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See detailDéfinition de propriétés acido-basiques dans les liquides ioniques de seconde génération
Robert, Thierry ULg

Doctoral thesis (2013)

The ionic liquids are salts having the particularity of being molten at temperatures lower than 100 °C. Consequently, these new solvents mainly made up of ions have original physicochemical properties ... [more ▼]

The ionic liquids are salts having the particularity of being molten at temperatures lower than 100 °C. Consequently, these new solvents mainly made up of ions have original physicochemical properties. Within a few years, the ionic liquids passed from a laboratory curiosity to a true field of research impossible to circumvent, currently in full rise. Indeed, the replacement of usual organic solvents in catalytic and/or separation processes by these neoteric solvents offers many advantages but also new opportunities for the “Green Chemistry”. However, the systematic exploitation of the ionic liquids as reactional media rests in particular on the understanding of their chemical properties, which for some of them are still scarcely known, such as the acidity for example. This thesis thus aims to undertake a study of the acido-basic properties of (and in) these solvents, and more particularly to determine the accessible levels of acidity for acid solutions (with added HOTf or HNTf2) in second generation ionic liquids such as [HNEt3][NTf2], [BMIm][NTf2], [BHIm][NTf2], [BMIm][BF4], [BMIm][OTf], [BMIm][PF6] and [BMIm][SbF6]. In order to evaluate these acidity levels, we propose two different methods, each one resting on an extra-thermodynamic assumption. The first, the Hammett acidity function H0, is based on the protonation equilibrium of indicators whose pKa's are proposed as solvent independent. The second, the Strehlow potentiometric function R0(H+), consists in measuring, in a given solvent, the electrochemical potential of the proton compared to the ferricinium/ferrocene redox couple whose potential is supposed to be independent of the solvent, and then to refer it versus the Normal Hydrogen Electrode (NHE) in water. The two methods lead to the same conclusions. Firstly, the ionic liquids are generally contaminated by residual basic impurities (from solvents needed for the synthesis…) which need to be neutralized before reaching the acidity characteristic of the medium. The levels of acidity then obtained are very high and can reach values as high as R00(H+) = -10 in the case of [BMIm][BF4]. Then, the accessible level of acidity in an ionic liquid depends mainly on the nature of its anion, and not of that of its cation. We thus obtain the following classification, by decreasing acidity: [PF6-] > [BF4-] > [NTf2-] > [OTf-], indicating that the triflate is the more solvating anion It was found however that the Hammett acidity function led, for the same concentration in acid, to different levels of acidity, depending on the indicator used. The ionic liquids would consequently be media less dissociating than estimated in the literature and the Hammett function would then be related to an apparent acidity (H0)app, underestimating the real acidity. Finally, a difference in acidity between HNTf2 and HOTf is observed in [BMIm][NTf2] and [BMIm][OTf], HNTf2 showing an acidic character stronger than HOTf. On the other hand, in [BMIm][OTf] these two acids show the same acidity since that of HNTf2 has been leveled by solvent. [less ▲]

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See detailDifferentiation between stoichiometric and anticatalytic antioxidant properties of benzoic acid analogues: A structure/redox potential relationship study.
Franck, Thierry ULg; Mouithys-Mickalad, Ange ULg; Robert, Thierry ULg et al

in Chemico-biological interactions (2013), 206(2), 194-203

We investigated the antioxidant activities of some phenolic acid derivatives on a cell free system and on cellular and enzymatic models involved in inflammation. The stoichiometric antioxidant activities ... [more ▼]

We investigated the antioxidant activities of some phenolic acid derivatives on a cell free system and on cellular and enzymatic models involved in inflammation. The stoichiometric antioxidant activities of phenolic acid derivatives were studied by measuring their capacity to scavenge the radical cation 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS+) and reactive oxygen species (ROS) produced by stimulated neutrophils. The anticatalytic antioxidant capacity of the molecules was evaluated on the activity of myeloperoxidase (MPO), an oxidant enzyme present in and released by the primary granules of neutrophils. The ROS produced by PMA-stimulated neutrophils were measured by lucigenin-enhanced chemiluminescence (CL) and the potential interaction of the molecules with MPO was investigated without interferences due to medium by Specific Immuno-Extraction Followed by Enzyme Detection (SIEFED). The antioxidant activities of the phenolic compounds were correlated to their redox potentials measured by differential pulse voltammetry (DPV), and discussed in relation to their molecular structure. The ability of the phenolic molecules to scavenge ABTS radicals and ROS derived from neutrophils was inversely correlated to their increased redox potential. The number of hydroxyl groups (three) and their position (catechol) were essential for their efficacy as stoichiometric antioxidants or scavengers. On MPO activity, the inhibitory capacity of the molecules was not really correlated with their redox potential. Likewise, for the inhibition of MPO activity the number of OH groups and mainly the elongation of the carboxylic group were essential, probably by facilitating the interaction with the active site or the structure of the enzyme. The redox potential measurement, combined with ABTS and CL techniques, seems to be a good technique to select stoichiometric antioxidants but not anticatalytic ones, as seen for MPO, what rather involves a direct interaction with the enzyme. [less ▲]

