81 research outputs found
Structure of a model salt bridge in solution investigated with 2D-IR spectroscopy
Salt bridges are known to be important for the stability of protein
conformation, but up to now it has been difficult to study their geometry in
solution. Here we characterize the spatial structure of a model salt bridge
between guanidinium (Gdm+) and acetate (Ac-) using two-dimensional vibrational
(2D-IR) spectroscopy. We find that as a result of salt bridging the infrared
response of Gdm+ and Ac- change significantly, and in the 2D-IR spectrum, salt
bridging of the molecules appears as cross peaks. From the 2D-IR spectrum we
determine the relative orientation of the transition-dipole moments of the
vibrational modes involved in the salt bridge, as well as the coupling between
them. In this manner we reconstruct the geometry of the solvated salt bridge
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Elucidating the structure of chiral molecules by using amplified vibrational circular dichroism: from theory to experimental realization
Recent experimental observations of enhanced vibrational circular dichroism (VCD) in molecular systems with low-lying electronically excited states suggest interesting new applications of VCD spectroscopy. The theory describing VCD enhancement through vibronic coupling schemes was derived by Nafie in 1983, but only recently experimental evidence of VCD amplification has demonstrated the extent to which this effect can be
exploited as a structure elucidation tool to probe local structure. In this Concept paper, we give an overview of the physics behind vibrational circular dichroism, in particular the equations governing the VCD amplification effect, and review the latest experimental developments with a prospective view on the application of amplified VCD to locally probe biomolecular structure
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Excited-state electronic asymmetry prevents photoswitching in terthiophene compounds
The diarylethene moiety is one of the most extensively used switches in the field of molecular electronics. Here we report on spectroscopic and quantum chemical studies of two diarylethene-based compounds with a non-C3-symmetric triethynyl terthiophene core symmetrically substituted with RuCp*(dppe) or trimethylsilyl termini. The ethynyl linkers are strong IR markers that we use in time-resolved vibrational spectroscopic studies to get insight into the character and dynamics of the electronically excited states of these compounds on the picosecond to nanosecond time scale. In combination with electronic transient absorption studies and DFT calculations, our studies show that the conjugation of the non-C3-symmetric triethynyl terthiophene system in the excited state strongly affects one of the thiophene rings involved in the ring closure. As a result, cyclization of the otherwise photochromic 3,3âł-dimethyl-2,2âČ:3âČ,2âł-terthiophene core is inhibited. Instead, the photoexcited compounds undergo intersystem crossing to a long-lived triplet excited state from which they convert back to the ground state
Mechanism for vibrational relaxation in water investigated by femtosecond infrared spectroscopy
We present a study on the relaxation of the O¿H stretch vibration in a dilute HDO:D2O solution using femtosecond mid-infrared pump-probe spectroscopy. We performed one-color experiments in which the 01 vibrational transition is probed at different frequencies, and two-color experiments in which the 12 transition is probed. In the one-color experiments, it is observed that the relaxation is faster at the blue side than at the center of the absorption band. Furthermore, it is observed that the vibrational relaxation time T1 shows an anomalous temperature dependence and increases from 0.74 ± 0.01 ps at 298 K to 0.90 ± 0.02 ps at 363 K. These results indicate that the O¿HO hydrogen bond forms the dominant accepting mode in the vibrational relaxation of the O¿H stretch vibration. ©1999 American Institute of Physics
Bimodal dynamics of mechanically constrained hydrogen bonds revealed by vibrational photon echoes
We have investigated the dynamics of the hydrogen bonds that connect the components of a [2]rotaxane in solution. In this rotaxane, the amide groups in the benzylic-amide macrocycle and the succinamide thread are connected by four equivalent NâHâ
â
â
O=C hydrogen bonds. The fluctuations of these hydrogen bonds are mirrored by the frequency fluctuations of the NH-stretch modes, which are probed by means of three-pulse photon-echo peak shift spectroscopy. The hydrogen-bond fluctuations occur on three different time scales, with time constants of 0.1, 0.6, and >=200 ps. Comparing these three time scales to the ones found in liquid formamide, which contains the same hydrogen-bonded amide motif but without mechanical constraints, we find that the faster two components, which are associated with small-amplitude fluctuations in the strength of the NâHâ
â
â
O=C hydrogen bonds, are very similar in the liquid and the rotaxane. However, the third component, which is associated with the breaking and subsequent reformation of hydrogen bonds, is found to be much slower in the rotaxane than in the liquid. It can be concluded that the mechanical bonding in a rotaxane does not influence the amplitude and time scale of the small-amplitude fluctuations of the hydrogen bonds, but strongly slows down the complete dissociation of these hydrogen bonds. This is probably because in a rotaxane breaking of the macrocycle-axle contacts is severely hindered by the mechanical constraints. The hydrogen-bond dynamics in rotaxane-based molecular machines can therefore be regarded as liquidlike on a time scale 1 ps and less, but structurally frozen on longer (up to at least 200 ps) time scales
The structure of salt bridges between Arg +
Salt bridges play an important role in protein folding and in supramolecular chemistry, but they are difficult to detect and characterize in solution. Here, we investigate salt bridges between glutamate (Gluâ) and arginine (Arg+) using two-dimensional infrared (2D-IR) spectroscopy. The 2D-IR spectrum of a salt-bridged dimer shows cross peaks between the vibrational modes of Gluâ and Arg+, which provide a sensitive structural probe of GluââŻArg+ salt bridges. We use this probe to investigate a ÎČ-turn locked by a salt bridge, an α-helical peptide whose structure is stabilized by salt bridges, and a coiled coil that is stabilized by intra- and intermolecular salt bridges. We detect a bidentate salt bridge in the ÎČ-turn, a monodentate one in the α-helical peptide, and both salt-bridge geometries in the coiled coil. To our knowledge, this is the first time 2D-IR has been used to probe tertiary side chain interactions in peptides, and our results show that 2D-IR spectroscopy is a powerful method for investigating salt bridges in solution
Direct Observation of a Dark State in the Photocycle of a Light-Driven Molecular Motor
Controlling the excited-state properties
of light driven molecular
machines is crucial to achieving high efficiency and directed functionality.
A key challenge in achieving control lies in unravelling the complex
photodynamics and especially in identifying the role played by dark
states. Here we use the structure sensitivity and high time resolution
of UV-pump/IR-probe spectroscopy to build a detailed and comprehensive
model of the structural evolution of light driven molecular rotors.
The photodynamics of these chiral overcrowded alkene derivatives are
determined by two close-lying excited electronic states. The potential
energy landscape of these âbrightâ and âdarkâ
states gives rise to a broad excited-state electronic absorption band
over the entire mid-IR range that is probed for the first time and
modeled by quantum mechanical calculations. The transient IR vibrational
fingerprints observed in our studies allow for an unambiguous identification
of the identity of the âdarkâ electronic excited state
from which the photonâs energy is converted into motion, and
thereby pave the way for tuning the quantum yield of future molecular
rotors based on this structural motif
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