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Inorganics, Volume 4, Issue 2 (June 2016)

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Research

Jump to: Review

Open AccessArticle Synthesis and Textural Characterization of Mesoporous and Meso-/Macroporous Silica Monoliths Obtained by Spinodal Decomposition
Inorganics 2016, 4(2), 9; doi:10.3390/inorganics4020009
Received: 26 February 2016 / Revised: 21 March 2016 / Accepted: 22 March 2016 / Published: 18 April 2016
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Abstract
Silica monoliths featuring either mesopores or flow-through macropores and mesopores in their skeleton are prepared by combining spinodal phase separation and sol-gel condensation. The macroporous network is first generated by phase separation in acidic medium in the presence of polyethyleneoxides while mesoporosity is
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Silica monoliths featuring either mesopores or flow-through macropores and mesopores in their skeleton are prepared by combining spinodal phase separation and sol-gel condensation. The macroporous network is first generated by phase separation in acidic medium in the presence of polyethyleneoxides while mesoporosity is engineered in a second step in alkaline medium, possibly in the presence of alkylammonium cations as surfactants. The mesoporous monoliths, also referred as aerogels, are obtained in the presence of alkylpolyethylene oxides in acidic medium without the use of supercritical drying. The impact of the experimental conditions on pore architecture of the monoliths regarding the shape, the ordering, the size and the connectivity of the mesopores is comprehensively discussed based on a critical appraisal of the different models used for textural analysis. Full article
(This article belongs to the Special Issue Mesoporous Materials)
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Open AccessArticle Direct Control of Spin Distribution and Anisotropy in Cu-Dithiolene Complex Anions by Light
Inorganics 2016, 4(2), 7; doi:10.3390/inorganics4020007
Received: 15 January 2016 / Revised: 16 March 2016 / Accepted: 21 March 2016 / Published: 30 March 2016
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Abstract
Electrical and magnetic properties are dominated by the (de)localization and the anisotropy in the distribution of unpaired electrons in solids. In molecular materials, these properties have been indirectly controlled through crystal structures using various chemical modifications to affect molecular structures and arrangements. In
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Electrical and magnetic properties are dominated by the (de)localization and the anisotropy in the distribution of unpaired electrons in solids. In molecular materials, these properties have been indirectly controlled through crystal structures using various chemical modifications to affect molecular structures and arrangements. In the molecular crystals, since the energy band structures can be semi-quantitatively known using band calculations and solid state spectra, one can anticipate the (de)localization of unpaired electrons in particular bands/levels, as well as interactions with other electrons. Thus, direct control of anisotropy and localization of unpaired electrons by locating them in selected energy bands/levels would realize more efficient control of electrical and magnetic properties. In this work, it has been found that the unpaired electrons on Cu(II)-complex anions can be optically controlled to behave as anisotropically-delocalized electrons (under dark) or isotropically-localized electrons like free electrons (under UV), the latter of which has hardly been observed in the ground states of Cu(II)-complexes by any chemical modifications. Although the compounds examined in this work did not switch between conductors and magnets, these findings indicate that optical excitation in the [Cu(dmit)2]2− salts should be an effective method to control spin distribution and anisotropy. Full article
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Open AccessArticle Hexacoordinate Silicon Compounds with a Dianionic Tetradentate (N,N′,N′,N)-Chelating Ligand
Inorganics 2016, 4(2), 8; doi:10.3390/inorganics4020008
Received: 17 March 2016 / Revised: 6 April 2016 / Accepted: 7 April 2016 / Published: 14 April 2016
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Abstract
In the context of our systematic investigations of penta- and hexacoordinate silicon compounds, which included dianionic tri- (O,N,O′; O,N,N′) and tetradentate (O,N,N,O; O,
