Evaluation of surface sediment contamination by polycyclic aromatic hydrocarbons in colony Z3—(Patos Lagoon, Brazil)

This paper describes the extraction and analysis of Polyaromatic Hydrocarbons (PAHs) in five points of the Patos Lagoon Estuary. These points were in the area named “colony Z3”, which is a craft fishermen community in Pelotas City (southern Brazil). Samples were collected in July of 2007, and the concentrations of 16 USEPA priority polycyclic aromatic hydrocarbons (PAHs) were determined by gas chromatography coupled to a mass spectrometry detector (GC/MS). The PAH concentrations ranged from 4.7 to 112.5 µg kg^− 1 dry weight. Sediment samples with the highest PAH concentrations appeared at point 2, which is a pier. The correlation between the total organic material (TOM) and the total PAH concentration suggests that TOM plays an important role in controlling the PAH levels in sediments. According to the observed ratios of individual PAHs, the contamination in the studied areas originated both from high-temperature pyrolytic processes and petrogenic sources. The levels of PAHs at the studied sites in the Z3 colony (Patos Lagoon) were low enough that they should not exert adverse biological effects.     

The reaction of anthranilonitrile and triethylorthoformate revisited: formation of dimeric and trimeric species

The reaction of anthranilonitrile and triethylorthoformate was performed under different experimental conditions, leading to substituted quinazolines, triazachrysenes or quinazolinyl-aminophenyl quinazolines. A mechanistic proposal is presented to rationalize the formation of these compounds. The fluorescence properties of the highly conjugated triazachrysene structures were studied and the fluorescence quantum yield for compounds 5 and 13 was comparable to that of pyrene.     

Mechanistic Investigations into the Asymmetric Transfer Hydrogenation of Ketones Catalyzed by Pseudo‐Dipeptide Ruthenium Complexes

Lithium‐powered : A kinetic investigation into the asymmetric transfer hydrogenation of non‐activated aryl alkyl ketones, catalyzed by N‐Boc‐protected α‐amino acid hydroxyamide ruthenium–arene complexes, has revealed that the reactions proceed through an unprecedented bimetallic outer‐sphere mechanism. Under optimized conditions, these catalysts provide access to secondary alcohols in high yields and with excellent enantioselectivities (>99 % ee).

     

Private initiatives, public support, and war practices: development of fertilisers in Russia

The scarcity of experiments with fertilisers, the poor domestic industry, and high prices for imported products made Russia lag far behind the leading agrarian countries in the research and use of fertilisers. The first experiments on fertilisers were connected mostly with the private estates of Russian nobility. Things began to change slowly by the turn of the twentieth century, when the Ministry of Agriculture launched a policy of agricultural science promotion, including the development of agricultural chemistry. It was the outbreak of World War I that created a powerful stimulus for fertiliser research in Russia. A specific Russian "symbiosis" emerged between military industry and agricultural chemistry. The numerous factories of explosives set up ad hoc produced vast amounts of waste products; modified, they could serve as fertilisers. In 1915, the Public Committee for Support of Fertilisers was organised. Eventually, this committee gave birth to the Institute of Fertilisers, the first institute founded by the Bolshevik government. Thus, the project of "chemicalisation of agriculture," usually described as a revolutionary endeavour, was firmly rooted in World War I.     

Noncovalent Complexation of Monoamine Neurotransmitters and Related Ammonium Ions by Tetramethoxy Tetraglucosylcalix[4]arene

The noncovalent complexation of monoamine neurotransmitters and related ammonium and quaternary ammonium ions by a conformationally flexible tetramethoxy glucosylcalix[4]arene was studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. The glucosylcalixarene exhibited highest binding affinity towards serotonin, norepinephrine, epinephrine, and dopamine. Structural properties of the guests, such as the number, location, and type of hydrogen bonding groups, length of the alkyl spacer between the ammonium head-group and the aromatic ring structure, and the degree of nitrogen substitution affected the complexation. Competition experiments and guest-exchange reactions indicated that the hydroxyl groups of guests participate in intermolecular hydrogen bonding with the glucocalixarene.     

