Interactions of Polyvinylpyrrolidone with Chlorin e6-Based Photosensitizers Studied by NMR and Electronic Absorption Spectroscopy

Interactions of Polyvinylpyrrolidone with Chlorin e6-Based Photosensitizers Studied by NMR and Electronic Absorption Spectroscopy
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DOI:
10.1021/acs.jpcb.5b05761
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发表时间:
2015-09-10
影响因子:
3.3
通讯作者:
Vermathen, Martina
Vermathen, Martina
中科院分区:
化学3区
文献类型:
--
作者:
Haedener, Marianne;Gjuroski, Ilche;Vermathen, Martina

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聚乙烯吡咯烷酮(PVP)可以作为光动力学治疗(PDT)中卟啉类光敏剂的潜在药物载体,以提高其稳定性并防止卟啉自缔合。在本研究中,PVP(分子量10 kDa)的相互作用进行了探测与五种不同的衍生物的二氢卟酚e6(CE 6)轴承的氨基酸丝氨酸,赖氨酸,酪氨酸或精氨酸,或单氨基己酸作为取代基。CE 6(xCE)的所有衍生物在毫摩尔范围内在水性缓冲液中形成类似结构的聚集体。在PVP的存在下,所有xCE聚集体的单体化可以通过H-1 NMR光谱来证明。xCE-PVP复合物的形成通过1H-1 NMR T-2弛豫和扩散有序光谱(DOSY)证实。(HH)-H-1-H-1-NOESY数据表明,PVP聚合物基质中的xCE摄取受疏水相互作用控制。xCE在微摩尔范围内的紫外-可见吸收和荧光发射带显示特征PVP诱导的红移。所提出的数据指出了PVP作为二氢卟酚e6的两亲性衍生物的载体系统的潜力。PVP使xCE聚集体单体化的能力可以提高它们作为PDT中可能的光敏剂的效率。
Polyvinylpyrrolidone (PVP) can act as potential drug delivery vehicle for porphyrin-based photosensitizers in photodynamic therapy (PDT) to enhance their stability and prevent porphyrin self-association. In the present study the interactions of PVP (MW 10 kDa) were probed with five different derivatives of chlorin e6 (CE6) bearing either one of the amino acids serine, lysine, tyrosine or arginine, or monoamino-hexanoic acid as substituent. All derivatives of CE6 (xCE) formed aggregates of a similar structure in aqueous buffer in the millimolar range. In the presence of PVP monomerization of all xCE aggregates could be proved by H-1 NMR spectroscopy. xCE-PVP complex formation was confirmed by H-1 NMR T-2 relaxation and diffusion ordered spectroscopy (DOSY). (HH)-H-1-H-1-NOESY data suggested that the xCE uptake into the PVP polymer matrix is governed by hydrophobic interactions. UV-vis absorption and fluorescence emission bands of xCE in the micromolar range revealed characteristic PVP-induced bathochromic shifts. The presented data point out the potential of PVP as carrier system for amphiphilic derivatives of chlorin e6. The capacity of PVP to monomerize xCE aggregates may enhance their efficiency as possible photosensitizers in PDT.