Abstract
The affinity of cyclodextrins for organic and even inorganic pollutants has led to the development of numerous remediation methods at the laboratory scale. Indeed, the hydrophobic cavity of cyclodextrins constitute a versatile vehicle for the efficient transfer of various pollutants from their initial environmental compartment to the cyclodextrin cavity. This transfer can be applied to any environmental media such as soil, water or atmosphere, because cyclodextrins can be dissolved in water solutions or immobilized on solid supports. Both recovery or destructive processes have thus been designed on the basis of cyclodextrin affinity for the target pollutants. As a consequence, the stability of host-guest edifices is of crucial importance for the efficiency of cyclodextrin applications. Therefore, formation constants of such inclusion compounds have been thoroughly investigated, aiming at the custom design of host-guest couples for a given application. Indeed, the molecular shape of the cavity, and consequently the inclusion compound stability, can be tuned by using cyclodextrins of different size or by taking advantage of chemical modifications on the macrocycle.
Nevertheless, the rational design of the perfect cyclodextrin may be hindered by a large uncertainty on the complex stability. Indeed, large discrepancies are observed for a given complex in the cyclodextrin literature. There is a lack of a generalized scheme for the measurement of affinity. Therefore, this chapter reviews the common experimental approaches and proposes a unified framework for measuring binding constants of cyclodextrins inclusion compounds. This unified approach relies on the use of minimization algorithms and is decomposed into major associated concepts, with the description of experimental protocols, equilibriums, analytical methods and data treatments. The chapter discusses the concept of global analysis and the issues of stability accuracy, optimization of experimental conditions and evaluation of thermodynamic parameters. Future research will probably focus on the generalization of algorithmic treatments, global analysis and statistical evaluation.
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Notes
- 1.
To the contrary, similar shapes would be obtained by signal integration, i.e. if each recorded heat is added to the sum of the previous ones.
- 2.
The use of Δn is specific to ITC measurements. The exact equation defining Δn can be found in Bertaut and Landy 2014.
- 3.
The limiting partner refers here to the partner which is used at the lower concentration during the binding experiment. For instance, in titration experiments, the limiting partner is the titrate.
References
Abe K, Ogawa N, Nagase H, Endo T, Ueda H (2011) Evaluation of the abilities of γ-cyclodextrin to form complexes by surface plasmon resonance with a Biacore® system. J Incl Phenom Macrocycl Chem 70(3–4):385–388. https://doi.org/10.1007/s10847-010-9883-4
Almansa López E, Bosque-Sendra JM, Cuadros Rodríguez L, García Campaña AM, Aaron JJ (2003) Applying non-parametric statistical methods to the classical measurements of inclusion complex binding constants. Anal Bioanal Chem 375(3):414–423. https://doi.org/10.1007/s00216-002-1693-0
Anand R, Ottani S, Manoli F, Manet I, Monti S (2012) A close-up on doxorubicin binding to γ-cyclodextrin: an elucidating spectroscopic, photophysical and conformational study. RSC Adv 2(6):2346–2357. https://doi.org/10.1039/c2ra01221a
Benesi HA, Hildebrand JH (1949) Solubility of iodine in 1, 2-dichloroethanes, cis- and trans- dichloroethylenes and perfluoro-n-heptane. J Am Chem Soc 70(12):3978–3981. https://doi.org/10.1021/ja01192a003
