One-pot synthesis of novel phosphoramidates with porphine and nitrogenous drug was accomplished. In the absence of light, MTT test showed that they killed the BEL-7402 liver cancer cells effectively in vitro. The cell viability studied on normal liver and cancer cells showed that porphine phosphoramidates selectively kill the cancer cells, which was in sharp contrast with the non-porphine containing compound 4-formylphenyl N,N-bis(2-chloroethyl)-phosphoramidate. These results, coupled with the cell uptake test showing that they could differentiate the tumor cells from the normal cells by their selective accumulation in cancer cells, gave strong support to the notion that the introduction of porphine moiety in these molecules was responsible for the effectiveness and cell differentiability of these porphine phosphoramidates.

In this paper, a series of nanoparticle bonded metalloporphyrins with different saturation magnetization were synthesized by a modified silanation method. Under geomagnetic field (5 × 10−5 T), with the increase of the saturation magnetizations, the growth rate of yields of cyclohexanol in the cyclohexane oxidation with iodosylbenzene catalyzed by these nanoparticle bonded metalloporphyrins followed the order of ironporphyrin > manganeseporphyrin > cobaltporphyrin.

A novel and convenient approach to chlorophins and bacteriophins has been developed through a degradation of nickel(II) 2,3,12,13-tetrabromo-5,10,15,20-tetraarylporphyrins by the anion of E-benzaldoxime. The UV−vis spectra of these chlorophins and bacteriophins are similar to those of metalated chlorin and bacteriochlorin systems but with more intense and bathochromically shifted Q-bands.

An efficient oxidative Mannich reaction between tertiary amines and unmodified methyl ketones has been developed, using copper salts as the catalyst and O2 as the oxidant.

Four novel porphyrins containing nitric oxide (NO) donors were synthesized, and the structures of all the products were characterized by IR, UV–vis, 1H NMR, and elementary analysis. Interestingly, these new compounds not only were able to release NO, but also showed cancer cell-oriented accumulation. Higher accumulation of these new porphyrins containing NO donors in BEL-7402 liver cancer cells than in L-02 liver normal cells was corroborated by UV–vis spectroscopy. The biological activity of these porphyrins against BEL-7402 liver cancer cells was tested with a MTT assay. The studies indicated that they had more effective killing of BEL-7402 liver cancer cells than that of L-02 liver normal cells, and they had similar activity against MCF-7 breast cancer cells when compared to 5-fluorouracil in the absence of light.Four porphyrins with NO donors were synthesized, and the cancer cell-oriented accumulation and NO release from the porphyrins were found. The porphyrins with NO donor had more effective killing of BEL-7402 liver cancer cells than L-02 liver normal cells.

o-Acetaminophenols (2) reacted with Vilsmeier reagent under Meth-Cohn conditions to yield 2-formylpyrido[2,1-b]benzoxazoles (5) unexpectedly besides the known compounds 2-(benzoxazol-2′-yl)-3-dimethylaminoacroleins (4). Refluxing 4 in acetic anhydride gave 4-formylpyrido[2,1-b]benzoxazoles (6), an isomer of 5. Both 5a and 6a were structurally characterized by X-ray crystallography. A mechanism for the formation of 5 involving sequential chlorination, dimerization, intramolecular elimination of HCl to form the oxazole ring, formylation twice, and regioselective intramolecular nucleophilic cyclization to construct the pyridone ring is proposed.

