Jaros Sabina W, Guedes da Silva M Fátima C, Król Jarosław, Conceição Oliveira M, Smoleński Piotr, Pombeiro Armando J L, Kirillov Alexander M
Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa , Av. Rovisco Pais, 1049-001 Lisbon, Portugal.
Department of Pathology, Wrocław University of Environmental and Life Sciences , ul. Norwida 31, 50-375 Wrocław, Poland.
Inorg Chem. 2016 Feb 15;55(4):1486-96. doi: 10.1021/acs.inorgchem.5b02235. Epub 2016 Jan 26.
Three novel bioactive silver-organic networks, namely, the 2D polymer [Ag(μ3-PTA)(chc)]n·n(Hchc)·2nH2O (1), the 3D bioMOF [Ag2(μ3-PTA)2(μ2-chdc)]n·5nH2O (2), and the 2D polymer [Ag2(μ2-PTA)2(μ4-H2chtc)]n·6nH2O (3), were constructed from 1,3,5-triaza-7-phosphaadamantane (PTA) and various flexible cyclohexanecarboxylic acids as building blocks {cyclohexanecarboxylic (Hchc), 1,4-cyclohexanedicarboxylic (H2chdc), and 1,2,4,5-cyclohexanetetracarboxylic (H4chtc) acid, respectively}. The obtained products 1-3 were fully characterized by IR and NMR spectroscopy, ESI-MS(±) spectrometry, elemental and thermogravimetric (TGA) analyses, and single-crystal and powder X-ray diffraction. Their structural diversity originates from distinct coordination modes of cyclohexanecarboxylate moieties as well as from the presence of unconventional N,N,P-tridentate or N,P-bidentate PTA spacers. Topological classification of underlying metal-organic networks was performed, disclosing the hcb, 4,4L28, and a rare fsc-3,4-Pbcn-3 topology in 1, 2, and 3, respectively. Moreover, combination of aqueous solubility (S25°C ≈ 4-6 mg mL(-1)), air stability, and appropriate coordination environments around silver centers favors a release of bioactive Ag(+) ions by 1-3, which thus act as potent antibacterial and antifungal agents against Gram-positive (S. aureus) and Gram-negative (E. coli and P. aeruginosa) bacteria as well as a yeast (C. albicans). The best normalized minimum inhibitory concentrations (normalized MIC) of 10-18 (for bacterial strains) or 57 nmol mL(-1) (for a yeast strain) were achieved. Detailed ESI-MS studies were performed, confirming the relative stability of 1-3 in solution and giving additional insight on the self-assembly formation of polycarboxylate Ag-PTA derivatives and their crystal growth process.
通过以1,3,5 - 三氮杂 - 7 - 磷杂金刚烷（PTA）和各种柔性环己烷羧酸为结构单元{分别为环己烷羧酸（Hchc）、1,4 - 环己烷二甲酸（H2chdc）和1,2,4,5 - 环己烷四甲酸（H4chtc）}，构建了三种新型生物活性银 - 有机网络，即二维聚合物[Ag(μ3 - PTA)(chc)]n·n(Hchc)·2nH2O（1）、三维生物金属有机框架[Ag2(μ3 - PTA)2(μ2 - chdc)]n·5nH2O（2）以及二维聚合物[Ag2(μ2 - PTA)2(μ4 - H2chtc)]n·6nH2O（3）。通过红外光谱、核磁共振光谱、电喷雾电离质谱（ESI - MS(±)）、元素分析和热重分析（TGA）以及单晶和粉末X射线衍射对所得到的产物1 - 3进行了全面表征。它们的结构多样性源于环己烷羧酸部分不同的配位模式以及非常规的N,N,P - 三齿或N,P - 双齿PTA间隔基的存在。对基础金属 - 有机网络进行了拓扑分类，分别在1、2和3中揭示了hcb、4,4L28以及罕见的fsc - 3,4 - Pbcn - 3拓扑结构。此外，水溶性（25°C时S≈4 - 6 mg mL(-1)）、空气稳定性以及银中心周围合适的配位环境相结合，有利于1 - 3释放生物活性Ag(+)离子，因此它们对革兰氏阳性菌（金黄色葡萄球菌）、革兰氏阴性菌（大肠杆菌和铜绿假单胞菌）以及酵母菌（白色念珠菌）具有强效抗菌和抗真菌活性。实现了10 - 18（针对细菌菌株）或57 nmol mL(-1)（针对酵母菌菌株）的最佳归一化最低抑菌浓度（归一化MIC）。进行了详细的ESI - MS研究，证实了1 - 3在溶液中的相对稳定性，并对多羧酸银 - PTA衍生物的自组装形成及其晶体生长过程提供了更多见解。
