Plutonium (Pu) is a chemically and radiologically toxic element, primarily of anthropogenic origin. Reagents that specifically sequester Pu have been developed in the frame of nuclear waste processing and storage. Other potential applications of Pu chelators are in vivo decorporation and environmental remediation. Although the medical application has been addressed for a long time by the development of Pu-specific binders, studies concerning the environmental application are scarce. A desferrioxamine-B ([(DFO)H4]+)-derived tetrahydroxamate chelator, 1H4, which was originally designed for the sequestration of Zr4+ for 89Zr-ImmunoPET applications, was grafted on a commercial hydrophilic resin, CM Sephadex C-25 (R). The resin beads were subsequently embedded in an agarose gel, and the resulting material was used for the extraction of 238Pu(iv) from dilute aqueous solutions at pH 6.5. Comparison of the results with those obtained using the commercial Chelex (R)-100 resin and the H3DFO-based CM Sephadex C-25 (R) extracting materials showed that Pu was more strongly bound to the 1H4-functionalized resin than to Chelex (R)-100 and the H3DFO-based resins, which confirms that the tetrahydroxamate chelator 14- forms a more stable Pu(iv) complex than the trihydroxamate DFO3- siderophore. The fabricated material could be considered in the development of diffusive gradients in thin-films (DGT) devices for the environmental monitoring of Pu.

We report herein the synthesis and full spectroscopic characterization of two A2B-corrole phosphonic acids. Thanks to the presence of a phosphonic acid functional group at the 10-meso-position, the corroles were covalently linked to the hexanuclear Zr clusters of a PCN-222 metal-organic framework (MOF). After the insertion of cobalt into the corrole macrocycle, the metal complexes are able to bind small volatile molecules such as carbon monoxide (CO). Interestingly, the resulting doped porous materials were used for selective detection of CO, with excellent selectivity for CO vs. CO2, N2, and O2.

Two 3D MOFs based on triphenylcorrole and its cobalt-metalated analog (CoCorr-MOF) are presented. They show a hexagonal structure, a homogeneous particle size, and microporosity with a specific area of 390 and 304 m2 g-1, respectively. The CoCorr-MOF presents a better affinity for CO than for other interferents (N2, CO2 and O2), demonstrating a CO chemisorption capacity of 7.2 cm3 g-1 with high selectivity.

89Zr-immunoPET is a hot topic as 89Zr cumulates the advantages of 64Cu and 124I without their drawbacks. We report the synthesis of a model ligand of a chiral bioconjugable tetrahydroxamic chelator combining the desferriferrioxamine B siderophore and 1-hydroxy-2-piperidone ((PIPO)H), a chiral cyclic hydroxamic acid derivative, and the study by NMR spectroscopy of its zirconium complex. Nuclear Overhauser effect measurements (ROESY) indicated that the complex exists in the form of two diastereomers, in 77 : 23 ratio, resulting from the combination of the central chiralities at the 3-C of the (PIPO)H component and at the Zr4+ cation. The 44 lowest energy structures out of more than 1000 configurations/conformations returned by calculations based on density functional theory were examined. Comparison of the ROESY data and the calculated interatomic H⋅⋅⋅H distances allowed us to select the most probable configuration and conformations of the major complex.

The high risk of CO poisoning justifies the need for indoor air quality control and warning systems based on the detection of low concentrations (ppm‐ppb) of CO. Cobalt corrole complexes selectively bind CO vs. O2, CO2, N2, opening new fields of applications. By combining the CO chemisorption properties of cobalt corroles with the known sorption capacity of MOFs, we hope to obtain high performance sensing materials for CO detection. In addition, the exposed metal sites of MOFs lead to CO2 physisorption, allowing the co‐detection of CO and CO2. In this work, PCN‐222 a stable Zr‐based MOF made from Ni(TCPP) with natural vacancies has been used as a porous matrix for the grafting of electron‐poor metallocorroles. The materials were characterized by powder XRD, SEM and optical microscopy, BET analyses and gas adsorption measurements at 298 K. No degradation of the crystalline structure of PCN‐222 was observed. At 1 atm, the adsorbed CO(g) volumes measured for the best materials were 12.15 cm3 g‐1 and 14.01 cm3 g‐1 for CoCorr2@PCN‐222 and CoCorr3@PCN‐222 respectively, and both materials exhibited high CO chemisorption and selectivity against O2, N2, and CO2 at low pressure due to the highest energy of the chemisorption process vs physisorption. (198 Words)

