Zn-Induced Interactions Between SARS-CoV-2 orf7a and BST2/Tetherin

We present in this work a first X-ray Absorption Spectroscopy study of the interactions of Zn with human BST2/tetherin and SARS-CoV-2 orf7a proteins as well as with some of their complexes. The analysis of the XANES region of the measured spectra shows that Zn binds to BST2, as well as to orf7a, thus resulting in the formation of BST2-orf7a complexes. This structural information confirms the the conjecture, recently put forward by some of the present Authors, according to which the accessory orf7a (and possibly also orf8) viral protein are capable of interfering with the BST2 antiviral activity. Our explanation for this behavior is that, when BST2 gets in contact with Zn bound to the orf7a Cys₁₅ ligand, it has the ability of displacing the metal owing to the creation of a new disulfide bridge across the two proteins. The formation of this BST2-orf7a complex destabilizes BST2 dimerization, thus impairing the antiviral activity of the latter.     

Total synthesis of phytoprostane F1 and its 16 epimer

The first synthesis of the two enantiomers of phytoprostane F₁ methyl ester 1 and 2 is described using the syn-anti-syn alcoxy ester 3 as starting material.     

Mechanistic Origin of the Vibrational Coherence Accompanying the Photoreaction of Biomimetic Molecular Switches

The coherent photoisomerization of a chromophore in condensed phase is a rare process in which light energy is funneled into specific molecular vibrations during electronic relaxation from the excited to the ground state. In this work, we employed ultrafast spectroscopy and computational methods to investigate the molecular origin of the coherent motion accompanying the photoisomerization of indanylidene–pyrroline (IP) molecular switches. UV/Vis femtosecond transient absorption gave evidence for an excited‐ and ground‐state vibrational wave packet, which appears as a general feature of the IP compounds investigated. In close resemblance to the coherent photoisomerization of rhodopsin, the sudden onset of a far‐red‐detuned and rapidly blue‐shifting photoproduct signature indicated that the population arriving on the electronic ground state after nonadiabatic decay through the conical intersection (CI) is still very focused in the form of a vibrational wave packet. Semiclassical trajectories were employed to investigate the reaction mechanism. Their analysis showed that coupled double‐bond twisting and ring inversions, already populated during the excited‐state reactive motion, induced periodic changes in π‐conjugation that modulate the ground‐state absorption after the non‐adiabatic decay. This prediction further supports that the observed ground‐state oscillation results from the reactive motion, which is in line with a biomimetic, coherent photoisomerization scenario. The IP compounds thus appear as a model system to investigate the mechanism of mode‐selective photomechanical energy transduction. The presented mechanism opens new perspectives for energy transduction at the molecular level, with applications to the design of efficient molecular devices.     

Protein structure prediction and biomolecular recognition: from protein sequence to peptidomimetic design with the human beta3 integrin

Computational tools can bridge the gap between sequence and protein 3D structure based on the notion that information is to be retrieved from the databases and that knowledge-based methods can help in approaching a solution of the protein-folding problem. To this aim our group has implemented neural network-based predictors capable of performing with some success in different tasks, including predictions of the secondary structure of globular and membrane proteins, the topology of membrane proteins and porins and stable alpha-helical segments suited for protein design. Moreover we have developed methods for predicting contact maps in proteins and the probability of finding a cysteine in a disulfide bridge, tools which can contribute to the goal of predicting the 3D structure starting from the sequence (the so called ab initio prediction). All our predictors take advantage of evolution information derived from the structural alignments of homologous (evolutionary related) proteins and taken from the sequence and structure databases. When it is necessary to build models for proteins of unknown spatial structure, which have very little homology with other proteins of known structure, non-standard techniques need to be developed and the tools for protein structure predictions may help in protein modeling. The results of a recent simulation performed in our lab highlights the role of high performing computing technology and of tools of computational biology in protein modeling and peptidomimetic design.     

