Article
Chemistry, Analytical
Steven A. Diaz, David W. Mccamant
Summary: By improving the collection optics, we have developed two new diffuse reflectance-based femtosecond stimulated Raman spectroscopy (drFSRS) techniques for collecting Raman spectra of opaque systems. The experimental results demonstrate the current capabilities of collecting high-quality Raman spectra using drFSRS.
ANALYTICAL CHEMISTRY
(2023)
Article
Nanoscience & Nanotechnology
Cheng Zong, Ji-Xin Cheng
Summary: Plasmon-enhanced stimulated Raman scattering (PESRS) microscopy has been developed to achieve single-molecule detection limit. The dispersive-like vibrational line shapes observed in PESRS can be explained by the interference between the local enhanced electromagnetic field induced by the plasmonic nanostructure and the molecular dipole-induced field. The PESRL and PESRG signals exhibit similar signal magnitudes but show reversed dispersive profiles under the same laser wavelength.
Article
Spectroscopy
Aristides Marcano Olaizola, Ameen Zerrad, Fahim Janneto, David H. Kingsley
Summary: We confirm the Raman origin of the singlet oxygen photogenerated in water environments without using photosensitizers. The experimental results show that nanosecond light pulses in the blue region of the spectra can generate Raman Stokes excitation of singlet oxygen in the red region when focused on pure distilled water. The time evolution and power dependence of the singlet oxygen and stretching modes correspond to the characteristics of a Raman process. The signals also exhibit high refractive ring structures due to the stimulated Raman process.
JOURNAL OF RAMAN SPECTROSCOPY
(2023)
Article
Multidisciplinary Sciences
Zhong Yin, Yi-Ping Chang, Tadas Balciunas, Yashoj Shakya, Aleksa Djorovic, Geoffrey Gaulier, Giuseppe Fazio, Robin Santra, Ludger Inhester, Jean-Pierre Wolf, Hans Jakob Worner
Summary: Researchers have revealed the femtosecond proton-transfer dynamics in ionized urea dimers in aqueous solution using table-top water-window X-ray absorption spectroscopy. By combining quantum-mechanical and molecular-mechanics calculations, they were able to identify the subsequent rearrangement of the urea dimer and the associated change of the electronic structure with site selectivity. These findings highlight the potential of table-top X-ray absorption spectroscopy in elucidating ultrafast dynamics in biomolecular systems.
Article
Biochemistry & Molecular Biology
Cheng Chen, J. Nathan Henderson, Dmitry A. Ruchkin, Jacob M. Kirsh, Mikhail S. Baranov, Alexey M. Bogdanov, Jeremy H. Mills, Steven G. Boxer, Chong Fang
Summary: This study systematically analyzed the vibrational properties of FP chromophores by using FSRS and quantum calculations. A bond-stretching mode characteristic of the quinoidal resonance structure was found to be present in most FPs and model chromophores, which can serve as a vibrational marker for interpreting chromophore-environment interactions and structural effects on the electronic properties of the chromophore.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Qiaozhi Yu, Zhengjian Yao, Haolin Zhang, Zhibin Li, Zhixing Chen, Hanqing Xiong
Summary: Researchers have developed a new ultrafast time-domain spectroscopy technique called transient stimulated Raman excited fluorescence (T-SREF), which enables background-free Raman spectra of electronic-coupled vibrational modes. By exciting the sample with two successive broadband femtosecond pulse pairs and performing Fourier transform on the resulting time-domain fluorescence trace, T-SREF achieves high sensitivity at the level of a few molecules, paving the way for supermultiplexed fluorescence detection and molecular dynamics sensing.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Hosung Ki, Seungjoo Choi, Jungmin Kim, Eun Hyuk Choi, Seonggon Lee, Yunbeom Lee, Kihwan Yoon, Chi Woo Ahn, Doo-Sik Ahn, Jae Hyuk Lee, Jaeku Park, Intae Eom, Minseok Kim, Sae Hwan Chun, Joonghan Kim, Hyotcherl Ihee, Jeongho Kim
Summary: In this study, an alternative method, femtosecond time-resolved X-ray liquidography (fs-TRXL), was used to monitor microscopic structural motions related to the Optical Kerr effect response in molecular liquids using X-ray solution scattering. Different types of molecular motions were successfully resolved selectively without the need for theoretical modeling, based on anisotropy and extra structural information in the scattering data.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Biochemistry & Molecular Biology
