| 1. |
- Essalhi, Mohamed, et al.
(författare)
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Polyvinylidene fluoride membrane formation using carbon dioxide as a non-solvent additive for nuclear wastewater decontamination
- 2022
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Ingår i: Chemical Engineering Journal. - : Elsevier. - 1385-8947 .- 1873-3212. ; 446:4
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Tidskriftsartikel (refereegranskat)abstract
- Polyvinylidene fluoride (PVDF) membranes were prepared by phase inversion in the most commonly used solvents for membrane manufacture, with CO2 as a non-solvent additive. The effects of changing the polymer concentration (10, 12.5 and 15% by weight), the type of solvent (NMP, DMAc and DMF) and the coagulation bath with three levels of CO2 concentration on the phase inversion process, as well as the phase diagram, morphology and transport properties of the membranes were studied. The best performing membranes were used to desalinate salt aqueous solutions and decontaminated simulated nuclear wastewater by membrane distillation using two configurations (DCMD and AGMD). All selected membranes showed high rejection with acceptable permeate fluxes reaching an infinite decontamination factor. The proposed approach of this novel idea of using CO2 dissolved in water as a coagulation medium in the field of membranes avoids the increase of the harmful effect on the environment caused by the addition of a harsh non-solvent to the coagulation bath. It constitutes a beneficial use of carbon dioxide that reduces the negative environmental impact of membrane manufacturing and represents a decisive step towards its sustainability. Furthermore, this study highlights the potential benefits of using these membranes in DM for desalination and treatment of simulated nuclear wastewater.
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| 2. |
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| 3. |
- Knighton, Richard C., et al.
(författare)
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Solution, Solid-State, and Computational Analysis of Agostic Interactions in a Coherent Set of Low-Coordinate Rhodium(III) and Iridium(III) Complexes
- 2018
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Ingår i: Chemistry - A European Journal. - : John Wiley & Sons. - 0947-6539 .- 1521-3765. ; 24:19, s. 4927-4938
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Tidskriftsartikel (refereegranskat)abstract
- A homologous family of low‐coordinate complexes of the formulation trans‐[M(2,2′‐biphenyl)(PR3)2][BArF4] (M=Rh, Ir; R=Ph, Cy, iPr, iBu) has been prepared and extensively structurally characterised. Enabled through a comprehensive set of solution phase (VT 1H and 31P NMR spectroscopy) and solid‐state (single crystal X‐ray diffraction) data, and analysis in silico (DFT‐based NBO and QTAIM analysis), the structural features of the constituent agostic interactions have been systematically interrogated. The combined data substantiates the adoption of stronger agostic interactions for the IrIII compared to RhIII complexes and, with respect to the phosphine ligands, in the order PiBu3>PCy3>PiPr3>PPh3. In addition to these structure–property relationships, the effect of crystal packing on the agostic interactions was investigated in the tricyclohexylphosphine complexes. Compression of the associated cations, through inclusion of a more bulky solvent molecule (1,2‐difluorobenzene vs. CH2Cl2) in the lattice or collection of data at very low temperature (25 vs. 150 K), lead to small but statistically significant shortening of the M−H−C distances.
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| 4. |
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| 5. |
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| 6. |
- Ohlin, C. Andre, et al.
(författare)
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The first peroxotitanoniobate cluster - [N(CH3)(4)](10)[Ti12Nb6O38(O-2(I))(6)]
- 2010
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Ingår i: Inorganica Chimica Acta. - : Elsevier BV. - 0020-1693 .- 1873-3255. ; 363:15, s. 4405-4407
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Tidskriftsartikel (refereegranskat)abstract
- The synthesis and structure of the first discrete peroxotitanoniobate cluster, [N(CH3)(4)](10)[Ti12Nb6O38(O-2(I))(6)], is described. (C) 2010 Elsevier B.V. All rights reserved.
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| 7. |
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| 8. |
- Panasci, Adele F., et al.
(författare)
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Cooperation between bound waters and hydroxyls in controlling isotope-exchange rates
- 2012
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Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 78, s. 18-27
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Tidskriftsartikel (refereegranskat)abstract
- Mineral oxides differ from aqueous ions in that the bound water molecules are usually attached to different metal centers, or vicinal, and thus separated from one another. In contrast, for most monomeric ions used to establish kinetic reactivity trends, such as octahedral aquo ions (e.g., Al(H(2)O)(6)(3+)), the bound waters are closely packed, or geminal. Because of this structural difference, the existing literature about ligand substitution in monomer ions may be a poor guide to the reactions of geochemical interest. To understand how coordination of the reactive functional groups might affect the rates of simple water-exchange reactions, we synthesized two structurally similar Rh(III) complexes, [Rh(phen)(2)(H(2)O)(2)](3+) [1] and [Rh(phen)(2)(H(2)O)Cl](2+) [2] where (phen) = 1,10-phenanthroline. Complex [1] has two adjacent, geminal, bound waters in the inner-coordination sphere and [2] has a single bound water adjacent to a bound chloride ion. We employed Rh(III) as a trivalent metal rather than a more geochemically relevant metal like Fe(III) or Al(III) to slow the rate of reaction, which makes possible measurement of the rates of isotopic substitution by simple mass spectrometry. We prepared isotopically pure versions of the molecules, dissolved them into isotopically dissimilar water, and measured the rates of exchange from the extents of (18)O and (16)O exchange at the bound waters. The pH dependency of rates differ enormously between the two complexes. Pseudo-first-order rate coefficients at 298 K for water exchanges from the fully protonated molecules are close: k(0)(298) = 5 x 10(-8) (+/- 0.5 x 10(-8)) s(-1) for [1] and k(0)(298) = 2.5 x 10(-9)(+/- 1 x 10(-9)) for [2]. Enthalpy and entropy activation parameters (Delta H(double dagger) and Delta S(double dagger)) were measured to be 119(+/- 3) kJ mol(-1), and 14(+/- 1) J mol(-1) K(-1), respectively for [1]. The corresponding parameters for the mono-aquo complex, [2], are 132(+/- 3) kJ mol(-1) and 41.5(+/- 2) J mol(-1) K(-1). Rates increase by many orders of magnitude upon deprotonation of one of the bound waters in complex [1] because of the close proximity of a transferable proton that can convert the bound hydroxyl to a bound water. This interconversion allows the oxygen to exchange as a bound water, rather than as a bound hydroxyl, which is slow at near-neutral pH conditions. (C) 2011 Elsevier Ltd. All rights reserved.
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| 9. |
- Pilgrim, C. D., et al.
(författare)
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27Al MQMAS of the δ-Al13-Keggin†
- 2017
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Ingår i: Dalton Transactions. - 1477-9226 .- 1477-9234. ; 46:7, s. 2249-2254
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Tidskriftsartikel (refereegranskat)abstract
- One-dimensional 27Al, 23Na Magic-Angle-Spinning (MAS) NMR and 27Al Multiple-Quantum Magic-Angle-Spinning NMR (MQMAS) measurements are reported for the [small delta]-isomer of the Al13 Keggin structure at high spinning speed and 14.1 T field. Values for the CQ and [small eta] parameters are on the same scale as those seen in other isomers of the Al13 structure. Density functional theory (DFT) calculations are performed for comparison to the experimental fits using the B3PW91/6-31+G* and PBE0/6-31+G* levels of theory, with the Polarizable Continuum Model (PCM).
