Benjamin P. Fingerhut

Ludwig-Maximilians-Universität München

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Thomas Elsaesser

Max-Born-Institute for Nonlinear Optics and Short Pulse Spectroscopy

Shaul Mukamel

University of California, Irvine

Regina de Vivie‐Riedle

Ludwig-Maximilians-Universität München

Achintya Kundu

Max-Born-Institute for Nonlinear Optics and Short Pulse Spectroscopy

Jakob Schauss

Max-Born-Institute for Nonlinear Optics and Short Pulse Spectroscopy

Konstantin E. Dorfman

Hainan University

Ehud Pines

Ben-Gurion University of the Negev

Wolfgang Zinth

Ludwig-Maximilians-Universität München

Fabian Dahms

Max-Born-Institute for Nonlinear Optics and Short Pulse Spectroscopy

Erik T. J. Nibbering

Max-Born-Institute for Nonlinear Optics and Short Pulse Spectroscopy

Cooperative Institutions

Ludwig-Maximilians-Universität München

Max-Born-Institute for Nonlinear Optics and Short Pulse Spectroscopy

Center for Integrated Protein Science Munich

University of California, Irvine

LMU Klinikum

Centre National de la Recherche Scientifique

University of California, Berkeley

Lawrence Berkeley National Laboratory

Technical University of Munich

Freie Universität Berlin

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Ultrafast terahertz Stark spectroscopy reveals the excited-state dipole moments of retinal in bacteriorhodopsin

Proceedings of the National Academy of Sciences (2024)

Jia Zhang Poonam Singh Dieter Engel Benjamin P. Fingerhut Matthias Broser

The photoinduced all-trans to 13-cis isomerization of the retinal Schiff base represents the ultrafast first step in the reaction cycle of bacteriorhodopsin (BR). Extensive experimental and theoretical work has addressed excited-state dynamics and isomerization via a conical intersection with the ground state. In conflicting molecular pictures, the excited state potential energy surface has been modeled as a pure S 1 state that intersects with the ground state, or in a 3-state picture involving the S 1 and S 2 states. Here, the photoexcited system passes two crossing regions to return to the ground state. The electric dipole moment of the Schiff base in the S 1 and S 2 state differs strongly and, thus, its measurement allows for assessing the character of the excited-state potential. We apply the method of ultrafast terahertz (THz) Stark spectroscopy to measure electric dipole changes of wild-type BR and a BR D85T mutant upon electronic excitation. A fully reversible transient broadening and spectral shift of electronic absorption is induced by a picosecond THz field of several megavolts/cm and mapped by a 120-fs optical probe pulse. For both BR variants, we derive a moderate electric dipole change of 5 ± 1 Debye, which is markedly smaller than predicted for a neat S 1 -character of the excited state. In contrast, S 2 -admixture and temporal averaging of excited-state dynamics over the probe pulse duration gives a dipole change in line with experiment. Our results support a picture of electronic and nuclear dynamics governed by the interaction of S 1 and S 2 states in a 3-state model.

10.1073/pnas.2319676121

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Citations (1)

Automated Method for Serum Glucose with p-Hydroxybenzoic Acid Hydrazide

Clinical Chemistry (1973)

Benjamin P. Fingerhut

Abstract A new automated method for serum glucose is presented, based on the reaction between glucose and p-hydroxybenzoic acid hydrazide in alkaline solution. Results for 70 non-uremic sera averaged 60 mg/liter greater than those given by an automated glucose oxidase (EC 1.1.3.4) procedure. Values for uremic sera indicated the proposed method to be more specific for such sera than is the automated ferricyanide-reduction technique. Within-run and day-to-day values had a standard deviation of 17 and 32 mg/ liter, respectively. Recoveries ranged from 99.5 to 104.5% (mean, 102.2%).

Glucose oxidase

Liter

Ferricyanide

Serum glucose

10.1093/clinchem/19.9.1022

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Citations (11)

Coherent Dynamics of Phosphate Ions in Bulk H2O

International Conference on Ultrafast Phenomena (2016)

René Costard Tobias Tyborski Benjamin P. Fingerhut

Phosphates as important biomolecular building blocks are studied by 2D-IR spectroscopy. Excitation with spectrally broad pulses generates a coherent superposition of phosphate stretching modes resulting in the observation of quantum beats in aqueous solution.

Coherent spectroscopy

10.1364/up.2016.uth3b.7

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Short-Range Slowdown of Water Solvation Dynamics around SO42- - Mg2+ Ion Pairs

The International Conference on Ultrafast Phenomena (UP) 2022 (2022)

Achintya Kundu Shavkat Mamatkulov Florian N. Brünig Douwe Jan Bonthuis Roland R. Netz

2D-IR spectroscopy in the fingerprint region of SO 4 2- ions in water reveals a counterion specific slowdown of solvation dynamics. Hydration structures of solvent shared SO 4 2- - Mg 2+ ion pairs are identified as the molecular origin.

Slowdown

Solvation shell

10.1364/up.2022.f2a.2

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Titanium‐Catalyzed Intermolecular Hydroamination of Vinylarenes.

ChemInform (2005)

Ludwig T. Kaspar Benjamin P. Fingerhut Lutz Ackermann

Abstract For Abstract see ChemInform Abstract in Full Text.

