Spin-polarized photo-electron

The use of LICS in the production of spin-polarized photo-electrons has also been investigated [90]. The general theoretical results have been applied to Rb and Cs. In both cases, enhancement of a factor of 2 in the degree of spin polarization has been obtained by the introduction of a dressing laser at intensity larger than 10 W/cm. ... 

For magnetically ordered materials, photoemitted electrons have a characteristic spin polarization that reflects the electron spin orientation occurring in the sample before the photoemission process. Recently, techniques have been developed to measure this photoelectron spin polarization (photo ESP) (21). 

Here the sum runs over all possible initial states and the operator describes the interaction of the electrons and the radiation field with wave vector q and polarization A. In Eq. (1) it has been assumed that the detector selectively counts photo electrons with energy E, wave vector k, and spin polarization The corresponding final... 

Great advances in the elucidation of electronic structure and the dynamics of optical spin polarization in organic triplet-state molecules have been made by ESR spectroscopy since the first successful experiment of Hutchison and Mangum (39) in 1958. Most of the triplet ESR studies can be grouped into two sections the photo-excited phosphorescent triplet states and the photochemical ly prepared ground triplet-state intermediates. 

The TREPR results clearly show that cryptochromes (exemplified for the DASH-type) readily form radical-pair species upon photoexcitation. Spin correlation of such radical-pair states (singlet vs triplet), which is a necessary condition for magnetoselectivity of radical-pair reactions, manifests itself as electron-spin polarization of EPR transitions, which can be directly detected by TREPR in real time. Such observations support the conservation of photo-induced radical-pair reactions and their relevance among proteins of the photolyase/cryptochrome family. The results are of high relevance for studies of magnetosensors based on radical-pair (photo-)chemistry in general [114], and for the assessment of the suitability of cryptochrome radical pairs in animal magnetoreception in particular [17, 115]. 

Biochemical applications have been made more recently O, ). Here, cyclic photochemical reactions are employed to generate nuclear spin-polarization in biological macromolecules. The information obtained is of a structural nature rather than mechanistic. In the case of proteins aromatic amino acid residues (tyrosine, histidine and tryptophan) can be polarized by reversible hydrogen atom or electron transfer reactions with a photo-excited dye. These reactions require direct contact of the dye with the amino acid side-chains so that they only occur for residues lying at the surface of the protein. 

Figure 1 Photo-excitation and radical-pair generation by triplet-sensitized electron transfer with the spin polarization mechanisms acting in this scheme...

Photo-induced Electron Transfer. Electron transfer is one of the most fundamental and widespread reactions in nature and has been extensively studied. In addition to the optical absorption spectroscopy widely used, TR EPR has become established as an appropriate method to study electron-transfer processes. In most of these investigations CIDEP effects are observed. The spin-polarization effects originate in the spin selectivity of chemical and physical processes involved in free-radical formation and decay, as well as in the spin-state evolution in transient paramagnetic precursors. For this reason, CIDEP constitutes a unique probe of the mechanistic details of electron-transfer processes. 

Using the OPENCORE spectrometer, a research group led by M. Kitagawa in Osaka have developed an experimental setup for dynamic nuclear polarization (DNP) using electron spins in the photo-excited triplet state. This nuclear hyperpolarization technique, called hereafter triplet DNP,... 

The fact that dynamic 13C polarization is only possible through the indirect way via tire 1H spins suggests the mechanism of polarization transfer. Since the polarization transfer between the electrons and nuclei are driven by the dipolar interactions between them, and the fraction of the guest triplet molecules was small, it would be natural to assume that the polarization of the electron spins in the photo-excited triplet state is given to those H spins which happen to be close to the electron spins, and then the 1H polarization would be transported away over the whole volume of the sample by spin diffusion among the 1H spins. 

Appropriate modification of the ESR spectrometer and generation of free radicals by flash photolysis enables time-resolved (TR) ESR spectroscopy [22]. Spectra observed under these conditions are remarkable for their signal directions and intensities. They can be enhanced as much as one-hundredfold and appear as absorption, emission, or a combination of both. Effects of this type are a result of chemically induced dynamic electron polarization (CIDEP) these spectra indicate the intermediacy of radicals whose sublevel populations deviate substantially from equilibrium populations. Significantly, the splitting pattern characteristic of the spin-density distribution of the intermediate remains unaffected thus, the CIDEP enhancement not only facilitates the detection of short-lived radicals at low concentrations, but also aids their identification. Time-resolved ESR techniques cannot be expected to be of much use for electron-transfer reactions from alkanes, because their oxidation potentials are prohibitively high. Even branched alkanes have oxidation potentials well above the excited-state reduction potential of typical photo-... 

Figure 11 shows the result of this experiment on a solution of 5 mM N-acetyl tryptophan and 0.2 mM 3-N-carboxy-methyl lumiflavin, hereafter simply called flavin (see Figure 10). Positive enhancements can be observed for the aromatic C-2, C-4 and C-6 protons, while the CH2 group shows emission. This polarization pattern corresponds with a tryptophyl radical in which the electron spin is delocalized over the aromatic ring. It can further be noted that almost no flavin polarization is present in the difference spectrum. Figure 11c (weak lines are present at 2.6 and 4.0 ppm). This is due to cancellation of recombination and escape polarization as will be discussed in Section 5. The mechanism of the photoreaction undoubtedly involves triplet flavin (17). Since 1-N-methyl tryptophan shows similar CIDNP effects, the primary step most probably is electron transfer to the photo-excited flavin. This is also supported by a flash photolysis study by Heelis and Phillips (18). The nature of the primary step in the photoreactions with amino acids is important in view of the interpretation of "accessibility" of an amino acid side chain in a protein as seen by the photo-CIDNP method. This question is therefore the subject of further study.

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