Aristides Marcano Olaizola, Robinson Kuis, Anthony Johnson, David Kingsley
Summary: This study investigates the generation of singlet oxygen from dissolved oxygen in water and heavy water using Raman stimulation. Without singlet oxygen photosensitizers, nanosecond-pulsed visible blue laser light can produce a red Stokes peak that is oxygen-dependent. This peak is absent in the presence of an oxygen quencher, and the temporal photodepletion of uric acid absorbance peak supports singlet oxygen generation. The authors suggest a two-photon stimulated Raman process as the mechanism behind singlet oxygen production from dissolved O2 in the solvents.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY B-BIOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Mason L. L. Valentine, Guoxin Yin, Julius J. J. Oppenheim, Mircea Dinca, Wei Xiong
Summary: We investigated the water H-bond network and its dynamics in Ni2Cl2BTDD using linear and ultrafast IR spectroscopy. We found that water forms an extensive H-bonding network in Ni2Cl2BTDD, which can rearrange within a confined cone up to 50 degrees within 1.3 ps. This reorientation indicates H-bond rearrangement, similar to bulk water. The picosecond H-bond rearrangement in Ni2Cl2BTDD supports its reversibility in water sorption.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Victor M. Freixas, Daniel Keefer, Sergei Tretiak, Sebastian Fernandez-Alberti, Shaul Mukamel
Summary: This study explores the photoinduced ultrafast coherent inter-chromophore energy redistribution in a triarylamine trimer using nonadiabatic excited state molecular dynamics followed by simulations of X-ray Raman signals. The research reveals the presence of multiple non-deterministic photoinduced pathways during the ultrafast inter-branch migration of the excitation, resulting in spatial exciton scrambling and loss of phase information at long times. The study demonstrates that X-ray Raman spectroscopy is a valuable tool for detecting ultrafast molecular coherences or their absence.
Article
Biochemical Research Methods
Rajeev Ranjan, Giovanni Costa, Maria Antonietta Ferrara, Mario Sansone, Luigi Sirleto
Summary: In this study, the relationship between hardware characteristics and image processing in SRS microscopy literature was explored, with a focus on statistical analysis of image noise. The results demonstrated an improvement in image denoising with the adapted singular spectrum analysis method.
JOURNAL OF BIOPHOTONICS
(2022)
Article
Chemistry, Multidisciplinary
Mauro Falconieri, Davide Tedeschi, Serena Gagliardi, Flaminia Rondino, Michele Marrocco, Waruna D. D. Kulatilaka
Summary: Femtosecond coherent Raman techniques are valuable for sensitive and non-intrusive measurements of temperature, pressure, and composition of gas mixtures. This paper demonstrates an experimental setup using a low-energy and low-average-power femtosecond oscillator to measure the pure-rotational spectrum of nitrogen at atmospheric pressure. Gas temperature can be derived with reasonable accuracy using a simplified model to analyze the experimental data.
APPLIED SCIENCES-BASEL
(2022)
Article
Chemistry, Physical
Xiujuan Wang, Jiayi Li, Juncheng Lei, Xuefang Xu, Yang Zheng, Junhua Chen, Xiao Tian, Qian Gou
Summary: The rotational spectra of 4-fluoroacetophenone monomer and its monohydrate were studied using Fourier transform microwave spectroscopy and quantum chemical calculations. Different conformers and isomers were observed, stabilized by hydrogen bonds. The effects of fluorination on geometries, intermolecular interactions, and internal rotation were analyzed.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Multidisciplinary Sciences
Kristina S. Zinchenko, Fernando Ardana-Lamas, Issaka Seidu, Simon P. Neville, Joscelyn van der Veen, Valentina Utrio Lanfaloni, Michael S. Schuurman, Hans Jakob Worner
Summary: In this study, the fastest electronic relaxation dynamics to date was observed using attosecond transient-absorption spectroscopy (ATAS) extended to the carbon K-edge. By selectively launching wave packets in the two lowest electronic states of C2H4+, the electronic relaxation process was visualized and multidimensional structural dynamics of the molecule were simultaneously observed. These results demonstrate the capability to resolve the fastest electronic and structural dynamics in a broad class of organic molecules, showing that electronic relaxation in organic chromophores can occur within less than a single vibrational period.
