Article
Chemistry, Multidisciplinary
Sonia Vela-Gallego, Zulay Pardo-Botero, Cristian Moya, Andres de la Escosura
Summary: Understanding the origins of life is a major challenge. This study explores how replication networks can engage in an evolutionary process. By constructing a network using simple biological components, the researchers shed light on the problem. The experimental and simulated results suggest that interactions between the components drive replication and assembly processes, with sequence complementarity leading to enhanced replication rates and potential bias for selection.
Review
Biochemistry & Molecular Biology
Gaia Micca Longo, Luca Vialetto, Paola Diomede, Savino Longo, Vincenzo Laporta
Summary: The modeling of plasmas or ionized gases with compositions compatible with primordial atmospheres has seen recent progress. Plasma kinetics involve processes where free electrons activate weakly reactive molecules and exchange energy between molecules. Concepts such as the electron velocity distribution function and the vibrational distribution function can provide insights into prebiotic processes initiated by electron-molecule collisions.
Article
Astronomy & Astrophysics
Per Nornberg, Kai Finster, Jan Thogersen, Thaddeus W. Golbek, Tobias Weidner, Tue Hassenkam, Walter Goetz, Mathias Oehlke, Svend J. Knak Jensen
Summary: Experiments show that quartz grains in a methane atmosphere acquire a reddish color on their surface, similar to what is observed on Triton, Pluto, and Charon. The coated grains are found to contain a substance with C-C and C-O bonds, with an average thickness of 2.3 angstrom. The measurements suggest a pathway for synthesis of complex molecules with C = C bonds on planets and moons with a solid surface and a methane-containing atmosphere.
Article
Chemistry, Multidisciplinary
Ander Camiruaga, Imanol Usabiaga, Camilla Calabrese, Iker Lamas, Francisco J. Basterretxea, Jose A. Fernandez
Summary: The article discusses why nature chose CGAT as the alphabet of life. Through analysis of intermolecular interactions and determination of dimer structures, it was found that adenine-theobromine and 4-aminopyrimidine-theobromine dimers have binding energies close to canonical nucleobases and can adopt Watson-Crick conformations. Nature may have had many options available for building the first informational polymers before ultimately selecting the now canonical CGAT.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Engineering, Environmental
Ruize Sun, Mingyu Yu, Guangqian Luo, Xian Li, Hong Tian, Hong Yao
Summary: This research investigates the reaction mechanism between sulfur and Hg-0 through quantum chemical calculations and electronic wavefunction analysis. It shows that branched S-n isomers react with Hg-0 spontaneously with heat release, and have higher reaction rate constants than cyclic S-n molecules. Furthermore, electronic wavefunction analysis characterizes the breaking and formation of Hg-S and S-S bonds during the reaction process.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Chemistry, Physical
Julie Hottechamps, Thomas Noblet, Marie Erard, Laurent Dreesen
Summary: The fluorescence emission of water-soluble CdTe quantum dots (QDs) capped with mercaptocarboxylic acids (MCAs) is pH-dependent, with emission being quenched below a critical pH of 6.87 and further quenched by light excitation. A mathematical model with three parameters accurately predicts the fluorescence decay of QDs over time, at any pH, linking the critical pH value to QD surface properties and providing coherence to literature with inconsistent observations.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Mahipal Yadav, Sunil Pulletikurti, Jayasudhan R. Yerabolu, Ramanarayanan Krishnamurthy
Summary: The study reveals that cyanide acts as a mild and efficient reducing agent in mediating abiotic transformations of tricarboxylic acid intermediates and derivatives. The results suggest the existence of a simpler prebiotic metabolic pathway, bypassing the challenging reductive carboxylation steps.
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
Chemistry, Multidisciplinary
David Serrano-Molina, Carlos Montoro-Garcia, Maria J. Mayoral, Alberto de Juan, David Gonzalez-Rodriguez
Summary: Self-sorting phenomena play a crucial role in various (bio)chemical processes, and the chelate cooperativity is identified as a key factor in achieving high self-sorting fidelities.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Biology
Lena Vincent, Stephanie Colon-Santos, H. James Cleaves II, David A. Baum, Sarah E. Maurer
Summary: This paper discusses principles for selecting chemical mixtures for prebiotic chemistry experiments, reviews natural environmental conditions that may have created such mixtures, and suggests reasonable guidelines for designing recipes. It explores assembled and synthesized mixtures, and addresses practical concerns such as balancing prebiotically realistic mixtures with experimental tractability. The development of standardized prebiotic recipes and a public prebiotic chemistry database are advocated to facilitate coordination among researchers and identify promising mechanisms in the origin of life.
