Vincenzo Cucinotta - Academia.edu (original) (raw)
Papers by Vincenzo Cucinotta
Journal of Pharmaceutical and Biomedical Analysis, 2017
Highlights A new capped derivative of β-cyclodextrin was synthesised and characterised The fo... more Highlights A new capped derivative of β-cyclodextrin was synthesised and characterised The formation of its complex with copper(II) ion was observed in solution. Its ability as selector both for chiral and non chiral separation was verified in capillary electrophoresis.
Tetrahedron Letters, 2008
Cyclodextrins are commonly used in separation sciences 1 because of their ability to interact wit... more Cyclodextrins are commonly used in separation sciences 1 because of their ability to interact with a high number of species in aqueous solutions and for their intrinsic chirality. 2 Functionalized cyclodextrins, by coupling the specific interactions due to the substituting moiety to the ...
Chromatographic Science Series, 2009
Zeitschrift für Kristallographie - New Crystal Structures, 1999
C54H80O32S4, monoclinic, P12il (No. 4), a = 17.334(6) A, b = 7.814(6) A, c = 24.278(6) A, β = 99.... more C54H80O32S4, monoclinic, P12il (No. 4), a = 17.334(6) A, b = 7.814(6) A, c = 24.278(6) A, β = 99.82(2)°, V= 3240.2 A, Z= 2, Rg(F) = 0.083, RJF) = 0.203, 7 = 293 K. Source of material The title compound was obtained by a one-step synthesis [1]. In order to select the primary site, the most reactive, the reaction was carried out at low temperature, followed by an accurate purification by reverse-phase chromatography, thus obtaining the product in short time and in good yield. The compound was crystallised from methanol and water mixture and is characterized by two independent molecules (A and B) in the asymmetric unit. Discussion Hydrogen atom s of the solvent molecules are not refined. The α,α'-trehalose is a peculiar disaccharide, in which two Dglucopyrasinic rings are linked by a bond between their anomeric carbon atoms, with a consequent non-reductive behaviour, while the molecule is symmetric. Owing to this peculiarity, this compound has attracted the interest of many reserchers and many derivatives have been synthesized. One of the key intermediates in these syntheses is the 6,6'-ditosyl-trehalose, which was first synthesized and characterized in 1958 [2]. The two independent molecules are almost superimposable with angle between the planes of the two glucosidic rings of 46.5(4)° and 53.5(5)° for molecule A and B, respectively. The major difference between the two independent molecules is represented by one dihedral angles in one tosyl moiety (C62A-062A-S2A-C7A = 69(1)° and C63B-063B-S1B-C4B = 177.1(8)°). Table 1. Data collection and handling. Crystal: colorless needle, size 0.2 χ 0.3 χ 0.6 mm Wavelength: Cu Ka radiation (1.54056 A) μ : 21.30 cm" ' Diffractometer, scan mode: Nonius CAD4-Turbo, ω/2θ
Proceedings of the National Academy of Sciences, 1992
The structural characterization of a beta-cyclodextrin monosubstituted with the peptide cyclo(L-H... more The structural characterization of a beta-cyclodextrin monosubstituted with the peptide cyclo(L-His-L-Leu) is reported. This work provides an x-ray example of a covalently bound group that folds in such a way that the terminal apolar side chain is retained in the hydrophobic interior of the cone-shaped cyclodextrin cavity. 6-Deoxy-6-cyclo(L-histidyl-L-leucyl)-beta-cyclodextrin crystallizes in the space group P1 with cell dimensions a = 14.728(8) A, b = 15.084(7) A, c = 18.182(10) A, alpha = 94.36(6) degrees, beta = 95.81(5) degrees, gamma = 116.08(9) degrees; overall isotropic agreement R = 10.6% for 5703 observed reflections (Fo greater than 3 sigma). The molecular structure consists of two independent molecules with the formula C54H86N4O36.7.25H2O. Each molecule assumes a "sleeping swan"-like overall shape with the hydrophobic leucine side chain inserted inside the cavity of the macrocycle. The two independent units give rise to a head-to-tail dimer linked by hydrogen bo...
Journal of Inorganic Biochemistry, 1993
Journal of Chromatography B, 2004
The systems that the 3-amino derivative of -cyclodextrin (CD3NH2) forms with the proton, the cop... more The systems that the 3-amino derivative of -cyclodextrin (CD3NH2) forms with the proton, the copper(II) ion and each of the enantiomers of certain amino acids (alanine, phenylalanine, tyrosine and tryptophan) were investigated. The enantioselectivity shown by the potentiometric measurements carried out on the phenylalanine ternary systems was exploited in capillary electrophoresis by ligand exchange capillary electrophoresis (LECE) to obtain the separation of phenylalanine racemate. The tyrosine racemate was also separated by LECE. The comparison between thermodynamic and capillary electrophoresis (CE) results is discussed, in order to get a better insight into the separation mechanism.
