Supplementary Material
Characterization of Alkyldiol-Cyclodextrin Complexes. Acid Denitrosation of N-Methyl-N-nitroso-p-toluenesulfonamide as a Chemical Probe
Figure S1. Influence of [CD] on the pseudo-first order rate constant for the acid denitrosation of MNTS in the absence (x) and presence of different 1,6-hexanodiol concentrations; ( ) 0.013M; ( ) 0.028M; (p) 0.056 M; (r) 0.085 M; (¢) 0.15 M and (£) 0.25M. [HCl]=0.16M, T=25ºC.
Figure S2. Influence of [CD] on the pseudo-first order rate constant for the acid denitrosation of MNTS in the absence (r) and the presence of a constant 0.19 M alcohol concentration; (¢) 1,3-propanediol; (£)1,4-butanediol; ( )1,5-pentanediol and ( )1,6-hexanediol. [HCl]=0.16M, T=25ºC.
Figure S3. Variation of the kobs / kw ratio with the concentration of free cyclodextrin obtained from eq 8 in the presence of 1,2-propanediol, = 1.0 M-1, [HCl]= 0.16 M. The curve represent the fit of eq 1 to the experimental data ( ), the closed squares (¢) corresponds to reaction in the absence of alcohol. Reciprocal plot of kobs as a function of the free cyclodextrin ( ); the line represents the fit to eq 2.
Tables S.1.A_S.1.H to Tables S.8.A_S.8.F. kobs for the acid denitrosation of MNTS in the presence of different cyclodextrin and alcohol concentrations ([MNTS]=3.33×10-5 M, [HCl]=0.16 M), as well as the corresponding calculated values for the free cyclodextrin concentrations obtained by Method A and Method B (denoted as A and B, see text for details).
Table S.9. Slopes of the linear regression between [CDfree]Method A vs [CDfree]Method B for the different alkyl diols, see text for details.
Figure S1. Influence of [CD] on the pseudo-first order rate constant for the acid denitrosation of MNTS in the absence (x) and presence of different 1,6-hexanodiol concentrations; ( ) 0.013M; ( ) 0.028M; (p) 0.056 M; (r) 0.085 M; (¢) 0.15 M and (£) 0.25M. [HCl]=0.16M, T=25ºC.
Figure S2. Influence of [CD] on the pseudo-first order rate constant for the acid denitrosation of MNTS in the absence (r) and the presence of a constant 0.19 M alcohol concentration; (¢) 1,3-propanediol; (£)1,4-butanediol; ( )1,5-pentanediol and ( )1,6-hexanediol. [HCl]=0.16M, T=25ºC.
Figure S3. Variation of the kobs / kw ratio with the concentration of free cyclodextrin obtained from eq 8 in the presence of 1,2-propanediol, = 1.0 M-1, [HCl]= 0.16 M. The curve represent the fit of eq 1 to the experimental data ( ), the closed squares (¢) corresponds to reaction in the absence of alcohol. Reciprocal plot of kobs as a function of the free cyclodextrin ( ); the line represents the fit to eq 2.
Tables S.1.A_S.1.H: kobs for the acid denitrosation of MNTS in the presence of different cyclodextrin and 1,2-hexanediol concentrations ([MNTS]=3.33×10-5 M, [HCl]=0.16 M), as well as the corresponding calculated values for the free cyclodextrin concentrations obtained by Method A and Method B (denoted as A and B, see text for details).