Benk M, Király Z (2012) Thermodynamics of inclusion complex formation of β-cyclodextrin with a variety of surfactants differing in the nature of headgroup. J Chem Thermodyn 54:221–216. https://doi.org/10.1016/j.jct.2012.03.033
Bertaut E, Landy D (2014) Improving ITC studies of cyclodextrin inclusion compounds by global analysis of conventional and non-conventional experiments. Beilstein J Org Chem 10:2630–2641. https://doi.org/10.3762/bjoc.10.275
Blyshak LA, Dodson KY, Patonay G, Warner IM, May WE (1989) Determination of cyclodextrin formation constants using dynamic coupled-column liquid chromatography. Anal Chem 61(9):955–960. https://doi.org/10.1021/ac00184a008
Brown SE, Easton CJ, Kelly JB (2003) Surface plasmon resonance to determine apparent stability constants for the binding of cyclodextrins to small immobilized guests. J Incl Phenom Macrocycl Chem 46(3–4):167–173. https://doi.org/10.1023/A:1026311003881
Connors KA (1995) Population characteristics of cyclodextrin complex ctabilities in aqueous solution. J Pharm Sci 84(7):843–848
Connors KA (1996) Measurement of cyclodextrin complex stability constants. In: Szejtli Z, Osa T (eds) Comprehensive supramolecular chemistry, vol 3. Elsevier Science Ltd., Rugby, Netherland, pp 205–242
Connors KA (1997) The stability of cyclodextrin complexes in solution. Chem Rev 97:1325–1358. https://doi.org/10.1021/cr960371r
Cooper A, Nutley M, MacLean EJ, Cameron K, Fielding L, Mestres J, Palin R (2005) Mutual induced fit in cyclodextrin-rocuronium complexes. Org Biomol Chem 3(10):1863–1871. https://doi.org/10.1039/b415903a
Dahab AA, El DH (2012) Rapid analysis of NSAIDs binding to β-cyclodextrin using the simultaneous measurement of absorption and circular dichroism with a novel multi-cell low-volume device. Anal Bioanal Chem 404:1839–1850. https://doi.org/10.1007/s00216-012-6286-y
De Feyter S, Van Stam J, Boens N, De Schryver FC (1996) On the use of dynamic fluorescence measurements to determine equilibrium and kinetic constants. The inclusion of pyrene in β-cyclodextrin cavities. Chem Phys Lett 249(1–2):46–52. https://doi.org/10.1016/0009-2614(95)01365-2
Dodziuk H, Nowinski KS, Kozminski W, Dolgonos G (2003) On the impossibility of determination of stepwise binding constants for the 1:2 complex of (+)-camphor with α-cyclodextrin. Org Biomol Chem 1(3):581–584. https://doi.org/10.1039/b209272g
Exner O (1997) Calculating equilibrium constants from spectral data: reliability of the Benesi-Hildebrand method and its modifications. Chemom Intell Lab Syst 39(1):85–93. https://doi.org/10.1016/S0169-7439(97)00057-9
Fakayode SO, Brady PN, Pollard DA, Mohammed AK, Warner IM (2009) Multicomponent analyses of chiral samples by use of regression analysis of UV-visible spectra of cyclodextrin guest-host complexes. Anal Bioanal Chem 394(6):1645–1653. https://doi.org/10.1007/s00216-009-2853-2
Fang N, Chen DDY (2005) Enumeration algorithm for determination of binding constants in capillary electrophoresis. Anal Chem 77(8):2415–2420. https://doi.org/10.1021/ac048509q
Fielding L (2000) Determination of association constants (K(a)) from solution NMR data. Tetrahedron 56(34):6151–6170. https://doi.org/10.1016/S0040-4020(00)00492-0
Fourmentin S, Outirit M, Blach P, Landy D, Ponchel A, Monflier E, Surpateanu G (2007) Solubilisation of chlorinated solvents by cyclodextrin derivatives: a study by static headspace gas chromatography and molecular modelling. J Hazard Mater 141(1):92–97. https://doi.org/10.1016/j.jhazmat.2006.06.090