Comments on Inorganic Chemistry, 1990
ABSTRACT The thermodynamic stereoselectivity of a wide series of dipeptide complexes with proton ... more ABSTRACT The thermodynamic stereoselectivity of a wide series of dipeptide complexes with proton and copper (II) ions is examined. In particular, it is shown that non-covalent interactions are the driving forces of the chirality discrimination. Furthermore, the diagnostic character of ΔH° and ΔS° values is brought to light and compared with the spectroscopy approach for correlating the stereoselectivity with the structural properties of complexes.
Inorganica Chimica Acta, 1981
Journal of Chromatography a, Dec 6, 2002
Six different racemates of the profen family were used as analytes in order to test the chiral se... more Six different racemates of the profen family were used as analytes in order to test the chiral selector properties of three members of a new class of cyclodextrin derivatives, hemispherodextrins (HMs), in capillary electrophoresis. In addition to experiments carried out to separate each enantiomeric pair one by one, other experiments were carried out on samples containing all six enantiomeric pairs. Electropherograms were obtained either by adding a single HM to the background electrolyte (BGE), or a binary mixture of HMs. The results obtained confirm the excellent chiral selector properties of the HMs, and furthermore show that these compounds can also be used for achiral selection. When mixing different HMs, a complementary effect in chiral selectivity is observed, which, in our opinion, deserves further study.
J Chem Soc Perkin Trans 2, 1996
ABSTRACT
Journal of the Chemical Society Chemical Communications, 1992
ABSTRACT
J Incl Phenom Macrocycl Chem, 1996
In order to obtain better abiotic receptors for analytical and kinetic applications, the new capp... more In order to obtain better abiotic receptors for analytical and kinetic applications, the new capped derivative of cyclomaltoheptaose (CDTH) was synthesized by reaction of 6,6'-dideoxy-6,6'-di(S-cysteamine)-et, c~,'-trehalose ~ 6&6D-dideoxy-6A,6D-diiodo-cyclo-maltoheptaose. The CDTH-ACS (anthraqttinone-2-sulfonic acid sodium salt) system was investigated, by 1H NMR spectroscopy and by i.c.d. (induced circul~ dicroism), and a deep inclusion of ACS inside the CDTH cavity, with an association constant about six times larger with respect to ACS-~-CD system was formal. i.
Journal of the Chemical Society Dalton Transactions, 1992
![Research paper thumbnail of Coordination properties of 6-deoxy-6-[1-(2-amino) ethylamino]-?-cyclodextrin and the ability of its copper(II) complex to recognize and separate amino acid enantiomeric pairs](https://attachments.academia-assets.com/71849790/thumbnails/1.jpg)
](J Incl Phenom Macrocycl Chem, 1993
The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]-/3-cyclodextrin was synthesized... more The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]-/3-cyclodextrin was synthesized, and an NMR, EPR, pH-metric, and calorimetric investigation was carried out in aqueous solution in order to ascertain its behaviour towards protonation and copper(II) complex formation. The thermodynamic parameters of the ternary complex formation with alanine, phenylalanine and tryptophan enantiomeric pairs were also determined (25 ~ C and I = 0.1 mol dm-3). No thermodynamic enantioselectivity was observed in these systems, while a chiral, though poor, discrimination was observed in LEC: c.d. spectra also show enantiomeric stereoselectivity. The results of the present investigation, compared with previously reported results, suggest the occurence of a cis-complex trans-complex equilibrium in such systems.
Http Dx Doi Org 10 1080 07328319708002538, Aug 20, 2006
ABSTRACT DSC measurements of binary, decanucleotide/L,L or L,D Ala-Trp, and ternary decanucleotid... more ABSTRACT DSC measurements of binary, decanucleotide/L,L or L,D Ala-Trp, and ternary decanucleotide/L,L or L,D Ala-Trp/Copper(II), systems have been carried out. The results obtained show the different behaviour of the two diastereoisomers both in the binary and in the ternary systems, ascribable to the different disposition of the side-chains in the dipeptides.
J Pharmaceut Biomed Anal, 2005
J Incl Phenom Macrocycl Chem, 1993
The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]-/3-cyclodextrin was synthesized... more The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]-/3-cyclodextrin was synthesized, and an NMR, EPR, pH-metric, and calorimetric investigation was carried out in aqueous solution in order to ascertain its behaviour towards protonation and copper(II) complex formation. The thermodynamic parameters of the ternary complex formation with alanine, phenylalanine and tryptophan enantiomeric pairs were also determined (25 ~ C and I = 0.1 mol dm-3). No thermodynamic enantioselectivity was observed in these systems, while a chiral, though poor, discrimination was observed in LEC: c.d. spectra also show enantiomeric stereoselectivity. The results of the present investigation, compared with previously reported results, suggest the occurence of a cis-complex trans-complex equilibrium in such systems.