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| 10. |
- Son, Jung-Ho, et al.
(författare)
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Synthesis and Characterization of a Soluble Vanadium-Containing Keggin Polyoxoniobate by ESI-MS and 51V NMR : (TMA)9[V3Nb12O42]center dot 18H2O
- 2013
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; :10-11, SI, s. 1748-1753
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Tidskriftsartikel (refereegranskat)abstract
- The vanadium-containing heteropolyoxoniobate (TMA)9[V3Nb12O42]center dot 18H2O was synthesised by hydrothermal reaction of V2O5 and hydrous niobium oxide in tetramethylammonium hydroxide solution. The cluster has an -Keggin structure with a central VO4 and two trans-bicapped VO5. The water-soluble product was characterised by X-ray crystallography, ESI-MS and both liquid- and solid-state 51V NMR spectroscopy. The solid- and solution-phase 51V NMR spectra indicate two major peaks corresponding to one VO4 and two VO5 sites.
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| 11. |
- Acharya, Shravan, et al.
(författare)
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Rates of water exchange in 2,2'-bipyridine and 1,10-phenanthroline complexes of CoII and MnII
- 2017
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Ingår i: Australian journal of chemistry (Print). - 0004-9425 .- 1445-0038. ; 70:6, s. 751-754
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Tidskriftsartikel (refereegranskat)abstract
- The rates and activation parameters of water exchange at pH 3.0 have been determined using variable temperature 17O NMR spectroscopy for four CoII complexes and one MnII complex: [Co(bpy)(H2O)4]2+, [Co(bpy)2 (H2O)2]2+, [Co(phen)-(H2O)4]2+, [Co(phen)2 (H2O)2]2+, and [Mn(bpy)(H2O)4]2+ (bpy = 2,2′-bipyridyl and phen = 1,10-phenanthroline). Substitution of aquo ligands with 1,10-phenanthroline or 2,2′-bipyridyl leads to an increase in the rate of exchange in the manganese complexes, from k298 (1.8 ± 0.1) × 107 s-1 for [Mn(H2O)6]2+ to (7.2 ± 0.3) × 107 s-1 for [Mn(phen)2 (H2O)2]2+, whereas the trends are more complex for the cobalt complexes. We have used the new data in conjunction with literature data for similar complexes to analyse the effect of M–OH2 distance and degree of substitution.
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| 12. |
- Acharya, Shravan S., et al.
(författare)
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Diverse composites of metal-complexes and PEDOT facilitated by metal-free vapour phase polymerization
- 2017
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Ingår i: Reactive & functional polymers. - : Elsevier. - 1381-5148 .- 1873-166X. ; 116, s. 101-106
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Tidskriftsartikel (refereegranskat)abstract
- Abstract Oxidative polymerization for the manufacture of conducting polymers such as poly(3,4-ethylenedioxy-thiophene) has traditionally employed iron(III) salts. Demonstrated in this study is vapour phase polymerization of 3,4-ethylenedio- xythiophene using a metal-free oxidant, ammonium persulfate, leading to films with an estimated conductivity of 75 S/cm. Additionally, a route for embedding active transition metal complexes into these poly(3,4-ethylenedioxythiophene)/-poly(styrene-4-sulfonate) (PEDOT/PSS) films via vapour assisted complexation is outlined. Here, the vapour pressure of solid ligands around their melting temperatures was exploited to ensure complexation to metal ions added into the oxidant mixture prior to polymerization of PEDOT. Four composite systems are discussed, viz. PEDOT/PSS embedded with tris(8-hydroxyquinolinato)cobalt(III), tris(2,2-bipyridine)cobalt(II), tris(1,10- phenanthroline)cobalt(II) and tris(8-hyd-roxyquinolinato)aluminium(III). Using these composites, electrochemical reduction of nitrite to ammonia with a faradaic efficiency of 61% was reported.
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| 13. |
- Andrew, Rhiann E., et al.
(författare)
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Coordination Induced Atropisomerism in an NHC-Based Rhodium Macrocycle
- 2015
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Ingår i: Organometallics. - : American Chemical Society (ACS). - 0276-7333 .- 1520-6041. ; 34:5, s. 913-917
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Tidskriftsartikel (refereegranskat)abstract
- Reversible interaction with carbon monoxide results in the onset of dynamic atropisomerism at 298 K in an otherwise static NHC-based rhodium pincer complex, [Rh(C boolean AND N boolean AND C-(CH2)(12))(CO)][BArF4] (1, ArF = 3,5-C6H3(CF3)(2)). The mechanism of this process has been comprehensively interrogated by a combination of variable-temperature NMR spectroscopy, IR spectroscopy, and computational modeling. In addition, a structural analogue of a high-energy symmetrical intermediate species-invoked in the process but not directly observed spectroscopically-has been prepared and characterized in solution and the solid-state.
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| 14. |
- Aureliano, Manuel, et al.
(författare)
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Characterization of decavanadate and decaniobate solutions by Raman spectroscopy
- 2016
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Ingår i: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; 45:17, s. 7391-7399
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Tidskriftsartikel (refereegranskat)abstract
- The decaniobate ion, (Nb-10 = [Nb10O28](6-)) being isoelectronic and isostructural with the decavanadate ion (V-10 = [V10O28](6-)), but chemically and electrochemically more inert, has been useful in advancing the understanding of V-10 toxicology and pharmacological activities. In the present study, the solution chemistry of Nb-10 and V-10 between pH 4 and 12 is studied by Raman spectroscopy. The Raman spectra of V-10 show that this vanadate species dominates up to pH 6.45 whereas it remains detectable until pH 8.59, which is an important range for biochemistry. Similarly, Nb-10 is present between pH 5.49 and 9.90 and this species remains detectable in solution up to pH 10.80. V-10 dissociates at most pH values into smaller tetrahedral vanadate oligomers such as V-1 and V-2, whereas Nb-10 dissociates into Nb-6 under mildly (10 > pH > 7.6) or highly alkaline conditions. Solutions of V-10 and Nb-10 are both kinetically stable under basic pH conditions for at least two weeks and at moderate temperature. The Raman method provides a means of establishing speciation in the difficult niobate system and these findings have important consequences for toxicology activities and pharmacological applications of vanadate and niobate polyoxometalates.
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| 15. |
- Aureliano, M., et al.
