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Encapsulation of Volatile Hydrocarbons by Cucurbiturils CHAPTER 2 the inner CB cavity. As a result, dispersion interactions certainly do not afford an enthalpic driving force for guest inclusion and the complexation of neutral guests with CBn can be considered as purely hydrophobic in nature. Table 2.1.1. Binding affinities and volumes of hydrophobic residues encapsulated by the CB7 cavity. [a] Recognition motif, R Guest K [M –1 ] V [Å 3 ] [b] CH 2 OH R = 1-adamantyl 2.3 × 10 10 147 R = ferrocenyl Fe CH 2 OH 3.2 × 10 9 141 1-hydroxymethyladamantane hydroxymethylferrocene R = bicyclo[2.2.2]octane CH 2 OH BCO CH 2 OH 6.1 × 10 9 121 R = 2,3-diazabicyclo[2.2.2]- oct-2-ene [c] N DBO N 5.8 × 10 6 111 [a] From ref. [100] . [b] Calculated volume corresponds to that of the immersed residue, R, in the CB7 cavity. Volume calculation was performed with the QSAR module of HyperChem [101] after optimization with the AM1 semiempirical method. [c] From ref. [102] The first neutral guests detected to form inclusion complexes with CBn are water molecules, found in several crystal structures. [34] Their presence is inevitable and we have recently estimated the occupancy of the inner cavities of CBn with these very-high-energy guests. As expected, the number of water 26
Encapsulation of Volatile Hydrocarbons by Cucurbiturils CHAPTER 2 molecules found in the absence of other encapsulated guests increases with the size of the macrocyclic cavity: CB5 houses two water molecules, CB6 four (Figure 2.1.4), CB7 eight, and CB8 twelve molecules. [34] The number of expelled water molecules upon encapsulation of a guest can be estimated from the guest volume. The entropic contribution of the hosted water molecules represents, in addition to the “unimportance of dispersion interactions” (vide supra), a significant aspect of the driving force that leads to the encapsulation of hydrophobic residues inside the CB macrocycles. To illustrate how these unusual characteristics of the CB inner cavity are influential for the hydrophobic driving force leading to complexation, let us take the examples of several selected neutral guests or residues previously reported to form inclusion complexes with CBn. For instance, the tricyclic 1-hydroxymethyladamantyl, and the bicyclics hydroxymethyl-ferrocenyl, the bicyclo[2.2.2]octanederivative (BCO), and DBO, are known to bind strongly with CB7. In fact, the binding constants of some of these residues (with appended ammonium groups) with CB7 are so high, that they were compared to the biotin-avidin affinity. [51,100] Initially, attractive van der Waals interactions have been held responsible for the high binding between the hydrophobic cores of the guests and the CB cavity. However, upon closer inspection, it can be noted that all these guests are able to completely remove all water molecules, usually residing in the inner CB7 cavity. Thus, in reality, the differences in binding constants (Table 2.1.1) are due to the differential solvation of the hydrophobic residues. Note that this is a significant factor in the complexation thermodynamics of guest molecules with any macrocycle, not only with CBn. Since both, adamantyl and ferrocenyl, residues are almost isosteric (approximately same volume), one would expect identical affinities towards CB7. Yet, adamantyl displays slightly higher binding affinity, which can be explained by the differences in polarizability of the two residues: the more polarizable ferrocenyl undergoes a better solvation in water, leading to dispersive interactions to favor a stabilization of the residue in bulk water. A similar situation is encountered for DBO and BCO. The three orders of magnitude lower binding constant of DBO can be ascribed to the dipolar azo group, which renders this neutral compound highly water-soluble and polarizable. Consequently, a higher energy input is necessary for its desolvation. In fact, it has been reassuring to see how these results are highly supportive also towards our 27
Page 1: Applications of Fluorescent Displac
Page 5 and 6: TABLE OF CONTENTS Abstract.........
Page 7 and 8: ABSTRACT The present doctoral thesi
Page 9 and 10: ACKNOWLEDGEMENTS First of all, I wo
Page 11 and 12: LIST OF PUBLICATIONS 1. M. Florea,
Page 13 and 14: PARTICIPATION IN SCIENTIFIC CONFERE
Page 15 and 16: Park, MD, USA. M. Florea and W. M.