Journal of Pharmaceutical and Biomedical Analysis, 2017
Highlights A new capped derivative of β-cyclodextrin was synthesised and characterised The fo... more Highlights A new capped derivative of β-cyclodextrin was synthesised and characterised The formation of its complex with copper(II) ion was observed in solution. Its ability as selector both for chiral and non chiral separation was verified in capillary electrophoresis.
Tetrahedron Letters, 2008
Cyclodextrins are commonly used in separation sciences 1 because of their ability to interact wit... more Cyclodextrins are commonly used in separation sciences 1 because of their ability to interact with a high number of species in aqueous solutions and for their intrinsic chirality. 2 Functionalized cyclodextrins, by coupling the specific interactions due to the substituting moiety to the ...
Chromatographic Science Series, 2009
Zeitschrift für Kristallographie - New Crystal Structures, 1999
C54H80O32S4, monoclinic, P12il (No. 4), a = 17.334(6) A, b = 7.814(6) A, c = 24.278(6) A, β = 99.... more C54H80O32S4, monoclinic, P12il (No. 4), a = 17.334(6) A, b = 7.814(6) A, c = 24.278(6) A, β = 99.82(2)°, V= 3240.2 A, Z= 2, Rg(F) = 0.083, RJF) = 0.203, 7 = 293 K. Source of material The title compound was obtained by a one-step synthesis [1]. In order to select the primary site, the most reactive, the reaction was carried out at low temperature, followed by an accurate purification by reverse-phase chromatography, thus obtaining the product in short time and in good yield. The compound was crystallised from methanol and water mixture and is characterized by two independent molecules (A and B) in the asymmetric unit. Discussion Hydrogen atom s of the solvent molecules are not refined. The α,α'-trehalose is a peculiar disaccharide, in which two Dglucopyrasinic rings are linked by a bond between their anomeric carbon atoms, with a consequent non-reductive behaviour, while the molecule is symmetric. Owing to this peculiarity, this compound has attracted the interest of many reserchers and many derivatives have been synthesized. One of the key intermediates in these syntheses is the 6,6'-ditosyl-trehalose, which was first synthesized and characterized in 1958 [2]. The two independent molecules are almost superimposable with angle between the planes of the two glucosidic rings of 46.5(4)° and 53.5(5)° for molecule A and B, respectively. The major difference between the two independent molecules is represented by one dihedral angles in one tosyl moiety (C62A-062A-S2A-C7A = 69(1)° and C63B-063B-S1B-C4B = 177.1(8)°). Table 1. Data collection and handling. Crystal: colorless needle, size 0.2 χ 0.3 χ 0.6 mm Wavelength: Cu Ka radiation (1.54056 A) μ : 21.30 cm" ' Diffractometer, scan mode: Nonius CAD4-Turbo, ω/2θ
Proceedings of the National Academy of Sciences, 1992
The structural characterization of a beta-cyclodextrin monosubstituted with the peptide cyclo(L-H... more The structural characterization of a beta-cyclodextrin monosubstituted with the peptide cyclo(L-His-L-Leu) is reported. This work provides an x-ray example of a covalently bound group that folds in such a way that the terminal apolar side chain is retained in the hydrophobic interior of the cone-shaped cyclodextrin cavity. 6-Deoxy-6-cyclo(L-histidyl-L-leucyl)-beta-cyclodextrin crystallizes in the space group P1 with cell dimensions a = 14.728(8) A, b = 15.084(7) A, c = 18.182(10) A, alpha = 94.36(6) degrees, beta = 95.81(5) degrees, gamma = 116.08(9) degrees; overall isotropic agreement R = 10.6% for 5703 observed reflections (Fo greater than 3 sigma). The molecular structure consists of two independent molecules with the formula C54H86N4O36.7.25H2O. Each molecule assumes a "sleeping swan"-like overall shape with the hydrophobic leucine side chain inserted inside the cavity of the macrocycle. The two independent units give rise to a head-to-tail dimer linked by hydrogen bo...
Journal of Inorganic Biochemistry, 1993
Journal of Chromatography B, 2004
The systems that the 3-amino derivative of -cyclodextrin (CD3NH2) forms with the proton, the cop... more The systems that the 3-amino derivative of -cyclodextrin (CD3NH2) forms with the proton, the copper(II) ion and each of the enantiomers of certain amino acids (alanine, phenylalanine, tyrosine and tryptophan) were investigated. The enantioselectivity shown by the potentiometric measurements carried out on the phenylalanine ternary systems was exploited in capillary electrophoresis by ligand exchange capillary electrophoresis (LECE) to obtain the separation of phenylalanine racemate. The tyrosine racemate was also separated by LECE. The comparison between thermodynamic and capillary electrophoresis (CE) results is discussed, in order to get a better insight into the separation mechanism.
