Can we beat the biotin-avidin pair?: cucurbit[7]uril-based ultrahigh affinity host-guest complexes and their applications.

The design of synthetic, monovalent host-guest molecular recognition pairs is still challenging and of particular interest to inquire into the limits of the affinity that can be achieved with designed systems. In this regard, cucurbit[7]uril (CB[7]), an important member of the host family cucurbit[n]uril (CB[n], n = 5-8, 10, 14), has attracted much attention because of its ability to form ultra-stable complexes with multiple guests. The strong hydrophobic effect between the host cavity and guests, ion-dipole and dipole-dipole interactions of guests with CB portals helps in cooperative and multiple noncovalent interactions that are essential for realizing such strong complexations. These highly selective, strong yet dynamic interactions can be exploited in many applications including affinity chromatography, biomolecule immobilization, protein isolation, biological catalysis, and sensor technologies. In this review, we summarize the progress in the development of high affinity guests for CB[7], factors affecting the stability of complexes, theoretical insights, and the utility of these high affinity pairs in different challenging applications.

[1]  D. Bardelang,et al.  Comprehensive Synthesis of Monohydroxy-Cucurbit[n]urils (n = 5, 6, 7, 8): High Purity and High Conversions. , 2015, Journal of the American Chemical Society.

[2]  Nam Ki Lee,et al.  High Affinity Host-Guest FRET Pair for Single-Vesicle Content-Mixing Assay: Observation of Flickering Fusion Events. , 2015, Journal of the American Chemical Society.

[3]  Sung Tae Kim,et al.  Supramolecular regulation of bioorthogonal catalysis in cells using nanoparticle-embedded transition metal catalysts. , 2015, Nature chemistry.

[4]  Nam Hoon Kim,et al.  Reversible morphological transformation between polymer nanocapsules and thin films through dynamic covalent self-assembly. , 2015, Angewandte Chemie.

[5]  V. Rotello,et al.  Regulating exocytosis of nanoparticles via host-guest chemistry. , 2015, Organic & biomolecular chemistry.

[6]  S. Ryu,et al.  A simple modular aptasensor platform utilizing cucurbit[7]uril and a ferrocene derivative as an ultrastable supramolecular linker. , 2015, Chemical communications.

[7]  W. Nau,et al.  Cucurbiturils: from synthesis to high-affinity binding and catalysis. , 2015, Chemical Society reviews.

[8]  Franz L. Dickert,et al.  Biomimetic Receptors and Sensors , 2014, Sensors.

[9]  Hans-Jörg Schneider,et al.  The hydrophobic effect revisited--studies with supramolecular complexes imply high-energy water as a noncovalent driving force. , 2014, Angewandte Chemie.

[10]  Jinying Yuan,et al.  Ferrocene-based supramolecular structures and their applications in electrochemical responsive systems. , 2014, Chemical communications.

[11]  T. Lu,et al.  Strong underwater adhesives made by self-assembling multi-protein nanofibres. , 2014, Nature nanotechnology.

[12]  Andrew T. Fenley,et al.  Bridging Calorimetry and Simulation through Precise Calculations of Cucurbituril–Guest Binding Enthalpies , 2014, Journal of chemical theory and computation.

[13]  M. Guo,et al.  Flexible and voltage-switchable polymer velcro constructed using host–guest recognition between poly(ionic liquid) strips , 2014 .

[14]  N. Kim,et al.  Highly stable, water-dispersible metal-nanoparticle-decorated polymer nanocapsules and their catalytic applications. , 2014, Angewandte Chemie.

[15]  J. Sivaguru,et al.  Supramolecular photocatalysis: combining confinement and non-covalent interactions to control light initiated reactions. , 2014, Chemical Society reviews.

[16]  Lyle Isaacs,et al.  Stimuli Responsive Systems Constructed Using Cucurbit[n]uril-Type Molecular Containers , 2014, Accounts of chemical research.

[17]  Hui Yang,et al.  Supramolecular chemistry at interfaces: host-guest interactions for fabricating multifunctional biointerfaces. , 2014, Accounts of chemical research.