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In the context of our systematic investigations of penta- and hexacoordinate silicon compounds, which included dianionic tri- (O,N,O′; O,N,N′) and tetradentate (O,N,N,O; O,N,N′,O′) chelators, we have now explored silicon coordination chemistry with a dianionic tetradentate (N,N′,N′,N) chelator. The ligand [o-phenylene-bis(pyrrole-2-carbaldimine), H2L] was obtained by condensation of o-phenylenediamine and pyrrole-2-carbaldehyde and subsequently silylated with chlorotrimethylsilane/triethylamine. Transsilylation of this ligand precursor (Me3Si)2L with chlorosilanes SiCl4, PhSiCl3, Ph2SiCl2, (Anis)2SiCl2 and (4-Me2N-C6H4)PhSiCl2 afforded the hexacoordinate Si complexes LSiCl2, LSiPhCl, LSiPh2, LSi(Anis)2 and LSiPh(4-Me2N-C6H4), respectively (Anis = anisyl = 4-methoxyphenyl). 29Si NMR spectroscopy and, for LSiPh2, LSi(Anis)2 and LSiPh(4-Me2N-C6H4), single-crystal X-ray diffraction confirm hexacoordination of the Si atoms. The molecular structures of LSiCl2 and LSiPhCl were elucidated by computational methods. Despite the two different N donor sites (pyrrole N, X-type donor; imine N, L-type donor), charge delocalization within the ligand backbone results in compounds with four similar Si–N bonds. Charge distribution within the whole molecules was analyzed by calculating the Natural Charges (NCs). Although these five compounds carry electronically different monodentate substituents, their constituents reveal rather narrow ranges of their charges (Si atoms: +2.10–+2.22; monodentate substituents: −0.54–−0.56; L2−: −1.02–−1.11). Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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Open AccessArticle Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates
Inorganics 2016, 4(2), 14; doi:10.3390/inorganics4020014
Received: 31 March 2016 / Revised: 27 April 2016 / Accepted: 3 May 2016 / Published: 12 May 2016
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Abstract
New organophosphonate derivatives of monovacant Keggin-type polyoxotungstates that contain naphthyl groups have been synthesized and characterized in both solid state and solution. Single-crystal structural analysis shows that two phosphonate groups occupy the vacant position of the lacunary cluster unit in the isostructural compounds
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New organophosphonate derivatives of monovacant Keggin-type polyoxotungstates that contain naphthyl groups have been synthesized and characterized in both solid state and solution. Single-crystal structural analysis shows that two phosphonate groups occupy the vacant position of the lacunary cluster unit in the isostructural compounds [N(C4H9)4]3[H(POC11H9)2(α-HBW11O39)] (TBA-1) and [N(C4H9)4]3[H(POC11H9)2(α-SiW11O39)] (TBA-2). Liquid-solution UV–Vis transmittance and solid-state diffuse reflectance spectroscopy studies reveal the presence of a new absorption band in the visible region, the charge transfer character of which has been further confirmed by time-dependent density functional theory (TD-DFT) calculations. The latter evidence that the charge transfer process is dominated by transitions from the highest occupied molecular orbital (HOMO), localized in the aromatic ring of the organic group, to the lowest unoccupied molecular orbital (LUMO), localized in the Keggin anion. Photoluminescence studies show that the fluorescent properties of the 1-naphthylmethylphosphonate group are quenched upon its incorporation into the inorganic oxo-tungstate skeleton. The solution stability of the hybrid clusters has been evaluated by a combination of 1H-, 13C- and 31P-Nuclear Magnetic Resonance spectroscopy and Electrospray Ionization-Mass Spectrometry. The hybrid polyanion [H(POC11H9)2(α-HBW11O39)]3− (1) herein constitutes the first structurally characterized organo-p-block containing borotungstate, and hence it confirms that this strategy for the organic functionalization of polyoxometalate clusters can be applied to new platforms belonging to the family of group-13 heteropolyoxotungstates. Full article
(This article belongs to the Special Issue Organophosphorus Chemistry 2016)
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Open AccessArticle β,β-Isomer of Open-Wells–Dawson Polyoxometalate Containing a Tetra-Iron(III) Hydroxide Cluster: [{Fe4(H2O)(OH)5}(β,β-Si2W18O66)]9−
Inorganics 2016, 4(2), 15; doi:10.3390/inorganics4020015
Received: 15 April 2016 / Revised: 7 May 2016 / Accepted: 9 May 2016 / Published: 17 May 2016
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Abstract
The β,β-isomer of open-Wells–Dawson polyoxometalate (POM) containing a tetra-iron(III) cluster, K9[{Fe4(H2O)(OH)5}(β,β-Si2W18O66)]·17H2O (potassium salt of β,β-Fe4-open), was synthesized by reacting Na9H[A-β-SiW9O34
