Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Photoelectron Circular Dichroism in the Photodetachment of Amino Acid Anions.

ABSTRACT: The chirality of chemical compounds is of undisputed importance in science and technology. In particular with respect to pharmacological application most molecules of interest cannot be accessed by the powerful techniques developed in recent years for gas phase analytes. Here, we demonstrate that the combination of electrospray ionization (ESI) with the detection of photoelectron circular dichroism (PECD) provides access to chirality information applicable to molecular materials with negligible vapor pressure, for example, amino acids. To this end, glutamic acid and 3,4-dihydroxyphenylalanine (DOPA) have been electrosprayed into the source of a chirality spectrometer, where photodetachment is enforced and the PECD is detected. The technique can be expected to be conceptually applicable to all chemical systems with chirality based on molecular properties.

SUBMITTER: Kruger P

PROVIDER: S-EPMC8457165 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Photoelectron Circular Dichroism in the Photodetachment of Amino Acid Anions.

Krüger Peter P Weitzel Karl-Michael KM

Angewandte Chemie (International ed. in English) 20210708 33

The chirality of chemical compounds is of undisputed importance in science and technology. In particular with respect to pharmacological application most molecules of interest cannot be accessed by the powerful techniques developed in recent years for gas phase analytes. Here, we demonstrate that the combination of electrospray ionization (ESI) with the detection of photoelectron circular dichroism (PECD) provides access to chirality information applicable to molecular materials with negligible ...[more]

PMID: 34137142

Similar Datasets

Determination of the Molar Fraction and Enantiomeric Excess of Electrosprayed Amino Acid Anions Employing Photoelectron Circular Dichroism.

Project description:The quantification of molar fractions and enantiomeric excess has been demonstrated in mixtures of d- and l-tryptophan and d- and l-phenylalanine, respectively, avoiding derivatization of the analyte with additional reagents or separation steps. The technique is based on electrospray ionization (ESI), which allows the generation of anions of nonvolatile compounds such as amino acids or large biomolecules. Electrons are photodetached from these anions. The distribution of forward and backward scattered photoelectrons is analyzed, leading to photoelectron circular dichroism (PECD), the observable of interest. The quantification of the concept is proven by blind measurements analyzing mixtures of unknown composition. The quantification of enantiomeric excess (ee) values is not only possible for signals originating from the molecular anion but also for the molecular dimer anion. The ESI-PECD technique is known to be applicable to large chemical entities of several thousand Daltons.

| S-EPMC11883741 | biostudies-literature

Imaging Photoelectron Circular Dichroism in the Detachment of Mass-Selected Chiral Anions.

Project description:Photoelectron Circular Dichroism (PECD) is a forward-backward asymmetry in the photoemission from a non-racemic sample induced by circularly polarized light. PECD spectroscopy has potential analytical advantages for chiral discrimination over other chiroptical methods due to its increased sensitivity to the chiral potential of the molecule. The use of anions for PECD spectroscopy allows for mass-selectivity and provides a path to simple experimental schemes that employ table-top light sources. Evidence of PECD for anions is limited, and insight into the forces that govern PECD electron dynamics in photodetachment is absent. Here, we demonstrate a PECD effect in the photodetachment of mass-selected deprotonated 1-indanol anions. By utilizing velocity map imaging photoelectron spectroscopy with a tunable light source, we determine the energy-resolved PECD over a wide range of photon energies. The observed PECD reaches up to 11 %, similar to what has been measured for neutral species.

| S-EPMC10099851 | biostudies-literature

Femtosecond photoelectron circular dichroism of chemical reactions.

