Metal Coordination Core in Copper(II) Complexes Investigated by XAFS

Schiesaro, Irene; Venditti, Iole; Pellei, Maura; Santini, Carlo; Bagnarelli, Luca; Iucci, Giovanna; Battocchio, Chiara; Meneghini, Carlo

doi:10.1007/978-3-030-72005-6_13

Cited by 4 publications

(9 citation statements)

References 23 publications

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“…For complexes 9 and 5 , the Cl2p signal was also collected and analyzed, observing a single spin-orbit pair with the main Cl2p 3/2 peak centered around 199.1 eV for 9 and a couple of signals (Cl2p 3/2 BE = 199.2 eV and 201.3 eV, respectively) for 5 . While the lower BE signals are in good agreement with literature data about chlorine atoms coordinated to copper ions in coordination compounds with monomeric molecular structure (see Figure 2 ) [ 25 , 26 , 27 , 35 ], the C2p signal at higher BE values observed in 5 could suggest a Cu-Cl-Cu bridge, in which the double coordination at Cu(II) centers could be responsible for the observed BE shift towards more positive values for the chlorine atoms. This interpretation suggests that complex 9 is a monomer and complex 5 is a mixture of monomeric and dimeric structures.…”

Section: Resultssupporting

confidence: 90%

“…In the C K edge spectra of samples 2 and 5 , C1s→π* transitions below the edge are due, respectively, to C=C (π* C=C ) and C=N carbons (π* C=C ) of the pyrazole rings and to the O-C=O carbon of the ester function (π* C=O ), as already evidenced for similar complexes [ 25 , 26 , 27 ]. In the spectrum of sample 8 , the π* C=C resonance is split in two peaks, related to C=C carbons of the pyrazole rings and of the benzene rings of triphenylphosphine.…”

Section: Resultssupporting

confidence: 65%

“…The N1s spectra reported in Figure 3 b for ligand 2 and complexes 8 and 9 confirmed the chemical stability of the ligand and the coordination compound formation. Two spectral components could be individuated in the N1s spectrum of ligand 2 , as expected for pyrazole rings: the component at lower BE (399.9 eV) was attributed to amine-like nitrogen, and the peak at higher BE (401.8 eV) to imine-like N atoms [ 25 , 26 , 27 , 28 ]. On the other hand, the N1s spectra of complexes 8 , 5 , and 9 showed a single component at about 400 eV, corresponding to the symmetrized amine-like contributions, as expected for heterocycles coordinating metal ions [ 25 , 26 , 27 , 29 , 30 ].…”

Section: Resultsmentioning

confidence: 78%

“…The molecular and electronic structure of selected Cu(I) and Cu(II) coordination compounds were examined in the solid state by means of synchrotron radiation-induced X-ray photoelectron spectroscopy (SR-XPS), near edge X-ray absorption fine structure (NEXAFS), and X-ray absorption (XAS) spectroscopies. This approach encompassing several different and complementary techniques allowed us to probe the copper ion oxidation state stability, to properly describe its coordination geometry, and to establish the molecular structure stability of the ligands upon interaction with the metal center [ 25 , 26 , 27 ].…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Exploring the Antitumor Potential of Copper Complexes Based on Ester Derivatives of Bis(pyrazol-1-yl)acetate Ligands

Pellei

Santini

Bagnarelli

et al. 2022

IJMS

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Bis(pyrazol-1-yl)acetic acid (HC(pz)2COOH) and bis(3,5-dimethyl-pyrazol-1-yl)acetic acid (HC(pzMe2)2COOH) were converted into the methyl ester derivatives 1 (LOMe) and 2 (L2OMe), respectively, and were used for the preparation of Cu(I) and Cu(II) complexes 3–10. The copper(II) complexes were prepared by the reaction of CuCl2·2H2O or CuBr2 with ligands 1 and 2 in methanol solution. The copper(I) complexes were prepared by the reaction of Cu[(CH3CN)4]PF6 and 1,3,5-triaza-7-phosphaadamantane (PTA) or triphenylphosphine with LOMe and L2OMe in acetonitrile solution. Synchrotron radiation-based complementary techniques (XPS, NEXAFS, and XAS) were used to investigate the electronic and molecular structures of the complexes and the local structure around copper ions in selected Cu(I) and Cu(II) coordination compounds. All Cu(I) and Cu(II) complexes showed a significant in vitro antitumor activity, proving to be more effective than the reference drug cisplatin in a panel of human cancer cell lines, and were able to overcome cisplatin resistance. Noticeably, Cu complexes appeared much more effective than cisplatin in 3D spheroid cultures. Mechanistic studies revealed that the antitumor potential did not correlate with cellular accumulation but was consistent with intracellular targeting of PDI, ER stress, and paraptotic cell death induction.

