ion. The oxidative addition mechanism was originally proposed22i because of the lack of a strong rate dependence on polar factors and on the acidity of the medium. Later, however, the electrophilic substitution mechanism also was proposed. Recently, the oxidative addition mechanism was confirmed by investigations into the decomposition and protonolysis of alkylplatinum complexes, which are the reverse of alkane activation. There are two routes which operate in the decomposition of the dimethylplatinum(IV) complex Cs2Pt(CH3)2Cl4. The first route leads to chloride-induced reductive elimination and produces methyl chloride and methane. The second route leads to the formation of ethane. There is strong kinetic evidence that the ethane is produced by the decomposition of an ethylhydridoplatinum(IV) complex formed from the initial dimethylplatinum(IV) complex. In D2O-DCl, the ethane which is formed contains several D atoms and has practically the same multiple exchange parameter and distribution as does an ethane which has undergone platinum(II)-catalyzed H-D exchange with D2O. Moreover, ethyl chloride is formed competitively with H-D exchange in the presence of platinum(IV). From the principle of microscopic reversibility it follows that the same ethylhydridoplatinum(IV) complex is the intermediate in the reaction of ethane with platinum(II). Important results were obtained by Labinger and Bercaw62c in the investigation of the protonolysis mechanism of several alkylplatinum(II) complexes at low temperatures. These reactions are important because they could model the microscopic reverse of C-H activation by platinum(II) complexes. Alkylhydridoplatinum(IV) complexes were observed as intermediates in certain cases, such as when the complex (tmeda)Pt(CH2Ph)Cl or (tmeda)PtMe2 (tmeda ) N,N,N′,N′-tetramethylenediamine) was treated with HCl in CD2Cl2 or CD3OD, respectively. In some cases H-D exchange took place between the methyl groups on platinum and the, CD3OD prior to methane loss. On the basis of the kinetic results, a common mechanism was proposed to operate in all the reactions: (1) protonation of Pt(II) to generate an alkylhydridoplatinum(IV) intermediate, (2) dissociation of solvent or chloride to generate a cationic, fivecoordinate platinum(IV) species, (3) reductive C-H bond formation, producing a platinum(II) alkane σ-complex, and (4) loss of the alkane either through an associative or dissociative substitution pathway. These results implicate the presence of both alkane σ-complexes and alkylhydridoplatinum(IV) complexes as intermediates in the Pt(II)-induced C-H activation reactions. Thus, the first step in the alkane activation reaction is formation of a σ-complex with the alkane, which then undergoes oxidative addition to produce an alkylhydrido complex. Reversible interconversion of these intermediates, together with reversible deprotonation of the alkylhydridoplatinum(IV) complexes, leads to multiple H-D exchange

Activation of c-h bonds by metal complexes

Small-diameter (ca. 0.7 nm) single-wall carbon nanotubes are predicted to display enhanced reactivity relative to larger-diameter nanotubes due to increased curvature strain. The derivatization of these small-diameter nanotubes via electrochemical reduction of a variety of aryl diazonium salts is described. The estimated degree of functionalization is as high as one out of every 20 carbons in the nanotubes bearing a functionalized moiety. The functionalizing moieties can be removed by heating in an argon atmosphere. Nanotubes derivatized with a 4-tert-butylbenzene moiety were found to possess significantly improved solubility in organic solvents. Functionalization of the nanotubes with a molecular system that has exhibited switching and memory behavior is shown. This represents the marriage of wire-like nanotubes with molecular electronic devices.

Functionalization of carbon nanotubes by electrochemical reduction of aryl diazonium salts: a bucky paper electrode

The role of fossils in dating the tree of life has been misunderstood. Fossils can provide good "minimum" age estimates for branches in the tree, but "maximum" constraints on those ages are poorer. Current debates about which are the "best" fossil dates for calibration move to consideration of the most appropriate constraints on the ages of tree nodes. Because fossil-based dates are constraints, and because molecular evolution is not perfectly clock-like, analysts should use more rather than fewer dates, but there has to be a balance between many genes and few dates versus many dates and few genes. We provide "hard" minimum and "soft" maximum age constraints for 30 divergences among key genome model organisms; these should contribute to better understanding of the dating of the animal tree of life.

/pdf/paleontological-evidence-to-date-the-tree-of-life-5dhwbwgnyr.pdf

Paleontological Evidence to Date the Tree of Life

Glacial deposits of Sturtian and Marinoan age occur in the well-studied Neoproterozoic successions of northern Namibia, South Australia, and northwestern Canada. In all three regions, the Marinoan glaciation is presaged by a large negative δ 13 C anomaly, and the cap carbonates to both glacial units share a suite of unique sedimentological, stratigraphic, and geochemical features. These global chronostratigraphic markers are the bases of a new correlation scheme for the Neoproterozoic that corroborates radiometric data that indicate that there were three glacial epochs between ca. 750 and 580 Ma. Intraregional correlation of Neoproterozoic successions in the present-day North Atlantic region suggests that glacial diamictite pairs in the Polarisbreen Group in northeastern Svalbard and the Tillite Group in eastern Greenland were deposited during the Marinoan glaciation, whereas the younger of a pair of glacials (Mortensnes Formation) in the Vestertana Group of northern Norway was deposited during the third (Gaskiers) Neoproterozoic glaciation. Gaskiers-aged glacial deposits are neither globally distributed nor overlain by a widespread cap carbonate but are associated with an extremely negative δ 13 C anomaly. framework for a new, high-resolution model carbon-isotope record for the Neoproterozoic comprising new δ 13 C (carbonate) data from Svalbard (Akademikerbreen Group) and Namibia (Otavi Group) and data in the literature from Svalbard, Namibia, and Oman. A new U-Pb zircon age of 760 ± 1 Ma from an ash bed in the Ombombo Subgroup in Namibia provides the oldest direct time-calibration point in the compilation, but the time scale of this preliminary δ 13 C record remains

/pdf/toward-a-neoproterozoic-composite-carbon-isotope-record-4n6ste2vda.pdf

Toward a Neoproterozoic composite carbon-isotope record

The morphological and functional evolution of appendages has played a crucial role in the adaptive radiation of tetrapods, arthropods and winged insects. The origin and diversification of fins, wings and other structures, long a focus of palaeontology, can now be approached through developmental genetics. Modifications of appendage number and architecture in each phylum are correlated with regulatory changes in specific patterning genes. Although their respective evolutionary histories are unique, vertebrate, insect and other animal appendages are organized by a similar genetic regulatory system that may have been established in a common ancestor.

