Ion Mobility Mass Spectrometry to Probe Sequences in Supramolecular Copolymers.

The analysis of the microstructure of supramolecular copolymers is difficult because of their dynamic character. Here, benzene-1,3,5-tricarboxamide (BTA) co-assemblies are analysed by ion mobility - mass spectrometry (IM-MS) to reveal the presence of various sequences. For example, the IM-MS mobilogram for hexamers composed of 4 units from a first monomer and 2 units from a second monomer is a broad distribution due to the presence of 9 possible isomeric sequences, which can be sorted out based on calculated collision cross-sections.

Switchable supramolecular helices for asymmetric stereodivergent catalysis.

Despite recent developments on the design of dynamic catalysts, none of them have been exploited for the in-situ control of multiple stereogenic centers in a single molecular scaffold. We report herein that it is possible to obtain in majority any amongst the four possible stereoisomers of an amino alcohol by means of a switchable asymmetric catalyst built on supramolecular helices. Hydrogen-bonded assemblies between a benzene-1,3,5-tricarboxamide (BTA) achiral phosphine ligand coordinated to copper and a chiral BTA comonomer are engaged in a copper-hydride catalyzed hydrosilylation and hydroamination cascade process.

STAACS3: Simulation Tool for AAC with Single-Switch Scanning.

Communication for people with motor impairments is a difficult, yet necessary, task in daily activities. To do so, soft keyboards, digital counterpart of physical keyboards, are used. Depending on their features, several designs can be considered, however their thoughtful evaluation in real-life is not feasible.

Rationalizing the Extent of the "Sergeants-and-Soldiers" Effect in Supramolecular Helical Catalysts: Effect of Copper Coordination.

Aggregation of supramolecular helices, for example through interdigitation of their alkyl side chains or through more directional supramolecular interactions, leads to hierarchical architectures with original structural and chiroptical properties. However, when a chiral monomer (the "sergeant") is introduced as a minor component in these assemblies composed of a majority of achiral monomers (the "soldiers"), it is not clear how the aggregation changes the ability of the sergeant to induce a preferential helicity to the polymer main chain (the so-called "sergeants-and-soldiers" effect). This study reports a detailed investigation of the influence of [Cu(OAc) ⋅H O] coordination on the structure and chiroptical properties of helical hydrogen-bonded co-assemblies composed of a catalytically-active benzene-1,3,5-tricarboxamide (BTA) monomer, acting as the "soldier", and an enantiopure BTA monomer derived from cyclohexylalanine, playing the role of the "sergeant".

Interplay Between Hydrogen Bonding and Electron Transfer in Mixed Valence Assemblies of Triarylamine Trisamides.

Hydrogen-bonding interactions are assumed to play a critical role in the long-range transport of light or charge recently observed in supramolecular assemblies of C -symmetrical discotic molecules. Herein, the structure of mixed valence assemblies formed by irradiating triarylamine trisamide (TATA) molecules was determined by multifarious techniques under various conditions with the aim of probing the interplay between the hydrogen bonding network and the rate of electron transport in different states (solution, gel, film). Irradiation was performed under initial states that vary by the degree of association of TATA monomers through hydrogen bonds.

Spatial-Spectral Analysis of Hyperspectral Images Reveals Early Detection of Downy Mildew on Grapevine Leaves.

Downy mildew is a highly destructive disease of grapevine. Currently, monitoring for its symptoms is time-consuming and requires specialist staff. Therefore, an automated non-destructive method to detect the pathogen before the visible symptoms appear would be beneficial for early targeted treatments.

LAMP for in-field quantitative assessments of airborne grapevine downy mildew inoculum.

Aims: Cheap, rapid tools for measuring emissions of Plasmopara viticola sporangia directly in the field are required to protect grapevines efficiently and sustainably against downy mildew. To this end, we adapted an existing loop-mediated isothermal amplification (LAMP) protocol based on ITS2 sequences, coupled with a rotating-arm sampler and simple cell lysis, for the in-field measurement of airborne sporangia of P. viticola.

Possible chemical and physical scenarios towards biological homochirality.

The single chirality of biological molecules in terrestrial biology raises more questions than certitudes about its origin. The emergence of biological homochirality (BH) and its connection with the appearance of life have elicited a large number of theories related to the generation, amplification and preservation of a chiral bias in molecules of life under prebiotically relevant conditions. However, a global scenario is still lacking.

Monitoring of plasma concentrations of dabrafenib and trametinib in advanced BRAFV600 melanoma patients.

Background: Dabrafenib (D) and trametinib (T) improved survival in patients with BRAFV600 melanoma. High plasma concentration of D (PCD) is weakly associated with adverse events (AE). We investigated the relationship between PCD/T and tumour control or AE.

Energetics of Competing Chiral Supramolecular Polymers.

Chirality can have unexpected consequences including on properties other than spectroscopic. We show herein that a racemic mixture of bis-urea stereoisomers forms thermodynamically stable supramolecular polymers that result in a more viscous solution than for the pure stereoisomer. The origin of this macroscopic property was probed by characterizing the structure and stability of the assemblies.

Experimental and computational diagnosis of the fluxional nature of a benzene-1,3,5-tricarboxamide-based hydrogen-bonded dimer.

Precise characterization of the hydrogen bond network present in discrete self-assemblies of benzene-1,3,5-tricarboxamide monomers derived from amino-esters (ester BTAs) is crucial for the construction of elaborated functional co-assemblies. For all ester BTA dimeric structures previously reported, ester carbonyls in the side chain acted as hydrogen bond acceptors, yielding well-defined dimers stabilized by six hydrogen bonds. The ester BTA monomer derived from glycine (BTA Gly) shows a markedly different self-assembly behaviour.

