Article
Geochemistry & Geophysics
Norio Kitadai, Shigeru Shimamura, Wataru Takahagi, Masayuki Miyazaki, Eiji Tasumi, Satoshi Okada
Summary: The origin of life in submarine hydrothermal systems has been supported by diverse scientific disciplines for a long time, but the chemical plausibility of this scenario remains uncertain. Many hypotheses propose peptides as important molecules in the prebiotic chemistry, but it is still unknown how peptides were formed from amino acids that were present in low concentrations. In this study, it was shown that a simple mix of elemental sulfur, hydrogen sulfide, and carbon monoxide enabled efficient dimerization of glycine at low concentrations. This finding supports the possibility of abiotic peptide formation and facilitates the hydrothermal origin of life.
GEOCHIMICA ET COSMOCHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Olivia Doppleb, Jennifer Bremer, Maren Bechthold, Carolina Sanchez Rico, Daniela Goehringer, Helmut Griesser, Clemens Richert
Summary: Proteins are composed of l-amino acids, while nucleic acids and most oligosaccharides contain d-sugars. Experimental results show that ribonucleotide residues not only facilitate the coupling of amino acids in aqueous medium, but also promote the formation of homochiral dipeptides.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Olivia Doppleb, Rainer Joachim Schwarz, Maria Landa, Clemens Richert
Summary: Peptide formation from amino acids is a crucial process associated with life, and RNA-induced peptide formation has attracted considerable interest. In this study, we investigated the potential of double-stranded DNA or RNA with four-helix bundle folding motifs and a gap near the 5'-phosphate as reaction sites for phosphoramidate formation. Our results showed that glycine could form phosphoramidate-linked peptido RNAs at these reaction sites. In contrast, phenylalanine and tryptophan showed accelerated peptide formation without covalent linkage to the nucleic acid. Additionally, the presence of gap-containing DNA or RNA 4HBs led to the formation of free peptides with up to 11 tryptophan or phenylalanine residues. These findings are intriguing in the context of prebiotic scenarios and suggest the existence of an RNA-induced pathway for oligomerization that is independent of translation.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Johannes N. Singer, Felix M. Mueller, Ewa Wegrzyn, Christina Hoelzl, Hans Hurmiz, Chuyi Liu, Luis Escobar, Thomas Carell
Summary: RNA is a molecule that plays a significant role in the origin of life as it can store genetic information and catalyze reactions. Recent studies have shown that RNA can form chimeras with amino acids, combining the information-coding properties of RNA with the catalytic potential of amino acids, which may have been the structures from which life emerged. This study reports a prebiotic chemistry method that allows the loading of nucleosides and RNAs with amino acids, paving the way for RNA-based peptide synthesis in a hypothetical RNA-peptide world.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Jianxi Ying, Ruiwen Ding, Yan Liu, Yufen Zhao
Summary: This article explores the central issues of prebiotic peptide synthesis and the origin of the genetic code, reviewing the chemical reactions in the early Earth aqueous environment and emphasizing the importance of considering the chiral properties of biomolecules in prebiotic chemical scenarios for further breakthroughs in research.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jianxi Ying, Ruiwen Ding, Yumeng Zhang, Bowen Han, Yeting Guo, Ning Wang, Dandan Guo, Yile Wu, Junwei Huang, Yan Liu, Feng Ni, Shaohua Huang, Yufen Zhao
Summary: This study reveals the mechanism of chiral selection in Earth's life and suggests the existence of a chiral system opposite to that on Earth, implying a world of life that is a complete mirror image of Earth.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Aayush Arya, Jessica Ray, Siddhant Sharma, Romulo Cruz Simbron, Alejandro Lozano, Harrison B. Smith, Jakob Lykke Andersen, Huan Chen, Markus Meringer, Henderson James Cleaves
Summary: The study focuses on a central question in the origins of life research, investigating the connection between non-entailed chemical processes and highly entailed ones. By developing an open-source chemoinformatic workflow, the researchers aim to model abiological chemistry and discover the entailment. The workflow automates the generation and analysis of chemical reaction networks and can help identify autocatalysis and potential self-organization in complex chemical systems.