Article
Chemistry, Physical
Tom Galle, Daniel Spittel, Nelli Weiss, Volodymyr Shamraienko, Helena Decker, Maximilian Georgi, Rene Huebner, Nadia Metzkow, Christine Steinbach, Dana Schwarz, Vladimir Lesnyak, Alexander Eychmueller
Summary: The research transforms CdSe NPLs into PbSe NPLs suitable for optoelectronic applications through cation exchange, ligand exchange, and electronic coupling, successfully fabricating a photodetector with fast light response at low operational voltages on a commercial substrate.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Ardita Kilaj, Silvan Kaser, Jia Wang, Patrik Stranak, Max Schwilk, Lei Xu, O. Anatole von Lilienfeld, Jochen Kuepper, Markus Meuwly, Stefan Willitsch
Summary: Recent advances in experimental methodology have allowed for studies on the quantum-state and conformational dependence of chemical reactions in the gas phase. In this study, samples of gauche and s-trans 2,3-dibromobutadiene (DBB) were generated and reacted with laser-cooled Ca+ ions in an ion trap. The results showed that the reaction rate strongly depends on the conformation of DBB and the electronic state of Ca+. The study emphasized the important role of molecular geometry in reactive systems and revealed differences in the reactivity of individual conformers in gas-phase ion-molecule reactions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Bernardo Ballotta, Tainah D. Marforio, Sergio Rampino, Emilio Martinez-Nunez, Vincenzo Barone, Mattia Melosso, Andrea Bottoni, Luca Dore
Summary: In this study, a detailed quantum chemical investigation of a new reaction mechanism leading to the formation of cyanoketene in the interstellar medium (ISM) was conducted. Different reaction channels were discovered and characterized at the density functional theory level. The results indicate that the barrier-less association reaction of the formyl radical to the cyanocarbene radical can lead to the formation of cyanoketene under the harsh conditions of the ISM. The study also suggests potential astronomical sources where cyanoketene can be detected based on the presence of HCO and HCCN.
ACS EARTH AND SPACE CHEMISTRY
(2023)
Article
Chemistry, Physical
Shankar Pandey, Yuan Xiang, Dirk Friedrich, Yongsheng Leng, Hanbin Mao
Summary: The study used optical tweezers to directly investigate the intermolecular mechanical force of nonspecific interactions between cholesterols, revealing that the IMMF of cholesterol dimers is orientation-dependent. Quantification of changes in free energy showed that cyclodextrins can easily solubilize cholesterols.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Review
Chemistry, Multidisciplinary
Maximilian Bechtel, Marian Ebeling, Laura Huber, Oliver Trapp
Summary: This article introduces the discovery of the formation of substituted imidazolidine-4-thiones (photoredox) organocatalysts from simple prebiotic building blocks such as aldehydes and ketones under Strecker reaction conditions with ammonia and cyanides in the presence of hydrogen sulfide. These organocatalysts enable alpha-alkylations and other important transformations.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Computer Science, Cybernetics
Pasquale Bufano, Niccolo Albertini, Simone Chiarelli, Vincenzo Barone, Marta Valleggi, Gianluca Parrini, Alessandro Tognetti, Valentina Cesari, Angelo Gemignani, Danilo Menicucci
Summary: Previous studies have shown that total sleep deprivation has a significant impact on sustained attention, but these studies have used tests that lack ecological validity. In this study, we evaluated the effects of total sleep deprivation on daily-life activities by using a virtual reality task, and found that sustained attention declines after 36 hours of total sleep deprivation, accompanied by greater cognitive effort.
INTERNATIONAL JOURNAL OF HUMAN-COMPUTER INTERACTION
(2023)
Article
Biochemistry & Molecular Biology
Vincenzo Barone, Silvia Di Grande, Cristina Puzzarini
Summary: The interplay between high-resolution rotational spectroscopy and quantum-chemical computations is crucial for investigating biomolecule building blocks in the gas phase. However, quantum-chemical methods have scalability issues. In this study, a model based on density functional theory is proposed and demonstrated to accurately predict rotational constants for glycine and serine, providing a cost-effective approach for characterizing flexible building blocks of biomolecules.
Article
Chemistry, Physical
Ningjing Jiang, Mattia Melosso, Silvia Alessandrini, Luca Bizzocchi, Marie-Aline Martin-Drumel, Olivier Pirali, Cristina Puzzarini
Summary: This article provides a detailed spectroscopic and structural characterization of aminoacetonitrile, an interstellar molecule with potential prebiotic role. The authors accurately compute equilibrium geometry, fundamental bands, and molecular parameters using a composite scheme rooted in the coupled-cluster theory. They also report the analysis of the three strongest fundamental bands observed in high-resolution infrared spectra.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Review
Chemistry, Physical
Cristina Puzzarini, John F. Stanton
Summary: Rotational spectroscopy is the preferred technique for studying molecular structures in the gas phase. Rotational constants are strongly linked to the geometry of the molecules, making them useful for evaluating the accuracy of quantum chemical approaches. This review article discusses how the accuracy of computed equilibrium geometry can be measured by comparing rotational constants, and also explores the required accuracy for providing useful molecular structures and rotational constants. Quantum chemical methodologies for achieving 0.1% accuracy in rotational constants are reviewed, ranging from small molecules to small polycyclic aromatic hydrocarbons. This level of accuracy opens up possibilities for future applications, such as accurately characterizing non-covalent interactions in biological and technological processes.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Vincenzo Barone, Jacopo Lupi, Zoi Salta, Nicola Tasinato
Summary: A recently developed strategy for the computation of reliable barrier heights in gas-phase reactions has been extended to the use of explicitly correlated methods. The new model, referred to as junChS-F12, shows improved performance compared to traditional models and well-known model chemistries, without the need for empirical parameters and at affordable computational cost. Benchmark tests demonstrate that the combination of revDSD-PBEP86-D3(BJ) structures and force fields with junChS-F12 electronic energies provides accurate reaction rates in the framework of the ab initio transition-state theory.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Biochemistry & Molecular Biology
Silvia Alessandrini, Mattia Melosso, Victor M. Rivilla, Luca Bizzocchi, Cristina Puzzarini
Summary: By applying a new computational protocol based on the minimum-energy principle, we identified vinylisocyanate as the most stable isomer in the C3H3NO family, followed by oxazole. Pyruvonitrile, cyanoacetaldehyde, and cyanovinylalcohol were also found to be stable according to our calculations. We provided new rotational and vibrational spectroscopic data for these species.
