Fast reproducible identification and large-scale databasing of individual functional cognitive networks

Background  

Although cognitive processes such as reading and calculation are associated with reproducible cerebral networks, inter-individual variability is considerable. Understanding the origins of this variability will require the elaboration of large multimodal databases compiling behavioral, anatomical, genetic and functional neuroimaging data over hundreds of subjects. With this goal in mind, we designed a simple and fast acquisition procedure based on a 5-minute functional magnetic resonance imaging (fMRI) sequence that can be run as easily and as systematically as an anatomical scan, and is therefore used in every subject undergoing fMRI in our laboratory. This protocol captures the cerebral bases of auditory and visual perception, motor actions, reading, language comprehension and mental calculation at an individual level.     

CORSICA: correction of structured noise in fMRI by automatic identification of ICA components

When applied to functional magnetic resonance imaging (fMRI) data, spatial independent component analysis (sICA), a data-driven technique that addresses the blind source separation problem, seems able to extract components specifically related to physiological noise and brain movements. These components should be removed from the data to achieve structured noise reduction and improve any subsequent detection and analysis of signal fluctuations related to neural activity. We propose a new automatic method called CORSICA (CORrection of Structured noise using spatial Independent Component Analysis) to identify the components related to physiological noise, using prior information on the spatial localization of the main physiological fluctuations in fMRI data. As opposed to existing spectral priors, which may be subject to aliasing effects for long-TR data sets (typically acquired with TR >1 s), such spatial priors can be applied to fMRI data, regardless of the TR of the acquisitions. By comparing the proposed automatic selection to a manual selection performed visually by a human operator, we first show that CORSICA is able to identify the noise-related components for long-TR data with a high sensitivity and a specificity of 1. On short-TR data sets, we validate that the proposed method of noise reduction allows a substantial improvement of the signal-to-noise ratio evaluated at the cardiac and respiratory frequencies, even in the gray matter, while preserving the main fluctuations related to neural activity.     

Functionalized Graphene as a Gatekeeper for Chiral Molecules: An Alternative Concept for Chiral Separation

We propose a new method of chiral separation using functionalized nanoporous graphene as an example. Computational simulations based on density functional theory show that the attachment of a suitable chiral “bouncer” molecule to the pore rim prevents the passage of the undesired enantiomer while letting its mirror image through.     

Protein Allostery at Atomic Resolution

Protein allostery is a phenomenon involving the long range coupling between two distal sites in a protein. In order to elucidate allostery at atomic resoluion on the ligand-binding WW domain of the enzyme Pin1, multistate structures were calculated from exact nuclear Overhauser effect (eNOE). In its free form, the protein undergoes a microsecond exchange between two states, one of which is predisposed to interact with its parent catalytic domain. In presence of the positive allosteric ligand, the equilibrium between the two states is shifted towards domain–domain interaction, suggesting a population shift model. In contrast, the allostery-suppressing ligand decouples the side-chain arrangement at the inter-domain interface thereby reducing the inter-domain interaction. As such, this mechanism is an example of dynamic allostery. The presented distinct modes of action highlight the power of the interplay between dynamics and function in the biological activity of proteins.     

Reversible Assembly of Microgels by Metallo-Supramolecular Chemistry

The combination of supramolecular chemistry and soft colloids as microgels represents an ambitious way to develop multi-versatile colloidal assemblies. Hereafter, terpyridine-functionalized poly(N-isopropylacrylamide) (PNiPAM) microgel building blocks are shown to undergo an assemble–freeze–disassemble process. The microgel assemblies, which are controlled by monitoring the attractive and repulsive potentials between the soft colloidal particles, are then frozen by forming inter-particle metal–terpyridine bis-complexes upon addition of the metallic cation (such as Fe^II, Co^II). By oxidation of the metal–terpyridine bis-complex links, the aggregates open up, which is due to the complex dissociation releasing the connected particles in the form of single microgels. We extended our work to the development of 1D filaments and 2D membranes materials made of soft particles connected via supramolecular chemistry.     

Taming the Reactivity of Phosphiranium Salts: Site-Selective C-Centered Ring Opening for Direct Synthesis of Phosphinoethylamines

Advances in the field of phosphorus chemistry are documented, by revealing the synthetic utility of previously underutilized quaternary phosphiranium salts (QPrS) as three-chain-atom electrophilic building blocks. Notably, control of their challenging C-centered electrophilicity is disclosed with an expedient synthesis of tertiary β-anilino phosphines as a proof-of-concept.     

Synthetic Organic Design for Solar Fuel Systems

From the understanding of biological processes and metalloenzymes to the development of inorganic catalysts, electro‐ and photocatalytic systems for fuel generation have evolved considerably during the last decades. Recently, organic and hybrid organic systems have emerged to challenge the classical inorganic structures through their enormous chemical diversity and modularity that led earlier to their success in organic (opto)electronics. This Minireview describes recent advances in the design of synthetic organic architectures and promising strategies toward (solar) fuel synthesis, highlighting progress on materials from organic ligands and chromophores to conjugated polymers and covalent organic frameworks.     

Gelatin‐Alginate Gels and Their Enzymatic Modifications: Controlling the Delivery of Small Molecules

The release of molecules entrapped within biogels is dictated by diffusion laws. Innovative biogel architectures are conceived and tested to control small molecule delivery from gelatin gels. The ionic interactions modulate the release of small molecules. Alginate is then added to gelatin gels and further hydrolyzed; the influence of viscosity is discussed. Next, various mixed gels are compared, such as a gelatin‐alginate IPN and the original architecture of an alginate gel entrapped in a gelatin gel with or without a polysaccharidase. The relative influence of ionic interactions and diffusional constraints on the delivery of small charged molecules is explored, and a solution for controlling diffusion is proposed for any situation.

     

Optimization of Hydrogen‐Evolving Photochemical Molecular Devices

A molecular photocatalyst consisting of a Ru^II photocenter, a tetrapyridophenazine bridging ligand, and a PtX₂ (X=Cl or I) moiety as the catalytic center functions as a stable system for light‐driven hydrogen production. The catalytic activity of this photochemical molecular device (PMD) is significantly enhanced by exchanging the terminal chlorides at the Pt center for iodide ligands. Ultrafast transient absorption spectroscopy shows that the intramolecular photophysics are not affected by this change. Additionally, the general catalytic behavior, that is, instant hydrogen formation, a constant turnover frequency, and stability are maintained. Unlike as observed for the Pd analogue, the presence of excess halide does not affect the hydrogen generation capacity of the PMD. The highly improved catalytic efficiency is explained by an increased electron density at the Pt catalytic center, this is confirmed by DFT studies.