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The β,β-isomer of open-Wells–Dawson polyoxometalate (POM) containing a tetra-iron(III) cluster, K9[{Fe4(H2O)(OH)5}(β,β-Si2W18O66)]·17H2O (potassium salt of β,β-Fe4-open), was synthesized by reacting Na9H[A-β-SiW9O34]·23H2O with FeCl3·6H2O at pH 3, and characterized by X-ray crystallography, FTIR, elemental analysis, TG/DTA, UV–Vis, and cyclic voltammetry. X-ray crystallography revealed that the {Fe3+4(H2O)(OH)5}7+ cluster was included in the open pocket of the β,β-type open-Wells–Dawson polyanion [β,β-Si2W18O66]16− formed by the fusion of two trilacunary β-Keggin POMs, [A-β-SiW9O34]10−, via two W–O–W bonds. The β,β-open-Wells–Dawson polyanion corresponds to an open structure of the standard γ-Wells–Dawson POM. β,β-Fe4-open is the first example of the compound containing a geometrical isomer of α,α-open-Wells–Dawson structural POM. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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Open AccessArticle Synthesis, Structure, and Characterization of In10-Containing Open-Wells–Dawson Polyoxometalate
Inorganics 2016, 4(2), 16; doi:10.3390/inorganics4020016
Received: 12 April 2016 / Revised: 7 May 2016 / Accepted: 10 May 2016 / Published: 17 May 2016
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Abstract
We have successfully synthesized K17{[{KIn2(μ-OH)2}(α,α-Si2W18O66)]2[In6(μ-OH)13(H2O)8]}·35H2O (potassium salt of In10-open), an open-Wells–Dawson polyoxometalate (POM) containing ten indium metal
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We have successfully synthesized K17{[{KIn2(μ-OH)2}(α,α-Si2W18O66)]2[In6(μ-OH)13(H2O)8]}·35H2O (potassium salt of In10-open), an open-Wells–Dawson polyoxometalate (POM) containing ten indium metal atoms. This novel compound was characterized by X-ray crystallography, 29Si NMR, FTIR, complete elemental analysis, and TG/DTA. X-ray crystallography results for {[{KIn2(μ-OH)2}(α,α-Si2W18O66)]2[In6(μ-OH)13(H2O)8]}17− (In10-open) revealed two open-Wells–Dawson units containing two In3+ ions and a K+ ion, [{KIn2(μ-OH)2}(α,α-Si2W18O66)]11−, connected by an In6-hydroxide cluster moiety, [In6(μ-OH)13(H2O)8]5+. In10-open is the first example of an open-Wells–Dawson POM containing a fifth-period element. Moreover, to the best of our knowledge, it exhibits the highest nuclearity among the indium-containing POMs reported to date. Full article
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Open AccessArticle Olivine-Based Blended Compounds as Positive Electrodes for Lithium Batteries
Inorganics 2016, 4(2), 17; doi:10.3390/inorganics4020017
Received: 15 April 2016 / Revised: 23 May 2016 / Accepted: 24 May 2016 / Published: 31 May 2016
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Abstract
Blended cathode materials made by mixing LiFePO4 (LFP) with LiMnPO4 (LMP) or LiNi1/3Mn1/3Co1/3O2 (NMC) that exhibit either high specific energy and high rate capability were investigated. The layered blend LMP–LFP and the physically mixed
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Blended cathode materials made by mixing LiFePO4 (LFP) with LiMnPO4 (LMP) or LiNi1/3Mn1/3Co1/3O2 (NMC) that exhibit either high specific energy and high rate capability were investigated. The layered blend LMP–LFP and the physically mixed blend NMC–LFP are evaluated in terms of particle morphology and electrochemical performance. Results indicate that the LMP–LFP (66:33) blend has a better discharge rate than the LiMn1−yFeyPO4 with the same composition (y = 0.33), and NMC–LFP (70:30) delivers a remarkable stable capacity over 125 cycles. Finally, in situ voltage measurement methods were applied for the evaluation of the phase evolution of blended cathodes and gradual changes in cell behavior upon cycling. We also discuss through these examples the promising development of blends as future electrodes for new generations of Li-ion batteries. Full article
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Open AccessArticle Tetrapropylammonium Occlusion in Nanoaggregates of Precursor of Silicalite-1 Zeolite Studied by 1H and 13C NMR
Inorganics 2016, 4(2), 18; doi:10.3390/inorganics4020018
Received: 23 April 2016 / Revised: 18 May 2016 / Accepted: 24 May 2016 / Published: 1 June 2016
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Abstract
The dynamic behavior of tetrapropylammonium (TPA) cations in the clear precursor sols for silicalite synthesis has been investigated by 1H diffusion ordered spectroscopy (DOSY), T1, T2, and T1H relaxation, as well as 1H→13
