Synchroneity of Pliocene planktonic foraminiferal datums in the North Atlantic

Leg 94 of the Deep Sea Drilling Project has provided a unique set of paleomagnetically dated cores, taken along a N-S transect in the North Atlantic. High deposition rates in the sediments, combined with the palaeomagnetic ages, have enabled existing planktonic foraminiferal zonations to be tested and a new zonation for the mid- to high latitudes to be erected. The PL zonation of Berggren (1973, 1977) is shown to be adequate as far north as 41°N, although both the LAD's of Globigerina nepenthes and Globorotalia margaritae occur earlier than in tropical regions. North of 41°N these two species have very diachronous LAD's, even though they are common during their range in the northern sites. The new zonation for the mid to high latitude North Atlantic is based on the FAD of G. margaritae, FAD of G. puncticulata, LAD of G. cf. crassula, LAD of N. atlantica, FAD of G. inflata and FAD of sinistrally coiled encrusted N. pachyderma.

Stable isotope composition of Neogene planktonic foraminifera from ODP Leg 130 sites

We produced a preliminary record for shallow-dwelling planktonic foraminifer d18O at Site 807 for the late Pleistocene, early Pliocene, and early Miocene. Site 807 d18O values between 4 and 5 Ma average 0.75 per mil more than Holocene values and show an average variation of 0.5 per mil. For the early Pliocene, peak maximum d18O at Site 807 attain values equivalent with the last glacial maximum whereas peak minimum d18O were never less than Holocene d18O. Shallow-dwelling planktonic d18O at Site 807 between 16 and 24 Ma average more than 1.0 per mil more positive than Holocene d18O and exhibit 0.5 per mil average amplitude. Assuming that the global ice budget for the early Pliocene and early Miocene was restricted to Antarctica, it is difficult to attribute the very positive Site 807 d18O for these intervals to ice on Antarctica. Site 807 d18O for these intervals more likely reflect sea-surface temperatures cooler than at present, sea-surface salinity greater than at present, increased dissolution, or some combination of these changes.

Calcareous nannofossil stratigraphy and datums of sediments from ODP Leg 198 sites

A relatively complete lower Paleocene to lower Oligocene sequence was recovered from the Southern High of Shatsky Rise at Sites 1209, 1210, and 1211. The sequence consists of nannofossil ooze and clay-rich nannofossil ooze. Samples from these sites have been the target of intensive calcareous nannofossil biostratigraphic investigations. Calcareous nannofossils are moderately preserved in most of the recovered sequence, which extends from nannofossil Zones CP1 to CP16. Most traditional zonal markers are present; however, the rarity and poor preservation of key species in the uppermost Paleocene and lower Eocene inhibits zonal subdivision of part of this sequence.

Calcareous nannofossils in Neogene sediments of ODP Leg 117 holes

Calcareous nannofossils were studied in 574 Neogene samples recovered from eight sites drilled in block-faulted basins on the continental margin of Oman. This portion of the Arabian Sea experiences seasonal upwelling associated with the southwest monsoon. Not surprisingly, some of the more typical Neogene warm-water nannoplankton are either missing entirely or are extremely rare in these sediments. Coccolithus pelagicus, a typical cold-water indicator, is extremely abundant in many samples of late Pliocene to early Pleistocene age. These intervals correspond to periods of Northern Hemisphere glaciation. Reworked Late Cretaceous and Cenozoic nannofossils are found in a majority of the samples. They were probably carried from the Arabian Peninsula or the continent of Africa on strong southwest summer winds. Ages for the various nannofossil events were calculated by projecting the nannofossil datums onto the magnetostratigraphic scale for Sites 724, 727, and 728. These are the first ages for the various nannofossil datums derived from Oman Margin sediments. The following ages have been calculated for these nannofossil events: FAD Emiliania huxleyi, 0.23 Ma; LAD Pseudoemiliania lacunosa, 0.38 Ma; FAD Helicosphaera inversa, 0.42 Ma; top of acme of Reticulofenestra sp. A, 0.70 Ma; FAD Gephyrocapsaparallela, 0.85 Ma; LAD Gephyrocapsa spp. (large), 1.07 Ma; LAD Helicosphaera sellii, 1.34 Ma; LAD Calcidiscus macintyrei, 1.47 Ma; FAD Gephyrocapsa oceanica, 1.53 Ma; FAD Gephyrocapsa caribbeanica, 1.80 Ma; LAD Discoaster brouweri, 2.03 Ma; LAD Discoasterpentaradiatus, 2.31 Ma; LAD Discoaster surculus, 2.42; LAD Discoaster tamalis, 2.77 Ma; LAD Sphenolithus abies, 3.44 Ma; and LAD Reticulofenestra pseudoumbilica, 3.44 Ma.

