Deep sampling and testing in soft stratified clay

A 37-m thick layer of stratified clay encountered during a site investigation at Swann's Bridge, near the sea-coast at Limavady, Northern Ireland, is one of the deepest and thickest layers of this type of material recorded in Ireland. A study of the relevant literature and stratigraphic evidence obtained from the site investigation showed that despite being close to the current shoreline, the clay was deposited in a fresh-water glacial lake formed approximately 13 000 BP. The 37-m layer of clay can be divided into two separate zones. The lower zone was deposited as a series of laminated layers of sand, silt, and clay, whereas the upper zone was deposited as a largely homogeneous mixture. A comprehensive series of tests was carried out on carefully selected samples from the full thickness of the deposit. The results obtained from these tests were complex and confusing, particularly the results of tests done on samples from the lower zone. The results of one-dimensional compression tests, unconsolidated undrained triaxial tests, and consolidated undrained triaxial compression tests showed that despite careful sampling, all of the specimens from the lower zone exhibited behaviour similar to that of reconstituted clays. It was immediately clear that the results needed explanation. This paper studies possible causes of the results from tests carried out on the lower Limavady clay. It suggests a possible mechanism based on anisotropic elasticity, yielding, and destructuring that provides an understanding of the observed behaviour.Key words: clay, laminations, disturbance, yielding, destructuring, reconstituted.

Equilibrium polymerization of cyclic carbonate oligomers. III. Chain branching and the gel transition

Ring-opening polymerization of cyclic polycarbonate oligomers, where monofunctional active sites act on difunctional monomers to produce an equilibrium distribution of rings and chains, leads to a "living polymer." Monte Carlo simulations [two-dimensional (2D) and three-dimensional (3D)] of the effects of single [J. Chem. Phys. 115, 3895 (2001)] and multiple active sites [J. Chem. Phys. 116, 7724 (2002)] are extended here to trifunctional active sites that lead to branching. Low concentrations of trifunctional particles c(3) reduce the degree of polymerization significantly in 2D, and higher concentrations (up to 32%) lead to further large changes in the phase diagram. Gel formation is observed at high total density and sizable c(3) as a continuous transition similar to percolation. Polymer and gel are much more stable in 3D than in 2D, and both the total density and the value of c(3) required to produce high molecular weight aggregates are reduced significantly. The degree of polymerization in high-density 3D systems is increased by the addition of trifunctional monomers and reduced slightly at low densities and low c(3). The presence of branching makes equilibrium states more sensitive (in 2D and 3D) to changes in temperature T. The stabilities of polymer and gel are enhanced by increasing T, and-for sufficiently high values of c(3)-there is a reversible polymer-gel transformation at a density-dependent floor temperature. (C) 2002 American Institute of Physics.

Equilibrium polymerization of cyclic carbonate oligomers. II. Role of multiple active sites

Ring opening polymerization of bisphenol A polycarbonate is studied by Monte Carlo simulations of a model comprising a fixed number of Lennard-Jones particles and harmonic bonds [J. Chem. Phys. 115, 3895 (2001)]. Bond interchanges produced by a low concentration (0.10%less than or equal toc(a)less than or equal to0.36%) of chemically active particles lead to equilibrium polymerization. There is a continuous transition in both 2D and 3D from unpolymerized cyclic oligomers at low density to a system of linear chains at high density, and the polymeric phase is much more stable in three dimensions than in two. The steepness of the polymerization transition increases rapidly as c(a) decreases, suggesting that it is discontinuous in the limit c(a)-->0. The transition is entropy driven, since the average potential energy increases systematically upon polymerization, and there is a steady decline in the degree of polymerization as the temperature is lowered. The mass distribution functions for open chains and for rings are unimodal, with exponentially decaying tails that can be fitted by Zimm-Schulz functions and simpler exponential forms. (C) 2002 American Institute of Physics.

