Synthesis and characterization of novel zinc phthalocyanines as potential photosensitizers for photodynamic therapy of cancers.

Two novel zinc phthalocyanines (Pcs): tetramethyl tetrakis-2,(3)-[(4-methyl-2-pyridyloxy)phthalocyaninato] zinc(II) (4) and (the negatively charged form) tetrakis-2,(3)-[(3-carboxylicacid-6-sulfanylpyridine)phthalocyaninato] zinc(II) (5), water soluble by virtue of their ionic substituent groups were synthesized. The spectroscopic properties of both compounds were determined and their photodynamic activities were investigated in a human tumor cell model. In aqueous media the two peripherally substituted water soluble Pcs are highly aggregated. The phototoxic activity of the two novel Pcs (Pc 4 and Pc 5; 0-20 µM) was shown to be time- and dose-dependent in human pancreatic carcinoid BON cells, leading to a reduction of tumor cells of >80% compared to the controls. The effectiveness of the treatment appeared to be attenuated by the aggregation of Pcs under aqueous conditions. Interestingly, even those cells that were not immediately killed by the photoactivated photosensitizer seemed to be affected by the Pc photodynamic activity, as a single PDT induced long-lasting effects on cell survival. Even 4 days after PDT, the number of surviving cells did not re-increase or still dropped, as compared to control cells. The underlying mechanism of this observation has to be deciphered in future investigations.

Secondary metabolites from Tetracera potatoria stem bark with anti-mycobacterial activity.

ETHNOPHARMACOLOGICAL RELEVANCE: Tetracera potatoria Afzel. Exg. Don (Dilleniaceae) is a medicinal plant used traditionally in Africa for the treatment of tuberculosis related ailments and respiratory infections. The antibacterial activity of the medium polar extracts of T. potatoria leaves and stem bark was recently reported against Mycobacterium smegmatis (MIC 25µg/mL) and M. aurum (65µg/mL), two fast-growing Mycobacterium strains used as model micro-organisms for the more pathogenic strain Mycobacterium tuberculosis (Fomogne-Fodjo et al., 2014). The aim of this study was consequently to isolate the compounds possibly contributing to this activity, and which may therefore be promising precursors to be used for the development of novel anti-TB drugs. MATERIALS AND METHODS: T. potatoria medium polar extract [MeOH/DCM (1:1, v/v)] was fractionated sequentially with petroleum ether to which EtOAC and MeOH were gradually added to increase the polarity. The examination of T. potatoria extract and its fractions was guided by bioassays for anti-mycobacterial activity against M. smegmatis (ATCC 23246) and M. aurum (NCTC 10437) using the minimum inhibitory concentration (MIC) method. All the isolated compounds were structurally elucidated using spectroscopic techniques and evaluated for their anti-mycobacterial activity. RESULTS: Two novel secondary metabolites (1, 2) named tetraceranoate and N-hydroxy imidate-tetracerane, together with five known compounds [ß-stigmasterol (3), stigmast-5-en-3ß-yl acetate (4), betulinic acid (5), betulin (6) and lupeol (7)] were isolated and identified. Tetraceranoate exhibited the best activity against M. smegmatis with a minimum inhibitory concentration (MIC) of 7.8µg/mL, while ß-stigmasterol, betulinic acid and betulin showed appreciable anti-mycobacterial activity against both strains (MIC 15µg/mL). CONCLUSION: Seven compounds were isolated from the medium polar extract [MeOH/DCM (1:1, v/v)] of T. potatoria stem bark. Only tetraceranoate one of the isolated compounds showed antibacterial activity against M. smegmatis having efficacy as high as rifampicin (one of a three drug regimen recommended in the initial phase short-course anti-tuberculosis therapy). Thus, tetraceranoate might be an interesting target for systematic testing of anti-TB treatment and management. This research supports the use of T. potatoria in African traditional medicine for the treatment of tuberculosis related symptoms.

Antibacterial effects of Alchornea cordifolia (Schumach. and Thonn.) Müll. Arg extracts and compounds on gastrointestinal, skin, respiratory and urinary tract pathogens.