Late Eocene to Recent deep-sea benthic foraminifera from the Central equatorial Pacific Ocean

Benthic foraminifers were studied in upper Eocene to Recent core-catcher samples from DSDP Sites 573, 574, and 575. The sites are on a north-south transect from the equator to about 05°N at about 133°W, water depth 4300 to 4600 m. At Site 574 additional samples were used to study the Eocene/Oligocene boundary in detail. About 200 specimens were counted per sample. The fauna is highly diverse (about 50 to 70 species per sample) and is of low dominance. The diversity is not related to age or sub-bottom depth. Many species are cosmopolitan and probably have wide environmental tolerances. Fluctuations in frequency of some taxa (e.g., Nuttallides umbonifera, Epistominella exigua, and Uvigerina spp.) cannot be correlated from one site to another. Several common species (e.g. Oridorsalis umbonatus and Globocassidulina subglobosa) range from late Eocene to Recent. First and last appearances are generally difficult to define precisely because many species are rare. For some species these datums differ from one site to another, but several datum levels are within 1 m.y. at all sites. First and last appearances are most numerous in two intervals, the late Eocene to early Oligocene (about 32 to 37 Ma) and the early to middle Miocene (about 13 to 18.5 Ma). Isotopic events occur within each of these periods of benthic faunal change, but the isotopic events have a shorter duration and start after the initiation of the changes in the fauna. Changes in deep-sea benthic faunal composition are not directly related to short-term oceanographic changes as expressed in isotopic records.

Planktonic foraminiferal datum levels of ODP Leg 133 sites

This preliminary report does not present the distribution of selected key planktonic species in each Leg 133 hole, but rather, extracts the best chronodatum levels in two sets of holes, which comprise the Queensland Trough and Townsville Trough transects. In general, the sampling interval was 1.5 m, but sometimes was larger. To convert the datum levels into time, the absolute ages of Berggren et al. (1985, doi:10.1144/GSL.MEM.1985.010.01.18) were used. Extinction levels were employed in the main, because they are the most easily recognized, the order of events seems to be consistent from hole to hole, and they correlate reasonably well with chronodatum levels obtained from nannofossil biostratigraphy (see Gartner et al., 1993, doi:10.2973/odp.proc.sr.133.213.1993).

Hādhā Kitāb Iʻlām al-wará fī aʻlām al-hudá [microform] /

Edited by Abū al-Qāsim al-Sadahī al-Iṣfahānī.

Hādhā kitāb al-Alfayn [microform] /

His Kashf al-yaqīn fī faḍāʼil Amīr al-Muʼminīn: 101 p. (2d group).

Disputatio pro religione Mohammedanorum adversus Christianos [microform] /

Abridgment of al-Jaʻfarī's Takhjīl man ḥarrafa al-Injīl.

Reclaiming Community? From Welfare Society to Welfare State in Australian Catholic Social Thought

Influenced by both conservative and left wing communitarian thinking, current debate about welfare governance in Australia reflects an inflated evaluation of the potential role of the third sector or civil society organisations in the production fo welfare. This paper gives an overview of twentieth century Australian Catholics social thinking about state, market and civil society relations in the production of welfare. It highlights the neglected, historical role of the Catholic Church in promoting a 'welfare society' over a 'welfare state' in Australia. It points to the reasons for the Church's later embrace of the welfare state and suggests that these reasons should make us deeply sceptical of the current communitarian fad.

