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951.
Heinrich JM Niizawa I Botta FA Trombert AR Irazoqui HA 《Photochemistry and photobiology》2012,88(4):952-960
In a previous study, we developed a methodology to assess the intrinsic optical properties governing the radiation field in algae suspensions. With these properties at our disposal, a Monte Carlo simulation program is developed and used in this study as a predictive autonomous program applied to the simulation of experiments that reproduce the common illumination conditions that are found in processes of large scale production of microalgae, especially when using open ponds such as raceway ponds. The simulation module is validated by comparing the results of experimental measurements made on artificially illuminated algal suspension with those predicted by the Monte Carlo program. This experiment deals with a situation that resembles that of an open pond or that of a raceway pond, except for the fact that for convenience, the experimental arrangement appears as if those reactors were turned upside down. It serves the purpose of assessing to what extent the scattering phenomena are important for the prediction of the spatial distribution of the radiant energy density. The simulation module developed can be applied to compute the local energy density inside photobioreactors with the goal to optimize its design and their operating conditions. 相似文献
952.
Romain C Heinrich B Laponnaz SB Dagorne S 《Chemical communications (Cambridge, England)》2012,48(16):2213-2215
A readily accessible and robust Zr-NHC complex was found to polymerize rac-lactide in a highly controlled, living and stereoselective manner to afford heterotactic PLA. 相似文献
953.
Katarzyna Wójcik Petra Ecorchard Dieter Schaarschmidt Tobias Rüffer Heinrich Lang Prof. Dr. Michael Mehring 《无机化学与普通化学杂志》2012,638(11):1723-1730
Abstract. The cyclopentadienyl‐substituted iron‐bismuth complexes [{Cp(CO)2Fe}BiCl2] ( 1 ), [{Cp(CO)2Fe}BiBr2] ( 2 ), [{Cp′′(CO)2Fe}BiBr2] ( 3 ) and [{Cp*(CO)2Fe}BiBr2] ( 4 ) were prepared with high yields starting from [Cpx(CO)2Fe]2 [Cpx = C5H5 (Cp), C5H3‐1, 3‐tBu2 (Cp′′), C5Me5 (Cp*)] and the corresponding bismuth halides. The single crystal X‐ray structure analyses of compounds 2 – 4 are reported. Comparison of their solubility demonstrates that the steric hindrance in this type of compounds is only slightly higher for compound 3 compared with compound 2 but significantly lower compared with the Cp* derivative 4 . Compounds 1 – 4 react with nucleophililic reagents such as KOtBu, NaOCH2CH2OCH3, and NaOSiMe3 as well as with water in the presence of an amine to give a mixture of [{Cpx(CO)2Fe}BiX] (X = Cl, Br) and [{Cpx(CO)2Fe}3Bi]. In case of a reaction with nBu4NCl and DMAP (dimethylaminopyridine) no such dismutation is observed. Instead the complexes [{Cp(CO)2Fe}BiBr2(DMAP)2] ( 5 ), [NnBu4]2[{{Cp(CO)2Fe}BiBr3}2] ( 6 ) and [NnBu4]2[{{Cp(CO)2Fe}BiCl3}2] ( 7 ) were isolated and characterized by single‐crystal X‐ray diffraction. 相似文献
954.
Jarosław Grolik Łukasz Dudek Julita Eilmes Andrzej Eilmes Marcin Górecki Jadwiga Frelek Benoît Heinrich Bertrand Donnio 《Tetrahedron》2012,68(20):3875-3884
Two optically pure derivatives of dibenzotetraaza[14]annulene, bearing four (S)- or (R)- 3,7-dimethyloctoxy peripheral chiral tails, respectively, and two hydroxybenzoyl meso substituents were synthesized using a convergent multi-step route. The structure of the products was determined by 1H and 13C NMR spectroscopy, ESI-MS, and elemental analysis. The mesomorphic behavior of the two chiral compounds, deciphered by differential scanning calorimetry (DSC), small-angle X-ray diffractometry (SA-XRD), and polarizing optical microscopy (POM) investigations, revealed the induction of two lamello-columnar phases, i.e., columnar stacks confined in smectic layers, whose columns may be arranged either according to the pg rectangular planar symmetry (for the low-temperature phase) or without registry between vicinal layers (for the high-temperature mesophase). Evidence of a helical organization of the molecules in the mesophases was obtained using a combination of electronic circular dichroism (ECD) and SA-XRD results, Molecular Dynamics simulations and quantum-chemical calculations. 相似文献
955.
