For publications prior to 2017 please see the pages of the respective PI: BjörnBoily, Holmboe, and Ohlin.

Quicklinks: 2017 2018 2019 2020


4. Polyoxoniobates as molecular building blocks in thin films

in Dalton Transactions, 2021, 50, 16030-16038. Link

Mark RambaranAndrás GorzsásMichael HolmboeCA Ohlin.

Abstract: Niobium oxide thin films have been prepared by spin-coating aqueous solutions of tetramethylammonium salts of the isostructural polyoxometalate clusters [Nb10O28]6- , [TiNb10O28]7- and [Ti2Nb8O28]8- onto silicon wafers, and annealing them. The [Nb10O28]6- cluster yields films of Nb2O5 in the orthorhombic and monoclinic crystal phases when annealed at 800 °C and 1,000 °C, respectively, whereas the [TiNb10O28]7-  and [Ti2Nb8O28]8- clusters yield the monoclinic crystal phases of Ti2Nb12O29 and TiNb2O7 (titanium-niobium oxides) in different ratios. We also demonstrate a protocol for depositing successive layers of metal oxide films. Finally, we explore factors affecting the roughness of the films.

3. Polyoxometalates as Effective Nano-inhibitors of Amyloid Aggregation of Pro-inflammatory S100A9 Protein Involved in Neurodegenerative Diseases

in ACS Appl. Mater. Interfaces, 2021, 13(23), 26721-26734.

Chaudhary, Himanshi; Iaschishyn, Igor A.; Romanova, Nina V.; Rambaran, Mark A.; Musteikyte, Greta; Smirnovas, Vytautas; Holmboe, Michael; Ohlin, C. André; Svedruzić, Zelsko M.; Morozova-Roche, Ludmilla A.

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.

2. The Smallest Polyoxotungstate Retained by TRIS-Stabilization

in Inorg. Chem.202160(17), 12671-12675

Gumerova, Nadiia I.; Prado-Roller, Alexander; Rambaran, Mark A.; Ohlin, C. André; Rompel, Annette

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.

1. Computational exploration of heterometal substitution into the decaniobate framework, [Nb10O28]6-

in Phys. Chem. Chem. Phys.202123, 10402-10408. Link

C. A. Ohlin

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.


2. The Performance-Determining Role of Lewis Bases in Dye-Sensitized Solar Cells Employing Copper-Bisphenanthroline Redox Mediators

in Adv. Energy Mater., 2020, 10(37), 2002067. Link

Fürer, Sebastian O.; Milhuisen, Rebecca A.; Kashif, Muhammad K.; Raga, Sonia R.; Acharya, Shravan S.; Forsyth, Craig; Liu, Maning; Frazer, Laszlo; Duffy, Noel W.; Ohlin, C. André; Funston, Alison M.; Tachibana, Yasuhiro; Bach, Udo

Abstract: Copper redox mediators have enabled open-circuit voltages (VOC) 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 1H-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.

1. Energetics of paramagnetic oxide clusters: the Fe(III) oxyhydroxy Keggin ion

in Phys. Chem. Chem. Phys., 2020, 22, 4043-4050. Link

C. A. Ohlin

The energetics of the different spin states of the five Baker-Figgis isomers of the iron(III) Keggin ion, [Fe(O4)(Fe(OH)2 (OH2))12]7+, has 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, 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 systems is also provided.


5. “Deconvolution of Smectite Hydration Isotherms
in ACS Earth and Space Chemistry, 2019Published Sept 26Link
Jerry LindholmJean-François Boily and Michael Holmboe*

Abstract: Sorption isotherm models have traditionally served as an invaluable tool to characterize synthesized and natural mineral particles, but often fail to describe the behavior of swelling materials. This research presents a novel composite isotherm model that describes water uptake by adsorption, step-wise intercalation, and condensation.