[18]  L. Isaacs,et al.  Design, Synthesis, and X‐ray Structural Analyses of Diamantane Diammonium Salts: Guests for Cucurbit[n]uril (CB[n]) Hosts , 2014 .

[19]  Z. Tao,et al.  Self-assemblies based on the "outer-surface interactions" of cucurbit[n]urils: new opportunities for supramolecular architectures and materials. , 2014, Accounts of chemical research.

[20]  R. Custelcean Anion encapsulation and dynamics in self-assembled coordination cages. , 2014, Chemical Society reviews.

[21]  C. Lü,et al.  A novel FRET-based fluorescent chemosensor of β-cyclodextrin derivative for TNT detection in aqueous solution , 2014 .

[22]  Liping Cao,et al.  Cucurbit[7]uril⋅guest pair with an attomolar dissociation constant. , 2014, Angewandte Chemie.

[23]  Z. Tao,et al.  Cucurbit[n]uril-based coordination chemistry: from simple coordination complexes to novel poly-dimensional coordination polymers. , 2013, Chemical Society reviews.

[24]  M. Vendruscolo,et al.  Cucurbit[8]uril and blue-box: high-energy water release overwhelms electrostatic interactions. , 2013, Journal of the American Chemical Society.

[25]  Y. Ko,et al.  Host-guest chemistry from solution to the gas phase: an essential role of direct interaction with water for high-affinity binding of cucurbit[n]urils. , 2013, The journal of physical chemistry. B.

[26]  Yunqian Zhang,et al.  Twisted cucurbit[14]uril. , 2013, Angewandte Chemie.

[27]  C. Park,et al.  Free-standing, single-monomer-thick two-dimensional polymers through covalent self-assembly in solution. , 2013, Journal of the American Chemical Society.

[28]  L. Brunsveld,et al.  Supramolecular control of cell adhesion via ferrocene-cucurbit[7]uril host-guest binding on gold surfaces. , 2013, Chemical communications.

[29]  R. Cao,et al.  Cucurbituril: A promising organic building block for the design of coordination compounds and beyond , 2013 .

[30]  Kimoon Kim,et al.  Supramolecular velcro for reversible underwater adhesion. , 2013, Angewandte Chemie.

[31]  Dana A. Uhlenheuer,et al.  Immobilization of Ferrocene-Modified SNAP-Fusion Proteins , 2013, International journal of molecular sciences.

[32]  Yuan Chen,et al.  Structural interrogation of a cucurbit[7]uril-ferrocene host–guest complex in the solid state: a Raman spectroscopy study , 2013 .

[33]  A. Kaifer,et al.  Combining proton and electron transfer to modulate the stability of cucurbit[7]uril complexes. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[34]  Oren A Scherman,et al.  Release of high-energy water as an essential driving force for the high-affinity binding of cucurbit[n]urils. , 2012, Journal of the American Chemical Society.

[35]  Joe R. Cannon,et al.  Synthesis and self-assembly processes of monofunctionalized cucurbit[7]uril. , 2012, Journal of the American Chemical Society.

[36]  Michael K Gilson,et al.  Grid inhomogeneous solvation theory: hydration structure and thermodynamics of the miniature receptor cucurbit[7]uril. , 2012, The Journal of chemical physics.

[37]  M. Hersam,et al.  Biomolecule-directed assembly of self-supported, nanoporous, conductive, and luminescent single-walled carbon nanotube scaffolds. , 2012, Small.

[38]  A. Hoffman,et al.  In situ supramolecular assembly and modular modification of hyaluronic acid hydrogels for 3D cellular engineering. , 2012, ACS nano.

[39]  Xiaoyong Lu,et al.  Cucurbituril chemistry: a tale of supramolecular success , 2012 .

[40]  Ying Liu,et al.  A new FRET nanoprobe for trypsin using a bridged β-cyclodextrin dimer-dye complex and its biological imaging applications. , 2011, The Analyst.

