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691.
Markus Lindqvist Dr. Kirill Axenov Dr. Martin Nieger Dr. Minna Räisänen Prof. Markku Leskelä Prof. Timo Repo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(31):10412-10418
Dimethylamino‐(+)‐camphorenamine reacted with an equimolar amount of Piers’ borane, HB(C6F5)2, to give the corresponding iminium–hydroborate zwitterionic salt. Being in equilibrium with the parent enamine–HB(C6F5)2 N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the iminium group in the molecule. Detailed studies revealed that the hydrogen splitting in this reaction proceeded through an intermolecular pathway leading to a bornylamine–HB(C6F5)2 adduct. When the starting enamine is present in excess over HB(C6F5)2, the produced bornylamine–HB(C6F5)2 adduct breaks up, eliminating free bornylamine and forming the initial camphorenamine– HB(C6F5)2 pair. This results in hydrogenation of the camphorenamine framework in a catalytic fashion. 相似文献
692.
We consider a random walk in a random potential on a square lattice of arbitrary dimension. The potential is a function of an ergodic environment and steps of the walk. The potential is subject to a moment assumption whose strictness is tied to the mixing of the environment, the best case being the i.i.d. environment. We prove that the infinite volume quenched point-to-point free energy exists and has a variational formula in terms of entropy. We establish regularity properties of the point-to-point free energy, and link it to the infinite volume point-to-line free energy and quenched large deviations of the walk. One corollary is a quenched large deviation principle for random walk in an ergodic random environment, with a continuous rate function. 相似文献
693.
We show that the geometric lifting of the RSK correspondence introduced by A.N. Kirillov (Physics and Combinatorics. Proc. Nagoya 2000 2nd Internat Workshop, pp. 82–150, 2001) is volume preserving with respect to a natural product measure on its domain, and that the integrand in Givental’s integral formula for \(\mathit{GL}(n,{\mathbb{R}})\) -Whittaker functions arises naturally in this context. Apart from providing further evidence that Whittaker functions are the natural analogue of Schur polynomials in this setting, our results also provide a new ‘combinatorial’ framework for the study of random polymers. When the input matrix consists of random inverse gamma distributed weights, the probability distribution of a polymer partition function constructed from these weights can be written down explicitly in terms of Whittaker functions. Next we restrict the geometric RSK mapping to symmetric matrices and show that the volume preserving property continues to hold. We determine the probability law of the polymer partition function with inverse gamma weights that are constrained to be symmetric about the main diagonal, with an additional factor on the main diagonal. The third combinatorial mapping studied is a variant of the geometric RSK mapping for triangular arrays, which is again showed to be volume preserving. This leads to a formula for the probability distribution of a polymer model whose paths are constrained to stay below the diagonal. We also show that the analogues of the Cauchy-Littlewood identity in the setting of this paper are equivalent to a collection of Whittaker integral identities conjectured by Bump (Number Theory, Trace Formulas, and Discrete Groups, pp. 49–109, 1989) and Bump and Friedberg (Festschrift in Honor of Piatetski-Shapiro, Part II, pp. 47–65, 1990) and proved by Stade (Am. J. Math. 123:121–161, 2001; Israel J. Math. 127:201–219, 2002). Our approach leads to new ‘combinatorial’ proofs and generalizations of these identities, with some restrictions on the parameters. 相似文献
694.
Farshid Manoocheri Meelis Sildoja Timo Dönsberg Mikko Merimaa Erkki Ikonen 《Optical Review》2014,21(3):320-324
Silicon photodiodes with induced junction structure can reach low-loss photon-to-electron conversion. The calculated conversion efficiency in the visible wavelength range typically deviates less than 10 ppm from unity and its uncertainty is about 100 ppm at room temperature or as low as 1 ppm at 78 K. Here we show experimentally that our dedicated induced junction photodiodes indeed have very low conversion losses when they are assembled in a light trapping structure as provided by, for example, the predictable quantum efficient detector (PQED). It is concluded that the remaining measured losses, if any, are probably due to surface recombination of electrons and holes close to the silicon/silicon dioxide interface of the photodiode. 相似文献
695.
Teemu Niemi Dr. Jesus E. Perea‐Buceta Dr. Israel Fernández Dr. Sami Alakurtti Erika Rantala Prof. Timo Repo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(29):8867-8871
The reaction of β‐ and γ‐haloamines with carbon dioxide to give pharmaceutically relevant 2‐oxazolidinones and 1,3‐dioxazin‐2‐ones, was found to proceed efficiently in the presence of a base and in the absence of catalyst. After optimization of reaction conditions, the system was successfully expanded to a variety of haloamines, even at multigram scale. The reaction was further studied in silico by DFT calculations. 相似文献
696.
