(Table 1) Organic carbon, hydrogen and oxygen index and hydrocarbons at DSDP Hole 93-603B

C2-C8 hydrocarbon concentrations (about 35 compounds identified, including saturated, aromatic, and olefinic compounds) from 27 shipboard-sealed, deep-frozen core samples of DSDP Hole 603B off the east coast of North America were determined by a gas-stripping/thermovaporization method. Total yields representing the hydrocarbons dissolved in the pore water and adsorbed on the mineral surfaces of the sediments vary from 22 to 2400 ng/g of dryweight sediment. Highest yields are measured in the two black shale samples of Core 603B-34 (hydrogen index of 360 and 320 mg/g Corg, respectively). In organic-carbon-normalized units these samples have hydrocarbon contents of 12,700 and 21,500 ng/g Corg, respectively, indicating the immaturity of their kerogens. Unusually high organic-carbonnormalized yields are associated with samples that are extremely lean in organic carbon. It is most likely that they are enriched by small amounts of migrated light hydrocarbons. This applies even to those samples with high organic-carbon contents (1.3-2.2%) of Sections 603B-28-4, 603B-29-1, 603B-49-2, and 603B-49-3, because they have an extremely low hydrocarbon potential (hydrogen index between 40 and 60 mg/g Corg). Nearly all samples were found to be contaminated by varying amounts of acetone that is used routinely in large quantities on board ship during core-cutting procedures. Therefore, 48 samples from the original set of 75 collected had to be excluded from the present study.

Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.

Evaluation and comparison of durability of polycyclic aromatic hydrocarbon compounds (PAHs) and its relation to the lipid content in smoked fishes, Silver carp (Hypophthalmichthys molitrix), Rutilus frisii kutum and Herring (Alosa caspia)

Cold smoking method is one of the commonest ways for fish smoking. It is done by the smoke that is the result of burning hard and soft woods is smoking rooms. Smoke includes a number of chemical constructs and its main part is poly aromatic hydrocarbons. More than one hundred kinds of these constructs are recognized in smoke that is produced from saturated hydrocarbons resulted from the solution of the woods Ligno cellulose in high temperature and lack of oxygen conditions. The high poisoning potentials and carcinogenic features sixteen constructs among them are proved and observed on humans. In this research, the PAH compounds were identified and observed in a three month period after smoking and during storing among three types of smoked fishes Silver carp and Caspian sea Sefid and herring. They are the most produced and consumed smoked fish in Iran. To find the relationship between the concentrations of PAH constructs and the amount of lipid in fish, first, the amount of lipid were determined separately in the skin and flesh of 30 samples of each type. The method used was Bligh and Dyer (1959). PAH compounds derivation were made for all skin and flesh samples smoked fish using organic solvents with Soxeleh and the derived samples were injected to gas chromatography (GC) by Hamilton injectors for determining their components quality and their quantity. The height of the used column was 25 meters and its diameter was 0.32 mm with the silica filler, nitrogen gas as carrier and flame ionization detector (FID) that are special for these constructs. For data analysis, Statistical tests were used by computer soft ware identified that the difference in the amount of lipid within the flesh and skin of each species and also among each other is significant. The largest amount was in Herrings flesh and skin, 18.74% in skin and 14.47% in flesh. The least amount in the skin 4.19% and the flesh 3.10% of Sefid. The amount in Silver carp was 13.28%in skin and 8.16% in flesh. The examination of the PAH compounds in smoked fish showed that is carcinogenic compounds; exist in these in these fish with different quantities in each. It seems that its amount is directly related to the amount of their lipid. The amount is different in flesh and skin. One of the most important reasons is the direct content of smoke and the concentration of lipid in tissues of all three types. The maintenance of the smoked fish for three months showed that most of PAH compounds were solved and their density decreased. The changes in density within time in different in each type and in flesh and skin. The amount of their receiving in human through the consumption of the smoked fish depends on the resulted density, the way and the amount of consumption and now we can determine and execute standards for the maximum dosage per day and per month regarding effective factors.

Reduction of 1,2-dicarbonyl compounds and of their N-phenylimine derivatives by sodium cyanide under aprotic conditions

Some aromatic 1,2-dicarbonyl compounds, i.e. 9,10-phenanthrenequinone, acenaphthenequinone and benzil, and their corresponding N-phenyl monoimines, have been reduced, using dry acetonitrile as the solvent, in the presence of sodium cyanide as a reducing agent. Comparative potentiostatic preparative-scale electrolysis is described.

