13 research outputs found

    Hexadentate N,N,N’,N’-tetrapyrazolyl alkyl diamine metal complexes as scaffolds for bimetallic systems

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    Multielectron transformations are essential in the catalytic activity of many rare transition metals such as palladium-based catalysts. However, transposing this chemistry to more accessible and sustainable metals remains challenging as such elements tend to favor single-electron transfer. To overcome this limitation, placing two redox-active metal partners in close proximity can promote cooperative two-electron processes. Cooperativity is a key concept in chemistry, whereby multiple components work together to achieve a specific function. In particular, redox cooperativity refers to the facilitated transfer of multiple electrons involving several redox-active partners, i.e., multielectron transformations. Tetrapyrazole-based ligands represents a new class of ditopic hexadentate scaffolds, offering a tunable second coordination sphere through accessible N–H protons. Their ability to reversibly switch from pyrazole to pyrazolate donors allows control over metal redox properties and binding modes, paving the way for the formation of bimetallic complexes and the investigation of metal-metal redox cooperativity.(SC - Sciences) -- UCL, 202

    Towards the synthesis of ligands scaffold for cooperative bimetallic systems

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    Areas ranging from fine chemical synthesis to sustainable energy development rely on highly efficient metal-based catalysts to perform key chemical transformations [1]. Then metals such as Pd, Pt, Rh, Ir or Ru are used because they are proficient at mediating the multi-electron transfer steps required for these applications. In contrast to synthetic chemistry, biological systems do not use noble metals but rather employ cooperative reactivity between multiple redox sites [2]. These sites store and provide additional electrons to avoid unfavorable oxidation states at the reactive centers. Replicating this strategy of redox cooperativity in synthetic complexes could offer a valuable way to enhance the reactivity of base metal catalysts like iron, copper, etc. Such kind of systems have already been developed by Rauchfuss et al. to mimic Fe-Fe hydrogenase [3] and Bosnich and co-workers placed the basics for understanding bimetallic systems [4]. However, increase the comprehension of incorporating and controlling the additional redox centers is still a major challenge. Here, we planned to develop new bimetallic complexes where the two metals will be in a close proximity thanks to a ditopic ligand and then, to better understand the cooperativity between the metal centers and highlight the importance of the ligands design. Reference

    Towards the synthesis of ligand scaffold for bimetallic systems

    No full text
    Areas ranging from fine chemical synthesis to sustainable energy development rely on highly efficient metal-based catalysts to perform key chemical transformations [1]. Then metals such as Pd, Pt, Rh, Ir or Ru are used because they are proficient at mediating the multi-electron transfer steps required for these applications. In contrast to synthetic chemistry, biological systems do not use noble metals but rather employ cooperative reactivity between multiple redox sites [2]. These sites store and provide additional electrons to avoid unfavorable oxidation states at the reactive centers. However, these cooperative processes remain not well-known, specifically in multi-metallic systems [3]. Then, replicating this strategy of redox cooperativity in synthetic complexes could offer a valuable way to enhance the reactivity of first-row transition metals like iron, copper, etc. To address this challenge, our project seeks to develop and study the biomimetic strategy of incorporating metal-based electron reservoirs within the periphery of reactive metal centers. Thus, ditopic ligands able to interact with two metallic centers have been developed based on N,N,N’,N’-tetra(heterocyclic)propylene- and ethylene-diamines. Modifying the substituents on the heterocycles and the Bite angle may provide interesting properties to our bimetallic systems. For now, their monometallic counterparts have been synthesized and characterized through spectroscopic and electrochemical technics that brought promising results

    Ultra-Low Leakage ESD Protection Achieving 10.5 fA Leakage

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    A 310 nW Temperature Sensor Achieving 9.8 mK Resolution Using a DFLL-Based Readout Circuit

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    Biocatalytic synthesis of planar chiral macrocycles

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    Enzymes lock in planar chirality Molecules with very large rings—macrocycles—are often conformationally constrained, and some exhibit planar chirality when substituents of the ring cannot rotate freely. Restricted rotation is generally valued in macrocycles because it can hold the molecule in functional conformations. Using a well-established lipase enzyme, Gagnon et al. developed a synthesis of planar chiral macrocycles with handles that can be easily functionalized. Computational docking suggests how using an enzyme as the catalyst for sequential acylation reactions can impart the observed stereochemistry. Science , this issue p. 917 </jats:p

    Spinal cord compression caused by metastasis of a non-seminomatous testicular tumour with a predominant Yolk sac component in a 26-year-old man

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    Background: Pure testicular yolk sac tumours are extremely rare among adults, and there is no prior report of spinal cord compression syndrome due to yolk sac testis tumour metastasis in an adult. Case presentation: Here we describe the case of a 26-year-old male with a testicular yolk sac tumour that was found when a vertebral metastasis caused spinal cord compression. Symptoms included lower back pain and a growing painless testicular mass. Treatment comprised emergency surgical spinal cord decompression and orchidectomy, followed by 3 cycles of bleomycin, etoposide, and platinum (BEP) chemotherapy, and then 3 cycles of etoposide and platinum and 40 Gy vertebral radiotherapy. One year later, cement leaked into the spinal duct, prompting a return of compression syndrome. Corporectomy was performed, followed by osteosynthesis. The patient’s treatment was consolidated with 34 months and zoledronic acid administration. Although spinal metastasis from a yolk sac tumour is extremely rare, it must be considered in young adults with a testicular mass who exhibit pain or limb numbness. Such cases warrant rapid surgical decompression and radical orchidectomy, followed by adjuvant chemotherapy. Conclusion: Our case is atypical due to the patient’s age and the disease presentation. Spinal cord compression syndrome caused by yolk sac tumor metastasis is extremely rare in adulthood, and usually has a bad prognosis when diagnosed late
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