Comments on Inorganic Chemistry, 1990
ABSTRACT The thermodynamic stereoselectivity of a wide series of dipeptide complexes with proton ... more ABSTRACT The thermodynamic stereoselectivity of a wide series of dipeptide complexes with proton and copper (II) ions is examined. In particular, it is shown that non-covalent interactions are the driving forces of the chirality discrimination. Furthermore, the diagnostic character of ΔH° and ΔS° values is brought to light and compared with the spectroscopy approach for correlating the stereoselectivity with the structural properties of complexes.
Inorganica Chimica Acta, 1981
Journal of Chromatography a, Dec 6, 2002
Six different racemates of the profen family were used as analytes in order to test the chiral se... more Six different racemates of the profen family were used as analytes in order to test the chiral selector properties of three members of a new class of cyclodextrin derivatives, hemispherodextrins (HMs), in capillary electrophoresis. In addition to experiments carried out to separate each enantiomeric pair one by one, other experiments were carried out on samples containing all six enantiomeric pairs. Electropherograms were obtained either by adding a single HM to the background electrolyte (BGE), or a binary mixture of HMs. The results obtained confirm the excellent chiral selector properties of the HMs, and furthermore show that these compounds can also be used for achiral selection. When mixing different HMs, a complementary effect in chiral selectivity is observed, which, in our opinion, deserves further study.
J Chem Soc Perkin Trans 2, 1996
ABSTRACT
Journal of the Chemical Society Chemical Communications, 1992
ABSTRACT
J Incl Phenom Macrocycl Chem, 1996
In order to obtain better abiotic receptors for analytical and kinetic applications, the new capp... more In order to obtain better abiotic receptors for analytical and kinetic applications, the new capped derivative of cyclomaltoheptaose (CDTH) was synthesized by reaction of 6,6'-dideoxy-6,6'-di(S-cysteamine)-et, c~,'-trehalose ~ 6&6D-dideoxy-6A,6D-diiodo-cyclo-maltoheptaose. The CDTH-ACS (anthraqttinone-2-sulfonic acid sodium salt) system was investigated, by 1H NMR spectroscopy and by i.c.d. (induced circul~ dicroism), and a deep inclusion of ACS inside the CDTH cavity, with an association constant about six times larger with respect to ACS-~-CD system was formal. i.
Journal of the Chemical Society Dalton Transactions, 1992
J Incl Phenom Macrocycl Chem, 1993
The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]-/3-cyclodextrin was synthesized... more The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]-/3-cyclodextrin was synthesized, and an NMR, EPR, pH-metric, and calorimetric investigation was carried out in aqueous solution in order to ascertain its behaviour towards protonation and copper(II) complex formation. The thermodynamic parameters of the ternary complex formation with alanine, phenylalanine and tryptophan enantiomeric pairs were also determined (25 ~ C and I = 0.1 mol dm-3). No thermodynamic enantioselectivity was observed in these systems, while a chiral, though poor, discrimination was observed in LEC: c.d. spectra also show enantiomeric stereoselectivity. The results of the present investigation, compared with previously reported results, suggest the occurence of a cis-complex trans-complex equilibrium in such systems.
Http Dx Doi Org 10 1080 07328319708002538, Aug 20, 2006
ABSTRACT DSC measurements of binary, decanucleotide/L,L or L,D Ala-Trp, and ternary decanucleotid... more ABSTRACT DSC measurements of binary, decanucleotide/L,L or L,D Ala-Trp, and ternary decanucleotide/L,L or L,D Ala-Trp/Copper(II), systems have been carried out. The results obtained show the different behaviour of the two diastereoisomers both in the binary and in the ternary systems, ascribable to the different disposition of the side-chains in the dipeptides.
J Pharmaceut Biomed Anal, 2005
J Incl Phenom Macrocycl Chem, 1993
The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]-/3-cyclodextrin was synthesized... more The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]-/3-cyclodextrin was synthesized, and an NMR, EPR, pH-metric, and calorimetric investigation was carried out in aqueous solution in order to ascertain its behaviour towards protonation and copper(II) complex formation. The thermodynamic parameters of the ternary complex formation with alanine, phenylalanine and tryptophan enantiomeric pairs were also determined (25 ~ C and I = 0.1 mol dm-3). No thermodynamic enantioselectivity was observed in these systems, while a chiral, though poor, discrimination was observed in LEC: c.d. spectra also show enantiomeric stereoselectivity. The results of the present investigation, compared with previously reported results, suggest the occurence of a cis-complex trans-complex equilibrium in such systems.