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See detailAntioxidant and anti-inflammatory like properties of benzoic acid analogs on the oxidant response of neutrophils: structure/redox potential relationship study.
Franck, Thierry ULg; Mouithys-Mickalad, Ange ULg; Robert, Thierry ULg et al

in Free Radical Biology & Medicine (2012), 53(supplement 1),

We investigated the antioxidant capacity of phenolic acid derivatives by measuring their capacity to prevent ABTS oxidation and evaluating their anti-inflammatory like-properties on the oxidant response ... [more ▼]

We investigated the antioxidant capacity of phenolic acid derivatives by measuring their capacity to prevent ABTS oxidation and evaluating their anti-inflammatory like-properties on the oxidant response of neutrophils, especially on superoxide anion production and the activity of myeloperoxidase (MPO), an oxidant enzyme present and released by the primary granules of neutrophils. The superoxide anion production by PMA-stimulated neutrophils was measured by lucigenin-enhanced chimiluminescence (CL) and the activity of MPO by SIEFED to study the potential interaction of a molecule with the enzyme without interferences due to medium. The antioxidant and anti-inflammatory activities of the phenolic compounds were correlated to their redox potentials measured by voltammetry method, and discussed in relation to their molecular structure. The ability of the phenolic molecules to decrease ABTS oxidation and CL production was inversely correlated to their redox potential increasing as follows: propyl gallate > gallic acid > caffeic acid > 3,4-dihydroxybenzoic acid > ferulic acid > syringic acid > 2,6-dihydroxybenzoic acid > salicylic acid > benzoic acid. The number of hydroxyl groups (3) and their position (catechol) were essential for the efficacy of the molecules as stoichiometric antioxidants or scavengers. On MPO activity, the inhibitory capacity of the molecules was not really correlated with their redox potential and increased as follows: gallic acid > caffeic acid > 2,6-dihydroxybenzoic acid > propyl gallate > ferulic acid = syringic acid > 3,4-dihydroxybenzoic acid = salicylic acid > benzoic acid. The number of OH groups and the elongation of the carboxyl group were essential for the inhibition of MPO activity, probably by facilitating the interaction with the MPO active site or structure. The redox potential measurement seems to be a good technique to select stoichiometric antioxidants, but not anti-catalytic ones. [less ▲]

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See detailIonic Liquids: Past, Present and Future
Robert, Thierry ULg

Scientific conference (2011, August 24)

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See detailAbout Accessible Acidity Level in Ionic Liquids
Robert, Thierry ULg; Gilbert, Bernard ULg

Scientific conference (2011, April 27)

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See detailHammett Acidity Scale in Ionic Liquids : An Indication of Their Weak Dissociating Character
Robert, Thierry ULg; Magna, Lionel; Olivier-Bourbigou, Hélène et al

Poster (2010, August)

Ionic liquids are salts with the particularity to exhibit melting points near room temperature (below 100°C, by convention) with no vapour tension. For this last reason, ionic liquids are sometimes called ... [more ▼]

Ionic liquids are salts with the particularity to exhibit melting points near room temperature (below 100°C, by convention) with no vapour tension. For this last reason, ionic liquids are sometimes called “green solvents”. In addition, their exclusive materials and solvent properties has led to an amazing increase of interest from both academic and industrial community, confirmed by the explosion of the number of published papers in the last decade. The many combinations of organic and inorganic cations and anions allow an infinity of new ionic solvents then permitting the selection of the desired properties for a given application. Nevertheless, it is impossible to investigate all these combinations and the unusual complexity of these new solvents gives rise to many controversies. Consequently, the development of the general rules for understanding the chemistry in ionic liquids is crucial. A fundamental property of solvent is its solvating power, for instance towards the proton. Therefore, we are interested to investigate the acid-base properties in ionic liquids in order to ultimately find a correlation with the acidic catalysis activity. We then have proposed a colorimetric method to determine the acidity levels accessible in these new media: the Hammett acidity function H0. This spectroscopic method is based on the protonation equilibrium for a family of coloured indicator with pKa’s assumed as solvent independent (following the Hammett proposition). This presentation will summarize our Hammett acidity measurements in several ionic liquids. - At first, we will show that it is possible to evaluate the Hammett acidity function with two different coloured indicators, in the same ionic liquid. Since the Hammett acidity of a given mixture was found to depend on the choosen coloured indicator, this suggests the formation of ions associations in ionic liquids. As a result, the ionic liquids are clearly not as dissociating as initially thought and the Hammett acidity function is in fact an apparent function, underestimating the real acidity level. - The apparent acidity functions have then been compared for several ionic liquids to which an acid has been added ([BMIm][NTf2], [BMIm][BF4], [BMIm][OTf], [BHIm][NTf2], [BMIm][PF6], [HNEt3][NTf2]). The conclusions are as follows: 1) the accessible acidity level is not influenced by the nature of the cation; 2) on the contrary, the nature of anion is very critical and the solvating power towards the proton follows the order: OTf- > NTf2- > BF4- > PF6-. The more the proton is solvated, the less it is acidic. - Finally, the difference of acidity of two acids, HOTf and HNTf2 (both strong acids in water), has been investigated in [BMIm][BF4], [BMIm][NTf2] and [BMIm][OTf]. In [BMIm][OTf], these two acids show the same acidity (they behave as strong acids) due to the solvent levelling effect; on the other hand, in [BMIm][NTf2] and [BMIm][BF4] allowing higher acidity levels, HNTf2 is stronger than HOTf . The observed difference is also another indication of the lower proton solvation in [BMIm][BF4] or [BMIm][NTf2] versus that in [BMIm][OTf]. [less ▲]

