Figure S12. Kinetic plots for the C(2)-H/D exchange reaction of 2 CB[7] as a function

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1 Supporting Information Encapsulation of Vitamin B 1 and its Phosphate Derivatives by Cucurbit[7]uril: Tunability of the Binding Site and Affinity by the Presence of Phosphate Groups Shengke Li, Hang Yin, Ian W. Wyman, Qingwen Zhang, Donal H. Macartney,, and Ruibing Wang, State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Taipa, Macau, China Department of Chemistry, Queen s University, Kingston, ON, K7L 3N6, Canada Contents Theoretical calculations of C(2)-H/D exchange kinetics Figure S1. Electrospray mass spectrum for {1 CB[7]} + in water. Figure S2. Electrospray mass spectrum for {2 CB[7]} + in water. Figure S3. Electrospray mass spectrum for {3 CB[7]} + in water. Figure S4. The 1 H NMR spectra of free thiamine diphosphate (lower spectrum) and after the addition of 1.1 equivalents of CB[7] (upper spectrum) Figure S5. Job s plot for thiamine with CB[7] measured at 268 nm Figure S6. Job s plot for thiamine monophosphate with CB[7] measured at 250 nm Figure S7. Job s plot for thiamine diphosphate with CB[7] measured at 220 nm Figure S8. UV spectra of the thiamine 3 guests and its CB[7] host-guest complex Figure S9 Kinetic plots for the C(2)-H/D exchange reaction of 1 as a function of pd at 298K Figure S10. Kinetic plots for the C(2)-H/D exchange reaction of 1 CB[7] as a function of pd at 298K Figure S11. Kinetic plots for the C(2)-H/D exchange reaction of 2 as a function of pd at 298K Figure S12. Kinetic plots for the C(2)-H/D exchange reaction of 2 CB[7] as a function of pd at 298K Figure S13. Kinetic plots for the C(2)-H/D exchange reaction of 3 as a function of pd at 298K Figure S14. Kinetic plots for the C(2)-H/D exchange reaction of 3 CB[7] as a function of pd at 298K Figure S15. Energy minimized structure for {1 CB[7]} + with atom labeled with center numbers Table S1. Atomic coordinates for {1 CB[7]} + from energy-minimization calculations Figure S16. Energy minimized structure for {2 CB[7]} with atom labeled with center numbers Table S2. Atomic coordinates for {2 CB[7]} from energy-minimization calculations Figure S17. Energy minimized structure for {3 CB[7]} - with atom labeled with Page S3 S4 S4 S5 S6 S7 S7 S8 S9 S10 S10 S11 S11 S12 S12 S13 S13 S17 S17 S1

2 center numbers Table S3. Atomic coordinates for {3 CB[7]} - from energy-minimization calculations Full citation for reference 17 in paper S21 S21 S25 S2

3 Kinetics of C(2)-H/D exchange monitored by 1 H NMR Spectroscopy Determination of the first-order rate constants by semilogarithmic plots The proton/deuterium exchange was monitored via 1 H NMR spectroscopy as described above. Values describing the reaction progress, R, can be calculated from the integrations of the of C(2)-proton resonances [(I 2H ) t ] at time t, with an internal reference [(I 2H ) 0 ], at the beginning of the experiment (or at t = 0), according to equation (1). R = (I 2H ) t /(I 2H ) 0 (1) lnr = -k ex t (2) From equation (2), the first-order rate constant k ex can be determined from the slope of the linear semilogarithmic plot of the reaction progress versus the reaction time. Therefore, the first-order rate constant k ex values, in the presence and in the absence of CB[7], at various pd conditions can be determined. 1,2 Determination of the second-order rate constants The second-order rate constant, k DO, is calculated from the y-axis intercept of the linear fit with a fixed slope of one by plotting logk ex (first-order rate constants) against the pd values according to the equation (3). 1 log k ex = log (k DO K W /γ OL ) + pd (3) The value of pk W = (for deuterated water). Under our experimental conditions the activity coefficient for deuterium oxide is γ OL = 0.83, as estimated from the solvent conditions and the ionic strength. 1 The pk a values of the thiamines in the absence and in the presence of CB[7] were estimated based on the second-order rate constants k DO and with k DO /k HO = 2.4, K W (H 2 O) = 1.00 x 10 14, and k HOH = 1 x s -1 for the reverse protonation of the carbene by solvent water. 1 References (1) Amyes, T. L.; Diver, S. T.; Richard, J. P.; Rivas, F. M.; Toth, K. J. Am. Chem. Soc. 2004, 126, (2) Handy, S. T.; Okello, M. J. Org. Chem. 2005, 70, S3

4 Figure S1. Electrospray mass spectrum for {1 CB[7]} in water. Figure S2. Electrospray mass spectrum for {2 CB[7]} in water. S4