Article
Chemistry, Organic
Yves Yeboue, Nadia Rguioueg, Gilles Subra, Jean Martinez, Frederic Lamaty, Thomas-Xavier Metro
Summary: The synthesis of a gram-scale hexapeptide using solvent-less methods in a ball mill with high overall yield is achieved in this study. This work contributes to the knowledge required to synthesize longer and more difficult peptide chains by utilizing peptide fragment couplings in a ball mill.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Franziska Welsch, Eric Kervio, Peter Tremmel, Clemens Richert
Summary: Proline is a proteinogenic amino acid that exists in all kingdoms of life. It shows remarkable activity as an organocatalyst and plays a structural role in folded polypeptides. Prolinyl nucleotides with a phosphoramidate linkage, when combined with monosubstituted imidazoles as organocatalysts, can copy RNA in the absence of enzymes or ribozymes. These nucleotides can be incorporated into RNA primers in consecutive extension steps, following the template sequence. The study suggests that amino acid and nucleic acid condensation products can act as nucleoside triphosphates in the absence of enzymes or ribozymes, and the combination of these components may have been selected in molecular evolution due to their metastability and activation by catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Viktor Paczelt, Raffael C. Wende, Peter R. Schreiner, Andre K. Eckhardt
Summary: In this study, the formation and spectroscopic characterization of glycine imine, the simplest imino acid, were reported using cryogenic matrix isolation IR and UV/Vis spectroscopy. Glycine imine was found to form after UV irradiation of 2-azidoacetic acid and could be interconverted between anti-(E,E)- and anti-(Z,Z)-conformations. In aqueous solution, glycine imine hydrolyzed to produce hydroxy glycine and hydrated glyoxylic acid. It was also observed that glycine imine could undergo self-reduction by oxidative decarboxylation chemistry when present in higher concentrations or in the presence of (FeSO4)-S-II as a reducing agent.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemical Research Methods
Hayden R. Anderson, Wei L. Reeves, Andrew T. Bockus, Paolo Suating, Amy G. Grice, Madeleine Gallagher, Adam R. Urbach
Summary: We have developed a novel insulin derivative that exhibits high nanomolar affinity for the synthetic receptor cucurbit[7]uril (Q7), potentially enabling the development of continuous insulin detection methods for diabetes management.
BIOCONJUGATE CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ruvan de Graaf, Yannick De Decker, Victor Sojo, Reuben Hudson
Summary: The ongoing research on the emergence of life focuses on constructing hypothetical environments to produce organic molecules. Mineral catalysts are used in experiments to facilitate the supply of organics that may have produced prebiotic building blocks. However, most studies lack rigorous materials analyses and sub-stoichiometric amounts of metals or minerals, which are necessary to demonstrate the viability of catalysis. Future work should aim to decrease catalyst loading, increase productivity, and conduct rigorous materials analyses to provide evidence of true catalysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Luca Legnani, Andrea Daru, Alexander X. Jones, Donna G. Blackmond
Summary: Enantioenriched amino acids are produced through a hydrolytic kinetic resolution mediated by chiral pentose sugars, shedding light on their role in the emergence of homochirality in biological molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Jessica Spackova, Ieva Goldberga, Rishit Yadav, Guillaume Cazals, Aurelien Lebrun, Pascal Verdie, Thomas-Xavier Metro, Danielle Laurencin
Summary: O-17 NMR spectroscopy is a powerful technique for studying biomolecules. This study presents cost-effective strategies for enriching amino acids and peptides with O-17 using mechanochemistry. The enriched samples showed high levels of enrichment with no loss of purity, making them suitable for future NMR studies.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Geochemistry & Geophysics
Dingwei Gan, Yeting Guo, Xiangmin Lei, Min Zhang, Songsen Fu, Jianxi Ying, Yufen Zhao
Summary: The emergence of prebiotic peptides on the early Earth was a crucial step for the origin of life. Carbamoyl amino acids obtained with nearly 100% yield under prebiotic conditions were reported in this study. The reaction mechanism involves nucleophilic substitution with the release of NH3 from urea, which was verified by 15N-labeling approach. Meanwhile, experiments indicated that carbamoyl amino acids can be also well-obtained under UV radiation in the urea pool, which provides a better condition for carbamoyl amino acids to form prebiotic peptides. The study implies the presence of peptide precursors other than classical amino acids on the primitive Earth.
EARTH AND PLANETARY SCIENCE LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Karen J. Ardila-Fierro, Mirta Rubcic, Jose G. Hernandez
Summary: This work reports the mechanochemical synthesis of Rhodacycles and the unexpected formation of cocrystals between the substrates and the rhodium dimer prior to the C-H activation step. It also demonstrates the synthesis of a previously inaccessible metal complex. These findings contribute to the understanding of mechanochemical cyclometallations.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Jose G. Hernandez
Summary: This Perspective article presents various experimental strategies for the formation and scission of chemical bonds through mechanical force (mechanochemistry). Ultrasonication of polymeric matrices and ball milling of reaction partners are the two leading approaches for polymer and small molecule mechanochemistry, respectively. Although these practical strategies seem to create two distinct lines of thought, this article shows the overlap and connection between them through a series of studies.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Leonarda Vugrin, Maria Carta, Stipe Lukin, Ernest MeWovia, Francesco Delogu, Ivan Halasz
Summary: Inelastic collisions in ball milling provide energy for chemical transformations and also enable physical mixing of reactants. This study uses in situ reaction monitoring and numerical simulations to reveal the relationship between kinetics and energy input, providing a basis for planning and optimizing mechanochemical reactions.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Multidisciplinary
Jasna Alic, Tomislav Stolar, Zoran Stefanic, Krunoslav Uzarevic, Marina Sekutor
Summary: Diamondoids have shown promise as carbon-based nanomaterial building blocks due to their unique properties and potential for selective functionalization. Through mechanochemical synthesis, diamondoid ethers with different subunits were efficiently prepared, demonstrating the sustainability benefits of this approach compared to conventional methods. Single-crystal X-ray diffraction experiments confirmed the molecular structures of the target products and provided insights into their solid-state interactions.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Review
Chemistry, Multidisciplinary
Valentina Martinez, Tomislav Stolar, Bahar Karadeniz, Ivana Brekalo, Krunoslav Uzarevic
Summary: Mechanochemical processing is an efficient and unique tool for the synthesis and transformation of various materials. Recent advancements combine mechanochemical reactivity with other energy sources, achieving reactions not possible with traditional methods. Thermo-mechanochemistry, sono-mechanochemistry, electro-mechanochemistry, and photo-mechanochemistry represent significant advances in modern mechanochemistry, introducing a new level of solid-state reactivity.