[41]  Sung Ho Ryu,et al.  Theranostic systems assembled in situ on demand by host-guest chemistry. , 2011, Biomaterials.

[42]  Patricia Grob,et al.  In vitro system capable of differentiating fast Ca2+-triggered content mixing from lipid exchange for mechanistic studies of neurotransmitter release , 2011, Proceedings of the National Academy of Sciences.

[43]  Feng Zhou,et al.  Bioinspired catecholic chemistry for surface modification. , 2011, Chemical Society reviews.

[44]  Herbert Waldmann,et al.  Bioorthogonal chemistry for site-specific labeling and surface immobilization of proteins. , 2011, Accounts of chemical research.

[45]  A. Kaifer,et al.  Cucurbiturils as Versatile Receptors for Redox Active Substrates , 2011 .

[46]  W. Nau,et al.  Deep Inside Cucurbiturils: Physical Properties and Volumes of their Inner Cavity Determine the Hydrophobic Driving Force for Host–Guest Complexation , 2011 .

[47]  Michael K Gilson,et al.  New ultrahigh affinity host-guest complexes of cucurbit[7]uril with bicyclo[2.2.2]octane and adamantane guests: thermodynamic analysis and evaluation of M2 affinity calculations. , 2011, Journal of the American Chemical Society.

[48]  S. Ryu,et al.  Supramolecular fishing for plasma membrane proteins using an ultrastable synthetic host-guest binding pair. , 2011, Nature chemistry.

[49]  Sarit S. Agasti,et al.  Recognition-Mediated Activation of Therapeutic Gold Nanoparticles Inside Living Cells , 2010, Nature chemistry.

[50]  T. Ha,et al.  A single vesicle content mixing assay for SNARE-mediated membrane fusion , 2010, Nature communications.

[51]  Y. Ko,et al.  Reduction-sensitive, robust vesicles with a non-covalently modifiable surface as a multifunctional drug-delivery platform. , 2010, Small.

[52]  Eunju Kim,et al.  Direct synthesis of polymer nanocapsules: self-assembly of polymer hollow spheres through irreversible covalent bond formation. , 2010, Journal of the American Chemical Society.

[53]  C. Park,et al.  Facile, template-free synthesis of stimuli-responsive polymer nanocapsules for targeted drug delivery. , 2010, Angewandte Chemie.

[54]  Y. Ko,et al.  Unconventional U-shaped conformation of a bolaamphiphile embedded in a synthetic host. , 2010, Chemical communications.

[55]  R. Stewart,et al.  Adaptation of Caddisfly Larval Silks to Aquatic Habitats by Phosphorylation of H-fibroin Serines Materials and Methods , 2022 .

[56]  Vincent T. Moy,et al.  A streptavidin variant with slower biotin dissociation and increased mechanostability , 2010, Nature Methods.

[57]  Soumyadip Ghosh,et al.  Biological catalysis regulated by cucurbit[7]uril molecular containers. , 2010, Journal of the American Chemical Society.

[58]  R. Goody,et al.  Oriented immobilization of farnesylated proteins by the thiol-ene reaction. , 2010, Angewandte Chemie.

[59]  Lanti Yang,et al.  Strong and Reversible Monovalent Supramolecular Protein Immobilization , 2010, Chembiochem : a European journal of chemical biology.

[60]  Youngjoo Ahn,et al.  Galactosylated cucurbituril-inclusion polyplex for hepatocyte-targeted gene delivery. , 2010, Chemical communications.

[61]  H. Waldmann,et al.  Applications of Protein Biochips in Biomedical and Biotechnological Research , 2009, Angewandte Chemie.

[62]  J. Micklefield,et al.  Selective covalent protein immobilization: strategies and applications. , 2009, Chemical reviews.

[63]  Y. Kalaidzidis,et al.  Reconstitution of Rab- and SNARE-dependent membrane fusion by synthetic endosomes , 2009, Nature.

[64]  Michael K Gilson,et al.  Host-guest complexes with protein-ligand-like affinities: computational analysis and design. , 2009, Journal of the American Chemical Society.

