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1.
Phys Chem Chem Phys ; 18(3): 2070-9, 2016 Jan 21.
Article in English | MEDLINE | ID: mdl-26687828

ABSTRACT

Perovskite strontium titanate is a promising functional material for gas sensors and catalysis applications. Herein, we report the preparation of SrTi1-xCuxO3 nanoparticles with Cu doped in the B sites using a modified polymeric precursor method. This study describes in detail the structural and local atomic configurations for the substitution of Cu into the titanium sites and its reducibility using X-ray diffraction (XRD), field emission gun scanning and transmission electron microscopies (FEG-SEM and TEM), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) analyses. Our results indicate that copper is segregated for x≥ 0.06. After exposing the samples to a hydrogen-rich atmosphere at temperatures over 500 K, copper is reduced from Cu(2+) to metallic Cu. This reduction was attributed to copper atoms that originated primarily from the CuO phase.

2.
Inorg Chem ; 53(12): 6127-31, 2014 Jun 16.
Article in English | MEDLINE | ID: mdl-24897553

ABSTRACT

The influence of cobalt substitution on the local structural changes around Co atoms in the layered lithium nitridocobaltates Li(3-2x)Co(x)N for 0.05 ≤ x ≤ 0.44 is investigated using Co K-edge X-ray absorption spectroscopy (EXAFS and XANES). The Co-N bond length in Li(3-2x)Co(x)N compounds is obtained vs x by performing EXAFS fitting and found to be shorter (1.80 Å) than for x = 0 (Li3N), and its value does not change with x. A comparison of EXAFS data with XRD results is discussed. We show that the continuous decrease of interlayer distance versus Co content (x), described from XRD data, accounts for an average of the Co-N and Li-N distances, weighted by the number of these bond lengths. In addition, the present work supports the proposal that the Li1b-N bonds contract with x due to a significant increase of Coulombic attractive forces locally induced by the progressive Li(+)/Co(2+) substitution. XRD studies suggested that divalent Co ions bond to two nitrogen in Li(3-2x)Co(x)N. Although additional works are still needed to prove its valence, the present XAFS findings complements the local structure found by XRD, in good accord with the electrochemical properties previously reported.

3.
Biochimie ; 91(10): 1301-6, 2009 Oct.
Article in English | MEDLINE | ID: mdl-19607872

ABSTRACT

Three platinum complexes, cisplatin, carboplatin and oxaliplatin are currently used worldwide. Investigation of their main structural modifications in presence of sulfur nucleophiles is of particular interest because of the implication of thiol and thioether groups in biochemical mechanism of action, resistance mechanism and in vivo or in vitro detoxification. We present the main structural results we have obtained concerning the reaction of these drugs with diverse sulfur nucleophiles (cysteine, glutathione, methionine, thiosulfate and thiocyanate), monitored in solution or as precipitates by EXAFS spectroscopy. The reactivities of the carboxylate and amine ligands of both carboplatin and oxaliplatin are compared, on the basis of first-coordination sphere modeling. Among the new results of this EXAFS study, we present the first observation of oxaliplatin diaminocyclohexane ligand displacement by sulfur nucleophiles.


Subject(s)
Antineoplastic Agents/chemistry , Organoplatinum Compounds/chemistry , Sulfur/chemistry , Spectrometry, X-Ray Emission
4.
J Synchrotron Radiat ; 13(Pt 6): 477-83, 2006 Nov.
Article in English | MEDLINE | ID: mdl-17057326

ABSTRACT

Oxaliplatin is a second-generation platinum-based anticancer drug. Its degradation is studied in solution, in the presence of chloride ions (in neutral or acidic media) in excess. In both cases the degradation product precipitates immediately. The EXAFS spectra of these products show that they are identical. EXAFS modeling and refinement of the first coordination sphere shows that two light atoms are replaced by two chloride ions. The complete refinement of the local structure is possible by studying the multiple-scattering signal. The results show that the main multiple-scattering contribution is due to the binding oxalato group and that the degradation product is [Cl(2)-(diaminocyclohexane)-Pt(II)].


Subject(s)
Antineoplastic Agents/chemistry , Chlorides/chemistry , Organoplatinum Compounds/chemistry , X-Ray Diffraction/methods , Drug Stability , Kinetics , Oxaliplatin
5.
Inorg Chem ; 45(8): 3393-8, 2006 Apr 17.
Article in English | MEDLINE | ID: mdl-16602799

ABSTRACT

Platinum compounds constitute a discrete class of DNA-damaging anticancer drug agents, including cisplatin, carboplatin, and oxaliplatin. The toxicity of such drugs raises the problem of waste detoxification. Diethyl dithiocarbamate (DDTC) is recommended by the World Heath Organization (WHO) for the destruction of cisplatin, but the degradation product has not been structurally characterized. This paper deals with the extended X-ray absorption fine structure (EXAFS) and IR structural study of the reaction products of DDTC with cisplatin, carboplatin, and oxaliplatin. Cisplatin and carboplatin give the same reaction product: Pt(DDTC)2. In the case of oxaliplatin, we observed the formation of [(diaminocyclohexane)(DDTC)Pt(II)]. In all cases, the replacement of labile ligands by strong ligands should lead to inactive compounds. Our results suggest that the WHO inactivation protocol might be extended to carboplatin and oxaliplatin. Nevertheless, this should be validated by toxicity tests of the degradation products.


