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41.
Prof. Dr. Tunga Salthammer Friederike Monegel Nicole Schulz Dr. Erik Uhde Prof. Dr. Stefan Grimme Jakob Seibert Prof. Dr. Uwe Hohm Dr. Wolf-Ulrich Palm 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):1046-1056
The chemical background of olfactory perception has been subject of intensive research, but no available model can fully explain the sense of smell. There are also inconsistent results on the role of the isotopology of molecules. In experiments with human subjects it was found that the isotope effect is weak with acetone and D6-acetone. In contrast, clear differences were observed in the perception of octanoic acid and D15-octanoic acid. Furthermore, a trained sniffer dog was initially able to distinguish between these isotopologues of octanoic acid. In chromatographic measurements, the respective deuterated molecule showed weaker interaction with a non-polar liquid phase. Quantum chemical calculations give evidence that deuterated octanoic acid binds more strongly to a model receptor than non-deuterated. In contrast, the binding of the non-deuterated molecule is stronger with acetone. The isotope effect is calculated in the framework of statistical mechanics. It results from a complicated interplay between various thermostatistical contributions to the non-covalent free binding energies and it turns out to be very molecule-specific. The vibrational terms including non-classical zero-point energies play about the same role as rotational/translational contributions and are larger than bond length effects for the differential isotope perception of odor for which general rules cannot be derived. 相似文献
42.
Jakob Heller Tobias F. Pascher Dr. Christian van der Linde Dr. Milan Ončák Prof. Dr. Martin K. Beyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(66):16367-16376
Hydrated aluminium cations have been investigated as a photochemical model system with up to ten water molecules by UV action spectroscopy in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Intense photodissociation was observed starting at 4.5 eV for two to eight water molecules with loss of atomic hydrogen, molecular hydrogen and water molecules. Quantum chemical calculations for n=2 reveal that solvation shifts the intense 3s–3p excitations of Al+ into the investigated photon energy range below 5.5 eV. During the photochemical relaxation, internal conversion from S1 to T2 takes place, and photochemical hydrogen formation starts on the T2 surface, which passes through a conical intersection, changing to T1. On this triplet surface, the electron that was excited to the Al 3p orbital is transferred to a coordinated water molecule, which dissociates into a hydroxide ion and a hydrogen atom. If the system remains in the triplet state, this hydrogen radical is lost directly. If the system returns to singlet multiplicity, the reaction may be reversed, with recombination with the hydroxide moiety and electron transfer back to aluminium, resulting in water evaporation. Alternatively, the hydrogen radical can attack the intact water molecule, forming molecular hydrogen and aluminium dihydroxide. Photodissociation is observed for up to n=8. Clusters with n=9 or 10 occur exclusively as HAlOH+(H2O)n-1 and are transparent in the investigated energy range. For n=4–8, a mixture of Al+(H2O)n and HAlOH+(H2O)n-1 is present in the experiment. 相似文献
43.
Enzymatic Conversion of Flavonoids using Bacterial Chalcone Isomerase and Enoate Reductase
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Dipl.‐Biol. Mechthild Gall Dipl.‐Biochem. Maren Thomsen Dipl.‐Biochem. Christin Peters Dr. Ioannis V. Pavlidis M. Sc. Patrick Jonczyk M. Sc. Philipp P. Grünert Dr. Sascha Beutel Prof. Dr. Thomas Scheper Egon Gross Dr. Michael Backes Dr. Torsten Geißler Dr. Jakob P. Ley Dr. Jens‐Michael Hilmer Dr. Gerhard Krammer Dr. Gottfried J. Palm Prof. Dr. Winfried Hinrichs Prof. Dr. Uwe T. Bornscheuer 《Angewandte Chemie (International ed. in English)》2014,53(5):1439-1442
Flavonoids are a large group of plant secondary metabolites with a variety of biological properties and are therefore of interest to many scientists, as they can lead to industrially interesting intermediates. The anaerobic gut bacterium Eubacterium ramulus can catabolize flavonoids, but until now, the pathway has not been experimentally confirmed. In the present work, a chalcone isomerase (CHI) and an enoate reductase (ERED) could be identified through whole genome sequencing and gene motif search. These two enzymes were successfully cloned and expressed in Escherichia coli in their active form, even under aerobic conditions. The catabolic pathway of E. ramulus was confirmed by biotransformations of flavanones into dihydrochalcones. The engineered E. coli strain that expresses both enzymes was used for the conversion of several flavanones, underlining the applicability of this biocatalytic cascade reaction. 相似文献
44.
Organotin–Oxido Cluster‐Based Multiferrocenyl Complexes Obtained by Hydrolysis of Ferrocenyl‐Functionalized Organotin Chlorides
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Zhiliang You Robert Möckel Jakob Bergunde Prof. Dr. Stefanie Dehnen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(42):13491-13496
Three organotin–oxido clusters were formed by hydrolysis of ferrocenyl‐functionalized organotin chloride precursors in the presence of NaEPh (E=S, Se). [RFcSnCl3?HCl] ( C ; RFc = CMe2CH2C(Me)?N?N?C(Me)Fc) and [SnCl6]2? formed {(RFcSnCl2)3[Sn(OH)6]}[SnCl3] ( 3 a ) and {(RFcSnCl2)3[Sn(OH)6]}[PhSeO3] ( 3 b ), bearing an unprecedented [Sn4O6] unit, in a one‐pot synthesis or stepwise through [(RFcSnCl2)2Se] ( 1 ) plus [(RFcSnCl2)SePh] ( 2 ). A one‐pot reaction starting out from FcSnCl3 gave [(FcSn)9(OH)6O8Cl5] ( 4 ), which represents the largest Fc‐decorated Sn/O cluster reported to date. 相似文献
45.
