Refine
Year of publication
- 2016 (213) (remove)
Document Type
- Article (156)
- Doctoral Thesis (33)
- Postprint (21)
- Other (2)
- Review (1)
Is part of the Bibliography
- yes (213) (remove)
Keywords
- X-ray structure (4)
- nanoparticles (4)
- Ion mobility spectrometry (3)
- Nanoparticles (3)
- biomaterials (3)
- configuration (3)
- conformation (3)
- copper(II) (3)
- crystal structure (3)
- crystallization (3)
Institute
- Institut für Chemie (213) (remove)
For Vibrio cholerae, the coordinated import and export of Na+ is crucial for adaptation to habitats with different osmolarities. We investigated the Na+-extruding branch of the sodium cycle in this human pathogen by in vivo Na-23-NMR spectroscopy. The Na+ extrusion activity of cells was monitored after adding glucose which stimulated respiration via the Na+-translocating NADH:quinone oxidoreductase (Na+-NQR). In a V. cholerae deletion mutant devoid of the Na+-NQR encoding genes (nqrA-F), rates of respiratory Na+ extrusion were decreased by a factor of four, but the cytoplasmic Na+ concentration was essentially unchanged. Furthermore, the mutant was impaired in formation of transmembrane voltage (Delta psi, inside negative) and did not grow under hypoosmotic conditions at pH 8.2 or above. This growth defect could be complemented by transformation with the plasmid encoded nqr operon. In an alkaline environment, Na+/H+ antiporters acidify the cytoplasm at the expense of the transmembrane voltage. It is proposed that, at alkaline pH and limiting Na+ concentrations, the Na+-NQR is crucial for generation of a transmembrane voltage to drive the import of H+ by electrogenic Na+/H+ antiporters. Our study provides the basis to understand the role of the Na+-NQR in pathogenicity of V. cholerae and other pathogens relying on this primary Na+ pump for respiration. (C) 2015 Elsevier B.V. All rights reserved.
Oligospirothioketal (OSTK) rods are presented as an adjustable scaffold for optical membrane probes. The OSTK rods are readily incorporated into lipid bilayers due to their hydrophobic backbones. Because of their high length-over-diameter aspect ratio, only a minimal disturbance of the lipid bilayer is caused. OSTK rods show outstanding rigidity and allow defined labeling with fluorescent dyes, yielding full control of the orientation between the dye and OSTK skeleton. This. allows the construction of novel Forster resonance energy transfer probes with highly defined relative orientations of the transition dipole moments of the donor and acceptor dyes and makes the class of OSTK probes a power-fill, flexible toolbox for optical biosensing applications. Data on steady-state and time-resolved fluorescence experiments investigating the incorporation of coumarin- and [1,3]-dioxolo[4,5-f][1,3]benzo-dioxole-labeled OSTKs in large unilamellar vesicles are presented as a show case.
Poly(2-alkyl-2-oxazoline)s (PAOx) exhibit different crystallization behavior depending on the length of the alkyl side chain. PAOx having methyl, ethyl, or propyl side chains do not show any bulk crystallization. Crystallization in the heating cycle, that is, cold crystallization, is observed for PAOx with butyl and pentyl side chains. For PAOx with longer alkyl side chains crystallization occurs in the cooling cycle. The different crystallization behavior is attributed to the different polymer chain mobility in line with the glass transition temperature (T-g) dependency on alkyl side chain length. The decrease in chain mobility with decreasing alkyl side chain length hinders the relaxation of the polymer backbone to the thermodynamic equilibrium crystalline structure. Double melting behavior is observed for PButOx and PiPropOx which is explained by the melt-recrystallization mechanism. Isothermal crystallization experiments of PButOx between 60 and 90 degrees C and PiPropOx between 90 and 150 degrees C show that PAOx can crystallize in bulk when enough time is given. The decrease of Tg and the corresponding increase in chain mobility at T > T-g with increasing alkyl side chain length can be attributed to an increasing distance between the polymer backbones and thus decreasing average strength of amide dipole interactions. (C) 2015 Wiley Periodicals, Inc.
Time- and temperature-resolved in situ birefringence measurements were applied to analyze the effect of nanoparticles on the electric field-induced alignment of a microphase separated solution of poly(styrene)-block-poly(isoprene) in toluene. Through the incorporation of isoprene-confined CdSe quantum dots the reorientation behavior is altered. Particle loading lowers the order-disorder transition temperature, and increases the defect density, favoring nucleation and growth as an alignment mechanism over rotation of grains. The temperature dependent alteration in the reorientation mechanism is analyzed via a combination of birefringence and synchrotron SAXS. The detailed understanding of the effect of nanoparticles on the reorientation mechanism is an important prerequisite for optimization of electricfield-induced alignment of block copolymer/nanoparticle composites where the block copolymer guides the nanoparticle self-assembly into anisotropic structures.