The crystal structures of Klebsiella pneumoniae acetolactate synthase with enzyme-bound cofactor and with an unusual intermediate

Acetohydroxyacid synthase (AHAS) and acetolactate synthase (ALS) are thiamine diphosphate (ThDP)-dependent enzymes that catalyze the decarboxylation of pyruvate to give a cofactor-bound hydroxyethyl group, which is transferred to a second molecule of pyruvate to give 2-acetolactate. AHAS is found in plants, fungi, and bacteria, is involved in the biosynthesis of the branched-chain amino acids, and contains non-catalytic FAD. ALS is found only in some bacteria, is a catabolic enzyme required for the butanediol fermentation, and does not contain FAD. Here we report the 2.3-Angstrom crystal structure of Klebsiella pneumoniae ALS. The overall structure is similar to AHAS except for a groove that accommodates FAD in AHAS, which is filled with amino acid side chains in ALS. The ThDP cofactor has an unusual conformation that is unprecedented among the 26 known three-dimensional structures of nine ThDP-dependent enzymes, including AHAS. This conformation suggests a novel mechanism for ALS. A second structure, at 2.0 Angstrom, is described in which the enzyme is trapped halfway through the catalytic cycle so that it contains the hydroxyethyl intermediate bound to ThDP. The cofactor has a tricyclic structure that has not been observed previously in any ThDP-dependent enzyme, although similar structures are well known for free thiamine. This structure is consistent with our proposed mechanism and probably results from an intramolecular proton transfer within a tricyclic carbanion that is the true reaction intermediate. Modeling of the second molecule of pyruvate into the active site of the enzyme with the bound intermediate is consistent with the stereochemistry and specificity of ALS.

Electron transfer in acetohydroxy acid synthase as a side reaction of catalysis. implications for the reactivity and partitioning of the carbanion/enamine form of (alpha-hydroxyethyl)thiamin diphosphate in a "nonredox" flavoenzyme

Acetohydroxy acid synthases (AHAS) are thiamin diphosphate- (ThDP-) and FAD-dependent enzymes that catalyze the first common step of branched-chain amino acid biosynthesis in plants, bacteria, and fungi. Although the flavin cofactor is not chemically involved in the physiological reaction of AHAS, it has been shown to be essential for the structural integrity and activity of the enzyme. Here, we report that the enzyme-bound FAD in AHAS is reduced in the course of catalysis in a side reaction. The reduction of the enzyme-bound flavin during turnover of different substrates under aerobic and anaerobic conditions was characterized by stopped-flow kinetics using the intrinsic FAD absorbance. Reduction of enzyme-bound FAD proceeds with a net rate constant of k' = 0.2 s(-1) in the presence of oxygen and approximately 1 s(-1) under anaerobic conditions. No transient flavin radicals are detectable during the reduction process while time-resolved absorbance spectra are recorded. Reconstitution of the binary enzyme-FAD complex with the chemically synthesized intermediate 2-(hydroxyethyl)-ThDP also results in a reduction of the flavin. These data provide evidence for the first time that the key catalytic intermediate 2-(hydroxyethyl)ThDP in the carbanionic/enamine form is not only subject to covalent addition of 2-keto acids and an oxygenase side reaction but also transfers electrons to the adjacent FAD in an intramolecular redox reaction yielding 2-acetyl-ThDP and reduced FAD. The detection of the electron transfer supports the idea of a common ancestor of acetohydroxy acid synthase and pyruvate oxidase, a homologous ThDP- and FAD-dependent enzyme that, in contrast to AHASs, catalyzes a reaction that relies on intercofactor electron transfer.

