Daniele Corsi - Academia.edu (original) (raw)

Papers by Daniele Corsi

Magnetic Resonance in Chemistry, 2001

The bulk magnetic susceptibility (BMS) shifts of 1 H NMR resonance signals for inert reference co... more The bulk magnetic susceptibility (BMS) shifts of 1 H NMR resonance signals for inert reference compounds caused by the addition of paramagnetic lanthanide(III) compounds were exploited in order to determine lanthanide(III) concentrations in solution. The BMS shifts of an inert reference compound in the samples were measured by comparing the chemical shifts with those of an external reference. The concentration values obtained were in good agreement with results acquired from inductively coupled plasma analysis.

Dalton Transactions, Jan 28, 2003

The cationic [Ln(EDTA-PA 2)] ϩ complexes (EDTA-PA 2 = EDTA-bispropylamide) have been characterise... more The cationic [Ln(EDTA-PA 2)] ϩ complexes (EDTA-PA 2 = EDTA-bispropylamide) have been characterised by a multinuclear NMR study. 89 Y and 13 C NMR data indicate the formation of 1 : 1 and 1 : 2 (Ln : ligand) complexes in aqueous solution. The stability constants of these complexes, as determined by potentiometric measurements, are log K GdL = 10.3 and log K GdL 2 = 14.3. 13 C Relaxation times of the Nd 3ϩ complex show hexadentate binding of the organic ligand via the two amines, the two carboxylates and the two amide oxygen atoms. The complexes are present in solution as a mixture of three isomers: two trans forms and a cis one. Luminescence measurements demonstrate that both Eu 3ϩ and Tb 3ϩ complexes are nona-coordinated at low concentrations (∼10 Ϫ3 M). Three water molecules then complete the coordination sphere. At higher concentrations, the complexes exist in solution as a mixture of nona-and octa-coordinated species, the relative concentration of the latter increases with increasing concentration as a consequence of intermolecular interactions operating in aqueous solutions. Data sets obtained from variabletemperature 17 O NMR at 7.05 T and variable-temperature 1 H nuclear magnetic relaxation dispersion (NMRD) on the Gd 3ϩ complex were fitted simultaneously to give insight into the parameters governing the water 1 H relaxivity. Fast rotation limits the relaxivity at 10-40 MHz.

Inorganic Chemistry, Mar 1, 1999

Molecules, 2021

Superoxide dismutases (SODs) are metalloenzymes that play a major role in antioxidant defense aga... more Superoxide dismutases (SODs) are metalloenzymes that play a major role in antioxidant defense against oxidative stress in the body. SOD supplementation may therefore trigger the endogenous antioxidant machinery for the neutralization of free-radical excess and be used in a variety of pathological settings. This paper aimed to provide an extensive review of the possible uses of SODs in a range of pathological settings, as well as describe the current pitfalls and the delivery strategies that are in development to solve bioavailability issues. We carried out a PubMed query, using the keywords “SOD”, “SOD mimetics”, “SOD supplementation”, which included papers published in the English language, between 2012 and 2020, on the potential therapeutic applications of SODs, including detoxification strategies. As highlighted in this paper, it can be argued that the generic antioxidant effects of SODs are beneficial under all tested conditions, from ocular and cardiovascular diseases to neurod...

International Journal of Biological Macromolecules, 2021

This is a PDF file of an article that has undergone enhancements after acceptance, such as the ad... more This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Inorganic Chemistry, 2000

