Article
Chemistry, Physical
Nicolas Schork, Masooma Ibrahim, Ananya Baksi, Steffen Kraemer, Annie K. Powell, Gisela Guthausen
Summary: Selectivity and image contrast in magnetic resonance imaging (MRI) are challenging and can be addressed by contrast agents. The relaxation properties of these agents, specifically the paramagnetic relaxation enhancement (PRE), need to be understood and improved. This study focused on the H-1-relaxivities of high-spin heterometallic clusters and investigated the effects of rotational and diffusion correlation times as well as solvent viscosity on relaxivities. The variation of lanthanide and transition-metal ions in the clusters also provided insights into the sensitivity of PRE to electron spin properties and cooperative effects.
Article
Multidisciplinary Sciences
Marianne Le Dantec, Milos Rancic, Sen Lin, Eric Billaud, Vishal Ranjan, Daniel Flanigan, Sylvain Bertaina, Thierry Chaneliere, Philippe Goldner, Andreas Erb, Ren Bao Liu, Daniel Esteve, Denis Vion, Emmanuel Flurin, Patrice Bertet
Summary: By selecting a host matrix with low nuclear-spin density (CaWO4) and quenching spectral diffusion at millikelvin temperatures, a 23-ms coherence time on Er3+ electron spin transition has been achieved, establishing Er3+:CaWO4 as a potential platform for quantum networks.
Article
Chemistry, Inorganic & Nuclear
Rui F. S. Carvalho, Giovannia A. L. Pereira, Joao Rocha, M. Margarida C. A. Castro, Carlos M. Granadeiro, Helena I. S. Nogueira, Joop A. Peters, Carlos F. G. C. Geraldes
Summary: The relaxivities of decatungstolanthanoate core-shell nanoparticles were studied, showing that GdPOM has higher relaxivity than Gd-DTPA due to second-sphere relaxation effects. The nanoparticles have core-shell structures with LnPOM-containing cores and amorphous silica shells, exhibiting negative zeta potentials and time-dependent hydrodynamic diameters in water suspensions. The relaxivities of GdPOM@SiO2 NPs suspensions are considerably larger than for the GdPOM solutions, indicating their porous silica shell and potential as dual modality MRI/optical imaging contrast agents.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Maja A. Dunstan, Dominic S. Brown, Lorenzo Sorace, Richard A. Mole, Colette Boskovic
Summary: Incorporating lanthanoid(III)-radical magnetic exchange coupling is a possible route to improving the performance of lanthanoid single-molecule magnets, which exhibit slow relaxation and low temperature quantum tunnelling of the magnetization. In this study, Gd(III) complexes were used as model systems to study the Ln-radical exchange coupling. Two new Gd(III)-radical compounds were synthesized, and their structures were confirmed using various characterization techniques. The compounds showed differences in low temperature magnetic properties, with compound 1 exhibiting slow magnetic relaxation in applied magnetic fields and compound 2 relaxing much faster, pointing to the major role of packing effects in modulating slow relaxation of the magnetization.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
You-Song Ding, William J. A. Blackmore, Yuan-Qi Zhai, Marcus J. Giansiracusa, Daniel Reta, Inigo Vitorica-Yrezabal, Richard E. P. Winpenny, Nicholas F. Chilton, Yan-Zhen Zheng
Summary: The hexagonal-bipyramidal lanthanide(III) complex exhibits an energy barrier for magnetization reversal of about 1000 K in zero direct-current field. Temperature-dependent X-ray diffraction studies reveal bending of the Cl-Ln-(OBu)-Bu-t angle at low temperature. Ab initio calculations show that significant bending of the O-Dy-Cl angle upon cooling leads to a decrease in the energy of the excited electronic states. The magnetic relaxation rate is influenced by multiple mechanisms such as Orbach, Raman-I, quantum tunnelling of magnetization, and Raman-II.
INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Physical
Aneta J. Lenard, Frans A. A. Mulder, Tobias Madl
Summary: Solvent paramagnetic relaxation enhancement (sPRE) is a versatile NMR-based method that characterizes the structure and dynamics of biomolecular systems by providing quantitative experimental information on the solvent accessibility of NMR-active nuclei. This review discusses recent progress in sPRE-based characterization of biomolecules and their complexes, highlighting the diverse applications of the method. By combining sPRE with complementary biophysical techniques, it is possible to advance biomolecular structure determination, identify interaction surfaces within protein complexes, probe conformational changes and low-population transient states, and gain insights into weak, nonspecific, and transient interactions between proteins and co-solutes. Additionally, the incorporation of solvent paramagnetic probes can improve the sensitivity of NMR experiments and hold promise for applications in metabolomics, drug discovery, and the study of intrinsically disordered proteins.
PROGRESS IN NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
(2022)
Article
Engineering, Electrical & Electronic
Sergey P. Babailov, Marina A. Polovkova, Gayane A. Kirakosyan, Alexander G. Martynov, Evgeny N. Zapolotsky, Yulia G. Gorbunova
Summary: This paper demonstrates the thermosensing properties of binuclear triple-decker terbium(III) and dysprosium(III) complexes at physiological temperature range, with terbium-containing complex showing the highest sensitivity among published complexes in nonpolar solutions. The significant impact of Curie-spin contribution on paramagnetic spin-spin relaxation rate enhancement with pronounced temperature dependence is also highlighted.
SENSORS AND ACTUATORS A-PHYSICAL
(2021)
Article
Multidisciplinary Sciences
Z. Wang, L. Balembois, M. Rancic, E. Billaud, M. Le Dantec, A. Ferrier, P. Goldner, S. Bertaina, T. Chaneliere, D. Esteve, D. Vion, P. Bertet, E. Flurin
Summary: Electron spin resonance spectroscopy is the preferred method for characterizing paramagnetic impurities, but it only provides ensemble-averaged quantities due to limited signal-to-noise ratio. To achieve single-electron spin sensitivity, we use spin fluorescence detection method and a microwave photon counter at millikelvin temperatures. By coupling individual paramagnetic erbium ions in a scheelite crystal to a high-quality-factor planar superconducting resonator to enhance their radiative decay rate, we obtain a fluorescence signal with a signal-to-noise ratio of 1.9 in one second integration time. This method has the potential for single-spin detection in a volume as large as the resonator magnetic mode volume, making it orders of magnitude larger than other single-spin detection techniques.
Article
Physics, Multidisciplinary
Yu-Hui Chen, Sebastian P. Horvath, Jevon J. Longdell, Xiangdong Zhang
Summary: A new dynamical phase of intrinsic optical instability was experimentally revealed, where the transmission through the sample became unstable under intense laser inputs and transient net gain was observed if the light passed the sample twice. The phase transition between states in and out of a dynamical equilibrium was induced by dipole-dipole interactions between nearby erbium ions.
PHYSICAL REVIEW LETTERS
(2021)
Article
Biochemistry & Molecular Biology
Chandrashekhar Honrao, Nathalie Teissier, Bo Zhang, Robert Powers, Elizabeth M. O'Day
Summary: The addition of a gadolinium-based PRE agent can enhance the sensitivity of NMR spectral data, improve the detection of a wide range of metabolites, and increase the repeatability of intensity measurements in metabolomics samples.