In the present work, the synthesis, characterization, and gas adsorption properties of new 2D covalent organic framework (COF) (2D-COF-Cor) and 3D COF (3D-COF-Cor) based on corrole macrocycles are reported. The two COFs have been synthesized by Schiff base condensation from readily available C-3-symmetric aldehyde or Td-symmetric aldehyde as platforms, and diamine-functionalized free-base corrole as building block linker, to access 2D and 3D polymers, respectively. Cobalt-metalated COFs were also synthesized using a post-metalation procedure to give 2D-COF-CorCo and 3D-COF-CorCo as porous materials. The design of the 2D and 3D structures of the materials are reported, as well as the relationship between their structure and their performances for carbon monoxide (CO) adsorption. Spectroscopy analyses such as H-1 NMR, Fourier-Transform InfraRed (FTIR), powder X-ray diffraction, microscopic analyses, and sorption measurements were used to fully characterize the structure and the porosity of the COF materials. Their properties for capture and sensing of CO were also studied with the analysis of their isotherms using a multisite Langmuir isotherm model and the Ideal Adsorbed Solution Theory (IAST) theory. The affinity, capacity and selectivity of these materials for CO sorption were calculated. Compared to 3D-COF-CorCo, 2D-COF-CorCo reveals the highest adsorption capacity of 32.2 cm(3)/g for CO (298 K, 1 atm) with a high selectivity over N-2, O-2, CO2, up to 50, 130, 5090, 3170, respectively. In addition, FTIR analysis gave clear evidence of the involved solid-gas interactions, and the reversibility of CO binding on the cobalt metal center of the corrole within the materials. These results point out an appealing way of using cobalt corrole-based COF as efficient chemosensors to detect trace amounts of CO. (c) 2022 Elsevier Ltd. All rights reserved.

We report here a complete study of coordination of the 5-aminomethyl-[13] aneN 4 ligand by three metals: Cu(II), Ni(II) and Cr(III) in order to determine the effect of the C-functionalization of the macrocycle on the stability of the metal complexes even if we change the size of the metal used.The results obtained by spectrometry, EPR and X-ray of the metal complexes showed that the copper is pentacoordinate in square-based pyramidal environment, but the chromium and nickel complexes are hexacoordinated in octahedral geometry.In all metal complexes, the coordination of the nitrogen atom is observed in the primary amine function.

Visual Abstract 227Th is a promising radioisotope for targeted α-particle therapy. It produces 5 α-particles through its decay, with the clinically approved 223Ra as its first daughter. There is an ample supply of 227Th, allowing for clinical use; however, the chemical challenges of chelating this large tetravalent f-block cation are considerable. Using the CD20-targeting antibody ofatumumab, we evaluated chelation of 227Th4+ for α-particle–emitting and radiotheranostic applications. Methods: We compared 4 bifunctional chelators for thorium radiopharmaceutical preparation: S-2-(4-Isothiocyanatobenzyl)-1,4,7,10-tetraazacyclododecane tetraacetic acid (p-SCN-Bn-DOTA), 2-(4-isothicyanatobenzyl)-1,2,7,10,13-hexaazacyclooctadecane-1,4,7,10,13,16-hexaacetic acid (p-SCN-Bn-HEHA), p-isothiacyanatophenyl-1-hydroxy-2-oxopiperidine-desferrioxamine (DFOcyclo*-p-Phe-NCS), and macrocyclic 1,2-HOPO N-hydroxysuccinimide (L804-NHS). Immunoconstructs were evaluated for yield, purity, and stability in vitro and in vivo. Tumor targeting of the lead 227Th-labeled compound in vivo was performed in CD20-expressing models and compared with a companion 89Zr-labeled PET agent. Results: 227Th-labeled ofatumumab-chelator constructs were synthesized to a radiochemical purity of more than 95%, excepting HEHA. 227Th-HEHA-ofatumumab showed moderate in vitro stability. 227Th-DFOcyclo*-ofatumumab presented excellent 227Th labeling efficiency; however, high liver and spleen uptake was revealed in vivo, indicative of aggregation. 227Th-DOTA-ofatumumab labeled poorly, yielding no more than 5%, with low specific activity (0.08 GBq/g) and modest long-term in vitro stability (<80%). 227Th-L804-ofatumumab coordinated 227Th rapidly and efficiently at high yields, purity, and specific activity (8 GBq/g) and demonstrated extended stability. In vivo tumor targeting confirmed the utility of this chelator, and the diagnostic analog, 89Zr-L804-ofatumumab, showed organ distribution matching that of 227Th to delineate SU-DHL-6 tumors. Conclusion: Commercially available and novel chelators for 227Th showed a range of performances. The L804 chelator can be used with potent radiotheranostic capabilities for 89Zr/227Th quantitative imaging and α-particle therapy.

