Molecular Tweezers with Varying Anions - A Comparative Study
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- Δαμιανός Αντωνόπουλος
- 5 χρόνια πριν
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1 Molecular Tweezers with Varying Anions - A Comparative Study SomDutt a, ConstanzeWilch a, Thomas Gersthagen a, Peter Talbiersky a, Kenny Bravo- Rodriguez b, MattiHanni c, Elsa Sánchez-García* b,christian chsenfeld* c, Frank-Gerrit Klärner* a, Thomas Schrader* a a University of Duisburg-Essen, Department of Chemistry, Universitätsstr. 7, Essen, Germany b Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 4547 Mülheim an der Ruhr, Germany c Chair of Theoretical Chemistry, Department of Chemistry, University of Munich (LMU), Butenandtstr. 7, Munich, Germany and Center for Integrated Protein Science (CIPSM) at the Department of Chemistry, University of Munich (LMU), Butenandtstr.5-13, Munich, Germany esanchez@mpi-muelheim.mpg.de; christian.ochsenfeld@uni-muenchen.de; frank.klaerner@uni-duisburg-essen.de; thomas.schrader@uni-due.de Supporting Information Table of Contents 1. Experimental Section: Page H NMR and 13 C NMR spectra of the tweezers 1c, 1g, and 1d Dimerisation of the molecular tweezers determined by NMR titration Host-guest complex formation of the molecular tweezers with various amino acid and peptide guest molecules containing lysine or arginine moieties determined by fluorescence titration Host-guest complex formation of the molecular tweezers with various amino acid and peptide guest molecules containing lysine or arginine moieties determined by 1 H-NMR titration Solvent-dependent 1 H-NMR spectra of host-guest complexes Host-guest complex formation of the molecular tweezers with various amino acid and peptide guest molecules containing lysine or arginine moieties determined by isothermal titration calorimetry (ITC) Computational Section: 2.1 Calculation of host-guest complex structures by QM/MM Calculation of 1 H NMR shifts of the guest signals by ab initio methods 64 1
2 1 Experimental Section H NMR and 13 C NMR spectra of the tweezers 1c, 1g, and 1d S S H-NMR in CD 3 D: 1c ppm ppm ppm H-NMR in D 2 : 1c ppm ppm ppm
3 13 C-NMR in CD 3 D: 1c 3
4 3 CH CH 3 1 H-NMRin CDCl 3 : 1g 4
5 13 C-NMRin CDCl 3 : 1g 5
6 Na Na 1 H-NMR in D 2 : 1d 6
7 13 C-NMR in D 2 : 1d 7
8 1.2 Dimerisation of the molecular tweezers determined by NMR titration Dilution titration of the phosphate tweezer 1a Receptor (R) 1a M R g/mol] 1a.19 Solvent Phosphate buffer m R (1a) [mg] 1.1 Substrate T [ C] Itself 25 V [ml] [R] [mm] δ (5-H, 11-H, 16-H, 22-H) = P 24 a i 4 Li δ (6-H, 1-H, 17-H, 21-H) = i 25 a 9 2 δ (1-H, 4-H, 12-H, 15-H) = P δ (2-H, 3-H, 13-H, 14-H) = a i i a [1a] [mm] δ obs (2-H, 3-H, 13-H, 14-H) δ obs δ calc ,,8 obs [ppm],6,4,2 K dim [M -1 ] = 6 ± 1 δ max (5-H, 11-H, 16-H, 22-H) = -.2 δ max (6-H, 1-H, 17-H, 21-H) = -.28 δ max (1-H, 4-H, 12-H, 15-H) =.37 δ max (2-H, 3-H, 13-H, 14-H) = 2.23,,,1,2,3,4,5 [R] [mol/l] 8
9 1.2.2 Dilution titration of the sufate tweezer 1c Receptor(R) 1c M R [g/mol] Solvent Phosphate buffer m R [mg] 1.13 T[ o C] 25 V [ml] 2.3 Substrate Itself [R] [mm] 1.13 S 2Na S [R][mM] δ obs [ppm] δ monomercalc - δ obs = δ calc [ppm] , 6,8 obs [ppm] 6,6 6,4 6,2 K dim [M -1 ] = 37 ± 8 δ max [ppm] = 2.2 δ monomercalc [ppm] = ,,,2,4,6,8,1,12 [R] [mol/l] 9
10 1.2.3 Concentration-dependent 1 H NMR spectra of tweezer 1a in aqueous phosphate buffer (7 mm, ph 7.2, 25 C) Concentration-dependent 1 H NMR spectra of tweezer 1c in aqueous phosphate buffer (1 mm, ph 7.2, 25 C) 1
11 1.3 Fluorescence titrations UV-Vis and Fluorescence spectra of molecular tweezers and 1,4-dimethoxybenzene 1,4-dimethoxybenzene, DMB 1f (R 1 =R 2 =Ac) 1a (R 1 =R 2 =P 3 2-2Li + ) Compound 1a (R 1 =R 2 = P 3 2-2Li + ) 1f:(R 1 =R 2 = Ac) 1,4-dimethoxybenzene Solvent H 2 CD 3 CN CD 3 CN Absorption max ε max [nm] [M -1 cm -1 ] Emission max Ф em [nm] [ns] Figure S1. UV-VIS and fluorescence spectra of the molecular tweezers substituted by phosphate or acetoxy groups in the central benzene bridge and of 1,4-dimethoxybenzene (determined by P. Ceroni, Dipartimento di ChimicaCiamicianUniversita' di Bologna Via Selmi, 2, 4126 Bologna, Italy). 11
12 1.3.2 Fluorescence titrations Fluorescence titrations for Ac Lys Me Titration of Ac Lys Me and tweezer 1b in phosphate buffer (2mM, ph 7.64) λ exc = 28 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1b Guest Ac Lys Me HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 336 ) I obs E-5.E E-5 3.4E E-5 6.7E E E E-5 1.3E E-5 1.9E E E E-5 3.1E E E E E E E E E E E E E I calc V(AcLysMe) = µl V(AcLysMe) = 1 µl V(AcLysMe) = 2 µl V(AcLysMe) = 3 µl V(AcLysMe) = 4 µl V(AcLysMe) = 6 µl V(AcLysMe) = 8 µl V(AcLysMe) = 1 µl V(AcLysMe) = 12 µl V(AcLysMe) = 15 µl V(AcLysMe) = 18 µl V(AcLysMe) = 22 µl V(AcLysMe) = 26 µl V(AcLysMe) = 3 µl [AcLysMe]/[1b] [nm] K a [M -1 ] = ± 1%, K d [µm] = 68 ± 1% 12