Dissecting the Role of the Sergeants in Supramolecular Helical Catalysts: From Chain Capping to Intercalation.

Controlling the properties of supramolecular assemblies requires unveiling the specific interactions between their components. In the present work, the catalytic properties and structure of co-assemblies composed of a benzene-1,3,5-tricarboxamide (BTA) ligand coordinated to copper (the soldier) and seven enantiopure BTAs (the sergeants) have been determined. Whatever the sergeant, the enantioselectivity of the reaction is directly proportional to the optical purity of the supramolecular helices.

Tuning the Organogelating and Spectroscopic Properties of a C -Symmetric Pyrene-Based Gelator through Charge Transfer.

Two-component organogels and xerogels based on a C -symmetric pyrene-containing gelator have been deeply characterized through a wide range of techniques. Based on the formation of charge transfer complexes, the gelation phenomenon proved to be highly dependent on the nature of the electron poor dopant. This parameter significantly influenced the corresponding gelation domains, the critical gelation concentrations of acceptor dopants, the gel-to-sol transition temperatures, the microstructures formed in the xerogel state and their spectroscopic properties.

Delaying the first grapevine fungicide application reduces exposure on operators by half.

Downy mildew is a severe disease of grapevines treated by repeated fungicide applications during the growing season. The impact of these treatments on human health is currently under scrutiny. Fungicide application long before disease onset is not thought to be greatly beneficial for grape production, but the first fungicide treatment is applied at least six weeks before disease onset in more than 50% of the vineyards in the Bordeaux region, a major French vine-growing area.

Forecasting severe grape downy mildew attacks using machine learning.

Grape downy mildew (GDM) is a major disease of grapevine that has an impact on both the yields of the vines and the quality of the harvested fruits. The disease is currently controlled by repetitive fungicide treatments throughout the season, especially in the Bordeaux vineyards where the average number of fungicide treatments against GDM was equal to 10.1 in 2013.

Emergence of Homochiral Benzene-1,3,5-tricarboxamide Helical Assemblies and Catalysts upon Addition of an Achiral Monomer.

Chirality amplification refers to the ability of a small chiral bias to fully control the main chain helicity of polymers and assemblies. Further implementation of functional chirally amplified helices as switchable asymmetric catalysts, chiral sensors, and circularly polarized light emitters will require a greater control of the energetics governing these chirality amplification effects. In this work, we report on the counterintuitive ability of an achiral molecule to suppress conformational defects in supramolecular helices, thus leading to the emergence of homochirality in a system containing a very small chiral bias.

When a Pathological Forearm Fracture Led to Explore the Neck: About a Case.

The majority of patients with parathyroid carcinoma (PC) have significant clinical signs and simultaneous symptoms related to the unregulated hypersecretion of parathyroid hormone (PTH) by the tumor. The aim of this case was to report a patient presenting an isolated bone fracture leading to the diagnosis of PC. A 20-years-old female patient presenting a fracture of both bones of the forearm following a fall from her own height.

A Competing Hydrogen Bonding Pattern to Yield a Thermo-Thickening Supramolecular Polymer.

Introduction of competing interactions in the design of a supramolecular polymer (SP) creates pathway complexity. Ester-bis-ureas contain both a strong bis-urea sticker that is responsible for the build-up of long rod-like objects by hydrogen bonding and ester groups that can interfere with this main pattern in a subtle way. Spectroscopic (FTIR and CD), calorimetric (DSC), and scattering (SANS) techniques show that such ester-bis-ureas self-assemble into three competing rod-like SPs.

Extra hydrogen bonding interactions by peripheral indole groups stabilize benzene-1,3,5-tricarboxamide helical assemblies.

Benzene-1,3,5-tricarboxamide monomers derived from alkyl esters of tryptophan (BTA Trp) self-assemble into helices with an inner threefold hydrogen bond network surrounded by a second network involving the indole N-H groups. As a consequence of this extra stabilization of its helical assemblies, BTA Trp forms more viscous solutions than a range of ester and alkyl BTAs.

Organogel Formation Rationalized by Hansen Solubility Parameters: Shift of the Gelation Sphere with the Gelator Structure.

To rationalize how the gelation ability of a low molecular weight gelator is influenced by its molecular structure, we performed extensive solubility tests of a group of thiazole-based gelators and made use of Hansen solubility parameter formalism. We observe that the increase of a linear alkyl chain in these gelators promotes an increase of the radius of the gelation sphere as well as a gradual shift of its center to lower values of the polar (δ) and hydrogen bonding (δ) components. The molecular packing within the fibers and the crystal habit were determined by a combination of X-ray diffraction and molecular modeling.

Performance of F-sodium fluoride positron emission tomography with computed tomography to assess inflammatory and structural sacroiliitis on magnetic resonance imaging and computed tomography, respectively, in axial spondyloarthritis.

Purpose: To assess increased sacroiliac joint (SIJ) uptake on F-NaF PET/CT and to compare with MRI for inflammation and with CT scan for structural damages in a population of 23 patients with spondyloarthritis (SpA).

Methods: Twenty-three patients with active SpA according to the Assessment of SpondyloArthritis international Society (ASAS) and/or modified NY criteria were included. All patients had a pelvic radiograph, MRI, and CT scan of the SIJ and F-NaF PET/CT examinations within a month, analyzed by three blinded readers.