[65]  James W. Wollack,et al.  Purification of prenylated proteins by affinity chromatography on cyclodextrin-modified agarose. , 2009, Analytical biochemistry.

[66]  A. Coelho,et al.  First Insights into the Biochemistry of Tube Foot Adhesive from the Sea Urchin Paracentrotus lividus (Echinoidea, Echinodermata) , 2009, Marine Biotechnology.

[67]  Kimoon Kim,et al.  Cucurbituril-based nanoparticles: a new efficient vehicle for targeted intracellular delivery of hydrophobic drugs. , 2009, Chemical communications.

[68]  G. Elia Biotinylation reagents for the study of cell surface proteins , 2008, Proteomics.

[69]  T. Govindaraju,et al.  Surface immobilization of biomolecules by click sulfonamide reaction. , 2008, Chemical communications.

[70]  Akira Harada,et al.  Chemical Sensors Based on Cyclodextrin Derivatives , 2008, Sensors.

[71]  H. McMahon,et al.  Mechanisms of membrane fusion: disparate players and common principles , 2008, Nature Reviews Molecular Cell Biology.

[72]  Cheng-an Tao,et al.  A general and efficient method to form self-assembled cucurbit[n]uril monolayers on gold surfaces. , 2008, Chemical communications.

[73]  Toshiaki Watanabe,et al.  Biotin deficiency affects the proliferation of human embryonic palatal mesenchymal cells in culture. , 2008, The Journal of nutrition.

[74]  Michael K. Gilson,et al.  A synthetic host-guest system achieves avidin-biotin affinity by overcoming enthalpy–entropy compensation , 2007, Proceedings of the National Academy of Sciences.

[75]  Y. Ko,et al.  Carbohydrate wheels: cucurbituril-based carbohydrate clusters. , 2007, Angewandte Chemie.

[76]  M. Bogyo,et al.  Proteomics Evaluation of Chemically Cleavable Activity-based Probes* , 2007, Molecular & Cellular Proteomics.

[77]  J. Clifton,et al.  Mammalian plasma membrane proteomics , 2007, Proteomics.

[78]  Bruce P. Lee,et al.  A reversible wet/dry adhesive inspired by mussels and geckos , 2007, Nature.

[79]  O. Laitinen,et al.  Brave new (strept)avidins in biotechnology. , 2007, Trends in biotechnology.

[80]  M. Kozlov,et al.  How Synaptotagmin Promotes Membrane Fusion , 2007, Science.

[81]  C. Park,et al.  Direct synthesis of polymer nanocapsules with a noncovalently tailorable surface. , 2007, Angewandte Chemie.

[82]  Kimoon Kim,et al.  Noncovalent immobilization of proteins on a solid surface by cucurbit[7]uril-ferrocenemethylammonium pair, a potential replacement of biotin-avidin pair. , 2007, Journal of the American Chemical Society.

[83]  Young Ho Ko,et al.  Functionalized cucurbiturils and their applications. , 2007, Chemical Society reviews.

[84]  Heng Zhu,et al.  Protein chip fabrication by capture of nascent polypeptides , 2006, Nature Biotechnology.

[85]  Neel S. Joshi,et al.  An affinity-based method for the purification of fluorescently-labeled biomolecules. , 2006, Bioconjugate chemistry.

[86]  A. Kaifer,et al.  Electrochemically switchable cucurbit[7]uril-based pseudorotaxanes. , 2006, Organic letters.

[87]  Po-Chiao Lin,et al.  Site-specific protein modification through Cu(I)-catalyzed 1,2,3-triazole formation and its implementation in protein microarray fabrication. , 2006, Angewandte Chemie.

[88]  S. Kingsmore Multiplexed protein measurement: technologies and applications of protein and antibody arrays , 2006, Nature Reviews Drug Discovery.

[89]  Pieter C Dorrestein,et al.  A monovalent streptavidin with a single femtomolar biotin binding site , 2006, Nature Methods.