Article
Physics, Applied
A. J. X. Choorakuttil, A. Pruccoli, M. J. Winterhalder, P. Zirak, D. Gudavicius, G. Martynaitis, D. Petrulionis, D. Samsonas, L. Kontenis, A. Zumbusch
Summary: We present an experimental scheme for stimulated Raman scattering (SRS) microscopy using visible light excitation, allowing for electronically preresonant imaging of a wide range of chromophores with sensitivities as low as 1 mu M. Our experiment utilizes two synchronously pumped optical parametric oscillators (OPOs) in the near-infrared region, and by combining spectral focusing and tuning, we demonstrate the recording of epr-SRS spectra over the entire range of molecular vibrations at a speed 20 times faster than classical wavelength tuning. The imaging capabilities of this setup are demonstrated with material scientific and cellular samples.
APPLIED PHYSICS LETTERS
(2023)
Article
Chemistry, Organic
Dominik Madea, Taufiqueahmed Mujawar, Ales Dvorak, Katerina Pospisilova, Lucie Muchova, Petra Cubakova, Miroslav Kloz, Jakub Svenda, Libor Vitek, Petr Klan
Summary: This study investigates the photochemical properties and biological activities of a subunit of bilirubin, (Z)-isovinylneoxanthobilirubic acid methyl ester. The subunit undergoes wavelength-dependent and reversible photoisomerization under blue-green light, with fast isomerization rates and high efficiencies. The study also explores the sensitized photooxidation of the subunit and its effects on various biological processes.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Immunology
Kibaek Choe, Yusaku Hontani, Tianyu Wang, Eric Hebert, Dimitre G. Ouzounov, Kristine Lai, Ankur Singh, Wendy Beguelin, Ari M. Melnick, Chris Xu
Summary: Intravital three-photon microscopy allows for the visualization of immune cell behavior in mouse lymph nodes at depths of 600-900 μm. This technique enables measurement of migration ability in different depths and the observation of inflammation effects on T cell motility.
Article
Plant Sciences
Callum Gray, Tiejun Wei, Tomas Polivka, Vangelis Daskalakis, Christopher D. P. Duffy
Summary: Higher plants have a defense mechanism called Non-Photochemical Quenching (NPQ) to protect themselves from intense light. This involves the participation of energy transfer and the S-1 state. Previous models of NPQ have limitations and this study aims to address them by parameterizing the vibronic structure and relaxation dynamics of lutein, as well as analyzing multiple minima. The results suggest that the previous quenching mechanism based on S-1 energy transfer is unlikely, and the real mechanism may involve short-range interaction and/or non-trivial inter-molecular states.
FRONTIERS IN PLANT SCIENCE
(2022)
Article
Multidisciplinary Sciences
Yusaku Hontani, Najva Akbari, Kristine E. Kolkman, Chunyan Wu, Fei Xia, Kibaek Choe, Grace Zhang Wang, Mariya Sokolova, Joseph R. Fetcho, Chris Xu
Summary: Multiphoton microscopy techniques, such as two-photon microscopy (2PM) and three-photon microscopy (3PM), are powerful tools for deep-tissue in vivo imaging with subcellular resolution. Three-photon microscopy has advantages over two-photon microscopy in terms of longer attenuation length and less background fluorescence generation. Commercial laser sources and microscopes are available for 3PM, making it readily accessible for biology research laboratories.
JOVE-JOURNAL OF VISUALIZED EXPERIMENTS
(2022)
Article
Multidisciplinary Sciences
Pu Qian, Alastair T. Gardiner, Ivana Simova, Katerina Naydenova, Tristan Croll, Philip J. Jackson, Nupur, Miroslav Kloz, Petra Cubakova, Marek Kuzma, Yonghui Zeng, Pablo Castro-Hartmann, Bart van Knippenberg, Kenneth N. Goldie, David Kaftan, Pavel Hrouzek, Jan Hajek, Jon Agirre, C. Alistair Siebert, David Bina, Kasim Sader, Henning Stahlberg, Roman Sobotka, Christopher J. Russo, Tomas Polivka, C. Neil Hunter, Michal Koblizek
Summary: Phototrophic Gemmatimonadetes have evolved the ability to use solar energy through horizontal gene transfer. The study reveals the unique solar energy harvesting and trapping architecture of Gemmatimonas phototrophica, as well as the flow of energy within the complex.
Article
Chemistry, Physical
Tuhin Khan, Valentyna Kuznetsova, Maria Agustina Dominguez-Martin, Cheryl A. Kerfeld, Tomas Polivka
Summary: This study investigated the ultrafast spectroscopic response of OCP and HCPs in cyanobacteria, focusing on the reaction of carotenoid and amino acids under UV excitation. The results showed enhanced signals of canthaxanthin and formation of canthaxanthin radical cation under UV excitation, as well as accelerated product formation in the OCP photocycle through excess energy excitation and direct excitation of amino acids.