Diamonds are formed from carbon at high pressures and high temperatures in the inner part of the earth. Doping with very small amounts of boron leads to diamonds with blue colour. Two of the most famous historical blue diamonds, the Wittelsbach and Hope Diamond, were found in the Indian Kollur mine. The latter was brought to Europe by the French gem merchant Tavernier. Today it is displayed in the Smithsonian Institute. The Wittelsbach Diamond was for a long time in the possession of the House Wittelsbach until it was secretly sold in Antwerp in 1951. In 2008, it was purchased by auction by the jeweller Graff who recut the gem. In 2011, it was sold to an unknown buyer. As the Wittelsbach and the Hope diamond share origin and colour, it was assumed for a long time that both are pieces from a larger crystal. By optical investigation it was now shown that they have indeed some similar optical properties, but differ strikingly in other ones. Hence, they cannot originate from the same crystal. 相似文献
956.
The title compound (short version: BTE) occurs in (E)‐ and (Z)‐isomers (both with b.p. of ca. 100°) which equilibrate with nucleophilic catalysts. Both undergo (2+2) cycloadditions with methyl vinyl ether at 25°. Three stereogenic centers in the cyclobutanes led to four rac‐diastereoisomers, which were obtained in pure and crystalline state. The structures were elucidated by 19F‐NMR spectroscopy and confirmed by two X‐ray analyses. The cycloadditions were not stereospecific: e.g., (E)‐BTE furnished 73% trans‐adducts (with respect to the CF3 groups) and 27% cis‐adducts. The loss of stereochemical integrity occurs in the intermediate gauche‐zwitterions which can cyclize or rotate, but not dissociate. Under extreme conditions (2M LiClO4 in Et2O, 70°, 3 months), the thermodynamic equilibrium of the four cyclobutanes was achieved. Considerations of Coulombic attraction and conformational strain in the zwitterionic intermediates allow us to rationalize the observed proportions of diastereoisomeric cyclobutanes. Ethyl vinyl ether and butyl vinyl ether furnished cyclobutanes in similar diastereoisomer ratios. 相似文献
957.
Milde B Schaarschmidt D Rüffer T Lang H 《Dalton transactions (Cambridge, England : 2003)》2012,41(17):5377-5390
The consecutive syntheses of imidazoles 1-(4-X-C(6)H(4))-4,5-R(2)-(c)C(3)HN(2) (3a, X = Br, R = H; 3b, X = I, R = Me; 3c, X = H, R = Me; 5, X = Fc, R = H; 7, X = C≡CFc, R = H; 9, X = C(6)H(5), R = Me; Fc = Fe(η(5)-C(5)H(4))(η(5)-C(5)H(5))), phosphino imidazoles 1-(4-X-C(6)H(4))-2-PR'(2)-4,5-R(2)-(c)C(3)N(2) (11a-k; X = Br, I, Fc, FcC≡C, Ph; R = H, Me; R' = Ph, (c)C(6)H(11), (c)C(4)H(3)O), imidazolium salts [1-(4-X-C(6)H(4))-3-R'-4,5-R(2)-(c)C(3)HN(2)]I (16a; X = Br, R = H, R' = n-Bu; 16b, X = Br, R = H, R' = n-C(8)H(17); 16c, X = I, R = Me, R' = n-C(8)H(17), 16d, X = H, R = Me, R' = n-C(8)H(17)) and phosphino imidazolium salts [1-C(6)H(5)-2-PR'(2)-3-n-C(8)H(17)-4,5-Me(2)-(c)C(3)N(2)]PF(6) (17a, R' = C(6)H(5); 17b, R' = (c)C(6)H(11)) or [1-(4-P(C(6)H(5))(2)-C(6)H(4))-3-n-C(8)H(17)-4,5-Me(2)-(c)C(3)HN(2)]PF(6), (20) and their selenium derivatives 1-(4-X-C(6)H(4))-2-P([double bond, length as m-dash]Se)R'(2)-4,5-R(2)-(c)C(3)N(2) (11a-Se-f-Se; X = Br, I; R = H, Me; R' = C(6)H(5), (c)C(6)H(11), (c)C(4)H(3)O) are reported. The structures of 11a-Se and [(1-(4-Br-C(6)H(4))-(c)C(3)H(2)N(2)-3-n-Bu)(2)PdI(2)] (19) in the solid state were determined. Cyclovoltammetric measurements were performed with