Table S.1.A: [1,2-hexanediol] = 0.020 M
/Table S.1.B: [1,2-hexanediol] = 0.042 M
[CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-1 / [CD]·103 / M / kobs 103 / s-1 / A[CDf]·103 / M / B[CDf]·103 / M / K11 / M-10 / 4.89 / - / - / - / 0 / 4.74 / - / - / -
0.2 / 4.09 / 0.12 / - / - / 0.2 / 4.32 / 0.09 / - / -
0.5 / 3.20 / 0.31 / - / - / 0.5 / 3.55 / 0.22 / - / -
1 / 2.37 / 0.62 / - / - / 1 / 2.86 / 0.44 / - / -
2 / 1.72 / 1.25 / - / - / 2 / 2.10 / 0.88 / - / -
3 / 1.36 / 1.89 / - / - / 3 / 1.68 / 1.34 / - / -
4 / 1.02 / 2.54 / - / - / 4 / 1.34 / 1.80 / - / -
6 / 0.79 / 3.86 / - / - / 6 / 1.05 / 2.75 / - / -
8 / 0.64 / 5.22 / - / - / 8 / 0.86 / 3.72 / - / -
10 / 0.55 / 6.61 / - / - / 10 / 0.68 / 4.47 / - / -
Table S.1.C: [1,2-hexanediol] = 0.054 M
/Table S.1.D: [1,6-hexanediol] = 0.067 M
[CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-1 / [CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-10 / 4.84 / - / - / 0 / 4.74 / - / - / -
0.2 / 4.42 / 0.07 / 0.06 / 41.86 / 0.2 / 4.30 / 0.07 / 0.07 / 29.97
0.5 / 3.66 / 0.18 / 0.21 / 26.19 / 0.5 / 3.74 / 0.16 / 0.17 / 28.49
1 / 3.08 / 0.37 / 0.37 / 32.07 / 1 / 3.16 / 0.33 / 0.32 / 31.70
2 / 2.25 / 0.74 / 0.75 / 32.11 / 2 / 2.29 / 0.66 / 0.69 / 28.80
3 / 1.84 / 1.12 / 1.05 / 35.93 / 3 / 1.90 / 1.00 / 0.97 / 32.36
4 / 1.51 / 1.51 / 1.43 / 35.22 / 4 / 1.65 / 1.35 / 1.21 / 35.88
6 / 1.17 / 2.30 / 2.04 / 39.23 / 6 / 1.24 / 2.05 / 1.82 / 36.41
8 / 0.93 / 3.11 / 2.70 / 40.67 / 8 / 0.94 / 2.73 / 2.60 / 33.69
10 / 0.81 / 3.95 / 3.20 / 45.50 / 10 / 1.09 / 3.51 / - / -
Table S.1.E: [1,2-hexanediol] = 0.080 M
/Table S.1.F: [1,2-hexanediol] = 0.13 M
[CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-1 / [CD]·103 / M / kobs 103 / s-1 / A[CDf]·103 / M / B[CDf]·103 / M / K11 / M-10 / 5.04 / - / - / - / 0 / 4.77 / - / - / -
0.2 / 4.66 / 0.06 / 0.05 / 34.59 / 0.2 / 4.48 / 0.04 / 0.04 / 27.42
0.5 / 4.16 / 0.14 / 0.14 / 33.29 / 0.5 / 4.14 / 0.10 / 0.10 / 30.51
1 / 3.54 / 0.29 / 0.27 / 33.53 / 1 / 3.68 / 0.20 / 0.19 / 31.61
2 / 2.56 / 0.58 / 0.63 / 27.69 / 2 / 2.75 / 0.40 / 0.47 / 24.34
3 / 2.16 / 0.88 / 0.86 / 31.80 / 3 / 2.53 / 0.60 / 0.57 / 32.29
4 / 1.75 / 1.19 / 1.22 / 29.47 / 4 / 2.23 / 0.80 / 0.73 / 34.04
6 / 1.45 / 1.86 / 1.60 / 36.19 / 6 / 1.78 / 1.21 / 1.09 / 34.87
