Various Sizes and Shapes of Mixed-Anion Fe(NHtrz)(BF)(SiF)@SiO Nanohybrid Particles Undergoing Spin Crossover Just Above Room Temperature.

Spin crossover (SCO) iron (II) coordination compounds in the form of nanohybrid SCO@SiO particles were prepared using a reverse micelles technique based on the TritonX-100/cyclohexane/water ternary system. Tetraethyl orthosilicate (TEOS) acts as precursor of both the SiF counter-anion and SiO to obtain Fe(NHtrz)(BF)(SiF)@SiO nanoparticles with different sizes and morphologies while modifying the TEOS concentration and reaction time. The adjustable mixed-anion strategy leads to a range of quite scarce abrupt spin crossover behaviors with hysteresis just above room temperature (ca.

Conditioning a collective avoidance response in rummy-nose tetra.

Escape waves in animal groups, such as bird flocks and fish schools, have attracted a lot of attention, as they provide the opportunity to better understand how information can efficiently propagate in moving groups, and how individuals can coordinate their actions under the threat of predators. There is a lack of appropriate experimental protocols to study escape waves in highly social fish, in which the number of individuals initiating the escape and the identity of the initiators are controlled. Indeed, highly social fish or obligate schoolers have a tendency to not respond well or to freeze when tested in experimental setups designed for single individuals.

Gradual spin crossover behavior encompasing room temperature in an iron(II) complex based on a heteroscorpionate ligand.

In this paper, we report the synthesis of six novel triazole-based heteroscorpionate ligands based on heterocycle metathesis reactions and their iron(II) complexes. Single crystal structure analyses were performed, the spectroscopic and magnetic properties of the obtained complexes were studied and their spin crossover-structural relationships were compared to those obtained for their pyrazole-based analogues reported in the literature. In particular, the amino derivative complex bis[hydrobis(pyrazol-1-yl)(3-amino-1,2,4-triazol-1-yl)]iron(II) obtained by post-synthetic catalytic nitro-group reduction under pressure of hydrogen in an autoclave presents a scarce gradual spin crossover behavior at room temperature.

Cosmology and fundamental physics with the ELT-ANDES spectrograph.

State-of-the-art 19th century spectroscopy led to the discovery of quantum mechanics, and 20th century spectroscopy led to the confirmation of quantum electrodynamics. State-of-the-art 21st century astrophysical spectrographs, especially ANDES at ESO's ELT, have another opportunity to play a key role in the search for, and characterization of, the new physics which is known to be out there, waiting to be discovered. We rely on detailed simulations and forecast techniques to discuss four important examples of this point: big bang nucleosynthesis, the evolution of the cosmic microwave background temperature, tests of the universality of physical laws, and a real-time model-independent mapping of the expansion history of the universe (also known as the redshift drift).

Synthesis and Spectroscopic Properties of Diarylethene-Subporphyrinoid Hybrids.

Two novel diarylethene-fused subporphyrinoids were prepared and characterized. A mono diarylethene derivative was obtained via a statistical condensation reaction with 2 eq. of 1,2-dicyanobenzene and 1 eq.

Dinuclear tricarbonylrhenium(I) complexes: impact of regioisomerism on the photoluminescence properties.

Dinuclear Re(I) complexes have proportionally been much less studied than mononuclear analogues. In particular, very little information is available about their solid-state emission properties. In this work, two structural isomers of dinuclear complexes (Bi-Re-metaPhe and Bi-Re-paraPhe), which differ by the relative position of the coordination spheres on a central phenyl ring, were synthesized and compared with each other and with the parent mononuclear compound (Mono-Re-Phe), from a theoretical and experimental point of view.

Uncovering the functions and mechanisms of regulatory elements-associated non-coding RNAs.

Over the past decade, regulatory non-coding RNAs (ncRNAs) produced by RNA Pol II have been revealed as meaningful players in various essential cellular functions. In particular, thousands of ncRNAs are produced at transcriptional regulatory elements such as enhancers and promoters, where they may exert multiple functions to regulate proper development, cellular programming, transcription or genomic stability. Here, we review the mechanisms involving these regulatory element-associated ncRNAs, and particularly enhancer RNAs (eRNAs) and PROMoter uPstream Transcripts (PROMPTs).

Spatial Control of 2D Nanomaterial Electronic Properties Using Chiral Light Beams.