Hydroamination

10.1002/chin.200602048

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Oscillatory Dynamics of the Spin-Boson Model with Ultrastrong Interactions with the Environment

The 22nd International Conference on Ultrafast Phenomena 2020 (2020)

Nirmalendu Acharyya Martin Richter Benjamin P. Fingerhut

We numerically investigate the impact of non-diagonal system-bath interaction on real-time dissipative dynamics of the Spin-Boson model. For Ohmic environments, a novel class of coherences emerges that induce longtime entanglement between system and environment.

Dynamics

10.1364/up.2020.tu4a.35

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Contact Ion Pairs of Phosphate Groups in Water: Two-Dimensional Infrared Spectroscopy of Dimethyl Phosphate and ab Initio Simulations

The Journal of Physical Chemistry Letters (2019)

Jakob Schauss Achintya Kundu Benjamin P. Fingerhut Thomas Elsaesser

The interaction of phosphate groups with ions in an aqueous environment has a strong impact on the structure and folding processes of DNA and RNA. The dynamic variety of ionic arrangements, including both contact pairs and water separated ions, and the molecular coupling mechanisms are far from being understood. In a combined experimental and theoretical approach, we address the properties of contact ion pairs of the prototypical system dimethyl phosphate with Na+, Ca2+, and Mg2+ ions in water. Linear and femtosecond two-dimensional infrared (2D-IR) spectroscopy of the asymmetric (PO2)- stretching vibration separates and characterizes the different species via their blue-shifted vibrational signatures and 2D-IR line shapes. Phosphate-magnesium contact pairs stand out as the most compact geometry while the contact pairs with Ca2+ and Na+ display a wider structural variation. Microscopic density functional theory simulations rationalize the observed frequency shifts and reveal distinct differences between the contact geometries.

Folding (DSP implementation)

10.1021/acs.jpclett.9b02157

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Citations (26)

Aqueous Contact Ion Pairs of Phosphate Groups with Na⁺, Ca²⁺ and Mg²⁺ – Structural Discrimination by Femtosecond Infrared Spectroscopy and Molecular Dynamics Simulations

Zeitschrift für Physikalische Chemie (2020)

Benjamin P. Fingerhut Jakob Schauss Achintya Kundu Thomas Elsaesser

Abstract The extent of contact and solvent shared ion pairs of phosphate groups with Na + , Ca 2+ and Mg 2+ ions in aqueous environment and their relevance for the stability of polyanionic DNA and RNA structures is highly debated. Employing the asymmetric phosphate stretching vibration of dimethyl phosphate (DMP), a model system of the sugar-phosphate backbone of DNA and RNA, we present linear infrared, femtosecond infrared pump-probe and absorptive 2D-IR spectra that report on contact ion pair formation via the presence of blue shifted spectral signatures. Compared to the linear infrared spectra, the nonlinear spectra reveal contact ion pairs with increased sensitivity because the spectra accentuate differences in peak frequency, transition dipole moment strength, and excited state lifetime. The experimental results are corroborated by long time scale MD simulations, benchmarked by density functional simulations on phosphate-ion-water clusters. The microscopic interpretation reveals subtle structural differences of ion pairs formed by the phosphate group and the ions Na + , Ca 2+ and Mg 2+ . Intricate properties of the solvation shell around the phosphate group and the ion are essential to explain the experimental observations. The present work addresses a challenging to probe topic with the help of a model system and establishes new experimental data of contact ion pair formation, thereby underlining the potential of nonlinear 2D-IR spectroscopy as an analytical probe of phosphate-ion interactions in complex biological systems.

Solvation shell

10.1515/zpch-2020-1614

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Citations (7)

Large-amplitude transfer motion of hydrated excess protons mapped by ultrafast 2D IR spectroscopy

Science (2017)

Fabian Dahms Benjamin P. Fingerhut Erik T. J. Nibbering Ehud Pines Thomas Elsaesser

Solvation and transport of excess protons in aqueous systems play a fundamental role in acid-base chemistry and biochemical processes. We mapped ultrafast proton excursions along the proton transfer coordinate by means of two-dimensional infrared spectroscopy, both in bulk water and in a Zundel cation (H5O2)+ motif selectively prepared in acetonitrile. Electric fields from the environment and stochastic hydrogen bond motions induce fluctuations of the proton double-minimum potential. Within the lifetime of a particular hydration geometry, the proton explores a multitude of positions on a sub-100-femtosecond time scale. The proton transfer vibration is strongly damped by its 20- to 40-femtosecond population decay. Our results suggest a central role of Zundel-like geometries in aqueous proton solvation and transport.

Femtochemistry

Two-dimensional infrared spectroscopy

Proton Transport

Solvation shell

10.1126/science.aan5144

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Citations (147)

The First Picoseconds in the Life of Benzhydryl Cations: Ultrafast Generation and Chemical Reactions

International Conference on Ultrafast Phenomena (2010)

Christian F. Sailer Benjamin P. Fingerhut Johannes Ammer Christoph Nolte Igor Pugliesi

For benzhydryl chloride compounds we observe that photodissociation only leads to radical pairs. The typically observed cations are formed by subsequent electron transfer. Reactions of cations in neat alcohols can then occur within 2.6 ps.

Picosecond

10.1364/up.2010.the14

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