Measuring nitrification in sediments--comparison of two techniques and three 15NO(-)3 measurement methods

Nitrification is a crucial process in sediment nitrogen cycling. We compared two (15)N tracer-based nitrification measurement techniques (isotope pairing technique (IPT) combined with (15)N nitrate pool dilution and (15)N ammonium oxidation) and three different (15)N analyses from bottom water nitrate (ammonia diffusion, denitrifier and SPINMAS) in a sediment mesocosm. The (15)N nitrate pool dilution technique combined with IPT can be used to quantify the in situ nitrification, but the minimum detection limit for the total nitrification is higher than that in the (15)N ammonium oxidation technique. The (15)N ammonium oxidation technique, however, is not applicable for sediments that have high ammonium content. If nitrate concentration and the amount of (15)N label in the sample are low, the (15)N nitrate analysis should be done with the denitrifier method. In higher (15)N concentrations, the less sensitive SPINMAS method can also be applied. The ammonia diffusion method is not suitable for bottom water (15)N nitrate analyses.     

Regiocontrolled synthesis of pyrrole-2-carboxaldehydes and 3-pyrrolin-2-ones from pyrrole Weinreb amides

A regiocontrolled synthesis of 3,4-disubstituted pyrrole-2-carboxaldehydes was completed in two steps from acyclic starting materials. A Barton-Zard pyrrole synthesis between N-methoxy-N-methyl-2-isocyanoacetamide and alpha-nitroalkenes or beta-nitroacetates provided N-methoxy-N-methyl pyrrole-2-carboxamides (pyrrole Weinreb amides), which were converted into the corresponding pyrrole-2-carboxaldehydes by treatment with lithium aluminum hydride. A regioselective oxidation of the pyrrole-2-carboxaldehydes gave the corresponding 3,4-disubstituted 3-pyrrolin-2-ones.     

Preparation of aqueous crosslinked dispersions of functionalized poly(d,l-lactic acid) with a thermomechanical method

Aqueous crosslinked microparticle dispersions were prepared from a copolymer of d,l-lactic acid, 1,4-butanediol, and itaconic acid with a thermomechanical method. The copolymer was prepared in one step polycondensation reaction using Sn(Oct)₂ as a catalyst. A polymer with M_n of 2800 g mol^?1 and a molecular weight distribution of 1.41 was obtained (as determined by SEC), that contained double bonds introduced by the itaconic acid monomer units (6 mol-%, as determined by NMR). Crosslinking ability of the prepared copolymer was demonstrated in bulk by adding a thermal initiator and altering amounts of ethylene glycol dimethacrylate (EGDMA) crosslinking agent into molten polymer at 60–150 °C. A crosslinked gel was formed in less than 15 min at 80 °C when 10 wt.% of EGDMA was added and benzoyl peroxide (BPO) was used as the initiator. Aqueous dispersions were prepared of the non-crosslinked copolymer with a thermomechanical method that involved slow addition of aqueous polyvinyl alcohol (PVA) solution into molten copolymer at 60 °C under shear. Dispersions were prepared with 10 wt.% of EGDMA and 2 wt.% of BPO. Crosslinking of the dispersed microparticles was achieved by heating the dispersions at 80 °C for 30 or 60 min. The dispersions were characterized by SEM, DSC, TGA, FT-IR, solid state NMR, and gel content measurements. The effect of crosslinking was clearly seen in SEM images of films cast from the dispersions. The films cast from non-crosslinked dispersions had smooth morphology whereas in films cast from crosslinked dispersions separate spherical particles were observed. During the crosslinking reactions, glass transition temperatures increased (as determined by DSC), thermal stability of the samples increased (as determined by TGA), and the gel content of the samples increased.