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61.
Vera Krewald Marius Retegan Nicholas Cox Johannes Messinger Wolfgang Lubitz Serena DeBeer Frank Neese Dimitrios A. Pantazis 《Chemical science》2015,6(3):1676-1695
A central question in biological water splitting concerns the oxidation states of the manganese ions that comprise the oxygen-evolving complex of photosystem II. Understanding the nature and order of oxidation events that occur during the catalytic cycle of five Si states (i = 0–4) is of fundamental importance both for the natural system and for artificial water oxidation catalysts. Despite the widespread adoption of the so-called “high-valent scheme”—where, for example, the Mn oxidation states in the S2 state are assigned as III, IV, IV, IV—the competing “low-valent scheme” that differs by a total of two metal unpaired electrons (i.e. III, III, III, IV in the S2 state) is favored by several recent studies for the biological catalyst. The question of the correct oxidation state assignment is addressed here by a detailed computational comparison of the two schemes using a common structural platform and theoretical approach. Models based on crystallographic constraints were constructed for all conceivable oxidation state assignments in the four (semi)stable S states of the oxygen evolving complex, sampling various protonation levels and patterns to ensure comprehensive coverage. The models are evaluated with respect to their geometric, energetic, electronic, and spectroscopic properties against available experimental EXAFS, XFEL-XRD, EPR, ENDOR and Mn K pre-edge XANES data. New 2.5 K 55Mn ENDOR data of the S2 state are also reported. Our results conclusively show that the entire S state phenomenology can only be accommodated within the high-valent scheme by adopting a single motif and protonation pattern that progresses smoothly from S0 (III, III, III, IV) to S3 (IV, IV, IV, IV), satisfying all experimental constraints and reproducing all observables. By contrast, it was impossible to construct a consistent cycle based on the low-valent scheme for all S states. Instead, the low-valent models developed here may provide new insight into the over-reduced S states and the states involved in the assembly of the catalytically active water oxidizing cluster. 相似文献
62.
Dimitrios A. Lamprou Thomas G. Nevell Colin R. Willis 《Applied Surface Science》2010,256(6):1961-5087
Measurements of surface-liquid interactions (contact-angle goniometry) and tip-surface adhesion forces (atomic force microscopy) combined with infrared spectroscopic studies have been used to investigate surface-preparation and solution-deposition conditions for the reproducible formation of self-assembled molecular structures on gold-coated tips and substrates for atomic force microscopy. Preliminary data show that surface-saturated self-assembled monolayers form reproducibly on prolonged (>20 h) exposure of gold-coated glass substrates to ethanolic solutions of ω-functionalised alkanethiols in the concentration range 80-160 mmol dm−3. The data also show that exposure for 16 h to alkanethiol concentrations in the range 160-240 mmol dm−3 promote bilayer formation whereas concentrations of 240-320 mmol dm−3 result in the deposition of multilayers, the average orientation of which is parallel to that of the first molecular layer; the use of parent 1-undecanethiol solutions at concentrations of 1-80 mmol dm−3 results in incomplete monolayer coverage. 相似文献
63.
We consider two-stage tandem queueing systems attended by two specialized and one flexible server, where all servers have time varying rates. Assuming exponential processing times and linear holding costs, we derive properties of server allocation policies that minimize expected costs over an infinite time horizon. 相似文献
64.
65.
Nadeem A. Choudry Dimitrios K. Kampouris Rashid O. Kadara Craig E. Banks 《Electrochemistry communications》2010,12(1):6-9
We demonstrate that the electron transfer properties of disposable screen printed electrodes can be readily tailored via the introduction of a polymeric formulation into the ink used to fabricate these electrochemical platforms. This approach allows the role of the binder on the underpinning electrochemical properties to be explored and allows the electrochemical reactivity of the screen printed electrodes to be tailored from that of edge plane to basal plane of highly ordered pyrolytic graphite. 相似文献
66.
Application of Complexity Theory to an Information Processing Model in Science Education 总被引:2,自引:0,他引:2
Dimitrios Stamovlasis Georgios Tsaparlis 《Nonlinear dynamics, psychology, and life sciences》2001,5(3):267-287
The current work examines the role of working-memory capacity in problem solving in science education. It treats an information-processing model with tools of complexity theory. Nonlinear methods are used to correlate the subjects' achievement scores with working-memory capacity. Data have been taken from the achievement scores in simple organic-synthesis chemical problems. The subjects (N = 319) were in grade twelve (age 17–18). Problems of various Z-demands (that is the number of steps needed to solve the problem) from two to eight were used. Rank-order sequences of the subjects, according to their scores, were generated, and each score was then replaced by the value of subject's working memory capacity measured by the digit backward span test. Then the sequences were mapped onto a one-dimensional random walk model and when treated as dynamic flows were found to possess fractal geometry with characteristics depending on the Z-demand of the problem. The findings were interpreted using concepts from complexity theory, such as correlation exponents, fractal dimensions and entropy. The null hypothesis was tested with surrogate data. 相似文献
67.
Mohamed Khairy Dimitrios K. Kampouris Rashid O. Kadara Craig E. Banks 《Electroanalysis》2010,22(21):2496-2501
Gold ensembles for the trace level sensing of arsenic(III) in the presence of copper(II) are reported. The gold ensembles are fabricated using citrate capped gold nanoparticles which are chemically synthesised in an aqueous solution with an aliquot of this simply cast onto an economical and disposable screen printed electrode. After drying at room temperature, the gold ensembles are ready for use. The gold ensembles are explored towards the sensing of arsenic(III) in the presence of copper(II) using anodic stripping voltammetry where the corresponding stripping peaks are well resolved and using this protocol it is possible to readily detect 3 µg L?1 (3 ppb) with a detection limit of 0.4 µg L?1 (0.4 ppb). Proof‐of‐concept is also shown for the sensing of arsenic(III) in a canal water sample. Given the low cost of the sensor and ease of fabrication, the gold ensembles hold promise for the sensing of arsenic(III) in water samples where copper(II) may be present. 相似文献
68.
Temporal cleaning of a high-energy fiber-based ultrafast laser using cross-polarized wave generation
Zaouter Y Ramirez LP Papadopoulos DN Hönninger C Hanna M Druon F Mottay E Georges P 《Optics letters》2011,36(10):1830-1832
We report the use of cross-polarized wave generation to perform both pulse shortening and temporal cleaning of a high-energy ytterbium-doped fiber-based femtosecond laser system. The nonlinear processes allow both a highly efficient nonlinear conversion of 20% and a large compression ratio of 3.5, with inherently improved coherent and incoherent contrasts. This results in the generation of 37 μJ, 115 fs pulses at a repetition rate of 100 kHz with high temporal quality. 相似文献
69.
Dimitrios G. Konstantinides Christos E. Kountzakis 《Journal of Theoretical Probability》2017,30(4):1726-1762
This paper relies on the application of Kantorovich functionals on quasi-interior points of the positive cone for certain classes of Orlicz spaces. Particularly we provide the asymptotic calculation of the ruin probability in the renewal risk model under heavy-tailed claims in the Orlicz spaces. This application assures the extension of classical asymptotic theory of regular variation. 相似文献
70.
Callegari A Marcaccio M Paolucci D Paolucci F Tagmatarchis N Tasis D Vázquez E Prato M 《Chemical communications (Cambridge, England)》2003,(20):2576-2577
Amidoferrocenyl-functionalised single wall carbon nanotubes (Fc-SWNT) are efficient exoreceptors for the redox recognition of H2PO4-. 相似文献