Is the protactinium(V) mono-oxo bond weaker than what we thought?

The bond distance is the simplest and most obvious indicator of the nature of a given chemical bond. However, for rare chemistry, it may happen that it is not yet firmly established. In this communication, we will show that the formally-triple protactinium(V) mono-oxo bond is predicted to be longer than what was previously reported in the solid state and in solution, based on robust quantum mechanical calculations, supported by an extensive methodological study.

Excited states of polonium(IV): electron correlation and spin-orbit coupling in the Po free ion and in the bare and solvated [PoCl] and [PoCl] complexes.

Polonium (Po, = 84) is a main-block element with poorly known physico-chemical properties. Not much information has been firmly acquired since its discovery by Marie and Pierre Curie in 1898, especially regarding its speciation in aqueous solution and spectroscopy. In this work, we revisit the absorption properties of two complexes, [PoCl] and [PoCl], using quantum mechanical calculations.

Coordination and thermodynamic properties of aqueous protactinium(V) by first-principle calculations.

Protactinium ( = 91) is a very rare actinide with peculiar physico-chemical properties. Indeed, although one may naively think that it behaves similarly to either thorium or uranium by its position in the periodic table, it may in fact follow its own rules. Because of the quite small energy gap between its valence shells (in particular the 5f and 6d ones) and also the strong influence of relativistic effects on its properties, it is actually a challenging element for theoretical chemists.

Generalization aspect of accurate machine learning models for CSI-based localization.

Localization is the process of determining the position of an entity in a given coordinate system. Due to its wide range of applications (e.g.

Characterization of Uranyl Coordinated by Equatorial Oxygen: Oxo in UO versus Oxyl in UO.

Uranium trioxide, UO, has a T-shaped structure with bent uranyl, UO, coordinated by an equatorial oxo, O. The structure of cation UO is similar but with an equatorial oxyl, O. Neutral and cationic uranium trioxide coordinated by nitrates were characterized by collision induced dissociation (CID), infrared multiple-photon dissociation (IRMPD) spectroscopy, and density functional theory.

The electron affinity of astatine.

One of the most important properties influencing the chemical behavior of an element is the electron affinity (EA). Among the remaining elements with unknown EA is astatine, where one of its isotopes, At, is remarkably well suited for targeted radionuclide therapy of cancer. With the At anion being involved in many aspects of current astatine labeling protocols, the knowledge of the electron affinity of this element is of prime importance.

Design and Evaluation of Flooding-Based Location Service in Vehicular Ad Hoc Networks.

Location-based routing protocols for vehicular ad hoc networks (VANETs) use location information to determine routing decisions. This information is provided by a location service that is queried by nodes in order to properly forward packets to communication partners. This paper presents the semiflooding location service, a proactive flooding-based location service that drastically reduces the number of update packets sent over the network compared to traditional flooding-based location services.

Environment Monitoring for Anomaly Detection System Using Smartphones.

Currently, the popularity of smartphones with networking capabilities equipped with various sensors and the low cost of the Internet have opened up great opportunities for the use of smartphones for sensing systems. One of the most popular applications is the monitoring and the detection of anomalies in the environment. In this article, we propose to enhance classic road anomaly detection methods using the Grubbs test on a sliding window to make it adaptive to the local characteristics of the road.

Timeline representation of clinical data: usability and added value for pharmacovigilance.

Background: Pharmacovigilance consists in monitoring and preventing the occurrence of adverse drug reactions (ADR). This activity requires the collection and analysis of data from the patient record or any other sources to find clues of a causality link between the drug and the ADR. This can be time-consuming because often patient data are heterogeneous and scattered in several files.

Over-voluming predicted by pre-operative planning in 24% of total knee arthroplasty.

Purpose: Numerous studies demonstrated that prosthetic overhang and over-sizing cause pain and stiffness following total knee arthroplasty (TKA), but none considered volume changes within the joint capsule. This study was designed to investigate differences in volumes of resected bone compared to implanted components in TKA, and to determine the incidence and factors related to 'over-voluming'.

Methods: Three-dimensional reconstructions were created from 100 magnetic resonance imaging scans taken to design patient-specific instruments for TKA.

Factors influencing the development of primary care data collection projects from electronic health records: a systematic review of the literature.

Background: Primary care data gathered from Electronic Health Records are of the utmost interest considering the essential role of general practitioners (GPs) as coordinators of patient care. These data represent the synthesis of the patient history and also give a comprehensive picture of the population health status. Nevertheless, discrepancies between countries exist concerning routine data collection projects.

Heptavalent Neptunium in a Gas-Phase Complex: (NpO)(NO).

A central goal of chemistry is to achieve ultimate oxidation states, including in gas-phase complexes with no condensed phase perturbations. In the case of the actinide elements, the highest established oxidation states are labile Pu(VII) and somewhat more stable Np(VII). We have synthesized and characterized gas-phase AnO(NO) complexes for An = U, Np, and Pu by endothermic NO elimination from AnO(NO).

QTAIM Analysis in the Context of Quasirelativistic Quantum Calculations.

Computational chemistry currently lacks ad hoc tools for probing the nature of chemical bonds in heavy and superheavy-atom systems where the consideration of spin-orbit coupling (SOC) effects is mandatory. We report an implementation of the Quantum Theory of Atoms-In-Molecules in the framework of two-component relativistic calculations. Used in conjunction with the topological analysis of the Electron Localization Function, we show for astatine (At) species that SOC significantly lowers At electronegativity and boosts its propensity to make charge-shift bonds.