(författare)
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Decavanadate in vitro and in vivo effects : facts and opinions
- 2014
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Ingår i: Journal of Inorganic Biochemistry. - : Elsevier BV. - 0162-0134 .- 1873-3344. ; 137, s. 123-130
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Tidskriftsartikel (refereegranskat)abstract
- This review covers recent advances in the understanding of the in vitro and in vivo effects of decavanadate, (V10O28)(6-), particularly in mitochondria. In vivo toxicological studies involving vanadium rarely account for the fact that under physiological conditions some vanadium may be present in the form of the decavanadate ion, which may behave differently from ortho- and metavanadates. It has for example been demonstrated that vanadium levels in heart or liver mitochondria are increased upon decavanadate exposure. Additionally, in vitro studies have shown that mitochondrial depolarization (IC50, 40 nM) and oxygen consumption (IC50, 99 nM) are strongly affected by decavanadate, which causes reduction of cytochrome b (complex III). We review these recent findings which together suggest that the observed cellular targets, metabolic pathway and toxicological effects differ according to the species of vanadium present. Finally, the toxicological effects of decavanadate depend on several factors such as the mode of administration, exposure time and type of tissue. (C) 2014 Elsevier Inc. All rights reserved.
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| 16. |
- Aureliano, Manuel, et al.
(författare)
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Ion pumps as biological targets for decavanadate
- 2013
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Ingår i: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; 42:33, s. 11770-11777
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Tidskriftsartikel (refereegranskat)abstract
- The putative applications of poly-, oligo-and mono-oxometalates in biochemistry, biology, pharmacology and medicine are rapidly attracting interest. In particular, these compounds may act as potent ion pump inhibitors and have the potential to play a role in the treatment of e. g. ulcers, cancer and ischemic heart disease. However, the mechanism of action is not completely understood in most cases, and even remains largely unknown in other cases. In the present review we discuss the most recent insights into the interaction between mono-and polyoxometalate ions with ion pumps, with particular focus on the interaction of decavanadate with Ca2+-ATPase. We also compare the proposed mode of action with those of established ion pump inhibitors which are currently in therapeutic use. Of the 18 classes of compounds which are known to act as ion pump inhibitors, the complete mechanism of inhibition is only known for a handful. It has, however, been established that most ion pump inhibitors bind mainly to the E2 ion pump conformation within the membrane domain from the extracellular side and block the cation release. Polyoxometalates such as decavanadate, in contrast, interact with Ca2+-ATPase near the nucleotide binding site domain or at a pocket involving several cytoplasmic domains, and therefore need to cross through the membrane bilayer. In contrast to monomeric vanadate, which only binds to the E2 conformation, decavanadate binds to all protein conformations, i.e. E1, E1P, E2 and E2P. Moreover, the specific interaction of decavanadate with sarcoplasmic reticulum Ca2+-ATPase has been shown to be non-competitive with respect to ATP and induces protein cysteine oxidation with concomitant vanadium reduction which might explain the high inhibitory capacity of V-10 (IC50 = 15 mu M) which is quite similar to the majority of the established therapeutic drugs.
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| 17. |
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| 18. |
- Chaudhary, Himanshu, et al.
(författare)
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Polyoxometalates as Effective Nano-inhibitors of Amyloid Aggregation of Pro-inflammatory S100A9 Protein Involved in Neurodegenerative Diseases
- 2021
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 13:23, s. 26721-26734
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Tidskriftsartikel (refereegranskat)abstract
- Pro-inflammatory and amyloidogenic S100A9 protein is central to the amyloid-neuroinflammatory cascade in neurodegenerative diseases. Polyoxometalates (POMs) constitute a diverse group of nanomaterials, which showed potency in amyloid inhibition. Here, we have demonstrated that two selected nanosized niobium POMs, Nb10 and TiNb9, can act as potent inhibitors of S100A9 amyloid assembly. Kinetics analysis based on ThT fluorescence experiments showed that addition of either Nb10 or TiNb9 reduces the S100A9 amyloid formation rate and amyloid quantity. Atomic force microscopy imaging demonstrated the complete absence of long S100A9 amyloid fibrils at increasing concentrations of either POM and the presence of only round-shaped and slightly elongated aggregates. Molecular dynamics simulation revealed that both Nb10 and TiNb9 bind to native S100A9 homo-dimer by forming ionic interactions with the positively charged Lys residue-rich patches on the protein surface. The acrylamide quenching of intrinsic fluorescence showed that POM binding does not perturb the Trp 88 environment. The far and near UV circular dichroism revealed no large-scale perturbation of S100A9 secondary and tertiary structures upon POM binding. These indicate that POM binding involves only local conformational changes in the binding sites. By using intrinsic and 8-anilino-1-naphthalene sulfonate fluorescence titration experiments, we found that POMs bind to S100A9 with a Kd of ca. 2.5 μM. We suggest that the region, including Lys 50 to Lys 54 and characterized by high amyloid propensity, could be the key sequences involved in S1009 amyloid self-assembly. The inhibition and complete hindering of S100A9 amyloid pathways may be used in the therapeutic applications targeting the amyloid-neuroinflammatory cascade in neurodegenerative diseases.
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| 19. |
- Colla, Christopher A., et al.
(författare)
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Computational prediction of Mg-isotope fractionation between aqueous [Mg(OH2)6]2+ and brucite
- 2018
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Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier. - 0016-7037 .- 1872-9533. ; 227, s. 64-74
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Tidskriftsartikel (refereegranskat)abstract
- The fractionation factor in the magnesium-isotope fractionation between aqueous solutions of magnesium and brucite changes sign with increasing temperature, as uncovered by recent experiments. To understand this behavior, the Reduced Partition Function Ratios and isotopic fractionation factors (Δ26/24Mgbrucite-Mg(aq)) are calculated using molecular models of aqueous [Mg(OH2)6]2+ and the mineral brucite at increasing levels of density functional theory. The calculations were carried out on the [Mg(OH2)6]2+·12H2O cluster, along with different Pauling-bond-strength-conserving models of the mineral lattice of brucite. Three conclusions were reached: (i) all levels of theory overestimate 〈Mg‒O〉 bond distances in the aqua ion complex relative to Tutton’s salts; (ii) the calculations predict that brucite at 298.15 K is always enriched in the heavy isotope, in contrast with experimental observations; (iii) the temperature dependencies of Wimpenny et al. (2014) and Li et al. (2014) could only be achieved by fixing the 〈Mg‒O〉 bond distances in the [Mg(OH2)6]2+·12H2O cluster to values close to those observed in crystals that trap the hydrated ion.
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| 20. |
- Fraqueza, Gil, et al.