Article
Chemistry, Inorganic & Nuclear
Jerome Long, Alexander N. Selikhov, Anton Cherkasov, Yulia Nelyubina, Fabrice Salles, Yannick Guari, Joulia Larionova, Alexander A. Trifonov
Summary: The synthesis and structures of two base-free alkoxide dysprosium(III) complexes are reported, and the magnetic properties of one of the complexes are investigated, revealing the occurrence of a field-induced slow relaxation of the magnetization.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Physics, Applied
Mark A. Hughes, Naitik A. Panjwani, Matias Urdampilleta, Nafsika Theodoropoulou, Ilana Wisby, Kevin P. Homewood, Ben Murdin, Tobias Lindstrom, J. David Carey
Summary: Erbium-implanted silicon shows promise for both photonic and quantum-technology platforms, but the presence of various Er centers generated during implantation and annealing processes could hinder its development. By coimplanting silicon with Er and O ions and utilizing the appropriate annealing process, one of these Er centers can be eliminated at higher Er concentrations. The coupling strength between a superconducting NbN resonator and Er-implanted silicon at low concentrations provides a basis for future networks of hybrid quantum systems exchanging quantum information over the telecommunication network.
PHYSICAL REVIEW APPLIED
(2021)
Article
Materials Science, Multidisciplinary
Benedikt Tissot, Guido Burkard
Summary: The study provides a theoretical framework for the interaction between transition metal defects in silicon carbide and nuclear spin, with potential applications for nuclear spin manipulation and long-lived nuclear-spin based quantum memories.
Article
Materials Science, Multidisciplinary
S. Reale, A. Singha, S. L. Ahmed, D. Krylov, L. Colazzo, C. Wolf, C. S. Casari, A. Barla, E. Fernandes, F. Patthey, M. Pivetta, S. Rusponi, H. Brune, F. Donati
Summary: This study explores the use of lanthanide atoms adsorbed on surfaces as a platform for atomic-scale magnetic information storage. The authors propose a combined experimental and theoretical method to evaluate the performance of these atoms for quantum coherent operations. Using X-ray absorption spectroscopy and scanning tunneling microscopy, they investigate the magnetic and electronic properties of Er and Tm on MgO(100)/Ag(100) and identify their adsorption sites. They suggest that these atoms could be used for electron spin resonance scanning tunneling microscopy and possess a nontrivial nuclear spin that could be exploited for two-qubit operations or quantum state storage.
Article
Biochemistry & Molecular Biology
Hae-Jun Park, Jinhwa Jang, Kyung-Suk Ryu, Jinhyuk Lee, Sung-Hee Lee, Hyung-Sik Won, Eun-Hee Kim, Min-Duk Seo, Ji-Hun Kim
Summary: In this study, the structural characteristics of Caveolin 3 (Cav3) were analyzed using solution NMR, focusing on the whole N-terminal part composed of the flexible N-terminus and the scaffolding domain. The results revealed complex structural interactions among different segments, providing novel insights into the molecular basis of Cav3-related diseases.
Article
Chemistry, Physical
Jayoti Roy, Papri Chakraborty, Ganesan Paramasivam, Ganapati Natarajan, Thalappil Pradeep
Summary: The gas phase fragmentation events of highly symmetric FN-like titanium oxo-cluster anions were investigated. Collision induced dissociation studies revealed that the protecting ligands were stripped off first, followed by systematic TiO2 losses, resulting in the formation of various fragments. Similar fragmentation was observed for monoanionic species. Computational studies showed that the fragmentation of TOF was comparable to the fragmentation of C-60 ions, suggesting topological similarity.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Inorganic & Nuclear
Muhammad Nadeem Akhtar, Valeriu Mereacre, Ghenadie Novitchi, Murad A. AlDamen, Christopher E. Anson, Annie K. Powell
Summary: This study reports three isostructural heterometallic coordination clusters with different magnetic behaviors.
INORGANICA CHIMICA ACTA
(2022)
Article
Chemistry, Multidisciplinary
Changming Hu, Thomas Jochmann, Papri Chakraborty, Marco Neumaier, Pavel A. Levkin, Manfred M. Kappes, Frank Biedermann
Summary: The insufficient selectivity of chemosensors often makes it difficult to distinguish biorelevant metabolites. In this study, a novel cucurbit[7]uril-dye conjugate was used to differentiate 14 bioorganic analytes by adding salts step by step. This method requires low synthetic effort and provides additional information about the system.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Lisa-Lou Gracia, Elham Barani, Jonas Braun, Anthony B. Carter, Olaf Fuhr, Annie K. Powell, Karin Fink, Claudia Bizzarri
Summary: In this study, a new iron complex was synthesized for photocatalytic reduction of carbon dioxide to produce CO gas. The complex showed significant activity under visible light and can be combined with other complexes to achieve the use of earth-abundant elements.