ETHNOPHARMACOLOGICAL RELEVANCE: The leaves, stems and roots of Alchornea cordifolia (Schumach. and Thonn.) Müll. Arg. are used as traditional medicine in many African countries for the management of gastrointestinal, respiratory and urinary tract infections as well as for the treatment of wounds. AIM OF THE STUDY: To determine the in vitro antibacterial activity of the crude extracts of leaves and stems of A. cordifolia on gastrointestinal, skin, respiratory and urinary tract pathogens and to identify the compounds in the extracts that may be responsible for this activity. MATERIALS AND METHODS: The antibacterial activities of crude extracts [hexane, chloroform (CHCl3), ethyl acetate (EtOAc), ethanol (EtOH), methanol (MeOH) and water (H2O)] as well as pure compounds isolated from these extracts were evaluated by means of the micro-dilution assay against four Gram-positive bacteria, i.e. Bacillus cereus ATCC 11778, Enterococcus faecalis ATCC 29212, Staphylococcus aureus ATCC 25923 and S. saprophyticus ATCC 15305, as well as four Gram-negative bacterial strains, i.e. Escherichia coli ATCC 25922, Klebsiella pneumoniae ATCC 13883, Moraxella catarrhalis ATCC 23246 and Proteus mirabilis ATCC 43071. The isolation of the active constituents was undertaken by bio-autographic assays in conjunction with chromatographic techniques. The identification and characterisation of the isolated compounds were done using mass spectrometry (MS) and Fourier transformed infrared spectrometry (FTIR) as well as 1D- and 2D- nuclear magnetic resonance (NMR) analyses. RESULTS: The leaves and stems of A. cordifolia exhibited varied antibacterial activity against all eight pathogens. Most of the MIC values ranged between 63 and 2000µg/ml. The highest activities for the crude extracts (63µg/ml) were observed against S. saprophyticus [stem (EtOAc, CHCl3 and hexane), leaves (MeOH, EtOH, EtOAc and CHCl3)], E. coli [stem (MeOH and EtOH), leaves (MeOH, EtOH, EtOAc and CHCl3)], M. catarrhalis [leaves (EtOAc and CHCl3)], K. pneumoniae [stem (CHCl3), leaves (CHCl3)] and S. aureus [leaves (CHCl3)]. Seven constituents [stigmasterol (1), stigmasta-4,22-dien-3-one (2), friedelin (3), friedelane-3-one-28-al (4), 3-O-acetyl-aleuritolic acid (5), 3-O-acetyl-erythrodiol (6) and methyl-3,4,5-trihydroxybenzoate (methyl gallate) (7)] were isolated from the stem MeOH extract. All these compounds displayed some antibacterial activity against the eight pathogens with highest activity against S. saprophyticus (2µg/ml). Furthermore, this is the first report of compounds 1, 2, 3, 4, 6 and 7 isolated from A. cordifolia and where a complete set of 2D-NMR data for fridelane-3-one-28-al (4) is presented. CONCLUSION: The study demonstrated that the antibacterial activities of A. cordifolia extracts may be due to the presence of the seven isolated compounds, where compounds 3-6 showed the best activity. The observed activity against gastrointestinal, skin, respiratory and urinary tract pathogens supports the traditional use for the treatment of such ailments.

Preparation and use of maize tassels' activated carbon for the adsorption of phenolic compounds in environmental waste water samples.

The determination and remediation of three phenolic compounds bisphenol A (BPA), ortho-nitrophenol (o-NTP), parachlorophenol (PCP) in wastewater is reported. The analysis of these molecules in wastewater was done using gas chromatography (GC) × GC time-of-flight mass spectrometry while activated carbon derived from maize tassel was used as an adsorbent. During the experimental procedures, the effect of various parameters such as initial concentration, pH of sample solution, eluent volume, and sample volume on the removal efficiency with respect to the three phenolic compounds was studied. The results showed that maize tassel produced activated carbon (MTAC) cartridge packed solid-phase extraction (SPE) system was able to remove the phenolic compounds effectively (90.84-98.49%, 80.75-97.11%, and 78.27-97.08% for BPA, o-NTP, and PCP, respectively). The MTAC cartridge packed SPE sorbent performance was compared to commercially produced C18 SPE cartridges and found to be comparable. All the parameters investigated were found to have a notable influence on the adsorption efficiency of the phenolic compounds from wastewaters at different magnitudes.

Antibacterial activities of plants from Central Africa used traditionally by the Bakola pygmies for treating respiratory and tuberculosis-related symptoms.

