Crystallization and preliminary X-ray diffraction analysis of naphthalene dioxygenase from Rhodococcus sp strain NCIMB 12038

The three-component naphthalene dioxygenase (NDO) enzyme system carries out the first step in the aerobic degradation of naphthalene to (+)-cis-(1R,2S)-dihydroxy-1,2-dihydronaphthalene by Rhodococcus sp. strain NCIMB 12038. The terminal oxygenase component (naphthalene 1,2-dioxygenase) that catalyzes this reaction belongs to the aromatic ring hydroxylating dioxygenase family and has been crystallized. These enzymes utilize a mononuclear nonheme iron centre to catalyze the addition of dioxygen to their respective substrates. In this reaction, two electrons, two protons and a dioxygen molecule are consumed. The Rhodococcus enzyme has only 33 and 29% sequence identity to the corresponding alpha- and beta-subunits of the NDO system of Pseudomonas putida NCIMB 9816-4, for which the tertiary structure has been reported. In order to determine the three-dimensional structure of the Rhodococcus NDO, diffraction-quality crystals have been prepared by the hanging-drop method. The crystals belongs to space group P2(1)2(1)2(1), with unit-cell parameters a = 87.5, b = 144, c = 185.6 Angstrom, alpha = beta = gamma = 90degrees, and diffract to 2.3 Angstrom resolution.

Enzymatic and chemoenzymatic synthesis of arene trans-dihydrodiols

Several potential approaches to the enzyme-catalysed synthesis of arene trans-diols have been examined including epoxidation/hydrolysis, bis-benzylic hydroxylation, cis-dihydroxylation/alcohol dehydrogenation/ketone reduction, cisdihydroxylation/cis-trans isomerisation. and multi-enzyme synthesis of trans-dihydrodiol secondary metabolites from primary metabolites. The lack of general applicability of these enzymatic methods has led to the development of several chemoenzymatic routes for the synthesis of a series of trans-dihydrodiols from the readily available cis-dihydrodiol precursors. Partial hydrogenation of cis-dihydrodiol metabolites to yield the corresponding cis-tetrahydrodiols followed by a regioselective Mitsunobu inversion process gave trans-tetrahydrodiols that were in turn converted to trans-dihydrodiols. The formation of anti-benzene dioxides or iron tricarbonyl complexes from the corresponding cis-dihydrodiol precursors provided shorter and more convenient chemoenzymatic routes to trans-dihydrodiols. The application of cis-dihydrodiol metabolites of polycyclic azaarenes in the synthesis of the corresponding arene oxides followed by chemical hydrolysis provides a convenient route to trans-dihydrodiols. (C) 2002 Elsevier Science B.V. All rights reserved.

Examination of the conformational restraints to a chiral diimine bridged 2,2 '-bipyridine

The synthesis of a new bis(2,2-bipyridine), bridged by a Schiff base cyclohexane moiety is described. Surprisingly, this compound does not appear to form discrete oligonuclear metal complexes on the addition of zinc(II) and iron(II) cations. In order to rationalise this behaviour, the compound's conformation has been explored using a combination of circular dichroism, X-ray crystallography and DFT calculations, indicating that at least two energy barriers need to be overcome to orientate the ligand in a suitable conformation to permit the formation of coordination helicates with control over the metal centred stereochemistry. (C) 2004 Elsevier Ltd. All rights reserved.

Stereoselective coordination chemistry of the tetradentate chelating ligand (2R,3R)-bis(2,2 '-dipyridyl-5-methoxyl) butane

The enantiomerically pure ligand L-3RR (2R, 3R)-bis(2,2'-dipyridyl-5-methoxyl) butane has been synthesised by linking two 2,2'-bipyridine units with (2R, 3R)-butandiol. The reaction of L-3RR with Zn(II) afforded a mononuclear species and the H-1 NMR spectroscopy points to a C-1 symmetry, expected for a distorted trigonal bipyramidal coordination environment. These observations were confirmed by MM2 calculations and electrospray mass spectrometry. The reaction of L-3RR with iron(II) indicated the formation of a dinuclear species by mass spectrometry. Solution state CD spectroscopy indicates that both complexes adopt a Lambda-configuration, implying a single stranded dinuclear iron(II) complex is present rather than the anticipated triple helical architecture.

Land-use patterns and cultural change in the Middle to Late Bronze Age in Ireland: inferences from pollen records

In Ireland, the Middle to Late Bronze Age (1500-600 cal. B.C.) is characterised by alternating phases of prolific metalwork production (the Bishopsland and Dowris Phases) and apparent recessions (the Roscommon Phase and the Late Bronze Age-Iron Age transition). In this paper, these changes in material culture are placed in a socio-economic context by examining contemporary settlement and land-use patterns interpreted from the pollen record. The vegetation histories of six tephrochronologically-linked sites are presented that provide high-resolution and chronologically well-resolved insights into changes in landscape use over the Middle to Late Bronze Age. The records are compared with published pollen records in an attempt to discern if there are any trends of woodland clearance and abandonment from which changes in settlement patterns can be inferred. The results suggest that prolific metalworking industries correlate chronologically with expansive farming activity, which indicates that they were supported by a productive subsistence economy. Conversely, declines in metalwork production occur during periods when farming activity is generally less extensive and perhaps more centralised, and it is proposed that disparate socio-economic or –political factors, rather than a collapse of the subsistence economy, lies behind the demise of metalworking industries.