13 Titration of AcLysMe and tweezer 1c in phosphate buffer (2mM, ph 7.64) λ exc = 285 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1c Guest Ac Lys Me HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 337 ) I obs I calc E-5.E E E E-5 7.9E E-5 1.5E E E E-5 2.1E E E E E E E E-5 4.5E E E E-5 6.1E E E E E l l 2 l 3 l 4 l 6 l 8 l 1 l 12 l 15 l 18 l 22 l 3 l [AcLysMe]/[1c] [nm] K a [M -1 ] = 36 ± 2 % K d [µm] = 28 ± 2 % 13
14 Titration of AcLysMe and tweezer 1d in phosphate buffer (2mM, ph 7.64) λ exc = 285 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1d Guest Ac Lys Me HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 349 ) I obs I calc 7 4.9E-5.E E E E E E E E-5 1.4E E E E E E E E E E-5 3.4E E E E E E E E E I I V(Ac-Lys-Me) = L V(Ac-Lys-Me) = 1 L V(Ac-Lys-Me) = 2 L V(Ac-Lys-Me) = 3 L V(Ac-Lys-Me) = 4 L V(Ac-Lys-Me) = 6 L V(Ac-Lys-Me) = 8 L V(Ac-Lys-Me) = 1 L V(Ac-Lys-Me) = 12 L V(Ac-Lys-Me) = 15 L V(Ac-Lys-Me) = 18 L V(Ac-Lys-Me) = 22 L V(Ac-Lys-Me) = 26 L V(Ac-Lys-Me) = 3 L [AcLysMe]/[1d] [nm] K a [M -1 ] = 4434 ± 14% K d [µm] = 226 ± 14% 14
15 Titration of AcLysMe and tweezer 1a in phosphate buffer (1 mm, ph 7.6) λ exc = 285 nm λ em = 334 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1a Guest AcLysMe HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 334 nm ) I obs I calc E-5.E E E E E E E E E E E E E E E E E E E E E E E l 1 l 2 l 3 l 4 l 6 l 8 l 1 l 14 l 18 l 24 l 3 l nm [AcLysMe]/[1a] K a [M -1 ] = 113 ± 6 % K d [µm] = 9 ± 6 % I max = 24 (4 %) 15
16 Titration of AcLysMe and tweezer 1c in phosphate buffer (1 mm, ph 7..2) λ exc = 285 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1c Guest Ac Lys Me HCl Guest V (µl) Receptor V (µl) [Receptor] [Guest] [mol/l] [mol/l] 2.33E-5.E+ 2.33E-5 3.6E E-5 7.9E E-5 1.5E E E E-5 2.2E E E E E E E E-5 4.5E E E E-5 6.1E E E E E-4 [Guest]/ [Receptor] F I (I 338 ) I obs I calc [AcLysMe]/[1c] µl 1 µl 2 µl 3 µl 4 µl 6 µl 8 µl 1 µl 12 µl 15 µl 18 µl 22 µl 26 µl 3 µl K a [M -1 ] = 515 ± 3 % K d [µm] = 19 ± 3 % I max = 48 (44 %) 16
17 Titration of AcLysMe and tweezer 1d in phosphate buffer (1 mm, ph 7.2) λ exc = 285 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1d Guest Ac Lys Me HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 348 ) I obs I calc E-5.E E E E E E E E E E E E-5 8.1E E E E E E E E E E E E E E E I I V(Ac-Lys-Me) = L V(Ac-Lys-Me) = 1 L V(Ac-Lys-Me) = 2 L V(Ac-Lys-Me) = 3 L V(Ac-Lys-Me) = 4 L V(Ac-Lys-Me) = 6 L V(Ac-Lys-Me) = 8 L V(Ac-Lys-Me) = 1 L V(Ac-Lys-Me) = 12 L V(Ac-Lys-Me) = 15 L V(Ac-Lys-Me) = 18 L V(Ac-Lys-Me) = 22 L V(Ac-Lys-Me) = 26 L V(Ac-Lys-Me) = 3 L [AcLysMe]/[1d] [nm] K a [M -1 ] = 1555 ± 7% K d [µm] = 643 ± 7% I max = 225 (36 %) 17
18 Fluorescence titrations for H Lys H Titration of H LysH and tweezer 1b in phosphate buffer (2 mm, ph 7.6) λ exc = 28 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1b Guest H Lys H HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 336 ) I obs E-5.E E E E E E E E E E E E E E-5 3.3E E E E E E E E E E E E E I calc V(HLysH) = µl V(HLysH) = 1 µl V(HLysH) = 2 µl V(HLysH) = 3 µl V(HLysH) = 4 µl V(HLysH) = 6 µl V(HLysH) = 8 µl V(HLysH) = 1 µl V(HLysH) = 12 µl V(HLysH) = 15 µl V(HLysH) = 18 µl V(HLysH) = 22 µl V(HLysH) = 26 µl V(HLysH) = 3 µl [HLysH]/[1b] [nm] K a [M -1 ] = 1144 ± 1% K d [µm] = 874 ± 1% 18
19 Titration of HLysH and tweezer 1c in phosphate buffer (1mM, ph 7.6) λ exc = 285 nm λ em = 338 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1c Guest H LysH HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 338 ) I obs I calc E-5.E E E E-5 7.6E E-5 1.5E E E E-5 2.1E E E E E E E E-5 5.2E E E E E l 1 l 2 l 3 l 4 l 6 l 8 l 1 l 14 l 18 l 24 l 3 l [HLysH]/[1c] [nm] K a [M -1 ] = 441 ± 6 % K d [µm] = 227 ± 6% 19
20 Titration of HLysH and tweezer 1d in phosphate buffer (1 mm, ph 7.2) λ exc = 285 nm λ em = 348 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1d Guest H LysH HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 348 ) I obs I calc E-5.E E E E E E E E E E E E E E E E E E-5 8.3E E E E-5 1.9E E E E E I I 6 V(H-Lys-H) = L V(H-Lys-H) = 1 L V(H-Lys-H) = 2 L 5 V(H-Lys-H) = 3 L V(H-Lys-H) = 4 L V(H-Lys-H) = 6 L 4 V(H-Lys-H) = 8 L V(H-Lys-H) = 1 L V(H-Lys-H) = 12 L V(H-Lys-H) = 15 L 3 V(H-Lys-H) = 18 L V(H-Lys-H) = 22 L V(H-Lys-H) = 26 L 2 V(H-Lys-H) = 3 L [HLysH]/[1d] [nm] K a [M -1 ] = 855 ± 2% K d [µm] = 117 ± 2% 2
21 Fluorescence titration for peptide KAA Titration of KAA and tweezer 1a in phosphate buffer (2 mm, ph 7.6) λ exc = 285 nm Tweezer 1a KAA Amount [mg]: Volume [ml]: Concentration [mol/l]:.164 ( mmol) ( mmol) V Guest V total [1a] [KAA] [KAA]/ I [ L] [ L] [mol/l] [mol/l] [1a] 334 nm I obs I calc V(KAA) = µl V(KAA) = 1 µl V(KAA) = 2 µl V(KAA) = 3 µl V(KAA) = 4 µl V(KAA) = 6 µl V(KAA) = 8 µl V(KAA) = 1 µl V(KAA) = 12 µl V(KAA) = 15 µl V(KAA) = 18 µl V(KAA) = 22 µl V(KAA) = 26 µl V(KAA) = 3 µl [KAA]/[1a] [nm] K a [M -1 ] = 3334 ± 3 % K d [µm] = 3 ± 3 % 21
22 Titration of KAA and tweezer 1b in phosphate buffer (2 mm, ph 7.6) λ exc = 28 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1b Guest KAA Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 334 ) I obs E-5.E E E E E E E E-5 1.3E E-5 1.9E E E E-5 3.E E E E E E E E E E-5 6.5E E-5 7.2E I calc V(KAA) = µl V(KAA) = 1 µl V(KAA) = 2 µl V(KAA) = 3 µl V(KAA) = 4 µl V(KAA) = 6 µl V(KAA) = 8 µl V(KAA) = 1 µl V(KAA) = 12 µl V(KAA) = 15 µl V(KAA) = 18 µl V(KAA) = 22 µl V(KAA) = 26 µl V(KAA) = 3 µl [KAA]/[1b] [nm] K a [M -1 ] = 115 ± 1% K d [µm] = 95 ± 1% 22
