Temperature-jump rate study of the chemical relaxation of aqueous boric acid solutions

Waton, Gilles; Mallo, P.; Candau, S. J.

doi:10.1021/j150659a032

Cited by 14 publications

(8 citation statements)

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“…Waton et al [7] reported much faster rate constant (1.07 · 10 7 M À1 s À1 ) for the same reaction which was obtained by the relaxation method with thymol blue as indicator. Pizer and Tihal [8] stated that the addition of OH À to phenylboronic acid (PhB(OH) 2 ) is much slower than diffusion controlled.…”

supporting

confidence: 53%

“…(1)), especially in the rate of the structural change. Anderson et al [6] performed kinetic studies on polyborate formation by the temperature jump technique and predicted the second-order rate constant ($10 10 M À1 s À1 ) for the forward reaction of boric acid B OH OH B OH + R OH R OH OH --Waton et al [7] reported much faster rate constant (1.07 · 10 7 M À1 s À1 ) for the same reaction which was obtained by the relaxation method with thymol blue as indicator. Pizer and Tihal [8] stated that the addition of OH À to phenylboronic acid (PhB(OH) 2 ) is much slower than diffusion controlled.…”

mentioning

confidence: 99%

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Direct kinetic measurements for the fast interconversion process between trigonal boronic acid and tetragonal boronate ion at low temperatures

Matsumura

Iwatsuki

Ishihara

2005

Inorganic Chemistry Communications

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supporting

confidence: 53%

mentioning

confidence: 99%

Direct kinetic measurements for the fast interconversion process between trigonal boronic acid and tetragonal boronate ion at low temperatures

Matsumura

Iwatsuki

Ishihara

2005

Inorganic Chemistry Communications

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“…In addition, there have also been studies of borate complexation processes using temperature jump method. 18-20 The rate is 10.7 M −1 s −1 for the reaction between boric acid and H 2 O at 25 °C. To put the observed k on values in perspective, a second order rate constant of 287 M −1 s −1 gives a half life of 3.5 s at 1 mM of starting material concentration, and 3484 s at 1 μM starting material concentration.…”

Section: Resultsmentioning

confidence: 99%

“…However, there are reports that it takes hours before equilibrium is reached. 11, 12 There have been some kinetic studies of the binding between boric acid/boronic acids and diol by using NMR, 13-15 stopped-flow 16, 17 and temperature jump 15, 18-20 techniques. However, there has never been a detailed study of exactly how fast the binding process occurs between boronic acids with carbohydrates.…”

Section: Introductionmentioning

confidence: 99%

Probing the general time scale question of boronic acid binding with sugars in aqueous solution at physiological pH

Laughlin

Ying-ji

et al. 2012

Bioorganic & Medicinal Chemistry

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The boronic acid group is widely used in chemosensor design due to its ability to reversibly bind diol-containing compounds. The thermodynamic properties of the boronic acid-diol binding process have been investigated extensively. However, there are few studies of the kinetic properties of such binding processes. In this report, stopped-flow method was used for the first time to study the kinetic properties of the binding between three model arylboronic acids, 4-, 5-, and 8-isoquinolinylboronic acids, and various sugars. With all the boronic acid-diol pair sexamined, reactions were complete within seconds. The kon values with various sugars follow the order of D-fructose >D-tagatose>D-mannose >D-glucose. This trend tracks the thermodynamic binding affinities for these sugars and demonstrates that the “on” rate is the key factor determining the binding constant.

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“…Such polyborate species are known to form in solutions where the borate concentration is above 50 mm. [11][12][13][14] The rates of oxygen-isotope exchange increase for most, but not all, structural oxygen atoms in the Ti 2 Nb 8 ion as the amount of borate increases in solution. In Figure 2, the rates of oxygen-isotope exchange for sites C (in dark gray) and site D (in light gray) in the Ti 2 Nb 8 ion are shown with re-spect to total dissolved borate concentration.…”

mentioning

confidence: 99%

Borate Accelerates Rates of Steady Oxygen‐Isotope Exchange for Polyoxoniobate Ions in Water

Villa

Ohlin

Casey

2010

Chemistry A European J

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Understanding simple oxygen-exchange reactions is important to a variety of communities concerned with the chemistry of oxides with water. Limitations in the methods available for studying reactions at these oxide-water interfaces, as well as difficulties in characterizing their structures, have led to the use of polyoxometalates (POMs) as model molecules. POMs are metal oxide ions composed of Group 5 and 6 metals. These ions constitute discrete and often soluble clusters than can be spectroscopically probed with great confidence. In addition, POMs are interesting in their own right, owing to their structural and chemical diversity, and are finding an increasing number of applications. [1][2][3][4][5] We have been investigating the oxygen-isotope-exchange kinetics in these ions and aqueous solution by 17 O-nuclear magnetic resonance (NMR) spectroscopy to help better recognize what controls the molecule-water interface processes on the level of individual oxygen sites.[6-10] These structures were chosen because the isotope-exchange reactions could be followed separately from dissociation or condensation of the structure.Borate is widely used as a pH buffer owing to its low cost and conveniently located pK a . In general, borate buffers are assumed to be inert. Most POMs are anions, as is borate, and it is reasonable to assume that the negative charges of the POM and the borate will minimise interactions in solution. Here we describe the interactions between borate and three different niobium-based POMs. These interactions are interesting in their own right, but also allow us to reconcile observed differences in the oxygen exchange rates between the hexaniobate and hexatantalate ions. [6,7] We observed a large increase in the rates of oxygen-isotope exchange when a borate buffer was employed in ex-

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Temperature-jump rate study of the chemical relaxation of aqueous boric acid solutions

Cited by 14 publications

References 0 publications

Direct kinetic measurements for the fast interconversion process between trigonal boronic acid and tetragonal boronate ion at low temperatures

Direct kinetic measurements for the fast interconversion process between trigonal boronic acid and tetragonal boronate ion at low temperatures

Probing the general time scale question of boronic acid binding with sugars in aqueous solution at physiological pH

Borate Accelerates Rates of Steady Oxygen‐Isotope Exchange for Polyoxoniobate Ions in Water

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