Fourmentin S, Ciobanu A, Landy D, Wenz G (2013) Space filling of β-cyclodextrin and β-cyclodextrin derivatives by volatile hydrophobic guests. Beilstein J Org Chem 9:1185–1191. https://doi.org/10.3762/bjoc.9.133
Freiburger LA, Auclair K, Mittermaier AK (2012) van 't Hoff global analyses of variable temperature isothermal titration calorimetry data. Thermochim Acta 527:148–157. https://doi.org/10.1016/j.tca.2011.10.018
Fujiki M, Deguchi T, Sanemasa I (1988) Association of naphthalene and its methyl derivatives with cyclodextrins in aqueous medium. Bull Chem Soc Jpn 61(4):1163–1167. https://doi.org/10.1246/bcsj.61.1163
Funasaki N, Nagaoka M, Hirota S (2005) Competitive potentiometric determination of binding constants between α-cyclodextrin and 1-alkanols. Anal Chim Acta 531(1):147–151. https://doi.org/10.1016/j.aca.2004.09.079
Granadero D, Bordello J, Pérez-Alvite MJ, Novo M, Al-Soufi W (2010) Host-guest complexation studied by fluorescence correlation spectroscopy: Adamantane-cyclodextrin inclusion. Int J Mol Sci 11(1):173–188. https://doi.org/10.3390/ijms11010173
Hamai S, Koshiyama T (1999) Electronic absorption, fluorescence, and circular dichroism spectroscopic studies on the inclusion complexes of tetrakis(4-sulfonatophenyl)porphyrin with cyclodextrins in basic aqueous solutions. J Photochem Photobiol A 127(1–3):135–141. https://doi.org/10.1016/S1010-6030(99)00144-6
Hansen LD, Fellingham GW, Russell DJ (2011) Simultaneous determination of equilibrium constants and enthalpy changes by titration calorimetry: methods, instruments, and uncertainties. Anal Biochem 409(2):220–229. https://doi.org/10.1016/j.ab.2010.11.002
Heerklotz HH, Binder H, Epand RM (1999) A “release” protocol for isothermal titration calorimetry. Biophys J 76(5):2606–2613. https://doi.org/10.1016/S0006-3495(99)77413-8
Higuchi T, Connors KA (1965) Phase-solubility techniques. Adv Anal Chem Instrum 4:117–212
Hirayama F, Uekama K (1987) Methods of investigating and preparing inclusion compounds. In: Duchêne D (ed) Cyclodextrins and their industrial uses. Editions de Santé, Paris, pp 131–172
Illapakurthy AC, Wyandt CM, Stodghill SP (2005) Isothermal titration calorimetry method for determination of cyclodextrin complexation thermodynamics between artemisinin and naproxen under varying environmental conditions. Eur J Pharm Biopharm 59(2):325–332. https://doi.org/10.1016/j.ejpb.2004.08.006
Job P (1928) Formation and stability of inorganic complexes in solution. Ann Chim 9:113–204
Kobayashi H, Endo T, Ogawa N, Nagase H, Iwata M, Ueda H (2011) Evaluation of the interaction between β-cyclodextrin and psychotropic drugs by surface plasmon resonance assay with a Biacore® system. J Pharm Biomed Anal 54(1):258–263. https://doi.org/10.1016/j.jpba.2010.08.012
Landy D, Fourmentin S, Salome M, Surpateanu G (2000) Analytical improvement in measuring formation constants of inclusion complexes between β-cyclodextrin and phenolic compounds. J Incl Phenom Macrocycl Chem 38(1–4):187–198. https://doi.org/10.1023/A:1008156110999
Landy D, Tetart F, Truant E, Blach P, Fourmentin S, Surpateanu G (2007) Development of a competitive continuous variation plot for the determination of inclusion compounds stoichiometry. J Incl Phenom Macrocycl Chem 57(1–4):409–413. https://doi.org/10.1007/s10847-006-9226-7
Landy D, Mallard I, Ponchel A, Monflier E, Fourmentin S (2012) Remediation technologies using cyclodextrins: an overview. Environ Chem Lett 10(3):225–237. https://doi.org/10.1007/s10311-011-0351-1