23 Titration of KAA and tweezer1c in phosphate buffer (1 mm, ph 7.6) λ exc = 285 nm λ em = 338 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1c Guest KAA Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 338 ) I obs I calc E-5.E E E E-5 7.9E E-5 1.5E E E E-5 2.1E E E E E c E E E E E E E E l 1 l 2 l 3 l 4 l 6 l 4 8 l 1 l 14 l 18 l 24 l 2 3 l [KAA]/[1c] [nm] K a [M -1 ] = 33 ± 5 % K d [µm] = 33 ± 5 % 23
24 Titration of KAA and tweezer 1d in phosphate buffer (1 mm, ph 7.2) λ exc = 285 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1d Guest KAA Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 348 ) I obs I calc E-5.E E-5 1.3E E E E E E E E E E E E E E E E E E E E-5 2.2E E E E E I [KAA]/[1d] I [nm] V(KAA) = L V(KAA) = 1 L V(KAA) = 2 L V(KAA) = 3 L V(KAA) = 4 L V(KAA) = 6 L V(KAA) = 8 L V(KAA) = 1 L V(KAA) = 12 L V(KAA) = 15 L V(KAA) = 18 L V(KAA) = 22 L V(KAA) = 26 L V(KAA) = 3 L K a [M -1 ] = 3 ± 83% K d [µm] = ± 83% 24
25 I Fluorescence titrations for KLVFF Titration of KLVFF and tweezer1a in phosphate buffer (2 mm, ph 7.6) λ exc = 28 nm Tweezer 1a KLVFF Amount [mg]: Volume [ml]: Concentration [mol/l]:.172 ( mmol) ( mmol) V Gast V gesamt [75] [KLVFF] I [KLVFF]/ [1a] [ L] [ L] [mol/l] [mol/l] 334 nm I obs I calc V(KLVFF) = µl V(KLVFF) = 1 µl V(KLVFF) = 2 µl V(KLVFF) = 3 µl V(KLVFF) = 4 µl V(KLVFF) = 6 µl V(KLVFF) = 8 µl V(KLVFF) = 1 µl V(KLVFF) = 12 µl V(KLVFF) = 15 µl V(KLVFF) = 18 µl V(KLVFF) = 22 µl V(KLVFF) = 26 µl V(KLVFF) = 3 µl [KLVFF]/[1a] [nm] K a [M -1 ] = ± 5 % K d [µm] =2 ± 5 % 25
26 Titration of KLVFF and tweezer 1c in phosphate buffer (1 mm, ph 7.6) λ exc = 285 nm λ em = 338 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1c Guest KLVFF Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 338 ) I obs I calc E-5.E E-5 1.6E E-5 2.8E E-5 3.8E E-5 4.5E E E E E E E E E E E E E E E b [KLVFF]/[1c] µl 1 µl 2 µl 3 µl 4 µl 6 µl 8 µl 1 µl 14 µl 18 µl 3 µl K a [M -1 ] = 262 ± 11 % K d [µm] =38 ± 11% λ ~ 2 nm,blue shift 26
27 Fluorescence titrations for KKLVFF Titration of KKLVFFand tweezer 1a in phosphate buffer (2 mm, ph 7.64) λ exc = 28 nm Tweezer1a KKLVFF Amount [mg]: Volume [ml]: Concentration [mol/l]:.172 ( mmol) ( mmol) V Guest V total [1a] [KKLVFF] [KKLVFF]/ I [ L] [ L] [mol/l] [mol/l] [1a] 334 nm I obs I calc V(KKLVFF) = µl V(KKLVFF) = 5 µl V(KKLVFF) = 1 µl V(KKLVFF) = 15 µl V(KKLVFF) = 2 µl V(KKLVFF) = 25 µl V(KKLVFF) = 3 µl V(KKLVFF) = 4 µl V(KKLVFF) = 6 µl V(KKLVFF) = 8 µl V(KKLVFF) = 1 µl V(KKLVFF) = 12 µl V(KKLVFF) = 15 µl V(KKLVFF) = 18 µl V(KKLVFF) = 22 µl V(KKLVFF) = 26 µl V(KKLVFF) = 3 µl [KKLVFF]/[1a] [nm] K a [M -1 ] = ± 1 % K d [µm] =4 ± 1 % 27
28 Titration of KKLVFF and tweezer 1b in phosphate buffer (2 mm, ph 7.64) λ exc = 28 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1b Guest KKLVFF Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 336 ) I obs E-5.E E E E E E E E E E E E E E-5 1.4E E E E E E-5 1.7E E E E E E E I calc V(KKLVFF) = µl V(KKLVFF) = 1 µl V(KKLVFF) = 2 µl V(KKLVFF) = 3 µl V(KKLVFF) = 4 µl V(KKLVFF) = 6 µl V(KKLVFF) = 8 µl V(KKLVFF) = 1 µl V(KKLVFF) = 12 µl V(KKLVFF) = 15 µl V(KKLVFF) = 18 µl V(KKLVFF) = 22 µl V(KKLVFF) = 26 µl V(KKLVFF) = 3 µl [KKLVFF]/[1b] [nm] K a [M -1 ] = 1448 ± 1% K d [µm] = 71 ± 1 28
29 Fluorescence titration of KKLVFFAK and tweezer 1a in phosphate buffer (2 mm, ph 7.64) λ exc = 28 nm Tweezer1a KKLVFFAK Amount [mg]: Volume [ml]: Concentration [mol/l]:.172 ( mmol) ( mmol) V Guest V total [1a] [KKLVFFAK] [KKLVFFAK]/ I [ L] [ L] [mol/l] [mol/l] [1a] 334 nm I obs I calc V(KKLVFFAK) = µl V(KKLVFFAK) = 5 µl V(KKLVFFAK) = 1 µl V(KKLVFFAK) = 15 µl V(KKLVFFAK) = 2 µl V(KKLVFFAK) = 25 µl V(KKLVFFAK) = 3 µl V(KKLVFFAK) = 4 µl V(KKLVFFAK) = 6 µl V(KKLVFFAK) = 8 µl V(KKLVFFAK) = 1 µl V(KKLVFFAK) = 12 µl V(KKLVFFAK) = 15 µl V(KKLVFFAK) = 18 µl V(KKLVFFAK) = 22 µl V(KKLVFFAK) = 26 µl V(KKLVFFAK) = 3 µl [KKLVFFAK]/[1a] [nm] K a [M -1 ] = ± 1 % K d [µm] = 7 ± 1 % 29
30 Fluorescence titration of H-KKKK-H and tweezer 1a in phosphate buffer (2 mm, ph 7.64) λ exc = 28 nm Tweezer1a H-KKKK-H Amount [mg]: Volume [ml]: Concentration [mol/l]:.172 ( mmol) ( mmol) V Guest V total [1a] [KKKK] [KKKK]/ I [ L] [ L] [mol/l] [mol/l] [1a] 334 nm I obs I calc I V(H-KKKK-H) = µl V(H-KKKK-H) = 5 µl V(H-KKKK-H) = 1 µl V(H-KKKK-H) = 15 µl V(H-KKKK-H) = 2 µl V(H-KKKK-H) = 25 µl V(H-KKKK-H) = 3 µl V(H-KKKK-H) = 35 µl V(H-KKKK-H) = 4 µl V(H-KKKK-H) = 6 µl V(H-KKKK-H) = 8 µl V(H-KKKK-H) = 1 µl V(H-KKKK-H) = 12 µl V(H-KKKK-H) = 15 µl V(H-KKKK-H) = 18 µl V(H-KKKK-H) = 22 µl V(H-KKKK-H) = 26 µl V(H-KKKK-H) = 3 µl [H-KKKK-H]/[1a] [nm] K a [M -1 ] = 9661 ± 7 % K d [µm] = 1 ± 7 % 3
