Amrutha Prabodh

Karlsruhe Institute of Technology

Author Statistics

Papers

Citation

H-Index

i-10 index

Research Trends

Author Order

Document Type

Co-Authors

Frank Biedermann

Karlsruhe Institute of Technology

Laura Grimm

Karlsruhe Institute of Technology

Stephan Sinn

Karlsruhe Institute of Technology

Stefan Bräse

Karlsruhe Institute of Technology

Zsombor Miskolczy

Institute of Materials and Environmental Chemistry

Yichuan Wang

Inner Mongolia Agricultural University

László Biczók

Institute of Materials and Environmental Chemistry

Mónika Megyesi

Institute of Materials and Environmental Chemistry

Ananya Baksi

TU Dortmund University

Lorenzo Delarue Bizzini

Princeton University

Cooperative Institutions

Karlsruhe Institute of Technology

Karlsruhe University of Education

Institute of Nanotechnology

University of Duisburg-Essen

Faculty (United Kingdom)

Essen University Hospital

Heidelberg University

Fritz Haber Institute of the Max Planck Society

Saarland University

Institute of Materials and Environmental Chemistry

Author Statistics

Papers

Citation

H-Index

i-10 index

Research Field

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

Chemical Science (2020)

Chang‐Ming Hu Laura Grimm Amrutha Prabodh Ananya Baksi Alicja Siennicka

Non-covalent chemosensing ensembles of cucurbit[n]urils (CBn) have been widely used in proof-of-concept sensing applications, but they are prone to disintegrate in saline media, e.g. biological fluids. We show here that covalent cucurbit[7]uril-indicator dye conjugates are buffer- (10× PBS buffer) and saline-stable (up to 1.4 M NaCl) and allow for selective sensing of Parkinson's drug amantadine in human urine and saliva, where the analogous non-covalent CB7⊃dye complex is dysfunctional. The in-depth analysis of the covalent host-dye conjugates in the gas-phase, and deionized versus saline aqueous media revealed interesting structural, thermodynamic and kinetic effects that are of general interest for the design of CBn-based supramolecular chemosensors and systems. This work also introduces a novel high-affinity indicator dye for CB7 through which fundamental limitations of indicator displacement assays (IDA) were exposed, namely an impractical slow equilibration time. Unlike non-covalent CBn⊃dye reporter pairs, the conjugate chemosensors can also operate through a SN2-type guest-dye exchange mechanism, which shortens assay times and opens new avenues for tailoring analyte-selectivity.

Conjugate

Aqueous medium

10.1039/d0sc03079a

Cite

Citations (48)

Fluorescence detected circular dichroism (FDCD) for supramolecular host–guest complexes

Chemical Science (2021)

Amrutha Prabodh Yichuan Wang Stephan Sinn Paolo Albertini Christian Spies

Fluorescence-detected circular dichroism (FDCD) spectroscopy is applied for the first time to supramolecular host-guest and host-protein systems and compared to the more known electronic circular dichroism (ECD). We find that FDCD can be an excellent choice for common supramolecular applications, e.g. for the detection and chirality sensing of chiral organic analytes, as well as for reaction monitoring. Our comprehensive investigations demonstrate that FDCD can be conducted in favorable circumstances at much lower concentrations than ECD measurements, even in chromophoric and auto-emissive biofluids such as blood serum, overcoming the sensitivity limitation of absorbance-based chiroptical spectroscopy. Besides, the combined use of FDCD and ECD can provide additional valuable information about the system, e.g. the chemical identity of an analyte or hidden aggregation phenomena. We believe that simultaneous FDCD- and ECD-based chiroptical characterization of emissive supramolecular systems will be of general benefit for characterizing fluorescent, chiral supramolecular systems due to the higher information content obtained by their combined use.

Chirality

Supramolecular chirality

Absorbance

10.1039/d1sc01411k

Cite

Citations (27)

Analyte sensing with unselectively binding synthetic receptors: virtues of time-resolved supramolecular assays

Chemical Communications (2022)

Amrutha Prabodh Stephan Sinn Frank Biedermann

The cross-reactivity to many analytes is one major limitation of most synthetic receptors (SRs) known so far. Herein, we show that through time-resolved competitive binding assays, even unselectively binding SRs can be utilized for analyte distinction and quantification. Furthermore, our methodology has also been applied to analyte mixtures and can be used in a microplate format.

