Synthesis, electro-spectroelectrochemical characterization and electrocatalytic behavior towards dioxygen reduction of a new water-soluble cobalt phthalocyanine containing naphthoxy-4-sulfonic acid sodium salt

A new water-soluble cobalt phthalocyanine, 2(3), 9(10), 16(17), 23(24)-tetrakis(4-(1-naphthoxy-4-sulfonic acid sodium salt)) phthalocyaninato cobalt(II) NhtCoPc, where Nht indicates naphthoxy-4-sulfonic acid sodium salt, was synthesized and its electro-spectroelectrochemical and electrocatalytic behavior towards oxygen reduction reaction were investigated in details. The complexation reaction was monitored with the UV-vis spectral changes of NhtH₂Pc in methanol solution. The reaction was completed when the main Q-band was observed in maximum intensity. The electrochemical studies showed that the cobalt complex exhibited two reversible one-electron reductions with the corresponding anodic wave and an irreversible oxidation reaction in DMSO solution. These reduction processes were assigned to Co(2+)Pc(2−)/Co(+)Pc(2−) and Co(+)Pc(2−)/Co(+)Pc(3−) couples, respectively. The well-defined UV-vis spectra of the mono-anionic species [NhtCo(+)Pc(2−)]⁻, di-anionic species [NhtCo(+)Pc(3−)]²⁻, and mono-cationic species [NhtCo(3+)Pc(2−)]⁺, were obtained by the applied potentials (E_app = −0.60, −1.40, and 0.70 V, respectively) in a thin-layer cell. NhtCoPc was incorporated into the conductive polyaniline (PAni) films as a dopant-anion during electropolimerization in acid medium, and thus formed the Pt/PAni-NhtCoPc electrode. This modified electrode was characterized by scanning electron microscopy (SEM), as well. The addition of NhtCoPc to the polymerization solution changes markedly the morphology of the films obtained and increases the redox-activity towards oxygen reduction of the PAni film formed compared to those of Pt/PAni and bare platinum electrodes in the same experimental conditions.     

Sensory and Physico‐Chemical Properties of Cold Press‐Produced Tomato (Lycopersicon esculentum L.) Seed Oils

In this study, roasted and unroasted (control) tomato seeds were cold pressed and the seeds, oils, and seed presscakes (meals) were analyzed. Some physicochemical properties, total phenolic content and antioxidant capacity, thermal properties, mineral contents, fatty acids, sterols and tocopherols compositions, volatile compounds and sensory evaluation of the tomato seed oils were determined. The tomato seeds contained 3.3 % of ash, 17.3 % of oil and 27.2 % of protein. The cold press oil recovery rate was 7.2 and 10.28 % for control and roasted seeds, respectively. There were eight sensory terms defining the oils together with 34 different aromatic compounds quantified. The volatile compounds furfural, hexanal, benzaldehyde and 2‐isobutylthiazole were found with the highest frequency in the samples. Roasted, green and tomato were defined as characteristic sensory terms for tomato seeds oils. Fifteen different minerals, melting and crystallization temperatures and enthalpies of the oil samples were also quantified. This study provides important data for the tomato seed oils, and proves that pre‐roasted tomato seed oils are high quality, nutritious and aromatics oils with higher levels of consumer acceptability.     

Stimulation of Phenol Removal Efficiency of Aspergillus versicolor by Surfactants,a Promising Way to Treat Phenol-Containing Waste Waters

The effect of the cationic surfactant, dodecyl trimethyl ammonium bromide (DTAB), on phenol bioremoval efficiency of an Aspergillus versicolor strain was examined. The strain was grown in mineral salt (MS) medium and the effect of DTAB was investigated as a function of different pH values, phenol and surfactant concentrations. The effect of pH was tested within the range of 4–7 and the maximum bioremoval was found at pH 4. Initial phenol concentrations investigated ranged from 100 to 600 mg/L, and the effects of surfactant concentrations on the removal were tested with 0, 0.25, 0.5 and 1 mM DTAB, which showed that 0.5 mM surfactant was the most effective concentration. The maximum bioremoval rates found after 72 h incubation were 99.48 and 99.15 % in 100 and 200 mg/L initial phenol-containing samples, respectively, where the phenol removal capacity of the fungus was only 142.373 mg/g in the DTAB blank samples. The maximum phenol uptake capacity of 267.162 mg/g was measured in the presence of 0.5 mM DTAB at 200 mg/L initial phenol concentration. These results showed that DTAB considerably increased the bioremoval efficiency of the strain tested at relatively lower phenol concentrations. The feasibility of this bioremoval method for industrial wastewater treatment is discussed.     