Subject(s)
Antineoplastic Agents/chemistry , Environmental Restoration and Remediation , Platinum Compounds/chemistry , Carboplatin/chemistry , Cisplatin/chemistry , Ditiocarb/chemistry , Environmental Pollution/prevention & control , Molecular Structure , Organoplatinum Compounds/chemistry , Oxaliplatin , Spectrophotometry, Infrared , Spectrum Analysis , X-Rays
6.
Inorg Chem ; 44(26): 9743-51, 2005 Dec 26.
Article in English | MEDLINE | ID: mdl-16363843

ABSTRACT

The formation of hydroxo complexes based on a calix[6]trisimidazole ligand is described. Deprotonation of the mononuclear Cu(II)-aqua complex gives rise to a dinuclear bis(mu-hydroxo) complex that has been characterized by X-ray diffraction analysis. Spectroscopic studies (EPR and UV-vis), conducted in dichloromethane solutions in the presence of various coordinating cosolvents (DMF, EtOH, or RCN) or with acetamide, revealed the coexistence of a mononuclear hydroxo species. The latter could be trapped by acetic acid to provide an acetato-Cu(II) complex that presents close spectroscopic features. An EXAFS study first conducted on the hydroxo-Cu(II) complex led to an excellent fit for the dinuclear core. It then allowed for the characterization of the mononuclear acetato complex with an acetamide guest included in the calixarene cavity. Hence, this study illustrates the flexibility of calixarene-based ligands and the role of the second coordination sphere in the stabilization of acidic or basic Cu(II) complexes.

7.
Chemistry ; 8(21): 4992-5000, 2002 Nov 04.
Article in English | MEDLINE | ID: mdl-12489532

ABSTRACT

[Fe(hyptrz)3](4-chloro-3-nitrophenylsulfonate)22 H2O (1; hyptrz=4-(3-hydroxypropyl)-1,2,4-triazole) has been synthesized and its physical properties have been investigated by several physical techniques including magnetic susceptibility measurements, calorimetry, and Mössbauer, optical, and EXAFS spectroscopy. Compound 1 exhibits a spin transition below room temperature, together with a very wide thermal hysteresis of about 50 K. This represents the widest hysteresis loop ever observed for an FeII-1,2,4-triazole spin transition material. The cooperativity is discussed on the basis of temperature-dependent EXAFS studies and of the structural features of a CuII analogue. The EXAFS structural model of (1) in both spin states is compared to that obtained for a related material whose spin transition occurs above room temperature. EXAFS spectroscopy suggests that 1,2,4-triazole chain compounds retain a linear character whatever the spin state of the iron(II).

8.
Inorg Chem ; 37(16): 3910-3918, 1998 Aug 10.
Article in English | MEDLINE | ID: mdl-11670503

ABSTRACT

We describe the studies of new copper complexes [MeSPY2]CuPF(6), 2, and [MeSPY2]Cu(ClO(4))(2).CH(3)CN, 3, as models for the Cu(B) center of dopamine beta-hydroxylase and peptidylglycine alpha-hydroxylating monooxygenase. The structure of [MeSPY2]Cu(ClO(4))(2).CH(3)CN, 3, has been established by X-ray crystallography. The copper coordination exhibits a square pyramidal geometry where the equatorial plane is occupied by the SCH(3) group and three nitrogen atoms (tertiary amine, one pyridine, and acetonitrile solvent), whereas the axial position binds the second pyridine. Using FEFF calculations and multiscattering interaction, EXAFS refinements show that the SMe group lies in the coordination sphere of copper complexes [MeSPY2]CuPF(6), 2, and [MeSPY2]Cu(ClO(4))(2).CH(3)CN, 3. While [MeSPY2]CuPF(6), 2, reacts with dioxygen in dichloromethane without oxidation of the ligand, we observed an oxidation of the sulfide ligand when [MeSPY2]Cu(ClO(4))(2).CH(3)CN, 3, reacts with hydrogen peroxide in methanol. Considering results, we propose that Met(314), crucial for DBH and PHM activity, could be the site of the H(2)O(2) (or ascorbate) inactivation by oxidation to the sulfoxide group.

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