4. “Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium”
in Chem. Sci., 201910, 10755-10764. Link.
Samuel R. Lawrence,  C. André Ohlin, David B. Cordes,  Alexandra M. Z. Slawin, Andreas Stasch

Abstract: The reaction of the magnesium(I) complexes [{( Arnacnac)Mg}2], ( Arnacnac = HC(MeCNAr)2 , Ar =Dip (2,6-iPr2C6H3), Dep (2,6-Et2C6H3), Mes (2,4,6-Me3C6H2), Xyl (2,6-Me2C6H3 )) with fullerene C60 afforded a series of hydrocarbon-soluble fulleride complexes [{(Arnacnac)Mg}nC60], predominantly with n = 6, 4 and 2. 13C{1H} 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[{(Arnacnac)Mg}nC60] with n = 6, 4 and 2 can be described as inverse  coordination complexes of n [(Arnacnac)Mg]+ ions with C60n- anions showing predominantly ionic metal-ligand interactions, and include the first well-defined and soluble complexes of the C606- ion. Experimental studies show the flexible ionic nature of the {(Arnacnac)Mg}+····C606-  coordination bonds. DFT calculations on the model complex [{(Menacnac)Mg}6C60] (Menacnac = HC(MeCNMe)2) support the formulation as an ionic complex with a centralC606- anion and comparable frontier orbitals toC606- with a small HOMO-LUMO gap. The reduction of C60 to its hexaanion gives an indication about the reducing strength of dimagnesium(I) complexes.

3. “Microwave Synthesis of Alkali-Free Hexaniobate, Decaniobate, and Hexatantalate Polyoxometalate Ions
in Eur. J. Inorg. Chem., 2019, 35, 3913-3918. Link
Mark A. RambaranMagda Pascual-Borràs and C. André Ohlin

Abstract: Microwave synthesis of polyoxoniobates and -tantalates circumvents the prolonged heating required by conventional hydrothermal methods, while providing comparable or greater yields. Microwave irradiation allows synthesis of polyoxoniobates from anhydrous niobium pentoxide, in lieu of niobic acid and sets the precedent for the discovery of new polyoxoniobates and -tantalates.

2. Direct Single- and Double-Side Triol-Functionalization of the Mixed Type Anderson Polyoxotungstate [Cr(OH)3W6O21]6–”
in Inorganic Chemistry201958(1), 106-113. Link
Nadiia I. Gumerova, Tania Caldera Fraile, Alexander Roller, Gerald Giester, Magda Pascual-BorràsC. André Ohlin, and Annette Rompel

Abstract: Since the first successful triol-functionalization of the Anderson polyoxometalates, the protons of the central octahedron X(OH)6 (X—heteroatom) have been considered as a prerequisite for their functionalization and therefore the functionalization of Anderson structures from the unprotonated sides have never been reported. Herein, for the first time, we organically functionalized the mixed-type Anderson polyoxometalate with real-time observation of hybrid anion formation.

1. “Residence times of nanoconfined CO2 in layered aluminosilicates
in Environmental Science: Nano, 20196 (1), 146-151Link
Merve YeşilbaşMichael Holmboe and Jean-François Boily*

Abstract: Nanoconfinement of CO2 in layered aluminosilicates contributes to the capture and release of this green- house gas in soils. In this work, we show that the residence times of CO2 in montmorillonite are lowered by 15 min for each 1 °C increment in temperature during venting. Molecular simulations showed that acti- vation energies of release are no more than half of the experimentally derived value of 34 kJ mol-1. This raised the possibility of additional processes limiting CO2 mobility in real materials, including (chemi)sorp- tion at reactive sites or frayed edges or defects.


10. “Deciphering the Role of Water Column Redoxclines on Methylmercury Cycling Using Speciation Modeling and Observations From the Baltic Sea

Global Biogeochemical Cycles, 2018, Link

Anne L. Soerensen, Amina T. Schartup, Aleksandra Skrobonja, Sylvain Bouchet, David Amouroux, Van Liem‐Nguyen, and Erik Björn

