| 1. |
- Bergmann, U, et al.
(författare)
-
High-resolution X-ray spectroscopy of rare events : a different look at local structure and chemistry
- 2001
-
Ingår i: Journal of Synchrotron Radiation. - Univ Calif Berkeley, Lawrence Berkeley Lab, Phys Biosci Div, Berkeley, CA 94720 USA. Univ Calif Davis, Dept Appl Sci, Davis, CA 95616 USA. CALTECH, Jet Prop Lab, Pasadena, CA 91109 USA. : MUNKSGAARD INT PUBL LTD. - 0909-0495 .- 1600-5775. ; 8, s. 199-203
-
Tidskriftsartikel (refereegranskat)abstract
- The combination of large-acceptance high-resolution X-ray optics with bright synchrotron sources permits quantitative analysis of rare events such as X-ray fluorescence from very dilute systems, weak fluorescence transitions or X-ray Raman scattering. Transition-metal K beta fluorescence contains information about spin and oxidation state; examples of the characterization of the Mn oxidation states in the oxygen-evolving complex of photosystem II and Mn-consuming spores from the marine bacillus SG-1 are presented. Weaker features of the K beta spectrum resulting from valence-level and 'interatomic' ligand to metal transitions contain detailed information on the ligand-atom type, distance and orientation. Applications of this spectral region to characterize the local structure of model compounds are presented. X-ray Raman scattering (XRS) is an extremely rare event, but also represents a unique technique to obtain bulk-sensitive low-energy (<600 eV) X-ray absorption fine structure (XAFS) spectra using hard ( 10 keV) X-rays. A photon is inelastically scattered, losing part of its energy to promote an electron into an unoccupied level. In many cases, the cross section is proportional to that of the corresponding absorption process yielding the same X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) features. XRS finds application for systems that defy XAFS analysis at low energies, e.g. liquids or highly concentrated complex systems, reactive compounds and samples under extreme conditions (pressure, temperature). Recent results are discussed.
|
|
| 2. |
- Messinger, Johannes, 1963-, et al.
(författare)
-
Absence of Mn-centered oxidation in the S2 → S3 Transition: : Implications for the mechanism of photosynthetic water oxidation
- 2001
-
Ingår i: Journal of the American Chemical Society. - : AMER CHEMICAL SOC. - 0002-7863 .- 1520-5126. ; 123:32, s. 7804-7820
-
Tidskriftsartikel (refereegranskat)abstract
- A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen-evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S-3 --> [S-4] --> So transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn K beta X-ray emission spectroscopy (K beta XES) to this problem for the first time. The K beta XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electron paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S-2 --> S3 transition, in contrast to the S-0 --> S-1 and S-1 --> S-2 transitions. does not involve a Mn-centered oxidation. On the basis of new structural data from the S-3-state, manganese mu -oxo bridge radical formation is proposed for the S-2 --> S-3 transition, and three possible mechanisms for the O-O bond formation are presented.
|
|
| 3. |
- Both, C., et al.
(författare)
-
Large-scale geographical variation confirms that climate change causes birds to lay earlier
- 2004
-
Ingår i: Proceedings of the Royal Society of London Series B-Biological Sciences. - : The Royal Society. - 0962-8452 .- 1471-2954. ; 271:1549, s. 1657-1662
-
Tidskriftsartikel (refereegranskat)abstract
- Advances in the phenology of organisms are often attributed to climate change, but alternatively, may reflect a publication bias towards advances and may be caused by environmental factors unrelated to climate change. Both factors are investigated using the breeding dates of 25 long-term studied populations of Ficedula flycatchers across Europe. Trends in spring temperature varied markedly between study sites, and across populations the advancement of laying date was stronger in areas where the spring temperatures increased more, giving support to the theory that climate change causally affects breeding date advancement.
|
|
| 4. |
|
|
| 5. |
- Groenhof, Gerrit, et al.
(författare)
-
Photoactivation of the photoactive yellow protein : why photon absorption triggers a trans-to-cis Isomerization of the chromophore in the protein.
- 2004
-
Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 126:13, s. 4228-4233
-
Tidskriftsartikel (refereegranskat)abstract
- Atomistic QM/MM simulations have been carried out on the complete photocycle of Photoactive Yellow Protein, a bacterial photoreceptor, in which blue light triggers isomerization of a covalently bound chromophore. The "chemical role" of the protein cavity in the control of the photoisomerization step has been elucidated. Isomerization is facilitated due to preferential electrostatic stabilization of the chromophore's excited state by the guanidium group of Arg52, located just above the negatively charged chromophore ring. In vacuo isomerization does not occur. Isomerization of the double bond is enhanced relative to isomerization of a single bond due to the steric interactions between the phenyl ring of the chromophore and the side chains of Arg52 and Phe62. In the isomerized configuration (ground-state cis), a proton transfer from Glu46 to the chromophore is far more probable than in the initial configuration (ground-state trans). It is this proton transfer that initiates the conformational changes within the protein, which are believed to lead to signaling.
|
|
| 6. |
- Winblad, B, et al.
(författare)
-
Mild cognitive impairment--beyond controversies, towards a consensus: report of the International Working Group on Mild Cognitive Impairment.
- 2004
-
Ingår i: Journal of internal medicine. - : Wiley. - 0954-6820 .- 1365-2796. ; 256:3, s. 240-6
-
Forskningsöversikt (refereegranskat)abstract
- The First Key Symposium was held in Stockholm, Sweden, 2-5 September 2003. The aim of the symposium was to integrate clinical and epidemiological perspectives on the topic of Mild Cognitive Impairment (MCI). A multidisciplinary, international group of experts discussed the current status and future directions of MCI, with regard to clinical presentation, cognitive and functional assessment, and the role of neuroimaging, biomarkers and genetics. Agreement on new perspectives, as well as recommendations for management and future research were discussed by the international working group. The specific recommendations for the general MCI criteria include the following: (i) the person is neither normal nor demented; (ii) there is evidence of cognitive deterioration shown by either objectively measured decline over time and/or subjective report of decline by self and/or informant in conjunction with objective cognitive deficits; and (iii) activities of daily living are preserved and complex instrumental functions are either intact or minimally impaired.
|
|
