Toward Opto-Structural Correlation to Investigate Luminescence Thermometry in an Organometallic Eu(II) Complex

Lanthanide-based luminescent materials have unique properties and are well-studied for many potential applications. In particular, the characteristic 5d → 4f emission of divalent lanthanide ions such as EuII allows for tunability of the emissive properties via modulation of the coordination environment. We report the synthesis and photoluminescence investigation of pentamethylcyclopentadienyleuropium(II) tetrahydroborate bis(tetrahydrofuran) dimer (1), the first example of an organometallic, discrete molecular EuII band-shift luminescence thermometer. Complex 1 exhibits an absolute sensitivity of 8.2 cm–1 K–1 at 320 K, the highest thus far observed for a lanthanide-based band-shift thermometer. Opto-structural correlation via variable-temperature single-crystal X-ray diffraction and fluorescence spectroscopy allows rationalization of the remarkable thermometric luminescence of complex 1 and reveals the significant potential of molecular EuII compounds in luminescence thermometry.</p

Classical Ising model test for quantum circuits

We exploit a recently constructed mapping between quantum circuits and graphs in order to prove that circuits corresponding to certain planar graphs can be efficiently simulated classically. The proof uses an expression for the Ising model partition function in terms of quadratically signed weight enumerators (QWGTs), which are polynomials that arise naturally in an expansion of quantum circuits in terms of rotations involving Pauli matrices. We combine this expression with a known efficient classical algorithm for the Ising partition function of any planar graph in the absence of an external magnetic field, and the Robertson-Seymour theorem from graph theory. We give as an example a set of quantum circuits with a small number of non-nearest neighbor gates which admit an efficient classical simulation.Comment: 17 pages, 2 figures. v2: main result strengthened by removing oracular settin

Highly Durable Nanoporous Cu2–xS Films for Efficient Hydrogen Evolution Electrocatalysis under Mild pH Conditions

Copper-based hydrogen evolution electrocatalysts are promising materials to scale-up hydrogen production due to their reported high current densities; however, electrode durability remains a challenge. Here, we report a facile, cost-effective, and scalable synthetic route to produce Cu2–xS electrocatalysts, exhibiting hydrogen evolution rates that increase for ∼1 month of operation. Our Cu2–xS electrodes reach a state-of-the-art performance of ∼400 mA cm–2 at −1 V vs RHE under mild conditions (pH 8.6), with almost 100% Faradaic efficiency for hydrogen evolution. The rise in current density was found to scale with the electrode electrochemically active surface area. The increased performance of our Cu2–xS electrodes correlates with a decrease in the Tafel slope, while analyses by X-ray photoemission spectroscopy, operando X-ray diffraction, and in situ spectroelectrochemistry cooperatively revealed the Cu-centered nature of the catalytically active species. These results allowed us to increase fundamental understanding of heterogeneous electrocatalyst transformation and consequent structure–activity relationship. This facile synthesis of highly durable and efficient Cu2–xS electrocatalysts enables the development of competitive electrodes for hydrogen evolution under mild pH conditions.Funding for open access charge: CRUE-Universitat Jaume IICN2 acknowledges funding from Generalitat de Catalunya 2021SGR00457. This study is part of the Advanced Materials programme and supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1), Generalitat de Catalunya, and the Basque Government (grant IT1591-22). The authors thank the support from the projects (RED2022-134508-T, PID2020-116093RB-C41, PID2020-116093RB-C43, and PID2020-116093RB-C44) funded by MCIN/AEI/10.13039/501100011033/ and the project TED2021-129999A-C33 financed by MCIN/AEI/10.13039/501100011033 and European Union NextGenerationEU/PRTR. C.A.M. acknowledges funding from UJI postdoc fellowship POSDOC/2019/20, the Generalitat Valenciana for the APOSTD/2021/251 fellowship, and to MinCiencias Colombia through the Fondo Nacional de Financiamiento para la Ciencia, la Tecnología y la Innovación “Francisco José de Caldas”, call 848-2019. ICN2 is supported by the Severo Ochoa program from Spanish MCIN/AEI (Grant No.: CEX2021-001214-S) and is funded by the CERCA Programme/Generalitat de Catalunya. M.C.S. has received funding from the post-doctoral fellowship Juan de la Cierva Incorporation from MICINN (JCI-2019) and the Severo Ochoa programme. S.B. acknowledges grant RYC-2017-21931 funded by MCIN/AEI/10.13039/501100011033 and by ESF Investing in Your Future, EUR2020-112066 funded by MCIN/AEI /10.13039/501100011033 and by European Union NextGenerationEU/PRTR, and UPV/EHU project EHUrOPE19/01. J.R. acknowledges the Czech Science Foundation and funding from PIF outgoing project number 22-18079O

Target cell-specific synaptic dynamics of excitatory to inhibitory neuron connections in supragranular layers of human neocortex.