[90]  Y. Ko,et al.  Cucurbituril anchored silica gel , 2006 .

[91]  Lyle Isaacs,et al.  The cucurbit[n]uril family: prime components for self-sorting systems. , 2005, Journal of the American Chemical Society.

[92]  A. Kaifer,et al.  Complexation of ferrocene derivatives by the cucurbit[7]uril host: a comparative study of the cucurbituril and cyclodextrin host families. , 2005, Journal of the American Chemical Society.

[93]  Lyle Isaacs,et al.  The cucurbit[n]uril family. , 2005, Angewandte Chemie.

[94]  K. Raymond,et al.  The big squeeze: guest exchange in an M4L6 supramolecular host. , 2005, Journal of the American Chemical Society.

[95]  J. Rebek Simultaneous encapsulation: molecules held at close range. , 2005, Angewandte Chemie.

[96]  M. Fujita,et al.  In situ observation of a reversible single-crystal-to-single-crystal apical-ligand-exchange reaction in a hydrogen-bonded 2D coordination network. , 2005, Angewandte Chemie.

[97]  M. Dufva,et al.  Diagnostic and analytical applications of protein microarrays , 2005, Expert review of proteomics.

[98]  M. Gilson,et al.  Free energy, entropy, and induced fit in host-guest recognition: calculations with the second-generation mining minima algorithm. , 2004, Journal of the American Chemical Society.

[99]  B. Gibb,et al.  Well-defined, organic nanoenvironments in water: the hydrophobic effect drives a capsular assembly. , 2004, Journal of the American Chemical Society.

[100]  J. Homola,et al.  DNA-directed protein immobilization on mixed self-assembled monolayers via a streptavidin bridge. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[101]  I. Choi,et al.  Micropatterns of spores displaying heterologous proteins. , 2004, Journal of the American Chemical Society.

[102]  W. Nau,et al.  Mechanism of host-guest complexation by cucurbituril. , 2004, Journal of the American Chemical Society.

[103]  E. Keinan,et al.  Facile purification of rare cucurbiturils by affinity chromatography. , 2004, Organic letters.

[104]  Wei Zhang,et al.  Proteomic analysis of integral plasma membrane proteins. , 2004, Analytical chemistry.

[105]  Winston Ong,et al.  Salt effects on the apparent stability of the cucurbit[7]uril-methyl viologen inclusion complex. , 2004, The Journal of organic chemistry.

[106]  Andrew G. Leach,et al.  Binding affinities of host-guest, protein-ligand, and protein-transition-state complexes. , 2003, Angewandte Chemie.

[107]  A. Kaifer,et al.  Unusual Electrochemical Properties of the Inclusion Complexes of Ferrocenium and Cobaltocenium with Cucurbit[7]uril , 2003 .

[108]  R. Raines,et al.  Site-specific protein immobilization by Staudinger ligation. , 2003, Journal of the American Chemical Society.

[109]  Kimoon Kim,et al.  Facile synthesis of cucurbit[n]uril derivatives via direct functionalization: expanding utilization of cucurbit[n]uril. , 2003, Journal of the American Chemical Society.

[110]  M. White,et al.  Affinity enrichment of plasma membrane for proteomics analysis , 2003, Electrophoresis.

[111]  J. Fettinger,et al.  Acyclic congener of cucurbituril: synthesis and recognition properties. , 2003, The Journal of organic chemistry.

[112]  Jae Wook Lee,et al.  Cucurbituril homologues and derivatives: new opportunities in supramolecular chemistry. , 2003, Accounts of chemical research.

[113]  J. Fettinger,et al.  Preparation of glycoluril monomers for expanded cucurbit[ n ]uril synthesis , 2003 .

[114]  M. Wilchek,et al.  Rational Design of an Active Avidin Monomer* , 2003, Journal of Biological Chemistry.

[115]  A. Day,et al.  A Method for Synthesizing Partially Substituted Cucurbit[n]uril , 2003, Molecules : A Journal of Synthetic Chemistry and Natural Product Chemistry.