(författare)
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Decavanadate, decaniobate, tungstate and molybdate interactions with sarcoplasmic reticulum Ca2+-ATPase : quercetin prevents cysteine oxidation by vanadate but does not reverse ATPase inhibition
- 2012
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Ingår i: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; 41:41, s. 12749-12758
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Tidskriftsartikel (refereegranskat)abstract
- Recently we demonstrated that the decavanadate (V-10) ion is a stronger Ca2+-ATPase inhibitor than other oxometalates, such as the isoelectronic and isostructural decaniobate ion, and the tungstate and molybdate monomer ions, and that it binds to this protein with a 1 : 1 stoichiometry. The V-10 interaction is not affected by any of the protein conformations that occur during the process of calcium translocation (i.e. E1, E1P, E2 and E2P) (Fraqueza et al., J. Inorg. Biochem., 2012). In the present study, we further explore this subject, and we can now show that the decaniobate ion, [Nb-10 = Nb10O28](6-), is a useful tool in deducing the interaction and the non-competitive Ca2+-ATPase inhibition by the decavanadate ion [V-10 = V10O28](6-). Moreover, decavanadate and vanadate induce protein cysteine oxidation whereas no effects were detected for the decaniobate, tungstate or molybdate ions. The presence of the antioxidant quercetin prevents cysteine oxidation, but not ATPase inhibition, by vanadate or decavanadate. Definitive V(IV) EPR spectra were observed for decavanadate in the presence of sarcoplasmic reticulum Ca2+-ATPase, indicating a vanadate reduction at some stage of the protein interaction. Raman spectroscopy clearly shows that the protein conformation changes that are induced by V-10, Nb-10 and vanadate are different from the ones induced by molybdate and tungstate monomer ions. Here, Mo and W cause changes similar to those by phosphate, yielding changes similar to the E1P protein conformation. The putative reduction of vanadium(V) to vanadium(IV) and the non-competitive binding of the V-10 and Nb-10 decametalates may explain the differences in the Raman spectra compared to those seen in the presence of molybdate or tungstate. Putting it all together, we suggest that the ability of V-10 to inhibit the Ca2+-ATPase may be at least in part due to the process of vanadate reduction and associated protein cysteine oxidation. These results contribute to the understanding and application of these families of mono-and polyoxometalates as effective modulators of many biological processes, particularly those associated with calcium homeostasis.
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| 21. |
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| 22. |
- Fraqueza, Gil, et al.
(författare)
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Sarcoplasmic reticulum calcium ATPase interactions with decaniobate, decavanadate, vanadate, tungstate and molybdate
- 2012
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Ingår i: Journal of Inorganic Biochemistry. - : Elsevier BV. - 0162-0134 .- 1873-3344. ; 107:1, s. 82-89
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Tidskriftsartikel (refereegranskat)abstract
- Over the last few decades there has been increasing interest in oxometalate and polyoxometalate applications to medicine and pharmacology. This interest arose, at least in part, due to the properties of these classes of compounds as anti-cancer, anti-diabetic agents, and also for treatment of neurodegenerative diseases, among others. However, our understanding of the mechanism of action would be improved if biological models could be used to clarify potential toxicological effects in main cellular processes. Sarcoplasmic reticulum (SR) vesicles, containing a large amount of Ca(2+)-ATPase, an enzyme that accumulates calcium by active transport using ATP, have been suggested as a useful model to study the effects of oxometalates on calcium homeostasis. In the present article, it is shown that decavanadate, decaniobate, vanadate, tungstate and molybdate, all inhibited SR Ca(2+)-ATPase, with the following IC(50) values: 15, 35, 50, 400 mu M and 45 mM, respectively. Decaniobate (Nb(10)), is the strongest P-type enzyme inhibitor, after decavanadate (V(10)). Atomic-absorption spectroscopy (AAS) analysis, indicates that decavanadate binds to the protein with a 1:1 decavanadate:Ca(2+)-ATPase stoichiometry. Furthermore, V10 binds with similar extension to all the protein conformations, which occur during calcium translocation by active transport, namely El, El P, E2 and E2P, as analysed by MS. In contrast, it was confirmed that the binding of monomeric vanadate (H(2)VO(4)(2-):V(1)) to the calcium pump is favoured only for the E2 and E2P conformations of the ATPase, whereas no significant amount of vanadate is bound to the E1 and E1P conformations. Scatchard plot analysis, confirmed a 1:1 ratio for decavanadate-Ca(2+)-ATPase, with a dissociation constant, k(d) of 1 mu M(-1). The interaction of decavanadate V(10)O(28)(6-) (V(10)) with Ca(2+)-ATPase is prevented by the isostructural and isoelectronic decaniobate Nb(10)O(28)(6-) (Nb(10)), whereas no significant effects were detected with ATP or with heparin, a known competitive ATP binding molecule, suggesting that V(10) binds non-competitively, with respect to ATP, to the protein. Finally, it was shown that decaniobate inhibits SR Ca(2+)-ATPase activity in a non competitive type of inhibition, with respect to ATP. Taken together, these data demonstrate that decameric niobate and vanadate species are stronger inhibitors of the SR calcium ATPase than simple monomeric vanadate, tungstate and molybdate oxometalates, thus affecting calcium homeostasis, cell signalling and cell bioenergetics, as well many other cellular processes. The ability of these oxometalates to act either as phosphate analogues, as a transition-state analogue in enzyme-catalysed phosphoryl group transfer processes and as potentially nucleotide-dependent enzymes modulators or inhibitors, suggests that different oxometalates may reveal different mechanistic preferences in these classes of enzymes. (C) 2011 Elsevier Inc. All rights reserved.
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| 23. |
- Furer, Sebastian O., et al.
(författare)
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The Performance-Determining Role of Lewis Bases in Dye-Sensitized Solar Cells Employing Copper-Bisphenanthroline Redox Mediators
- 2020
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Ingår i: Advanced Energy Materials. - : Wiley-VCH Verlagsgesellschaft. - 1614-6832 .- 1614-6840. ; 10:37
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Tidskriftsartikel (refereegranskat)abstract
- Copper redox mediators have enabled open-circuit voltages (V-OC) of over 1.0 V in dye-sensitized solar cells (DSCs) and have helped to establish DSCs as the most promising solar cell technology in low-light conditions. The addition of additives such as 4-tert-butylpyridine (tBP) to these electrolytes has helped in achieving high solar cell performances. However, emerging evidence suggests that tBP coordinates to the Cu(II) species and limits the performance of these electrolytes. To date, the implications of this coordination are poorly understood. Here, the importance of Lewis base additives for the successful implementation of copper complexes as redox mediators in DSCs is demonstrated. Two redox couples, [Cu(dmp)(2)](+/2+)and [Cu(dpp)(2)](+/2+)(with dmp = 2,9-dimethyl-1,10-phenanthroline and dpp = 2,9-diphenyl-1,10-phenanthroline) in combination with three different Lewis bases, TFMP (4-(trifluoromethyl)pyridine), tBP, and NMBI (1-methyl-benzimidazole), are considered. Through single-crystal X-ray diffraction analysis, absorption, and(1)H-NMR spectroscopies, the coordination of Lewis bases to the Cu(II) centers are studied. This coordination efficiently suppresses recombination losses and is crucial for high performing solar cells. If, however, the coordination involves a ligand exchange, as is the case for [Cu(dpp)(2)](+/2+), the redox mediator regeneration at the counter electrode is significantly retarded and the solar cells show current limitations.
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| 24. |
- Gumerova, Nadiia I., et al.