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See detailQuantitative Evaluation of Imputities in Ionic Liquids
Robert, Thierry ULg; Olivier-Bourbigou, Hélène; Gilbert, Bernard ULg

Poster (2010, March)

Since several years, our laboratory is studying the acidity in ionic liquids and showed that very acidic levels can be reached in these media when a strong acid is added. These acidity levels were ... [more ▼]

Since several years, our laboratory is studying the acidity in ionic liquids and showed that very acidic levels can be reached in these media when a strong acid is added. These acidity levels were determined using Hammett acidity1 (spectroscopic method) and Strehlow acidity2 (potentiometric method) measurements. Considering the attainable acidity levels, it turns out that the purity of these ionic solvents is very critical because all impurities (i.e methylimidazole, water, acetone, chloride …) can act as (strong) bases. Therefore, it is imperative to quantify these impurities to obtain reproducible results. [less ▲]

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See detailThe Hydrogen Electrode in Ionic Liquids: Acidity Measurements and Titrations
Robert, Thierry ULg; Malherbe, Cédric ULg; Magna, lionel et al

Poster (2010, March)

The acidity level in ILs containing acid was first determined using the Hammett acidity function (H0)1-2 in our laboratory. It was demonstrated that this attainable acidity, extending from -3 to -8, is ... [more ▼]

The acidity level in ILs containing acid was first determined using the Hammett acidity function (H0)1-2 in our laboratory. It was demonstrated that this attainable acidity, extending from -3 to -8, is exclusively depending of the nature of anion and follow the order: PF6 > BF4 > NTf2 > OTf. Nevertheless, the Hammett acidity function is an apparent function in this media and must then be corrected for. Consequently, in a second step, we tried to evaluate directly the proton activity from the determination of a potentiometric acidity function (R0) based on the extrathermodynamic Strehlow assumption.3 Therefore, the equilibrium potential of the H+/H2 couple was measured with an hydrogen electrode versus the ferricinium/ferrocene couple for which the potential is considered as independent of the solvent. [less ▲]

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See detailAcidity in Ionic liquids: from the determination of an acidity scale to the application in catalytic reactions
Olivier-Bourbigou, Hélène; Gilbert, Bernard ULg; Magna, Lionel et al

Conference (2009)

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See detailTentative determination of the acidity level in room temperature ionic liquids by electrochemical methods
Malherbe, Cédric ULg; Robert, Thierry ULg; Magna, Lionel et al

in ECS Transactions (2009), 16(49), 3

In our attempt to evaluate the acidity levels reached by acidified ionic liquids (BMImBF4, BMImNTf2 and BMImOTf + HOTf or HNTf2), the uncertainty on the pKas of the indicators needed for the Hammett ... [more ▼]

In our attempt to evaluate the acidity levels reached by acidified ionic liquids (BMImBF4, BMImNTf2 and BMImOTf + HOTf or HNTf2), the uncertainty on the pKas of the indicators needed for the Hammett spectrophotometric procedure was pointed out. As consequence another method is proposed, based on the H+/H2 couple potential measurement. In this purpose, if dynamic methods failed mainly for lack of sufficient reversibility, potentiometry with a hydrogen electrode gave meaningful results. The R0(H+) Strehlow function, could be calculated, using the Fc+-Fc couple as reference assumed as solvent independent. The obtained results show that i) the acidities are much higher than those in water; ii) the acidities measured by the hydrogen electrode are higher than those measured by the Hammett method; iii) the sequence of acidities for solutions of similar content of added acid is still BF4 > NTf2 > OTf as previously measured with the Hammett method. [less ▲]

