| 1. |
- Gao, W. M., et al.
(författare)
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Synthesis, structures and electrochemical properties of amino-derivatives of diiron azadithiolates as active site models of Fe-only hydrogenase
- 2006
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Ingår i: Inorganica Chimica Acta. - : Elsevier BV. - 0020-1693 .- 1873-3255. ; 359:4, s. 1071-1080
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Tidskriftsartikel (refereegranskat)abstract
- The preparation and characterization of two novel amino-incorporated sulfur-bridged dinuclear iron (I) complexes of the type [NR(mu-SCH2)2]Fe-2(CO)(6), one being amino protected [N(CH2CH2NHTs)(mu-SCH2)(2)]Fe-2(CO)(6) (8) and the other [(mu-SCH2)(2)Fe-2(-CO)(6)NCH2CH2N (mu-SCH2)(2)]Fe-2(CO)(6) (9) are described. These two complexes are readily prepared in a S(N)2 manner between double lithium anion and bis(chloromethyl) amine derivatives. The structures of 8 and 9 were characterized by IR, H-1, C-13 NMR, MS and HRMS spectra and further determined by X-ray analyses. Protonation of complex 8 gave the mono N-protonated product, while for 9 the protonation occurred in both of the N atoms. The redox properties were evaluated by cyclic voltammograms. It was shown that these two complexes can catalyze electrochemical reduction of proton to molecular hydrogen.
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| 2. |
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| 3. |
- Li, P., et al.
(författare)
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Influence of tertiary phosphanes on the coordination configurations and electrochemical properties of iron hydrogenase model complexes : Crystal structures of (mu-S2C3H6)Fe-2(CO)(6-n)L-n (L = PMe2Ph, n=1, 2; PPh3 P(OEt)(3), n=1)
- 2005
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; :12, s. 2506-2513
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Tidskriftsartikel (refereegranskat)abstract
- A series of mono- and disubstituted diiron complexes [(mu-pdt)-Fe-2(CO)(5)L] [pdt = 1,3-propanedithiolato; L = PMe3 (2), PMe2Ph (3), PPh3 (4), P(OEt)(3) (5)] and [(mu-pdt)Fe-2(CO)(4)L-2] [L = PMe2Ph (6), PPh3 (7), P(OEt)3 (8)] were prepared as Fe-only hydrogenase-active-site models by controllable CO displacement of [(mu-pdt)Fe-2(CO)(6)] by tertiary phosphanes. The coordination configurations of 3-6 were characterized by X-ray crystallography. Disubstituted diiron complex 6 features an apical/apical coordination mode, instead of the typical transoid basal/basal configuration. The electrochemistry of 2-6 and 8 was studied by cyclic voltammetry to evaluate the effects of different tertiary phosphane ligands on the redox properties of the iron atoms of model complexes.
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| 4. |
- Abrahamsson, M. L. A., et al.
(författare)
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Ruthenium-manganese complexes for artificial photosynthesis : Factors controlling intramolecular electron transfer and excited-state quenching reactions
- 2002
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 41:6, s. 1534-1544
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Tidskriftsartikel (refereegranskat)abstract
- Continuing our work toward a system mimicking the electron-transfer steps from manganese to P-680(+) in photosystem II (PS II), we report a series of ruthenium(II)-manganese(II) complexes that display intramolecular electron transfer from manganese(II) to photooxidized ruthenium(III). The electron-transfer rate constant (k(ET)) values span a large range, 1 X 10(5)-2 x 10(7) s(-1), and we have investigated different factors that are responsible for the variation. The reorganization energies determined experimentally (lambda = 1.5-2.0 eV) are larger than expected for solvent reorganization in complexes of similar size in polar solvents (typically lambda approximate to 1.0 eV). This result indicates that the inner reorganization energy is relatively large and, consequently, that at moderate driving force values manganese complexes are not fast donors. Both the type of manganese ligand and the link between the two metals are shown to be of great importance to the electron-transfer rate. In contrast, we show that the quenching of the excited state of the ruthenium(II) moiety by manganese(II) in this series of complexes mainly depends on the distance between the metals. However, by synthetically modifying the sensitizer so that the lowest metal-to-ligand charge transfer state was localized on the nonbridging ruthenium(II) ligands, we could reduce the quenching rate constant in one complex by a factor of 700 without changing the bridging ligand. Still, the manganese(II)-ruthenium (III) electrontransfer rate constant was not reduced. Consequently, the modification resulted in a complex with very favorable properties.