Abstract: Oxygen‐depleted areas are spreading in coastal and offshore waters worldwide, but the implication for production and bioaccumulation of neurotoxic methylmercury (MeHg) is uncertain. We combined observations from six cruises in the Baltic Sea with speciation modeling and incubation experiments to gain insights into mercury (Hg) dynamics in oxygen depleted systems. We then developed a conceptual model describing the main drivers of Hg speciation, fluxes, and transformations in water columns with steep redox gradients. MeHg concentrations were 2–6 and 30–55 times higher in hypoxic and anoxic than in normoxic water, respectively, while only 1–3 and 1–2 times higher for total Hg (THg). We systematically detected divalent inorganic Hg (HgII) methylation in anoxic water but rarely in other waters. In anoxic water, high concentrations of dissolved sulfide cause formation of dissolved species of HgII: HgS2H(aq) and Hg (SH)20(aq). This prolongs the lifetime and increases the reservoir of HgII readily available for methylation, driving the high MeHg concentrations in anoxic zones. In the hypoxic zone and at the hypoxic‐anoxic interface, Hg concentrations, partitioning, and speciation are all highly dynamic due to processes linked to the iron and sulfur cycles. This causes a large variability in bioavailability of Hg, and thereby MeHg concentrations, in these zones. We find that zooplankton in the summertime are exposed to 2–6 times higher MeHg concentrations in hypoxic than in normoxic water. The current spread of hypoxic zones in coastal systems worldwide could thus cause an increase in the MeHg exposure of food webs.

9. “Rapid Dissolution of Cinnabar in Crude Oils at Reservoir Temperatures Facilitated by Reduced Sulfur Ligands”

ACS Earth and Space Chemistry, 2018, 2, 1022-1028. Link

Lars Lambertsson, Charles J. Lord, Wolfgang Frech, and Erik Björn

Abstract: Mercury (Hg) is present in petrochemical samples, including crude oils, and the processing and use of petroleum products contribute to global Hg emissions. We present a refined theory on geochemical processes controlling Hg concentrations in crude oil by studying dissolution kinetics and solubility thermodynamics of cinnabar (α-HgS(s)) in different crude oils held at reservoir temperatures. In a black light crude oil, α-HgS(s) dissolved in an apparent zero-order reaction with a rate of 0.14–0.58 μmoles m–2 s–1 at 170–230 °C and an estimated activation energy of 43 kJ mol–1. For crude oil samples with a total sulfur concentration spanning 0.15–2.38% (w/w), the measured dissolution rate varied between 0.05 and 0.24 μmoles m–2 s–1 at 200 °C. Separate tests showed that thiols and, to a lesser extent, organic sulfides increased the solubility of α-HgS(s) in isooctane at room temperature compared to thiophenes, disulfides, and elemental sulfur. Long-term (14 days) α-HgS(s) solubility tests in a crude oil at 200 °C generated dissolved Hg concentrations in the 0.3% (w/w) range. The high α-HgS(s) dissolving capacity of the crude oils was more than 2 orders of magnitude greater than the highest reported Hg concentration in crude oils globally. On the basis of the kinetic and solubility data, it was further concluded that α-HgS(s) is not stable under typical petroleum reservoir conditions and would decompose to elemental mercury (Hg0). Our results suggest that source/reservoir temperature, abundance of reduced sulfur compounds in the crude oil, and dissolved Hg0 evasion processes are principal factors controlling the ultimate Hg concentration in a specific crude oil deposit.

8. “Protonation and water exchange kinetics in sandwich polyoxometalates”

in Dalton Transactions., 2018, 47, 13602-13607. Link.

C. André Ohlin, Magda Pascual-Borràs

Abstract: Density functional theory is used to explore the locus and consequences of protonation in [Zn4(H2O)2(PW9 O34)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.

7. “17O NMR as a Tool in Discrete Metal Oxide Cluster Chemistry”

in Annual Reports on NMR Spectroscopy, 2018, 94, 187-248. Link.

C. André Ohlin, William H. Casey

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 thBinding Geometries of Silicate Species on Ferrihydrite Surfacese 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.

6. “Solution, solid-state, and computational analysis of agostic interactions in a coherent set of low-coordinate rhodium(III) and iridium(III) complexes”

in Chem. — Eur. J., 2018, 24(19), 4927-4938. Link.

Knighton, Richard C.; Emerson-King, Jack; Rourke, Jonathan P.; Ohlin, C. André; Chaplin, Adrian B

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.

5. “Ice and Cryosalt Formation in Saline Microporous Clay Gels”

ACS Earth and Space Chemistry.