31 Fluorescence titrations for Ac ArgMe Titration of AcArgMe and tweezer 1a in phosphate buffer (2mM, ph 7.6) λ exc = 285 nm λ em = 335 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1a Guest AcArgMe HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 335 nm ) I obs I calc E-5.E E E E-5 7.9E E-5 1.5E E E E-5 2.1E E E E E E E E-5 4.5E E E E-5 6.1E E E E E l 1 l 2 l 3 l 4 l 6 l 8 l 1 l 12 l 15 l 18 l 22 l 26 l 3 l [AcArgMe]/[1a] [nm] K a [M -1 ] = 164 ± 2 % K d [µm] = 6± 2 % 31
32 Titration of AcArgMeand tweezer 1c in phosphate buffer (2mM, ph 7.6) λ exc = 285 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1c Guest Ac ArgMe HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 337 ) I obs I calc E-5.E E-5 3.6E E-5 7.1E E-5 1.5E E E E-5 2.2E E E E E E E E E E E E E E E E E l 1 l 2 l 3 l 4 l 6 l 8 l 1 l 12 l 15 l 18 l 22 l 26 l 3 l [AcArgMe]/[1c] [nm] K a [M -1 ] = 56 ± 4 % K d [µm] = 178 ± 4 % 32
33 Titration of AcArgMe and tweezer 1a in phosphate buffer (1mM, ph 7.6) λ exc = 285 nm λ em = 334 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1a Guest AcArgMe HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 334 nm ) I obs I calc E-5.E E E E E E E E E E E E E E E E E E E E E E-5 1.5E l 1 l 2 l 3 l 4 l 6 l 8 l 1 l 14 l 18 l 24 l 34 l [nm] [AcArgMe]/[1a] K a [M -1 ] = 56 ± 5 % K d [µm] = 2 ± 5 % ΔI max = 282 (47 %) 33
34 Titration of AcArgMe and tweezer 1c in phosphate buffer (1mM, ph 7.2) λ exc = 285 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1c Guest Ac ArgMe HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 338 ) I obs I calc E-5.E E E E-5 7.9E E-5 1.5E E E E-5 2.1E E E E E E E E-5 4.5E E E E-5 6.1E E E E E [nm] l 1 l 2 l 3 l 4 l 6 l 8 l 1 l 12 l 15 l 18 l 22 l 24 l 3 l [AcArgMe]/[1c] K a [M -1 ] = 13 ± 5 % K d [µm] = 77 ± 5 % I max = 274 (3 %) 34
35 Titration of AcArgMe and tweezer 1d in phosphate buffer (2mM, ph 7.6) λ exc = 285 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1d Guest Ac ArgMe HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 348 ) I obs I calc 7 9.7E-5.E E E E E E-5 8.1E E-5 1.5E E E E-5 2.E E E E E E E E E E E E E E E I I V(Ac-Arg-Me) = L V(Ac-Arg-Me) = 1 L V(Ac-Arg-Me) = 2 L V(Ac-Arg-Me) = 3 L V(Ac-Arg-Me) = 4 L V(Ac-Arg-Me) = 6 L V(Ac-Arg-Me) = 8 L V(Ac-Arg-Me) = 1 L V(Ac-Arg-Me) = 12 L V(Ac-Arg-Me) = 15 L V(Ac-Arg-Me) = 18 L V(Ac-Arg-Me) = 22 L V(Ac-Arg-Me) = 26 L V(Ac-Arg-Me) = 3 L [AcLysMe]/[1d] [nm] K a [M -1 ] = 1134 ± 26% K d [µm] = 882 ± 26% 35
36 Titration of AcArgMe and tweezer 1d in phosphate buffer (1mM, ph 7.2) λ exc = 285 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1d Guest Ac ArgMe HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 348 ) I obs I calc E-5.E E E E E E E E E E E E E E E E E E E E E E-5 1.6E E-5 2.1E I I 8 V(Ac-Arg-Me) = L V(Ac-Arg-Me) = 1 L V(Ac-Arg-Me) = 2 L V(Ac-Arg-Me) = 3 L V(Ac-Arg-Me) = 4 L 6 V(Ac-Arg-Me) = 6 L V(Ac-Arg-Me) = 8 L V(Ac-Arg-Me) = 1 L V(Ac-Arg-Me) = 12 L V(Ac-Arg-Me) = 15 L 4 V(Ac-Arg-Me) = 18 L V(Ac-Arg-Me) = 22 L V(Ac-Arg-Me) = 26 L V(Ac-Arg-Me) = 3 L [AcArgMe]/[1d] [nm] K a [M -1 ] = 3558 ± 18% K d [µm] = 281 ± 18% I max = 91 (13 %) 36
37 Fluorescence titrations for HArgH Titration of HArgH and tweezer 1c in phosphate buffer (1mM, ph 7.6) λ exc = 285 nm λ em = 338 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1c Guest H Arg H HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 338 ) I obs I calc E-5.E E E E-5 7.7E E-5 1.5E E E E-5 2.1E E E E E E E E E E-5 6.5E E E l 1 l 2 l 3 l 4 l 6 l 8 l 1 l 14 l 18 l 24 l 3 l [HArgH]/[1c] [nm] K a [M -1 ] = 143 ± 15 % K d [µm] = 699 ± 15 % 37
38 Titration of HArgH and tweezer 1d in phosphate buffer (1mM, ph 7.2) λ exc = 285 nm λ em = 348 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1d Guest H Arg H HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 338 ) I obs I calc E-5.E E E E E E E E E E E E E E E E E E-5 8.1E E E E-5 1.1E E E E E I I V(H-Arg-H) = L V(H-Arg-H) = 1 L V(H-Arg-H) = 2 L V(H-Arg-H) = 3 L V(H-Arg-H) = 4 L V(H-Arg-H) = 6 L V(H-Arg-H) = 8 L V(H-Arg-H) = 1 L V(H-Arg-H) = 12 L V(H-Arg-H) = 15 L V(H-Arg-H) = 18 L V(H-Arg-H) = 22 L V(H-Arg-H) = 26 L V(H-Arg-H) = 3 L [HArgH]/[1d] [nm] K a [M -1 ] = 1643 ± 27% K d [µm] = 69 ± 27% 38
39 Fluorescence titrations for HArgMe Titration of HArgMe and tweezer 1c in phosphate buffer (1mM, ph 7.6) λ exc = 285 nm λ em = 338 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1c Guest H ArgMe 2HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 338 nm ) I obs I calc 7 2,33E-5,E+, 668,334,, ,33E-5 3,59E-5 1,54 68,912 59,422 51, ,33E-5 7,9E-5 3,4 571,524 96,81 88, ,33E-5 1,5E-4 4,5 552, ,99 115, ,33E-5 1,38E-4 5,92 536, ,74 136, ,33E-5 2,1E-4 8,64 55, , , ,33E-5 2,62E-4 11,23 482, , , ,33E-5 3,19E-4 13,68 47,43 198,291 21, ,33E-5 4,25E-4 18,25 451, ,1 221, ,33E-5 5,22E-4 22,39 435, , , ,33E-5 6,51E-4 27,95 418, , , ,33E-5 7,65E-4 32,84 411,15 257, , l 1 l 2 l 3 l 4 l 6 l 8 l 1 l 14 l 18 l 24 l 3 l [HArgMe]/[1c] [nm] K a = 626 ± 6 % K d [µm] = 16 ± 6 % 39
40 Titration of RGD and tweezer 1a in phosphate buffer (2mM, ph 7.6) λ exc = 28 nm Tweezer 1a H ArgGly Asp H Amount [mg]: Volume [ml]: Concentration [mol/l]:.164 ( mmol) ( mmol) V Guest V t [75] [RGD] [RGD]/ I [ L] [ L] [mol/l] [mol/l] [1a] 334 nm I obs I calc [RGD]/[1a] V(NAD + ) = µl 4 V(NAD + ) = 1 µl V(NAD + ) = 2 µl V(NAD + ) = 3 µl V(NAD + ) = 4 µl V(NAD + ) = 6 µl 35 V(NAD + = 8 µl V(NAD + ) = 1 µl V(NAD + ) = 12 µl V(NAD + ) = 15 µl 3 V(NAD + ) = 18 µl V(NAD + ) = 22 µl V(NAD + ) = 26 µl V(NAD + ) = 3 µl [nm] K a [M -1 ] = 1166 ± 1 % K d [µm] = 86 ± 1 % 4