(författare)
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Direct Single- and Double-Side Triol-Functionalization of the Mixed Type Anderson Polyoxotungstate [Cr(OH)3W6O21]6–
- 2019
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 58, s. 106-113
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Tidskriftsartikel (refereegranskat)abstract
- Since the first successful triol-functionalization of the Anderson polyoxometalates, the six protons of their central octahedron X(OH)6 (X—heteroatom, p- or d-element) have been considered as a prerequisite for their functionalization with tripodal alcohols, and therefore, the functionalization of Anderson structures from the unprotonated sides have never been reported. Here, we describe the triol-functionalization of [Cr(OH)3W6O21]6– leading to the single-side grafted anions [Cr(OCH2)3CRW6O21]6– (CrW6-tris-R, R = −C2H5, −NH2, −CH2OH) and the unprecedented double-side functionalized anion [Cr((OCH2)3CC2H5)2W6O18]3– (CrW6-(tris-C2H5)2), despite the lack of protons in the parent anion in the solid state. CrW6-(tris-C2H5)2 demonstrates the first example of double-side functionalized Anderson POT with the partially one-side protonated corresponding parent anion. The new heteropolytungstates were characterized by single-crystal X-ray diffraction, elemental analysis, Fourier-transform infrared spectroscopy, thermal gravimetric analysis, cyclic voltammetry, and electrospray ionization mass spectrometry. Density functional theory calculations were performed to investigate and compare the stability among the different isomers of the parent anion [Cr(OH)3W6O21]6–.
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| 25. |
- Gumerova, Nadiia I., et al.
(författare)
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The Smallest Polyoxotungstate Retained by TRIS-Stabilization
- 2021
-
Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 60:17, s. 12671-12675
-
Tidskriftsartikel (refereegranskat)abstract
- A polycondensation reaction of the orthotungstate anion WO42–, buffered at pH 7.5 in a TRIS-HCl (0.15 M) solution, results in the first example of a discrete polyoxotungstate anion, with just two W ions stabilized with TRIS ligands. It was isolated and characterized as Na2[WVI2O6(C4O3NH10)2]·6H2O by single-crystal and powder X-ray diffraction, FT-IR spectroscopy, thermogravimetrical analysis (TGA), and elemental analysis in solid state and by electro-spray ionization mass spectrometry (ESI-MS), 13C, and 183W NMR, as well as Raman spectroscopy in solution. This synthesis demonstrates the crucial and new role of the added tris-alkoxy ligand in the development of a new hybrid TRIS-isopolytungstate with the lowest known nuclearity (so far) and the terminal oxygens substituted with two nitrogen atoms arising from amines of the TRIS ligands.
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| 26. |
- Harley, Steven J., et al.
(författare)
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Geochemical kinetics via the Swift-Connick equations and solution NMR
- 2011
-
Ingår i: Geochimica et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 75:13, s. 3711-3725
-
Tidskriftsartikel (refereegranskat)abstract
- Signal analysis in Nuclear Magnetic Resonance spectroscopy is among the most powerful methods to quantify reaction rates in aqueous solutions. To this end, the Swift-Connick approximations to the Bloch-McConnell equations have been used extensively to estimate rate parameters for elementary reactions. The method is primarily used for O-17 NMR in aqueous solutions, but the list of geochemically relevant nuclei that can be used is long, and includes Si-29, Al-27, F-19, C-13 and many others of particular interest to geochemists. Here we review the derivation of both the Swift-Connick and Bloch-McConnell equations and emphasize assumptions and quirks. For example, the equations were derived for CW-NMR, but are used with modern pulse FT-NMR and can be applied to systems that have exchange rates that are shorter than the lifetime of a typical pulse. The method requires a dilute solution where the minor reacting species contributes a negligible amount of total magnetization. We evaluate the sensitivity of results to this dilute-solution requirement and also highlight the need for chemically well-defined systems if reliable data are to be obtained. The limitations in using longitudinal relaxation to estimate reaction rate parameters are discussed. Finally, we provide examples of the application of the method, including ligand exchanges from aqua ions and hydrolysis complexes, that emphasize its flexibility. Once the basic requirements of the Swift-Connick method are met, it allows geochemists to establish rates of elementary reactions. Reactions at this scale lend themselves well to methods of computational simulation and could provide key tests of accuracy. (C) 2011 Elsevier Ltd. All rights reserved.
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| 27. |
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| 28. |
- Hawley, Andrew L., et al.
(författare)
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Heavier Group 13 Metal(I) Heterocycles Stabilized by Sterically Demanding Diiminophosphinates : a Structurally Characterized Monomer–Dimer Pair For Gallium
- 2017
-
Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 23:2, s. 447-455
-
Tidskriftsartikel (refereegranskat)abstract
- We have synthesized and characterized the monomeric diiminophosphinate-stabilized Group 13 metal(I) complexes [DipLE:], DipL=Ph2P(NDip)2, Dip=2,6-iPr2C6H3; E=Ga (1), In (2) and Tl (3). In addition, we structurally characterized the dimeric complex [(DipLGa)2], 12. Similar synthetic attempts using MesL=Ph2P(NMes)2, Mes=2,4,6-Me3C6H2 afforded product mixtures from which the mixed oxidation state species [(MesL)3Ga4I3] 4 was isolated. [DipLGa:] 1 is converted with dry air to the gallium(III) oxide species [(DipLGaO)2] 5. Density Functional Theory studies on [DipLE:] and [(DipLE)2], E=Al−Tl, shed light on the bonding in these compounds and show that the newly formed E−E bonding interactions can be described as weak single σ-bond with no significant π-bonding contribution for E=Al, Ga. A large contribution to the dimer binding enthalpies results from London dispersion forces.
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| 29. |
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| 30. |
- Johnson, Rene L., et al.
(författare)
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O-17 NMR and Computational Study of a Tetrasiliconiobate Ion, [H2+xSi4Nb16O56]((14-x)-)
- 2011
-
Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 17:34, s. 9359-9367
-
Tidskriftsartikel (refereegranskat)abstract
- Rates of oxygen-isotope exchange were measured in the tetrasiliconiobate ion [H2+xSi4Nb16O56]((14-x)-) to better understand how large oxide ions interact with water. The molecule has 19 nonequivalent oxygen sites and is sufficiently complex to evaluate hypotheses derived from our previous work on smaller clusters. We want to examine the extent to which individual oxygen atoms react independently with particular attention given to the order of protonation of the various oxygen sites as the pH decreases from 13 to 6. As in our previous work, we find that the set of oxygen sites reacts at rates that vary over approximately 104 across the molecule at 6 < pH < 13 but with similar pH dependencies. There is NMR evidence of an intra-or intermolecular reaction at pH similar to 7, where new peaks began to slowly form without losing the O-17 isotopic tag, and at pH <= 6 these new peaks formed rapidly. The oxygen atoms bonded to silicon atoms began to isotopically exchange at pH 9 and below. The 17O NMR peak positions also vary considerably with pH for some, but not all, nonequivalent oxygen sites. This variation could be only partly accounted by electronic calculations, which indicate that oxygen atoms should shift similarly upon protonation. Instead, we see that some sites change enormously with pH, whereas other, similarly coordinated oxygen atoms are less affected, suggesting that either some protons are exchanging so rapidly that the oxygen sites are seeing an averaged charge, or that counterions are modulating the effect of the coordinated protons.
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| 31. |
- Lawrence, Samuel R., et al.