the ferrocenyl-containing molecules 5 and 7 showing reversible redox events at E(0) = 0.108 V (ΔE(p) = 0.114 V) (5) and E(0) = 0.183 V (ΔE(p) = 0.102 V) (7) indicating that 7 is more difficult to oxidise. Imidazole oxidation does not occur up to 1.3 V in dichloromethane using [(n-Bu)(4)N][B(C(6)F(5))(4)] as supporting electrolyte, whereas an irreversible reduction is observed between -1.2 - -1.5 V. The phosphino imidazoles 11a-k and the imidazolium salts 17a,b and 20, respectively, were applied in the Suzuki C-C cross-coupling of 2-bromo toluene with phenylboronic acid applying [Pd(OAc)(2)] as palladium source. Depending on the electronic character of 11a-k, 17a,b and 20 the catalytic performance of the in situ generated catalytic active species can be predicted. As assumed, more electron-rich phosphines with their higher donor capability show higher activity and productivity. Additionally, 11e was applied in the coupling of 4-chloro toluene with phenylboronic acid showing an excellent catalytic performance when compared to catalysts used by Fu, Beller and Buchwald. Furthermore, 11e is eligible for the synthesis of sterically hindered biaryls under mild reaction conditions. C-C Coupling reactions with the phosphino imidazolium salts 17b and 20 in ionic liquids [BMIM][PF(6)] and [BDMIM][BF(4)] were performed, showing less activity than in common organic solvents. 相似文献
958.
Zander W Irschik H Augustiniak H Herrmann M Jansen R Steinmetz H Gerth K Kessler W Kalesse M Höfle G Müller R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(20):6264-6271
Sulfangolids are the first sulfate ester containing secondary metabolites from myxobacteria. The metabolites 1-4 and the structurally related kulkenon (5) were isolated from different strains of the species Sorangium cellulosum. In the course of isolation all metabolites proved to be rather sensitive due to their conjugated double bond systems and the strong acidic nature of the sulfate ester in sulfangolids. The relative configuration of sulfangolid C (3) was assigned by extensive 1D and 2D NMR analysis and molecular modelling. In addition, the biosynthesis of 3 was studied by feeding experiments. 相似文献
959.
The axial next-nearest-neighbour Ising (ANNNI) model is a spin model which locks into an infinite number of modulated phases as a function of the interaction parameters and the temperature. In this paper we discuss the effect of allowing this system to contain annealed vacancies. We find that a small concentration of vacancies does not qualitatively affect the structure of the phase diagram and that the vacancies form defect-density waves which mirror the periodicity of the underlying modulated structure. 相似文献
960.
We study the following problem: How to verify Brillinger-mixing of stationary point processes in $ {{\mathbb{R}}^d} $ by imposing conditions on a suitable mixing coefficient? For this, we define an absolute regularity (or β-mixing) coefficient for point processes and derive, in terms of this coefficient, an explicit condition that implies finite total variation of the kth-order reduced factorial cumulant measure of the point process for fixed $ k\geqslant 2 $ . To prove this, we introduce higher-order covariance measures and use Statulevi?ius’ representation formula for mixed cumulants in case of random (counting) measures. To illustrate our results, we consider some Brillinger-mixing point processes occurring in stochastic geometry. 相似文献