Department of Medicinal Chemistry, Delbert M. Shankel Structural Biology Center, and The Small-Molecule X-ray Crystallography Laboratory, University of Kansas, Lawrence, Kansas 66047, USA.
Mol Pharm. 2011 Feb 7;8(1):297-301. doi: 10.1021/mp100363f. Epub 2010 Dec 17.
Aqueous solubilities of many drugs in current clinical use are very low, necessitating formulations that often present problems for parenteral administration, including toxicities due to the excipients used. Recognizing that pharmacologically active compounds frequently possess amines, we asked whether pyridoxal phosphate (PLP), an inoccuous, water-soluble vitamin, could be utilized to form prodrug-like complexes via the formation of imine or iminium adducts and whether the vitamin would impart solubilizing properties to such complexes. Direct spectroscopic and crystallographic data obtained using model primary and secondary amines showed that PLP forms stable imine adducts with primary amines under entirely aqueous conditions and at physiologic pH, while no reaction was observed for secondary amines; the basis of the exceptional stability appears to be a consequence of favorable H-bond interactions of the imine nitrogen with the 5-OH group of PLP. Amphotericin B and nystatin in their native forms display marked aqueous insolubility and possess lone primary amines. We were able to utilize PLP in achieving excellent solubilization of both of these antifungal agents, surpassing aqueous solubilities of 100 mg/mL. In in vitro bioassays, both polyenes in their PLP-adducted form display attenuated antifungal potencies which are attributable to "prodrug-like" complexes. These results point to the utility of excipient-free, entirely aqueous formulations of amphotericin B for parenteral use, and may also be extended to other primary amine-bearing compounds exhibiting poor aqueous solubility.
许多目前临床使用的药物的水溶解度非常低,这就需要制剂,而这些制剂常常给注射给药带来问题,包括由于所用赋形剂引起的毒性。鉴于具有药理活性的化合物通常含有胺,我们想知道吡哆醛磷酸盐(PLP)是否可以被用来通过形成亚胺或亚胺加合物来形成前药样复合物,以及维生素是否会赋予这些复合物溶解性质。使用模型伯胺和仲胺获得的直接光谱和晶体学数据表明,PLP 在完全水条件下和生理 pH 值下与伯胺形成稳定的亚胺加合物,而仲胺则没有反应;这种异常稳定性的基础似乎是亚胺氮与 PLP 的 5-OH 基团之间有利的氢键相互作用的结果。两性霉素 B 和制霉菌素在其天然形式下显示出明显的水不溶性,并具有单独的伯胺。我们能够利用 PLP 实现这两种抗真菌剂的优异溶解,超过 100mg/ml 的水溶解度。在体外生物测定中,两种多烯在其 PLP 加合物形式下均显示出减弱的抗真菌效力,这归因于“前药样”复合物。这些结果表明,两性霉素 B 的无赋形剂、完全水制剂可用于注射,并且也可扩展到其他具有较差水溶解度的含有伯胺的化合物。