The formation of ion-pair adducts between the cationic complex La(THP)3+ (THP = 1,4,7,10-tetrakis... more The formation of ion-pair adducts between the cationic complex La(THP)3+ (THP = 1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane) and the anionic complexes Tm(DOTA)- (DOTA = 1,4,7,10-tetraazacyclododecane-N,N',N",N"'-tetraacetate), Tm(DTPA)2- (DTPA = diethylenetriamine-N,N,N',N",N"-pentaacetate), Tm(TTHA)3- (TTHA = triethylenetetraamine-N,N,N',N",N"',N"'-hexaacetate), and Tm(DOTP)5- (DOTP = 1,4,7,10-tetraazacyclododecane-N,N',N",N"'-tetrakis(methylenephosphonate)) is examined by 13C NMR spectroscopy. The induced 13C shifts of the La(THP)3+ complex are followed by titration of the Tm(III) complexes of DOTA, DTPA, and TTHA at pH 7. From these data, the stability constants are calculated to be beta 1 = 64 M-1 (1:1), beta 1 = 296 M-1 (1:1), and beta 2 = 26,000 M-2 (2:1) for the ion pairs of La(THP)3+, with Tm(DOTA)-, Tm(DTPA)2-, and Tm(TTHA)3-, respectively. The La(THP)3+,Tm(DOTP)5- system elicits chiral resolution of the rapidly interconverting Tm(DOTP)5- isomers.

Inorganic Chemistry, 1999

A range of small molecules, such as cyanide, are known to bind and/or inhibit the active site of ... more A range of small molecules, such as cyanide, are known to bind and/or inhibit the active site of the heme-copper oxidase enzymes. As such, model studies are aimed at elucidating ligand binding modes and their subsequent impact on spectroscopic properties of derived complexes. We describe here the isolation and characterization of two compounds containing the Fe-CN-Cu moiety, [(py)(F 8-TPP)Fe III-CN-Cu II (TMPA)] 2+ (5) and [(F 8-TPP)-Fe III-(CN) 2-{Cu II (TMPA)} 2 ] 3+ (6) [py) pyridine, TMPA) tris(2-pyridylmethyl)amine, and (F 8-TPP)) tetrakis-(2,6-difluorophenyl)porphyrinate(2-)]. [Cu II (TMPA)(CH 3 CN)](ClO 4) 2 and [(py)(F 8-TPP)Fe III (CN)] (3) react to yield 5, while 6 is formed by combination of [Cu II (TMPA)(CN)]PF 6 (2-(PF 6)) and [(F 8-TPP)Fe III (PF 6)] (4). Complex 2-(PF 6) crystallizes in the orthorhombic space group Iba2 with a) 17.2269(5) Å, b) 17.3143(4) Å, and c) 14.4971(4) Å, Z) 8, complex (5-(Sb/P)F 6) 1.5 (ClO 4) 0.5 was obtained in the orthorhombic space group P222 with a) 17.9541(2) Å, b) 20.5359(1) Å, and c) 21.2023(2) Å, Z) 4, and 6-(PF 6) 3 crystallized in the monoclinic space group P2 1 /c with a) 15.318(4) Å, b) 33.921(2) Å, and c) 19.649(6) Å,) 109.69(2)°, and Z) 4. Compound 5 possesses a low-spin iron(III) center, bridged via cyanide to copper. The iron-cyanide vector deviates slightly from linearity (174.6(5)°). The copper(II) ion is five-coordinated by the TMPA N-donor atoms and the cyanide carbon atom. The Cu(TMPA) moiety is bent with an angle of 163.8(5)°around the cyanide-copper vector. Compound 6 possesses a low-spin iron(III) atom axially coordinated by two cyanide ligands capped on either side by trigonally coordinated [Cu(TMPA)] moieties. The [Cu(1)(TMPA)] unit is twisted somewhat (∠Cu1-NtC) 168°), whereas the [Cu(2)(TMPA)] unit is coordinated in a nearly linear fashion with respect to the cyanide-iron vector (∠Cu2-NtC4) 175°). 1 H and 2 H NMR spectroscopy on 5 and 6 confirmed the low-spin nature of these iron complexes (pyrrole resonance found at-11.1 and-8 ppm, respectively). The NMR data as well as observed solution magnetic moment (µ B) 2.7 for 5; µ B) 3.4 for 6) suggest ferromagnetic coupling between the paramagnetic metal ions. This gives rise to an enhancement of the electronic relaxation rate for Cu(II) in both 5 and 6 allowing for the observation of the sharp and downfield shifted TMPA ligand proton signals.

