sp‐9‐Acetyl­fluorene,the initial acetyl­ation product of 9‐fluorenyl­lithium

The reaction of 9‐fluorenyl­lithium with acetyl chloride (tetra­hydro­furan, 213 K, under argon) provided four products which we have isolated and whose structures we have unequivocally identified for the first time. That of the initially formed component, 9‐acetyl­fluorene (C₁₅H₁₂O), described here, shows it to be exclusively the sp rotamer in its crystalline form. The acetyl C—C=O plane is essentially perpendicular to the planar fluorene ring and there is no indication of rotational restriction. In contrast, related 9‐pivaloyl­fluorene, which we reported previously, is rotationally restricted and exists exclusively as its ap rotamer, in which the pivaloyl C—C=O plane is also almost perpendicular to the fluorene ring.     

Thermodynamic laws and consistent Eulerian formulation of finite elastoplasticity with thermal effects

Recently it has been demonstrated that, on the basis of the separation D=D^e+D^p arising from the split of the stress power and two consistency criteria for objective Eulerian rate formulations, it is possible to establish a consistent Eulerian rate formulation of finite elastoplasticity in terms of the Kirchhoff stress and the stretching, without involving additional deformation-like variables labelled “elastic” or “plastic”. It has further been demonstrated that this consistent formulation leads to a simple essential structure implied by the work postulate, namely, both the normality rule for plastic flow D^p and the convexity of the yield surface in Kirchhoff stress space. Here, we attempt to place such an Eulerian formulation on the thermodynamic grounds by extending it to a general case with thermal effects, where the consistency requirements are treated in a twofold sense. First, we propose a general constitutive formulation based on the foregoing separation as well as the two consistency criteria. This is accomplished by employing the corotational logarithmic rate and by incorporating an exactly integrable Eulerian rate equation for D^e for thermo-elastic behaviour. Then, we study the consistency of the formulation with thermodynamic laws. Towards this goal, simple forms of restrictions are derived, and consequences are discussed. It is shown that the proposed Eulerian formulation is free in the sense of thermodynamic consistency. Namely, a Helmholtz free energy function in explicit form may be found such that the restrictions from the thermodynamic laws can be fulfilled with positive internal dissipation for arbitrary forms of constitutive functions included in the constitutive formulation. In particular, that is the case for the foregoing essential constitutive structure in the purely mechanical case. These results eventually lead to a complete, explicit constitutive theory for coupled fields of deformation, stress and temperature in thermo-elastoplastic solids at finite deformations.     

Finite Bending of a Rectangular Block of an Elastic Hencky Material

Hencky's elasticity model is an isotropic, finite hyperelastic equation obtained by simply replacing the Cauchy stress tensor and the infinitesimal strain tensor in the classical Hooke's law for isotropic infinitesimal elasticity with the Kirchhoff stress tensor and Hencky's logarithmic strain tensor. A study by Anand in 1979 and 1986 indicates that it is a realistic finite elasticity model that is in good accord with experimental data for a variety of engineering materials for moderate deformations. Most recently, by virtue of well-founded physical grounds and rigorous mathematical procedures it has been demonstrated by these authors that this model may be essential to achieving self-consistent Eulerian rate type theories of finite inelasticity, e.g., the J ₂-flow theory for metal plasticity, etc. Its predictions have been studied for some typical deformation modes, including extension, simple shear and torsion, etc. Here we are concerned with finite bending of a rectangular block. We show that a closed-form solution may be obtained. We present explicit expressions for the bending angle and the bending moment in terms of the maximum or minimum circumferential stretch in a general case of compressible deformations for any assigned stretch normal to the bending plane. In particular, simplified results are derived for the plane strain case and for the case of incompressibility. This revised version was published online in June 2006 with corrections to the Cover Date.     

A Convenient Synthesis and Resolution of R- and S- Atrolactic Acid in High Enantiomeric Purity

Although chiral atrolactic acid has been the subject of extensive studies by Prelog¹ and others,² there is no simple method to obtain either enantiomer in high purity. During the course of an investigation designed to assess the utility of chiral oxazolines³ as vehicles for asymmetric syntheses, we encountered an efficient technique to obtain either R or S atrolactic acid 4 from a single chiral precursor.     

Radiochronological age of a uranium metal sample from an abandoned facility

A piece of scrap uranium metal bar buried in the dirt floor of an old, abandoned metal rolling mill was analyzed using multi-collector inductively coupled plasma mass spectroscopy (MC-ICP-MS). The mill rolled uranium rods in the 1940 and 1950s. Samples of the contaminated dirt in which the bar was buried were also analyzed. The isotopic composition of uranium in the bar and dirt samples were both the same as natural uranium, though a few samples of dirt also contained recycled uranium; likely a result of contamination with other material rolled at the mill. The time elapsed since the uranium metal bar was last purified can be determined by the in-growth of the isotope ²³⁰Th from the decay of ²³⁴U, assuming that only uranium isotopes were present in the bar after purification. The age of the metal bar was determined to be 61 years at the time of this analysis and corresponds to a purification date of July 1950 ± 1.5 years.     

Superior performance of liposomes over enzymatic amplification in a high-throughput assay for myoglobin in human serum

Myoglobin is one of several cardiac markers which become elevated in the blood following an acute myocardial infarction and can aid in the diagnosis of a heart attack. Here, a sandwich immunoassay for myoglobin was developed, including a thorough optimization of fluorescent dye-encapsulating liposomes versus enzymatic amplification (alkaline phosphatase and horseradish peroxidase) at each step. The optimized microtiter plate-based assay was capable of detecting as low as 11.3 pg/mL myoglobin and was successfully applied for the quantification of myoglobin in human serum. In comparison to enzymatic approaches, the liposomes demonstrated lower limits of detection, significantly reduced limits of quantification, improved signal discrimination through substantial signal enhancement, and reduced assay time. Liposomes were stable and functional at ambient temperatures for over 400 days. Finally, ease of use was greater due to lack of reliance on additional reagents, non-time-based signal enhancement, and excellent photostability. Optimal conditions identified for enzymatic approaches can also be used for liposome amplification, which makes substitution of these liposomes into existing assays straightforward. Thus, the extensive studies carried out here suggest that liposomes may be incorporated into formats currently utilizing enzymatic enhanced fluorescence with a potential for increased performance on various levels.