Quantitative structure–activity relationship (QSAR) studies were performed on the ironporphyrin-catalyzed biomimetic oxidation of cyclohexane. Through quantum chemical calculations, the molecular structures of nine different ironporphyrin catalysts have been optimized and their respective quantum chemical descriptors (FMO energies EHOMO, ELUMO, FMO energy gap DEHL, partition coefficient log P) have been obtained. The ironporphyrin-catalyzed cyclohexane hydroxylation with PhIO was chosen as the model reaction. The yield of cyclohexanol (yield (%)) and the reaction rate constant (lg k) were obtained experimentally, and the reaction kinetics was studied accordingly. 2D-QSAR studies for ironporphyrin catalysts were performed by using multiple linear regression (MLR) analysis. From the established QSAR model equations of lg k, yield (%) and the quantum chemical descriptors (lg k = −1.433 + 0.009 log P − 0.406ELUMO-bR = 0.968 and yield (%) = 9.556 + 0.500 log P − 8.997ELUMO-bR = 0.821), we conclude that it is the frontier molecular orbital (FMO) energy level ELUMO-b which has the most significant effect on the catalytic activity of the ironporphyrins. Further molecular graphics studies and Mulliken's electron population analysis indicated that the energy level of ELUMO-b can be altered by introducing peripheral substituting groups on the meso-phenyl ring. Since the electron withdrawing substituents could lower ELUMO-b and disperse the electron density of around the centro-metal core of porphyrin better, they can facilitate ironporphyrin's binding with the oxidant and, consequently increase the catalytic activity of ironporphyrin. We also notice that the partition coefficient log P of ironporphyrin molecule affects the reaction rate and the yield of the cyclohexane hydroxylation reaction as well. Our study may be beneficial for future catalyst design for the metalloporphyrin-catalyzed hydrocarbon oxidations.QSAR studies had been applied to investigate the cyclohexane hydroxylation reaction catalyzed by nine ironporphyrin derivatives. The ironporphyrin molecular structures’ optimization and quantum chemical descriptors have been obtained based on quantum chemical calculations. Bi-parametric QSAR model equations for the rate constant lg k and cyclohexanol yield had been built separately by the MLR analysis.

The aerobic liquid-phase oxidation of p-xylene (PX) over metalloporphyrin and Co(OAc)2 was studied, and the co-catalysis between metalloporphyrin and Co(OAc)2 for the oxidation of PX was discovered for the first time. The results showed that both the PX conversion and terephthalic acid yield could be increased significantly despite the fact that only a minute amount of metalloporphyrin was added to the reaction mixture in addition to the Co(OAc)2 catalyst. The effects of the structure of metalloporphyrin and reaction conditions such as temperature, air pressure and catalyst concentration on the overall reaction performance were also studied. A possible mechanism for the observed synergy between metalloporphyrin and Co(OAc)2 as co-catalysts for the aerobic liquid-phase oxidation of PX was proposed based on some experimental observations. The results suggested that the PX oxidation was improved because of the acceleration of the chain initiation of PX oxidation by metalloporphyrin, and the acceleration of the chain initiation itself was due to the ease of peroxide formation over metalloporphyrin.The aerobic liquid-phase oxidation of p-xylene (PX) over metalloporphyrin–Co(OAc)2 was studied, and the co-catalysis between metalloporphyrin and Co(OAc)2 for the oxidation of PX was discovered. A possible mechanism for the observed synergy between metalloporphyrin and Co(OAc)2 as co-catalysts for the aerobic liquid-phase oxidation of PX was proposed based on some experimental observations.

The aerobic oxidation of p-menthane to p-menthane hydroperoxide (PMHP) in the presence of metalloporphyrins was investigated in an intermittent mode under an atmospheric pressure of air. Several important reaction parameters, such as the structure of metalloporphyrin, the air flow rate, and the temperature, were studied. The preliminary mechanism of the aerobic oxidation of p-menthane catalyzed by metalloporphyrins was also discussed. The results show that the reaction is greatly accelerated by the addition of metalloporphyrins at very low concentration, in terms of both the yield and formation rate of PMHP, and the high selectivity of PMHP is maintained during the reaction. Temperature of 120 °C and reaction time of around 5 h are the optimal conditions for the best result in the presence of 0.06 mmol/L monomanganeseporphyrins ((p-Cl)TPPMnCl). Furthermore, the yield of PMHP is increased remakably when the reaction is carried out under programmed temperature compared with the constant temperature. When the reaction is catalyzed by 0.06 mmol/L((p-Cl)TPPMnCl) at the air flow rate of 600 mL/min and 120 °C for 4 h, and then the temperature is reduced to 110 °C, for another 4 h, the yield of PMHP reaches 24.3%, which is higher than that of the reaction at a constant temperature of 120 °C or 110 °C for 8 h.

An efficient oxidative Mannich reaction between tertiary amines and unmodified methyl ketones has been developed, using copper salts as the catalyst and O2 as the oxidant.