Merve Yeşilbaş, Chen Choo Lee, and Jean-François Boily.

Hydrated clay minerals that are common to Earth’s atmosphere and terrestrial and aquatic environments can form gels that host saline solutions. Using cryogenic electron microscopy and vibration spectroscopy, we show that saline gels of montmorillonite frozen at < –90 °C host elongated hexagonal ice (Ih) microcrystals embedded in a network of honeycomb micropores. Freezing segregates salts into walls of aggregated clay nanoparticles sharing face-to-face contacts. Above ∼ –50 °C, clay gels that are sufficiently dense (≫10 g/L) and flexible (Na-exchanged montmorillonite) also host the cryosalt mineral hydrohalite (NaCl·2H2O), either co-existing or entirely replacing Ih in the gels. Hydrohalite does not form in gels of low-density (<10 g/L) or rigid (Ca-exchange montmorillonite) clay particles. These results suggest that hydrohalite forms in expandable clay gels that are sufficiently dense and flexible to retain saline solutions within their walls, possibly through interparticle capillary and hydration forces. These forces effectively oppose water diffusion to growing ice microcrystals within micropores, thus prolonging the lifetime of hydrohalite within these hydrated clay gels. Our findings tie the fate of ice and cryosalt nucleation and growth to the water-retention capability of expandable clay gels.

4. “Computational Prediction of Mg-Isotope Fractionation Between Aqueous [Mg(OH2)6]2+ and Brucite”

in Geochim. Cosmochim. Acta., 2018, 227, 64-74. Link.

Christopher A. Colla, W. H. Casey, C. André Ohlin

Abstract: The fractionation factor in the magnesium-isotope fractionation between aqueous solutions of magnesium and brucite remarkably 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 of the calculations 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.

3. “Silicate Binding and Precipitation on Iron Oxyhydroxides”

in Environmental Science and Technology.

Masakazu Kanematsu, Glenn A. Waychunas, and Jean-François Boily*

Silica-bearing waters in nature often alter the reactivity of mineral surfaces via deposition of Si complexes and solids. In this work, Fourier transform infrared (FTIR) spectroscopy was used to identify hydroxo groups at goethite (α-FeOOH) and lepidocrocite (γ-FeOOH) surfaces that are targeted by ligand exchange reactions with monomeric silicate species. Measurements of samples first reacted in aqueous solutions then dried under N2(g) enabled resolution of the signature O–H stretching bands of singly (−OH), doubly (μ–OH), and triply coordinated (μ3–OH) groups. Samples reacted with Si for 3 and 30 d at pH 4 and 7 revealed that −OH groups were preferentially exchanged by silicate and that μ–OH and μ3–OH groups were not exchanged. Based on knowledge of the disposition of −OH groups on the major crystallographic faces of goethite and lepidocrocite, and the response of these groups to ligand exchange prior oligomerization, our work points to the predominance of rows of mononuclear monodentate silicate species, each separated by at least one −OH group. These species are the attachment sites from which oligomerization and polymerization reactions occur, starting at loadings exceeding ∼1 Si/nmand corresponding to soluble Si concentrations that can be as low as ∼0.7 mM after 30 d reaction time. Only above such loadings can reaction products grow away from rows of −OH groups and form hydrogen bonds with nonexchangeable μ–OH and μ3–OH groups. These findings have important repercussions for our understanding of the fate of waterborne silicate ions exposed to minerals.

2.”Binding Geometries of Silicate Species on Ferrihydrite Surfaces”

in ACS Earth and Space Chemistry.