Single-layer two-dimensional (2D) nanomaterials exhibit physical and chemical properties which can be dynamically modulated through out-of-plane deformations. Existing methods rely on intricate micromechanical manipulations (., poking, bending, rumpling), hindering their widespread technological implementation.

Probing the electronic structure and ground state symmetry of gas phase C60+ via VUV photoionization and comparison with theory.

Recently, some of us reviewed and studied the photoionization dynamics of C60 that are of great interest to the astrochemical community as four of the diffuse interstellar bands (DIBs) have been assigned to electronic transitions in the C60+ cation. Our previous analysis of the threshold photoelectron spectrum (TPES) of C60 [Hrodmarsson et al., Phys.

Boosting the Reactivity of Bis-Lactones to Enable Step-Growth Polymerization at Room Temperature.

The development of new sustainable polymeric materials endowed with improved performances but minimal environmental impact is a major concern, with polyesters as primary targets. Lactones are key monomers thanks to ring-opening polymerization, but their use in step-growth polymerization has remained scarce and challenging. Herein, we report a powerful bis(γ-lactone) () that was efficiently prepared on a gram scale from malonic acid by Pd-catalyzed cycloisomerization.

Spin crossover in {Fe(pyrazine)[M(CN)]} (M = Ni, Pt) thin films assembled on fused silica substrates.

Thin films with thicknesses in the range between . 10-50 nm of the spin crossover (SCO) compound {Fe(pyrazine)[μ-M(CN)]} (M = Ni, Pt) have been deposited on fused silica substrates using a sequential assembly method and 4-pyridinecarboxylic acid as anchoring layer. Film morphology and crystallinity were assessed by means of atomic force microscopy and grazing incidence X-ray diffraction, respectively.

Room temperature spin crossover properties in a series of mixed-anion Fe(NHtrz)(BF)(SiF) complexes.

A series of mixed-anion Fe(NHtrz)(BF)(SiF) spin crossover complexes is obtained modifying the reaction time but also using an increase amount of tetraethyl orthosilicate as the source for the production and the incorporation of SiF competing with the BF anions present in the mother solution. The increase of the SiF anion inclusion to the detriment of the BF counterpart induces a shift of the temperature transition toward high temperatures leading to interesting bistability properties around room temperature with spanning from 300 K to 325 K. Moreover, the implementation of a solid-liquid post synthetic modification approach from the Fe(NHtrz)(BF) parent complex with identical TEOS proportions and under certain experimental conditions lead systematically to the same Fe(NHtrz)(BF)(SiF) composition.

Exploring Molecular Energy Landscapes by Coupling the DFTB Potential with a Tree-Based Stochastic Algorithm: Investigation of the Conformational Diversity of Phthalates.

Exploring the global energy landscape of relatively large molecules at the quantum level is a challenging problem. In this work, we report the coupling of a nonredundant conformational space exploration method, namely, the robotics-inspired iterative global exploration and local optimization (IGLOO) algorithm, with the quantum-chemical density functional tight binding (DFTB) potential. The application of this fast and efficient computational approach to three close-sized molecules of the phthalate family (DBP, BBP, and DEHP) showed that they present different conformational landscapes.

Temperature driven transformations of glycine molecules embedded in interstellar ice.

The formation of glycine amino acid on ice grains in space raises fundamental questions about glycine chemistry in interstellar media. In this work, we studied glycine conformational space and the related tautomerization mechanisms in water media by means of QM/MM molecular dynamics simulations of four glycine conformational isomers (, , , and ). Interstellar low density amorphous (LDA) ice and = 20 K were considered as representative for a cold interstellar ice environment, while temperatures of 250 and 450 K were included to model rapid local heating in the ice.

Colloidal ruthenium catalysts for selective quinaldine hydrogenation: Ligand and solvent effects.

Colloidal Ru nanoparticles (NP) display interesting catalytic properties for the hydrogenation of (hetero)arenes as they proceed efficiently in mild reaction conditions. In this work, a series of Ru based materials was used in order to selectively hydrogenate quinaldine and assess the impact of the stabilizing agent on their catalytic performances. Ru nanoparticles stabilized with polyvinylpyrrolidone (PVP) and 1-adamantanecarboxylic acid (AdCOOH) allowed to obtain 5,6,7,8-tetrahydroquinaldine with a remarkable selectivity in mild reaction conditions by choosing the suitable solvent.

