A Comprehensive Discussion of HMBC Pulse Sequences: 4. Establishing Two-Bond Correlations from HMBC and Related Experiments

The utility of the HMBC experiment for structure elucidation is unquestionable, but the nature of the coupling pathways leading to correlations in an HMBC experiment creates the potential for misinterpretation. This misinterpretation potential is intimately linked to the size of the long-range heteronuclear couplings involved, and may become troublesome in those cases of a particularly strong 2JCH correlation that might be mistaken for a 3JCH correlation or a 4JCH correlation of appreciable strength that could be mistaken for a weaker 3JCH correlation. To address these potential avenues of confusion, work from several laboratories has been focused on the development of what might be considered “coupling pathway edited” long-range heteronuclear correlation experiments that are derived from or related to the HMBC experiment. The first example of an effort to address the problems associated with correlation path length was seen in the heteronucleus-detected XCORFE experiment described by Reynolds and co-workers that predated the development of the HMBC experiment. Proton-detected analogs of the HMBC experiment intended to differentiate 2JCH correlations from nJCH correlations where n = 3, 4, include the 2J,3J-HMBC, HMBC-RELAY, H2BC, edited-HMBC, and HAT H2BC experiments. The principles underlying the critical components of each of these experiments are discussed and experimental verification of the results that can be obtained using model compounds are shown. This contribution concludes with a brief discussion of the 1,1-ADEQUATE experiments that provide an alternative means of identifying adjacent protonated and non-protonated carbon correlations by exploiting 1JCC correlations at natural abundance.

SHRIMP U-Pb dating of high-grade migmatites and related magmatites from Northwestern Oates Land, East Antarctica

High- to very-high-grade migmatitic basement rocks of the Wilson Hills area in northwestern Oates Land (Antarctica) form part of a low-pressure high-temperature belt located at the western inboard side of the Ross-orogenic Wilson Terrane. Zircon, and in part monazite, from four very-high grade migmatites (migmatitic gneisses to diatexites) and zircon from two undeformed granitic dykes from a central granulite-facies zone of the basement complex were dated by the SHRIMP U-Pb method in order to constrain the timing of metamorphic and related igneous processes and to identify possible age inheritance. Monazite from two migmatites yielded within error identical ages of 499 +/- 10 Ma and 493 +/- 9 Ma. Coexisting zircon gave ages of 500 +/- 4 Ma and 484 +/- 5 Ma for a metatexite (two age populations) and 475 +/- 4 Ma for a diatexite. Zircon populations from a migmatitic gneiss and a posttectonic granitic dyke yielded well-defined ages of 488 +/- 6 Ma and 482 +/- 4 Ma, respectively. There is only minor evidence of age inheritance in zircons of these four samples. Zircon from two other samples (metatexite, posttectonic granitic dyke) gave scattered 206Pb-238U ages. While there is a component similar in age and in low Th/U ratio to those of the other samples, inherited components with ages up to c. 3 Ga predominate. In the metatexite, a major detrital contribution from 545 - 680 Ma old source rocks can be identified. The new age data support the model that granulite- to high-amphibolite-facies metamorphism and related igneous processes in basement rocks of northwestern Oates Land were confined to a relatively short period of time of Late Cambrian to early Ordovican age. An age of approximately 500 Ma is estimated for the Ross-orogenic granulite-facies metamorphism from consistent ages of monazite from two migmatites and of the older zircon age population in one metatexite. The variably younger zircon ages are interpreted to reflect mineral formation in the course of the post-granulite-facies metamorphic evolution, which led to a widespread high-amphibolite-facies retrogression and in part late-stage formation of ms+bi assemblages in the basement rocks and which lasted until about 465 Ma. The presence of inherited zircon components of latest Neoproterozoic to Cambrian age indicates that the high- to very-grade migmatitic basement in northwestern Oates Land originated from clastic series of Cambrian age and, therefore, may well represent the deeper-crustal equivalent of lower-grade metasedimentary series of the Wilson Terrane.

Raw-data to morphometric investigations about the Neogene planktonic foraminifer Globorotalia menardii and related forms from ODP Hole 154-925B (Céara Rise, western tropical Atlantic)

Evolutionary prospection is the study of morphological evolution and speciation in calcareous plankton from selected time-slices and key sites in the world oceans. In this context, the Neogene menardiform globorotalids serve as study objects for morphological speciation in planktic foraminifera. A downcore investigation of test morphology of the lineage of G. menardii-limbata-multicamerata during the past 8 million years was carried out in the western tropical Atlantic ODP Hole 925B. A total of 4669 specimens were measured and analyzed from 38 stratigraphic levels and compared to previous studies from DSDP Sites 502 and 503. Collection of digital images and morphometric measurements from digitized outlines were achieved using a microfossil orientation and imaging robot called AMOR and software, which was especially developed for this purpose. Most attention was given to the evolution of spiral height versus axial length of tests in keel view, but other parameters were investigated as well. The variability of morphological parameters in G. menardii, G. limbata, and G. multicamerata through time are visualized by volume density diagrams. At Hole 925B results show gradual test size increase in G. menardii until about 3.2 Ma. The combination of taxonomic determination in the light microscope with morphometric investigations shows strong morphological overlap and evolutionary continuity from ancestral to extant G. menardii (4-6 chambers in the final whorl) to the descendent but extinct G. limbata (seven chambers in the final whorl) and to G. multicamerata (>=8 chambers in the final whorl). In the morphospace defined by spiral height (dX) and axial length (dY) Globorotalia limbata and G. multicamerata strongly overlap with G. menardii. Distinction of G. limbata from G. menardii is only possible by slight differences in the number of chambers of the final whorl, nuances in spiral convexity, upper keel angles, radii of osculating circles, or by differences in reflectance of their tests. Globorotalia multicamerata can be distinguished from the other two forms by more than eight chambers in the final whorl. It appeared as two stratigraphically separate clusters during the Pliocene. Between 2.88 and 2.3 Ma G. menardii was severely restricted in size and abundance. Thereafter, it showed a rapid and prominent expansion of the upper test size extremes between 2.3 and 1.95 Ma persisting until present. The size-frequency distributions at Hole 925B are surprisingly similar to trends of menardiform globorotalids from Caribbean DSDP Site 502. There, the observations were explained as an adaptation to changes in the upper water column due to the emergence of the Isthmus of Panama. In light of more recent paleontological and geological investigations about the completion of the permanent land connection between North and South America since about 3 Ma the present study gives reason to suspect the sudden test size increase of G. menardii to reflect immigration of extra-large G. menardii from the Indian Ocean or the Pacific. It is hypothesized that during the Late Pliocene dispersal of large G. menardii into the southern to tropical Atlantic occurred during an intermittent episode of intense Agulhas Current leakage around the Cape of Good Hope and from there via warm eddy transport to the tropical Atlantic (Agulhas dispersal hypothesis).

Bibliography of poverty and related topics in Costa Rica /

Includes indexes.

Selected bibliography of physico-chemical properties in liquid ammonia and related solvents /

Mode of access: Internet.

A compendium of bilingual education and related projects at the national institute of education /

Compilation of abstracts of current bilingual research projects funded through the National Institute of Education.