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991.
Dr. Clemens Taube Jannis Fidelius Dr. Kai Schwedtmann Dr. Christopher Ziegler Florian Kreuter Dr. Leigh Loots Prof. Dr. Leonard J. Barbour Prof. Dr. Ralf Tonner-Zech Prof. Dr. Robert Wolf Prof. Dr. Jan J. Weigand 《Angewandte Chemie (International ed. in English)》2023,62(47):e202306706
Although diphosphene transition metal complexes are known to undergo E to Z isomerization upon irradiation with UV light, their potential for photoswitching has remained poorly explored. In this study, we present diphosphene complexes capable of reversible photoisomerizations through haptotropic rearrangements. The compounds [( 2 -κ2P,κ6C)Mo(CO)2][OTf] ( 3 a [OTf]), [( 2 -κ2P,κ6C)Fe(CO)][OTf] ( 3 b [OTf]), and [( 2 -κ2P)Fe(CO)4][OTf] ( 4 [OTf]) were prepared using the triflate salt [(LC)P=P(Dipp)][OTf] ( 2 [OTf) as a precursor (LC=4,5-dichloro-1,3-bis(2,6-diisiopropylphenyl)-imidazolin-2-yl; Dipp=2,6-diisiopropylphenyl, OTf=triflate). Upon exposure to blue or UV light (λ=400 nm, 470 nm), the initially red-colored η2-diphosphene complexes 3 a , b [OTf] readily undergo isomerization to form blue-colored η1-complexes [( 2 -κ1P,κ6C)M(CO)n][OTf] ( 5 a , b [OTf]; a : M=Mo, n=2; b : M=Fe, n=1). This haptotropic rearrangement is reversible, and the (κ2P,κ6C)-coordination mode gradually reverts back upon dissolution in coordinating solvents or more rapidly upon exposure to yellow or red irradiation (λ=590 nm, 630 nm). The electronic reasons for the reversible visible-light-induced photoswitching observed for 3 a , b [OTf] are elucidated by DFT calculations. These calculations indicate that the photochromic isomerization originates from the S1 excited state and proceeds through a conical intersection. 相似文献
992.
Aberg KM Torgrip RJ Kolmert J Schuppe-Koistinen I Lindberg J 《Journal of chromatography. A》2008,1192(1):139-146
In this paper we present a new method, called TracMass, for analyzing data obtained using hyphenated chromatography-mass spectrometry (XC/MS). The method uses a Kalman filter to extract pure, noise-free ion chromatograms by exploiting the latent second order structure in the XC/MS data. TracMass differs from current state-of-the-art methodologies, which extract chromatograms by binning along the m/z axis and further processes the data in various ways, e.g. by baseline correction, component detection algorithm, peak detection, and curve resolution to extract molecular features. The proposed method was validated by analyzing two plasma datasets: one derived from 99 quality control samples where TracMass extracted 8880 Pure Ion Chromatograms (PICs) present in > or =90 of the samples. The second dataset was spiked with two different internal standard mixtures to test differential expression analysis. Here TracMass found 20000 PICs present in 10 samples, all differentially expressed analytes, and also a previously unreported discriminating metabolite. Finding as many PICs as possible is in this context essential to ensure that even small differentiating features are found (if they exist). The resulting data representation from TracMass (PICs) can be used directly for statistical analysis, and the method is fast (approximately 5min/sample), with few adjustable parameters. 相似文献
993.
Khare K Herminghaus S Baret JC Law BM Brinkmann M Seemann R 《Langmuir : the ACS journal of surfaces and colloids》2007,23(26):12997-13006
The morphology of liquids confined to linear micrometer-sized grooves of triangular and rectangular cross section is studied for different substrate wettabilities. Depending on the wettability and exact geometry, either droplike morphologies or elongated liquid filaments represent the generic equilibrium structures on the substrate. Upon changing the apparent contact angle of aqueous drops by electrowetting, we are able to trigger the transition between elongated filaments and droplets. In the case of rectangular grooves, this transition allows us to advance liquid reversibly into the grooves while crossing a certain threshold contact angle. In triangular grooves, however, these elongated filaments undergo a dynamic instability when the contact angle returns to a value above the filling threshold. The different filling and drainage behavior is explained by specific aspects of the triangular and rectangular groove geometry. 相似文献
994.
Ralf Schuster Tobias Wähler Dr. Miroslav Kettner Dr. Friederike Agel Dr. Tanja Bauer Prof. Peter Wasserscheid Prof. Jörg Libuda 《ChemistryOpen》2021,10(2):141-152
Low-temperature synthesis in ionic liquids (ILs) offers an efficient route for the preparation of metal oxide nanomaterials with tailor-made properties in a water-free environment. In this work, we investigated the role of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [C4C1Pyr][NTf2] in the synthesis of cobalt oxide nanoparticles from the molecular precursor Co2(CO)8 with ozone. We performed a model study in ultra-clean, ultrahigh vacuum (UHV) conditions by infrared reflection absorption spectroscopy (IRAS) using Au(111) as a substrate. Exposure of the pure precursor to ozone at low temperatures results in the oxidation of the first layers, leading to the formation of a disordered CoxOy passivation layer. Similar protection to ozone is also achieved by deposition of an IL layer onto a precursor film prior to ozone exposure. With increasing temperature, the IL gets permeable for ozone and a cobalt oxide film forms at the IL/precursor interface. We show that the interaction with the IL mediates the oxidation and leads to a more densely packed CoxOy film compared to a direct oxidation of the precursor. 相似文献
995.