NATURE REVIEWS CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jose G. Hernandez, Karen J. J. Ardila-Fierro, Sara Gomez, Tomislav Stolar, Mirta Rubcic, Edi Topic, Cacier Z. Z. Hadad, Albeiro Restrepo
Summary: A recent study found that the occurrence of crystalline intermediates in mechanochemical reactions is more common than previously thought. By using in-situ synchrotron X-ray powder diffraction, this study showed the formation of transient cocrystals between benzo[h]quinoline and [Cp*RhCl2](2) by ball milling, revealing the advantage of cocrystal formation before metalation-deprotonation. Computational studies also demonstrated how weak interactions between reagents in mechanochemical experiments can lead to stable supramolecular assemblies, enhancing substrate activation. This could explain the superior performance of mechanochemical reactions compared to solution-based counterparts.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Pharmacology & Pharmacy
Ivona Jasprica, Petar Horvat, Katarina Zrnc, Karl J. Bonney, Vidar Bjornstad, Lucija Hok, Robert Vianello, Nikola Bregovic, Josip Pozar, Katarina Leko, Vladislav Tomisic, Ernest Mestrovic
Summary: The discovery of cephalosporin and its improved stability in aqueous solution, as well as enhanced activity against penicillin-resistant organisms, were important advancements in beta-lactam antibiotics. This study investigated the degradation rates and mechanisms of ceftriaxone at therapeutic concentration in different water environments. Unique degradation products were observed, and the comparison between H2O and D2O provided valuable insight into the initial degradation. The effect of protium to deuterium isotope change on degradation kinetics was evaluated using HPLC analysis and H-1 NMR spectroscopy, and computational analysis offered molecular insight and explained the stabilizing effect of D2O.
EUROPEAN JOURNAL OF PHARMACEUTICAL SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Lucija Vujevic, Bahar Karadeniz, Nikola Cindro, Andraz Krajnc, Gregor Mali, Matjaz Mazaj, Stanislav M. Avdoshenko, Alexey A. Popov, Dijana Zilic, Krunoslav Uzarevic, Marina Kveder
Summary: We successfully introduced active spin qubits (diluted copper(ii)-porphyrins) into the diamagnetic frameworks PCN-223 and MOF-525 zirconium-MOF polymorph pair through mechanochemical methods. The encapsulation of fullerene during the MOF synthesis led to the formation of the PCN-223 framework with a controllable amount of fullerene. The incorporation of fullerene increased electron spin-lattice and phase-memory relaxation times, T-1 and T-m, by modulating the phonon density of states.
Article
Chemistry, Multidisciplinary
Tomislav Stolar, Jasna Alic, Gregor Talajic, Nikola Cindro, Mirta Rubcic, Kresimir Molcanov, Krunoslav Uzarevic, Jose G. Hernandez
Summary: A solvent-free thermo-mechanochemical approach for the direct coupling of carboxylic acids and amines is presented. Detailed analysis led to the observation of crystalline intermediates prior to the formation of amides, and this methodology was successfully applied for the synthesis of the active pharmaceutical ingredient moclobemide.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Tomislav Stolar, Jasna Alic, Ivor Loncaric, Martin Etter, Dahee Jung, Omar K. Farha, Ivica Dilovic, Ernest Mestrovic, Krunoslav Uzarevic
Summary: With the increasing need for sustainable chemistry, mechanochemistry has attracted much attention due to its ability to synthesize open coordination or covalent frameworks. In this study, we conducted a sustainable screening of the 2,6-diaminopurine (DAP) nucleobase and discovered five new DAP solid forms by mechanochemical and thermal routines. By selectively choosing the liquid additive in liquid-assisted grinding, we successfully formed two polymorphic DAP hydrogen-bonded organic frameworks (HOFs). In situ Raman spectroscopy and nitrogen adsorption isotherms were used to monitor and confirm the characteristics and stability of the DAP-HOF polymorphs. The study demonstrates the control of HOF polymorphism through mechanochemistry and its importance for properties and applications.