Li X, Li H, Liu M, Li G, Li L, Sun D (2011) From guest to ligand a study on the competing interactions of antitumor drug resveratrol with β-cyclodextrin and bovine serum albumin. Thermochim Acta 521(1–2):74–79. https://doi.org/10.1016/j.tca.2011.04.007
Lo Meo P, D'Anna F, Riela S, Gruttadauria M, Noto R (2006) Polarimetry as a useful tool for the determination of binding constants between cyclodextrins and organic guest molecules. Tetrahedron Lett 47(51):9099–9102. https://doi.org/10.1016/j.tetlet.2006.10.078
Loftsson T, Másson M, Brewster ME (2004) Self-association of cyclodextrins and cyclodextrin complexes. J Pharm Sci 93(5):1091–1099. https://doi.org/10.1002/jps.20047
López-Nicolás JM, Núñez-Delicado E, Pérez-López AJ, Barrachina AC, Cuadra-Crespo P (2006) Determination of stoichiometric coefficients and apparent formation constants for β-cyclodextrin complexes of trans-resveratrol using reversed-phase liquid chromatography. J Chromatogr A 1135(2):158–165. https://doi.org/10.1016/j.chroma.2006.09.013
Lowe AJ, Pfeffer FM, Thordarson P (2012) Determining binding constants from 1H NMR titration data using global and local methods: a case study using [n] polynorbornane-based anion hosts. Supramol Chem 24(8):585–594. https://doi.org/10.1080/10610278.2012.688972
Lu Z, Lu C, Meng Q (2008) An inclusion complex of β-cyclodextrin with mnt anion (mnt = maleonitriledithiolate) studied by induced circular dichroism. J Incl Phenom Macrocycl Chem 61(1–2):101–106. https://doi.org/10.1007/s10847-007-9400-6
Maskevich AA, Kurhuzenkau SA, Lickevich AY (2013) Fluorescence spectral analysis of thioflavin T-γ-cyclodextrin interaction. J Appl Spectrosc 80(1):36–42. https://doi.org/10.1007/s10812-013-9717-4
Mizoue LS, Tellinghuisen J (2004) Calorimetric vs. van't Hoff binding enthalpies from isothermal titration calorimetry: Ba2+-crown ether complexation. Biophys Chem 110(1–2):15–24. https://doi.org/10.1016/j.bpc.2003.12.011
Mohamed MH, Wilson LD, Headley JV, Peru KM (2009) A spectral displacement study of cyclodextrin/naphthenic acids inclusion complexes. Can J Chem 87(12):1747–1756. https://doi.org/10.1139/V09-140
Monti S, Marconi G, Manoli F, Bortolus P, Mayer B, Grabner G, Köhler G, Boszczyk W, Rotkiewicz KA (2003) Spectroscopic and structural characterization of the inclusion complexes of p-dimethylaminobenzonitrile with cyclodextrins. Phys Chem Chem Phys 5(6):1019–1026. https://doi.org/10.1039/b209689g
Ono N, Hirayama F, Arima H, Uekama K (2001) Analysis of the phase solubility diagram of a phenacetin/competitor/β-cyclodextrin ternary system, involving competitive inclusion complexation. Chem Pharm Bull 49(1):78–81. https://doi.org/10.1248/cpb.49.78
Osajima T, Deguchi T, Sanemasa I (1991) Association of cycloalkanes with cyclodextrins in aqueous medium. Bull Chem Soc Jpn 64(9):2705–2709. https://doi.org/10.1246/bcsj.64.2705
Pessine FBT, Calderini A, Alexandrino GL (2012) Review: cyclodextrin inclusion complexes probed by NMR techniques. In: Kim D (ed) Magnetic resonance spectroscopy, vol 12, pp 237–265. https://doi.org/10.5772/32029
Pirnau A, Floare CG, Bogdan M (2014) The complexation of flurbiprofen with β-cyclodextrin: a NMR study in aqueous solution. J Incl Phenom Macrocycl Chem 78(1–4):113–120. https://doi.org/10.1007/s10847-012-0277-7
Rundlett KL, Armstrong DW (1997) Methods for the estimation of binding constants by capillary electrophoresis. Electrophoresis 18(12–13):2194–2202. https://doi.org/10.1002/elps.1150181210
Sanemasa I, Akamine Y (1987) Association of benzene and alkylbenzenes with cyclodextrins in aqueous medium. Bull Chem Soc Jpn 60(6):2059–2066. https://doi.org/10.1246/bcsj.60.2059