Article
Chemistry, Multidisciplinary
Bernardo Ballotta, Emilio Martinez-Nunez, Sergio Rampino, Vincenzo Barone
Summary: Vinyl alcohol (Vy) and hydroxyl radical (OH) participate in various processes under different physical-chemical conditions. A detailed quantum chemical study was conducted to investigate the possible reaction paths between OH and both conformers of Vy. The formation of (Z)-1,2-ethenediol (Et) is strongly disfavored under the harsh conditions of the ISM.
ACS EARTH AND SPACE CHEMISTRY
(2023)
Article
Chemistry, Physical
Vincenzo Barone
Summary: An unsupervised computational protocol is proposed to obtain accurate structures of large molecules in the gas phase. The protocol is fully automated and provides optimized equilibrium geometries and ground state rotational constants for comparison with experiments. Results for biological or medicinal molecules show that the accuracy of the new tool is comparable to state-of-the-art composite wavefunction methods.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Vincenzo Barone
Summary: A general strategy for accurate computation of biomolecule building blocks in gas phase, with a special focus on tautomeric equilibria, has been improved with the use of cc-pVTZ-F12 basis set, inclusion of core-valence correlation, and complete basis set extrapolation at MP2-F12 level. The resulting model chemistry is applied to cytosine tautomers and shows remarkable agreement with experimental spectroscopic parameters, enabling unbiased interpretation in terms of structure and thermochemical features. This composite method provides accurate investigations of other molecular bricks of life at reasonable cost without any empirical parameter.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Vincenzo Barone, Luigi Crisci, Silvia Di Grande
Summary: A new strategy for computationally studying medium-sized molecules in the gas phase is proposed in this paper, which performs better than existing model chemistries without the need for empirical parameters. The method allows nonspecialists to accurately study medium- to large-sized molecules at a reasonable cost using standard electronic structure codes.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Luigi Crisci, Silvia Di Grande, Carlo Cavallotti, Vincenzo Barone
Summary: An enhanced computational protocol has been developed for accurately characterizing gas-phase barrier-less reactions using density functional theory and Monte Carlo sampling. The tool shows good performance in two prototypical reactions and can be used for systematic investigations of barrier-less elementary steps in gas-phase reactions.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Multidisciplinary
S. Di Grande, M. Kallay, V. Barone
Summary: The junChS-F12 composite method has been improved with the latest implementation of CCSD(F12*)(T+) ansatz and validated for thermochemistry of molecules containing atoms of the first three rows of the periodic table. Benchmark tests showed that this model, combined with cost-effective revDSD-PBEP86-D3(BJ) reference geometries, strikes an optimal balance between accuracy and computational cost. In addition, the model proves effective and reliable in pilot applications to noncovalent intermolecular interactions, conformational landscapes, and tautomeric equilibria.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Cristina Puzzarini, Roberto Linguerri, Majdi Hochlaf
Summary: In this study, state-of-the-art computational approaches were employed to provide accurate structural and spectroscopic characterization of HONCO in its electronic ground state. The results showed high accuracy in molecular structures, rotational constants, and vibrational fundamental bands. Additionally, the dissociation of HONCO upon UV-vis light absorption was predicted. The provided spectroscopic data can be valuable for future experimental investigations and characterizations in various applications.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Astronomy & Astrophysics
Hexu Ye, Silvia Alessandrini, Cristina Puzzarini
Summary: Sulphur is an important and ubiquitous element in the interstellar medium. This study finds that the reaction between H2CS and OH can produce isomers belonging to the CH2SO family, including trans-HC(S)OH and trans-HC(O)SH. The detection of trans-HC(O)SH suggests that trans-HC(S)OH is a promising candidate for astronomical observations.
MONTHLY NOTICES OF THE ROYAL ASTRONOMICAL SOCIETY
(2023)