Hydrolysis of N‐methyl‐N‐nitroso‐p‐toluenesulphonamide in micellar media

García‐Río, Luis; Hervés, Pablo; Leis, Jaan; Mejuto, J. C.; Pérez‐Juste, Jorge

doi:10.1002/(sici)1099-1395(199808/09)11:8/9<584::aid-poc59>3.3.co;2-6

Cited by 26 publications

(42 citation statements)

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“…Conductivity data were collected at 25°C and 1 kHz with a Wayne-Kerr B905 automatic precision bridge (WKR, England) using a Ingold conductivity cell type 980-K19/120 with platinum electrodes and a cell constant of 1.004 cm À1 , according to literature procedures [22][23][24][25][26][27]. The cell was calibrated with standard Crison KCl solutions of the appropriate concentration range.…”

Section: Conductance Measurementsmentioning

confidence: 99%

Dimeric and monomeric surfactants derived from sulfur-containing amino acids

Faustino

Calado

García‐Río

2010

Journal of Colloid and Interface Science

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Section: Conductance Measurementsmentioning

confidence: 99%

Dimeric and monomeric surfactants derived from sulfur-containing amino acids

Faustino

Calado

García‐Río

2010

Journal of Colloid and Interface Science

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“…Cyclodextrin complexation can give beneficial modification of guest molecules such as solubility enhancement, stabilization of labile guests, physical isolation of incompatible compounds and control of volatility and sublimation. Furthermore, the chemical reactivity of the guest is often changed by the incorporation into the cavity [16,17].…”

Section: Introductionmentioning

confidence: 99%

NMR diffusometry and conductometry study of the host–guest association between β-cyclodextrin and dodecane 1,12-bis(trimethylammonium bromide)

Cabaleiro-Lago

Nilsson²,

Valente³

et al. 2006

Journal of Colloid and Interface Science

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“…This cannot just be an effect of changing the medium as the Kemp elimination is known to be insensitive to ionic strength 29,30 and the addition of chloride has no effect on the rate of the background reaction. 32 [We note that, as well as being present in ~180 fold excess relative to hydroxide in solution at the pD of the experiment, chloride ions are preferentially bound to the interface region of cationic micelles (typically 10 fold 32,38,39 ) as they are less strongly solvated by water than hydroxide. This explains why the reduction in concentration of the catalytically active cage in the presence of chloride is greater than the ratio of the anion concentrations].…”

mentioning

confidence: 99%

Highly efficient catalysis of the Kemp elimination in the cavity of a cubic coordination cage

et al. 2016

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The hollow cavities of coordination cages can provide an environment for enzyme-like catalytic reactions of small-molecule guests . We report here a new example (catalysis of the Kemp elimination -reaction of benzisoxazole with hydroxide to form 2-cyanophenolate) in the cavity of a water-soluble M8L12 coordination cage, with two features of particular interest. Firstly, the rate enhancement is amongst the largest so far observed: at pD 8.3, kcat/kuncat is 2 x 10 5 , due to the accumulation of a high concentration of partially desolvated hydroxide ions around the bound guest arising from ion-pairing with the 16+ cage. Secondly, the catalysis is based on two orthogonal interactions: (i) hydrophobic binding of benzisoxazole in the cavity, and (ii) polar binding of hydroxide ions to sites on the cage surface, both of which were established by competition experiments. Hundreds of turnovers occur with no loss of activity due to expulsion of the hydrophilic, anionic product. 2Since the realisation that hollow molecular container molecules can accommodate guest molecules in their central cavities, 1-3 their ability to modify the reactivity of their bound guests has been of great interest. [4][5][6][7][8] Well known examples include Cram's stabilisation of highly-reactive cyclobutadiene; 4 Fujita's 'ship-in-a-bottle' synthesis of cyclic silanol oligomers; 5 Nitschke's stabilisation of P4 in a tetrahedral cage; 6 and the demonstration of unusual regioselectivity in a Diels-Alder reaction when the two reacting molecules are co-confined in a host cavity. 7 The ultimate expression of this behaviour is efficient catalysis of a reaction occurring in the cavity of a container molecule. 8 These synthetic systems have the potential to achieve the selectivity and catalytic rate enhancements displayed by biological systems. For example, artificial container molecules provide relatively rigid and hydrophobic central cavities that may mimic binding pockets in enzymes. These containers may be purely organic hydrogen-bonded assemblies (such as Rebek's 'softball' dimer) 9 or may be metal-ligand polyhedral coordination cages [such as Fujita's Pd6/tris(pyridyl)triazine cage]. 10 Coordination cages offer particular promise in this field because of the ease with which they can be formed by a self-assembly process from very simple component parts, using the predictable coordination geometries of metal ions to provide the three-dimensional ordering of the components which generates the necessary cavity. [1][2][3]8,11,12 In order for a container molecule to act as an efficient catalyst it needs to (i) recognise and bind the guest(s); (ii) accelerate the reaction by increasing the local concentration of reactants and/or stabilising the transition state; and (iii) expel the product to allow catalytic turnover. 8 Guest binding in cage cavities has been very well studied and is becoming a mature field, 1 to the extent that a modeling tool for quantitative prediction of guest binding has recently been reported by us. 13 For a reaction of t...

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Hydrolysis of N‐methyl‐N‐nitroso‐p‐toluenesulphonamide in micellar media

Cited by 26 publications

References 0 publications

Dimeric and monomeric surfactants derived from sulfur-containing amino acids

Dimeric and monomeric surfactants derived from sulfur-containing amino acids

NMR diffusometry and conductometry study of the host–guest association between β-cyclodextrin and dodecane 1,12-bis(trimethylammonium bromide)

Highly efficient catalysis of the Kemp elimination in the cavity of a cubic coordination cage

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