Article
Chemistry, Physical
Madhuri Jash, Arijit Jana, Ajay K. Poonia, Esma Khatun, Papri Chakraborty, Ankit Nagar, Tripti Ahuja, K. V. Adarsh, Thalappil Pradeep
Summary: Superstructures made by assemblies of metal nanoclusters (NCs) with atomic precision and exciting photophysical properties have been synthesized. The synthesis of phosphine-protected alloy NCs of silver with varying gold doping and the superstructures of such systems are reported for the first time. These alloy clusters show aggregation-induced emission (AIE) property and form cluster-assembled spherical hollow superstructures in the presence of water without any template. The assembly of the alloy NCs within the hollow spheres leads to highly efficient emitting states.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Amrita Chakraborty, Megha Maria Stanley, Biswajit Mondal, Nonappa, Mohammad Bodiuzzaman, Papri Chakraborty, M. P. Kannan, Thalappil Pradeep
Summary: Quantized energy levels and unique optoelectronic properties of atomically precise noble metal nanoclusters have made them important in various fields. Recent studies have shown that these nanoclusters can either participate in colloidal assembly or lead to products with atom exchange depending on the reactant. Furthermore, anisotropic plasmonic nanoparticles with sharp edges and protrusions exhibit higher chemical reactivity and can induce site-specific growth of foreign metals and metal oxide shells.
Article
Chemistry, Multidisciplinary
Arijit Jana, Madhuri Jash, Wakeel Ahmed Dar, Jayoti Roy, Papri Chakraborty, Ganesan Paramasivam, Sergei Lebedkin, Kaplan Kirakci, Sujan Manna, Sudhadevi Antharjanam, Jan Machacek, Monika Kucerakova, Sundargopal Ghosh, Kamil Lang, Manfred M. Kappes, Tomas Base, Thalappil Pradeep
Summary: This study presents a new class of thermally stable tetranuclear copper nanoclusters (Cu-4@oCBT, Cu-4@mCBT and Cu-4@ICBT) with tunable solid-state luminescence. They exhibit bright phosphorescence in their crystalline forms. Cu-4@oCBT and Cu-4@mCBT are green emitting, while Cu-4@ICBT is orange emitting. DFT calculations reveal the nature of their electronic transitions. Cu-4@oCBT and Cu-4@mCBT are thermally stable up to 400 degrees C, while Cu-4@ICBT is structurally flattened.
