Search results for "Circular dichroism"
showing 9 items of 419 documents
Methionine in a protein hydrophobic core drives tight interactions required for assembly of spider silk
2019
Web spiders connect silk proteins, so-called spidroins, into fibers of extraordinary toughness. The spidroin N-terminal domain (NTD) plays a pivotal role in this process: it polymerizes spidroins through a complex mechanism of dimerization. Here we analyze sequences of spidroin NTDs and find an unusually high content of the amino acid methionine. We simultaneously mutate all methionines present in the hydrophobic core of a spidroin NTD from a nursery web spider’s dragline silk to leucine. The mutated NTD is strongly stabilized and folds at the theoretical speed limit. The structure of the mutant is preserved, yet its ability to dimerize is substantially impaired. We find that side chains of…
Investigations of methyl lactate in the presence of reverse micelles by vibrational spectroscopy and circular dichroism
2012
Abstract The FT-IR and vibrational circular dichroism (VCD) spectra of ( S )- and -( R )-methyl lactate have been recorded for neat samples and at various concentrations in CCl 4 and DMSO solutions. These spectra are used to analyse the FT-IR and VCD spectra of methyl lactates in presence of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) in CCl 4 , where the surfactant molecules are known to form reverse micelles. Some tendency of methyl lactate to interact with AOT micellar aggregates is observed, but not as well defined as previously observed for dimethyl tartrate in analogous circumstances. Besides, near infrared (NIR) absorption and VCD data have been obtained for most of the above system…
A Tunable, Fullerene‐Based Molecular Amplifier for Vibrational Circular Dichroism
2019
Abstract Vibrational circular dichroism (VCD) studies are reported on a chiral compound in which a fullerene C60 moiety is used as an electron acceptor and local VCD amplifier for an alanine‐based peptide chain. Four redox states are investigated in this study, of which three are reduced species that possess low‐lying electronic states as confirmed by UV/Vis spectroelectrochemistry. VCD measurements in combination with (TD)DFT calculations are used to investigate (i) how the low‐lying electronic states of the reduced species modulate the amplification of VCD signals, (ii) how this amplification depends on the distance between oscillator and amplifier, and (iii) how the spatial extent of the…
Stability and disassembly properties of human naïve Hsp60 and bacterial GroEL chaperonins.
2015
Human Hsp60 chaperonin and its bacterial homolog GroEL, in association with the corresponding co-chaperonins Hsp10 and GroES, constitute important chaperone systems promoting the proper folding of several mitochondrial proteins. Hsp60 is also currently described as a ubiquitous molecule with multiple roles both in health conditions and in several diseases. Naïve Hsp60 bearing the mitochondrial import signal has been recently demonstrated to present different oligomeric organizations with respect to GroEL, suggesting new possible physiological functions. Here we present a combined investigation with circular dichroism and small-angle X-ray scattering of structure, self-organization, and sta…
Nitrated Fatty Acids Modulate the Physical Properties of Model Membranes and the Structure of Transmembrane Proteins
2017
Nitrated fatty acids (NO2 -FAs) act as anti-inflammatory signal mediators, albeit the molecular mechanisms behind NO2 -FAs' influence on diverse metabolic and signaling pathways in inflamed tissues are essentially elusive. Here, we combine fluorescence measurements with surface-specific sum frequency generation vibrational spectroscopy and coarse-grained computer simulations to demonstrate that NO2 -FAs alter lipid organization by accumulation at the membrane-water interface. As the function of membrane proteins strongly depends on both, protein structure as well as membrane properties, we consecutively follow the structural dynamics of an integral membrane protein in presence of NO2 -FAs. …
Chiral cyclohexane based fluorescent chemosensors for enantiomeric discrimination of aspartate
2008
Some new chiral cyclohexyl based fluorescent anion receptors have been synthesized and their absolute configuration has been determined by using circular dichroism (CD). Complexation experiments have been carried out with several dicarboxylates, and stoichiometries and complexation constants for the corresponding complexes have been determined. The chiral discrimination ability of these ligands for chiral dicarboxylates has been studied and the best results have been obtained with TMA aspartate.
Spectroscopic and Structural Investigation of the Confinement of D and L Dimethyl Tartrate in Lecithin Reverse Micelles
2009
The confinement of D and L dimethyl tartrate in lecithin reverse micelles dispersed in cyclohexane has been investigated by FT-IR, polarimetry, electronic and vibrational circular dichroism (ECD and VCD), 1H NMR, and small-angle X-ray scattering (SAXS). Measurements have been performed at room temperature as a function of the solubilizate-to-surfactant molar ratio (R) at fixed lecithin concentration. The analysis of experimental data indicates that the dimethyl tartrate molecules are solubilized within reverse micelles in proximity to the surfactant head groups in the same way for the D and L forms. The encapsulation of dimethyl tatrate within lecithin reverse micelles involves changes in i…
Polymorphic chiral squaraine crystallites in textured thin films
2020
Chirality 32(5), 619 - 631 (2020). doi:10.1002/chir.23213
ChemInform Abstract: Assignment of the Absolute Configuration and Total Synthesis of (+)-Caripyrin.
2015
The antifungal secondary metabolite (+)-caripyrin was studied by vibrational circular dichroism spectroscopy. Analysis of the recorded data, with the Boltzmann weighted-average of the spectra calculated at the B3LYP/6-311G(d,p) level of theory for all relevant conformers, unequivocally proved the (R,R)-configuration for the dextrorotatory natural product. Based on this finding, a short enantioselective synthesis of (+)-caripyrin was developed.