ETHNOPHARMACOLOGICAL RELEVANCE: The antibacterial activities of 18 plants from 10 different families were investigated for their antimicrobial efficacy, based on the traditional uses of these species by Bakola pygmies living in Central Africa, especially along the Ngoyang area in Cameroon for the treatment of respiratory and tuberculosis-related symptoms. The aim of the study is to test the antimicrobial efficacy of these plants against some pathogens associated with respiratory disease and to determine if there is any validation for the traditional use against Mycobacterium species. MATERIALS AND METHODS: Medium polar extracts were prepared in MeOH/DCM (1:1, v/v) from the plant parts of each species used traditionally and were assayed against pathogens associated with respiratory tract ailments [Staphylococcus aureus (ATCC 25923), Klebsiella pneumoniae (ATCC 13883) and Morexella cattarhalis (ATCC 14468)] using the minimum inhibitory concentration (MIC) method. Two additional faster growing Mycobacterium strains [Mycobacterium smegmatis (ATCC 23246) and Mycobacterium aurum (NCTC 10437)] were included in the assay as predictive test organisms for the more pathogenic strain Mycobacterium tuberculosis. RESULTS: Some plant species, such as Alchornea floribunda, Musanga cecropioides (both leaves and stem bark), Tetracera potatoria and Xylopia aethiopica (stem bark), were effective in inhibiting Morexella cattarhalis, having MIC values between 65 and 250 µg/mL. Some noteworthy antimycobacterial inhibition (MIC≤200 µg/mL and as low as MIC 6.5 µg/mL) for 54% of the extracts were observed. CONCLUSION: While moderate activity was shown for pathogens causing respiratory tract infections, these plant species seems to be selectively targeting Mycobacteria spp. suggesting that the traditional use for treating tuberculosis related symptoms may be indeed be accurate.

Antibacterial activity of the roots, stems and leaves of Alchornea floribunda.

ETHNOPHARMACOLOGICAL RELEVANCE: Alchornea floribunda Müll. Arg. is used in traditional medicine across Africa for the treatment of bacterial, fungal, parasitic and inflammatory disorders. AIM OF THE STUDY: To evaluate the antibacterial activity of the crude extracts of different plant parts in order to provide a scientific rationale for the proposed broad efficacy of Alchornea floribunda in the treatment of bacterial infections. MATERIALS AND METHODS: Extracts of roots, stems and leaves were prepared using solvents of various polarities in order to extract a wide range of phytochemicals. The antibacterial activity of these crude extracts was evaluated by micro-dilution assay, against Gram-positive (i.e. Bacillus cereus, Enterococcus faecalis, Staphylococcus aureus and Staphylococcus saprophyticus) as well as Gram-negative (i.e. Escherichia coli, Klebsiella pneumoniae, Moraxella catarrhalis and Proteus mirabilis) bacteria. RESULTS: Generally, the ethanol (EtOH), methanol (MeOH), ethyl acetate (EtOAc) and chloroform (CHCl3) extracts demonstrated the best activities, with the leaves exhibiting the highest average activity for six of the eight pathogens. Of these, the ethanolic leaf extract was the most active against Staphylococcus aureus with an MIC value of 50µg/mL. Some other notable activity was observed for the ethyl acetate and chloroform root extracts against Staphylococcus aureus (50µg/mL), and for selected stem extracts against Staphylococcus aureus (50µg/mL), Klebsiella pneumoniae (63µg/mL) and Staphylococcus saprophyticus (63µg/mL). CONCLUSION: This study demonstrates the promising antibacterial activity of Alchornea floribunda against both Gram-positive and Gram-negative bacteria responsible for gastrointestinal, skin, respiratory and urinary ailments, and validates its use in the ethnopharmacology of the region.

Synthesis and characterisation of Pd-modified N-doped TiO2 for photocatalytic degradation of natural organic matter (NOM) fractions.

INTRODUCTION: The removal of natural organic matter (NOM) from water is becoming increasingly important in order to prevent the formation of carcinogenic disinfection by-products. The inadequate removal of NOM has a bearing on the capacity of the other treatment processes to remove organic micro-pollutants or inorganic species that may be present in the water. New methods are therefore currently being sought to effectively characterise NOM and also to ensure that it is sufficiently removed from drinking water sources. METHODOLOGY: Nitrogen- and palladium-co-doped TiO(2) was synthesised by a modified sol-gel method and evaluated for its photocatalytic degradation activity on NOM fractions under simulated solar radiation. The photocatalyst was characterised by FT-IR, Raman, XRD, DRUV-vis, SEM, TEM, EDS, XPS and TGA. FT-IR confirmed the presence of OH groups on thermally stable, nearly spherical anatase nanoparticles with an average diameter of 20 nm. PdO species appeared on the surface of the TiO(2) as small uniformly dispersed particles (2 to 3 nm). A red shift in the absorption edge compared to commercial anatase TiO(2) was confirmed by DRUV-vis. In order to gain a better insight into the response of NOM to photodegradation, the NOM was divided into three different fractions based on its chemical nature. RESULTS AND DISCUSSION: Photodegradation efficiencies of 96, 38 and 15 % were realised for the hydrophobic, hydrophilic and transphilic NOM fractions, respectively. A reasonable mechanism was proposed to explain the photocatalytic degradation of the NOM fractions. The high photocatalytic activity could be attributed to the larger surface area, smaller crystalline size and synergistic effects of the co-dopants N and Pd in the TiO(2) crystal.