DFO@Purolite resin efficiently sorbs Fe( iii ) and Zr( iv ) above pH 1. The Gibbs–Donnan model enabled to determine the stoichiometry and stability of the complexes formed in the solid phase and to predict the sorption behaviour of the material.

A novel cobalt corrole bearing 4-vinylphenyl groups at the 5,10,15-meso-positions of the macrocycle has been synthesized from tris(4-bromophenyl)corrole using a Suzuki coupling reaction. The spectral and electrochemical properties are reported in CH2Cl2 along with its ability to form a highly stable six-coordinate complex and cross-linked corrole-based polymer in a 59% yield.

Four cationic amidotitanocene complexes [Cp2Ti(NRR ')]-[B(C6F5)4] (Cp = eta 5-C5H5; 1a: R = R ' = p-anisyl; 1b: R = p-fluorophenyl, R ' = p-anisyl; 1c: R = p-fluorophenyl, R ' = phenyl; 1d: R = phenyl, R ' = 2-pyridyl) were synthesized. Complexes 1a-d undergo Ti-N bond homolysis under visible light irradiation. Complexes 1a-c catalyze the polymerization of phenylsilane to yield branched polysilane polymers with molecular weights (Mw) up to approximately 3000 and dispersity indexes (D) of 1.4-1.6. Previously reported Group 4 cationic amidometallocene complexes [Cp2Ti(NPh2)][B(C6F5)4] (Ia) and Cp2Zr(NPh2)][MeB-(C6F5)3] (IIa) were also tested in the hydrosilylation of carbonyl com-pounds with triethylsilane (Et3SiH). In some cases, complex Ia afforded completely reduced products (e.g., ethylbenzene from acetophenone), while IIa was generally more selective (e.g., (1-phenylethoxy)-triethylsilane from acetophenone) but also more active. Complex IIa could also convert anisole derivatives to phenoxysilanes with high efficiency (TON = 2000).

During the last decades, the potential impact of indoor air quality on human health has stimulated an interest in hazardous compounds survey, such as carbon monoxide (CO). The detection of these compounds has consequently become a vital need. To address this issue, we propose a Surface Acoustic Wave (SAW) device functionalized with metallocorroles used for the selective detection of CO. Here, we insist on the necessity to detect CO in the presence of interferents, such as O2 that is obviously present in the air, carbon dioxide (CO2) present in significant quantity in urban area (400 ppm) and humidity (H2O) which is a well-known interferent in the case of SAW-based gas sensors. We will report on the interest of a differential configuration of the sensor that takes advantage of accurate organic layers, to improve the stability of the sensor’s signal and lower the sensitivity to interferents. Acknowledgments: this work was supported by the PIA-Excellence ISITE-BFC (CoMICS program 2019-2022: Chemistry of Molecular Interactions - Catalysis and Sensors) and the ISITE CO2DECIN. REFERENCES: [1] Di Natale, C.; Gros, C. P.; Paolesse, R., Chem. Soc. Rev. 2022, 000;[2] J.-M. Barbe, G. Canard, S. Brandès, F. Jerôme, G. Dubois, R. Guilard, Dalton Trans. 2004, 1208-1214; [3] Vanotti, M.; Poisson, S.; Soumann, V.; Quesneau, V.; Brandes, S.; Desbois, N.; Yang, J.; Andre, L.; Gros, C. P.; Blondeau-Patissier, V., Sensors and Actuators B: Chemical 2021, (332), 129507. [4] S. Brandès, V. Quesneau, O. Fonquernie, N. Desbois, V. Blondeau-Patissier, C. P. Gros, Dalton Trans. 2019, 48, 11651-11662 (Front Cover). Fig. 1.Double delay line SAW-based CO sensor (left) and Open-loop phase measurement (Right) Figure 1