Xiaoming Wang, James D. Kubicki, Jean-François Boily , Glenn A. Waychunas, Yongfeng Hu, Xionghan Feng, and Mengqiang Zhu

Abstract: Silicate sorption on ferrihydrite surfaces, as monomers, oligomers, and polymers, strongly affects ferrihydrite crystallinity, thermodynamic stability, and surface reactivity. How these silicate species bind on ferrihydrite surfaces is, however, not well understood. We have determined silicate binding geometries using a combination of X-ray absorption spectroscopy (XAS), differential atomic pair distribution function (d-PDF) analysis, and density functional theory (DFT) calculations. Silicon K-edge absorption pre-edges and DFT-predicted energies indicate that silicate forms monomeric monodentate–mononuclear (MM) complexes at low silicate sorption loadings. With increasing silicate loading, the pre-edge peak shifts to higher energies, suggesting changes in the silicate binding geometry toward multidentate complexation. The d-PDF analysis determines the Si–Fe interatomic distance to be ∼3.25 Å for the high-loading samples. The DFT calculations indicate that such distance corresponds to an oligomer in the bidentate–binuclear (BB) binding geometry. The transition of the silicate sorption geometry accompanied by polymerization can affect stability of ferrihydrite and its adsorption and redox reactivity and increase the degree of Si isotopic fractionation upon silicate sorption on Fe oxides. MM monomeric complexes and BB oligomeric complexes should be used for surface complexation models predicting silicate sorption on Fe oxide surfaces.

1. “Cohesive Vibrational and Structural Depiction of Intercalated Water in Montmorillonite”
in ACS Earth and Space Chemistry.
Merve Yeşilbaş , Michael Holmboe , and Jean-François Boily*

Abstract:   The vibrational spectral profiles of Na- and Ca-montmorillonite (MMT) of controlled water layer populations (nW) was extracted by chemometric analysis of new Fourier transform infrared (FTIR) spectroscopy data and validated by mixed-layer modeling of previously published X-ray diffraction data. These efforts resolved FTIR spectral profiles of 0W, 1W, and 2W interlayers, which can now be used to explore the distinct hydration states of MMT. These spectral profiles reflect water populations organized around interlayer cations (Na+, Ca2+), interacting with siloxane groups of the basal face of the interlayer, and with other bound and “free” water molecules. This cohesive description of water-bearing clays provides the link needed to relate vibrational to structural attributes of these geochemically important materials.


15. “Accumulation of counterions and coions evaluated by cryogenic XPS as a new tool for describing the structure of electric double layer at the silica/water interface”

Phys.Chem.Chem.Phys., 2017, 19, 29047-29052  DOI: 10.1039/C7CP06439J

Jiri Škvarla, Mária Kanuchová, Andrey Shchukarev, Ivan Brezáni, and Juraj Škvarla.

We introduce a new method of evaluating the structure of electric double layer (EDL) at the native solid/liquid interface using cryogenic X-ray photoelectron spectroscopy technique. This method isbased on evaluating the atomic concentration ratio of counterions and co-ions of supporting electrolyte at the close-to-in situ state surface of colloid particles by the cryo-XPS and comparing it withanalogous ratio predicted by EDL models. For silica colloids in aqueous KCl solutions at pH 6 to 8 it has been found that the latter ratio is higher than unity, as expected for the negatively charged surface of silica, but does not correspond with the prediction of the basic Gouy–Chapman EDL model for the ideal interface. However, it agrees with that deduced from experiments on electrolytic  coagulation kinetics of analogous silica colloids by applying a simple EDL model of swellable ion-permeable (Donnanian) polyelectrolyte gel layer. It turns out that the traditional Stern layer-based concept of EDL at solid/liquid interfaces is not justified for metal oxides at least in KCl solutions.

14. “PNacPNacE: (E = Ga, In, Tl) – monomeric group 13 metal(I) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide”

in Dalton Trans., 2017, 46, 16872-16877.

Christian P. Sindlinger, Samuel R. Lawrence, Shravan Acharya, C. André Ohlin, Andreas Stasch

The salt metathesis reaction of the sterically demanding bis(iminophosphoranyl)methanide alkali metal complexes LM (L – = HC(Ph 2 P=NDip) 2- , Dip = 2,6- i Pr 2 C 6 H 3 ; M = Li, Na, K) with “GaI”, InBr or TlBr afforded the monomeric group 13 metal(I) complexes LE:, E = Ga (1), In (2) and Tl (3), and small quantities of LGaI 2 4 in case of Ga, respectively. The molecular structures of LE: 1-3 from X-ray single crystal diffraction show them to contain puckered six-membered rings with N,N’-chelating methanide ligands and two-coordinated metal(I) centres. Reduction reactions of LAlI 2 5, prepared by iodination of LAlMe 2 , were not successful and no aluminium(I) congener could be prepared so far. DFT studies on LE:, E = Al–Tl, were carried out and support the formulation as an anionic, N,N’-chelating methanide ligand coordinating to group 13 metal(I) cations. The HOMOs of the molecules for E = Al-In show a dominant contribution from a metal-based lone pair that is high in s-character.