Rodent studies have demonstrated that synaptic dynamics from excitatory to inhibitory neuron types are often dependent on the target cell type. However, these target cell-specific properties have not been well investigated in human cortex, where there are major technical challenges in reliably obtaining healthy tissue, conducting multiple patch-clamp recordings on inhibitory cell types, and identifying those cell types. Here, we take advantage of newly developed methods for human neurosurgical tissue analysis with multiple patch-clamp recordings, post-hoc fluorescent in situ hybridization (FISH), machine learning-based cell type classification and prospective GABAergic AAV-based labeling to investigate synaptic properties between pyramidal neurons and PVALB- vs. SST-positive interneurons. We find that there are robust molecular differences in synapse-associated genes between these neuron types, and that individual presynaptic pyramidal neurons evoke postsynaptic responses with heterogeneous synaptic dynamics in different postsynaptic cell types. Using molecular identification with FISH and classifiers based on transcriptomically identified PVALB neurons analyzed by Patch-seq, we find that PVALB neurons typically show depressing synaptic characteristics, whereas other interneuron types including SST-positive neurons show facilitating characteristics. Together, these data support the existence of target cell-specific synaptic properties in human cortex that are similar to rodent, thereby indicating evolutionary conservation of local circuit connectivity motifs from excitatory to inhibitory neurons and their synaptic dynamics

Copying you copying me:Interpersonal motor co-ordination influences automatic imitation

Moving in a co-ordinated fashion with another individual changes our behaviour towards them; we tend to like them more, find them more attractive, and are more willing to co-operate with them. It is generally assumed that this effect on behaviour results from alterations in representations of self and others. Specifically, through neurophysiological perception-action matching mechanisms, interpersonal motor co-ordination (IMC) is believed to forge a neural coupling between actor and observer, which serves to blur boundaries in conceptual self-other representations and causes positive views of the self to be projected onto others. An investigation into this potential neural mechanism is lacking, however. Moreover, the specific components of IMC that might influence this mechanism have not yet been specified. In the present study we exploited a robust behavioural phenomenon - automatic imitation - to assess the degree to which IMC influences neural action observation-execution matching mechanisms. This revealed that automatic imitation is reduced when the actions of another individual are perceived to be synchronised in time, but are spatially incongruent, with our own. We interpret our findings as evidence that IMC does indeed exert an effect on neural perception-action matching mechanisms, but this serves to promote better self-other distinction. Our findings demonstrate that further investigation is required to understand the complex relationship between neural perception-action coupling, conceptual self-other representations, and social behaviour

Toward Opto-Structural Correlation to Investigate Luminescence Thermometry in an Organometallic Eu(II) Complex

Lanthanide-based luminescent materials have unique properties and are well-studied for many potential applications. In particular, the characteristic 5d → 4f emission of divalent lanthanide ions such as EuII allows for tunability of the emissive properties via modulation of the coordination environment. We report the synthesis and photoluminescence investigation of pentamethylcyclopentadienyleuropium(II) tetrahydroborate bis(tetrahydrofuran) dimer (1), the first example of an organometallic, discrete molecular EuII band-shift luminescence thermometer. Complex 1 exhibits an absolute sensitivity of 8.2 cm–1 K–1 at 320 K, the highest thus far observed for a lanthanide-based band-shift thermometer. Opto-structural correlation via variable-temperature single-crystal X-ray diffraction and fluorescence spectroscopy allows rationalization of the remarkable thermometric luminescence of complex 1 and reveals the significant potential of molecular EuII compounds in luminescence thermometry.</p

Diimine Triscarbonyl Re(I) of Isomeric Pyridyl-fulvene Ligands: an Electrochemical, Spectroscopic, and Computational Investigation

The synthesis and characterization of a novel family of positively charged <i>fac</i>-[Re­(bpy)­(CO)₃(<b>L</b>)]­PF₆ (bpy = 2,2′-bipyridine) complexes are reported, where <b>L</b> is a pyridine functionalized in <i>para</i> or <i>meta</i> position with a fulvene moiety, namely, 4-fluoren-9-ylidenemethyl-pyridine (<i><b>p</b></i><b>Fpy</b>) and 3-fluoren-9-ylidenemethyl-pyridine (<i><b>m</b></i><b>Fpy</b>). The complexes were prepared in high yield (86%) by direct addition at room temperature of the corresponding pyridine to the tetrahydrofuran (THF) adduct <i>fac</i>-[Re­(bpy)­(CO)₃(THF)]­[PF₆] precursor. Both ligand and complex structures were fully characterized by a variety of techniques including X-ray crystallography. The complexes did not exhibit the expected triplet mixed metal–ligand-to-ligand charge transfer (MLLCT) emission, because of its deactivation by the non-emissive triplet excited state of fulvene. The absorption profile shows that the MLLCT is overshadowed by the fulvene centered π–π* transition of higher molar absorptivity as shown by time dependent density functional theory (TD-DFT) calculations. The position of the fulvene on the pyridyl ring has a large effect on this transition, the <i>para</i> position displaying a much higher absorption coefficient (21.3 × 10³ M^–1 cm^–1) at lower energy (364 nm) than the meta position (331 nm, 16.0 × 10³ M^–1 cm^–1

Canadian Coastal Sediment Study - Final Report of the Steering Committee.

NRC publication: Ye