41 Titration of crgdfl and tweezer 1a in phosphate buffer (1 mm, ph 7.4) Receptor Tweezer1a Solvent Phosphate buffer ph 7.4 T [ C] 25 Substrate cgrgdfl m R [mg].12 m S [mg].25 [R] [M] [S] [M] V R [ml] 4. V S [ml].4 V Guest [ L] V Total [ L] [R][mol/L] [S][mol/L] [S]/[R] I335 nm I obs E-5.E E E E E E E E E E E E E E-5 1.1E E E E E E E E E E E E E I [S]/[R] I obs [nm] V s = µl V s = 1 µl V s = 2 µl V s = 3 µl V s = 4 µl V s = 6 µl V s = 8 µl V s = 1 µl V s = 12 µl V s = 15 µl V s = 18 µl V s = 22 µl V s = 26 µl V s = 3 µl [cgrgdfl]/[1a] K a = 3876 ±3125 K d [µm] =26 ± 8 % 41
42 Titration of crgdfv and tweezer 1ain phosphate buffer (1mM, ph 7.4) Receptor 1a Solvent Phosphate buffer ph 7.4 T [ C] 25 Substrate crgdfv m R [mg].892 m S [mg] 4.97 [R] [M] [S] [M] V R [ml] 11. V S [ml] 7.6 V Guest [ L] V Total [ L] [R][mol/L] [S][mol/L] [S]/[R] I334 nm I obs I [S]/[R] I obs [nm] V S = µl V S = 1 µl V S = 2 µl V S = 3 µl V S = 5 µl V S = 1 µ V S = 15 µ V S = 25 µ V S = 3 µ V S = 45 µ V S = 55 µ V S = 65 µ V S = 75 µ V S = 85 µ V S = 95 µ V S = 15 [crgdfv][1a] K a = ± 1817, K d [µm] = 59 ± 11 % 42
43 Fluorescence titrations of the tweezers and the amino acid guests in methanol and mixture of methanol-buffer Fluorescence titration of the tweezer 1a with AcLysMe in methanol λ exc = 285 nm λ em = 322 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1a Guest Ac Lys Me HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 322 ) - I obs - I calc E-5.E E E E E E E E E E E E-5 2.E E E E E E E l 1 l 2 l 3 l 4 l 6 l 1 l 18 l 22 l 26 l [AcLysMe]/[1a] [nm] K a [M -1 ] = 152 ± 11 % K d [µm] = 66 ± 11 % ΔI max = -37 (6 %) 43
44 Fluorescence titration of the tweezer 1a with AcArgMe in 1:9 mixture of methanol/buffer (1 mm, ph 7.6) λ exc = 285 nm λ em = 322 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1a Guest Ac ArgMe HCl Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 329 ) I obs I calc E-5.E E E E E E E E E E E E E E E E E E E E-5 4.6E E E l 1 l 2 l 3 l 4 l 6 l 8 l 1 l 14 l 18 l 24 l 3 l [AcArgMe]/[1a] [nm] K a [M -1 ] = 638 ± 8 % K d [µm] = 157 ± 8 % ΔI max = 158 (27 %) 44
45 Fluorescence titration of the tweezer 1c with AcLysMe in methanol λ exc = 285 nm λ em = 32 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1c Guest Ac Lys Me Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 32 ) - I obs - I calc E-5.E E E E-5 7.8E E-5 1.5E E E E-5 2.1E E E E E E E E E E E E E l 1 l 2 l 3 l 4 l 6 l 8 l 1 l 14 l 18 l 24 l 3 l [AcLysMe]/[1c] [nm] K a [M -1 ] = 498 ± 6 % K d [µm] = 2 ± 6 % ΔI max = -27 (44 %) 45
46 Fluorescence titration of the tweezer 1c with AcArgMe in methanol λ exc = 285 nm λ em = 32 nm Amount [mg]: Volume [ml]: Concentration [mol/l]: Receptor 1c Guest Ac ArgMe Guest Receptor [Receptor] [Guest] [Guest]/ F I V (µl) V (µl) [mol/l] [mol/l] [Receptor] (I 32 ) - I obs - I calc E-5.E E E E-5 7.9E E-5 1.5E E E E-5 2.2E E E E E E E E E E E E E l 1 l 2 l 3 l 4 l 6 l 8 l 1 l 14 l 18 l 24 l 3 l [AcArgMe]/[1c] [nm] K a [M -1 ] = 362 ± 7 % K d [µm] = 276 ± 7 % ΔI max = -91 (22 %) 46
47 1.4 1 H NMR titrations NMR titrations of the phosphate tweezer 1a Titration of tweezer 1a andaclysme in phosphate buffer (7 mm, ph 7.2) Receptor 1a M R [g/mol] 1a.19 Solvent Phosphate buffer M S [g/mol] T [ C] 25 m R [mg] 3.61 Substrat Ac Lys Me m S [mg] 1.39 H 3 N X HN CH 3 CH 3 δ (2-H) [ppm] = δ (6-H) [ppm] = 2.98 δ (-NAc) [ppm] = 2.31 δ (-CMe) [ppm] = V [ml] 2 [R] [mm] 2.41 [S] [mm] 2.49 X - 2- : im Phosphate buffer HP 3 [R] [mm] [S] [mm] obs (NAc-H) obs calc obs [ppm] K a [M -1 ] = 5835 ± * δ max (2-H) [ppm] =.51 δ max (6-H) [ppm] = 3.91 δ max (-NAc) [ppm] = -.32 δ max (-CMe) [ppm]= [R] [M] * Limit of 95% - confidence interval from the nonlinear regression of the signals of the Protons NAc-H. 47
48 Titration of tweezer 1a and HLysH in phosphate buffer (7 mm, ph 7.2) Receptor 1a M R [g/mol] 1a.19 Solvent Phosphate buffer M S [g/mol] T [ C] 25 m R [mg] 5. Substrat H Lys H m S [mg] 1.39 H 3 N NH 3 X - : in Phosphate buffer HP 3 2- X δ (2-H) [ppm] = δ (3-H) [ppm] = δ (5-H) [ppm] = δ (6-H) [ppm] = 3.9 V [ml] 2 [R] [mm] 2.82 [S] [mm] 3.24 [R] [mm] [S] [mm] obs (2-H) obs calc c obs [ppm] K a [M -1 ] = 256 ± 189* δ max (2-H) [ppm] =.24 δ max (3-H) [ppm] =.76 δ max (5-H) [ppm] = 4.47 δ max (6-H) [ppm] = [R] [M] * Limit of 95% - confidence interval from the nonlinear regression of the signals of the Protons 2-H. 48
49 Titration of tweezer 1a and KAA in phosphate buffer (7 mm, ph 7.2) Receptor 1a M R [g/mol] 1a.19 Solvent Phosphate buffer M S [g/mol] T [ C] 25 m R [mg] 3.57 Substrat KAA m S [mg] 1.75 H 3 N 5 H 6 7 N H CH 3 H 4 H N 2 H CH 3 1 X δ (1-H) [ppm] = δ (3-H) [ppm] = δ (4-H) [ppm] = 4.97 δ (5-H) [ppm] = δ (6-H) [ppm] = 1.95 δ (7-H) [ppm] = δ (8-H) [ppm] = δ (9-H, 9 -H) [ppm] = 3.13 V [ml] 2 [R] [mm] 2.38 [S] [mm] 2.13 NH 3 X - 2- : im Phosphate buffer HP 3 [R] [mm] [S] [mm] obs (5-H) obs calc obs [ppm] [R] [M] K a [M -1 ] = 983 ± 8423 δ max (1-H) [ppm] = -.13 δ max (3-H) [ppm] = -. δ max (4-H) [ppm] = -.17 δ max (5-H) [ppm] =.2 δ max (6-H) [ppm] = 1.9 δ max (7-H) [ppm] = 2.28 δ max (8-H) [ppm] = 3.22 δ max (9-H, 9 -H) [ppm] = 5.82, 5.92 * Limit of 95% - confidence interval from the nonlinear regression of the signals of the Protons 5-H. 49