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13. “Cryo-XPS: probing intact interfaces in nature and life”

Andrey Shchukarev and Madeleine Ramstedt

Surface and Interface Analysis, 2017, 49, 349-356 DOI: 10.1002/sia.6025


Experimental studies of solid-aqueous solution interfaces are of great importance for reaching better chemical understanding of interfacial phenomena at themolecular level. This perspective article presents a recently developed approach for investigation of intact interfaces, based on fast freezing of centrifuged wet pastes followed by traditional XPS measurements at liquid nitrogen temperatures. Sample preparation and handling protocols, applicable to any suspension or gel, are discussed in detail. For mineral suspensions, cryogenic XPS is an important complement to traditional analyses of supernatant solutions and dry solids that is capable of revealing novel insights of the electrical double layer in terms of structure and composition. It can be used to study changes in the biochemistry of bacterial cell walls as influenced by external stimuli, and interfacial features related to biocompatibility of implant materials. Herein we review how the technique has been applied to minerals in electrolyte solutions, intact bacterial surfaces, and biomaterial interfaces in biologically relevant media, and highlight some future requirements for development of interface analysis methodologies.

12. “Electrochemical Response of Bound Electrolyte Ions at Oriented Hematite Surfaces: A Local Electrochemical Impedance Spectroscopy Study”

J. Phys. Chem. C.

Marie Lucas and Jean-François Boily*

Abstract Image


The electrochemical response of millimeter-sized hematite (α-Fe2O3) electrode surfaces to bound ions of NaCl, NH4Cl, and NaHCO3 salts was monitored by alternating current scanning electrochemical microscopy (AC-SECM). Local electrochemical impedance spectroscopy (LEIS) measurements along 100 μm lines on the (001) and (012) faces of hematite were used to extract capacitance and resistance parameters affected by bound inorganic ions. Equivalent circuit modeling was used to suggest that (1) double layer capacitances are affected by the spatial distribution of ions, and that (2) compact plane capacitance and resistance are affected by the closeness of association of ions to surface hydroxo groups. This study confirms the sensitivity of the technique to electrolyte ion binding, and provides new and key insight into the micrometer-scale electrochemical properties of iron oxides exposed to environmentally relevant conditions.

11. “Cobinding of Pharmaceutical Compounds at Mineral Surfaces: Mechanistic Modeling of Binding and Cobinding of Nalidixic Acid and Niflumic Acid at Goethite Surfaces”

in Environmental Science and Technology

Jing Xu, Rémi Marsac§ , Cheng Wei, Feng Wu , Jean-François Boily, and Khalil Hanna*


Although emerging contaminants rarely exist individually in environmental contaminated systems, only limited information on their adsorption mechanisms in multicomponent solutions is currently available. To address this shortcoming, this work examines for the first time the accuracy of a surface complexation model in predicting the cooperative adsorption of nalidixic acid (NA) and niflumic acid (NFA) at goethite (α-FeOOH) surfaces. Our model adequately predicts cobinding of an outer-sphere (OS) complex of NFA onto NA bound to goethite through metal-bonded (MB), hydrogen-bonded (HB), or OS complexes. More positive charge is introduced in the system via sodium interactions in order to describe the NFA adsorption at high NaCl concentrations in both single and binary systems. Our model confidently predicts multilayers of NA on goethite as well as NFA binding on goethite-bound NA over a large range of pH and salinity values as well as NA and NFA loadings. These findings have strong implications in the assessment and prediction of contaminant fate in multicomponent contaminated systems by invoking a nontraditional form of ligand–ligand interaction in this field of study.