Fossils, genes and the evolution of animal limbs

Appearance of metazoans with mineralized skeletons, “explosion” in biotic diversity and disparity, infaunalization of the substrate, occurrence of metazoan Konservat Fossil-lagerstatten, establishment of most invertebrate phyla, strong faunal provincialism, dominance of trilobites, generally warm climate but with possible glacial–interglacial cycles in the later part, opening of the Iapetus Ocean, progressive equatorial drift and separation of Laurentia, Baltica, Siberia, and Avalonia from Gondwana characterize the Cambrian Period.

The Cambrian Period

Five anomalocaridids are described from the Lower Cambrian Chengjiang fauna of China: Anomalocaris saron sp.n., Anomalocaris sp., Amplectobelua symbrachiata gen. et sp.n., Cucumericrus decoratus gen. et sp.n., and Parapeytoia yunnanensis gen. et sp.n. Ventral trunk appendages are reported for the first time. In C. decoratus and P. yunnanensis, each appendage has a distal segmented walking leg, and a wide lateral extension of a long proximal portion forms the structure previously described as a lateral fin. Furthermore, the structure of the dorsum is elucidated. The supposed ventrolateral gills are flat scales covering the back in transverse rows. The mouth was directed backwards, as in the Middle Cambrian Opabinia regalis, and not directed ventrally as in previous reconstructions. The radial arrangement of the circum‐oral sclerites suggests that anomalocaridids were related to aschelminth worms rather than to arthropods. Hou, X.‐g., Bergstrom, J. & Ahlberg, P., 1995: Anomalocaris and other large ...

Anomalocaris and other large animals in the lower cambrian chengjiang fauna of southwest china

A core drilling (Andrarum-3), from the classical locality at Andrarum, Scania, southernmost Sweden, penetrated a 28.90-m-thick Cambrian succession. The core comprises dark grey to black, finely laminated mudstones and shales with early concretionary carbonate lenses (stinkstones or orsten) and a few primary carbonate beds. The middle Cambrian (provisional Series 3) part of the core comprises 17.35 m, whereas the Furongian Series (upper Cambrian) part covers the remaining 11.55 m. Nineteen trilobite and two phosphatocopine genera are present in the middle Cambrian, whereas the less diverse Furongian interval yielded four trilobite and three phosphatocopine genera. Other, less frequent, faunal elements include conodonts (s. l.), brachiopods, sponge spicules, bradoriids, and coprolites. Trilobites and phosphatocopines were used to subdivide the core into seven biozones ranging from the Ptychagnostus atavus Zone to the Parabolina spinulosa Zone (P. spinulosa Subzone). Carbon isotopic analyses (δ13Corg) through the core show two important excursions, the negative DrumIan Carbon isotope Excursion (DICE) in the Pt. atavus Zone, and the Steptoean Positive Carbon Isotope Excursion (SPICE) beginning near the first appearance of Glyptagnostus reticulatus and extending upward into the Olenus and Agnostus (Homagnostus) obesus Zone. The DICE displays a peak value, in the samples at hand, of –30.45‰δ13Corg in the lower part of the P. atavus Zone. The δ13Corg values increase through the overlying L. laevigata and A. pisiformis zones and display peak values of c. –28.00‰δ13Corg in the lowermost Furongian Olenus wahlenbergi and O. attenuatus subzones. Thereafter the values decrease significantly through the O. scanicus Subzone. Both isotopic excursions have been documented from several palaeocontinents, but never before from Baltica. Moreover, for the first time these excursions are recorded from organic matter in an alum shale setting. The recorded shift of +1.50–2.00‰δ13Corg is approximately half the magnitude of the SPICE documented from other regions. This discrepancy may be related to temporal variations in the type, origin, or diagenesis of the organic fraction analysed.

Cambrian high-resolution biostratigraphy and carbon isotope chemostratigraphy in Scania, Sweden: first record of the SPICE and DICE excursions in Scandinavia

The Lower Cambrian strata above the Rispebjerg Sandstone in Scania (Skane), southern Sweden are briefly described and the term Gislov Formation is introduced for them The vertical distribution of the faunal elements is described for the first time Holmia sulcata, a member of the Holmia kjerulfi group, and Proampyx cf linnarssoni are taken to indicate the presence of the Holmia kjerulfi-group Zone and the Proampyx linnarssoni Zone The correlation is discussed, inter alia on the basis of a specimen which may belong to Calodiscus lobatus Ellipsocephalus lunatus nsp is described

Per Ahlberg

Papers

The Cambrian Period

Anomalocaris and other large animals in the lower cambrian chengjiang fauna of southwest china

Cambrian high-resolution biostratigraphy and carbon isotope chemostratigraphy in Scania, Sweden: first record of the SPICE and DICE excursions in Scandinavia

Uppermost Lower Cambrian biostratigraphy in Scania, Sweden

Andreolepis and Lophosteus: scales, jaws and teeth of the earliest bony fishes