Successive photoswitching and derivatization effects in photochromic dithienylethene-based coordination cages

A new series of [Pd2(L)4] cages based on photochromic dithienylethene (DTE) ligands allowed us to gain insight into the successive photoswitching of multiple DTE moieties in a confined metallo‐supramolecular assembly. Three new X‐ray structures of [Pd2(o‐L4)4], [Pd2(o‐L1)2(c‐L1)2] and [Pd2(c‐L1)4] (o‐L and c‐L = open and closed forms of DTE ligands, respectively) were obtained. The structures deliver snapshots of three different combinations of DTE photoisomeric states within the cage, facilitating a comparison of the all‐open with the all‐closed, and most notably, an intermediate form where open and closed switches co‐exist in the same cage. Moreover, a series of spherical anionic borate clusters was introduced in order to study their roles in the light‐controllable host–guest chemistry. The binding guests show higher affinities with the flexible open cage [Pd2(o‐L1)4] than with the rigid closed cage [Pd2(c‐L1)4]. For the [B12F12]2− guest, thermodynamic data obtained from NMR experiments was compared to results from isothermal titration calorimetry (ITC)

Individual regional associations between Aβ-, tau- and neurodegeneration (ATN) with microglial activation in patients with primary and secondary tauopathies.

β-amyloid (Aβ) and tau aggregation as well as neuronal injury and atrophy (ATN) are the major hallmarks of Alzheimer's disease (AD), and biomarkers for these hallmarks have been linked to neuroinflammation. However, the detailed regional associations of these biomarkers with microglial activation in individual patients remain to be elucidated. We investigated a cohort of 55 patients with AD and primary tauopathies and 10 healthy controls that underwent TSPO-, Aβ-, tau-, and perfusion-surrogate-PET, as well as structural MRI. Z-score deviations for 246 brain regions were calculated and biomarker contributions of Aβ (A), tau (T), perfusion (N1), and gray matter atrophy (N2) to microglial activation (TSPO, I) were calculated for each individual subject. Individual ATN-related microglial activation was correlated with clinical performance and CSF soluble TREM2 (sTREM2) concentrations. In typical and atypical AD, regional tau was stronger and more frequently associated with microglial activation when compared to regional Aβ (AD: βT = 0.412 ± 0.196 vs. βA = 0.142 ± 0.123, p < 0.001; AD-CBS: βT = 0.385 ± 0.176 vs. βA = 0.131 ± 0.186, p = 0.031). The strong association between regional tau and microglia reproduced well in primary tauopathies (βT = 0.418 ± 0.154). Stronger individual associations between tau and microglial activation were associated with poorer clinical performance. In patients with 4RT, sTREM2 levels showed a positive association with tau-related microglial activation. Tau pathology has strong regional associations with microglial activation in primary and secondary tauopathies. Tau and Aβ related microglial response indices may serve as a two-dimensional in vivo assessment of neuroinflammation in neurodegenerative diseases

Individual regional associations between Aβ-, tau- and neurodegeneration (ATN) with microglial activation in patients with primary and secondary tauopathies

& beta;-amyloid (A & beta;) and tau aggregation as well as neuronal injury and atrophy (ATN) are the major hallmarks of Alzheimer's disease (AD), and biomarkers for these hallmarks have been linked to neuroinflammation. However, the detailed regional associations of these biomarkers with microglial activation in individual patients remain to be elucidated. We investigated a cohort of 55 patients with AD and primary tauopathies and 10 healthy controls that underwent TSPO-, A & beta;-, tau-, and perfusion-surrogate-PET, as well as structural MRI. Z-score deviations for 246 brain regions were calculated and biomarker contributions of A & beta;(A), tau (T), perfusion (N1), and gray matter atrophy (N2) to microglial activation (TSPO, I) were calculated for each individual subject. Individual ATN-related microglial activation was correlated with clinical performance and CSF soluble TREM2 (sTREM2) concentrations. In typical and atypical AD, regional tau was stronger and more frequently associated with microglial activation when compared to regional A & beta;(AD: & beta;(T) = 0.412 & PLUSMN;0.196 vs. & beta;(A) = 0.142 & PLUSMN;0.123, p < 0.001;AD-CBS: & beta;(T) = 0.385 & PLUSMN;0.176 vs. & beta;(A) = 0.131 & PLUSMN;0.186, p = 0.031). The strong association between regional tau and microglia reproduced well in primary tauopathies (& beta;(T) = 0.418 & PLUSMN;0.154). Stronger individual associations between tau and microglial activation were associated with poorer clinical performance. In patients with 4RT, sTREM2 levels showed a positive association with tau-related microglial activation. Tau pathology has strong regional associations with microglial activation in primary and secondary tauopathies. Tau and A & beta;related microglial response indices may serve as a two-dimensional in vivo assessment of neuroinflammation in neurodegenerative diseases

Head and Neck Cancer: United Kingdom National Multidisciplinary Guidelines, Sixth Edition.