50 Titration of tweezer 1a and AcArgMe in phosphate buffer (1 mm, ph 7.2) Receptor 1a M R [g/mol] Solvent Phosphate buffer M S [g/mol] T[ o C] 25 m R [mg].8 Substrate Ac ArgMe m S [mg].511 H 2 N X NH 2 C N H 5 X : HP HN CH 3 CH 3 δ (2-H) [ppm] = δ (5-H) [ppm] = δ (4-H) [ppm] = δ (-NAc) [ppm] = 2.52 δ (-C 2 Me) [ppm] = [R] [mm] [S] [mm] δ (5-H) [ppm] Δδ obs [ppm] Δδ calc [ppm] obs [ppm] 3 2 1,,5,1,15,2,25,3,35 [R] [mol/l] K a [M -1 ] = ± 265 K d [µm] = 22 ± 4 % Δδ max (5-H) [ppm] = ±.16 Δδ max (4-H) [ppm] = 2.54 ±.5 Δδ max (3-H) [ppm] = ±.7 Δδ max (2-H) [ppm] =.63 ±.2 * Limit of 95% - confidence interval from the nonlinear regression of the signals of the Protons 5-H. 5
51 NMR titrations of sulfate tweezer 1c Titration of tweezer 1c andaclysme in phosphate buffer (1 mm, ph 7.2) Receptor 1c M R [g/mol] Solvent Phosphate buffer M S [g/mol] T[ o C] 25 m R [mg].672 Substrate AcLysMe m S [mg].41 5 H 3 N 6 4 X X : HP HN CH 3 CH 3 δ (2-H) [ppm] = V [ml] 3. δ (6-H) [ppm] = [S ][mm].5725 δ (-NAc) [ppm] = 2.5 δ (-C 2 Me) [ppm] = 3.77 V [ml] [R][mM] δ (2-H) [ppm] Δδ obs [ppm] Δδ calc [ppm] ,4,3 K a [M -1 ] = ± 8889 [ppm],2,1 K d [µm] = 12 ± 11 % Δδ max (2-H) [ppm] =.37 Δδ max (3-H) [ppm] = 1.29 Δδ max (4-H) [ppm] = 2.64,,,2,4,6,8,1,12,14,16 [R][mol/l] Δδ max (6-H) [ppm] = 3.75 Δδ max (5-H) [ppm] = 4.41 * Limit of 95% - confidence interval from the nonlinear regression of the signals of the Protons 2-H. 51
52 Titration of tweezer 1c and AcArgMe in phosphate buffer (1 mm, ph 7.2) Receptor 1c M R [g/mol] Solvent Phosphate buffer M S [g/mol] T[ o C] 25 m R [mg].8 Substrate AcArgMe m S [mg].511 H 2 N X NH 2 C N H 5 X : HP HN CH 3 CH 3 δ (2-H) [ppm] = V [ml] 3.42 δ (5-H) [ppm] = [S] [mm].562 δ (4-H) [ppm] = δ (-NAc) [ppm] = 2.52 δ (-C 2 Me) [ppm] = V [ml] [R] [mm] δ (5-H) [ppm] Δδ obs [ppm] Δδ calc [ppm] ppm 3 2 1,,2,4,6,8,1,12,14,16,18,2 [R][mol/l] K a [M -1 ] = ± 561 K d [µm] = 88 ± 5 % Δδ max (2-H) [ppm] =.42 Δδ max (3-H) [ppm] = 1.32 Δδ max (4-H) [ppm] = 2.51 Δδ max (5-H) [ppm] = 3.86 * Limit of 95% - confidence interval from the nonlinear regression of the signals of the Protons 5-H. 52
53 NMR titrations of the carboxymethyl tweezer 1d Titration of tweezer 1d andaclysme in phosphate buffer (1 mm, ph 7.2) Receptor 1d M R [g/mol] Solvent Phosphate buffer (74 mm) M S [g/mol] T[ o C] 25 m R [mg].91 Substrate AcLysMe m S [mg] H 3 N 2 CH HN CH 3 X X : HP 4 2- δ (3b-H) [ppm] = V [ml] 3. δ (6-H) [ppm] = [S ][mm].771 δ (-NAc) [ppm] = 2.38 δ (-C 2 Me) [ppm] = V [ml] [R][mM] δ (3b-H) Δδ obs [ppm] Δδ calc [ppm] [ppm] ,5,4 ppm],3,2,1,,,5,1,15,2,25 [R][mol/L] K a [M -1 ] = 859 ± 11% Δδ max (3a-H) [ppm] =.52 Δδ max (3b-H) [ppm] =.77 Δδ max (4-H) [ppm] =.4 Δδ max (5-H) [ppm] =.54 Δδ max (6-H) [ppm] =.94 * Limit of 95% - confidence interval from the nonlinear regression of the signals of the Protons 3b-H. 53
54 Titration of tweezer 1d and AcArgMe in phosphate buffer (1 mm, ph 7.2) Receptor 1d M R [g/mol] Solvent Phosphate buffer (74 mm) M S [g/mol] T[ o C] 25 m R [mg].77 Substrate AcArgMe m S [mg].552 H 2 N X NH 2 C N H 5 X : HP HN CH 3 CH 3 δ (2-H) [ppm] = V [ml] 3. δ (5-H) [ppm] = [S] [mm].6898 δ (3-H) [ppm] = δ (-NAc) [ppm] = 2.41 δ (-C 2 Me) [ppm] = V [ml] [R] [mm] δ (5-H) [ppm] Δδ obs [ppm] Δδ calc [ppm] ,6,5 ppm,4,3,2,1 K a [M -1 ] = 718 ± 18% Δδ max (5-H) [ppm] =.96 Δδ max (4b-H) [ppm] =.62 Δδ max (4a-H) [ppm] =.48 Δδ max (3-H) [ppm] =.52,,,2,4,6,8,1,12,14,16,18,2 [R][mol/L] * Limit of 95% - confidence interval from the nonlinear regression of the signals of the Protons 5-H. 54
55 1.5 Solvent-dependent 1 H NMR spectra of the complexes Figure S2. 1 H-NMR spectra of 1:1 mixture of the phosphate tweezer 1a and AcLysMe in different polarity medium methanol/phosphate buffer (1mM, ph 7.2) mixture. Lysine side-chain protons are assigned by numbers. 1:1 complex in CD3D:PB (2:1) 1:1 complex in CD3D:PB (1:2) 1:1 complex in CD3D:PB (1:9) 1:1 complex in PB Figure S3. 1 H-NMR spectra of 1:1 mixture of the phosphate tweezer 1a and AcArgMeeach at 1. mm concentration in different polarity medium methanol/phosphate buffer (PB, 1mM, ph 7.2) mixture. The spectrum in methanol/buffer (1:9) was measured at.5 mm concentration of both host and guest. Arginine side chain protons are assigned by numbers. 55
56 Figure S4. 1 H-NMR spectra of 1:1 mixture of the sulfate tweezer 1c and AcLysMe, each at 1. mm concentration.signals of lysine side-chain are shifted upfieldin the similar range both in buffer and in methanol. 6-H protons of lysine shifted upfield by ~ 3.4 ppm in phosphate buffer (1 mm, ph 7.2) and by ~ 3. ppm in methanol. 1:1 complex in PB Figure S5. 1 H-NMR spectra of 1:1 ratio of the sulfate tweezer 1c and AcArgMe, each at 1. mm concentration.signals of the arginine side chain protons areshifted upfield strongly in buffer but only weakly in methanol. The signal of the arginine protons 5-H is shifted upfield by ~ 2.7 ppm in buffer and by ~.7 ppm in methanol. 56