Metal-Directed Synthesis of Enantiomerially Pure Dimetallic Lanthanide Luminescent Triple-Stranded Helicates

The synthesis and photophysical evaluation of two enatiomerially pure dimetallic lanthanide luminescent triple-stranded helicates is described. The two systems, formed from the chiral (R,R) ligand 1 and (S,S) ligand 2, were produced as single species in solution, where the excitation of either the naphthalene antennae or the pyridiyl units gave rise to Eu(III) emission in a variety of solvents. Excitation of the antennae also gave rise to circularly polarized Eu(III) luminescence emissions for Eu2:13 and Eu2:23 that were of equal intensity and opposite sign, confirming their enantiomeric nature in solution providing a basis upon which we were able to assign the absolute configurations of Eu2:13 and Eu2:23.

Fragmentation and plasmid strand breaks in pure and gold-doped DNA irradiated by beams of fast hydrogen atoms

The results of an investigation into the damage caused to dry plasmid DNA after irradiation by fast (keV) hydrogen atoms are presented. Agarose gel electrophoresis was used to assess single and double strand break yields as a function of dose in dry DNA samples deposited on a mica substrate. Damage levels were observed to increase with beam energy. Strand break yields demonstrated a considerable dependence on sample structure and the method of sample preparation. Additionally, the effect of high-Z nanoparticles on damage levels was investigated by irradiating DNA samples containing controlled amounts of gold nanoparticles. In contrast to previous (photonic) studies, no enhancement of strand break yields was observed with the particles showing a slight radioprotective effect. A model of DNA damage as a function of dose has been constructed in terms of the probability for the creation of single and double strand breaks, per unit ion flux. This model provides quantitative conclusions about the effects of both gold nanoparticles and the different buffers used in performing the assays and, in addition, infers the proportion of multiply damaged fragments.

Linking past cultural developments to palaeoenvironmental changes in Estonia

Connections between environmental and cultural changes are analysed in Estonia during the past c. 4,500 years. Records of cereal-type pollen as (agri)cultural indices are compared with high-resolution palaeohydrological and annual mean temperature reconstructions from a selection of Estonian bogs and lakes (and Lake Igelsjon in Sweden). A broad-scale comparison shows increases in the percentage of cereal-type pollen during a decreasing trend in annual mean temperatures over the past c. 4,300 years, suggesting a certain independence of agrarian activities from environmental conditions at the regional level. The first cereal-type pollen in the region is found from a period with a warm and dry climate. A slow increase in pollen of cultivated land is seen around the beginning of the late Bronze Age, a slight increase at the end of the Roman Iron Age and a significant increase at the beginning of the Middle Ages. In a few cases increases in agricultural pollen percentages occur in the periods of warming. Stagnation and regression occurs in the periods of cooling, but regression at individual sites may also be related to warmer climate episodes. The cooling at c. 400-300 cal b.p., during the 'Little Ice Age' coincides with declines in cereal-type and herb pollen curves. These may not, however, be directly related to the climate change, because they coincide with war activities in the region.

Task-specific ionic liquid for solubilizing metal oxides

Protonated betaine bis(trifluoromethylsulfonyl) imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium( II) oxide, mercury( II) oxide, nickel( II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese( II) oxide, and silver( I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis( trifluoromethylsulfonyl) imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C ( temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis( trifluoromethylsulfonyl) imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations.

Changes in solar activity and Holocene climatic shifts derived from C-14 wiggle-match dated peat deposits

Closely spaced sequences of accelerator mass spectrometer (AMS) C-14 dates of peat deposits display century-scale wiggles which can be fitted to the radiocarbon calibration curve. By wiggle-matching such sequences, high-precision calendar age chronologies can be generated which show that changes in mire surface wetness during the Bronze Age/Iron Age transition (c. 850 cal. BC) and the 'Little Ice Age' (Wolf, Sporer, Maunder and Dalton Minima) occurred during periods of suddenly increasing atmospheric concentration of C-14. Replicate evidence from peat-based proxy climate indicators in northwest Europe suggest these changes in climate may have been driven by temporary declines of solar activity. Carbon-accumulation rates of two raised peat bogs in the UK and Denmark record low values during the 'Little Ice Age' which reflects reduced primary productivity of the peat-forming vegetation during these periods of climatic deterioration.

Thermal study of selectively plated nickel sulfamate coatings

Nickel sulfamate solution was applied to mild steel substrates by the process of selective plating. The coated samples were heated to temperatures in the range of 50–1000 °C. Thermal analysis, X-ray diffraction and microscopy techniques were used to investigate the effect of secondary heating on the microstructure, mechanical properties and the composition of the surface coatings.

The microscopy analysis showed that the secondary heating caused diffusion within the coating itself and diffusion between the coating and the substrate as concentrations of iron increased in the coating and nickel appeared in the substrate. This diffusion redistribution also caused a phase transformation in the coating as NiO formed on the surface when the coating was heated in a furnace fitted with a nitrogen flow. However this transformation was found not to occur when the coating was heated in a sealed helium environment. Layer and grain growth occurred as temperature increased with the grains taking their preferred orientation as they were heated.

The surface hardness was found to initially rise up from 565 HV to 600 HV when heated to 200 °C. After 200 °C the surface hardness decreased in two stages before falling to 110 HV by 1000 °C. During tensile testing the coated samples performed marginally better in tension than the uncoated samples, however the temperatures used were not elevated high enough to show any real degradation during the tensile testing of the nickel coating that was shown during hardness testing and the microscopy analysis