An Integrated Workflow For Secondary Use of Patient Data for Clinical Research.

This work proposes an integrated workflow for secondary use of medical data to serve feasibility studies, and the prescreening and monitoring of research studies. All research issues are initially addressed by the Clinical Research Office through a research portal and subsequently redirected to relevant experts in the determined field of concentration. For secondary use of data, the workflow is then based on the clinical data warehouse of the hospital.

Synthesis and structures of plutonyl nitrate complexes: is plutonium heptavalent in PuO3(NO3)2(-) ?

Gas-phase plutonium nitrate anion complexes were produced by electrospray ionization (ESI) of a plutonium nitrate solution. The ESI mass spectrum included species with all four of the common oxidation states of plutonium: Pu(III), Pu(IV), Pu(V), and Pu(VI). Plutonium nitrate complexes were isolated in a quadrupole ion trap and subjected to collision-induced dissociation (CID).

Introducing the ELF Topological Analysis in the Field of Quasirelativistic Quantum Calculations.

We present an original formulation of the electron localization function (ELF) in the field of relativistic two-component DFT calculations. Using I2 and At2 species as a test set, we show that the ELF analysis is suitable to evaluate the spin-orbit effects on the electronic structure. Beyond these examples, this approach opens up new opportunities for the bonding analysis of large molecular systems involving heavy and superheavy elements.

Polyaminoquinoline iron chelators for vectorization of antiproliferative agents: design, synthesis, and validation.

Iron chelation in tumoral cells has been reported as potentially useful during antitumoral treatment. Our aim was to develop new polyaminoquinoline iron chelators targeting tumoral cells. For this purpose, we designed, synthesized, and evaluated the biological activity of a new generation of iron chelators, which we named Quilamines, based on an 8-hydroxyquinoline (8-HQ) scaffold linked to linear polyamine vectors.

Assessment of an effective quasirelativistic methodology designed to study astatine chemistry in aqueous solution.

A cost-effective computational methodology designed to study astatine (At) chemistry in aqueous solution has been established. It is based on two-component spin-orbit density functional theory calculations and solvation calculations using the conductor-like polarizable continuum model in conjunction with specific astatine cavities. Theoretical calculations are confronted with experimental data measured for complexation reactions between metallic forms of astatine (At(+) and AtO(+)) and inorganic ligands (Cl(-), Br(-) and SCN(-)).

Structural features and protonation site of epibatidine in the gas phase: an investigation through infrared multiphoton dissociation spectroscopy and computational chemistry.

The gas phase structures of epibatidine, one of the most potent agonists of nicotinic acetylcholine receptors (nAChRs), are determined by means of infrared multiphoton dissociation (IRMPD) spectroscopy and quantum chemistry calculations. Comparison of the experimental and theoretical spectra provides evidence that about 15% of epibatidine is protonated on the Nsp(2) nitrogen in the gas phase. In contrast, the computational study of deschloroepibatidine shows that in the gas phase, the molecule is present only protonated on the Nsp(2) nitrogen.

Electrochemical synthesis and characterisation of alternating tripyridyl-dipyrrole molecular strands with multiple nitrogen-based donor-acceptor binding sites.

Synthesis of alternating pyridine-pyrrole molecular strands composed of two electron-rich pyrrole units (donors) sandwiched between three pyridinic cores (acceptors) is described. The envisioned strategy was a smooth electrosynthesis process involving ring contraction of corresponding tripyridyl-dipyridazine precursors. 2,6-Bis[6-(pyridazin-3-yl)]pyridine ligands 2a-c bearing pyridine residues at the terminal positions were prepared in suitable quantities by a Negishi metal cross-coupling procedure.

An enthalpic scale of hydrogen-bond basicity. 4. Carbon pi bases, oxygen bases, and miscellaneous second-row, third-row, and fourth-row bases and a survey of the 4-fluorophenol affinity scale.

The thermodynamics of the O-H...

Theoretical study of the structures and hydrogen-bond properties of new alternated heterocyclic compounds.

The conformational preferences of a new bis-pyrrole derivative and its bis-pyridazine precursor have been investigated through quantum chemistry calculations (HF, DFT(MPWB1K), LMP2) and observations in the solid state. The global energetic minima are planar for both structures, with the conformational preferences being explained by pi-electronic conjugation between the aromatic systems and the occurrence of intramolecular hydrogen bonds (HB). For the bis-pyridazine derivative, the all-anti preferred conformation results from CH.

The exceptional hydrogen-bond properties of neutral and protonated lobeline.

The X-ray diffraction structure of (-)-lobeline, a high affinity nicotinic ligand, has been determined. A comparison with its hydrobromide and hydrochloride salts shows the great flexibility of the two lateral chains of the N-methylpiperidine ring. Infrared studies carried out on the same species, in the solid state and in solution, reveal the propensity of this molecular framework to accommodate very specific hydrogen bonds (HBs) depending on the state-neutral or protonated-of the molecule.

Surface potential mapping of dispersed proteins.

We describe a method for detecting proteins after transfer to PVDF membranes, based on the surface potential attributed to each protein. Proteins separated by classical two-dimensional polyacrylamide gel electrophoresis could be detected by scanning the membrane surface with a vibrating capacitor (also called a Kelvin probe) on the basis of differences between their surface potential and that of the membrane. Coupled to colloidal gold staining, the technique enables detection of proteins previously undetectable by classical staining methods.