Project description:Understanding the chirality of molecular reaction pathways is essential for a broad range of fundamental and applied sciences. However, the current ability to probe chirality on the time scale of primary processes underlying chemical reactions remains very limited. Here, we demonstrate time-resolved photoelectron circular dichroism (TRPECD) with ultrashort circularly polarized vacuum-ultraviolet (VUV) pulses from a tabletop source. We demonstrate the capabilities of VUV-TRPECD by resolving the chirality changes in time during the photodissociation of atomic iodine from two chiral molecules. We identify several general key features of TRPECD, which include the ability to probe dynamical chirality along the complete photochemical reaction path, the sensitivity to the local chirality of the evolving scattering potential, and the influence of electron scattering off dissociating photofragments. Our results are interpreted by comparison with high-level ab-initio calculations of transient PECDs from molecular photoionization calculations. Our experimental and theoretical techniques define a general approach to femtochirality.

| S-EPMC9286499 | biostudies-literature

Induced photoelectron circular dichroism onto an achiral chromophore.

Project description:An achiral chromophore can acquire a chiral spectroscopic signature when interacting with a chiral environment. This so-called induced chirality is documented in electronic or vibrational circular dichroism, which arises from the coupling between electric and magnetic transition dipoles. Here, we demonstrate that a chiroptical response is also induced within the electric dipole approximation by observing the asymmetric scattering of a photoelectron ejected from an achiral chromophore in interaction with a chiral host. In a phenol-methyloxirane complex, removing an electron from an achiral aromatic π orbital localised on the phenol moiety results in an intense and opposite photoelectron circular dichroism (PECD) for the two enantiomeric complexes with (R) and (S) methyloxirane, evidencing the long-range effect (~5 Å) of the scattering chiral potential. This induced chirality has important structural and analytical implications, discussed here in the context of growing interest in laser-based PECD, for in situ, real time enantiomer determination.

| S-EPMC10562374 | biostudies-literature

Photoelectron circular dichroism in angle-resolved photoemission from liquid fenchone.

Project description:We present an experimental X-ray photoelectron circular dichroism (PECD) study of liquid fenchone at the C 1s edge. A novel setup to enable PECD measurements on a liquid microjet [Malerz et al., Rev. Sci. Instrum., 2022, 93, 015101] was used. For the C 1s line assigned to fenchone's carbonyl carbon, a non-vanishing asymmetry is found in the intensity of photoelectron spectra acquired under a fixed angle in the backward-scattering plane. This experiment paves the way towards an innovative probe of the chirality of organic/biological molecules in aqueous solution.

| S-EPMC8985659 | biostudies-literature

Relaxation Dynamics in Photoexcited Chiral Molecules Studied by Time-Resolved Photoelectron Circular Dichroism: Toward Chiral Femtochemistry.

Project description:Unravelling the main initial dynamics responsible for chiral recognition is a key step in the understanding of many biological processes. However, this challenging task requires a sensitive enantiospecific probe to investigate molecular dynamics on their natural femtosecond time scale. Here we show that, in the gas phase, the ultrafast relaxation dynamics of photoexcited chiral molecules can be tracked by recording time-resolved photoelectron circular dichroism (TR-PECD) resulting from the photoionization by a circularly polarized probe pulse. A large forward-backward asymmetry along the probe propagation axis is observed in the photoelectron angular distribution. Its evolution with pump-probe delay reveals ultrafast dynamics that are inaccessible in the angle-integrated photoelectron spectrum or via the usual electron emission anisotropy parameter (β). PECD, which originates from the electron scattering in the chiral molecular potential, appears as a new sensitive observable for ultrafast molecular dynamics in chiral systems.

| S-EPMC5116763 | biostudies-literature

Chirality in Atomically Thin CdSe Nanoplatelets Capped with Thiol-Free Amino Acid Ligands: Circular Dichroism vs. Carboxylate Group Coordination.

