Practical Synthesis of Unsymmetrical Diarylacetylenes from Propiolic Acid and Two Different Aryl Bromides

A palladium catalyst that mediates the one-pot sequential Sonogashira and decarboxylative coupling of propiolic acid with two different aryl bromides has been developed. Selective coupling of the first aryl bromide was achieved in the presence of a copper-free, monometallic catalyst generated in situ from allylpalladium chloride dimer and SPhos with tetra-n-butylammonium fluoride as the base in an N-methyl-2-pyrrolidone/water solvent mixture. Upon addition of another aryl bromide and raising the temperature from 50 to 80 °C, the intermediate arylpropiolic acid underwent de-carboxylative coupling to give the corresponding diarylacetylene. Thus, the new system permits a one-pot threecomponent synthesis of unsymmetrical diarylacetylenes from widely available aryl bromides, rather than expensive aryl iodides, and propiolic acid, rather than (trimethylsilyl)acetylene, as an inexpensive and easy-to-handle acetylene synthon. The process is highly selective, modular, and gives access to a wide range of unsymmetrical diarylacetylenes in good yields

Volumetric Breast-Density Measurement Using Spectral Photon-Counting Tomosynthesis: First Clinical Results

Measurements of breast density have the potential to improve the efficiency and reduce the cost of screening mammography through personalized screening. Breast density has traditionally been evaluated from the dense area in a mammogram, but volumetric assessment methods, which measure the volumetric fraction of fibro-glandular tissue in the breast, are potentially more consistent and physically sound. The purpose of the present study is to evaluate a method for measuring the volumetric breast density using photon-counting spectral tomosynthesis. The performance of the method was evaluated using phantom measurements and clinical data from a small population (n=18). The precision was determined to 2.4 percentage points (pp) of volumetric breast density. Strong correlations were observed between contralateral (R2=0.95) and ipsilateral () breast-density measurements. The measured breast density was anti-correlated to breast thickness, as expected, and exhibited a skewed distribution in the range [3.7%, 55%] and with a median of 18%. We conclude that the method yields promising results that are consistent with expectations. The relatively high precision of the method may enable novel applications such as treatment monitoring. QC 20210108</p

Viscosity of ring polymer melts

We have measured the linear rheology of critically purified ring polyisoprenes, polystyrenes, and polyethyleneoxides of different molar masses. The ratio of the zero-shear viscosities of linear polymer melts η0,linear to their ring counterparts η0,ring at isofrictional conditions is discussed as a function of the number of entanglements Z. In the unentangled regime η0,linear/η 0,ring is virtually constant, consistent with the earlier data, atomistic simulations, and the theoretical expectation η0,linear/ η0,ring = 2. In the entanglement regime, the Z-dependence of ring viscosity is much weaker than that of linear polymers, in qualitative agreement with predictions from scaling theory and simulations. The power-law extracted from the available experimental data in the rather limited range 1 &amp;lt; Z &amp;lt; 20, η0,linear/η0,ring ∼ Z 1.2±0.3, is weaker than the scaling prediction (η0,linear/η0,ring ∼ Z 1.6±0.3) and the simulations (η0,linear/ η0,ring ∼ Z2.0±0.3). Nevertheless, the present collection of state-of-the-art experimental data unambiguously demonstrates that rings exhibit a universal trend clearly departing from that of their linear counterparts, and hence it represents a major step toward resolving a 30-year-old problem. © 2013 American Chemical Society