler method. NIRS spectra were recorded using a handheld instrument. Data analysis was performed using ANOVA for the HMF content and multivariate analysis for the NIRS data. For the latter, PCA, PCA-LDA, and PLSR models were built (using the 1300–1600 nm spectral range) and the wavelengths presenting the greatest change induced by the perturbations of temperature and time intervals were collected systematically, based on the difference spectra and the weights of the models. The most contributing wavelengths were used to visualize the spectral pattern changes on the aquagrams in the specific water matrix coordinates. Our results showed that the heat treatment highly contributed to the formation of free or less bonded water, however, the changes in the spectral pattern highly depended on the crystallization phase and the honey type.     

On γ-semi-open sets

Summary We introduce the concepts of γ-semi-open set, γ_s-set, γ^s-set, generalized γ_s-set, generalized γ^s-set, semi-T₁^γspace and semi-R₀^γspace by using γ-open-sets.     

Component testing of repairable systems in multistage missions

We consider the component testing problem of a device that is designed to perform a mission consisting of a sequence of stages. Once a stage is over, the device is overhauled to replace all failed components before the next stage starts to improve mission reliability. The components fail exponentially where the failure rate depends on the stage of the mission. The reliability structure of the device involves a series connection of redundant subsystems. The optimal component testing problem is formulated as a semi-infinite linear programme. We present an algorithmic procedure to compute optimal test times based on the column generation technique, and illustrate it with numerical results.     

Boundary-layer flow about a vertical spinning cone under mixed thermal boundary conditions and a magnetic field

A similarity analysis was performed to investigate the laminar boundary-layer flow in the presence of a transverse magnetic field over a down-pointing and spinning cone with mixed thermal boundary conditions. Boundary layer velocity and temperature profiles were determined numerically for various values of the magnetic and spin parameters and the Prandtl number. The spin of the cone compresses the velocity profiles towards the surface by inducing an upward flow and decreases the surface temperature. The magnetic field suppresses the velocity profiles and increases the surface temperature. A transformation relating the similarity solutions of the boundary-layer velocity and temperature profiles associated with different values of the mixed thermal boundary condition parameter was obtained.