Project description:Chiral semiconductor nanostructures and nanoparticles are promising materials for applications in biological sensing, enantioselective separation, photonics, and spin-polarized devices. Here, we studied the induction of chirality in atomically thin only two-monolayer-thick CdSe nanoplatelets (NPLs) grown using a colloidal method and exchanged with L-alanine and L-phenylalanine as model thiol-free chiral ligands. We have developed a novel two-step approach to completely exchange the native oleic acid ligands for chiral amino acids at the basal planes of NPLs. We performed an analysis of the optical and chiroptical properties of the chiral CdSe nanoplatelets with amino acids, which was supplemented by an analysis of the composition and coordination of ligands. After the exchange, the nanoplatelets retained heavy-hole, light-hole, and spin-orbit split-off exciton absorbance and bright heavy-hole exciton luminescence. Capping with thiol-free enantiomer amino acid ligands induced the pronounced chirality of excitons in the nanoplatelets, as proven by circular dichroism spectroscopy, with a high dissymmetry g-factor of up to 3.4 × 10-3 achieved for heavy-hole excitons in the case of L-phenylalanine.

| S-EPMC10779562 | biostudies-literature

A novel assay method for an amino acid racemase reaction based on circular dichroism.

Project description:We have established a novel assay method based on circular dichroism that can be used for the kinetic study of the activity of amino acid racemases, such as ALR (alanine racemase). Although an enzyme-coupled assay method has been used to measure racemase activity, the CD method is superior to the enzyme assay because it can accurately determine the immediate changes of an enantiomer on racemization between its L- and D-forms. The enzyme-coupled assay requires D-amino acid oxidase, which is inactivated by an inhibitor of ALR, D-cycloserine. This indicates that the inhibitory kinetic study for ALR with D-cycloserine by the enzyme-coupled assay method is restricted to the analysis of only the reaction resulting in the formation of L-Ala from D-Ala. However, since the CD assay does not require the coupled enzyme, it can be used to comprehensively evaluate the reactions that result in the formation both of D-Ala from L-Ala and of L-Ala from D-Ala at several substrate concentrations. Streptomyces ALR also catalyses the formation of D-Ser from L-Ser and of L-Ser from D-Ser, but the catalytic constants (kcat) are 4- and 10-fold lower than those for the formation of D-Ala from L-Ala and of L-Ala from D-Ala respectively.

| S-EPMC1175127 | biostudies-other

Linear dichroism and circular dichroism in photosynthesis research.

Project description:The efficiency of photosynthetic light energy conversion depends largely on the molecular architecture of the photosynthetic membranes. Linear- and circular-dichroism (LD and CD) studies have contributed significantly to our knowledge of the molecular organization of pigment systems at different levels of complexity, in pigment-protein complexes, supercomplexes, and their macroassemblies, as well as in entire membranes and membrane systems. Many examples show that LD and CD data are in good agreement with structural data; hence, these spectroscopic tools serve as the basis for linking the structure of photosynthetic pigment-protein complexes to steady-state and time-resolved spectroscopy. They are also indispensable for identifying conformations and interactions in native environments, and for monitoring reorganizations during photosynthetic functions, and are important in characterizing reconstituted and artificially constructed systems. This educational review explains, in simple terms, the basic physical principles, and theory and practice of LD and CD spectroscopies and of some related quantities in the areas of differential polarization spectroscopy and microscopy.

| S-EPMC2744782 | biostudies-literature

Circular Dichroism Microscopy Free from Commingling Linear Dichroism via Discretely Modulated Circular Polarization.

Project description:In this work, we developed a circular dichroism (CD) imaging microscope with a device to suppress the commingling of linear birefringence (LB) and linear dichroism (LD) signals. CD signals are, in principle, free from the commingling influence of LD and LB if the sample is illuminated with pure circularly polarized light, with no linear polarization contribution. Based on this idea, we here propose a novel circular polarization modulation method to suppress the contribution of linear polarization, which enables high-sensitivity CD detection (10-4 level in optical density unit or mdeg level in ellipticity) for microscopic imaging at a nearly diffraction limited spatial resolution (sub-μm level). The highly sensitive, diffraction-limited local CD detection will make direct analyses of chiral structures and spatial mappings of optical activity feasible for μm- to sub-μm-sized materials and may yield a number of applications as a unique optical imaging method.

| S-EPMC5071757 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data