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Section: Resultssupporting

confidence: 90%

Section: Resultssupporting

confidence: 65%

Section: Resultsmentioning

confidence: 78%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Exploring the Antitumor Potential of Copper Complexes Based on Ester Derivatives of Bis(pyrazol-1-yl)acetate Ligands

Pellei

Santini

Bagnarelli

et al. 2022

IJMS

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“…The molecular structure of selected coordination compounds was investigated in the solid state by means of synchrotron radiation-induced X-ray photoelectron spectroscopy (SR-XPS), near-edge X-ray absorption fine structure (NEXAFS), and X-ray absorption spectroscopy (XAS); the multitechnique approach allowed us to properly define the coordination geometry around the copper ion, as well as to ascertain the molecular structural stability of the ligands upon interaction with the metal. 53 …”

Section: Introductionmentioning

confidence: 99%

Cu(I) and Cu(II) Complexes Based on Lonidamine-Conjugated Ligands Designed to Promote Synergistic Antitumor Effects

et al. 2022

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Bis(pyrazol-1-yl)- and bis(3,5-dimethylpyrazol-1-yl)-acetates were conjugated with the 2-hydroxyethylester and 2-aminoethylamide derivatives of the antineoplastic drug lonidamine to prepare Cu(I) and Cu(II) complexes that might act through synergistic mechanisms of action due to the presence of lonidamine and copper in the same chemical entity. Synchrotron radiation-based complementary techniques [X-ray photorlectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS)] were used to characterize the electronic and molecular structures of the complexes and the local structure around the copper ion (XAFS) in selected complexes. All complexes showed significant antitumor activity, proving to be more effective than the reference drug cisplatin in a panel of human tumor cell lines, and were able to overcome oxaliplatin and multidrug resistance. Noticeably, these Cu complexes appeared much more effective than cisplatin against 3D spheroids of pancreatic PSN-1 cancer cells; among these, PPh 3 -containing Cu(I) complex 15 appeared to be the most promising derivative. Mechanistic studies revealed that 15 induced cancer cell death by means of an apoptosis-alternative cell death.

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Cu(I) Coordination Compounds Conjugated to Au Nanorods for Future Applications in Drug Delivery: Insights in Molecular, Electronic and Cu Local Structure in Solid and Liquid Phase

Lopez,

Amatori,

Olivieri

et al. 2024

ChemPhysChem

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In the framework of the design, synthesis and testing of a library of copper complexes and nanostructured assemblies potentially endowed with antitumor and antiviral activity and useful for several applications, from drugs and related delivery systems to the development of biocidal nanomaterials, we present the detailed spectroscopic investigation of the molecular and electronic structure of copper‐based coordination compounds and of a new conjugated system obtained by grafting Cu(I) complexes to gold nanorods. More in detail, the electronic and molecular structures of two Cu complexes and one AuNRs/Cu‐complex adduct were investigated by X‐ray photoelectron spectroscopy (XPS), synchrotron‐induced XPS (SR‐XPS) and near edge X‐ray absorption spectroscopy (NEXAFS) in solid state, and the local structure around copper ion was assessed by X‐ray absorption spectroscopy (XAS) both in solid state and water solution for the AuNRs/Cu‐complex nanoparticles. The proposed multi‐technique approach allowed to properly define the coordination geometry around the copper ion, as well as to ascertain the molecular structures of the coordination compounds, their stability and modifications upon interaction with gold nanoparticles, by comparing solid state and liquid phase data.

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Metal Coordination Core in Copper(II) Complexes Investigated by XAFS

Cited by 4 publications

References 23 publications

Exploring the Antitumor Potential of Copper Complexes Based on Ester Derivatives of Bis(pyrazol-1-yl)acetate Ligands

Exploring the Antitumor Potential of Copper Complexes Based on Ester Derivatives of Bis(pyrazol-1-yl)acetate Ligands

Cu(I) and Cu(II) Complexes Based on Lonidamine-Conjugated Ligands Designed to Promote Synergistic Antitumor Effects

Cu(I) Coordination Compounds Conjugated to Au Nanorods for Future Applications in Drug Delivery: Insights in Molecular, Electronic and Cu Local Structure in Solid and Liquid Phase

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