Elucidating the specificity of binding of sulfonylurea herbicides to acetohydroxyacid synthase

Acetohydroxyacid synthase (AHAS, EC 2.2.1.6) is the target for the sulfonylurea herbicides, which act as potent inhibitors of the enzyme. Chlorsulfuron (marketed as Glean) and sulforneturon methyl (marketed as Oust) are two commercially important members of this family of herbicides. Here we report crystal structures of yeast AHAS in complex with chlorsulfuron (at a resolution of 2.19 Angstrom), sulforneturon methyl (2.34 Angstrom), and two other sulfonylureas, metsulfuron methyl (2.29 Angstrom) and tribenuron methyl (2.58 Angstrom). The structures observed suggest why these inhibitors have different potencies and provide clues about the differential effects of mutations in the active site tunnel on various inhibitors. In all of the structures, the thiamin diphosphate cofactor is fragmented, possibly as the result of inhibitor binding. In addition to thiamin diphosphate, AHAS requires FAD for activity. Recently, it has been reported that reduction of FAD can occur as a minor side reaction due to reaction with the carbanion/enamine of the hydroxyethyl-ThDP intermediate that is formed midway through the catalytic cycle. Here we report that the isoalloxazine ring has a bent conformation that would account for its ability to accept electrons from the hydroxyethyl intermediate. Most sequence and mutation data suggest that yeast AHAS is a high-quality model for the plant enzyme.

Characterization of polyamine oxidase from the aquatic nitrogen-fixing fern Azolla imbricata

Biochemical properties of a polyamine oxidase (PAO; EC 1.5.3.3) purified from the aquatic nitrogen-fixing fern Azolla imbricata (Roxb.) Nak. were studied. The native molecular mass of the enzyme estimated by Sephadex G 200 get filtration was 66.2 kDa. SDS-PAGE gave a single protein band corresponding to a molecular mass of 65.5 kDa. The light yellow enzyme had absorption maxima at 278, 372 and 454 nm with 1 mol FAD per mole enzyme molecule as its cofactor. The PAO was active on both the triamine Spd and the tetraamine Spm as substrates. However, it was inactive on the diamines Put and Cad. It had a pH optimum of 6.5 for both Spd and Spm. The K-m(S) for Spd and Spm were 6.71 x 10(-2) and 1.13 x 10(-1) nM, respectively. Pre-incubation with 10 mM of K+ (KCl), Ca2(+) (CaCl2) or Mg2+ (MgCl2) had no effect on PAO activity. However, 10 mM Cu2+ (CuCl2), Mn2+ (MnCl2) and Fe2+ (FeSO4) inhibited enzyme activity by 37%, 43% and 58%, respectively. The metal chelator EDTA (10 mM), the carbonyl reagent hydroxylamine (0.5 mM) and the sulfhydryl reagent p-chloro-mercuribenzoate (0.5 mM) had no effect on PAO activity. (c) 2005 Elsevier Ireland Ltd. All rights reserved.

Effect of osmolytes on the interaction of flavin adenine dinucleotide with muscle glycogen phosphorylase b

The effect of three osmolytes, trimethylamine N-oxide (TMAO), betaine and proline, on the interaction of muscle glycogen phosphorylase b with allosteric inhibitor FAD has been examined. In the absence of osmolyte, the interaction is described by a single intrinsic dissociation constant (17.8 muM) for two equivalent and independent binding sites on the dimeric enzyme. However, the addition of osmolytes gives rise to sigmoidal dependencies of fractional enzyme-site saturation upon free inhibitor concentration. The source of this cooperativity has been shown by difference sedimentation velocity to be an osmolyte-mediated isomerization of phosphorylase b to a smaller dimeric state with decreased affinity for FAD. These results thus have substantiated a previous inference that the tendency for osmolyte-enhanced self-association of dimeric glycogen phosphorylase b in the presence of AMP was being countered by the corresponding effect of molecular crowding on an isomerization of dimer to a smaller, nonassociating state. (C) 2004 Elsevier Ltd. Inc. All rights reserved.