Comparative Analysis of a Series of pH‐Responsive Sulphonated Europium Complexes for Bioassays Monitoring Acidification

The synthesis and photophysical evaluation of a series of hydrophilic sulphonated and pH responsive luminescent europium(III) probes are reported. The Eu emission intensities and lifetimes increase very significantly on lowering pH, leading to a ‘switching on’ of Eu luminescence in more acidic media. By varying the nature of the substituents at an integral aniline nitrogen atom located in the sensitising chromophore, the pKa value of the complex can be tuned to between 4.3 and 6.3 for a set of five Eu(III) complexes. These systems are designed to allow conjugation to targeting vectors permitting, for example, the monitoring of receptor internalisation in cells. This approach can be used to tag proteins selectively and allows the monitoring of uptake into acidic organelles, enabling the creation of time-resolved internalisation assays to follow pH change in real time, both in vitro and in cellulo

Unlocking same‐sign CPL: solvent effects on spectral form and racemisation kinetics in nine‐coordinate chiral europium(III) complexes

Understanding the factors that shape the circularly polarised luminescence (CPL) emission profiles of europium(III)-based CPL emitters to have specific sign properties, e. g. monosignate individual CPL transitions, is key to design novel complexes for applications ranging from advanced security inks to bio-probes for live cell imaging. In order to correlate structure and spectral characteristics, a photophysical and kinetic investigation has been conducted on a series of coordinatively saturated nine-coordinate europium(III) systems based on 1,4,7-triazacyclononane. We highlight that lanthanide emission is sensitive to changes in the ligand field by showing the linear dependence of total emission intensity ratios as a function of solvent polarity, for europium(III) complexes displaying an internal charge transfer (ICT) excited state. This sensitivity increases by a factor of 20 when studying changes in CPL spectra, rendering these complexes accurate probes of local polarity. Solvent polarity, solvent-specific effects, and the nature of the chromophores’ coordinating donor atoms strongly influence the kinetic stability of europium(III) complexes with respect to enantiomer interconversion. Notably, we show that the choice of donor groups to coordinating to europium(III) and the nature and polarity of the solvent affects the rate of racemisation, leading to systems with very long half-lives at room temperature in non-polar media

Designing biodegradable alternatives to commodity polymers

The development and widespread adoption of commodity polymers changed societal landscapes on a global scale. Without the everyday materials used in packaging, textiles, construction and medicine, our lives would be unrecognisable. Through decades of use, however, the environmental impact of waste plastics has become grimly apparent, leading to sustained pressure from environmentalists, consumers and scientists to deliver replacement materials. The need to reduce the environmental impact of commodity polymers is beyond question, yet the reality of replacing these ubiquitous materials with sustainable alternatives is complex. In this tutorial review, we will explore the concepts of sustainable design and biodegradability, as applied to the design of synthetic polymers intended for use at scale. We will provide an overview of the potential biodegradation pathways available to polymers in different environments, and highlight the importance of considering these pathways when designing new materials. We will identify gaps in our collective understanding of the production, use and fate of biodegradable polymers: from identifying appropriate feedstock materials, to considering changes needed to production and recycling practices, and to improving our understanding of the environmental fate of the materials we produce. We will discuss the current standard methods for the determination of biodegradability, where lengthy experimental timescales often frustrate the development of new materials, and highlight the need to develop better tools and models to assess the degradation rate of polymers in different environments

Comparative analysis of lanthanide excited state quenching by electronic energy and electron transfer processes

The relative sensitivities of structurally related Eu(III) complexes to quenching by electron and energy transfer processes have been compared. In two sets of 9-coordinate complexes based on 1,4,7-triazacyclononane, the Eu emission lifetime decreased as the number of conjugated sensitising groups and the number of unbound ligand N atoms increased, consistent with photoinduced electron transfer to the excited Eu(III) ion that is suppressed by N-protonation. Quenching of the Eu 5D0 excited state may also occur by electronic energy transfer, and the quenching of a variety of 9-coordinate complexes by a cyanine dye with optimal spectral overlap occurs by an efficient FRET process, defined by a Förster radius (R0) value of 68 Å and characterised by second rate constants in the order of 109 M−1 s−1; these values were insensitive to changes in the ligand structure and to the overall complex hydrophilicity. Quenching of the Eu and Tb excited states by energy transfer to Mn(II) and Cu(II) aqua ions occurred over much shorter distances, with rate constants of around 106 M−1 s−1, owing to the much lower spectral overlap integral. The calculated R0 values were estimated to be between 2.5 to 4 Å in the former case, suggesting the presence of a Dexter energy transfer mechanism that requires much closer contact, consistent with the enhanced sensitivity of the rate of quenching to the degree of steric shielding of the lanthanide ion provided by the ligand

Field-domain rapid-scan EPR at 240GHz for studies of protein functional dynamics at room temperature.

