TEX86H proxy and BIT index of sediment core GeoB9528-3 and reconstructed temperature data from NW Africa surface sediments

Changes in the strength of Atlantic meridional overturning circulation (AMOC) are known to have profound impacts on global climate. Coupled modelling studies have suggested that, on annual to multi-decadal time scales, a slowdown of AMOC causes a deepening of the thermocline in the tropical Atlantic. However, this process has been poorly constrained by sedimentary geochemical records. Here, we reconstruct surface (UK'37 Index) and thermocline (TEX86H) water temperatures from the Guinea Plateau Margin (Eastern tropical Atlantic) over the last two glacial-interglacial cycles (~ 192 kyr). These paleotemperature records show that periods of reduced AMOC, as indicated by the d13 C benthic foraminiferal record from the same core, coincide with a reduction in the near-surface vertical temperature gradient, demonstrating for the first time that AMOC-induced tropical Atlantic thermocline adjustment exists on longer, millennial time scales. Modelling results support the interpretation of the geochemical records and show that thermocline adjustment is particularly pronounced in the eastern tropical Atlantic. Thus, variations in AMOC strength appear to be an important driver of the thermocline structure in the tropical Atlantic from annual to multi-millennial time scales.

The effect of boundary conditions in the numerical solution of 3-D thermoelastic problems

After the extensive research on the capabilities of the Boundary Integral Equation Method produced during the past years the versatility of its applications has been well founded. Maybe the years to come will see the in-depth analysis of several conflictive points, for example, adaptive integration, solution of the system of equations, etc. This line is clear in academic research. In this paper we comment on the incidence of the manner of imposing the boundary conditions in 3-D coupled problems. Here the effects are particularly magnified: in the first place by the simple model used (constant elements) and secondly by the process of solution, i.e. first a potential problem is solved and then the results are used as data for an elasticity problem. The errors add to both processes and small disturbances, unimportant in separated problems, can produce serious errors in the final results. The specific problem we have chosen is especially interesting. Although more general cases (i.e. transient)can be treated, here the domain integrals can be converted into boundary ones and the influence of the manner in which boundary conditions are applied will reflect the whole importance of the problem.

Recovery of respiration following the SOS response of Escherichia coli requires RecA-mediated induction of 2-keto-4-hydroxyglutarate aldolase.

Agents that damage DNA in Escherichia coli or interfere with its replication induce DNA repair and mutagenesis via the SOS response. This well-known activity is regulated by the RecA protein and the LexA repressor. Following repair or bypass of the DNA lesion, the cell returns to its resting state by a largely unknown process. We found that 2-keto-4-hydroxyglutarate aldolase (4-hydroxy-2-oxoglutarate aldolase; EC 4.1.3.16) is necessary for the recovery of respiration and that it is regulated by the SOS response. This protein was induced by DNA-damaging agents. Induction required RecA activation. When the LexA regulon was repressed, activation of RecA was not sufficient for induction, indicating the requirement for an additional protein under LexA control. Finally, a mutant in the corresponding hga gene was UV sensitive. 2-Keto-4-hydroxyglutarate aldolase also plays a role in respiratory metabolic pathways, which suggests a mechanism for respiration resumption during the termination of the SOS response.

Bulk sediment parameter of surface sediment samples (Table 3)

Comparison of rates of accumulation of organic carbon in surface marine sediments from the central North Pacific, the continental margins off northwest Africa, northwest and southwest America, the Argentine Basin, and the western Baltic Sea with primary production rates suggests that the fraction of primary produced organic carbon preserved in the sediments is universally related to the bulk sedimentation rate. Accordingly, less than 0.01% of the primary production becomes fossilized in slowly accumulating pelagic sediments [(2 to 6 mm (1000 y)**-1] of the Central Pacific, 0.1 to 2% in moderately rapidly accumulating [2 to 13 cm (1000 y)**-1] hemipelagic sediments off northwest Africa, northwest America (Oregon) and southeast America (Argentina), and 11 to 18% in rapidly accumulating [66 to 140 cm (1000 y)**-1] hemipelagic sediments off southwest America (Peru) and in the Baltic Sea. The emiprical expression: %Org-C = (0.0030*R*S**0.30)/(ps(1-Theta)) implies that the sedimentary organic carbon content (% Org-C) doubles with each 10-fold increase in sedimentation rate (S), assuming that other factors remain constant; i.e., primary production (R), porosity and sediment density (ps). This expression also predicts the sedimentary organic carbon content from the primary production rate, sedimentation rate, dry density of solids, and their porosity; it may be used to estimate paleoproductivity as well. Applying this relationship to a sediment core from the continental rise off northwest Africa (Spanish Sahara) suggests that productivity there during interglacial oxygen isotope stages 1 and 5 was about the same as today but was higher by a factor of 2 to 3 during glacial stages 2, 3, and 6.