Raili Pönni Timo Pääkkönen Markus Nuopponen Jaakko Pere Tapani Vuorinen 《Cellulose (London, England)》2014,21(4):2859-2869
Alkali treatment was used to increase the reactivity of birch kraft pulp prior to its 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) catalyzed oxidation with hypochlorite, which is a process commonly applied to prepare nanofibrillated cellulose. On contrary to the traditional use of NaBr as a cocatalyst, TEMPO was activated with HOCl prior to the oxidation. Commonly, the lack of bromide increases the oxidation time and impairs the formation of carboxylic groups. However, the reaction time of the bromide-free TEMPO catalyzed oxidation could be shortened from 2.5 to 0.5 h when the pulp was treated with 1 M NaOH prior to the oxidation (2.4 mmol NaOCl/g pulp). The beneficial effect was obtained even if the alkali treatment was executed at room temperature and only for few minutes. Moreover, the alkali pretreatment enabled selective production of a pulp with carboxylate content as high as 1.6 mmol/g with NaOCl dosage of 4.4 mmol/g. The changes in the cellulosic raw material during the alkali treatment were assessed by water retention value and carbohydrate analysis. 相似文献
697.
Kai S. Exner Josef Anton Timo Jacob Herbert Over 《Angewandte Chemie (International ed. in English)》2014,53(41):11032-11035
In the industrially important Chlor‐Alkali process, the chlorine evolution reaction (CER) over a ruthenium dioxide (RuO2) catalyst competes with the oxygen evolution reaction (OER). This selectivity issue is elucidated on the microscopic level with the single‐crystalline model electrode RuO2(110) by employing density functional theory (DFT) calculations in combination with the concept of volcano plots. We demonstrate that one monolayer of TiO2(110) supported on RuO2(110) enhances the selectivity towards the CER by several orders of magnitudes, while preserving the high activity for the CER. This win‐win situation is attributed to the different slopes of the volcano curves for the CER and OER. 相似文献
698.
Sumerin V Schulz F Atsumi M Wang C Nieger M Leskelä M Repo T Pyykkö P Rieger B 《Journal of the American Chemical Society》2008,130(43):14117-14119
The first ansa-aminoborane N-TMPN-CH2C6H4B(C6F5)2 (where TMPNH is 2,2,6,6-tetramethylpiperidinyl) which is able to reversibly activate H2 through an intramolecular mechanism is synthesized. This new substance makes use of the concept of molecular tweezers where the active N and B centers are located close to each other so that one H2 molecule can fit in this void and be activated. Because of the fixed geometry of this ansa-ammonium-borate it forms a short N-H...H-B dihydrogen bond of 1.78 A as determined by X-ray analysis. Therefore, the bound hydrogen can be released above 100 degrees C. In addition, the short H...H contact and the N-H...H (154 degrees) and B-H...H (125 degrees) angles show that the dihydrogen interaction in N-TMPNH-CH2C6H4BH(C6F5)2 is partially covalent in nature. As a basis for discussing the mechanism, quantum chemical calculations are performed and it is found that the energy needed for splitting H2 can arise from the Coulomb attraction between the resulting ionic fragments, or "Coulomb pays for Heitler-London". The air- and moisture-stable N-TMPNH-CH2C6H4BH(C6F5)2 is employed in the catalytic reduction of nonsterically demanding imines and enamines under mild conditions (110 degrees C and 2 atm of H2) to give the corresponding amines in high yields. 相似文献
699.
Comparative LC-MS/MS profiling of free and protein-bound early and advanced glycation-induced lysine modifications in dairy products 总被引:2,自引:0,他引:2
Free and protein-bound forms of early and advanced glycation-induced lysine (Lys) modifications were quantified in dairy products by LC-MS/MS using a stable isotope dilution assay. The glycation profiles for N(epsilon)-fructoselysine (FL), N(epsilon)-carboxymethyllysine (CML) and pyrraline (Pyr) were monitored in raw and processed cow milk to investigate whether free glycation products could serve as fast and simple markers to assess the extent of protein glycation in dairy products. In all milk samples, the fraction of free glycation adducts was predominantly composed of advanced modifications, e.g. 8.34+/-3.81 nmol CML per micromol of free Lys (Lys(free)) and 81.5+/-87.8 nmol Pyr micromol(-1) Lys(free)(-1) vs. 3.72+/-1.29 nmol FL micromol(-1) Lys(free)(-1). In contrast, the protein-bound early glycation product FL considerably outweighed the content of CML and Pyr in milk proteins of raw and processed cow milk, whereas severely heat treated milk products, e.g. condensed milk, contained a higher amount of protein-bound advanced glycation adducts. Typical values recorded for milk samples processed under mild conditions were 0.47+/-0.08 nmol FL micromol(-1) of protein-bound Lys (Lys(p-b)), 0.04+/-0.03 nmol CML micromol(-1) Lys(p-b)(-1) and 0.06+/-0.02 nmol Pyr micromol(-1)Lys(p-b)(-1). It was particularly noticeable, however, that mild heat treatment of raw milk, i.e. pasteurization and UHT treatment, did not significantly increase the amount of both free and protein-bound Lys modifications. In conclusion, the profiles of free and protein-bound glycation-induced Lys modifications were found to be different and a screening of free glycation adducts does, therefore, not allow for a conclusion about the protein glycation status of dairy products. 相似文献
700.
A variety of 1-allenyl-2-propargyl-substituted cyclopentanol derivatives were found to undergo facile intramolecular microwave-assisted [2+2] allenyne cycloaddition reactions to generate tricyclic 5-6-4 ring systems present in the sterpurenes. 相似文献