Electrostatic electronic interactions within oxidized multinuclear Pt(bipyridine)(dithiolene) complexes.

Bi- and trimetallic platinum(bipyridine)(dithiolene) complexes involving different organic linkers between the redox active platinum(dithiolene) moieties have been synthesized and studied by electrochemistry and spectroelectrochemistry. Cyclic voltammetry experiments carried out on these multinuclear complexes in dichloromethane using [NBu][PF] as the supporting salt show only one oxidation process involving the metallacycles. Nevertheless, spectro-electrochemical studies, carried out under the same conditions, show a different evolution of the spectra during oxidation depending on the position of the metallacycles on the phenyl ring.

Structure-activity relationship of anticancer and antiplasmodial gold bis(dithiolene) complexes.

Monoanionic gold bis(dithiolene) complexes were recently shown to display activity against ovarian cancer cells, Gram-positive bacteria, strains and the rodent malaria parasite, . To date, only monoanionic gold(III) bis(dithiolene) complexes with a thiazoline backbone substituted with small alkyl chains have been evaluated for biomedical applications. We now analyzed the influence of the length and the hydrophobicity hydrophilicity of these complexes' alkyl chain on their anticancer and antiplasmodial properties.

Radical and diradical states of bis(molybdenocene dithiolene) complexes.

The synthesis and characterization of two bis(dithiolene) proligands involving heteroatomic linkers such as 1,4-dithiine and dihydro-1,4-disiline between the two protected dithiolene moieties are described. Two bimetallic complexes involving these heteroatomic bridges between two redox active bis(cyclopentadienyl)molybdenum dithiolene moieties have been synthesized and characterized by electrochemistry, spectroelectrochemistry, and their properties rationalized with (TD-)DFT. Cyclic voltammetry experiments show sequential oxidation of the two redox centers with Δ values between successive one-electron transfers varying according to the nature of the bridge.

Training for a mass casualty incident: Conception, development, and implementation of a crew-resource management course for forward surgical teams.

Background: Since 2021, the predeployment training of French FSTs has included a simulation-based curriculum consisting of organizational and human factors. The purpose of this article is to describe the development of a crew-resource management (CRM) training course dedicated for the forward surgical teams (FSTs) of the French Military Health Service.

Methods: The approach was based on three steps: (1) establishment of a conceptual framework of FSTs deployment; (2) development of an aircrew-like CRM training combining lectures, laboratory exercises, and situational training exercises to consider four fundamental "nontechnical" (cognitive and social) skills for effective and safe combat casualty care: (a) leadership, (b) decision-making, (c) coordination, and (d) situational awareness; (3) Implementation of teamwork evaluation tools.

Evaluation of the Pedagogical Impact of "Traum'Cast" Podcast: A Pilot Study Based on Metacognition.

Introduction: With the evolution of educational tools, the French Military medical service has created a podcast program, Traum'Cast, about the principles of war medicine, accessible online for free.

Method: Our objective was to measure the learning effect of the Traum'Cast program's first episode. A non-randomized pilot trial between July and December 2021 included 80 health care providers: 40 in the video podcast group compared to 40 in a group reading a pdf file providing the same information.

Investigations of the Photothermal Properties of a Series of Molecular Gold-bis(dithiolene) Complexes Absorbing in the NIR-III Region.

The photothermal properties of a series of neutral radical gold-bis(dithiolene) complexes absorbing in the near-infrared-III window (1550-1870 nm) have been investigated. This class of complexes was found to be good photothermal agents (PTAs) in toluene under 1600 nm laser irradiation with photothermal efficiencies around 40 and 60 % depending on the nature of the dithiolene ligand. To the best of our knowledge, these complexes are the first small molecular photothermal agents to absorb so far into the near infrared.

Guidelines on human factors in critical situations 2023.

Objective: To provide guidelines to define the place of human factors in the management of critical situations in anaesthesia and critical care.

Design: A committee of nineteen experts from the SFAR and GFHS learned societies was set up. A policy of declaration of links of interest was applied and respected throughout the guideline-producing process.

Synthesis and Characterization of Tetraphenylethene AIEgen-Based Push-Pull Chromophores for Photothermal Applications: Could the Cycloaddition-Retroelectrocyclization Click Reaction Make Any Molecule Photothermally Active?

Three new tetraphenylethene (TPE) push-pull chromophores exhibiting strong intramolecular charge transfer (ICT) are described. They were obtained via [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) click reactions on an electron-rich alkyne-tetrafunctionalized TPE (TPE-alkyne) using both 1,1,2,2-tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F-TCNQ) as electron-deficient alkenes. Only the starting TPE-alkyne displayed significant AIE behavior, whereas for TPE-TCNE, a faint effect was observed, and for TPE-TCNQ and TPE-F-TCNQ, no fluorescence was observed in any conditions.