10. “Co-Binding of Pharmaceutical Compounds at Mineral Surfaces: Molecular Investigations of Dimer Formation at Goethite/Water Interfaces”

in Environmental Science and Technology,

Jing Xu, Rémi Marsac, Dominique Costa , Wei Cheng, Feng Wu, Jean-François Boily, and Khalil Hanna

Abstract ImageAbstract: The emergence of antibiotic and anti-inflammatory agents in aquatic and terrestrial systems is becoming a serious threat to human and animal health worldwide. Because pharmaceutical compounds rarely exist individually in nature, interactions between various compounds can have unforeseen effects on their binding to mineral surfaces. This work demonstrates this important possibility for the case of two typical antibiotic and anti-inflammatory agents (nalidixic acid (NA) and niflumic acid (NFA)) bound at goethite (α-FeOOH) used as a model mineral surface. Our multidisciplinary study, which makes use of batch sorption experiments, vibration spectroscopy and periodic density functional theory calculations, reveals enhanced binding of the otherwise weakly bound NFA caused by unforeseen intermolecular interactions with mineral-bound NA. This enhancement is ascribed to the formation of a NFA–NA dimer whose energetically favored formation (−0.5 eV compared to free molecules) is predominantly driven by van der Waals interactions. A parallel set of efforts also showed that no cobinding occurred with sulfamethoxazole (SMX) because of the lack of molecular interactions with coexisting contaminants. As such, this article raises the importance of recognizing drug cobinding, and lack of cobinding, for predicting and developing policies on the fate of complex mixtures of antibiotics and anti-inflammatory agents in nature.

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9. “Atomistic simulations of cation hydration in sodium and calcium montmorillonite nanopores”

in The Journal of Chemical Physics,

Guomin Yang, Ivars Neretnieks, and Michael Holmboe

During the last four decades, numerous studies have been directed to the swelling smectite-rich clays in the context of high-level radioactive waste applications and waste-liners for contaminated sites. The swelling properties of clay mineral particles arise due to hydration of the interlayer cations and the diffuse double layers formed near the negatively charged montmorillonite (MMT) surfaces. To accurately study the cation hydration in the interlayer nanopores of MMT, solvent-solute and solvent-clay surface interactions (i.e., the solvation effects and the shape effects) on the atomic level should be taken into account, in contrast to many recent electric double layer based methodologies using continuum models. Therefore, in this research we employed fully atomistic simulations using classical molecular dynamics (MD) simulations, the software package GROMACS along with the CLAYFF forcefield and the SPC/E water model. We present the ion distributions and the deformation of the hydrated coordination structures, i.e., the hydration shells of Na+ and Ca2+ in the interlayer, respectively, for MMT in the first-layer, the second-layer, the third-layer, the fourth-layer, and the fifth-layer (1W, 2W, 3W, 4W, and 5W) hydrate states. Our MD simulations show that Na+ in Na-MMT nanopores have an affinity to the ditrigonal cavities of the clay layers and form transient inner-sphere complexes at about 3.8 Å from clay midplane at water contents less than the 5W hydration state. However, these phenomena are not observed in Ca-MMT regardless of swelling states. For Na-MMT, each Na+ is coordinated to four water molecules and one oxygen atom of the clay basal-plane in the first hydration shell at the 1W hydration state, and with five to six water molecules in the first hydration shell within a radius of 3.1 Å at all higher water contents. In Ca-MMT, however each Ca2+ is coordinated to approximately seven water molecules in the first hydration shell at the 1W hydration state and about eight water molecules in the first hydration shell within a radius of 3.3 Å at all higher hydration states. Moreover, the MD results show that the complete hydration shells are nearly spherical with an orthogonal coordination sphere. They could only be formed when the basal spacing d001 ≥ 18.7 Å, i.e., approximately, the interlayer separation h ≥ 10 Å. Comparison between DFT and MD simulations shows that DFT failed to reproduce the outer-sphere complexes in the Stern-layer (within ∼5.0 Å from the clay basal-plane), observed in the MD simulations.