Open-cell Metallic Foams for the Electrochemical Conversion of Biomass-derived Compounds

The electrochemical conversion is a sustainable way for the production of added-value products, operating in mild conditions, using in-situ generated hydrogen/oxygen by water and avoiding the use of high H2/O2 pressures. The aim of this work is to investigate the electrocatalytic conversion of 5-hydroxymetilfurfural (HMF) and D-glucose, in alkaline media, using metallic open-cell foams based-catalysts. The electrochemical hydrogenation of HMF to 2,5-bis(hydroxymethyl)furan (BHMF) was performed using nanostructured Ag, deposited by galvanic displacement (GD) or electrodeposition (ED), on Cu foam, obtaining AgCu bimetallic nanoparticles (ED) or dendrites (GD) which enhanced electroactive surface area, charge and mass transfer, than bare foams. In diluted 0.02M HMF solutions, Ag/Cu samples selectively produce BHMF; the large surface area enhanced the productivity, compared to their 2D counterparts. Furthermore, at more concentrated solutions (0.05 – 0.10M) a gradually decrease of selectivity is observed. The performances of the electrodes is stable during the catalytic tests but a Cu-enrichment of particles occurred. The performances of Ni foam-based catalysts, obtained by calcination of Ni foam or by electrodeposition of Ni-hydroxide/Ni and Ni particle/Ni, were firstly investigated for the selective electrochemical oxidation of D-glucose toward gluconic acid (GO) and glucaric acid (GA). Then, the calcined catalyst was chosen to study the influence of the reaction conditions on the reaction mechanism. The GO and GA selectivities increase with the charge passed, while the formation of by-products from C-C cleavage/retro-aldol process is maximum at low charge. The fructose obtained from glucose isomerization favours the formation of by-products. The best glucose/NaOH ratio is between 0.5 and 0.1: higher values suppress the OER, while lower values favour the formation of low molecular weight products. The increases of the potential enhance the GO selectivity, nevertheless higher GA selectivity is observed at 0.6 – 0.7V vs SCE, confirmed by catalytic test performed in gluconate (30-35% GA selectivity).

Diet Carotenoid Lutein Modulates The Expression Of Genes Related To Oxygen Transporters And Decreases Dna Damage And Oxidative Stress In Mice.

Lutein (LT) is a carotenoid obtained by diet and despite its antioxidant activity had been biochemically reported, few studies are available concerning its influence on the expression of antioxidant genes. The expression of 84 genes implicated in antioxidant defense was quantified using quantitative reverse transcription polymerase chain reaction array. DNA damage was measured by comet assay and glutathione (GSH) and thiobarbituric acid reactive substances (TBARS) were quantified as biochemical parameters of oxidative stress in mouse kidney and liver. cDDP treatment reduced concentration of GSH and increased TBARS, parameters that were ameliorated in treatment associated with LT. cDDP altered the expression of 32 genes, increasing the expression of GPx2, APC, Nqo1 and CCs. LT changed the expression of 37 genes with an induction of 13 mainly oxygen transporters. In treatments associating cDDP and LT, 30 genes had their expression changed with a increase of the same genes of the cDDP treatment alone. These results suggest that LT might act scavenging reactive species and also inducing the expression of genes related to a better antioxidant response, highlighting the improvement of oxygen transport. This improved redox state of the cell through LT treatment could be related to the antigenotoxic and antioxidant effects observed.

Phylogenetic Analysis Of The Microbial Community In Hypersaline Petroleum Produced Water From The Campos Basin.

In this work the archaea and eubacteria community of a hypersaline produced water from the Campos Basin that had been transported and discharged to an onshore storage facility was evaluated by 16S recombinant RNA (rRNA) gene sequence analysis. The produced water had a hypersaline salt content of 10 (w/v), had a carbon oxygen demand (COD) of 4,300 mg/l and contains phenol and other aromatic compounds. The high salt and COD content and the presence of toxic phenolic compounds present a problem for conventional discharge to open seawater. In previous studies, we demonstrated that the COD and phenolic content could be largely removed under aerobic conditions, without dilution, by either addition of phenol degrading Haloarchaea or the addition of nutrients alone. In this study our goal was to characterize the microbial community to gain further insight into the persistence of reservoir community members in the produced water and the potential for bioremediation of COD and toxic contaminants. Members of the archaea community were consistent with previously identified communities from mesothermic reservoirs. All identified archaea were located within the phylum Euryarchaeota, with 98 % being identified as methanogens while 2 % could not be affiliated with any known genus. Of the identified archaea, 37 % were identified as members of the strictly carbon-dioxide-reducing genus Methanoplanus and 59 % as members of the acetoclastic genus Methanosaeta. No Haloarchaea were detected, consistent with the need to add these organisms for COD and aromatic removal. Marinobacter and Halomonas dominated the eubacterial community. The presence of these genera is consistent with the ability to stimulate COD and aromatic removal with nutrient addition. In addition, anaerobic members of the phyla Thermotogae, Firmicutes, and unclassified eubacteria were identified and may represent reservoir organisms associated with the conversion hydrocarbons to methane.