(författare)
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Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium
- 2019
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Ingår i: Chemical Science. - : Royal Society of Chemistry. - 2041-6520 .- 2041-6539. ; 10:46, s. 10755-10764
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Tidskriftsartikel (refereegranskat)abstract
- The reaction of the magnesium(i) complexes [{((Ar)nacnac)Mg}(2)], ((Ar)nacnac = HC(MeCNAr)(2), Ar = Dip (2,6-iPr(2)C(6)H(3)), Dep (2,6-Et2C6H3), Mes (2,4,6-Me3C6H2), Xyl (2,6-Me2C6H3)) with fullerene C-60 afforded a series of hydrocarbon-soluble fulleride complexes [{((Ar)nacnac)Mg}(n)C-60], predominantly with n = 6, 4 and 2. C-13{H-1} NMR spectroscopic studies show both similarities (n = 6) and differences (n = 4, 2) to previously characterised examples of fulleride complexes and materials with electropositive metal ions. The molecular structures of [{((Ar)nacnac)Mg}(n)C-60] with n = 6, 4 and 2 can be described as inverse coordination complexes of n [((Ar)nacnac)Mg](+) ions with C-60(n-) anions showing predominantly ionic metal-ligand interactions, and include the first well-defined and soluble complexes of the C-60(6-) ion. Experimental studies show the flexible ionic nature of the {((Ar)nacnac)Mg}+MIDLINE HORIZONTAL ELLIPSISC606- coordination bonds. DFT calculations on the model complex [{((Me)nacnac)Mg}(6)C-60] ((Me)nacnac = HC(MeCNMe)(2)) support the formulation as an ionic complex with a central C-60(6-) anion and comparable frontier orbitals to C-60(6-) with a small HOMO-LUMO gap. The reduction of C-60 to its hexaanion gives an indication about the reducing strength of dimagnesium(i) complexes.
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| 32. |
- Li, Xin, et al.
(författare)
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Re-writable multi-domain liquid crystal alignment layers through laser-induced micropatterning
- 2006
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Ingår i: Japanese Journal of Applied Physics. - 0021-4922 .- 1347-4065. ; 45:20-23, s. L591-L594
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Tidskriftsartikel (refereegranskat)abstract
- We report a method for the preparation of multi-domain liquid crystal (LC) alignment layers on polyimide surfaces with laser-induced periodic surface structures. Atomic force microscopy confirmed that the laser-induced microstructures could be easily erased and re-constructed by repeated laser exposure. The microstructures demonstrated excellent abilities to align LCs in a multi-domain way. The intricate micropatterning of LCs with high resolution was obtained. The opto-electric properties of the LC cells were also determined. In addition, the method is available to a wide range of polymeric substrates, including flexible ones such as poly(ethylene terephthalate).
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| 33. |
- Liu, Yu Ping, et al.
(författare)
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Lindqvist Polyoxoniobate Ion-Assisted Electrodeposition of Cobalt and Nickel Water Oxidation Catalysts
- 2015
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 7:30, s. 16632-16644
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Tidskriftsartikel (refereegranskat)abstract
- A method has been developed for the efficient electrodeposition of cobalt and nickel nanostructures with the assistance of the Lindqvist ion [Nb6O19](8). Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma optical emission spectrometry, and a range of electrochemical techniques have been used to characterize the morphology, composition, catalytic water oxidation activity and stability of the films in alkaline solution. SEM images show that films consisting of nanoparticles with diameters of ca. 30 to 40 nm are formed after 40-50 potential cycles of deposition. Nb and Co/Ni are detected in the films by EDX. ICP-MS results show an elemental ratio of 1:1 for Co:Nb and 1:3 for Ni:Nb, respectively. Raman spectra reveal the presence of both [Nb6O19](8) and Co(OH)(2)/Ni(OH)(2). The films exhibit excellent stability and efficiency for electrocatalytic water oxidation in alkaline solution. Turnover frequencies of 12.9 and 13.2 s(-1) were determined by rotating ring disk electrode voltammetry at an overpotential of 480 mV for Co and Ni films, respectively. Fourier transformed large amplitude alternating current (FTAC) voltammetry reveals an additional underlying oxidation process for Co under catalytic turnover conditions, which indicates that a Co-IV species is involved in the efficient catalytic water oxidation reactions. FTAC voltammetric data also suggest that the Ni films undergoes a clear phase transformation upon aging in aqueous 1 M NaOH and the electrogenerated higher oxidation state Ni from beta-NiOOH is the more active form of the catalyst.
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| 34. |
- Lyons, Trevor, et al.
(författare)
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Molecular parameters promoting high relaxivity in cluster–nanocarrier magnetic resonance imaging contrast agents
- 2022
-
Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 14:44, s. 49521-49531
-
Tidskriftsartikel (refereegranskat)abstract
- We have investigated the mechanism of relaxivity for two magnetic resonance imaging contrast agents that both employ a cluster-nanocarrier design. The first system termed Mn8Fe4-coPS comprises the cluster Mn8Fe4O12(L)16(H2O)4 or Mn8Fe4(1) (L = carboxylate) co-polymerized with polystyrene to form ∼75 nm nanobeads. The second system termed Mn3Bpy-PAm used the cluster Mn3(O2CCH3)6(Bpy)2 or Mn3Bpy (2) where Bpy = 2,2′-bipyridine, entrapped in ∼180 nm polyacrylamide nanobeads. Here, we investigate the rate of water exchange of the two clusters, and corresponding cluster-nanocarriers, in order to elucidate the mechanism of relaxivity in the cluster-nanocarrier. Swift-Connick analysis of O-17 NMR was used to determine the water exchange rates of the clusters and cluster-nanocarriers. We found distinct differences in the water exchange rate between Mn8Fe4and Mn8Fe4-coPS, and we utilized these differences to elucidate the nanobead structure. Using the transverse relaxivity from O-17 NMR line widths, we were able to determine the hydration state of the Mn3Bpy (2) cluster as well as Mn3Bpy-PAm. Using these hydration states in the Swift-Connick analysis of O-17 NMR, we found the water exchange rate to be extremely close in value for the cluster Mn3Bpy and cluster-nanocarrier Mn3Bpy-PAm.
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| 35. |
- McAlpin, J. Gregory, et al.
(författare)
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Electronic Structure Description of a [Co(III)(3)Co(IV)O-4] Cluster : A Model for the Paramagnetic Intermediate in Cobalt-Catalyzed Water Oxidation
- 2011
-
Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 133:39, s. 15444-15452
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Tidskriftsartikel (refereegranskat)abstract
- Multifrequency electron paramagnetic resonace (EPR) spectroscopy and electronic structure calculations were performed on [Co4O4(C5H5N)(4)(CH3CO2)(4)](+) (1(+)), a cobalt tetramer with total electron spin S = 1/2 and formal cobalt oxidation states III, III, III, and IV. The cuboidal arrangement of its cobalt and oxygen atoms is similar to that of proposed structures for the molecular cobaltate clusters of the cobalt-phosphate (Co-Pi) water-oxidizing catalyst. The Davies electron-nuclear double resonance (ENDOR) spectrum is well-modeled using a single class of hyperfine-coupled Co-59 nuclei with a modestly strong interaction (principal elements of the hyperfine tensor are equal to [-20(+/- 2), 77(+/- 1), -5(+/- 15)] MHz). Mims H-1 ENDOR spectra of 1(+) with selectively deuterated pyridine ligands confirm that the amount of unpaired spin on the cobalt-bonding partner is significantly reduced from unity. Multifrequency N-14 ESEEM spectra (acquired at 9.5 and 34.0 GHz) indicate that four nearly equivalent nitrogen nuclei are coupled to the electron spin. Cumulatively, our EPR spectroscopic findings indicate that the unpaired spin is delocalized almost equally across the eight core atoms, a finding corroborated by results from DFT calculations. Each octahedrally coordinated cobalt ion is forced into a low-spin electron configuration by the anionic oxo and carboxylato ligands, and a fractional electron hole is localized on each metal center in a Co 3d(xz,yz)-based molecular orbital for this essentially [Co4+3.125O4] system. Comparing the EPR spectrum of 1(+) with that of the catalyst film allows us to draw conclusions about the electronic structure of this water-oxidation catalyst.