57 1.6 Isothermal titration calorimetry (ITC) studies of thehost-guest complex formation of tweezers 1a and 1c. ITC experiments of the phosphate tweezer 1a complexes ITC titration of the tweezer 1a (.1 mm) with AcLysMe (1. mm) in phosphate buffer (1 mm, ph 7.6) Nr. K a [M -1 ] n H[kcal/mol] -T S[kcal/mol] G[kcal/mol] ± ± ± ± ± ± Time (min) Time (min) µcal/sec µcal/sec kcal/mole of injectant -2 kcal/mole of injectant Molar Ratio Molar Ratio ITC titration of the tweezer 1a (.1 mm) with AcArgMe (1. mm) in phosphate buffer (1 mm, ph 7.6) Nr. K a [M -1 ] n H[kcal/mol] -T S[kcal/mol] G[kcal/mol] ± ± ± ± ± ±
58 .2 Time (min) Time (min) µcal/sec µcal/sec kcal/mole of injectant -2 kcal/mole of injectant Molar Ratio Molar Ratio ITC titration of the tweezer 1a (.1 mm) with KLVFF (.65 mm) in phosphate buffer (1 mm, ph 7.6) Nr. K a [M -1 ] n H[kcal/mol] -T S[kcal/mol] G[kcal/mol] ± ± ± ± ± ± Time (min) Time (min) µcal/sec -.6 µcal/sec kcal/mole of injectant -2-4 kcal/mole of injectant Molar Ratio Molar Ratio 58
59 ITC experiments of the sulfate tweezer 1c complexes ITC titration of the tweezer 1c (.1 mm) with AcLysMe (1. mm) in phosphate buffer (1 mm, ph 7.6) Nr. K a [M -1 ] n H[kcal/mol] -T S[kcal/mol] G[kcal/mol] ± ± ± ± ± ± µcal/sec Time (min) µcal/sec Time (min) -2-2 kcal/mole of injectant -4 kcal/mole of injectant Molar Ratio Molar Ratio The ITC titration of the tweezer 1c (.1 mm) with AcArgMe (1. mm) in phosphate buffer (1 mm, ph 7.6) Nr. K a [M -1 ] n H[kcal/mol] -T S[kcal/mol] G[kcal/mol] ± 1.94 ± ± ± ± ±
60 Time (min) Time (min) µcal/sec -.4 µcal/sec kcal/mole of injectant -2 kcal/mole of injectant Molar Ratio Molar Ratio 2. Computational Section: 2.1 Calculation of host-guest complex structures by QM/MM: Material and Methods The models of the inclusion complexes between the anionic tweezers 1a -d and amino acids or short peptides were built by using the VMD program. 1 Since the phosphate tweezers 1a is partially protonated in buffered aqueous solution at almost neutral ph value, we also used the mono- and diprotonated structures 1a and 1a for the calculations (Figure 7). The neutralized initial structures were then submitted to energy minimizations with the CHARMM c33b1 program. 2 After that, the system was placed in a water sphere of 3 Å of radii centered on one of the central carbon atoms of the tweezers. To ensure a correct water distribution twelve hydration-minimization cycles were performed. To prevent the water molecules from vaporing off, a four order polynomial potential was applied to all water oxygen atoms. After this, the hydrated systems were submitted to 1 ns MD simulations at 3 K for which the program CHARMM c33b1 with the CHARMM22 force field and the TIP3P model for water were used. 3,4 The parameters for the tweezers and tosyl terminal group were generated using the Swissparam server and tested by us (unpublished data). 5 Randomly selected snapshots from the MD simulations were then submitted to QM/MM optimization. The QM/MM optimizations were performed with the program ChemShell v The Turbomole 5.1 program was used to handle the QM region and DL_PLY, as driver of the 6
61 CHARMM22force field, to treat the MM part. 7,8 The QM part which includes all atoms of the tweezers and part of the lateral chain of Lys or Arg (see Figure S) was described using the B3LYP density functional with empirical dispersive energy correction (B3LYP-D2) and the SVP basis set from the Turbomole basis set library. 9,1,11 pen valencies at the QM/MM border were saturated using hydrogen link atoms. 12 An electrostatic embedding scheme was used for the interactions between QM and MM regions. 13 To avoid overpolarization of the QM region at the boundary a charge shift scheme was applied. 14 No electrostatic cutoffs were used. The optimization was performed with the HDLC optimizer. 15 The active region consisted of a water sphere of 13 Å of radii centered on one of the central carbon atoms of the tweezers. All atoms within the active region were allowed to move in each optimization step. The optimization was finished when the maximum gradient component was below.45 a.u. Figure S6. A Distances (black dotted lines) and angle (blue dotted line) used to describe the interaction between the molecular tweezers and the amino acid and peptides models (Y = P, S, or C atom of the CH 2 C - 2 group of the tweezers, X = the N atom or the central C atom of the guanidinium moiety in the lateral chain of Lys or Arg respectively). B Atoms of the lateral chains of Arg and Lys included in the QM region used for the QM/MM optimizations are highlighted with a sphere representation. Table S1. Representative distances and the C 1 -C 2 -X angle for the isolated tweezers and the inclusion complexes between the tweezers and different Lys/Arg/peptide models (o stands for the guest not inserted in the tweezers cavity and i when the guest is threaded inside the tweezers). Depending on the systems X is the P, S or the C atom of the carboxylate group of the tweezers, while Y is the N or the central C atom of the guanidinium moiety in the lateral chain of Lys or Arg respectively. π H-cis the distance between the orto hydrogen atom of the last benzene ring and the center of the opposite benzene ring (see Figure 6). Values in 61