Sanemasa I, Takuma T, Deguchi T (1989) Association of some polynuclear aromatic hydrocarbons with cyclodextrins in aqueous medium. Bull Chem Soc Jpn 62(10):3098–3102. https://doi.org/10.1246/bcsj.62.3098
Scatchard G (1949) The attractions of proteins for small molecules and ions. Ann NY Acad Sci 51:660–672. https://doi.org/10.1111/j.1749-6632.1949.tb27297.x
Schönbeck C, Holm R, Westh P (2012) Higher order inclusion complexes and secondary interactions studied by global analysis of calorimetric titrations. Anal Chem 84(5):2305–2312. https://doi.org/10.1021/ac202842s
Scott RL (1956) Some comments on the Benesi Hildebrand equation. Recl Trav Chim Pays-Bas 75(7):787–789. https://doi.org/10.1002/recl.19560750711
Sigurskjold BW (2000) Exact analysis of competition ligand binding by displacement isothermal titration calorimetry. Anal Biochem 277(2):260–266. https://doi.org/10.1006/abio.1999.4402
Simova S, Berger S (2005) Diffusion measurements vs. chemical shift titration for determination of association constants on the example of camphor-cyclodextrin complexes. J Incl Phenom Macrocycl Chem 53(3):163–170. https://doi.org/10.1007/s10847-005-2631-5
Singh R, Bharti N, Madan J, Hiremath SN (2010) Characterization of cyclodextrin inclusion complexes – a review. J Pharm Sci Technol 2:171–183
Smith VJ, Bogdan D, Caira MR, Bogdan M, Bourne SA, F̌rcaş SI (2010) Cyclodextrin inclusion of four phenylurea herbicides: determination of complex stoichiometries and stability constants using solution 1H NMR spectroscopy. Supramol Chem 22(3):172–177. https://doi.org/10.1080/10610270902980655
Szaniszlo N, Fenyves E, Balla J (2005) Structure-stability study of cyclodextrin complexes with selected volatile hydrocarbon contaminants of soils. J Incl Phenom Macrocycl Chem 53(3):241–248. https://doi.org/10.1007/s10847-005-0245-6
Szejtli J (1996) Inclusion of guest molecules, selectivity and molecular recognition by cyclodextrins. In: Szejtli Z, Osa T (eds) Comprehensive supramolecular chemistry, vol 3. Elsevier Science Ltd., Rugby, Netherland, pp 189–204
Szente L (1996) Analytical methods for cyclodextrins, cyclodextrin derivatives, and cyclodextrin complexes. In: Szejtli Z, Osa T (eds) Comprehensive supramolecular chemistry, vol 3. Elsevier Science Ltd., Rugby, Netherland, pp 253–278
Takahashi AI, Veiga FJB, Ferraz HG (2012a) A literature review of cyclodextrin inclusion complexes characterization – part I: phase solubility diagram, dissolution and scanning electron microscopy. Int J Pharm Sci Rev Res 12(1):1–6
Takahashi AI, Veiga FJB, Ferraz HG (2012b) A literature review of cyclodextrin inclusion complexes characterization – part II: X-Ray diffraction, infrared spectroscopy and nuclear magnetic resonance. Int J Pharm Sci Rev Res 12(1):8–15
Takahashi AI, Veiga FJB, Ferraz HGA (2012c) Literature review of cyclodextrin inclusion complexes characterization – part III: differential scanning calorimetry and thermogravimetry. Int J Pharm Sci Rev Res 12(1):16–20
Tellinghuisen J (2000) Monte carlo study of precision, bias, inconsistency, and non-gaussian distributions in nonlinear least squares. J Phys Chem A 104(12):2834–2844. https://doi.org/10.1021/jp993279i
Tellinghuisen J (2004) Statistical error in isothermal titration calorimetry. Methods Enzymol 383:245–282. https://doi.org/10.1016/S0076-6879(04)83011-8
Tellinghuisen J (2005) Optimizing experimental parameters in isothermal titration calorimetry. J Phys Chem B 109(42):20027–20035. https://doi.org/10.1021/jp053550y
Tellinghuisen J (2007) Calibration in isothermal titration calorimetry: heat and cell volume from heat of dilution of NaCl(aq). Anal Biochem 360(1):47–55. https://doi.org/10.1016/j.ab.2006.10.015