A Bimetallic Benzene-1,2,4,5-Tetrathiolate (btt) Molybdenocene Complex Cp Mo(btt)MoCp : Radical and Diradical States.

Benzene-1,2,4,5-tetrathiolate (btt) has been used as a bridging ligand to prepare a redox active (molybdenocene dithiolene)-based bimetallic complex Cp Mo(btt)MoCp , which exhibits four successive electron transfers up to the tetracation. Spectro-electrochemical investigations together with DFT and TD-DFT calculations evidence that the two electroactive MoS C metallacycles are electronically coupled in the monocationic as in the dicationic state. Two salts of the dication [Cp Mo(btt)MoCp ] have been structurally characterized with PF and HSO counterions, showing different chair or boat conformations associated with variable folding angles of the two MoS C metallacycles along the S-S hinge.

Intrinsically Switchable Electroactive Fluorophores Based on λ -Biphosphinines.

The synthesis and full characterization of a family of stable λ -biphosphinines connected in 4,4-position through a variety of π-conjugated bridges is reported. The impact of the π-bridge on the optical (absorption/emission) and redox properties was investigated using a joint experimental/theoretical approach. In contrast to the π-extended ones, the λ -biphosphinines directly connected through a C-C bond in 4,4-position display two easily accessible and reversible oxidations highlighting their multi-stage redox character.

Toward A Serious Game to Help Future Military Doctors Face Mass Casualty Incidents.

Introduction: To prepare military doctors to face mass casualty incidents (MCIs), the French Army Health Service contributed to the development of TRAUMASIMS, a serious game (SG) for training medical responders to MCIs.

Methods: French military doctors participated in a three-phase training study. The initial war trauma training was a combination of didactic lectures (Phase 1), laboratory exercises (Phase 2), and situational training exercises (STX) (Phase 3).

Exploring the role of managers in the development of a safety culture in seven French healthcare facilities: a qualitative study.

Background: Numerous studies have been conducted over the past 15 years to assess safety culture within healthcare facilities; in general, these studies have shown the pivotal role that managers play in its development. However, little is known about what healthcare managers actually do to support this development, and how caregivers and managers represent managers'role. Thus the objectives of this study were to explore: i) caregivers and managers' perceptions and representations of safety, ii) the role of managers in the development of safety culture as perceived by themselves and by caregivers, iii) managers' activities related to the development of safety culture.

Multi-Stage Redox Systems Based on Dicationic P-Containing Polycyclic Aromatic Hydrocarbons.

We report the straightforward synthesis of unprecedented electron-acceptors based on dicationic P-containing PAHs (Polycyclic Aromatic Hydrocarbons) based on copper mediated radical approach. In these systems, two phosphoniums are connected through various PAHs backbones. The impact of π-extension on both the optical and redox properties is investigated using a joint experimental (UV/Vis absorption, fluorescence and cyclic voltammetry) and theoretical approach (TD-DFT calculations).

Improvement of the intermediate risk prostate cancer sub-classification by integrating MRI and fusion biopsy features.

Introduction: Treatment decision-making for intermediate-risk prostate cancer (CaP) is mainly based on grade and tumor involvement on systematic biopsy. We aimed to assess the added value of multi-parametric magnetic resonance imaging (mpMRI) and targeted biopsy (TB) features for predicting final pathology and for improving the well-established favourable/unfavourable systematic biopsy-based sub-classification.

Materials And Methods: From a prospective database of 377 intermediate risk CaP cases, we evaluated the performance of the standard intermediate risk classification (IRC), and the predictive factors for unfavourable disease on final pathology aiming to build a new model.

Revealing the pulmonary surfactant corona on silica nanoparticles by cryo-transmission electron microscopy.

When inhaled, nanoparticles (NPs) deposit in alveoli and transit through the pulmonary surfactant (PS), a biofluid made of proteins and phospholipid vesicles. They form a corona reflecting the PS-nanomaterial interaction. Since the corona determines directly the NPs' biological fate, the question of its nature and structure is central.

Tailoring the photoelectrochemistry of catalytic metal-insulator-semiconductor (MIS) photoanodes by a dissolution method.

Apart from being key structures of modern microelectronics, metal-insulator-semiconductor (MIS) junctions are highly promising electrodes for artificial leaves, i.e. photoelectrochemical cells that can convert sunlight into energy-rich fuels.

Molecular and Material Engineering of Photocathodes Derivatized with Polyoxometalate-Supported {MoS} HER Catalysts.

Molecular engineering of efficient HER catalysts is an attractive approach for controlling the spatial environment of specific building units selected for their intrinsic functionality required within the multistep HER process. As the {MoS} core derived as various coordination complexes has been identified as one as the most promising MoS-based HER electrocatalysts, we demonstrate that the covalent association between the {MoS} core and the redox-active macrocyclic {PW} polyoxometalate (POM) produces a striking synergistic effect featured by high HER performance. Various experiments carried out in homogeneous conditions showed that this synergistic effect arises from the direct connection between the {MoS} cluster and the toroidal {PW} units featured by a stoichiometry that can be tuned from two to four {MoS} cores per {PW} unit.