Zirconia supported La, Co oxides and LaCoO3 perovskite: structural characterization and catalytic CO oxidation

ZrO₂-supported La, Co oxide catalysts with different La, Co loading (2, 6, 8, 12 and 16 wt.% as LaCoO₃) were prepared by impregnation of tetragonal ZrO₂ with equimolar amounts of La and Co citrate precursors and calcination at 1073 K. The catalysts were characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and BET specific surface area determination. Catalytic CO oxidation was performed at 298–800 K. XRD revealed the presence of tetragonal zirconia with traces of the monoclinic phase. LaCoO₃ perovskite was also detected for loading higher than 6%. XAS experiments suggested that at high loading LaCoO₃ and Co₃O₄ were formed, while at low loading, La, Co oxide species interacting with support, and hard to be structurally defined, prevailed. The catalysis study evidenced that the catalytic activity was due to segregated and highly dispersed cobalt oxide species.     

First identification of excited states in 59Zn

Excited states in ⁵⁹Zn were observed for the first time following the fusion-evaporation reaction ²⁴Mg + ⁴⁰Ca at a beam energy of 60 MeV. The GASP array in conjunction with the ISIS Silicon ball and the NeutronRing allowed for the detection of γ-rays in coincidence with evaporated light particles. The mirror symmetry of ⁵⁹Zn and ⁵⁹Cu is discussed. Received: 28 May 2002 / Accepted: 10 July 2002 / Published online: 3 December 2002 RID="a" ID="a"Present address: Oliver Lodge Laboratory, University of Liverpool, P.O. Box 147, Liverpool, L69 7ZE, United Kingdom; e-mail: ca@ns.ph.liv.ac.uk. RID="b" ID="b"Present address: Physik-Departament, Technische Universit?t München, D-85748 Garching, Germany. Communicated by W. Henning     

Gas-phase reactions of nitronium ions with acetylene and ethylene: an experimental and theoretical study

A comparative study of the gas-phase reactions of NO2+ with acetylene and ethylene was performed by using FT-ICR, MIKE, CAD, and NfR/ CA mass spectrometric techniques, in conjunction with ab initio calculations at the MP2/6-31+G* level of theory. Both reactions proceed according to the same mechanism, that is, 1,3-dipolar cycloaddition, but yield products of different stability. The C2H2NO2+ adduct from acetylene has an aromatic character and hence is highly stabilized with respect to the C2H4NO2+ adduct from ethylene. Both cycloadducts tend to isomerize into O-nitroso derivatives, that is, nitrosated ketene and nitrosated acetaldehyde, which represent the thermodynamically most stable products from the addition of NO2+ to acetylene and ethylene, respectively. As prototypal examples of the reactivity of free nitronium ions with most simple pi systems, the reactions investigated are useful starting points to model the mechanism of aromatic nitration.     

3H‐1,2‐Dithiole‐3‐thione derivatives as novel solvatochromic dyes

The UV–Vis spectrum of 5‐(1‐butylthio)‐3H‐1,2‐dithiole‐3‐thione (1a) and that of the chromium pentacarbonyl complex of 5‐methyl‐3H‐1,2‐dithiole‐3‐thione (3) present significant changes with the solvent polarity. The two absorption bands shown by the compounds in the region above 300 nm were identified by theoretical calculations. For Compound 1a these are n→π^* and →π^* transitions and for Compound 3 the longest wavelength absorption corresponds to a charge transfer band and shows a remarkably negative solvatochromism. Not only has the wavelength of maximum absorption changed with the solvent but also the ratio of the absorbances at the two wavelengths. The effect of solvents was correlated with solvatochromic parameters such as π^* and α. The spectrum of 5‐(1‐butylthio)‐3H‐1,2‐dithiole‐3‐one ( 2 ) was also measured in different solvents but in this case the changes observed are less significant than for the other two compounds. The spectra of 1a and 3 were also determined in the presence of anionic (SDS), cationic (CTAB), and neutral surfactants (Brig‐35) and it is shown that these compounds can be used as probes for the polarity of the binding sites of organized assemblies. Copyright © 2008 John Wiley & Sons, Ltd.