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See detailAbout the Acidity-Catalytic Activity Relationship in Ionic Liquids: Application to the Selective Isobutene Dimerization
Magna, Lionel; Bildé, Jean; Olivier-Bourbigou, Hélène et al

in Oil & Gas Science and Technology (2009), 64(6), 669

The Brønsted acidity level was evaluated for ionic liquids to which a strong acid has been added. As a first approach, the evaluation method was based on the determination of the Hammett acidity functions ... [more ▼]

The Brønsted acidity level was evaluated for ionic liquids to which a strong acid has been added. As a first approach, the evaluation method was based on the determination of the Hammett acidity functions H0, using UV-Visible spectroscopy. The acidity of protons is mainly determined by their solvation state and consequently, the properties of protons depend on both the nature of the solvent and the nature and concentration of the acid. An apparent acidity scale was defined following this principle. It was found that, for the investigated ionic liquids, the cation does not play a dominant role on the acidity level ([BMIm] ~ [BHIm] ~ [HNEt3]), whereas changing the nature of the anion of the ionic liquid may lead to very different acidities ([SbF6] > [PF6] > [BF4] > [NTf2] > [OTf]). This “acidity scale” was tentatively compared with an “activity scale” obtained for the dimerization of isobutene into isooctenes. The tendencies concerning the cation effect were confirmed ([BMIm] ~ [BuMePyrr] ~ [HNEt3]). The anion effect in only partially validated with a different behaviour for NTf2 type ionic liquids ([NTf2] ~ [SbF6] > [PF6] ~ [BF4] > [OTf]). By an adequate choice of the ionic liquid, selectivity for isobutene dimers can reach 88 wt% (at 70% isobutene conversion) with possible recycling of the catalytic system without loss of activity and selectivity. [less ▲]

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See detailA Comparison of the Acidity Levels in Room-Temperature Ionic Liquids
Robert, Thierry ULg; Magna, Lionel; Olivier-Bourbigou, Hélène et al

in Journal of the Electrochemical Society (2009), 156(9), 115

The Broensted acidity level was evaluated for several ionic liqs. ([BMIm][BF4], [BMIm][PF6], [BMIm][SbF6], [BMIm][OTf], [BMIm][NTf2], [HNET3][NTf2], and [HBIm][NTf2]) to which a strong acid, such as HNTf2 ... [more ▼]

The Broensted acidity level was evaluated for several ionic liqs. ([BMIm][BF4], [BMIm][PF6], [BMIm][SbF6], [BMIm][OTf], [BMIm][NTf2], [HNET3][NTf2], and [HBIm][NTf2]) to which a strong acid, such as HNTf2 [NTf2=N(CF3SO2)2] and HOTf (OTf=CF3SO3), has been added. The main purpose is to tentatively measure the influence on the resulting acidity of (i) the solvent anion or cation structure and (ii) the added acid nature. The evaluation method is based on the detn. of the Hammett acidity functions H0 using UV/visible spectroscopy. The acidity of protons is mainly detd. by their solvation state, and consequently, the properties of protons depend on both the nature of the solvent and the nature and concn. of the acid. In practice, for the investigated ionic liqs., the cation as well as the added acid nature does not play a dominant role, whereas changing the anion nature may lead to very different acidities. Indeed, for a similar content of added acid, the measured acidity levels are in the order PF6- > BF4- > NTf2- > OTf-. The problems of the influence of impurities on the final acidity and of the dissocg. character of the ionic liq. are addressed. [less ▲]

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See detailAbout the Acidity Level in Room Temperature Ionic Liquids
Robert, Thierry ULg; Olivier-Bourbigou, Hélène; Magna, Lionel et al

in ECS Transactions (2007), 3(35), 71

The Brønsted acidity level was evaluated for ionic liquids to which a strong acid has been added. The evaluation method is based on the determination of the Hammett acidity functions H0, using UV-Visible ... [more ▼]

The Brønsted acidity level was evaluated for ionic liquids to which a strong acid has been added. The evaluation method is based on the determination of the Hammett acidity functions H0, using UV-Visible spectroscopy. The acidity of protons is mainly determined by their solvation state and consequently, the properties of protons depend on both the nature of the solvent and the nature and concentration of the acid. In practice, it was found that, for the investigated ionic liquids, the cation as well as the added acid nature does not play a dominant role, whereas changing the anion nature may lead to very different acidities. Indeed, for a similar content of added acid, the measured acidity levels are in the order: PF6- > BF4- > NTf2- > OTf-. The problems of the influence of impurities on the final acidity and of the weakly dissociating character of the ionic liquid are addressed. [less ▲]

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