Equilibrium polymerization of cyclic carbonate oligomers

A model of the polymerization of ring oligomers of bisphenol A polycarbonate (BPA-PC) is used to investigate the influence of dimensionality (2D or 3D), density and temperature on the size distribution of the polymer chains. The polymerization step is catalyzed by a single active particle, conserves the number and type of the chemical bonds, and occurs without a significant gain in either potential energy or configurational entropy. Monte Carlo and molecular dynamics simulations show that polymerization of cyclic oligomers occurs readily at high density and is driven by the entropy associated with the distribution of interparticle bonds. Polymerization competes at lower densities with long range diffusion, which favors small molecular species, and is prevented if the system is sufficiently dilute. Polymerization occurs in 2D via a weakly first order transition as a function of density and is characterized by low hysteresis and large fluctuations in the size of polymer chains. Polymerization occurs more readily in 3D than in 2D, and is favored by increasing temperature, as expected for an entropy-driven process. (C) 2001 American Institute of Physics.

Preparation of Potential Cell-Permeant Nucleoside-2',3'-Cyclic Phosphate Precursors

Uridine-3'-phosphorothiolate triesters bearing lipophilic moieties were prepared via Michaelis-Arbuzov chemistry. Subsequent deprotection of the S-cholesteryl phosphorothiolate triester afforded the corresponding diester which underwent spontaneous Cyclization to cleanly afford uridine 2',3'-cyclic phosphate. This transesterification reaction could be expedited by treatment with iodine under mild, neutral conditions.

Testing the timing of radiocarbon-dated events between proxy archives

For interpreting past changes on a regional or global scale, the timings of proxy-inferred events are usually aligned with data from other locations. However, too often chronological uncertainties are ignored in proxy diagrams and multisite comparisons, making it possible for researchers to fall into the trap of sucking separate events into one illusionary event (or vice versa). Here we largely solve this "suck in and smear syndrome" for radiocarbon (14C) dated sequences. In a Bayesian framework, millions of plausible age-models are constructed to quantify the chronological uncertainties within and between proxy archives. We test the technique on replicated high-resolution 14C-dated peat cores deposited during the "Little Ice Age" (c. AD 1400-1900), a period characterized by abrupt climate changes and severe 14C calibration problems. Owing to internal variability in proxy data and uncertainties in age-models, these (and possibly many more) archives are not consistent in recording decadal climate change. Through explicit statistical tests of palaeoenvironmental hypotheses, we can move forward to systematic interpretations of proxy data. However, chronological uncertainties of non-annually resolved palaeoclimate records are too large for answering decadal timescale questions.

Significantly improved PCR-based clonality testing in B-cell malignancies by use of multiple immunoglobulin gene targets: Report of the BIOMED-2 Concerted Action BHM4-CT98-3936.

Polymerase chain reaction (PCR) assessment of clonal immunoglobulin (Ig) and T-cell receptor (TCR) gene rearrangements is an important diagnostic tool in mature B-cell neoplasms. However, lack of standardized PCR protocols resulting in a high level of false negativity has hampered comparability of data in previous clonality studies. In order to address these problems, 22 European laboratories investigated the Ig/TCR rearrangement patterns as well as t(14;18) and t(11;14) translocations of 369 B-cell malignancies belonging to five WHO-defined entities using the standardized BIOMED-2 multiplex PCR tubes accompanied by international pathology panel review. B-cell clonality was detected by combined use of the IGH and IGK multiplex PCR assays in all 260 definitive cases of B-cell chronic lymphocytic leukemia (n¼56), mantle cell lymphoma (n¼54), marginal zone lymphoma (n¼41) and follicular lymphoma (n¼109). Two of 109 cases of diffuse large B-cell lymphoma showed no detectable clonal marker. The use of these techniques to assign cell lineage should be treated with caution as additional clonal TCR gene rearrangements were frequently detected in all disease categories. Our study indicates that the BIOMED-2 multiplex PCR assays provide a powerful strategy for clonality assessment in B-cell malignancies resulting in high Ig clonality detection rates particularly when IGH and IGK strategies are combined.

Theorising European Integration: Revisiting Neo-Functionalism and Testing its Suitability for Explaining the Development of EC Competition Policy?

This paper was published in the highly respected, peer reviewed and ISI ranked journal - 'European Integration on-line paper series