Article
Multidisciplinary Sciences
Arita Silapetere, Songhwan Hwang, Yusaku Hontani, Rodrigo G. Fernandez Lahore, Jens Balke, Francisco Velazquez Escobar, Martijn Tros, Patrick E. Konold, Rainer Matis, Roberta Croce, Peter J. Walla, Peter Hildebrandt, Ulrike Alexiev, John T. M. Kennis, Han Sun, Tillmann Utesch, Peter Hegemann
Summary: The authors conducted an in-depth investigation of excited state dynamics and molecular mechanism of voltage sensing in microbial rhodopsins. Their findings suggest that the voltage-modulated deprotonation of the chromophore plays a key role in voltage sensing. The study also identifies molecular constraints that may enhance fluorescence quantum yield and voltage sensitivity.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yusaku Hontani, Jennifer Mehlhorn, Tatiana Domratcheva, Sebastian Beck, Miroslav Kloz, Peter Hegemann, Tilo Mathes, John T. M. Kennis
Summary: This study investigates the structure of BLUF domains using a combination of spectroscopy techniques and confirms the presence of glutamine tautomerization and side-chain rotation in the BLUF photoreaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Yingliang Liu, Aditya S. Chaudhari, Aditi Chatterjee, Prokopis C. Andrikopoulos, Alessandra Picchiotti, Mateusz Rebarz, Miroslav Kloz, Victor A. Lorenz-Fonfria, Bohdan Schneider, Gustavo Fuertes
Summary: A broadband dual transient visible absorption (visTA)/femtosecond stimulated Raman spectroscopy (FSRS) set-up was developed to monitor the complete excited-state dynamics of flavin mononucleotide (FMN) in solution and embedded in bacterial light-oxygen-voltage (LOV) photoreceptor EL222. The set-up covers a wide range of time delays and Raman shifts, providing valuable information on short-lived conformationally excited states. Additional dynamical events were found in the low-frequency Raman region below 1000 cm(-1).
Article
Chemistry, Physical
Ivo H. M. van Stokkum, Yusaku Hontani, Johannes Vierock, Benjamin S. Krause, Peter Hegemann, John T. M. Kennis
Summary: In this study, the reaction dynamics of Chrimson channelrhodopsin were analyzed from femtoseconds to seconds. Multiple phases in the decay of excited state were identified, and early dynamics of K-like species on a 10 ps time scale were observed. Selective excitation at different wavelengths resulted in distinct spectral features, which gradually became indistinguishable over time. Protein motions underlying inhomogeneous broadening were resolved, demonstrating a dynamic interconversion between protein substates.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Correction
Plant Sciences
Minna M. Konert, Anna Wysocka, Peter Konik, Roman Sobotka
PHOTOSYNTHESIS RESEARCH
(2023)
Article
Plant Sciences
Jaroslav Nisler, Zuzana Kucerova, Radoslav Koprna, Roman Sobotka, Jana Slivkova, Stephen Rossall, Martina Spundova, Alexandra Husickova, Jan Pilny, Danuse Tarkowska, Ondrej Novak, Maria Skrabisova, Miroslav Strnad
Summary: Increasing crop productivity and mitigating yield losses under stressful conditions are major challenges in agriculture. A recently discovered compound, MTU, delays senescence and enhances the growth of wheat plants. Multiyear field trials demonstrate that treatment with MTU increases average grain yields of wheat and barley by 5-8%. This compound acts independently of cytokinins or other phytohormones and appears to be the only chemical known to affect the stability and activity of PSI.
FRONTIERS IN PLANT SCIENCE
(2023)
Article
Chemistry, Physical
Valentyna Kuznetsova, Marcel Fuciman, Tomas Polivka
Summary: This article investigates the excited states of carotenoids and finds differences between the S-UV and S-n states, each initiating specific relaxation pathways.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Review
Chemistry, Physical
Donatas Zigmantas, Tomas Polivka, Petter Persson, Villy Sundstroem
Summary: The development and progress of laser technology have enabled deeper research into the mechanisms of photosynthesis and solar energy conversion. Through the study of ultrafast pulses, there has been significant advancement in understanding complex biological systems and novel materials.
CHEMICAL PHYSICS REVIEWS
(2022)