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The dynamic behavior of tetrapropylammonium (TPA) cations in the clear precursor sols for silicalite synthesis has been investigated by 1H diffusion ordered spectroscopy (DOSY), T1, T2, and T 1H relaxation, as well as 1H→13C cross polarization (CP) nuclear magnetic resonance. The DOSY NMR experiments showed the presence of strong solute–solvent interactions in concentrated sols, which are decreasing upon dilution. Similarities in dependence of diffusion coefficients with fractional power of the viscosity constant observed for nanoparticles, TPA cations and water led to the conclusion that they aggregate as anisotropic silicate-TPA particles. Relaxation studies as well as 1H→13C CP experiments provide information on dynamic properties of ethanol, water and TPA cations, which are function of silicate aggregates. The general tendency showed that the presence of silicate as oligomers and particles decreases the relaxation times, in particular T2 and T1ρH, as a consequence of involvement of these latter in ion-pairing interactions with water-solvated TPA molecules slowing down their mobility. Furthermore, from the 1H→13C CP dynamics curve profiles a change in the CP transfer regime was observed from fast (TCH << T1ρH) for solutions without silicates to moderate (TCH~T1ρH) when silicates are interacting with the TPA cations that may reflect the occlusion of TPA into flexible silicate hydrate aggregates. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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Open AccessCommunication Monoanionic Tin Oligomers Featuring Sn–Sn or Sn–Pb Bonds: Synthesis and Characterization of a Tris(Triheteroarylstannyl)Stannate and -Plumbate
Inorganics 2016, 4(2), 19; doi:10.3390/inorganics4020019
Received: 20 May 2016 / Revised: 12 June 2016 / Accepted: 14 June 2016 / Published: 20 June 2016
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Abstract
The reaction of the lithium tris(2-pyridyl)stannate [LiSn(2-py6OtBu)3] (py6OtBu = C5H3N-6-OtBu), 1, with the element(II) amides E{N(SiMe3)2}2 (E = Sn, Pb) afforded complexes
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The reaction of the lithium tris(2-pyridyl)stannate [LiSn(2-py6OtBu)3] (py6OtBu = C5H3N-6-OtBu), 1, with the element(II) amides E{N(SiMe3)2}2 (E = Sn, Pb) afforded complexes [LiE{Sn(2-py6OtBu)3}3] for E = Sn (2) and E = Pb (3), which reveal three Sn–E bonds each. Compounds 2 and 3 have been characterized by solution NMR spectroscopy and X-ray crystallographic studies. Large 1J(119Sn–119/117Sn) as well as 1J(207Pb–119/117Sn) coupling constants confirm their structural integrity in solution. However, contrary to 2, complex 3 slowly disintegrates in solution to give elemental lead and the hexaheteroarylditin [Sn(2-py6OtBu)3]2 (4). Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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Review

Jump to: Research

Open AccessReview Adsorption of Water on Two-Dimensional Crystals: Water/Graphene and Water/Silicatene
Inorganics 2016, 4(2), 10; doi:10.3390/inorganics4020010
Received: 9 March 2016 / Revised: 14 April 2016 / Accepted: 18 April 2016 / Published: 25 April 2016
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Abstract
The adsorption of water on solid surfaces is a scientific evergreen which again recently prompted considerable attention in the materials, nano-, and surface science communities, respectively, due to conflicting evidence presented in the most highly regarded scientific journals. This mini review is a
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The adsorption of water on solid surfaces is a scientific evergreen which again recently prompted considerable attention in the materials, nano-, and surface science communities, respectively, due to conflicting evidence presented in the most highly regarded scientific journals. This mini review is a brief and personal perspective of the current literature (and our own data) about water adsorption for two examples, namely graphene and silicatene, which are both two-dimensional (2D) crystals. Silicatene, an inorganic companion of graphene, is intriguing as it presents us with the possibility to synthesize a 2D analog to zeolites by doping this crystalline silicon film. The wettability by water and whether or not support effects of epitaxial 2D crystals are present is of concern. Regarding applications: some 2D crystals appear promising for the hydrogen evolution reaction, i.e., hydrogen generation from water; a functionalization of graphene (by oxygen/water) to graphene oxide may be interesting for metal-free catalysis; the latest highlight in this field appears to be “icephobicity”, an application related to the hydrophobicity of surfaces. Full article