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| 5. |
- Yang, X. C., et al.
(författare)
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Axial ligand exchange reaction on ruthenium phthalocyanines
- 2005
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Ingår i: Journal of Porphyrins and Phthalocyanines. - 1088-4246 .- 1099-1409. ; 9:4, s. 248-255
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Tidskriftsartikel (refereegranskat)abstract
- Bis(4-methylpyridine)phthalocyaninato ruthenium(II) has been synthesized. It was proved by single-crystal X-ray diffraction that the central Ru(II) atom is bonded to six N atoms in an elongated octahedral configuration, and the axial ligands have a significantly longer Ru-N bond distance, 2.101(4) angstrom, than the independent pyrrol Ru-N bond, 1.99 angstrom. Therefore, the axial ligands can be exchanged by other ligands. The ligand exchange reactions with diethyl pyridyl-4-phosphonate and diethyl pyridylmethyl-4-phosphonate were studied in high boiling-point solvents at elevated temperatures, ca 160 degrees C. Mono-ligand as well as double-ligand replaced complexes were obtained. The complexes have been isolated by column chromatography. These complexes have potential applications, such as in dye sensitized solar cells.
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| 6. |
- Akermark, C, et al.
(författare)
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A prospective randomized controlled trial of plantar versus dorsal incisions for operative treatment of primary Morton's neuroma
- 2013
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Ingår i: Foot & ankle international. - : SAGE Publications. - 1071-1007 .- 1944-7876. ; 34:9, s. 1198-1204
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Tidskriftsartikel (refereegranskat)abstract
- There are a great number of studies on the outcome of surgery for Morton’s neuroma. However, there is a lack of controlled trials to determine the outcome in general and for the 2 most used surgical approaches. This prospective and randomized trial studied the outcome and adverse events of resected primary Morton’s neuromas, comparing plantar and dorsal incisions. Methods: Seventy-six patients were randomized to treatment with either a plantar or a dorsal incision by 2 senior surgeons. Questionnaires were evaluated and physical examinations performed at baseline and at 3 and 12 months postoperatively by the treating surgeon and at a mean of 34 months (range, 28-42 months) by an independent surgeon. The follow-up rate was 93%. Results: Histological examination of specimens verified resection of nerves in all cases except 1, which was in the dorsal group (artery). The main outcome variable, pain at daily activities, was significantly reduced by 96% (plantar) and 97% (dorsal) and restrictions in daily activities were reduced by 77% (plantar) and 67% (dorsal) at the final follow-up. Scar tenderness was noted by 3% (plantar) and 0% (dorsal) at the final evaluation. Clinically good results with surgery were noted in 87% (plantar) and 83% (dorsal) of cases. There were 5 complications in the plantar group and 6 in the dorsal group, with a difference in type of complications. Conclusions: This study demonstrated 87% (plantar) and 83% (dorsal) clinically good outcomes and no significant differences between the procedures in regard to pain, restrictions in daily activities, and scar tenderness. However, there was a difference between the groups in the type of complications. Level of Evidence: Level I, prospective randomized trial.
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| 7. |
- Akermark, C, et al.
(författare)
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Diet and muscle glycogen concentration in relation to physical performance in Swedish elite ice hockey players
- 1996
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Ingår i: International journal of sport nutrition. - : Human Kinetics. - 1050-1606. ; 6:3, s. 272-284
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Tidskriftsartikel (refereegranskat)abstract
- The effects of carbohydrate (CHO) loading on physical characteristics including muscle fiber distribution, muscle glycogen concentration, and physical performance were studied in two top Swedish ice hockey teams. Players were randomly allocated to two groups: those consuming a CHO-enriched diet (CHO group) and those consuming a mixed diet (controls). Biopsies from the vastus lateralis muscle were taken three times: after Game 1, before Game 2, and after Game 2. Muscle fiber distribution averaged 50 ± 2% slow twitch fibers (mean ± 1SEM). Muscle glycogen concentrations (measured in mmol glucose units · kg−1 wet muscle) were as follows: after Game 1, 43 ± 4 (ail players); before Game 2,99 ± 7 (CHO group) and 81 ± 7 (controls); and after Game 2, 46 ± 6 (CHO group) and 44 ± 5 (controls). Distance skated, number of shifts skated, amount of time skated within shifts, and skating speed improved with CHO loading. It was concluded that individual differences in performance could be related to muscle glycogen metabolism.
