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Alkyl radicals produced in the indirect reduction of alkyl halides or alkyldimethylsulfonium salts by electrochemically generated aromatic radical anions couple fast with the latter and alkylated or dialkylated dihydro compounds are formed. Rate constants measured for the coupling reaction between on one hand methyl, primary, secondary and tertiary alkyl radicals as well as benzyl and cumyl radicals and on the other hand a wide spectrum of electrochemically generated aromatic radical anions are found to be about 1×109 M−1 s−1. Previous measurements of coupling rate constants for primary alkyl radicals have been re-evaluated since they were affected by the presence of an SN2 reaction occurring between the alkyl halides used as radical precursors and the aromatic radical anions. New experiments are also included using alkyldimethylsulfonium salts as precursors in order to prevent such SN2 artefacts. It is concluded that sterical hindrance does not play a significant role for the radical-radical anion coupling reactions. In general the rate constants for the coupling reactions are all close to 109 M−1 s−1. 相似文献
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Troels C. Damgaard Arne J. Glenstrup Lars Birkedal Robin Milner 《Formal Aspects of Computing》2013,25(2):257-288
We analyze the matching problem for bigraphs. In particular, we present a sound and complete inductive characterization of matching in bigraphs with binding. Our results yield a specification for a provably correct matching algorithm, as needed by our prototype tool implementing bigraphical reactive systems. 相似文献
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Chaoren Shen Wanfang Li Hongfei Yin Anke Spannenberg Troels Skrydstrup Xiao‐Feng Wu 《Advanced Synthesis \u0026amp; Catalysis》2016,358(3):466-479
An unexpected palladium‐catalyzed carbonylative synthesis of 2,3‐disubstituted chromones has been developed. Starting from 2‐bromofluorobenzenes and ketones, the corresponding chromones were produced in good yields. By control experiments, this transformation was found to proceed through a sequential carbonylation/Claisen–Hasse rearrangement/intramolecular nucleophilic aromatic substitution approach (SNAr). More specifically, the reaction sequence started with a palladium‐catalyzed carbonylation of the ketone with o‐bromofluorobenzene to give the vinyl benzoates, which subsequently transformed into 1,3‐diketones via a Claisen–Hasse rearrangement. The final products were produced after an intramolecular SNAr reaction of the in situ formed 1,3‐diketone.
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5‐(Piperidin‐4‐yl)‐3‐Hydroxypyrazole: A Novel Scaffold for Probing the Orthosteric γ‐Aminobutyric Acid Type A Receptor Binding Site 下载免费PDF全文
Dr. Jacob Krall Dr. Kenneth T. Kongstad Birgitte Nielsen Troels E. Sørensen Dr. Thomas Balle Dr. Anders A. Jensen Dr. Bente Frølund 《ChemMedChem》2014,9(11):2475-2485
A series of bioisosteric N1‐ and N2‐substituted 5‐(piperidin‐4‐yl)‐3‐hydroxypyrazole analogues of the partial GABAAR agonists 4‐PIOL and 4‐PHP have been designed, synthesized, and characterized pharmacologically. The unsubstituted 3‐hydroxypyrazole analogue of 4‐PIOL ( 2 a ; IC50~300 μM ) is a weak antagonist at the α1β2γ2 GABAAR, whereas substituting the N1‐ or N2‐position with alkyl or aryl substituents resulted in antagonists with binding affinities in the high nanomolar to low micromolar range at native rat GABAARs. Docking studies using a α1β2γ2 GABAAR homology model along with the obtained SAR indicate that the N1‐substituted analogues of 4‐PIOL and 4‐PHP, 2 a – k , and previously reported 3‐substituted 4‐PHP analogues share a common binding mode to the orthosteric binding site in the receptor. Interestingly, the core scaffold of the N2‐substituted analogues of 4‐PIOL and 4‐PHP, 3 b – k , are suggested to flip 180° thereby adapting to the binding pocket and addressing a cavity situated above the core scaffold. 相似文献
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Madsen Per Jensen Ole Kiel Amtoft Torben Reynisson Ragnar V. Mikkelsen Jan Hvolgaard Laursen SØren Kolding Troels Emil Larsen Torben Jenner Michael Bohl 《Wireless Personal Communications》2002,23(1):55-66