8 / 1.24 / 2.44 / 1.98 / 40.86 / 8 / 1.55 / 1.64 / 1.35 / 38.80
10 / 1.07 / 3.09 / 2.40 / 43.54 / 10 / 1.37 / 2.06 / 1.60 / 41.83
Table S.1.G: [1,2-hexanediol] = 0.24 M
/Table S.1.H: [1,2-hexanediol] = 0.54 M
[CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-1 / [CD]·103 / M / kobs 103 / s-1 / A[CDf]·103 / M / B[CDf]·103 / M / K11 / M-10 / 4.59 / - / - / - / 0 / 4.30 / - / - / -
0.2 / - / - / - / - / 0.2 / - / - / - / -
0.5 / 4.08 / 0.06 / - / - / 0.5 / 3.85 / 0.03 / - / -
1 / 3.80 / 0.12 / 0.13 / 26.89 / 1 / 3.66 / 0.06 / - / -
2 / 3.36 / 0.24 / 0.24 / 31.27 / 2 / 3.64 / 0.12 / 0.12 / 29.88
3 / 3.07 / 0.36 / 0.32 / 35.36 / 3 / 3.25 / 0.16 / 0.21 / 25.26
4 / 2.77 / 0.49 / 0.42 / 35.69 / 4 / 3.06 / 0.23 / 0.26 / 26.77
6 / 2.23 / 0.73 / 0.68 / 33.10 / 6 / 2.83 / 0.35 / 0.33 / 31.87
8 / 2.03 / 0.98 / 0.81 / 37.83 / 8 / 2.59 / 0.47 / 0.43 / 33.47
10 / 1.62 / 1.24 / 1.18 / 32.18 / 10 / 2.44 / 0.59 / 0.49 / 36.71
Tables S.2.A_S.2.H: kobs for the acid denitrosation of MNTS in the presence of different cyclodextrin and 1,2-pentanediol concentrations ([MNTS]=3.33×10-5 M, [HCl]=0.16 M), as well as the corresponding calculated values for the free cyclodextrin concentrations obtained by Method A and Method B (denoted as A and B, see text for details).
Table S.2.A: [1,2-pentanediol] = 0.022M
/Table S.2.B: [1,2-pentanediol] = 0.047M
[CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-1 / [CD]·103 / M / kobs 103 / s-1 / A[CDf]·103 / M / B[CDf]·103 / M / K11 / M-10 / 4.99 / - / - / - / 0 / 5.09 / - / - / -
0.2 / 3.86 / 0.15 / - / - / 0.2 / 4.10 / 0.13 / - / -
0.5 / 2.93 / 0.39 / - / - / 0.5 / 3.19 / 0.32 / - / -
1 / 2.19 / 0.79 / - / - / 1 / 2.38 / 0.65 / - / -
2 / 1.40 / 1.59 / - / - / 2 / 1.54 / 1.29 / - / -
3 / 1.06 / 2.39 / - / - / 3 / 1.20 / 1.95 / - / -
4 / 0.86 / 3.20 / - / - / 4 / 0.97 / 2.61 / - / -
6 / 0.66 / 4.83 / - / - / 6 / 0.76 / 3.94 / - / -
8 / - / - / - / - / 8 / 0.63 / 5.29 / - / -
Table S.2.C: [1,2-pentanediol] = 0.061M
/Table S.2.D: [1,2-pentanediol] = 0.093M
[CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-1 / [CD]·103 / M / kobs 103 / s-1 / A[CDf]·103 / M / B[CDf]·103 / M / K11 / M-10 / 5.10 / - / - / - / 0 / 4.56 / - / - / -
0.2 / 4.17 / 0.11 / - / - / 0.2 / 3.94 / 0.09 / 0.10 / 10.30