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| 8. |
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| 9. |
- Berg, K. E., et al.
(författare)
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Covalently linked ruthenium(II)-manganese(II) complexes : Distance dependence of quenching and electron transfer
- 2001
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Ingår i: European Journal of Inorganic Chemistry. - 1434-1948 .- 1099-1948. ; 2001:4, s. 1019-1029
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Tidskriftsartikel (refereegranskat)abstract
- Continuing our development of artificial models for photosystem II in green plants, a series of compounds have been prepared in which a RU(bpy)(3)(2+) photosensitizer is covalently Linked to a manganese(II) electron donor. In addition to a trispicolylamine Ligand, two other manganese Ligands, dipicolylamine and aminodiacetic acid, have been introduced in order to study Ligands that are appropriate for the construction of manganese dimers with open coordination sites for the binding of water. Coordination equilibria of the manganese ions were monitored by EPR. The interactions between the ruthenium and manganese moieties were probed by flash photolysis, cyclic voltammetry and steady-state and time-resolved emission measurements. The quenching of the Ru-II excited state by Mn-II was found to be rapid in complexes with short Ru-Mn distances. Nevertheless, each Run species could be photo-oxidized by bimolecular quenching with methylviologen, and the subsequent electron transfer from Mn-II to Ru-III could be monitored.
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| 10. |
- Borgstrom, M., et al.
(författare)
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Electron donor-acceptor dyads and triads based on tris(bipyridine)ruthenium(II) and benzoquinone : Synthesis, characterization, and photoinduced electron transfer reactions
- 2003
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 42:17, s. 5173-5184
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Tidskriftsartikel (refereegranskat)abstract
- Two electron donor-acceptor triads based on a benzoquinone acceptor linked to a light absorbing [Ru(bpy)(3)](2+) complex have been synthesized. In triad 6 (denoted Ru-II-BQ-Co-III), a [Co(bpy)(3)](3+) complex, a potential secondary acceptor, was linked to the quinone. In the other triad, 8 (denoted PTZ-Ru-II-BQ), a phenothiazine donor was linked to the ruthenium moiety. The corresponding dyads Ru-II-BQ (4) and PTZ-Ru-II (9) were prepared for comparison. Upon light excitation in the visible band of the ruthenium moiety, electron transfer to the quinone occurred with a rate constant k(1) = 5 x 10(9) s(-1) (tau(1) = 200 ps) in all the quinone containing complexes. Recombination to the ground state followed, with a rate constant k(b) similar to 4.5 x 10(8) s(-1) (tau(b) similar to 2.2 ns), for both Ru-II-BQ and Ru-II-BQ-Co-III with no indication of a charge shift to generate the reduced Coll moiety. In the PTZ-Ru-II-BQ triad, however, the initial charge separation was followed by a rapid (k > 5 x 10(9) s(-1)) electron transfer from the phenothiazine moiety to give the fairly long-lived PTZ(.+)-Ru-II-BQ(.-) state (tau = 80 ns) in unusually high yield for a [Ru(bPY)(3)](2+)- based triad (> 90%), that lies at DeltaGdegrees = 1.32 eV relative to the ground state. Unfortunately, this triad turned out to be rather photolabile. Interestingly, coupling between the oxidized PTZ(.+) and the BQ(.-) moieties seemed to occur. This discouraged further extension to incorporate more redox active units. Finally, in the dyad PTZ-Ru-II a reversible, near isoergonic electron transfer was observed on excitation. Thus, a quasiequilibrium was established with an observed time constant of 7 ns, with ca. 82% of the population in the PTZ-Ru-*(II) state and 18% in the PTZ(.+)Ru(II)(bpy(.-)) state. These states decayed in parallel with an observed lifetime of 90 ns. The initial electron transfer to form the PTZ(.+)-Ru-II(bpy(.-)) state was thus faster than what would have been inferred from the Ru-*(II) emission decay (tau = 90 ns). This result suggests that reports for related PTZ-Ru-II and PTZ-Ru-II-acceptor complexes in the literature might need to be reconsidered.
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