The excitation of localized surface plasmons in noble metal nanoparticles (NPs) results in different nanoscale effects such as electric field enhancement, the generation of hot electrons and a temperature increase close to the NP surface. These effects are typically exploited in diverse fields such as surface-enhanced Raman scattering (SERS), NP catalysis and photothermal therapy (PTT). Halogenated nucleobases are applied as radiosensitizers in conventional radiation cancer therapy due to their high reactivity towards secondary electrons. Here, we use SERS to study the transformation of 8-bromoadenine (8BrA) into adenine on the surface of Au and AgNPs upon irradiation with a low-power continuous wave laser at 532, 633 and 785 nm, respectively. The dissociation of 8BrA is ascribed to a hot-electron transfer reaction and the underlying kinetics are carefully explored. The reaction proceeds within seconds or even milliseconds. Similar dissociation reactions might also occur with other electrophilic molecules, which must be considered in the interpretation of respective SERS spectra. Furthermore, we suggest that hot-electron transfer induced dissociation of radiosensitizers such as 8BrA can be applied in the future in PTT to enhance the damage of tumor tissue upon irradiation.
The aggregation kinetics of thermoresponsive core-shell micelles with a poly(N-isopropyl acrylamide) shell in pure water or in mixtures of water with the cosolvents methanol or ethanol at mole fractions of 5% is investigated during a temperature jump across the respective cloud point. Characteristically, these mixtures give rise to cononsolvency behavior. At the cloud point, aggregates are formed, and their growth is followed with time-resolved small-angle neutron scattering. Using the reversible association model, the interaction potential between the aggregates is determined from their growth rate in dependence on the cosolvents. The effect of the cosolvent is attributed to the interaction potential on the structured layer of hydration water around the aggregates. It is surmised that the latter is perturbed by the cosolvent and thus the residual repulsive hydration force between the aggregates is reduced. The larger the molar volume of the cosolvent, the more pronounced is the effect. This framework provides a molecular-level understanding of solvent-mediated effective interactions in polymer solutions and new opportunities for the rational control of self-assembly in complex soft matter systems.
Information about the strength of donor–acceptor interactions in push–pull alkenes is valuable, as this so-called “push–pull effect” influences their chemical reactivity and dynamic behaviour. In this paper, we discuss the applicability of NMR spectral data and barriers to rotation around the C[double bond, length as m-dash]C double bond to quantify the push–pull effect in biologically important 2-alkylidene-4-oxothiazolidines. While olefinic proton chemical shifts and differences in 13C NMR chemical shifts of the two carbons constituting the C[double bond, length as m-dash]C double bond fail to give the correct trend in the electron withdrawing ability of the substituents attached to the exocyclic carbon of the double bond, barriers to rotation prove to be a reliable quantity in providing information about the extent of donor–acceptor interactions in the push–pull systems studied. In particular all relevant kinetic data, that is the Arrhenius parameters (apparent activation energy Ea and frequency factor A) and activation parameters (ΔS‡, ΔH‡ and ΔG‡), were determined from the data of the experimentally studied configurational isomerization of (E)-9a. These results were compared to previously published related data for other two compounds, (Z)-1b and (2E,5Z)-7, showing that experimentally determined ΔG‡ values are a good indicator of the strength of push–pull character. Theoretical calculations of the rotational barriers of eight selected derivatives excellently correlate with the calculated C[double bond, length as m-dash]C bond lengths and corroborate the applicability of ΔG‡ for estimation of the strength of the push–pull effect in these and related systems.
Information about the strength of donor-acceptor interactions in push-pull alkenes is valuable, as this so-called "push-pull effect' influences their chemical reactivity and dynamic behaviour. In this paper, we discuss the applicability of NMR spectral data and barriers to rotation around the CQC double bond to quantify the push-pull effect in biologically important 2-alkylidene-4-oxothiazolidines. While olefinic proton chemical shifts and differences in C-13 NMR chemical shifts of the two carbons constituting the CQC double bond fail to give the correct trend in the electron withdrawing ability of the substituents attached to the exocyclic carbon of the double bond, barriers to rotation prove to be a reliable quantity in providing information about the extent of donor-acceptor interactions in the push-pull systems studied. In particular all relevant kinetic data, that is the Arrhenius parameters ( apparent activation energy Ea and frequency factor A) and activation parameters ( Delta S-double dagger, Delta H-double dagger and Delta G(double dagger)), were determined from the data of the experimentally studied configurational isomerization of ( E)-9a. These results were compared to previously published related data for other two compounds, ( Z)-1b and ( 2E, 5Z)-7, showing that experimentally determined Delta G(double dagger) values are a good indicator of the strength of push-pull character. Theoretical calculations of the rotational barriers of eight selected derivatives excellently correlate with the calculated CQC bond lengths and corroborate the applicability of Delta G(double dagger) for estimation of the strength of the push-pull effect in these and related systems.