0.5 / 3.38 / 0.29 / - / - / 0.5 / 3.26 / 0.24 / 0.26 / 10.21
1 / 2.45 / 0.58 / - / - / 1 / 2.55 / 0.48 / 0.51 / 10.38
2 / - / - / - / - / 2 / 1.84 / 0.96 / 0.96 / 11.86
3 / 1.29 / 1.76 / - / - / 3 / 1.44 / 1.45 / 1.40 / 12.47
4 / 1.04 / 2.35 / - / - / 4 / 1.19 / 1.94 / 1.83 / 13.02
6 / 0.80 / 3.55 / - / - / 6 / 0.85 / 2.93 / 2.80 / 12.70
8 / 0.68 / 4.77 / - / - / 8 / 0.73 / 3.93 / 3.39 / 15.35
Table S.2.E: [1,2-pentanediol] = 0.12 M
/Table S.2.F: [1,2-pentanediol] = 0.16 M
[CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-1 / [CD]·103 / M / kobs 103 / s-1 / A[CDf]·103 / M / B[CDf]·103 / M / K11 / M-10 / 4.75 / - / - / - / 0 / 4.48 / - / - / -
0.2 / 4.06 / 0.08 / 0.11 / 6.51 / 0.2 / 4.07 / 0.07 / 0.07 / 13.15
0.5 / 3.47 / 0.20 / 0.24 / 8.85 / 0.5 / 3.48 / 0.18 / 0.18 / 11.02
1 / 2.61 / 0.41 / 0.53 / 7.16 / 1 / 2.63 / 0.36 / 0.45 / 7.82
2 / 2.01 / 0.82 / 0.88 / 10.36 / 2 / 2.06 / 0.72 / 0.76 / 10.69
3 / 1.61 / 1.24 / 1.26 / 11.35 / 3 / 1.68 / 1.08 / 1.08 / 11.69
4 / 1.19 / 1.65 / 1.93 / 8.81 / 4 / 1.43 / 1.44 / 1.38 / 12.46
6 / 0.93 / 2.50 / 2.66 / 10.43 / 6 / 1.08 / 2.18 / 2.03 / 12.96
8 / 0.79 / 3.35 / 3.22 / 12.46 / 8 / 0.93 / 2.92 / 2.46 / 15.07
Table S.2.G: [1,2-pentanediol] = 0.19 M
/Table S.2.H: [1,2-pentanediol] = 0.22 M
[CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-1 / [CD]·103 / M / kobs 103 / s-1 / A[CDf]·103 / M / B[CDf]·103 / M / K11 / M-10 / 4.23 / - / - / - / 0 / 3.98 / - / - / -
0.2 / 3.78 / 0.06 / 0.08 / 8.56 / 0.2 / 3.53 / 0.06 / 0.08 / 6.48
0.5 / 3.27 / 0.16 / 0.19 / 8.81 / 0.5 / 3.09 / 0.14 / 0.19 / 7.80
1 / 2.67 / 0.31 / 0.38 / 8.90 / 1 / 2.62 / 0.28 / 0.34 / 9.12
2 / 2.05 / 0.63 / 0.68 / 10.43 / 2 / 1.92 / 0.57 / 0.69 / 8.71
3 / 1.67 / 0.95 / 0.99 / 11.07 / 3 / 1.58 / 0.86 / 0.98 / 9.59
4 / 1.49 / 1.28 / 1.18 / 13.02 / 4 / 1.53 / 1.15 / 1.04 / 13.31
6 / 1.13 / 1.93 / 1.76 / 13.22 / 6 / 1.30 / 1.73 / 1.33 / 16.53
8 / 0.92 / 2.58 / 2.33 / 13.47 / 8 / 1.05 / 2.32 / 1.81 / 16.25
Tables S.3.A_S.3.H: kobs for the acid denitrosation of MNTS in the presence of different cyclodextrin and 1,5-pentanediol concentrations ([MNTS]=3.33×10-5 M, [HCl]=0.16 M), as well as the corresponding calculated values for the free cyclodextrin concentrations obtained by Method A and Method B (denoted as A and B, see text for details).