Page 17 and 18: SUMMARY The goal of this PhD thesis
Page 19 and 20: CHAPTER 1 - Introduction -
Page 21 and 22: CHAPTER 1 Introduction 1.1 SUPRAMOL
Page 23 and 24: CHAPTER 1 Introduction antibody, wh
Page 25 and 26: CHAPTER 1 Introduction charged amin
Page 27 and 28: CHAPTER 1 Introduction differences
Page 29 and 30: CHAPTER 1 Introduction obstacles ar
Page 31 and 32: CHAPTER 1 Introduction N N N N NH N
Page 33 and 34: CHAPTER 1 Introduction Scheme 1.4.1
Page 35 and 36: CHAPTER 1 Introduction macrocyclic
Page 37 and 38: CHAPTER 2 - Encapsulation of Volati
Page 39 and 40: Encapsulation of Volatile Hydrocarb
Page 43: Encapsulation of Volatile Hydrocarb
Page 61 and 62: CHAPTER 3 - Analyte Sensing in the
Page 63 and 64: CHAPTER 3 Analyte Sensing in the Co
Page 91 and 92: CHAPTER 4 - Experimental Section -
Page 93 and 94: Experimental Section CHAPTER 4 4.1
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Experimental Section CHAPTER 4 Dens
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Experimental Section CHAPTER 4 Plea
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CHAPTER 5 Preliminary Results Towar
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CHAPTER 5 What’s next? In the ear
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CHAPTER 5 What’s next? Figure 5.1
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CHAPTER 5 What’s next? the develo
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CHAPTER 5 What’s next? to that of
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CHAPTER 5 What’s next? Figure 5.2
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CHAPTER 5 What’s next? messenger
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REFERENCES
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References [1] C. J. Pederson, Ange
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References [62] H. Bakirci, A. L. K
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References [123] L. Fusaro, E. Locc
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References [176] J. de Villiers, L.
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APPENDICES 105
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APPENDIX 1 A. Hennig, M. Florea, D.
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Design of Peptide Substrates for Na
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Scheme 1: Principles of fluorescent
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We have recently communicated a com
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Results and Discussion The peculiar
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acids not only by-passes the introd
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the efficiency of quenching by Tyr
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after cleavage (or which display th
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Fig. 4: Optimization of substrate-p
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References [1] L. Hedstrom, Serine
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[40] Y.-Q. Gu, L.L. Walling, Specif
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Figure Legends Scheme 1: Principles
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Table 2: Comparison of the increase
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134
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Introduction One of the most import
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were determined UV-spectrophotometr
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Photophysical Characterization of T
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fluorescence lifetimes are due to t
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fluorescence lifetimes before addit
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a 10% error. b Abbreviations used:
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The two methods are highly compleme
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the EGFR kinase favored peptide 2 a
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subsequently elaborated this method
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Conclusion We have introduced a con
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(27) Zhang, Z.-Y.; Clemens, J. C.;
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(78) Edison, A. M.; Barker, S. C.;
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160
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Fluoreszenzlebensdauern, so dass ei
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I TRF rel = I t delay Nano-TRF = +
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Produkt einer enzymatischen Reaktio
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werden, im Fall der Decarboxylasen
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(18) Geymayer P, Bahr N, Reymond J-
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Abbildungen Abb. 1. Chemische Struk
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Abb. 4: Experimentelle Fluoreszenzz
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Abb. 6: Fluoreszenzmessungen von Mi
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Abb. 8: Kontinuierlicher Fluoreszen
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182
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184
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Chart 1 Investigated library of mac
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eporter pairs into supramolecular t
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Instrumentation Fluorescence spectr
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192
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194
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The Inner Cavity of Cucurbiturils N
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The Inner Cavity of Cucurbiturils 2
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The Inner Cavity of Cucurbiturils B
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The Inner Cavity of Cucurbiturils T
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The Inner Cavity of Cucurbiturils s
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The Inner Cavity of Cucurbiturils a
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The Inner Cavity of Cucurbiturils 6
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The Inner Cavity of Cucurbiturils d
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Review C. Author et al. 212 18
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214
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volatile hydrocarbons, the binding
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(which afforded the same results) w
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220
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222
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06/2010 University of Cambridge, UK
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R. Sharma, M. Florea, W. M. Nau, K.
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