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| 36. |
- Ng, Chun Hin, et al.
(författare)
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Characterisation of a series of triarylmethane dyes as light harvesters for photo-electrochemical systems
- 2015
-
Ingår i: Dyes and pigments. - : Elsevier BV. - 0143-7208 .- 1873-3743. ; 115, s. 96-101
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Tidskriftsartikel (refereegranskat)abstract
- A series of commercially available dyes were characterised by electrochemical, spectroscopic and computational methods. Several dyes, including Fuchsin Basic and Malachite Green were found to have properties that make them potential candidates for use in photo-electrochemical systems. The risks of combining different characterisation methods are also highlighted, namely the combination of thermodynamic reactions (electrochemical redox reactions), electronic transitions (optical spectroscopy) and the use of computational techniques to describe them.
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| 37. |
- Ng, Chun Hin, et al.
(författare)
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Enhanced catalytic activity towards hydrogen evolution on polythiophene via microstructural changes
- 2017
-
Ingår i: International journal of hydrogen energy. - : Elsevier. - 0360-3199 .- 1879-3487. ; 42:2, s. 886-894
-
Tidskriftsartikel (refereegranskat)abstract
- The discovery of poly(2,20 -bithiophene) (PBTh) as a photo-electrochemical catalyst for the hydrogen evolution reaction (HER) presents a novel electrode material for the transition to a sustainable hydrogen energy economy. Nonetheless, it remains limited by a low hydrogen evolution rate. We here investigate two methods in which to increase the catalytic activity of PBTh: using humidity for alternative templating and substrate roughening. It was found that exposure of the oxidant solution to humidity prior to polymerisation causes the formation of new microstructures that was found to increase catalytic activity of the PBTh film by over four times, from 14 to 57 mA cm-2. It was also found that control of the atmospheric environment proved critical. In contrast, the roughening of the substrate did not consistently lead to an increase in performance and was attributed to poor adhesion and electrical contact of the film to the substrate. During these tests however, a photoelectrocatalytic current of 150 mA cm2 was recorded in pH 7.0 and an underpotential of 0.12 V on an un-roughened PBTh sample. This represents the highest reported value for PBTh thus far and a significant achievement for its further development towards a low-cost and efficient HER catalyst.
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| 38. |
- Ng, Chun Hin, et al.
(författare)
-
Exploration and optimisation of poly(2,2 ‘-bithiophene) as a stable photo-electrocatalyst for hydrogen production
- 2015
-
Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry (RSC). - 2050-7488 .- 2050-7496. ; 3:21, s. 11358-11366
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Tidskriftsartikel (refereegranskat)abstract
- An organic photo-electrochemical catalyst for the hydrogen evolution reaction (HER) based on the conducting polymer, poly(2,2 ‘-bithiophene) (PBTh), is further explored. Long-term stability testing shows the successful operation of the catalyst over a period of 12 days at neutral pH with corresponding turnover numbers exceeding 6 x 10(4). Experimental parameters such as substrate type, electrolyte, pH and thickness of the film are explored and their subsequent effects on catalytic behaviour and performance discussed. Significant findings include the four-fold increase in performance by the reduction of thickness to better facilitate charge transfer and the successful photo-catalysis of the HER at pH 11, with an onset that is 0.14 V below E-0. Faradaic efficiency was also determined with a maximum recorded efficiency of 80% despite known losses such as crossover reactions and H-2 escape from within the system.
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| 39. |
- Ng, Chun Hin, et al.
(författare)
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Mechanistic studies of the photo-electrochemical hydrogen evolution reaction on poly(2,2'-bithiophene)
- 2016
-
Ingår i: Catalysis Science & Technology. - : Royal Society of Chemistry (RSC). - 2044-4753 .- 2044-4761. ; 6:9, s. 3253-3262
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Tidskriftsartikel (refereegranskat)abstract
- The realisation of poly(2,2’-bithiophene) (PBTh) as an effective photo-electrocatalyst for the hydrogen evolution reaction is a novel discovery [Ng et al., Int. J. Hydrogen Energy, 2014, 39, 18230]; however, the underlying mechanism of this catalysis remains unknown. In this article, studies using electrochemical, photo-electrochemical, Raman spectroscopy and computational modelling are undertaken to shed some light on the mechanistic process. From these studies, a compelling reaction scheme is proposed involving the protonation of the PBTh chain via the sulphur atom and subsequent intersystem crossing to a long-lived triplet state for the reaction to form H-2. This suggested mechanism is tentative but cohesively integrates all experimental and computational findings. Importantly, these insights into the PBTh system form an important mechanistic milestone study and will help inspire new developments and applications for polythiophenes and conducting polymers.
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| 40. |
- Ng, Chun Hin, et al.
(författare)
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Photo-electrocatalytic H-2 evolution on poly(2,2 ‘-bithiophene) at neutral pH
- 2014
-
Ingår i: International journal of hydrogen energy. - : Elsevier BV. - 0360-3199 .- 1879-3487. ; 39:32, s. 18230-18234
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Tidskriftsartikel (refereegranskat)abstract
- Vapour phase polymerised (VPP) polybithiophene (PBTh) on glassy carbon is revealed to be an efficient photo-electrocatalytic electrode for the hydrogen evolution reaction (HER). An onset potential of -0.03 V vs SCE for the HER is observed on illumination using visible light in 0.1 mol L-1 phosphate buffer at pH 6.9, 600 mV lower in energy than E-o. Hydrogen evolution is confirmed using gas chromatography with a calculated faradaic efficiency of 34% when holding at a potential of -0.5 V. Importantly, this process occurs without platinum and under neutral aqueous conditions thus revealing a significant but overlooked application for PBTh: a potential low-cost cathode material for the splitting of water.
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| 41. |
- Ohlin, C. André, et al.