Flexible synthesis of enantiomerically pure 2,8-dialkyl-1,7-dioxaspiro[5.5]undecanes and 2,7-dialkyl-1,6-dioxaspiro[4.5]decanes from propargylic and homopropargylic alcohols

A new approach to enantiomerically pure 2,8-dialkyl-1,7-dioxaspiro[5.5]undecanes and 2,7-dialkyl-1,6-dioxaspiro [4.5] decanes is described and utilizes enantiomerically pure homopropargylic alcohols obtained from lithium acetylide opening of enantiomerically pure epoxides, which are, in turn, acquired by hydrolytic kinetic resolution of the corresponding racemic epoxides. Alkyne carboxylation and conversion to the Weinreb amide may be followed by triple-bond manipulation prior to reaction with a second alkynyllithium derived from a homo- or propargylic alcohol. In this way, the two ring components of the spiroacetal are individually constructed, with deprotection and cyclization affording the spiroacetal. The procedure is illustrated by acquisition of (2S,5R,7S) and (2R,5R,7S)-2-n-butyl-7-methyl-1,6-dioxaspiro[4.5]-decanes (1), (2S,6R,8S)-2-methyl-8-n-pentyl-1,7-dioxaspiro[5.5]undecane (2), and (2S,6R,8S)-2-methyl-8-n-propyl-1,7-dioxaspiro[5.5]undecane (3). The widely distributed insect component, (2S,6R,8S)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (4), was acquired by linking two identical alkyne precursors via ethyl formate. In addition, [H-2(4)]-regioisomers, 10,10,11,11-[H-2(4)] and 4,4,5,5-[H-2(4)] of 3 and 4,4,5,5-[H-2(4)]-4, were acquired by triple-bond deuteration, using deuterium gas and Wilkinson's catalyst. This alkyne-based approach is, in principle, applicable to more complex spiroacetal systems not only by use of more elaborate alkynes but also by triple-bond functionalization during the general sequence.

Non-classical inhibitors of dihydrofolate reductase

This thesis comprises two main objectives. The first objective involved the stereochemical studies of chiral 4,6-diamino-1-aryl-1,2-dihydro-s-triazines and an investigation on how the different conformations of these stereoisomers may affect their binding affinity to the enzyme dihydrofolate reductase (DHFR). The ortho-substituted 1-aryl-1,2-dihydro-s-triazines were synthesised by the three component method. An ortho-substitution at the C6' position was observed when meta-azidocycloguanil was decomposed in acid. The ortho-substituent restricts free rotation and this gives rise to atropisomerism. Ortho-substituted 4,6-diamino-1-aryl-2-ethyl-1,2-dihydro-2-methyl-s-triazine contains two elements of chirality and therefore exists as four stereoisomers: (S,aR), (R,aS), (R,aR) and (S,aS). The energy barriers to rotation of these compounds were calculated by a semi-empirical molecular orbital program called MOPAC and they were found to be in excess of 23 kcal/mol. The diastereoisomers were resolved and enriched by C18 reversed phase h.p.l.c. Nuclear overhauser effect experiments revealed that (S,aR) and (R,aS) were the more stable pair of stereoisomers and therefore existed as the major component. The minor diastereoisomers showed greater binding affinity for the rat liver DHFR in in vitro assay. The second objective entailed the investigation into the possibility of retaining DHFR inhibitory activity by replacing the classical diamino heterocyclic moiety with an amidinyl group. 4-Benzylamino-3-nitro-N,N-dimethyl-phenylamidine was synthesised in two steps. One of the two phenylamidines indicated weak inhibition against the rat liver DHFR. This weak activity may be due to the failure of the inhibitor molecule to form strong hydrogen bonds with residue Glu-30 at the active site of the enzyme.