Role of Calcium Signaling in GA101-Induced Cell Death in Malignant Human B Cells.

GA101/obinutuzumab is a novel type II anti-CD20 monoclonal antibody (mAb), which is more effective than rituximab (RTX) in preclinical and clinical studies when used in combination with chemotherapy. Ca signaling was shown to play a role in RTX-induced cell death. This report concerns the effect of GA101 on Ca signaling and its involvement in the direct cell death induced by GA101.

Electrochemically driven interfacial halogen bonding on self-assembled monolayers for anion detection.

Electrochemically driven interfacial halogen bonding between redox-active SAMs and halide anions was quantitatively studied for the first time. The halogen bond donor properties were switched on by electrochemically controlling the oxidation state of the adsorbates. Experimental data and simulation show high binding enhancement towards halide anions compared to homogeneous systems.

Modulation of emission properties of phosphine-sulfonate ligand containing copper complexes: playing with solvato-, thermo-, and mechanochromism.

Modulations of various neutral phosphine containing copper(i) complexes exhibiting phosphorescence and TADF are easily achieved by solvent modification restricting intramolecular rotation or by modifying the L-X phosphine-sulfonate chelate. This concept is not limited to solvents as the addition of metallic salts also led to the formation of original well-defined photoluminescent K2CuLX3 and KCuL2X2 cuprate complexes.

Anderson-Type Polyoxometalates Functionalized by Tetrathiafulvalene Groups: Synthesis, Electrochemical Studies, and NLO Properties.

Three polyoxometalates (POMs) functionalized by tetrathiafulvalene (TTF) molecules have been synthesized by a coupling reaction between the Anderson-type POMs [MnMoO{(OCH)CNH}] or [AlMoO(OH){(OCH)CNH}] and the TTF carboxylic acid derivative (MeS)TTF(S-CH-COH). The monofunctionalized TTF-AlMo POM contains one TTF group covalently grafted on an Al Anderson platform. The symmetrical TTF-MnMo-TTF POM possesses two TTF groups grafted on each side of a Mn Anderson derivative while the asymmetrical TTF-MnMo-SP POM contains a TTF and a spiropyran groups.

Ruthenium Carbon-Rich Group as a Redox-Switchable Metal Coupling Unit in Linear Trinuclear Complexes.

The preparation and properties of novel ruthenium carbon-rich complexes [(Ph-C≡C-)Ru(dppe)(-C≡C-bipyM(hfac))] (n = 1, 2; M = Cu, Mn; bipy = 2,2'-bipyridin-5-yl) characterized by single-crystal X-ray diffraction and designed for molecular magnetism are reported. With the help of EPR spectroscopy, we show that the neutral ruthenium system sets up a magnetic coupling between two remote paramagnetic Cu units. More specifically, these copper compounds are unique examples of bimetallic and linear heterotrimetallic compounds for which a complete rationalization of the magnetic interactions could be made for exceptionally long distances between the spin carriers (8.

Electronic Interplay between TTF and Extended-TCNQ Electrophores along a Ruthenium Bis(acetylide) Linker.

A bis(TTF-butadiynyl) ruthenium D-D'-D complex, with intramolecular electronic interplay between the three electron-donating electrophores, was easily converted through a cycloaddition-retroelectrocyclization with TCNQ into a D-A-D'-A-D pentad complex, which exhibits an intense intramolecular charge transfer together with an electronic interplay between the two acceptors along the conjugated organometallic bridge.

Impact of an Original Methodological Tool on the Identification of Corrective and Preventive Actions After Root Cause Analysis of Adverse Events in Health Care Facilities: Results of a Randomized Controlled Trial.

Objective: The aim of the study was to assess the effectiveness of a new methodological tool for the identification of corrective and preventive actions (CAPAs) after root cause analysis of health care-related adverse events.

Methods: From January to June 2010, we conducted a randomized controlled trial involving risk managers from 111 health care facilities of the Aquitaine Regional Center for Quality and Safety in Health Care (France). Fifty-six risk managers, randomly assigned to two groups (intervention and control), identified CAPAs in response to two sequentially presented adverse event scenarios.

Serious game training improves performance in combat life-saving interventions.

Aim: In modern warfare, almost 25% of combat-related deaths are considered preventable if life-saving interventions are performed. Therefore, Tactical Combat Casualty Care (TCCC) training for soldiers is a major challenge. In 2014, the French Military Medical Service supported the development of 3D-SC1, a serious game designed for the French TCCC program, entitled Sauvetage au Combat de niveau 1 (SC1).