Modes of tetra(4-pyridyl)porphyrinatomanganese(III) ion intercalation inside natural clays.

BACKGROUND: Metalloporphyrin ions, with planar shape, have been known to intercalate horizontally and diagonally between montmorillonite layers. Perpendicular intercalation inside montmorillonite has not been reported earlier. This work aims at achieving perpendicular intercalation inside montmorillonite in natural clays. Possible intercalation inside other forms of natural clay will also be investigated. METHODS: Natural clays were purified and characterized. The naked clay powder was then refluxed with tetra(4-pyridyl)porphyrinatomanganese(III) ion (MnTPyP(+)) solution in methanol with continuous stirring for different times. Electronic absorption spectra, atomic absorption spectra, Fourier Transform infrared spectra, scanning electron microscopy and X-ray diffraction were all used in clay characterization and in intercalation study. RESULTS: The natural clay involved different phases, namely montmorillonite, biotite, kaolinite, illite and traces of quartz. Montmorillonite clay allowed horizontal, diagonal and perpendicular intercalation of the metalloporphyrin ions. Biotite allowed only horizontal intercalation. The mode of intercalation was deduced by monitoring the clay inter-planar distance value change. Intercalation occurred inside both micro- and nano-size clay powders to different extents. The nano-powder (average size ~50 nm) showed uptake values up to 3.8 mg MnTPyP/g solid, whereas the micro-size powder (average size ~316 nm) exhibited lower uptake (2.4 mg MnTPyP/g solid). Non-expandable clay phases did not allow any intercalation. The intercalated MnTPyP(+) ions showed promising future supported catalyst applications. CONCLUSIONS: Depending on their phase, natural clays hosted metalloporphyrin ions. Montmorillonite can allow all three possible intercalation geometries, horizontal, diagonal and for the first time perpendicular. Biotite allows horizontal intercalation only. Non-expandable clays allow no intercalation. Graphical abstractMetalloporphyrin complexes can be intercalated into montmorillonite in horizontal, perpendicular and diagonal geometries.

In vitro antioxidant and antitumor activities of six selected plants used in the Traditional Arabic Palestinian herbal medicine.

CONTEXT: Despite several pharmacological applications of the medicinal plants in the Traditional Arabic Palestinian Herbal Medicine in Palestine (TAPHM), studies on their antioxidant properties are still scarce. OBJECTIVE: This work evaluates the antioxidant and antitumor activities of the ethanol extracts from different parts of six plants: [Arum palaestinum Boiss (Araceae), Urtica pilulifera L. (Urticaceae), Coridothymus capitatus (L.) Reichb (Lamiaceae), Majorana syriaca (L.) Rafin. (Lamiaceae), Teucrium creticum L. (Lamiaceae), and Teucrium capitatum L. (Lamiaceae)] used in the TAPHM. MATERIALS AND METHODS: The antioxidant activity was evaluated for the ethanol extracts by DPPH and ß-carotene-linoleic acid assays together with total contents of phenols and flavonoids. For the anti-carcinogenic evaluation, the extracts were tested for the ability to inhibit the proliferation of breast cancer cells (MCF-7) using the MTT reduction assay. RESULTS: Among the extracts, the U. pilulifera had the highest amount of total phenolics, possessing the second highest total flavonoids. It also showed a maximum cytotoxic activity (IC50 = 63 µg/ml), followed by C. capitatus, and A. palaestinum. Otherwise, the extract of T. creticum was demonstrated to be an efficient scavenger of O2 (IC50 = 83 µg/ml), followed by M. syriaca, C. capitatus, T. capitatum, A. palaestinum, and U. pilulifera. DISCUSSION AND CONCLUSION: The results suggest that the investigated plants have shown varied antioxidant capacities which were strongly correlated with their contents of phenolics. Accordingly, this study proposes that the therapeutic benefit of these plants can be, at least in part, attributed to its potential inhibition of oxidative processes.

Synthesis and Biological Evaluation of Novel Mono Acid Esters Derived from the Constituents of Urtica pilulifera.

New mono acid esters have been synthesized from the reaction of benzoic acid and mono-hydroxybenzoic acids with 2-phenoxyethanol separated from Urtica pilulifera, characterized, and screened for possible antioxidant, antifungal, antimicrobial and anticancer activities. These phenolic acid esters gave various degrees of free radical scavenging, but the values were lower than that of α-tocopherol. The concentrations of the tested compounds needed to reduce DPPH absorption by 50% at 517 nm were nearly in the range of 900-1100 µg/mL. While for α-tocopherol was 40 µg /mL. The compounds were tested in-vitro against six bacterial species which are known to cause dermic and mucosal infections in human. 2-phenoxyethyl benzoate showed significant activity in the range of 30% against P. aeruginosa to 70% against E. coli compared with the activity of Streptomycin. On the other hand 2-phenoxyethyl 2-hydroxybenzoate reveals 70% of gentamicin against K. pneumoniae. The tested compounds also showed complete inhibition at a concentration less than 37.5 µg/mL against M. canis and less than 50 µg/mL against T. rubrum. 2-phenoxyethyl 4-hydroxybenzoate showed considerable activity against MCF-7 with IC50 is less than 62.5 µg/mL.