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421.
The free-radical induced reaction between a tri-functional thiol (2-ethyl-(hydroxymethyl)-1,3-propanediol trimercapto propionate) and two 1,2-disubstituted alkenes (methyl oleate and methyl elaidate) has been investigated under photochemical conditions. The photoreaction was monitored via time-resolved FTIR, Raman and NMR spectroscopy to provide insights about the kinetics and efficiency in end-product formation. The information collected was subjected to numerical modelling using the GEPASI software using pre-established literature values for the rate coefficients in order to verify the proposed reaction scheme. The results confirm the thiol-ene reaction mechanism showing a very fast cis/trans-isomerization (<1.0 min) when compared with the total disappearance of unsaturations, indicating that the rate-limiting step controlling the reaction is the hydrogen transfer from the thiol involved in the formation of product. High thiol-ene conversions can be obtained at reasonable rates without major influence of side-reactions when performed in bulk indicating that this reaction is suitable for network forming purposes with monounsaturated fatty acid methyl esters derivatives. The kinetic and mechanistic information collected provides a basis for the design of new thiol-ene systems aiming at material and coating applications. 相似文献
422.
Petrignani A Hellberg F Thomas RD Larsson M Cosby PC van der Zande WJ 《The Journal of chemical physics》2005,122(23):234311
We present product state distributions and quantum yields from the dissociative recombination reaction of O2+ in its electronic and vibrational ground states as a function of electron collision energy between 0 and 300 meV. The experiments have been performed in the heavy-ion storage ring, CRYRING, and use a cold hollow-cathode discharge source for the production of cold molecular oxygen ions. The branching fractions over the different dissociation limits show distinct oscillations while the resulting product quantum yields are largely independent of electron collision energy above 40 meV. The branching results are well reproduced assuming an isotropic dissociation process, in contrast with recent theoretical predictions. 相似文献
423.
Jonas Lindh Jonas Sävmarker Peter Nilsson Dr. Per J. R. Sjöberg Dr. Mats Larhed Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(18):4630-4636
One Heck of a reaction : Treatment of arylboronic acids or aryltrifluoroborates with vinyl acetate by using a palladium(II) catalyst gives the corresponding styrenes (see scheme). No palladium reoxidant is needed and the vinylation is performed under non‐inert conditions
424.
Fechner P Pröll F Carlquist M Proll G 《Analytical and bioanalytical chemistry》2009,393(6-7):1579-1585
A label-free and time-resolved biosensor based on reflectometric interference spectroscopy (RIfS) has been developed to evaluate the agonistic or antagonistic effects of potential ligands with unknown behavior. The biosensor utilizes the specific interaction between the estrogen receptor alpha (ER alpha) and short specific peptides. The unique feature of these peptides allows the investigation of the behavior of ligands and the discrimination between the agonistic and antagonistic effects caused by conformational changes of the receptor. Thus, this developed biosensor allows not only the differentiation between ligands and nonligands of a receptor, but also the potential of these ligands to influence conformational changes in the receptor, leading to activation or inhibition of the receptor-dependent pathways. Owing to the robustness of the direct optical detection principle used, the biosensor is applicable to complex biological matrices, even crude cell extracts. Moreover, the reliability of the biosensor, including regeneration steps when performing subsequent measurements, has been verified. 相似文献
425.
Tengborg Charlotte Stenberg Kerstin Galbe Mats Zacchi Guido Larsson Simona Palmqvist Eva Hahn-Hägerdal Bärbel 《Applied biochemistry and biotechnology》1998,(1):3-15
The pretreatment of softwood with sulfuric acid impregnation in the production of ethanol, based on enzymatic hydrolysis,
has been investigated. The parameters investigated were: H2SO4 concentration (0.5 – 4.4% w/w liquid), temperature (180 – 240°C), and residence time (1-20 minutes). The combined severity
(log Ro-pH) was used to combine the parameters into a single reaction ordinate. The highest yields of fermentable sugars,
i.e., glucose and mannose, were obtained at a combined severity of 3. At this severity, however, the fermentability declined
and the ethanol yield decreased. In a comparison with previous results, SO2 impregnation was found to be preferable, since it resulted in approximately the same sugar yields, but better fermentability. 相似文献
426.