Doehlert Design-desirability Function Multi-criteria Optimal Separation Of 17 Phenolic Compounds From Extra-virgin Olive Oil By Capillary Zone Electrophoresis.

In Brazil, the consumption of extra-virgin olive oil (EVOO) is increasing annually, but there are no experimental studies concerning the phenolic compound contents of commercial EVOO. The aim of this work was to optimise the separation of 17 phenolic compounds already detected in EVOO. A Doehlert matrix experimental design was used, evaluating the effects of pH and electrolyte concentration. Resolution, runtime and migration time relative standard deviation values were evaluated. Derringer's desirability function was used to simultaneously optimise all 37 responses. The 17 peaks were separated in 19min using a fused-silica capillary (50μm internal diameter, 72cm of effective length) with an extended light path and 101.3mmolL(-1) of boric acid electrolyte (pH 9.15, 30kV). The method was validated and applied to 15 EVOO samples found in Brazilian supermarkets.

Intensification Of Bioactive Compounds Extraction From Medicinal Plants Using Ultrasonic Irradiation.

Extraction processes are largely used in many chemical, biotechnological and pharmaceutical industries for recovery of bioactive compounds from medicinal plants. To replace the conventional extraction techniques, new techniques as high-pressure extraction processes that use environment friendly solvents have been developed. However, these techniques, sometimes, are associated with low extraction rate. The ultrasound can be effectively used to improve the extraction rate by the increasing the mass transfer and possible rupture of cell wall due the formation of microcavities leading to higher product yields with reduced processing time and solvent consumption. This review presents a brief survey about the mechanism and aspects that affecting the ultrasound assisted extraction focusing on the use of ultrasound irradiation for high-pressure extraction processes intensification.

Design And Synthesis Of N-acylated Aza-goniothalamin Derivatives And Evaluation Of Their In Vitro And In Vivo Antitumor Activity.

Herein we describe the synthesis of a focused library of compounds based on the structure of goniothalamin (1) and the evaluation of the potential antitumor activity of the compounds. N-Acylation of aza-goniothalamin (2) restored the in vitro antiproliferative activity of this family of compounds. 1-(E)-But-2-enoyl-6-styryl-5,6-dihydropyridin-2(1H)-one (18) displayed enhanced antiproliferative activity. Both goniothalamin (1) and derivative 18 led to reactive oxygen species generation in PC-3 cells, which was probably a signal for caspase-dependent apoptosis. Treatment with derivative 18 promoted Annexin V/7-aminoactinomycin D double staining, which indicated apoptosis, and also led to G2 /M cell-cycle arrest. In vivo studies in Ehrlich ascitic and solid tumor models confirmed the antitumor activity of goniothalamin (1), without signs of toxicity. However, derivative 18 exhibited an unexpectedly lower in vivo antitumor activity, despite the treatments being administered at the same site of inoculation. Contrary to its in vitro profile, aza-goniothalamin (2) inhibited Ehrlich tumor growth, both on the ascitic and solid forms. Our findings highlight the importance of in vivo studies in the search for new candidates for cancer treatment.

Influence Of The Stage Of Ripeness On The Composition Of Iridoids And Phenolic Compounds In Genipap (genipa Americana L.).

Genipap fruits, native to the Amazon region, were classified in relation to their stage of ripeness according to firmness and peel color. The influence of the part of the genipap fruit and ripeness stage on the iridoid and phenolic compound profiles was evaluated by HPLC-DAD-MS(n), and a total of 17 compounds were identified. Geniposide was the major compound in both parts of the unripe genipap fruits, representing >70% of the total iridoids, whereas 5-caffeoylquinic acid was the major phenolic compound. In ripe fruits, genipin gentiobioside was the major compound in the endocarp (38%) and no phenolic compounds were detected. During ripening, the total iridoid content decreased by >90%, which could explain the absence of blue pigment formation in the ripe fruits after their injury. This is the first time that the phenolic compound composition and iridoid contents of genipap fruits have been reported in the literature.