[116]  A. Wego,et al.  Glycoluril derivatives as precursors in the preparation of substituted cucurbit[n]urils , 2003 .

[117]  M. Wilchek,et al.  Ligand Exchange between Proteins , 2002, The Journal of Biological Chemistry.

[118]  A. Day,et al.  The Effects of Alkali Metal Cations on Product Distributions in Cucurbit[n]uril Synthesis , 2002 .

[119]  E. Nakamura,et al.  Synthesis of disubstituted cucurbit[6]uril and its rotaxane derivative. , 2002, Organic letters.

[120]  W. Nau,et al.  Polarizabilities Inside Molecular Containers This work was supported by the Swiss National Science Foundation (projects 620-58000.99 and 4047-057552) within the program NFP 47 "Supramolecular Functional Materials". , 2001, Angewandte Chemie.

[121]  Kimoon Kim,et al.  Cucurbit[n]uril Derivatives Soluble in Water and Organic Solvents. , 2001, Angewandte Chemie.

[122]  Barry B Snushall,et al.  Controlling factors in the synthesis of cucurbituril and its homologues. , 2001, The Journal of organic chemistry.

[123]  Paul Tempst,et al.  Protein S-nitrosylation: a physiological signal for neuronal nitric oxide , 2001, Nature Cell Biology.

[124]  J. Rothman,et al.  Compartmental specificity of cellular membrane fusion encoded in SNARE proteins , 2000, Nature.

[125]  Yoshihisa Inoue,et al.  Chiral Recognition Thermodynamics of β-Cyclodextrin: The Thermodynamic Origin of Enantioselectivity and the Enthalpy−Entropy Compensation Effect , 2000 .

[126]  Peter A. Kollman,et al.  A Ligand That Is Predicted to Bind Better to Avidin than Biotin: Insights from Computational Fluorine Scanning , 2000 .

[127]  Meir Wilchek,et al.  Recombinant NeutraLite Avidin: a non‐glycosylated, acidic mutant of chicken avidin that exhibits high affinity for biotin and low non‐specific binding properties , 2000, FEBS letters.

[128]  M. Wilchek,et al.  Mutation of a critical tryptophan to lysine in avidin or streptavidin may explain why sea urchin fibropellin adopts an avidin‐like domain , 1999, FEBS letters.

[129]  Y. Inoue,et al.  Complexation Thermodynamics of Cyclodextrins. , 1998, Chemical reviews.

[130]  M. J. Swamy Thermodynamic analysis of biotin binding to avidin. A high sensitivity titration calorimetric study. , 1995, Biochemistry and molecular biology international.

[131]  A. Chilkoti,et al.  Site-directed mutagenesis studies of the high-affinity streptavidin-biotin complex: contributions of tryptophan residues 79, 108, and 120. , 1995, Proceedings of the National Academy of Sciences of the United States of America.

[132]  David J. Williams,et al.  Decamethylcucurbit[5]uril† , 1992 .

[133]  Hans-Jörg Schneider,et al.  Mechanisms of Molecular Recognition : Investigations of Organic Host–Guest Complexes , 1991 .

[134]  Wolfram Saenger,et al.  Cyclodextrin Inclusion Compounds in Research and Industry , 1980 .

[135]  Kimoon Kim,et al.  Supramolecular Hydrogels for Long‐Term Bioengineered Stem Cell Therapy , 2015, Advanced healthcare materials.

[136]  M. Berberan-Santos Fluorescence of Supermolecules, Polymers, and Nanosystems , 2008 .

[137]  Zhen Liu,et al.  Immunoaffinity purification of plasma membrane with secondary antibody superparamagnetic beads for proteomic analysis. , 2007, Journal of proteome research.

[138]  T. Südhof,et al.  Membrane fusion and exocytosis. , 1999, Annual review of biochemistry.

[139]  M. Wilchek,et al.  Applications of avidin-biotin technology: literature survey. , 1990, Methods in enzymology.

[140]  Green Nm,et al.  Avidin and streptavidin. , 1990 .