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8. “Hydrothermal Solutions”

Boily, Jean-François;

Encyclopedia of Geochemistry

7. “Colloids”

Boily, Jean-François;

Encyclopedia of Geochemistry

6. “Solubility”

Boily, Jean-François;

Encyclopedia of Geochemistry

5. “Surface chemistry of carbon dioxide revisited”

in Surface Chemistry,

Taifan, William; Boily, Jean-François; Baltrusaitis, Jonas.

This review discusses modern developments in CO2 surface chemistry by focusing on the work published since the original review by H.J. Freund and M.W. Roberts two decades ago (Surface Science Reports 25 (1996) 225–273). It includes relevant fundamentals pertaining to the topics covered in that earlier review, such as conventional metal and metal oxide surfaces and CO2 interactions thereon. While UHV spectroscopy has routinely been applied for CO2 gas–solid interface analysis, the present work goes further by describing surface–CO2 interactions under elevated CO2 pressure on non-oxide surfaces, such as zeolites, sulfides, carbides and nitrides. Furthermore, it describes additional salient in situ techniques relevant to the resolution of the interfacial chemistry of CO2, notably infrared spectroscopy and state-of-the-art theoretical methods, currently used in the resolution of solid and soluble carbonate species in liquid–water vapor, liquid–solid and liquid–liquid interfaces. These techniques are directly relevant to fundamental, natural and technological settings, such as heterogeneous and environmental catalysis and CO2 sequestration.

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4. “Diverse composites of metal-complexes and PEDOT facilitated by metal-free vapour phase polymerization”

in Reactive and Functional Polymers, 2017, 116, 101-106.

Acharya, Shravan S.; Eastone, Christopher D.; McCoy, Thomas M.; Spiccia, Leone; Ohlin, C. André; Winther-Jensen, Bjorn

Schematic representation of production of metal complex PEDOT composites

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-hydroxyquinolinato)aluminium(III). Using these composites, electrochemical reduction of nitrite to ammonia with a faradaic efficiency of 61% was reported.

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3. “Rates of water exchange in 2,2′-bipyridine and 1,10-phenanthroline complexes of Co(II) and Mn(II)”

in Australian Journal of Chemistry, 2017, 70, 751-754,

Acharya, Shravan S.; Winther-Jensen, Bjorn; Spiccia, Leone; Ohlin, C. André

Abstract: The rates and activation parameters of water exchange at pH 3.0 have been determined using variable temperature 17O NMR for four Co(II) complexes and one Mn(II) complex, viz. [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+. Substitution of 1,10-phenanthroline or 2,2′-bipyridyl for aquo ligands leads to an increase in the rate of exchange in the manganese complexes, from k 298 (1.8 ± 0.1) · 10 7 for [Mn(H2O)6]2+ to (7.2 ± 0.3) · 10 7 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 impact of M-OH2 distance and degree of substitution.

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2. “27Al MQMAS of the δ-Al13-Keggin”

in Dalton Transactions, 2017, 46, 2249-2254.

Pilgrim, Corey D.; Callahan, Joseph R.; Christopher A. Colla; Ohlin, C. André; Harris E., Mason; Casey, William H.

Abstract: One-dimensional 27Al, 23Na, Magic-Angle-Spinning (MAS) NMR and 27Al Multiple-Quantum Magic-Angle-Spinning NMR (MQMAS) measurements are reported for the δ-isomer of the Al13 Keggin structure at high spinning speed and 14.1 T field. Values for the CQ and η 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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1. “A Non-Aqueous Microwave Assisted Protocol for Accessing Molybdovanadates”

in Angewandte Chemie, International Edition, 2017, 56(29), 8568–8572.

Spillane, Samuel; Sharma, Rupali; Zavras, Athanasios; Mulder, Roger; Ohlin, C. André; Goerigk, Lars; Best, Stephen P.; O’Hair, Richard A. J.; Ritchie, Chris

Abstract: We report a novel approach for the synthesis of heterohexa- and heterodecametalates via the use of non-aqueous, microwave assisted reaction conditions. The two novel molybdovanadates have been isolated and characterized in the solid and solution states using single-crystal X-ray diffraction, FT-IR, UV/Vis, multinuclear NMR, and ESI-MS. The relative stabilities of the possible structural isomers were probed using DFT calculations for both polyoxometalate systems.

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