Anthocyanin And Other Phenolic Compounds In Ceylon Gooseberry (dovyalis Hebecarpa) Fruits.

Ceylon gooseberry is a deep-purple exotic berry that is being produced in Brazil with great market potential. This work aimed to determine major phenolic compounds in this specie by HPLC-PDA-ESI/MS. Samples were collected in two different seasons. Pulp and skin were analyzed separately. Non-acylated rutinoside derivatives of delphinidin (∼60-63%) and cyanidin (∼17-21%) were major anthocyanins tentatively identified. All anthocyanins had higher concentration in skin than in pulp (64-82 and 646-534mg of cyaniding-3-glucoside equivalents/100g skin and pulp, respectively). Moreover, anthocyanin profile changed between sampling dates (p<0.05). Mainly for delphinidin-3-rutinoside which could be a result of season variation. In this specie, non-anthocyanin polyphenols represent less than 35% of total extracted polyphenols. The tentative identification proposed a flavonol and three ellagitannins as major compounds of the non-anthocyanin phenolics fraction. Finally, anthocyanin is the major phenolic class in this fruit and its composition and content are significantly affected by season.

Sorghum Flour Fractions: Correlations Among Polysaccharides, Phenolic Compounds, Antioxidant Activity And Glycemic Index.

Nutrients composition, phenolic compounds, antioxidant activity and estimated glycemic index (EGI) were evaluated in sorghum bran (SB) and decorticated sorghum flour (DSF), obtained by a rice-polisher, as well as whole sorghum flour (WSF). Correlation between EGI and the studied parameters were determined. SB presented the highest protein, lipid, ash, β-glucan, total and insoluble dietary fiber contents; and the lowest non-resistant and total starch contents. The highest carbohydrate and resistant starch contents were in DSF and WSF, respectively. Phenolic compounds and antioxidant activities were concentrated in SB. The EGI values were: DSF 84.5±0.41; WSF 77.2±0.33; and SB 60.3±0.78. Phenolic compounds, specific flavonoids and antioxidant activities, as well as total, insoluble and soluble dietary fiber and β-glucans of sorghum flour samples were all negatively correlated to EGI. RS content was not correlated to EGI.

Hypobromous Acid, A Powerful Endogenous Electrophile: Experimental And Theoretical Studies.

Hypobromous acid (HOBr) is an inorganic acid produced by the oxidation of the bromide anion (Br(-)). The blood plasma level of Br(-) is more than 1,000-fold lower than that of chloride anion (Cl(-)). Consequently, the endogenous production of HOBr is also lower compared to hypochlorous acid (HOCl). Nevertheless, there is much evidence of the deleterious effects of HOBr. From these data, we hypothesized that the reactivity of HOBr could be better associated with its electrophilic strength. Our hypothesis was confirmed, since HOBr was significantly more reactive than HOCl when the oxidability of the studied compounds was not relevant. For instance: anisole (HOBr, k2=2.3×10(2)M(-1)s(-1), HOCl non-reactive); dansylglycine (HOBr, k2=7.3×10(6)M(-1)s(-1), HOCl, 5.2×10(2)M(-1)s(-1)); salicylic acid (HOBr, k2=4.0×10(4)M(-1)s(-1), non-reactive); 3-hydroxybenzoic acid (HOBr, k2=5.9×10(4)M(-1)s(-1), HOCl, k2=1.1×10(1)M(-1)s(-1)); uridine (HOBr, k2=1.3×10(3)M(-1)s(-1), HOCl non-reactive). The compounds 4-bromoanisole and 5-bromouridine were identified as the products of the reactions between HOBr and anisole or uridine, respectively, i.e. typical products of electrophilic substitutions. Together, these results show that, rather than an oxidant, HOBr is a powerful electrophilic reactant. This chemical property was theoretically confirmed by measuring the positive Mulliken and ChelpG charges upon bromine and chlorine. In conclusion, the high electrophilicity of HOBr could be behind its well-established deleterious effects. We propose that HOBr is the most powerful endogenous electrophile.