Microbial oil production from thermophile cyanobacteria for biodiesel production

Compared to lipid extraction from algae, little work has been performed for cyanobacteria. In this article it is aimed to show high lipid accumulation potential of Synechococcus sp., Cyanobacterium aponinum and Phormidium sp. cells in BG-11 medium. Four different pH values (6–9) and NaNO₃ (0.25, 0.5, 1.0, 1.5 g/L) concentrations were examined at different incubation days to discover the highest lipid accumulation. The maximum lipid content could be achieved in the medium containing 0.25 g/L NaNO₃ at pH 7 for Synechococcus sp., pH 8 for C. aponinum and pH 9 for Phormidium sp. after 15 days. The maximum lipid contents and C16 and C18 methyl ester yields were measured as 42.8% and 46.9% for Synechococcus sp., 45.0% and 67.7% for C. aponinum, 38.2% and 90.6% for Phormidium sp. The saturated compounds were 74.5%, 77.9%, 84.7% for Synechococcus sp., C. aponinum and Phormidium sp., respectively. These crude lipids could be promising feedstock for biodiesel production.     

Influence of additional thermal stabilizers on the reprocessing of postconsumer poly(vinyl chloride) bottles

The addition of heat stabilizers is essential for preventing the degradation of poly(vinyl chloride) (PVC) during its processing. The heat stabilizers consumed in the first run have to be made up before the reprocessing of recycled PVC. In this study, solvent‐cast films, which were prepared from granulated postconsumer PVC bottles mixed with plasticizers and thermal stabilizers, were used. The films were subjected to various heat treatments. No considerable structural change upon heat treatments at 140–160°C was found in IR and differential scanning calorimetry analyses. Polyene formation observed through ultraviolet analysis was not severe, indicating that the added stabilizers worked well in preventing degradation. The weight loss during the heat treatments was attributed partly to the decomposition of PVC and the evaporation of volatile components and mainly to the removal of the solvent upon heating. Although this study was conducted with water bottles that were to be recycled, it may be equally well applied to other similarly formulated PVC‐based materials, such as packaging films. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3994–3999, 2003     

Evaluation of the electrochemical properties of 3-hydroxyflavone using voltammetric methods

Electrochemical behavior of ring C of 3-hydroxyflavone (3-HF) has been investigated by cyclic and differential pulse voltammetry, using a glassy carbon electrode (GCE) in different buffer systems. It exhibited a sensitive diffusion controlled anodic peak at 0.70 V (vs Ag/AgCl) in a buffer system at pH 2.0. At higher pH, 8.0, while the peak at 0.70 V shifted to 0.41 V, a new peak at 0.8 V appeared. Moreover, electrochemical method was applied to investigate the antioxidant effect and metal chelating properties of 3-HF with Cd²⁺, Cu²⁺, Hg²⁺ and Pb²⁺ as they could have possible toxicological effects, for which fluorescence technique were also applied. Antioxidant effect was determined in terms of trolox equivalent antioxidant capacity (TEAC) using the peak areas of cyclic voltammetry (CV), which indicated that 1.0 mM 3-HF is equivalent to 0.2 mM of trolox. Such a result might be another indication of the importance of hydroxyl groups on the other rings of flavones. Electrochemical and fluorescence spectroscopic methods revealed that the best interactions of the cations could be obtained depending on the pH of the medium. Selective interactions of Cd²⁺ and Cu²⁺ at pH 2 and 7, respectively, were observed.     

Biological activities and chemical composition of three honeys of different types from Anatolia