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Courtage sémantique de services de calcul

La recherche de services de calcul qui correspondent aux besoins d'un utilisateur sur une grille de calcul est une activité complexe. L'objet des travaux réalisés consiste à utiliser une description formelle du domaine d'application comportant l'ensemble des données et des opérateurs du domaine ainsi que leurs propriétés. Cette description est effectuée sous forme d'une spécification algébrique. Le courtage consiste alors à effectuer un filtrage modulo la théorie équationnelle associée à la spécification, entre le terme représentant le service souhaité et les termes représentant les services disponibles. Nous proposons et avons implanté deux algorithmes différents inspirés d'un parcours de l'arbre de recherche des solutions contraint par une quantité d'énergie. Nous présentons les domaines applicatifs algèbre linéaire et optimisation et nous nous intéressons au traitement de la combinaison de domaines. Enfin, nous concluons et présentons les perspectives principales de nos travaux.The search for a computing service which corresponds to the user's needs on a grid is a complex activity. The object of this work consists in using a formal description of the dedicated domain : the data, the operators and their properties. This description is carried out as an algebraic specification. Trading then consists in computing an equational matching modulo the theory associated to the specification, between the term representing the required service and the terms representing the available services. We propose two algorithms inspired from a traversal of the solution search tree constrained by an amount of energy. We present some applications in linear algebra and optimization and an interaction between these domain.TOULOUSE-ENSEEIHT (315552331) / SudocSudocFranceF

Reactions of (CF₃)₃BCO with Amines and Phosphines

Reactions of tris(trifluoromethyl)borane carbonyl, (CF3)3BCO, with ammonia yielded either a mixture of [NH4][(CF3)3BC(O)NH2], [NH4][(CF3)3BCN], and [NH4]2[{(CF3)3BC(O)}2NH] or neat [NH4]2[{(CF)BC(O)}NH] depending on the reaction conditions. The salt K[(CF3)3BC(O)NH] was obtained as the sole product from the reaction of NH3 with K[(CF3)BC(O)F]. A simple synthesis for cyanotris(trifluoromethyl)borates, M[(CF)3BCN], was developed by dehydration of M[(CF)3BC(O)NH] (M = [NH4], K) using phosgene. In addition, syntheses of the tris(trifluoromethyl)boron species [(CF3)BC(O)NHnPr]-, [(CF3)3BC(O)NMe]-, and (CF3)BC(O)NMe3, as well as of (CF)BC(O)PMe, were performed. All species were characterized by multinuclear NMR spectroscopy. As far as neat substances resulted, IR and Raman spectra were recorded and their thermal behaviors were studied by differential scanning calorimetry. The interpretation of reaction pathways, structures, and vibrational spectra are supported by DFT calculations. The solid-state structure of K2[{(CF3)BC(O)}NH]·2MeCN was determined by single-crystal X-ray diffraction

Haloacyl complexes of boron, [(CF₃)₃BC(O)Hal]⁻ (Hal = F, Cl, Br, I)

The haloacyltris(trifluoromethyl)borate anions [(CF3)3BC(O)Hal]− (Hal=F, Cl, Br, I) have been synthesized by reacting (CF3)3BCO with either MHal (M=K, Cs; Hal=F) in SO2 or MHal (M=[nBu4N]+, [Et4N]+, [Ph4P]+; Hal=Cl, Br, I) in dichloromethane. Metathesis reactions of the fluoroacyl complex with Me3SiHal (Hal=Cl, Br, I) led to the formation of its higher homologues. The thermal stabilities of the haloacyltris(trifluoromethyl)borates decrease from the fluorine to the iodine derivative. The chemical reactivities decrease in the same order as demonstrated by a series of selected reactions. The new [(CF3)3BC(O)Hal]− (Hal=F, Cl, Br) salts are used as starting materials in the syntheses of novel compounds that contain the (CF3)3B-C fragment. All borate anions [(CF3)3BC(O)Hal]− (Hal=F, Cl, Br, I) have been characterized by multinuclear NMR spectroscopy (11B, 13C, 17O, 19F) and vibrational spectroscopy. [PPh4][(CF3)3BC(O)Br] crystallizes in the monoclinic space group P2/c (no. 13) and the bond parameters are compared with those of (CF3)3BCO and K[(CF3)3BC(O)F]. The interpretation of the spectroscopic and structural data are supported by DFT calculations [B3LYP/6‐311+G(d)]

[(CF₃)₃BCP]⁻ and [(CF₃)₃BCAs]⁻: Thermally Stable Phosphaethynyl and Arsaethynyl Complexes

Make mine a triple: The tetraphenyl phosphonium salts of [(CF3)3BCX]− (X=P, As) are stable even well above room temperature. The synthesis of these first phospha‐ and arsaethynyl complexes of boron from (CF3)3BCO is carried out in two steps (see scheme). The complex [(CF3)3BCAs]− is the first stable anionic arsaalkyne

(PPh₃)₃RhCNB(CF₃)₃ and (PPh₃)₃RhNCB(CF₃)₃: Isocyano- and Cyanoborate Complexes of Tris(triphenylphosphine)rhodium(I)

The reactions of K[(CF3)3BNC] and K[(CF3)3BCN] with (PPh3)3RhCl in ethanol resulted in the rhodium(I) complexes (PPh3)3RhNCB(CF3)3 and (PPh3)3RhCNB(CF3)3, respectively. Their 15N-labeled isotopomers were synthesized from the corresponding borate anions. The complexes were characterized by UV, Raman, and multi-NMR spectroscopy, and the crystal structures were obtained. The spectroscopic and structural data are compared to those of the potassium borates and to related rhodium(I) complexes