5 Figure S3. Electrospray mass spectrum for {ThDP CB[7]} - (m/z for [M+2H] + and for [M+H+Na] + ) in water. S5

6 1 6 5 N N 3 7 O 2 S N NH 2 4 -O P O P O -O O OH Figure S4. 1 H NMR spectra of free thiamine diphosphate (2 mm) (lower spectrum) and after the addition of 1.1 equivalents of CB[7] (upper spectrum) S6

7 Absorbance change [CB[7]]/([CB[7]] + [Th]) Figure S5. Job s plot for thiamine with CB[7] measured at 268 nm Absorbance change [CB[7]]/([CB[7]] + [ThMP]) Figure S6. Job s plot for 2 with CB[7] measured at 250 nm. S7

8 Absorbance change [CB[7]]/([CB[7]] + [ThDP]) Figure S7. Job s plot for 3 with CB[7] measured at 220 nm. S8

9 Figure S8. UV spectra of the thiamine 3 guests (0.1 mm) and its CB[7] (10 equiv.) host-guest complex in aqueous solution. S9

10 ln(r) Time, s Figure S9. Kinetic plots for the C(2)-H/D exchange reaction of thiamine as a function of pd at 298K: pd = 4.12 ( ), 4.36 ( ), 4.52 ( ), and 4.66 ( ) ln(r) Time, s Figure S10. Kinetic plots for the C(2)-H/D exchange reaction of {Th CB[7]} + as a function of pd at 298K: pd = 4.98 ( ), 4.93 ( ), 4.80 ( ), and 4.70 ( ). S10

11 ln(r) Time, s Figure S11. Kinetic plots for the C(2)-H/D exchange reaction of ThMP as a function of pd at 298K: pd = 3.45 ( ), 4.27 ( ), 4.66 ( ), and 4.84 ( ) ln(r) Time, s Figure S12. Kinetic plots for the C(2)-H/D exchange reaction of {ThMP CB[7]} as a function of pd at 298K: pd = 4.96 ( ), 4.79 ( ), 4.66 ( ), and 4.32 ( ). S11

12 ln(r) Time, s Figure S13. Kinetic plots for the C(2)-H/D exchange reaction of ThDP - as a function of pd at 298K: pd = 3.21 ( ), 4.20 ( ), 4.56 ( ), and 5.79 ( ) ln(r) Time, s Figure S14. Kinetic plots for the C(2)-H/D exchange reaction of {ThDP CB[7]} - as a function of pd at 298K: pd = 5.08( ), 4.93 ( ), 4.74( ), and 4.64 ( ). S12

13 Figure S15. Energy minimized structure for {1 CB[7]} + with atom labeled with center numbers (see table below) Table S1. Atomic coordinates for {1 CB[7]} from energy-minimization calculations (total energy = ) Standard orientation: Center Atomic Coordinates (Angstroms) Number Type X Y Z C C N C N N C N O O C C N C N N C N S13

14 19 O O C C C C N C N N C N O O C C N C N N C N C N C C C N H H H C C N C S C C C C C O H H H H H H H H H H H H H H H S14

15 76 N O O C C C C C C N C N N C N O O C C N C N N C N O O C C C C C C C C C C N N N C N C O O H H H H H H H H H H H H S15

16 133 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S16

17 Figure S16. Energy minimized structure for {2 CB[7]} with atom labeled with center numbers (see table below) Table S2. Atomic coordinates for {2 CB[7]} from energy-minimization calculations (total energy = au) Standard orientation: Center Atomic Coordinates (Angstroms) Number Type X Y Z C C N C N N C N O O C C N C N N C N O O C S17

18 22 C C C N C N N C N O O C C N C N N C C C N C S C C C N C N C C N H H C C C O P O O H O H H H H H H H H H H H H H H S18

19 79 H N O O C C C C C C N C N N C N O O C C N C N N C N O O C C C C C C C C C C N N N C N C O O H H H H H H H H H H H S19

20 136 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S20

21 Figure S17. Energy minimized structure for {3 CB[7]} with atom labeled with center numbers (see table below) Table S3. Atomic coordinates for {3 CB[7]} from energy-minimization calculations (total energy = au Standard orientation: Center Atomic Coordinates (Angstroms) Number Type X Y Z O O N O N N O N O O O O N O N N O S21

22 18 N O O O O O O N O N N O N O O O O N O N N O O O N O S O O O N O N O O N H H O O O O P O O H O P O O H O H H H H H S22

23 75 H H H H H H H H H H N O O O O O O O O N O N N O N O O O O N O N N O N O O O O O O O O O O O O N N N O N O O O H H S23

24 132 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S24

25 Full Citation for Reference 17 (17) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A. Jr.; Vreven, T.; Kudin, N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision C.02, Gaussian, Pittsburgh, PA S25