Detection of carbon monoxide (CO) at few ppm levels is a critical point for quality control of domestic and industrial environment. CO is responsible for thousands of intoxications and hundreds of deaths per year in the world. Moreover, CO is a residual gas found in the industrial dihydrogen used for Proton Exchange Membrane fuel cell, and deactivates the fuel cell prematurely. Corroles have been largely used in sensing applications.[1] Cobalt corroles display high binding affinity for carbon monoxide even in the presence of nitrogen and dioxygen.[2] The affinity of the Co(III) metallocorroles for CO is directly correlated with the Lewis acid character of the metal center. The electrochemistry and spectro-electrochemistry properties have been studied. We have shown that structural modifications on the aromatic ring have a direct influence on the reactivity of the metal complex. We have recently obtained very low CO detection level (ppm) using SAW devices functionalized by cobalt corrole deposited as a film on a silica or a gold surface.[3] Our previous work on the synthesis of porous sol-gel materials functionalized by cobalt corroles gave us encouraging results for CO sorption and detection and prompted us to prepare new porous structured materials functionalized by corrole complexes for gas detection applications. Among all the methods of synthesis of porous architectures, organic materials belonging to the POP (Porous Organic Polymer) family are an appealing and original approach in this research field.[4] The synthesis of new POPs functionalized by cobalt corroles (Fig. 1) will be reported. Their selective sorption properties for CO over N2, O2 and CO2 will be also presented. Preliminary results concerning the design of Molecularly Imprinted Polymers (MIPS) as enzyme mimics for the decontamination of a broad spectrum of pesticides and chemical warfare agents will be also reported. Authors would like to acknowledge the ANR program (MIPEnz-Decontam, 20-CE39-0016-01), the FEDER and the “Région Bourgogne” for financial support (ISITE CO2DECIN) REFERENCES: [1] Di Natale, C.; Gros, C. P.; Paolesse, R., Chem. Soc. Rev. 2022, 000;[2] J.-M. Barbe, G. Canard, S. Brandès, F. Jerôme, G. Dubois, R. Guilard, Dalton Trans. 2004, 1208-1214; [3] Vanotti, M.; Poisson, S.; Soumann, V.; Quesneau, V.; Brandes, S.; Desbois, N.; Yang, J.; Andre, L.; Gros, C. P.; Blondeau-Patissier, V., Sensors and Actuators B: Chemical 2021, (332), 129507. [4] S. Brandès, V. Quesneau, O. Fonquernie, N. Desbois, V. Blondeau-Patissier, C. P. Gros, Dalton Trans. 2019, 48, 11651-11662 (Front Cover). Figure 1

Our laboratories have long been interested in the redox properties of four-, five- and six-coordinate metallocorroles (Chart 1) with different donor axial ligands and a variety of peripheral corrole substituents. In this work, we describe and compare our most recent results on different transition metal derivatives containing highly electron withdrawing substituents at the meso-positions of the macrocycle. Figure 1

Five isostructural microporous supramolecular architectures prepared by H-bonded assembly between the hexa-anionic complex [Zr-2(Ox)(7)](6-) (Ox=oxalate, (C2O4)(2-)) and tripodal cations (H-3-TripCH(2)-R)(3+) with R=H, CH3, OH and OBn (Bn=CH2Ph) are reported. The possibility to obtain the same structure using a mixture of tripodal cations with different R group (R=OH and R=CH3) has also been successfully explored, providing a unique example of three-component H-bonded porous framework. The resulting SPA-1(R) materials feature 1D pores decorated by R groups, with apparent pore diameters ranging from 3.0 to 8.5 angstrom. Influence of R groups on the sorption properties of these materials is evidenced through CO2 and H2O vapor sorption/desorption experiments, as well as with I-2 capture/release experiments in liquid media. This study is one of the first to demonstrate the possibility of tuning the porosity and exerting precise control over the chemical functionalization of the pores in a given H-bonded structure, without modifying the topology of the reference structure, and thus finely adjusting the sorption characteristics of the material.

A reusable sensor based on a phosphonate-substituted Ru(ii) complex allows for selective detection as low as 10−13M of Cu2+ions in aqueous solutions.