Tellinghuisen J (2012) Designing isothermal titration calorimetry experiments for the study of 1:1 binding: problems with the “standard protocol”. Anal Biochem 424(2):211–220. https://doi.org/10.1016/j.ab.2011.12.035
Tellinghuisen J, Chodera JD (2011) Systematic errors in isothermal titration calorimetry: concentrations and baselines. Anal Biochem 414(2):297–299. https://doi.org/10.1016/j.ab.2011.03.024
Thordarson P (2011) Determining association constants from titration experiments in supramolecular chemistry. Chem Soc Rev 40(3):1305–1323. https://doi.org/10.1039/c0cs00062k
Tran CD, De Paoli Lacerda SH (2002) Determination of binding constants of cyclodextrins in room-temperature ionic liquids by near-infrared spectrometry. Anal Chem 74(20):5337–5341. https://doi.org/10.1021/ac020320w
Tutaj B, Kasprzyk A, Czapkiewicz J (2003) The spectral displacement technique for determining the binding constants of β-cyclodextrin – alkyltrimethylammonium inclusion complexes. J Incl Phenom Macrocycl Chem 47(3–4):133–136. https://doi.org/10.1023/B:JIPH.0000011783.40427.56
Ulatowski F, Dabrowa K, Bałakier T, Jurczak J (2016) Recognizing the limited applicability of job plots in studying host-guest interactions in supramolecular chemistry. J Org Chem 81(5):1746–1756. https://doi.org/10.1021/acs.joc.5b02909
Valente AJM, Söderman O (2014) The formation of host-guest complexes between surfactants and cyclodextrines. Adv Colloid Interf Sci 205:156–176. https://doi.org/10.1016/j.cis.2013.08.001
Wahl J, Furuishi T, Yonemochi E, Meinel L, Holzgrabe U (2017) Characterization of complexes between phenethylamine enantiomers and β-cyclodextrin derivatives by capillary electrophoresis-determination of binding constants and complex mobilities. Electrophoresis 38(8):1188–1200. https://doi.org/10.1002/elps.20160052
Wang ZX (1995) An exact mathematical expression for describing competitive binding of two different ligands to a protein molecule. FEBS Lett 360(2):111–114. https://doi.org/10.1016/0014-5793(95)00062-E
Wilson LD, Siddall SR, Verrall RE (1997) A spectral displacement study of the binding constants of cyclodextrin-hydrocarbon and -fluorocarbon surfactant inclusion complexes. Can J Chem 75(7):927–933. https://doi.org/10.1139/v97-111
Wintgens V, Amiel C (2004) New 4-amino-N-alkylphthalimides as fluorescence probes for β-cyclodextrin inclusion complexes and hydrophobic microdomains of amphiphilic systems. J Photochem Photobiol A 168(3):217–226. https://doi.org/10.1016/j.jphotochem.2004.06.002
Yang C, Liu L, Mu TW, Guo QX (2000) The performance of the Benesi-Hildebrand method in measuring the binding constants of the cyclodextrin complexation. Anal Sci 16(5):537–539. https://doi.org/10.2116/analsci.16.537
Zhukov A, Karlsson R (2007) Statistical aspects of van't Hoff analysis: a simulation study. J Mol Recognit 20(5):379–385. https://doi.org/10.1002/jmr.845
Zughul MB, Badwan AA (1998) SL2 type phase solubility diagrams, complex formation and chemical speciation of soluble species. J Incl Phenom Macrocycl Chem 31(3):243–264. https://doi.org/10.1023/A:1007965424219
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Landy, D. (2018). Measuring Binding Constants of Cyclodextrin Inclusion Compounds. In: Fourmentin, S., Crini, G., Lichtfouse, E. (eds) Cyclodextrin Fundamentals, Reactivity and Analysis. Environmental Chemistry for a Sustainable World, vol 16. Springer, Cham. https://doi.org/10.1007/978-3-319-76159-6_5
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