15 Works

Rational design and implementation of a cucurbit[8]uril-based indicator-displacement assay for application in blood serum

Stephan Sinn, Eduard Spuling, Stefan Braese & Frank Biedermann
In this study, we report the first supramolecular indicator displacement assay (IDA) based on cucurbit[n]uril (CBn) host and a [2.2]paracyclophane derivative as indicator that is operational in blood serum.

Covalent cucurbit[7]uril–dye conjugates for sensing in aqueous saline media and biofluids

Changming Hu, Laura Marie Grimm, Amrutha Prabodh, Ananya Baksi, Alicja Siennicka, Pavel Levkin, Manfred Kappes & Frank Biedermann
Unimolecular chemosensor shows superior stability and detection capabilities in biofluids compared to bimolecular reporter pairs.

Cucurbit[8]uril and Blue-Box: High-Energy Water Release Overwhelms Electrostatic Interactions

Frank Biedermann, Michele Vendruscolo, Oren A. Scherman, Alfonso De Simone & Werner M. Nau
The design of high-affinity and analyte-selective receptors operating in aqueous solutions is an outstanding problem in supramolecular chemistry. Directing the focus toward the unique properties of water, we present here a new strategy toward this goal and support it by molecular dynamics simulations and calorimetric measurements. We illustrate the procedure in the case of self-assembled 1:1 complexes of the rigid macrocycle cucurbit[8]uril (CB8) and dicationic auxiliary guests (AG). These CB8•AG complexes contain residual water molecules...

Release of High-Energy Water as an Essential Driving Force for the High-Affinity Binding of Cucurbit[n]urils

Werner M. Nau, Oren A. Scherman, Vanya D. Uzunova, Frank Biedermann & Alfonso De Simone
Molecular dynamics simulations and isothermal titration calorimetry (ITC) experiments with neutral guests illustrate that the release of high-energy water from the cavity of cucurbit[n]uril (CBn) macrocycles is a major determinant for guest binding in aqueous solutions. The energy of the individual encapsulated water molecules decreases with increasing cavity size, because larger cavities allow for the formation of more stable H-bonded networks. Conversely, the total energy of internal water increases with the cavity size because the...

Size Selective Supramolecular Cages from Aryl-Bisimidazolium Derivatives and Cucurbit[8]uril

Dezhi Jiao, Frank Biedermann & Oren A. Scherman
A series of bisimidazolium salts were synthesized as novel guests for the macrocyclic host molecule cucurbit[8]uril (CB[8]). These bisimidazolium-CB[8] binary complexes exhibited a unique cage structure with the imidazolium rings acting as lids, leading to a size-dependent binding selectivity by altering the hydrophobic linker between the two imidazolium moieties. This new class of CB[8] complexes was also capable of binding small solvent molecules, including acetone, acetonitrile, diethyl ether, and tetrahydrofuran (THF) in an aqueous environment.

Associative chemosensing by fluorescent macrocycle–dye complexes – a versatile enzyme assay platform beyond indicator displacement

Frank Biedermann, Denisa Hathazi & Werner M. Nau
Enzymatic reactions of aromatic substrates can be monitored by fluorescence with μM sensitivity in real time by using self-assembled fluorescent receptors.

Triple Emission fromp-Dimethylaminobenzonitrile-Cucurbit[8]uril Triggers the Elusive Excimer Emission

Mhejabeen Sayed, Frank Biedermann, Vanya D. Uzunova, Khaleel I. Assaf, Achikanath C. Bhasikuttan, Haridas Pal, Werner M. Nau & Jyotirmayee Mohanty
Abstract The intriguing dual-emission behavior of p- dimethylaminobenzonitrile (DMABN) and the identity of the associated excited states is, arguably, the most extensively investigated and also con...

Strongly Fluorescent, Switchable Perylene Bis(diimide) Host-Guest Complexes with Cucurbit[8]uril In Water

Frank Biedermann, Einat Elmalem, Indrajit Ghosh, Werner M. Nau & Oren A. Scherman
Supramolecular complexation of perylene bis(diimide) (PDI) dyes with the macrocyclic host cucurbit[8]uril (CB[8]) prevents self-aggregation of the dye molecules and enables their use as highly (photo...

Benzobis(imidazolium)-Cucurbit[8]uril Complexes for Binding and Sensing Aromatic Compounds in Aqueous Solution

Frank Biedermann, Urs Rauwald, Monika Cziferszky, Kyle A. Williams, Lauren D. Gann, Bi Y. Guo, Adam R. Urbach, Christopher W. Bielawski & Oren A. Scherman
Abstract The utilities of benzobis(imidazolium) salts (BBIs) as stable and fluorescent components of supramolecular assemblies involving the macrocyclic host, cucurbit[8]uril (CB[8]), are described...

Binding affinities of cucurbit[n]urils with cations

Shuai Zhang, Laura Marie Grimm, Zsombor Miskolczy, Laszlo Biczok, Frank Biedermann & Werner Nau
High binding constants of 19 inorganic cations with the cucurbit[n]uril homologues (CBn, n = 5, 6, 7, 8) in water were determined and the far-reaching consequences and interferences of the high affinities (millimolar to micromolar) are discussed.

Nanomolar Binding of Steroids to Cucurbit[n]urils: Selectivity and Applications

Alexandra I. Lazar, Frank Biedermann, Kamila R. Mustafina, Khaleel I. Assaf, Andreas Hennig & Werner M. Nau
Cucurbit[n]urils (CBn, n = 7, 8) serve as artificial receptors for steroids (21 tested), including the hormones testosterone and estradiol as well as steroidal drugs. Fluorescence displacement titrations and isothermal titration calorimetry (ITC) provided up to nanomolar binding affinities in aqueous solution for these hydrophobic target molecules, exceeding the values of known synthetic receptors. Remarkable binding selectivities, even for homologous steroid pairs, were investigated in detail by NMR, X-ray crystal diffraction, ITC, and quantum chemical...

Noncovalent Chirality Sensing Ensembles for the Detection and Reaction Monitoring of Amino Acids, Peptides, Proteins, and Aromatic Drugs

Frank Biedermann & Werner M. Nau
Strong and diagnostic induced circular dichroism signals in the near-UV or visible region are obtained when chiral, optically transparent analytes bind to an achiral chemosensing ensemble composed of...

Teaching old indicators even more tricks: binding affinity measurements with the guest-displacement assay (GDA)

Stephan Sinn, Joana Krämer & Frank Biedermann
A simple change has important consequences: the guest-displacement assay (GDA) is introduced which allows for binding affinity determinations of supramolecular complexes with spectroscopically silent hosts and guests.

Cucurbit[8]uril Mediated Donor–Acceptor Ternary Complexes: A Model System for Studying Charge-Transfer Interactions

Frank Biedermann & Oren A. Scherman
A supramolecular self-assembly approach is described which allows for the convenient preparation of a wide range of charge-transfer (CT) donor–acceptor complexes in aqueous solutions. When one equiv of the macrocyclic host cucurbit[8]uril (CB[8]) is added to an aqueous donor and acceptor solution, a heteroternary complex forms inside the host’s cavity with a well-defined face-to-face π–π-stacking geometry of the donor and acceptor. This heteroternary, CB[8]-mediated complex offers the opportunity to study the CT phenomena at low...

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  • Institute of Nanotechnology
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