(S)-6-Methyl-∊-caprolactone

The chiral title compound, C7H12O2, a lactone derivative, features a seven-membered ring that adopts a chair conformation. The crystal structure is stabilized by weak C—H⋯O inter­actions occurring in the (100) plane. The absolute configuration was assigned on the basis of the enantioselective synthesis

(4aS,5R,7R,8S,8aR)-8-(1,3-Dioxolan-2-yl)-7,8-dimethyl-5-(1-methyl­ethen­yl)perhydro­naphthalen-2-one

In the chiral title compound, C18H28O3, the two six-membered rings of the perhydronaphthalenone adopt a rigid chair–chair conformation and the five-membered dioxolanyl ring adopts an envelope conformation. The crystal structure is stabilized only by weak inter­actions

Quantum paramagnetism in a non-Kramers rare-earth oxide: Monoclinic Pr2Ti2O7\rm Pr_2Ti_2O_7

Little is so far known about the magnetism of the $\rm A_2B_2O_7$ monoclinic layered perovskites that replace the spin-ice supporting pyrochlore structure for $r_A/r_B>1.78$. We show that high quality monoclinic Pr$_2$Ti$_2$O$_7$ single crystals with a three-dimensional network of non-Kramers Pr$^{3+}$ ions that interact through edge-sharing super-exchange interactions, form a singlet ground state quantum paramagnet that does not undergo any magnetic phase transitions down to at least 1.8 K. The chemical phase stability, structure, and magnetic properties of the layered perovskite Pr$_2$Ti$_2$O$_7$ were investigated using x-ray diffraction, transmission electron microscopy, and magnetization measurements. Synthesis of polycrystalline samples with the nominal compositions of Pr$_2$Ti$_{2+x}$O$_7$ ($-0.16 \leq x \leq 0.16$) showed that deviations from the Pr$_2$Ti$_2$O$_7$ stoichiometry lead to secondary phases of related, structures including the perovskite phase Pr$_{2/3}$TiO$_3$ and the orthorhombic phases Pr$_4$Ti$_9$O$_{24}$ and Pr$_2$TiO$_5$. No indications of site disordering (stuffing and anti-stuffing) or vacancy defects were observed in the Pr$_2$Ti$_2$O$_7$ majority phase. A procedure for growth of high-structural-quality, stoichiometric single crystals of Pr$_2$Ti$_2$O$_7$ by the traveling solvent floating zone (TSFZ) method is reported. Thermo-magnetic measurements of single-crystalline Pr$_2$Ti$_2$O$_7$ reveal an isolated singlet ground state that we associate with the low symmetry crystal electric field environments that split the $2J+1=9$-fold degenerate spin-orbital multiplets of the four differently coordinated Pr$^{3+}$ ions into 36 isolated singlets resulting in an anisotropic temperature independent van-Vleck susceptibility at low $T$. A small isotropic Curie term is associated with 0.96(2)\% non-interacting Pr$^{4+}$ impurities.Comment: 18 pages, 7 figures, 6 table

Ruthenium-Locked Helical Chirality: A Barrier of Inversion and Formation of an Asymmetric Macrocycle

Upon coordination to metal centers, tetradentate ligands based on the 6,6'-bis(2 ''-aminopyridyl)-2,2'-bipyridine (bapbpy) structure form helical chiral complexes due to the steric clash between the terminal pyridines of the ligand. For octahedral ruthenium(II) complexes, the two additional axial ligands bound to the metal center, when different, generate diastereotopic aromatic protons that can be distinguished by NMR. Based on these geometrical features, the inversion barrier of helical [Ru-II(L)(RR'SO)Cl](+) complexes, where L is a sterically hindered bapbpy derivative and RR'SO is a chiral or achiral sulfoxide ligand, was studied by variable-temperature H-1 NMR The coalescence energies for the inversion of the helical chirality of [Ru(bapbpy)(DMSO)(Cl)]Cl and [Ru(bapbpy)(MTSO)(Cl)]Cl (where MTSO is (R)-methyl p-tolylsulfoxide) were found to be 43 and 44 kJ/mol, respectively. By contrast, in [Ru(biqbpy)(DMSO)(Cl)]Cl (biqbpy = 6,6'-bis(aminoquinolyl)-2,2'-bipyridine increased strain caused by the larger terminal quinoline groups resulted in a coalescence temperature higher than 376 K, which pointed to an absence of helical chirality inversion at room temperature. Further increasing the steric strain by introducing methoxy groups ortho to the nitrogen atoms of the terminal pyridyl groups in bapbpy resulted in the serendipitous discovery of a ring-closing reaction that took place upon trying to make [Ru(OMe-bapbpy)(DMSO)Cl](+) (OMe-bapbpy = 6,6'-bis(6-methoxy-aminopyridyl)2,2'-bipyridine). This reaction generated, in excellent yields, a chiral complex [Ru(L '')(DMSO)Cl]Cl, where L '' is an asymmetric tetrapyridyl macrocycle. This unexpected transformation appears to be specific to ruthenium(II) as macrocyclization did not occur upon coordination of the same ligand to palladium(II) or rhodium(III).Macromolecular Biochemistr