TurboGenius: Python suite for high-throughput calculations of ab initio quantum Monte Carlo methods.

TurboGenius is an open-source Python package designed to fully control ab initio quantum Monte Carlo (QMC) jobs using a Python script, which allows one to perform high-throughput calculations combined with TurboRVB [Nakano et al. J. Phys.

A mini scanning device for profiling charged beams.

In this article, we present the development of a mini scanner device to characterize the full transverse spatial density of a charged particle beam using computed tomography. The profiler consists of a wire mounted on a linear translator that can rotate around the beam. Tests were performed on a millimeter electron beam with 200 eV energy and 100 nA intensity, which allowed us to control and monitor both beam focusing and deflection.

Stabilization of Luminescent Mononuclear Three-Coordinate Cu Complexes by Two Distinct Cavity-Shaped Diphosphanes Obtained from a Single α-Cyclodextrin Precursor.

Slightly different reaction conditions afforded two distinct cavity-shaped cis-chelating diphosphanes from the same starting materials, namely diphenyl(2-phosphanylphenyl)phosphane and an α-cyclodextrin-derived dimesylate. Thanks to their metal-confining properties, the two diphosphanes form only mononuclear [CuX(PP)] complexes (X=Cl, Br, or I) with the tricoordinated metal ion located just above the center of the cavity. The two series of Cu complexes display markedly different luminescence properties that are both influenced by the electronic properties of the ligand and the unique steric environment provided by the cyclodextrin (CD) cavity.

Addressing electronic and dynamical evolution of molecules and molecular clusters: DFTB simulations of energy relaxation in polycyclic aromatic hydrocarbons.

We present a review of the capabilities of the density functional based Tight Binding (DFTB) scheme to address the electronic relaxation and dynamical evolution of molecules and molecular clusters following energy deposition either collision or photoabsorption. The basics and extensions of DFTB for addressing these systems and in particular their electronic states and their dynamical evolution are reviewed. Applications to PAH molecules and clusters, carbonaceous systems of major interest in astrochemical/astrophysical context, are reported.

Low-Energy Transformation Pathways between Naphthalene Isomers.

The transformation pathways between low-energy naphthalene isomers are studied by investigating the topology of the energy landscape of this astrophysically relevant molecule. The threshold algorithm is used to identify the minima basins of the isomers on the potential energy surface of the system and to evaluate the probability flows between them. The transition pathways between the different basins and the associated probabilities were investigated for several lid energies up to 11 eV, this value being close to the highest photon energy in the interstellar medium (13.

Kinetic measurements of human CD8 T cell cytotoxic activity in a 384-well plate format.

The elimination of infected or cancerous cells by CD8 cytotoxic T lymphocytes (CTL) is a crucial effector mechanism of the immune system. Upon antigen recognition, CTL stop migrating, establish a tight contact with target cells and deliver cytotoxic molecules such as perforin and granzymes that lead to target cell apoptosis. The ability of CTL to control a population of infected cells or a tumor depends on multiple parameters, such as the relative numbers of CTL and target cells, the intrinsic cytotoxic activity of CTL, the intrinsic resistance of target cells and the repertoire of immune checkpoints tuning cytotoxic activity at the CTL:target cell interface.

Spin crossover in mixed-anion Fe(NHtrz)(BF)(SiF) crystalline rod-shaped particles: the strength of the solid-liquid post synthetic modification.

A pure mixed-anion Fe(NHtrz)(BF)(SiF) spin crossover complex is obtained implementing a solid-liquid post synthetic modification approach from the Fe(NHtrz)(BF) parent complex. This method allows obtaining highly crystalline powder samples incorporating homogeneous micrometric (1 μm long) rod-shaped particles. This compound presents an abrupt spin crossover behaviour with a narrow (10 K) hysteresis loop centred just above room temperature (320 K) which makes it very interesting for future integration into devices for various applications.

Real-world study of the efficacy and safety of belantamab mafodotin (GSK2857916) in relapsed or refractory multiple myeloma based on data from the nominative ATU in France: the IFM 2020-04 study.

Belantamab mafodotin (BM) is an anti-BCMA antibody-drug conjugate (GSK2857916) that represents an alternative option in multiple myeloma. We sought to assess the efficacy and safety of BM in a real-world setting in patients who benefited from an early access program. We conducted an observational, retrospective, multicenter study.