Crispin X Cornil J Friedlein R Okudaira KK Lemaur V Crispin A Kestemont G Lehmann M Fahlman M Lazzaroni R Geerts Y Wendin G Ueno N Brédas JL Salaneck WR 《Journal of the American Chemical Society》2004,126(38):11889-11899
Discotic liquid crystals emerge as very attractive materials for organic-based (opto)electronics as they allow efficient charge and energy transport along self-organized molecular columns. Here, angle-resolved photoelectron spectroscopy (ARUPS) is used to investigate the electronic structure and supramolecular organization of the discotic molecule, hexakis(hexylthio)diquinoxalino[2,3-a:2',3'-c]phenazine, deposited on graphite. The ARUPS data reveal significant changes in the electronic properties when going from disordered to columnar phases, the main feature being a decrease in ionization potential by 1.8 eV following the appearance of new electronic states at low binding energy. This evolution is rationalized by quantum-chemical calculations performed on model stacks containing from two to six molecules, which illustrate the formation of a quasi-band structure with Bloch-like orbitals delocalized over several molecules in the column. The ARUPS data also point to an energy dispersion of the upper pi-bands in the columns by some 1.1 eV, therefore highlighting the strongly delocalized nature of the pi-electrons along the discotic stacks. 相似文献
427.
M Klett M Giesecke A Nyman F Hallberg RW Lindström G Lindbergh I Furó 《Journal of the American Chemical Society》2012,134(36):14654-14657
Poor mass transport in the electrolyte of Li ion batteries causes large performance losses in high-power applications such as vehicles, and the determination of transport properties under or near operating conditions is therefore important. We demonstrate that in situ (7)Li NMR imaging in a battery electrolyte can directly capture the concentration gradients that arise when current is applied. From these, the salt diffusivity and Li(+) transport number are obtained within an electrochemical transport model. Because of the temporal, spatial, and chemical resolution it can provide, NMR imaging will be a versatile tool for evaluating electrochemical systems and methods. 相似文献
428.
We have employed hybrid DFT and SCS-MP2 calculations at the SMD-PCM-6-311++G(2d,2p)//6-31+G(d) level to investigate the relationship between three possible channels for forming a Diels-Alder adduct from a highly nucleophilic diene and moderately to highly electrophilic dienophiles. We discuss geometries optimized using the B3LYP and M06-2X functionals with the 6-31+(d) basis set. The transition states and intermediates are characterized on the basis of geometric and electronic properties, and we also address the possibility of predicting detectability of a zwitterionic intermediate based on its relative stability. Our results show that a conventional Diels-Alder transition state conformation yields intermediates in all four investigated cases, but that these are too short-lived to be detected experimentally for the less activated reactants. The stepwise trans pathway, beginning with a conjugate addition-like transition state, becomes increasingly competitive with more activated reactants and is indeed favored for the most electrophilic dienophiles. Addition of a trans diene leads to a dead-end as the trans intermediates have insurmountable rotation barriers that prohibit formation of the second bond, unless another, heterocyclic intermediate is formed. We also show that introduction of a hydrogen bond donating catalyst favors a stepwise pathway even for less activated dienophiles. 相似文献
429.
A stereoselective and 1,4-benzoquinone-mediated palladium(II)-catalyzed Heck/Suzuki domino reaction involving metal coordinating cyclic methylamino vinyl ethers and a number of electronically diverse arylboronic acids has been developed and studied. Diastereomeric ratios up to 39:1 and 78 % isolated yields were obtained. The stereoselectivity of the reaction was found to be highly dependent on the nature of the arylboronic acid and the amount of water present in the reaction mixture. Thus, a domino β,α-diarylation–reduction of chelating vinyl ethers can now be accomplished and stereochemically controlled, given that optimized conditions and an appropriate chiral auxiliary are used. To the best of our knowledge, this represents the first example of a stereoselective, oxidative Heck/Suzuki domino reaction in the literature. 相似文献
430.