Magnetic Resonance in Chemistry, 2001

The bulk magnetic susceptibility (BMS) shifts of 1 H NMR resonance signals for inert reference co... more The bulk magnetic susceptibility (BMS) shifts of 1 H NMR resonance signals for inert reference compounds caused by the addition of paramagnetic lanthanide(III) compounds were exploited in order to determine lanthanide(III) concentrations in solution. The BMS shifts of an inert reference compound in the samples were measured by comparing the chemical shifts with those of an external reference. The concentration values obtained were in good agreement with results acquired from inductively coupled plasma analysis.

Dalton Transactions, Jan 28, 2003

The cationic [Ln(EDTA-PA 2)] ϩ complexes (EDTA-PA 2 = EDTA-bispropylamide) have been characterise... more The cationic [Ln(EDTA-PA 2)] ϩ complexes (EDTA-PA 2 = EDTA-bispropylamide) have been characterised by a multinuclear NMR study. 89 Y and 13 C NMR data indicate the formation of 1 : 1 and 1 : 2 (Ln : ligand) complexes in aqueous solution. The stability constants of these complexes, as determined by potentiometric measurements, are log K GdL = 10.3 and log K GdL 2 = 14.3. 13 C Relaxation times of the Nd 3ϩ complex show hexadentate binding of the organic ligand via the two amines, the two carboxylates and the two amide oxygen atoms. The complexes are present in solution as a mixture of three isomers: two trans forms and a cis one. Luminescence measurements demonstrate that both Eu 3ϩ and Tb 3ϩ complexes are nona-coordinated at low concentrations (∼10 Ϫ3 M). Three water molecules then complete the coordination sphere. At higher concentrations, the complexes exist in solution as a mixture of nona-and octa-coordinated species, the relative concentration of the latter increases with increasing concentration as a consequence of intermolecular interactions operating in aqueous solutions. Data sets obtained from variabletemperature 17 O NMR at 7.05 T and variable-temperature 1 H nuclear magnetic relaxation dispersion (NMRD) on the Gd 3ϩ complex were fitted simultaneously to give insight into the parameters governing the water 1 H relaxivity. Fast rotation limits the relaxivity at 10-40 MHz.

Inorganic Chemistry, Mar 1, 1999

Molecules, 2021

Superoxide dismutases (SODs) are metalloenzymes that play a major role in antioxidant defense aga... more Superoxide dismutases (SODs) are metalloenzymes that play a major role in antioxidant defense against oxidative stress in the body. SOD supplementation may therefore trigger the endogenous antioxidant machinery for the neutralization of free-radical excess and be used in a variety of pathological settings. This paper aimed to provide an extensive review of the possible uses of SODs in a range of pathological settings, as well as describe the current pitfalls and the delivery strategies that are in development to solve bioavailability issues. We carried out a PubMed query, using the keywords “SOD”, “SOD mimetics”, “SOD supplementation”, which included papers published in the English language, between 2012 and 2020, on the potential therapeutic applications of SODs, including detoxification strategies. As highlighted in this paper, it can be argued that the generic antioxidant effects of SODs are beneficial under all tested conditions, from ocular and cardiovascular diseases to neurod...

International Journal of Biological Macromolecules, 2021

This is a PDF file of an article that has undergone enhancements after acceptance, such as the ad... more This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Inorganic Chemistry, 2000