We present field-domain rapid-scan (RS) electron paramagnetic resonance (EPR) at 8.6T and 240GHz. To enable this technique, we upgraded a home-built EPR spectrometer with an FPGA-enabled digitizer and real-time processing software. The software leverages the Hilbert transform to recover the in-phase (I) and quadrature (Q) channels, and therefore the raw absorptive and dispersive signals, χ and χ , from their combined magnitude (I +Q ). Averaging a magnitude is simpler than real-time coherent averaging and has the added benefit of permitting long-timescale signal averaging (up to at least 2.5×10 scans) because it eliminates the effects of source-receiver phase drift. Our rapid-scan (RS) EPR provides a signal-to-noise ratio that is approximately twice that of continuous wave (CW) EPR under the same experimental conditions, after scaling by the square root of acquisition time. We apply our RS EPR as an extension of the recently reported time-resolved Gd-Gd EPR (TiGGER) [Maity et al., 2023], which is able to monitor inter-residue distance changes during the photocycle of a photoresponsive protein through changes in the Gd-Gd dipolar couplings. RS, opposed to CW, returns field-swept spectra as a function of time with 10ms time resolution, and thus, adds a second dimension to the static field transients recorded by TiGGER. We were able to use RS TiGGER to track time-dependent and temperature-dependent kinetics of AsLOV2, a light-activated phototropin domain found in oats. The results presented here combine the benefits of RS EPR with the improved spectral resolution and sensitivity of Gd chelates at high magnetic fields. In the future, field-domain RS EPR at high magnetic fields may enable studies of other real-time kinetic processes with time resolutions that are otherwise difficult to access in the solution state. [Abstract copyright: Published by Elsevier Inc.

A GIANT LY alpha NEBULA IN THE CORE OF AN X-RAY CLUSTER AT Z=1.99 : IMPLICATIONS FOR EARLY ENERGY INJECTION

We present the discovery of a giant >= 100 kpc Ly alpha nebula detected in the core of the X-ray emitting cluster CL J1449 +0856 at z = 1.99 through Keck/LRIS narrow-band imaging. This detection extends the known relation between Lya nebulae and overdense regions of the universe to the dense core of a 5-7 x 10(13) M-circle dot cluster. The most plausible candidates to power the nebula are two Chandra-detected AGN host cluster members, while cooling from the X-ray phase and cosmological cold flows are disfavored primarily because of the high Ly alpha to X-ray luminosity ratio (L-Ly alpha/L-X approximate to 0.3, greater than or similar to 10-1000 times. higher than in local cool-core clusters) and by current modeling. Given the physical conditions of the Ly alpha-emitting gas and the possible interplay with the X-ray phase, we argue that the Ly alpha nebula would be short-lived (less than or similar to 10 Myr) if not continuously replenished with cold gas at a rate of greater than or similar to 1000 M-circle dot yr(-1). We investigate the possibility that cluster galaxies supply the required gas through outflows and we show that their total mass outflow rate matches the replenishment necessary to sustain the nebula. This scenario directly implies the extraction of energy from galaxies and its deposition in the surrounding intracluster medium (ICM), as required to explain the thermodynamic properties of local clusters. We estimate an energy injection of the order of approximate to 2 keV per particle in the ICM over a 2 Gyr interval. In our baseline calculation, AGNs provide up to 85% of the injected energy and two-thirds. of the mass, while the rest is supplied by supernovae-driven winds.Peer reviewe

Synthesis, photophysical properties and biomolecule labelling using luminescent lanthanide complexes

Ce travail de thèse a consisté en la synthèse multi-étape et convergente de nouveaux marqueurs luminescents à base d'ions lanthanides possédant une antenne de type 2,6-bispyrazol-1-yl-pyridine et des bras chélatants iminodiacetates. La première partie duThe aim of this thesis was the multi-step synthesis of new luminescent dyes based on lanthanide ions with a core based on 2,6-bispyrazol-1-yl-pyridine and chelating arms such as iminodiacetate. The first part of this project was the synthesis of ligands

Le nettoyage en place dans l'industrie pharmaceutique (approche globale et principes de validation)

STRASBOURG ILLKIRCH-Pharmacie (672182101) / SudocSudocFranceF