In this study, we investigated and compared some chemical properties and in vitro biological activities of three different types of Turkish honey. The first two honey samples were monofloral from chestnut and rhododendron flowers, collected from the east Black Sea region, and the third sample was the heterofloral form of astragalus (Astragalus microcephalus Willd.), thyme (Thymus vulgaris) and other several mountain flowers, collected from Erzincan in Eastern Anatolia. The chemical properties of the honey samples, such as total moisture, ash, total protein, sucrose, invert sugar, diastase activity, hydroxymethylfurfural content and acidity, were determined. Total phenolics, superoxide radical- and peroxynitrite-scavenging activities, and ferric reducing/antioxidant power measurements were used as antioxidant capacity determinants with ±-catechin, butylated hydroxytoluene, ascorbic acid, and trolox^® used as reference. The antimicrobial activity was studied by the agar diffusion method, using eight bacteria and two yeasts. The mineral contents were also determined by an AAS method. The chestnut flower honey had the highest phenolic content, superoxide radical-scavenging activity and reducing power, while the heterofloral honey sample exhibited the highest peroxynitrite-scavenging activity. The antioxidant activities were also found to be related to the sample concentrations. The mineral content of the chestnut honey was much higher than the others. The samples showed moderate antimicrobial activity against some microorganisms, especially Helicobacter pylori ATCC 49503, Staphylococcus aureus ATCC 25923, Bacillus subtilis ATCC 6633, Candida tropicalis ATCC 13803 and Candida albicans ATCC 10231. The honey samples studied proved to be a good source of antioxidants and antimicrobial agents that might serve to protect health and fight against several diseases.     

An integrated maritime surveillance system based on high-frequencysurface-wave radars. 1. Theoretical background and numerical simulations

An integrated maritime surveillance (IMS) system, based on high-frequency surface-wave radars (HFSWR), is described. IMS provides low-cost, 24-hour, real-time, over-the-horizon surveillance of large ocean areas, out to the 200 nautical mile Exclusive Economic Zone (EEZ). The system can be used to coordinate search and rescue operations, and to combat smuggling, drug trafficking, illegal dumping of pollutants, and other undesirable activities. The major challenges in using HFSWR are (i) operating within the crowded HF spectrum; and (ii) maintaining effective operation in high environmental noise, ocean clutter, ionospheric clutter and other undesirable sources of interferences. The system is outlined and these problems are addressed. Numerical simulation, as well as stochastic modeling, are presented to demonstrate the physics behind the system     

PRODUCTION OF BIOFUEL FROM SOFT SHELL OF PISTACHIO (PISTACIA VERA L.)

Soft shell of pistachio (Pistacia vera L.) pyrolysis experiments were performed in a fixed-bed reactor to produce bio-oil. The effects of temperature, heating rate, and sweep gas (N₂) flow rates on the yields and compositions of products were investigated. Pyrolysis runs were performed using reactor temperatures between 350° and 500°C with heating rates of 15° and 50°C/min. Nitrogen flow rates varied between 50 and 200 cm³/min and mean particle size was 0.8 mm. The maximum bio-oil yield of 33.18% was obtained in a nitrogen atmosphere with nitrogen flow rate of 150 cm³/min and at 450°C pyrolysis temperature with a heating rate of 50°C/min.The elemental analysis and gross heating value of the bio-oil were determined, and then the chemical composition of the bio-oil was investigated using chromatographic and spectroscopic techniques. The chemical characterization has shown that the bio-oil obtained from soft shell of pistachio can be used as a renewable fuel and chemical feedstock.     

Grayanotoxin-III Detection and Antioxidant Activity of Mad Honey

“Mad honey” is a complex mixture of numerous chemicals produced by honeybees from Rhododendron flowers. Consumption of mad honey leads to diarrhea, perspiration, dizziness, changes in consciousness, syncope, diplopia, as well as blurred vision, hypotension, and bradycardia due to the presence of grayanotoxins (GTXs). Therefore, it is important to detect the level grayanotoxins in mad honey. Besides its toxicity, mad honey also has antioxidant activity. This study was designed to determine the level of grayanotoxin-III toxin and antioxidant activity of ten different mad honey samples collected from the Black Sea region of Turkey. Liquid chromatography-tandem mass spectrometry was used for the quantitation of grayanotoxin-III. Antioxidant activity was evaluated using total phenolic contents, total ferric reducing antioxidant power, scavenging of 2,2-diphenyl-1-picrylhydrazyl and 3-(2-pyridyl)-5, 6-diphenyl-1,2,4-triazine-4’,4’’-disulfonic acid radicals. Quantities of grayanotoxin-III levels ranged from 68.754 to 0.701 µg grayanotoxin-III/g honey. Mad honey MH7 from Artvin/Hopa had the highest grayanotoxin-III level. Although there were varying levels of grayanotoxin-III, mad honey samples were outstanding in terms of antioxidant activity. MH₃ had the highest antioxidant potential. Although toxicity effect comprises, a metered dose of mad honey might also be explored as a potential source in clinical trials due to high bioactivity levels.