62 parentheses are for QM/MM optimized structures. All distances are in Å and the angle in degrees. System C p -C p C m -C m X-Y C 1 -C 2 -X π H-c 1a 5.51 ± ± ± (5.24) (3.51) (3.81) 1a 5.71 ± ± ± (5.43) (3.8) (4.13) 1a H Lys H 5.51 ± ± ± ± 3 (5.24) (3.71) (3.39) (88) - 1a KAA 5.8 ± ± ±.1 92 ± 3 (5.32) (3.85) (3.29) (89) - 1a Ac Lys Me 6.24 ± ± ±.1 95 ± 3 (5.63) (4.24) (3.91) (98) - 1a Ac ArgMe 5.62 ± ± ±.7 91 ± 3 (5.52) (3.76) (4.) (89) - 1b 1b Ac Lys Me 1b TsArgMe 6.49 ±.24 (5.94) 7.23 ±.22 (7.83) 5.53 ±.18 (5.33) 4.96 ±.26 (4.33) 6.29 ±.21 (6.82) 3.86 ±.17 (3.83) ±.12 (4.6) 3.88 ±.1 (3.95) 65 ± 3 (65) 86 ± 3 (82) 5.66 ±.31 (4.76) - - 1c 1c Ac Lys Me 1c Ac ArgMe 5.81 ±.22 (5.49) 5.69 ±.22 (5.48) 5.58 ±.17 (5.16) 3.96 ±.2 (3.89) 4.82 ±.22 (4.52) 3.72 ±.15 (3.48) ±.1 (4.6) 4.1 ±.1 (4.28) 64 ± 3 (62) 82 ± 3 (78) 4.14 ±.25 (4.5) - - 1d 1d Ac Lys Me (i) 1d Ac Lys Me (o) 1d Ac ArgMe (i) 1d Ac Arg Me (o) 5.54 ±.2 (5.25) 5.3 ±.19 (4.97) 5.48 ±.19 (5.54) 5.55 ±.18 (5.2) 5.67 ±.22 (5.4) 3.73 ±.17 (3.51) 3.77 ±.16 (3.53) 3.78 ±.18 (3.68) 3.79 ±.16 (3.42) 3.97 ±.21 (3.67) ±.19 (3.48) 3.32 ±.14 (3.2) 3.64 ±.1 (3.6) 3.84 ±.1 (3.9) 74 ± 3 (72) 64 ± 3 (62) 77 ± 3 (77) 69 ± 3 (65) 4.38 ±.25 (3.87) References (1) Humphrey, W., A. Dalke, and K. Schulten, VMD: Visual Molecular Dynamics. J. Mol. Graphics, : p (2) Brooks, B.R., et al., CHARMM: a program for macromolecular energy, minimization, and dynamics calculations. J. Comput. Chem (2): p
63 (3) Jorgensen, W.L., et al., Comparison of simple potential functions for simulating liquid water. The Journal of Chemical Physics, (2): p (4) Mackerell, A.D., Jr, M. Feig, and C.L. Brooks, III, Extending the Treatment of Backbone Energetics in Protein Force Fields: Limitations of Gas-Phase Quantum Mechanics in Reproducing Protein Conformational Distributions in Molecular Dynamics Simulations. J. Comput. Chem., : p (5) Zoete, V., et al., SwissParam: A Fast Force Field Generation Tool for Small rganic Molecules. J. Comp. Chem., : p (6) Chemshell, a Computational Chemistry Shell ( (7) Ahlrichs, R., et al., Electronic Structure calculation on workstation computers: The program system TURBMLE. Chem. Phys. Lett., : p (8) Smith, W. and T.R. Forester, DL-PLY _2.: a general-purpose parallel molecular dynamics simulation package. J. Mol. Graphics, (3): p (9) Lee, C., W. Yang, and R.G. Parr, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B, : p (1) Grimme, S., Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J ComputChem, (15): p (11) Schäfer, A., H. Horn, and R. Ahlrichs, Fully optimized contracted Gaussian basis sets for atoms Li to Kr. J. Chem. Phys., : p (12) Antes, I. and W. Thiel, n the treatment of link atoms in hybrid methods. ACS Symp. Ser., (Combined Quantum Mechanical and Molecular Mechanical Methods): p (13) Bakowies, D. and W. Thiel, Hybrid Models for Combined Quantum Mechanical and Molecular Mechanical Approaches. J. Phys. Chem., : p (14) de Vries, A.H., et al., Zeolite Structure and Reactivity by Combined Quantum-Chemical- Classical Calculations. J. Phys. Chem. B, (29): p (15) Billeter, S.R., A.J. Turnera, and W. Thiel, Linear scaling geometry optimisation and transition state search in hybrid delocalised internal coordinates.phys. Chem. Chem. Phys.2. 2: p
64 2.2 Calculation of 1 H NMR shifts of the guest signals by ab initio methods The solvent effects were modelled using optimized QM/MM structures with an explicit, static 4-Å water layer around both (the host-guest complex and the pure guest molecule as well). Figure S7 shows the compexstructures used for the computation of 1 H NMR shifts without the water layer: 1a H Lys H, 1 1a H Lys H, 2 1a H Lys H 1a H Lys H 1a H Lys H 1a Ac Lys Me, 1 64
65 1a Ac Lys Me, 2 1a Ac Lys Me 1a Ac Lys Me 1a KAA, 1 1a KAA, 2 1a KAA 65
66 1a KAA 1a H Arg H, 1 1a H Arg H, 2 1a H Arg H 1a H Arg H 1a Ac ArgMe, 1 66
67 1a Ac ArgMe, 2 1a Ac ArgMe 1a Ac ArgMe Figure S7. Host-guest complex structures of the differently protonated phosphate tweezers 1a ( 1: R 1 = P 2-3, R 2 = P(H) - 2 ), 1a ( 1: R 1 = R 2 = P(H) - 2 ), 1a ( 1: R 1 = R 2 = P 2-3 ) with lysine and arginine derivatives (without counterions) optimized by QM/MM calculations, each structure contains a 4Å water layer. In each host-guest complex of the tweezer1a there are two conformers, one with the positively charged lysine ammonium or arginine guanidinium end group pointing toward the doubly negatively charged phosphate group (1) and the other one pointing away from the doubly negatively charged phosphate group (2). 67
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