title: Metal-organic frameworks with phosphotungstate incorporated for hydrolytic cleavage of a DNA-model phosphodiester.
abstract: Five phosphotungstate-incorporated metal-organic frameworks {[Eu(4)(dpdo)(9)(H(2)O)(16)PW(12)O(40)]}(PW(12)O(40))(2)·(dpdo)(3)·Cl(3) (1); {ZnNa(2)(μ-OH)(dpdo)(4)(H(2)O)(4)[PW(12)O(40)]}·3H(2)O (2); {Zn(3)(dpdo)(7)}[PW(12)O(40)](2)·3H(2)O (3); and [Ln(2)H(μ-O)(2)(dpdo)(4)(H(2)O)(2)][PW(12)O(40)]·3H(2)O (Ln = Ho for 4 and Yb for 5) (dpdo = 4,4'-bipyridine-N,N'-dioxide) have been synthesized through a one-step hydrothermal reaction and characterized by elemental analyses, infrared (IR) spectroscopy, photoluminescence, and single-crystal X-ray diffraction (XRD). The structural analyses indicate that 1-5 display diversity structure from one-dimensional (1D) to three-dimensional (3D) series of hybrids. Kinetic experiments for the hydrolytic cleavage of DNA-model phosphodiester BNPP (bis(p-nitrophenyl)phosphate) were followed spectrophotometrically for the absorbance increase at 400 nm in EPPS (4-(2-hydroxyethyl)piperazine-1-propane sulfonic acid) buffer solution, because of the formation of p-nitrophenoxide with 1-5 under conditions of pH 4.0 and 50 °C. Ultraviolet (UV) spectroscopy indicate that the cleavage of the phosphodiester bond proceeds with the pseudo-first-order rate constant in the range of 10(-7)-10(-6) s(-1), giving an inorganic phosphate and p-nitrophenol as the final products of hydrolysis. The results demonstrate that 1-5 have good catalytic activity and reusability for hydrolytic cleavage of BNPP.
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian Technology of University, Dalian, 116023, People's Republic of China.
authors.forename: Qiuxia
authors.initials: Q
authors.lastname: Han
authors.forename: Lejie
authors.initials: L
authors.lastname: Zhang
authors.forename: Cheng
authors.initials: C
authors.lastname: He
authors.forename: Jiangyang
authors.initials: J
authors.lastname: Niu
authors.forename: Chunying
authors.initials: C
authors.lastname: Duan
mesh_terms: D004247:DNA / Q000737:chemistry*; D004952:Esters; D006868:Hydrolysis; D008163:Luminescent Measurements; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D017973:Tungsten Compounds / Q000737:chemistry*
chemical_list: D004952:Esters; D009942:Organometallic Compounds; D017973:Tungsten Compounds; D010758:Phosphorus; D004247:DNA; C045951:tungstate