Andrea Preuß Marcus Korb Tobias Rüffer Jörn Bankwitz Colin Georgi Alexander Jakob Stefan E. Schulz Heinrich Lang 《无机化学与普通化学杂志》2020,646(13):670-680
The template synthesis of ethylenediamine ( 1 ) with 2-acetylcyclopentanone ( 2 ) and [Cu(OAc)2 · H2O] ( 5 ) produced [Cu(1-(2-cC5H6(O))C(Me)NCH2)2)] ( 6 ) in 82 % yield. Reaction of 5 with bis(benzoylacetone)diethylenetriamine ( 7 , = L H)[1] gave [Cu(μ-OAc)( L )(H2O)]2 ( 8 ). The solid-state structures of 6 and 8 were determined confirming that 8 possesses intra- and intermolecular hydrogen bonds resulting in a dimer formation. The thermal behavior of 6 – 8 was studied by TG and TG-MS. Under oxygen CuO was formed, whereas under Ar Cu/Cu2O ( 6 ) or Cu ( 8 ) was obtained. Complex 6 was used as CVD precursor for Cu and Cu-oxide deposition (substrate temp., 400–500 °C, N2, 60 mL · min–1; O2, 60 mL · min–1; pressure, 0.87–1.5 mbar). The as-obtained deposits show separated particles of different appearance at the substrate surface as evidenced by SEM. Non-volatile 8 was applied as spin-coating precursor for Cu and CuO formation [conc. 0.25 mol · L–1; volume 0.2 mL; 3000 rpm; depos. time 2 min; heating rate 50 K · min–1; holding time 60 min (Ar), 120 min (air) at 800 °C]. The samples on silicon consist of granulated particles (Ar) or are non-dense with a grainy topography (air). EDX and XPS measurements confirmed the formation of Cu (Ar) or CuO (O2) with up to 13 mol-% C impurity. 相似文献
46.
Henrik Høyer Matti Knaapila Jakob Kjelstrup‐Hansen Xuhai Liu Geir Helgesen 《Journal of Polymer Science.Polymer Physics》2012,50(7):477-483
We demonstrate micromechanical strain sensors with integrated readout based on carbon nanocones and discs (CNCs) which are aligned into a string‐like formation using an alternating electric field and studied by AC impedance spectroscopy and electromechanical methods. The CNC particles are first dispersed into a polymer matrix with a particle fraction of 0.1 vol %. This value is well below the percolation threshold (~ 2 vol %), which suppresses particle aggregation and facilitates transparency allowing the use of an UV‐curable polymer. Alignment was carried out with a 1 kHz, 4 kV/cm electric field and is a consequence of dielectrophoretic effect. It develops in minutes and makes the initially insulating, nonaligned material conductive. This is followed by UV curing of the polymer matrix, which renders a solid state device. The stretching of the aligned strings in the cured polymer leads to a reversible piezoresistive effect, and a gauge factor of about 50 is observed. This is in a sharp contrast to CNC films with particle fraction above percolation threshold (13 vol %), which are conductive but not sensitive to stretching. The strings are Ohmic in nature and moreover show higher DC conductivity (22–500 S/m) compared to identically prepared carbon black strings (1–22 S/m). © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011 相似文献
47.
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49.
Given a precompact subset of a type Banach space , where , we prove that for every and all
holds, where is the absolutely convex hull of and denotes the dyadic entropy number. With this inequality we show in particular that for given and with for all the inequality holds true for all . We also prove that this estimate is asymptotically optimal whenever has no better type than . For this answers a question raised by Carl, Kyrezi, and Pajor which has been solved up to now only for the Hilbert space case by F. Gao.
holds, where is the absolutely convex hull of and denotes the dyadic entropy number. With this inequality we show in particular that for given and with for all the inequality holds true for all . We also prove that this estimate is asymptotically optimal whenever has no better type than . For this answers a question raised by Carl, Kyrezi, and Pajor which has been solved up to now only for the Hilbert space case by F. Gao.
50.
Jakob J. Keller 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1996,47(6):821-836
Introducing a vector potential, that is based on a pair of stream functions, and a velocity potential, antisymmetric equations for the stream functions are derived with the help of a variational principle. It is found that the equations are in a suitable form to investigate flows with helical symmetry, and, for example, to connect upstream axisymmetric flows with downstream helical flows. The special case of a transition from an upstream solid-body vortex to a downstream helical flow is investigated in detail. Furthermore, the stream-function equations are particularly useful to investigate general small-amplitude inertia waves on vortex flows. Time-dependent helical flows that are time-independent in a suitably rotating frame of reference can also be discussed with the proposed method. 相似文献