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Open AccessReview Manganese and Iron Catalysts in Alkyd Paints and Coatings
Inorganics 2016, 4(2), 11; doi:10.3390/inorganics4020011
Received: 25 March 2016 / Revised: 20 April 2016 / Accepted: 22 April 2016 / Published: 29 April 2016
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Abstract
Many paint, ink and coating formulations contain alkyd-based resins which cure via autoxidation mechanisms. Whilst cobalt-soaps have been used for many decades, there is a continuing and accelerating desire by paint companies to develop alternatives for the cobalt soaps, due to likely classification
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Many paint, ink and coating formulations contain alkyd-based resins which cure via autoxidation mechanisms. Whilst cobalt-soaps have been used for many decades, there is a continuing and accelerating desire by paint companies to develop alternatives for the cobalt soaps, due to likely classification as carcinogens under the REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) legislation. Alternative driers, for example manganese and iron soaps, have been applied for this purpose. However, relatively poor curing capabilities make it necessary to increase the level of metal salts to such a level that often coloring of the paint formulation occurs. More recent developments include the application of manganese and iron complexes with a variety of organic ligands. This review will discuss the chemistry of alkyd resin curing, the applications and reactions of cobalt-soaps as curing agents, and, subsequently, the paint drying aspects and mechanisms of (model) alkyd curing using manganese and iron catalysts. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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Open AccessReview Advances in Engineered Hemoproteins that Promote Biocatalysis
Inorganics 2016, 4(2), 12; doi:10.3390/inorganics4020012
Received: 31 March 2016 / Revised: 22 April 2016 / Accepted: 26 April 2016 / Published: 4 May 2016
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Abstract
Some hemoproteins have the structural robustness to withstand extraction of the heme cofactor and replacement with a heme analog. Recent reports have reignited interest and exploration in this field by demonstrating the versatility of these systems. Heme binding proteins can be utilized as
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Some hemoproteins have the structural robustness to withstand extraction of the heme cofactor and replacement with a heme analog. Recent reports have reignited interest and exploration in this field by demonstrating the versatility of these systems. Heme binding proteins can be utilized as protein scaffolds to support heme analogs that can facilitate new reactivity by noncovalent bonding at the heme-binding site utilizing the proximal ligand for support. These substituted hemoproteins have the capability to enhance catalytic reactivity and functionality comparatively to their native forms. This review will focus on progress and recent advances of artificially engineered hemoproteins utilized as a new target for the development of biocatalysts. Full article
(This article belongs to the Special Issue Traversing the Boundaries of Inorganic Chemistry)
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Open AccessReview Synthesis, Characterization and Applications in Catalysis of Polyoxometalate/Zeolite Composites
Inorganics 2016, 4(2), 13; doi:10.3390/inorganics4020013
Received: 7 March 2016 / Revised: 22 April 2016 / Accepted: 26 April 2016 / Published: 4 May 2016
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Abstract
An overview of the synthesis, characterization and catalytic applications of polyoxometalates/zeolites composites is given. The solids obtained by direct synthesis of the polyoxometalate in the presence of the zeolite are first described with their applications in catalysis. Those obtained by a direct mixing
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An overview of the synthesis, characterization and catalytic applications of polyoxometalates/zeolites composites is given. The solids obtained by direct synthesis of the polyoxometalate in the presence of the zeolite are first described with their applications in catalysis. Those obtained by a direct mixing of the two components are then reviewed. In all cases, special care is taken in the localization of the polyoxometalate, inside the zeolite crystal, in mesopores or at the external surface of the crystals, as deduced from the characterization methods. Full article
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