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91.
Jaime Aspas-Caceres Marc Rico-Pasto Isabel Pastor Felix Ritort 《Entropy (Basel, Switzerland)》2022,24(7)
Nonequilibrium work relations and fluctuation theorems permit us to extract equilibrium information from nonequilibrium measurements. They find application in single-molecule pulling experiments where molecular free energies can be determined from irreversible work measurements by using unidirectional (e.g., Jarzynski’s equality) and bidirectional (e.g., Crooks fluctuation theorem and Bennet’s acceptance ratio (BAR)) methods. However, irreversibility and the finite number of pulls limit their applicability: the higher the dissipation, the larger the number of pulls necessary to estimate G within a few . Here, we revisit pulling experiments on an RNA three-way junction (3WJ) that exhibits significant dissipation and work-distribution long tails upon mechanical unfolding. While bidirectional methods are more predictive, unidirectional methods are strongly biased. We also consider a cyclic protocol that combines the forward and reverse work values to increase the statistics of the measurements. For a fixed total experimental time, faster pulling rates permit us to efficiently sample rare events and reduce the bias, compensating for the increased dissipation. This analysis provides a more stringent test of the fluctuation theorem in the large irreversibility regime. 相似文献
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Dr. Qingquan Lu Steffen Greßies Felix J. R. Klauck Prof. Dr. Frank Glorius 《Angewandte Chemie (International ed. in English)》2017,56(23):6660-6664
A MnI-catalyzed regioselective C−H allenylation is reported that allows a broad range of 2-allenylindoles to be synthesized regioselectively on a gram scale under simple conditions. Notably, a highly efficient chirality transfer was observed (up to 93 % ee) in this transformation. This procedure was further found to allow, for the first time, the direct preparation of ketones by MnI-catalyzed C−H activation. Mechanistic investigations revealed that the precoordination of the oxygen atom to the manganese center as well as the congested tertiary carbon atom in the propargylic carbonates play a crucial role. 相似文献
95.
Felix Becker Klaus Zimmermann Tatiana Volkova Vladimir T. Minchenya 《Regular and Chaotic Dynamics》2013,18(1-2):63-74
This article concerns microrobots for solid and liquid environments. A short overview of microrobotics, suitable actuators and energy systems is given. The principles of terrestrial and aquatic locomotion are discussed and illustrated with examples from the literature on robotics. The state of the art with a focus on piezo microrobots for solid and liquid environments is presented. Furthermore, we report an amphibious prototype, which can move on flat solid ground and on the free surface of water. The design, characteristic parameters and experiments on locomotion are described. The robot is characterized by a light and simple design and can perform twodimensional locomotion in different environments with a speed up to 30 mm/s. An analytical model to predict the maximum carrying capacity of the robot on water is solved numerically. 相似文献
96.
Roman Tkachov Lukas Stepien Aljoscha Roch Hartmut Komber Felix Hennersdorf Jan J. Weigand Ingmar Bauer Anton Kiriy Christoph Leyens 《Tetrahedron》2017,73(16):2250-2254
Herein, aiming at optimization of the polymerization process leading to a family of hole- and electron-conducting 1,1,2,2-ethenetetrathiolate-based polymers, such as poly(nickel-1,1,2,2-ethenetetrathiolate), poly[Kx(Ni-ett)], we investigated transformations of the monomer precursor 1,3,4,6-tetrathiapentalene-2,5-dione (TPD) occurring under polymerization conditions. We found that only one ring of TPD opens upon its reaction with potassium methoxide under inert conditions at room temperature which leads to the formation of potassium 2-oxo-1,3-dithiol-4,5-dithiolate (K2[3]). Heating of K2[3] under reflux in methanol solution under inert conditions opens the second ring, however the resulting product is not potassium ethenetetrathiolate (K4[2]), the product of an exhaustive methanolysis of TPD, but potassium tetrathiooxalate (K2[4]), the product of the decarbonylation of K2[3]. Preliminary experiments reveal that the involvement of K2[4] in the polymerization process is beneficial for reproducible formation of high quality 1,1,2,2-ethenetetrathiolate-based polymers suitable for thermoelectric applications. 相似文献
97.
Sarah Crotty Felix H. Schacher Ulrich S. Schubert 《Journal of polymer science. Part A, Polymer chemistry》2012,50(23):4958-4965
We report the synthesis and characterization of well‐defined homo‐ and diblock copolymers containing poly(furfuryl glycidyl ether) (PFGE) via living anionic ring‐opening polymerization using different initiators. The obtained materials were characterized by SEC, MALDI‐TOF MS, and 1H NMR spectroscopy and molar masses of up to 9400 g/mol were obtained for PFGE homopolymers. If the amphiphilic diblock copolymer PEG‐block‐PFGE was dissolved in water, micelles with a PFGE core and a PEG corona were formed. Hereby, the hydrophobic PFGE core domains were used for the incorporation of a suitable bismaleimide and heating to 60 °C induced the crosslinking of the micellar core via Diels‐Alder chemistry. This process was further shown to be reversible. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
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Bhaskar Garg Shiou-Ling Lei Shou-Ching Liu Tanuja Bisht Jen-Yu Liu Yong-Chien Ling 《Analytica chimica acta》2012
The time-of-flight secondary ion mass spectrometry (TOF-SIMS) has emerged as a powerful tool for the unswerving detection of biomolecules, in particular, proteins and peptides. To date, there is very little information available on the direct determination of trimethyl/triethyl amines using TOF-SIMS. One major hurdle in this regard is an ultrahigh vacuum system, usually needed in TOF-SIMS, which hampers its usability to trimethyl/triethyl amines owing to their high evaporation rate. We designed an efficient and sensitive protocol for rapid identification and sensitive determination of tertiaryalkyl amines using TOF-SIMS. The amines were derivatized by reaction with 1,4-butane sultone and sulphuric acid sequentially to afford the corresponding sulphonic acidic ionic liquids (ILs). The TOF-SIMS analysis of these task-specific ILs (TSILs) was carried out in both positive and negative polarity. The positive ion mass spectra of TSILs showed sharp fragmented peaks for tertiaryalkyl amines at typical level and up to 10 ppm. The possible mechanism for different fragmentation pathways in positive polarity was discussed. 相似文献