Review
Chemistry, Multidisciplinary
Guillermo Moreno-Alcantar, Pierre Picchetti, Angela Casini
Summary: The discovery of medicinal properties of gold complexes has led to the development of new anticancer drugs, which are unique in their modes of action. Current research focuses on designing drug leads with enhanced pharmacological activities and improving physicochemical properties of gold compounds. Encapsulation of gold compounds in nanocarriers or their grafting onto targeted delivery vectors may lead to new nanomedicines for clinical applications. This article provides an overview of gold anticancer compounds and a detailed review of nanoparticle-based delivery systems for gold chemotherapeutics.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Papri Chakraborty, Sami Malola, Marco Neumaier, Patrick Weis, Hannu Hakkinen, Manfred M. Kappes
Summary: The fragmentation dynamics of ligated coinage metal clusters provides insights into their structural and bonding properties. However, the challenges in methodology have limited the investigation of fragment structures. In this study, we used trapped ion mobility mass spectrometry to determine the geometric structures of the primary fragments of [Ag29L12](3-) and compared them to density functional theory calculations. We also observed a new dissociation channel in the further dissociation of [Ag19L6](-), indicating a competition between retaining electronic stability and increasing steric strain of ligands and staples. These findings have potential implications for studying the catalytic behavior of Ag clusters on supports through soft-landing deposition.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xiang Zhong, Zhao-Bo Hu, Tong-Kai Luo, Yan Peng, Sui-Jun Liu, Christopher E. Anson, Annie K. Powell, He-Rui Wen
Summary: Three one-dimensional Ln(III) complexes based on hydrazone Schiff-base ligands were reported. The Dy-III analogue exhibited a field-induced SMM behavior with U (eff) = 43 K, while the Gd-III analogue showed a significant magnetic thermal effect with a maximum -ΔS(m) value of 21.32 J kg(-1) K-1 at 3 K and 7 T. The structures of the complexes were also characterized. The SMM behavior in the Dy-III compound was attributed to its single-ion properties, which was confirmed by comparing it with the Y/Dy diluted complex. On the other hand, the magnetocaloric effect in the Gd-III analogue was observed, with a maximum entropy change -ΔS(m) of 21.32 J kg(-1) K-1 at ΔH = 7 T and 3 K.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Biochemical Research Methods
Papri Chakraborty, Marco Neumaier, Patrick Weis, Manfred M. Kappes
Summary: Cyclodextrin (CD) macrocycles are used to create various supramolecular architectures for applications including gas adsorption, drug delivery, and catalysis. However, predicting their assemblies and identifying possible isomers in CD oligomers has been challenging due to their dynamic nature. In this study, CD oligomers linked by Cu2+ metal ions were created and characterized using mass spectrometry and trapped ion mobility spectrometry, allowing the separation and estimation of isomers. The isomeric heterogeneity reflects the size-specific packing patterns of individual CDs, and the existence of kinetically trapped structures was also observed.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2023)
Article
Chemistry, Multidisciplinary
Nilima Manoj Kumar, Patrick Gruhs, Angela Casini, Frank Biedermann, Guillermo Moreno-Alcantar, Pierre Picchetti
Summary: In this article, a cucurbit[7]uril-based chemosensor with electrochemical signal readout for the detection of pancuronium bromide is presented. The design avoids the need for immobilization on electrode surfaces and can be used with commercially available screen-printed electrodes.
Article
Chemistry, Multidisciplinary
Pierre Picchetti, Stefano Volpi, Marianna Rossetti, Michael D. Dore, Tuan Trinh, Frank Biedermann, Martina Neri, Alessandro Bertucci, Alessandro Porchetta, Roberto Corradini, Hanadi Sleiman, Luisa De Cola
Summary: The development of smart nanoparticles with responsive features has expanded the applications of NP-based drugs, vaccines, and diagnostic tools. By combining nucleic acid interactions and sol-gel chemistry, researchers have successfully incorporated synthetic nucleic acids into organosilica nanoparticles, enabling them to respond to various biological, physical, and chemical inputs.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Pierre Picchetti, Stefano Volpi, Maria Sancho-Albero, Marianna Rossetti, Michael D. Dore, Tuan Trinh, Frank Biedermann, Martina Neri, Alessandro Bertucci, Alessandro Porchetta, Roberto Corradini, Hanadi Sleiman, Luisa De Cola
Summary: Organosilica nanoparticles with responsive organic building blocks offer promising opportunities for drug formulation, biomolecule delivery, and diagnostics. In this study, the researchers combined nucleic acid interactions with sol-gel chemistry to create dynamic supramolecular bridging units in the silica-based nanoparticles. These nanoparticles exhibit programmable responses to temperature and biological inputs.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Paulami Bose, Krishnadas Kumaranchira Ramankutty, Papri Chakraborty, Esma Khatun, Thalappil Pradeep
Summary: This review provides a comprehensive account of the chemistry, diversity, and kinetics of atomically precise noble metal nanoclusters. These clusters exhibit molecule-like properties and undergo intercluster reactions in solution, leading to the formation of composites and hybrid materials.