(författare)
-
17O NMR as a Tool in Discrete Metal Oxide Cluster Chemistry
- 2018
-
Ingår i: Annual Reports on NMR Spectroscopy. - : Elsevier. - 9780128152126 ; , s. 187-248
-
Bokkapitel (refereegranskat)abstract
- This chapter covers recent developments in 17O NMR spectroscopy as applied to discrete metal oxide clusters, particularly in the context of their use as models in geochemistry and catalysis. Dynamic 17O NMR methods based on the McConnell–Bloch equations are explored in depth, and recent advances are reviewed. High-pressure NMR methods are also discussed and reviewed, as are recent developments in the use of density functional theory in the computation of 17O NMR shifts in polyoxometalates. The emphasis of the chapter is on the new developments that promise to reinvigorate 17O NMR as a central tool in the study of aqueous chemical kinetics, with the most urgent challenges being understanding the rates of isotopic substitution into bridging oxygens in clusters.
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| 42. |
- Ohlin, C André, et al.
(författare)
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Carbon dioxide reduction in biphasic aqueous-ionic liquid systems by pressurized hydrogen
- 2003
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Ingår i: High Pressure Research. - : Informa UK Limited. - 0895-7959 .- 1477-2299. ; 23:3, s. 239-242
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Tidskriftsartikel (refereegranskat)abstract
- This work reports the hydrogenation of carbon dioxide/inorganic carbonate salts to formic acid/formate in two phase systems comprising an ionic phase, in which the catalyst is immobilized, and an aqueous phase in which the carbonates and formate are confined, is reported. The reactions were followed in situ by multinuclear NMR. Pressurized H-2 gas was used for the reduction.
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| 43. |
- Ohlin, C. André, et al.
(författare)
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Carbon monoxide solubility in ionic liquids : determination, prediction and relevance to hydroformylation
- 2004
-
Ingår i: Chemical Communications. - : Royal Society of Chemistry (RSC). - 1359-7345 .- 1364-548X. ; :9, s. 1070-1071
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Tidskriftsartikel (refereegranskat)abstract
- The solubility of carbon monoxide in 37 ionic liquids and in some organic solvents has been determined using high-pressure (13)C NMR spectroscopy; a method for predicting the CO solubility is demonstrated, and it was shown that the rate of the hydroformylation of 5-hexen-2-one does not correlate with the CO solubility, as expected from the determined relative solubility of CO compared to H(2).
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| 44. |
- Ohlin, C. André
(författare)
-
Computational exploration of heterometal substitution into the decaniobate framework, [Nb10O28]6-
- 2021
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 23:17, s. 10402-10408
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Tidskriftsartikel (refereegranskat)abstract
- The factors governing the substitution of group 4B-12B metals into the decaniobate framework are explored using density functional theory in order to ascertain whether (1) recently isolated [MNb9O28]x- clusters are kinetic or thermodynamic products, (2) density functional theory is a sufficient level of theory to accurately predict substitution patterns in polyoxometalates where ion pairing and other effects may operate, and (3) it can be used to guide future synthetic efforts. Computations using restricted, unrestricted and open-shell density functional theory at PBE0/def2-tzvp were found to correctly predict substitution patterns in known clusters, and were subsequently used to calculate the relative energies of a large series of [MNb9O28]x- clusters, to reveal trends and suggest potential synthetic approaches. OPBE/def2-tzvp correctly predicted favoured spin states of known substituted decametalates.
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| 45. |
- Ohlin, C. Andre, et al.
(författare)
-
Dissolution of insulating oxide materials at the molecular scale
- 2010
-
Ingår i: Nature Materials. - 1476-1122 .- 1476-4660. ; 9:1, s. 11-19
-
Forskningsöversikt (refereegranskat)abstract
- Our understanding of mineral and glass dissolution has advanced from simple thermodynamic treatments to models that emphasize adsorbate structures. This evolution was driven by the idea that the best understanding is built at the molecular level. Now, it is clear that the molecular questions cannot be answered uniquely with dissolution experiments. At the surface it is unclear which functional groups are present, how they are arranged, and how they interact with each other and with solutes as the key bonds are activated. An alternative approach has developed whereby reactions are studied with nanometre-sized aqueous oxide ions that serve as models for the more complicated oxide interface. For these ions, establishing the structure is not a research problem in itself, and bond ruptures and dissociations can be followed with much confidence. We review the field from bulk-dissolution kinetics to the new isotope-exchange experiments in large oxide ions.
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| 46. |
- Ohlin, C. André
(författare)
-
Energetics of paramagnetic oxide clusters : the Fe(iii) oxyhydroxy Keggin ion
- 2020
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 22:7, s. 4043-4050
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Tidskriftsartikel (refereegranskat)abstract
- The energetics of the different spin states of the five Baker-Figgis isomers of the iron(iii) Keggin ion, [Fe(O-4)(Fe(OH)(2)(OH2))(12)](7+), have been investigated using density functional theory in order to demonstrate how the energy landscape of medium-to-large discrete paramagnetic transition metal oxide clusters with large numbers of antiferromagnetically coupled centres can be resolved. Antiferromagnetic coupling causes the energies to span a surprisingly large range of 30 kcal mol(-1), as determined by calculating the energies of all 664 unique spin configurations based on determination of the antiferromagnetic coupling constants by density functional theory. A program which simplifies the resolution of the energetics of this type of system is also provided.
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| 47. |
- Ohlin, C. André, et al.
(författare)
-
Heterogeneous dehalogenation of arylhalides in the presence of ionic liquids
- 2007
-
Ingår i: Applied organometallic chemistry. - : Wiley. - 0268-2605 .- 1099-0739. ; 21:3, s. 156-160
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Tidskriftsartikel (refereegranskat)abstract
- Dehydrohalogenation of haloaromatics in ionic liquids derived from ethylmethylimidazolium or similar salts has been performed using Pd-C, Pd(OAc)(2) and other catalysts using formate salts as a hydrogen source. In the ionic liquid [emim][BF4], chlorobenzene was dehalogenated by up to 40%, bromobenzene up to 25% and iodobenzene up to 41% in 2 h. Reactions in the absence of the ionic liquid were also performed.
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| 48. |
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| 49. |
- Ohlin, C. Andre, et al.
(författare)
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Oxygen isotopic exchange in an (MnMn3IV)-Mn-III-oxo cubane
- 2009
-
Ingår i: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; :27, s. 5278-5280
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Tidskriftsartikel (refereegranskat)abstract
- The rate and activation parameters for oxygen exchange of the mu(3)-oxo bridges in a manganese tetranuclear cluster with (H2O)-O-18 have been measured by ESI-MS; the observed Delta S double dagger of -146 +/- 22 J K-1 mol(-1) is consistent with the expected associative mechanism of substitution.
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| 50. |
- Ohlin, C. André, et al.
(författare)
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Protonation and water exchange kinetics in sandwich polyoxometalates
- 2018
-
Ingår i: Dalton Transactions. - : Royal Society of Chemistry. - 1477-9226 .- 1477-9234. ; 47:38, s. 13602-13607
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Tidskriftsartikel (refereegranskat)abstract
- Density functional theory is used to explore the locus and consequences of protonation in [Zn4(HO)2(PW9O34)2]10−. The results are used to explain recent observations regarding the contrasting pH effects on the water-ligand exchange in [Mn4(H2O)2(P2W15O56)2]16− and [Co4(H2O)2(P2W15O56)2]16−, and the general effect of protonation on solvent exchange in metal oxides is discussed.
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