Cardiano Paola, Crea Francesco, Foti Claudia, Giuffrè Ottavia, Sammartano Silvio
Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, Università di Messina, Viale F. Stagno d'Alcontres 31, 98166 Messina, Italy.
Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, Università di Messina, Viale F. Stagno d'Alcontres 31, 98166 Messina, Italy.
Biophys Chem. 2017 May;224:59-66. doi: 10.1016/j.bpc.2017.04.001. Epub 2017 Apr 4.
A potentiometric, UV and H NMR study on Cu-ampicillin [(2S,5R,6R)-6-([(2R)-2-amino-2-phenylacetyl]amino)-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid] and -amoxicillin [(2S,5R,6R)-6-{[(2R)-2-amino-2-(4-hydroxyphenyl)-acetyl]amino}-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-24-carboxylic acid] systems in NaCl aqueous solution at I=0.15molL and t=25°C is reported. On the basis of potentiometric results two speciation models were proposed for each system. It was found that spectrophotometric and H NMR measurements are essential for selecting the most reliable speciation models. They included ML, MLOH and ML(OH) species in both systems and, only for Cu-ampicillin, also MLH species. The stability constants obtained by UV and H NMR titrations were comparable to the ones calculated by potentiometry. The sequestering ability of the ligands under study towards Cu by pL empiric parameter (ligand concentration required to sequester 50% of the metal cation present in traces) at several pH values was calculated as well. For ampicillin and amoxicillin, pL=7.19 and 6.67, respectively, at physiological pH, I=0.15molL and t=25°C were obtained.
报道了在I = 0.15mol/L且t = 25°C的NaCl水溶液中,对铜-氨苄青霉素[(2S,5R,6R)-6-([(2R)-2-氨基-2-苯乙酰基]氨基)-3,3-二甲基-7-氧代-4-硫杂-1-氮杂双环[3.2.0]庚烷-2-羧酸]和铜-阿莫西林[(2S,5R,6R)-6-{[(2R)-2-氨基-2-(4-羟基苯基)-乙酰基]氨基}-3,3-二甲基-7-氧代-4-硫杂-1-氮杂双环[3.2.0]庚烷-2-羧酸]体系进行的电位、紫外和氢核磁共振研究。基于电位测定结果,为每个体系提出了两种物种形成模型。发现分光光度法和氢核磁共振测量对于选择最可靠的物种形成模型至关重要。两个体系中均包括ML、MLOH和ML(OH)物种,且仅对于铜-氨苄青霉素体系还包括MLH物种。通过紫外和氢核磁共振滴定获得的稳定常数与通过电位法计算的稳定常数相当。还计算了在几个pH值下,所研究配体通过pL经验参数(螯合痕量中存在的50%金属阳离子所需的配体浓度)对铜的螯合能力。对于氨苄青霉素和阿莫西林,在生理pH、I = 0.15mol/L且t = 25°C时,分别得到pL = 7.19和6.67。