Tabla S.3.A: [1,5-pentanediol] = 0.021 M
/Table S.3.B: [1,5-pentanediol] = 0.031 M
[CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-1 / [CD]·103 / M / kobs 103 / s-1 / A[CDf]·103 / M / B[CDf]·103 / M / K11 / M-10 / 5.43 / - / - / - / 0 / 5.26 / - / - / -
0.2 / 4.31 / 0.14 / - / - / 0.2 / 4.33 / 0.13 / - / -
0.5 / - / 0.36 / - / - / 0.5 / 3.42 / 0.32 / - / -
1 / 2.41 / 0.72 / - / - / 1 / 2.54 / 0.65 / - / -
2 / 1.59 / 1.46 / - / - / 2 / 1.74 / 1.31 / - / -
4 / 1.01 / 2.96 / - / - / 4 / 1.03 / 2.65 / - / -
6 / 0.77 / 4.47 / - / - / 6 / 0.78 / 4.02 / - / -
8 / 0.63 / 6.01 / - / - / 8 / 0.65 / 5.40 / - / -
Table S.3.C: [1,5-pentanediol] = 0.046 M
/Table S.3.D: [1,5-pentanediol] = 0.061M
[CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-1 / [CD]·103 / M / kobs 103 / s-1 / A[CDf]·103 / M / B[CDf]·103 / M / K11 / M-10 / 5.16 / - / - / - / 0 / 5.34 / - / - / -
0.2 / 4.27 / 0.11 / - / - / 0.2 / 4.61 / 0.10 / 0.10 / 15.30
0.5 / 3.58 / 0.28 / - / - / 0.5 / 3.87 / 0.24 / 0.24 / 17.09
1 / 2.73 / 0.56 / - / - / 1 / 3.05 / 0.49 / 0.49 / 17.39
2 / 1.89 / 1.13 / - / - / 2 / 0.00 / - / -
4 / 1.13 / 2.28 / - / - / 4 / 1.27 / 2.00 / 2.06 / 15.75
6 / 0.85 / 3.46 / - / - / 6 / 0.93 / 3.03 / 3.06 / 16.36
8 / 0.70 / 4.65 / - / - / 8 / 0.76 / 4.08 / 3.92 / 18.14
Table S.3.E: [1,5-pentanediol] = 0.077 M
/Table S.3.F: [1,5-pentanediol] = 0.092 M
[CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-1 / [CD]·103 / M / kobs 103 / s-1 / A[CDf]·103 / M / B[CDf]·103 / M / K11 / M-10 / 5.06 / - / - / - / 0 / 5.11 / - / - / -
0.2 / 4.44 / 0.09 / 0.09 / 15.90 / 0.2 / 4.55 / 0.08 / 0.08 / 16.21
0.5 / 3.78 / 0.22 / 0.22 / 16.74 / 0.5 / 3.88 / 0.19 / 0.20 / 15.71
1 / 2.97 / 0.43 / 0.46 / 15.69 / 1 / 3.15 / 0.39 / 0.40 / 16.20
2 / 2.14 / 0.87 / 0.88 / 16.84 / 2 / 2.33 / 0.79 / 0.77 / 17.43
4 / 1.34 / 1.77 / 1.80 / 16.39 / 4 / 1.43 / 1.59 / 1.66 / 15.64
6 / 0.97 / 2.67 / 2.73 / 16.29 / 6 / 1.08 / 2.41 / 2.41 / 16.83
8 / 0.81 / 3.60 / 3.39 / 18.80 / 8 / 0.88 / 3.24 / 3.09 / 18.21
Table S.3.G: [1,5-pentanediol] = 0.12 M
/Table S.3.H: [1,5-pentanediol] = 0.19 M
[CD]·103 / M / kobs ·103 / s-1 / A[CDf]·103/ M / B[CDf]·103 / M / K11/ M-1 / [CD]·103 / M / kobs 103 / s-1 / A[CDf]·103 / M / B[CDf]·103 / M / K11 / M-10 / 5.17 / - / - / - / 0 / 5.22 / - / - / -
0.2 / 4.75 / 0.06 / 0.06 / 20.19 / 0.2 / 4.78 / 0.06 / 0.06 / 15.38
0.5 / 4.08 / 0.16 / 0.17 / 15.49 / 0.5 / 4.30 / 0.14 / 0.14 / 17.06
1 / 3.46 / 0.32 / 0.32 / 17.31 / 1 / 3.65 / 0.28 / 0.28 / 17.02
2 / 2.57 / 0.65 / 0.65 / 17.00 / 2 / 2.83 / 0.56 / 0.54 / 17.55
4 / 1.61 / 1.32 / 1.42 / 15.04 / 4 / 1.86 / 1.13 / 1.16 / 16.14
6 / 1.23 / 2.00 / 2.08 / 15.84 / 6 / 1.41 / 1.70 / 1.75 / 16.25
8 / 0.99 / 2.68 / 2.73 / 16.43 / 8 / 1.12 / 2.29 / 2.36 / 16.10
Tables S.4.A_S.4.H: kobs for the acid denitrosation of MNTS in the presence of different cyclodextrin and 1,2-butanediol concentrations ([MNTS]=3.33×10-5 M, [HCl]=0.16 M), as well as the corresponding calculated values for the free cyclodextrin concentrations obtained by Method A and Method B (denoted as A and B, see text for details).