Zengqi Zhang

Synthetic Methodology for the Fabrication of Porous Porphyrin Materials with Metal-Organic-Polymer Aerogels.

A promising fabrication strategy used for designing porous porphyrin materials and a group of rigid carboxyl porphyrins based metal-organic-polymer aerogels (MOPAs) has been proposed recently. These newly synthesized MOPAs were exemplarily characterized by FT-IR, UV-vis-DRS, EDS, PXRD, TGA, SEM, TEM, and gas sorption measurements. A gelation study has shown that solvents, molar ratio, temperature, and peripheral carboxyl number in porphyrins all affect gel generation. The MOPA series exhibit eminent thermal stability, high removal efficiency in dye adsorption, versatile morphologies, and permanent tunable porosity; also the BET surface areas fall within the range 249-779 m(2) g(-1). All of the mentioned properties are significantly superior to some other porous materials, which enable these compounds to be potential candidates for dye uptake, gas storage, and separation.

Synthesis and photodynamic activities of a new metronidazole-appended porphyrin and its Zn(II) complex

One novel porphyrin 5,10,15-tris(phenyl)-20-[4-(2-(2-methyl-5-nitro-imidazolyl)ethoxyl)phenyl] porphyrin and its zinc(II) metalloporphyrin were synthesized and characterized by IR, UV-vis, 1H NMR, MS and elemental analysis. The single crystal structure of zinc(II) porphyrin shows that the Zn(II) ion is coordinated with four nitrogen atoms of porphyrin ring and one oxygen atom of ethanol from axial, forming a five-coordinated square pyramidal geometry. Their cytotoxicity and photodynamic activity against breast cancer cells were studied. The results indicate that both of the porphyrins display high phototoxicity to the breast cancer cells with the negligible dark toxicity. In addition, the photodynamic activity of zinc(II) porphyrin was obviously higher than that of the free porphyrin.

Syntheses and structures of four transition metal coordination polymers constructed from 2,2′-bipyridyl-4,4′-dicarboxylate

Four transition metal(II) coordination polymers, [Mn(bpdc)(H2O)2] n (1), {Ni[(bpdc)(H2O)2] 2H2O}n (2), [Ni(bpdc)(H2O)2] n (3), and [Cu(bpdc)H2O)] n (4) (bpdc2− = 2,2′-bipyridyl-4,4′-dicarboxylate), have been assembled from 2,2′-bipyridyl-4,4′-dicarboxylic acid and corresponding transition metal(II) salts under hydrothermal conditions. Single-crystal X-ray diffraction studies show that each metal ion in 1–3 is coordinated by two nitrogens of bpdc2−, two carboxylate oxygens from bpdc2−, and two waters to give a distorted octahedral geometry. Copper in 4 is coordinated by two nitrogens of bpdc2−, two carboxylate oxygens from bpdc2−, and one water to form a pyramid geometry. Compounds 1 and 3 are 3-D coordination polymers bridged by bpdc2−, while 2 and 4 exhibit 2-D layer structures bridged by bpdc2−; the layers are further assembled through hydrogen bonds to form 3-D supramolecular frameworks. Thermogravimetric analyzes of 1–4 show high thermal stability.

Three metalloporphyrin frameworks containing imidazole groups: synthesis, characterization and properties

In this paper, we designed and synthesized three novel free-base imidazolyl porphyrins via the Macdonald [2 + 2] method, and their reactions with different metal ions afforded three new metalloporphyrin frameworks (MPFs) [Co(tBu-Ph)2(Im-Ph)2Por]·2DMF (1), [Co(F3-Ph)2(Im-Ph)2Por]·1.5DMF (2), and [Fe(Me2N, F4-Ph)2(Im-Ph)2Por]·3DMF (3), which display rich structural diversity. Complexes 1 and 2 are isostructural two-dimensional (2D) grid layers, which feature the rare rotaxane-like bilayer and an offset-stacking ABCD fashion of layers, as well as the significantly saddled porphyrin macrocycles. Differently, complex 3 forms a 4-connected lvt 3D framework with the slightly ruffled porphyrin macrocycles, which contains not only interesting helical channels but also uncommon tetrahedral cages. Gas adsorption studies of three complexes reveal the moderate CO2 adsorption capacity. Meanwhile, all three complexes exhibit preferable catalytic activity for ethylbenzene oxidation.

Novel porphyrin–Schiff base conjugates: synthesis, characterization and in vitro photodynamic activities

Three novel porphyrin–Schiff base conjugates derived from tetra(4-aminophenyl)porphyrin (TAPP), namely, tetra[4-(4-hydroxy benzylideneamino)]phenyl porphyrin (3a), tetra[4-(2-thienyldeneamino)]phenyl porphyrin (3b) and tetra[4-(2-pyridyldeneamino)]phenyl porphyrin (3c), were synthesized and characterized by IR, UV-vis, 1H NMR, HRMS and elementary analysis. Their biological activities against human epidermoid carcinoma (A431) cells were evaluated with an MTT assay. As we expected, the porphyrin conjugates showed negligible cytotoxicity to A431 cells in the absence of light, while their phototoxic activities were improved after irradiated with LED lamp (425 nm) and increased significantly with increased doses. The fluorescence microscope pictures revealed that the three porphyrin–Schiff conjugates could diffuse into skin cancer cells, demonstrating that these compounds are potential candidates for photodynamic therapy agents.

Synthesis of three novel imidazolyl-appended porphyrins and their cytostatic and phototoxic activity on A431 cells

Three imidazolyl-appended porphyrins were synthesized and characterized by 1H NMR, elemental analyses, MS and UV-vis spectra. Anticancer activities of porphyrins have been evaluated against cutaneous squamous cell carcinoma (A431 cells) in vitro. The results indicate that the porphyrins have high selective cytotoxicity towards A431 cells in the absence of light and improved phototoxic activity upon exposure to UV light. The yield of singlet oxygen generated by porphyrins were also evaluated by measuring the absorption decay of 1,3-diphenylisobenzofuran (DPBF) in DMF. The phototoxicities of porphyrins against A431 cells were enhanced along with the increase of singlet oxygen.