Dr. Mateja Klika Škopić Christian Gramse Dr. Rosario Oliva Sabrina Pospich Laura Neukirch Magiliny Manisegaran Prof. Dr. Stefan Raunser Prof. Dr. Roland Winter Prof. Dr. Ralf Weberskirch Dr. Andreas Brunschweiger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(39):10048-10057
The development of DNA-compatible reaction methodologies is a central theme to advance DNA-encoded screening library technology. Recently, we were able to show that sulfonic acid-functionalized block copolymer micelles facilitated Brønsted acid-promoted reactions such as the Povarov reaction on DNA-coupled starting materials with minimal DNA degradation. Here, the impact of polymer composition on micelle shape, and reaction conversion was investigated. A dozen sulfonic acid-functionalized block copolymers of different molar mass and composition were prepared by RAFT polymerization and were tested in the Povarov reaction, removal of the Boc protective group, and the Biginelli reaction. The results showed trends in the polymer structure-micellar catalytic activity relationship. For instance, micelles composed of block copolymers with shorter acrylate ester chains formed smaller particles and tended to provide faster reaction kinetics. Moreover, fluorescence quenching experiments as well as circular dichroism spectroscopy showed that DNA-oligomer-conjugates, although highly water-soluble, accumulated very effectively in the micellar compartments, which is a prerequisite for carrying out a DNA-encoded reaction in the presence of polymer micelles. 相似文献
996.
Characterization of hydro-mechanical processes in reservoir rocks is an essential issue for many geo investigations such as characterization of subsurface fluid flow or geothermal exploitation. For geothermal applications, the role of fractures as storage and transport components of a hydraulic system are highly important. In the present contribution we focus on investigating the effective Skempton coefficient of a damaged porous rock analyzing a modified Cryer problem, which provides a simple model of a porous rock containing a storage and transport pat. The effective Skempton coefficient is defined as the ratio of the increase in mean pore pressure induced by change in confining pressure for undrained boundary conditions. Using approaches from computational homogenization, we evaluate the confining pressure as the negative volume average of the total mean stress. Similarly, we compute the effective fluid pressure in terms of the volume-averaged fluid pressure in the rocks. We compare the numerical results to those from typical experiments and highlight the problems with the latter. The proposed concept for determination of an effective Skempton coefficient based on numerically evaluated volume averages helps to generate a better understanding of the process-inherent constituents. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
997.
Employing the nonperturbative numerical renormalization group method, we study the dynamics of the spin-boson model, which describes a two-level system coupled to a bosonic bath with a spectral density J(omega) proportional to omega(s). We show that, in contrast with the case of Ohmic damping, the delocalized phase of the sub-Ohmic model cannot be characterized by a single energy scale only, due to the presence of a nontrivial quantum phase transition. In the strongly sub-Ohmic regime, s<1, weakly damped coherent oscillations on short time scales are possible even in the localized phase--this is of crucial relevance, e.g., for qubits subject to electromagnetic noise. 相似文献
998.
We investigated the properties of an array of spherical microresonators used as a miniaturized high-resolution spectroscopic device. Sixteen spherical microspheres made from polymethyl methacrylate were placed on a microscope slide serving as an optical wave guide. Light of a tunable narrowband laser source was coupled into this slide so that an evanescent wave was excited on the topside of the slide, where the resonators were placed. This evanescent field generated a particular intensity pattern in the array that depended sensitively on the wavelength. After calibration, that pattern was recorded by a CCD camera and used to identify the wavelength with a resolution of R ~ lambda/Deltalambda = 7 x 10(4). 相似文献
999.
1000.
Regtmeier J Grauwin S Eichhorn R Reimann P Anselmetti D Ros A 《Journal of separation science》2007,30(10):1461-1467
Recently, the counter intuitive migration phenomenon of absolute negative mobility (ANM) has been demonstrated to occur for colloidal particles in a suitably arranged post array within a microfluidic device [1]. This effect is based on the interplay of Brownian motion, nonlinear dynamics induced through microstructuring, and nonequilibrium driving, and results in a particle movement opposite to an applied static force. Simultaneously, the migration of a different particle species along the direction of the static force is possible [19], thus providing a new tool for particle sorting in microfluidic device format. The so far demonstrated maximum velocities for micrometer-sized spheres are slow, i. e., in the order of 10 nm per second. Here, we investigate numerically, how maximum ANM velocities can be significantly accelerated by a careful adjustment of the post size and shape. Based on this numerical analysis, a post design is developed and tested in a microfluidic device made of PDMS. The experiment reveals an order of magnitude increase in velocity. 相似文献