Competitive binding

Chemical sensor

Reactivity

10.1039/d2cc04831k

Cite

Citations (6)

Fluorescent Paracyclophanes: Unveiling Ultra‐Strong Binding with Cucurbit[8]uril in Aqueous Environments

ChemistryEurope (2024)

Laura Grimm Yichuan Wang Amrutha Prabodh Emma Barilli Sebastian Spicher

Abstract In supramolecular chemistry, the pursuit of highly efficient molecular recognition systems holds paramount significance. This study introduces new [2.2]paracyclophanes (PCP) as exceptional guest molecules for cucurbit[8]uril (CB8). This well‐matched host‐guest interaction is marked by ultra‐high binding affinities ( K a up to 10 15 M −1 in water) accompanied by unprecedented exothermic contributions (Δ H up to −20.6 kcal mol −1 ) observed in CB8 binding, rivaling the exceptional affinities of cucurbit[7]uril (CB7), which has until now been recognized as the gold standard for high‐affinity binding in water. The PCPs demonstrate an excellent fit within the CB8 cavity without structural deformation of the host. Our research methodology incorporates organic synthesis, NMR, fluorescence titration, and isothermal titration calorimetry (ITC) experiments, as well as quantum mechanical simulations, to systematically examine the binding characteristics of fluorescent mono‐ and dicationic PCP guests within the CB8 cavity. This study not only corroborates but also critically reevaluates certain aspects of the “high‐energy water release model” for cucurbit[ n ]uril systems. Furthermore, the ease of modifying PCP compounds, combined with their superior water solubility compared to di‐ and triamantanes, and their characteristic fluorescent response in forming and disassembling host‐guest complexes, elevates PCPs as promising candidates for the creation of advanced supramolecular CB8‐functional materials and sensing assays.

10.1002/ceur.202400003

Cite

Citations (0)

Pillar[n]arene‐Based Fluorescence Turn‐On Chemosensors for the Detection of Spermine, Spermidine, and Cadaverine in Saline Media and Biofluids

Chemistry - A European Journal (2024)

Amrutha Prabodh Laura Grimm Pronay Kumar Biswas Vahideh Mahram Frank Biedermann

Polyamines are essential analytes due to their critical role in various biological processes and human health in general. Due to their role as regulators for cell growth and proliferation (putrescine and spermine), as neuroprotectors, gero-, and cardiovascular protectors (spermidine), and as bacterial growth indicators (cadaverine), rapid, simple, and cost-effective methods for polyamine detection in biofluids are in demand. The present study focuses on the development and investigation of self-assembled and fluorescent host⋅dye chemo-sensors based on sulfonated pillar[5]arene for the specific detection of polyamines. Binding studies, as well as stability and functionality assessments of the turn-on chemosensors for selective polyamine detection in saline and biologically relevant media, are shown. Furthermore, the practical applicability of the developed chemo-sensors is demonstrated in biofluids such as human urine and saliva.

Polyamine

Pillar

10.1002/chem.202401071

Cite

Citations (1)

Teaching indicators to unravel the kinetic features of host–guest inclusion complexes

Chemical Communications (2020)

Amrutha Prabodh Stephan Sinn Laura Grimm Zsombor Miskolczy Mónika Megyesi

Three new, practically convenient methods are introduced for measuring kinetic parameters of supramolecular host–guest and protein–ligand complexes. Combined with thermodynamic data, this allows for an in-depth of the binding mechanism.

Kinetic control

10.1039/d0cc03715j

Cite

Citations (26)

Chirality sensing of terpenes, steroids, amino acids, peptides and drugs with acyclic cucurbit[n]urils and molecular tweezers

Chemical Communications (2020)

Amrutha Prabodh Daniel J. Bauer Stefan Kubik Philipp Rebmann Frank Gerritt Klärner

Achiral chromophoric tweezer-shaped molecular hosts were found to respond with characteristic Circular Dichroism spectra to the presence of micromolar concentrations of chiral hydrocarbons, terpenes, steroids, amino acids and drugs in water.

Terpene

Chirality

Molecular tweezers

Tweezers

10.1039/d0cc00707b

Cite

Citations (39)

Kinetics and Mechanism of Cation‐Induced Guest Release from Cucurbit[7]uril

Chemistry - A European Journal (2020)

Zsombor Miskolczy Mónika Megyesi László Biczók Amrutha Prabodh Frank Biedermann

The release of two organic guests from cucurbit[7]uril (CB7) was selectively monitored by the stopped-flow method in aqueous solutions of inorganic salts to reveal the mechanistic picture in detail. Two contrasting mechanisms were identified: The symmetric dicationic 2,7-dimethyldiazapyrenium shows a cation-independent complex dissociation mechanism coupled to deceleration of the ingression in the presence of alkali and alkaline earth cations (Mn+ ) due to competitive formation of CB7-Mn+ complexes. A much richer, unprecedented kinetic behaviour was observed for the ingression and egression of the monocationic and non-symmetric berberine (B+ ). The formation of ternary complex B+ -CB7-Mn+ was unambiguously revealed. A difference of more than two orders of magnitude was found in the equilibrium constants of Mn+ binding to B+ -CB7 inclusion complex. Large cations, such as K+ and Ba2+ , also promoted B+ expulsion from the ternary complex in a bimolecular process. This study reveals a previously hidden mechanistic picture and motivates systematic kinetic investigations of other host-guest systems.

Ternary complex

10.1002/chem.201905633

Cite

Citations (29)