Shorter Alkyl Chains Enhance Molecular Diffusion and Electron Transfer Kinetics between Photosensitisers and Catalysts in CO2 -Reducing Photocatalytic Liposomes.

Funder: Nederlandse Organisatie voor Wetenschappelijk Onderzoek; Id: http://dx.doi.org/10.13039/501100003246Covalent functionalisation with alkyl tails is a common method for supporting molecular catalysts and photosensitisers onto lipid bilayers, but the influence of the alkyl chain length on the photocatalytic performances of the resulting liposomes is not well understood. In this work, we first prepared a series of rhenium-based CO2 -reduction catalysts [Re(4,4'-(Cn H2n+1 )2 -bpy)(CO)3 Cl] (ReCn ; 4,4'-(Cn H2n+1 )2 -bpy=4,4'-dialkyl-2,2'-bipyridine) and ruthenium-based photosensitisers [Ru(bpy)2 (4,4'-(Cn H2n+1 )2 -bpy)](PF6 )2 (RuCn ) with different alkyl chain lengths (n=0, 9, 12, 15, 17, and 19). We then prepared a series of PEGylated DPPC liposomes containing RuCn and ReCn , hereafter noted Cn , to perform photocatalytic CO2 reduction in the presence of sodium ascorbate. The photocatalytic performance of the Cn liposomes was found to depend on the alkyl tail length, as the turnover number for CO (TON) was inversely correlated to the alkyl chain length, with a more than fivefold higher CO production (TON=14.5) for the C9 liposomes, compared to C19 (TON=2.8). Based on immobilisation efficiency quantification, diffusion kinetics, and time-resolved spectroscopy, we identified the main reason for this trend: two types of membrane-bound RuCn species can be found in the membrane, either deeply buried in the bilayer and diffusing slowly, or less buried with much faster diffusion kinetics. Our data suggest that the higher photocatalytic performance of the C9 system is due to the higher fraction of the more mobile and less buried molecular species, which leads to enhanced electron transfer kinetics between RuC9 and ReC9

Mechanomyographic Analysis for Muscle Activity Assessment during a Load-Lifting Task

International audienceThe purpose of this study was to compare electromyographic (EMG) with mechanomyographic (MMG) recordings during isometric conditions, and during a simulated load-lifting task. Twenty-two males (age: 25.5 ± 5.3 years) first performed maximal voluntary contractions (MVC) and submaximal isometric contractions of upper limb muscles at 25%, 50% and 75% MVC. Participants then executed repetitions of a functional activity simulating a load-lifting task above shoulder level, at 25%, 50% and 75% of their maximum activity (based on MVC). The low-frequency part of the accelerometer signal (<5 Hz) was used to segment the six phases of the motion. EMG and MMG were both recorded during the entire experimental procedure. Root mean square (RMS) and mean power frequency (MPF) were selected as signal extraction features. During isometric contractions, EMG and MMG exhibited similar repeatability scores. They also shared similar RMS vs. force relationship, with RMS increasing to 75% MVC and plateauing to 100%. MPF decreased with increasing force to 75% MVC. In dynamic condition, RMSMMG exhibited higher sensitivity to changes in load than RMSEMG. These results confirm the feasibility of MMG measurements to be used during functional activities outside the laboratory. It opens new perspectives for future applications in sports science, ergonomics and human–machine interface conception

Reliability and sensitivity of MMG and EMG signals during isometric contractions of upper limb muscles

International audienc