The formation of ion-pair adducts between the cationic complex La(THP)3+ (THP = 1,4,7,10-tetrakis... more The formation of ion-pair adducts between the cationic complex La(THP)3+ (THP = 1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane) and the anionic complexes Tm(DOTA)- (DOTA = 1,4,7,10-tetraazacyclododecane-N,N',N",N"'-tetraacetate), Tm(DTPA)2- (DTPA = diethylenetriamine-N,N,N',N",N"-pentaacetate), Tm(TTHA)3- (TTHA = triethylenetetraamine-N,N,N',N",N"',N"'-hexaacetate), and Tm(DOTP)5- (DOTP = 1,4,7,10-tetraazacyclododecane-N,N',N",N"'-tetrakis(methylenephosphonate)) is examined by 13C NMR spectroscopy. The induced 13C shifts of the La(THP)3+ complex are followed by titration of the Tm(III) complexes of DOTA, DTPA, and TTHA at pH 7. From these data, the stability constants are calculated to be beta 1 = 64 M-1 (1:1), beta 1 = 296 M-1 (1:1), and beta 2 = 26,000 M-2 (2:1) for the ion pairs of La(THP)3+, with Tm(DOTA)-, Tm(DTPA)2-, and Tm(TTHA)3-, respectively. The La(THP)3+,Tm(DOTP)5- system elicits chiral resolution of the rapidly interconverting Tm(DOTP)5- isomers.

Inorganic Chemistry, 1999

A range of small molecules, such as cyanide, are known to bind and/or inhibit the active site of ... more A range of small molecules, such as cyanide, are known to bind and/or inhibit the active site of the heme-copper oxidase enzymes. As such, model studies are aimed at elucidating ligand binding modes and their subsequent impact on spectroscopic properties of derived complexes. We describe here the isolation and characterization of two compounds containing the Fe-CN-Cu moiety, [(py)(F 8-TPP)Fe III-CN-Cu II (TMPA)] 2+ (5) and [(F 8-TPP)-Fe III-(CN) 2-{Cu II (TMPA)} 2 ] 3+ (6) [py) pyridine, TMPA) tris(2-pyridylmethyl)amine, and (F 8-TPP)) tetrakis-(2,6-difluorophenyl)porphyrinate(2-)]. [Cu II (TMPA)(CH 3 CN)](ClO 4) 2 and [(py)(F 8-TPP)Fe III (CN)] (3) react to yield 5, while 6 is formed by combination of [Cu II (TMPA)(CN)]PF 6 (2-(PF 6)) and [(F 8-TPP)Fe III (PF 6)] (4). Complex 2-(PF 6) crystallizes in the orthorhombic space group Iba2 with a) 17.2269(5) Å, b) 17.3143(4) Å, and c) 14.4971(4) Å, Z) 8, complex (5-(Sb/P)F 6) 1.5 (ClO 4) 0.5 was obtained in the orthorhombic space group P222 with a) 17.9541(2) Å, b) 20.5359(1) Å, and c) 21.2023(2) Å, Z) 4, and 6-(PF 6) 3 crystallized in the monoclinic space group P2 1 /c with a) 15.318(4) Å, b) 33.921(2) Å, and c) 19.649(6) Å,) 109.69(2)°, and Z) 4. Compound 5 possesses a low-spin iron(III) center, bridged via cyanide to copper. The iron-cyanide vector deviates slightly from linearity (174.6(5)°). The copper(II) ion is five-coordinated by the TMPA N-donor atoms and the cyanide carbon atom. The Cu(TMPA) moiety is bent with an angle of 163.8(5)°around the cyanide-copper vector. Compound 6 possesses a low-spin iron(III) atom axially coordinated by two cyanide ligands capped on either side by trigonally coordinated [Cu(TMPA)] moieties. The [Cu(1)(TMPA)] unit is twisted somewhat (∠Cu1-NtC) 168°), whereas the [Cu(2)(TMPA)] unit is coordinated in a nearly linear fashion with respect to the cyanide-iron vector (∠Cu2-NtC4) 175°). 1 H and 2 H NMR spectroscopy on 5 and 6 confirmed the low-spin nature of these iron complexes (pyrrole resonance found at-11.1 and-8 ppm, respectively). The NMR data as well as observed solution magnetic moment (µ B) 2.7 for 5; µ B) 3.4 for 6) suggest ferromagnetic coupling between the paramagnetic metal ions. This gives rise to an enhancement of the electronic relaxation rate for Cu(II) in both 5 and 6 allowing for the observation of the sharp and downfield shifted TMPA ligand proton signals.