Unified RF requirements are derived for an UMTS Terrestrial RadioAccess/Frequency Division Duplex (UTRA/FDD) compliant mobile transceiver. Aset of transceiver requirements are proposed with consideration to systemissues including duplex aspects. From these design-compatible requirements areproposed for each functional block in the transceiver. 相似文献
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Anna Helena Stygar Mogens Agerbo Krogh Troels Kristensen Søren Østergaard Anders Ringgaard Kristensen 《Journal of dairy science》2017,100(7):5758-5773
Evolutionary operations is a method to exploit the association of often small changes in process variables, planned during systematic experimentation and occurring during the normal production flow, to production characteristics to find a way to alter the production process to be more efficient. The objective of this study was to construct a tool to assess the intervention effect on milk production in an evolutionary operations setup. The method used for this purpose was a dynamic linear model (DLM) with Kalman filtering. The DLM consisted of parameters describing milk yield in a herd, individual cows from a herd, and an intervention effect on a given day. The model was constructed to handle any number of cows, experimental interventions, different data sources, or presence of control groups. In this study, data from 2 commercial Danish herds were used. In herd 1, data on 98,046 and 12,133 milkings registered from an automatic milking system (AMS) were used for model building and testing, respectively. In herd 2, data on 3,689 milkings on test days were used for estimating the initial model parameters. For model testing, data from both bulk tank milk yield (85 observations) and test-day milkings (1,471) were used. In herd 1, the manager wanted to explore the possibility of reducing the amount of concentrate provided to the cows in an AMS. In herd 2, the manager wanted to know if the milk yield could be increased by elevating the energy level provided to the cows in a total mixed ration. The experiment conducted in herd 1 was designed with a treatment and a control group, whereas in herd 2 we used a pretest/posttest design. The constructed tool provided estimates (mean and confidence intervals) for each of 3 interventions carried out in both herds. In herd 1, we concluded that the reduction in concentrate amount provided in the AMS had no negative influence on milk yield. For herd 2, the increased level of energy had a significant positive effect on milk yield but only for the first intervention. In this herd, the effect of intervention was also evaluated for cows in the first lactation and without bulk tank records. The presented model proved to be a flexible and dynamic tool, and it was successfully applied for systematic experimentation in dairy herds. The model can serve as a decision support tool for on-farm process optimization exploiting planned changes in process variables and the response of production characteristics. 相似文献
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Back Christoffer Olling Slaats Tijs Hildebrandt Thomas Troels Marquard Morten 《International Journal on Software Tools for Technology Transfer (STTT)》2022,24(4):563-587
International Journal on Software Tools for Technology Transfer - Declarative process modeling formalisms—which capture high-level process constraints—have seen growing interest,... 相似文献
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In this study, we have investigated the lubricating properties of an aqueous fluid prepared with polyoxamer triblock copolymer in water, namely “F127-20” (F127 at the concentration of 20% wt./vol.). In coherence with its well-known thermo-responsive rheological properties, lubricating properties of F127-20 also displayed varying lubricating properties, both in the lubricating mechanism and efficacy, as a function of temperature, speed and tribopairs. F127-20 was most effective in lubricating a soft interface (PDMS–PDMS) based on its gel-forming properties in 22.5–60 °C and feasible formation of hydrodynamic lubricating films at all speeds. More importantly, enhanced shear thinning of F127-20 and an optimum pressure opposed from PDMS–PDMS tribological contact led to a substantial reduction in viscosity of the lubricant and smooth gliding of the interface while maintaining fluidic lubricating films. At temperatures lower or higher than temperature range 22.5–60 °C, F127-20 behaved as a liquid, and boundary lubrication became the dominant lubrication mechanism. 相似文献