Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Serial magnetic resonance imaging in patients following acute myocardial infarction.

The detection of serial changes in magnetic resonance (MR) signal intensity of the heart following acute myocardial infarction may provide a useful method of characterizing tissue healing. Fourteen patients with acute Q-wave infarction underwent T2-weighted, spin-echo cardiac imaging during hospitalization, followed by one or more additional MR studies (total 31) over a 6- to 27-wk period (mean: 3 mo). Visual assessment of the images demonstrated a gradual reduction in signal intensity and localization of the bright signal to the subendocardium of the infarction region over the three-mo study period. A quantitative measurement of signal intensity (infarction/normal myocardium) fell from 1.81 +/- 0.42 on the initial study to 1.34 +/- 0.37 (p less than 0.05) at a mean of 14 wk. Two patients had an increase in signal intensity on the follow-up study and both patients had been readmitted with acute coronary syndromes. In summary, characterization of changes in signal intensity may provide a useful method of assessing myocardial healing following acute myocardial infarction. Further studies are indicated to determine the prognostic significance of these parameters.     

Novel antibiotics: second generation macrocyclic peptides designed to trap Holliday junctions

Described are the syntheses of 15 macrocyclic peptides designed to trap Holliday junctions (HJs) in bacteria during site-specific and homologous recombination. This leads to inhibiting bacterial growth. These second generation macrocycles were based on the C-2 symmetrical HJ. They were synthesized using a strategy that permits elucidation of the amino acid role in binding HJs. The syntheses of these macrocycles are an important step in the development of a new class of antibiotics.     

Free radical-mediated vinyl amination: a mild, general pyrrolidinyl enamine synthesis

The complete scope of free radical-mediated vinyl amination is described, using 5-exo-trig cyclizations of vinyl radicals to the nitrogen of azomethines. The focus is primarily on N,N-dialkyl enamines since their nucleophilicity renders them the most challenging enamines to synthesize using redox conditions. These studies establish several encouraging precedents for the broader application of this strategy.     

Does iron inhibit cryptoendolithic microbial communities?

Photosynthetic activity of three cryptoendolithic microbial communities was studied under controlled conditions in the laboratory. In two of these communities, the dominant organisms were lichens, collected from Linnaeus Terrace and from Battleship Promontory. The third community, dominated by cyanobacteria, was collected from Battleship Promontory. Both sites are in the ice-free valleys of southern Victoria Land. Previous efforts have shown how physical conditions can influence metabolic activity in endolithic communities (Kappen and Friedmann 1983; Kappen, Friedmann, and Garty 1981; Vestal, Federle, and Friedmann 1984). Biological activity can also be strongly influenced by the chemical environment. Inorganic nutrients such as nitrate, ammonia, and phosphate are often limiting factors, so their effects on photosynthetic carbon-14 bicarbonate incorporation were investigated. Iron and manganese are two metals present in Linnaeus Terrace and Battleship Promontory sandstones, and their effects on photosynthesis were also studied. The results may add to our understanding of biogeochemical interactions within this unique microbial community.     

Liquid chromatographic determination of 4,4'-dinitrocarbanilide, the active component of the infertility agent nicarbazin, in chicken, duck, goose, and snake eggs

4,4'-Dinitrocarbanilide (DNC) was extracted from chicken, duck, goose, and snake eggs and isolated by reversed-phase liquid chromatography. DNC was detected by ultraviolet absorbance at 347 nm and quantitated by comparison with a calibration standard. Recoveries of DNC from fortified control chicken, duck, goose, and snake egg samples were determined for DNC levels of 0.16, 10, and 16 microg/g. The mean recoveries from chicken, duck, goose, and snake eggs were 92 +/- 4, 88 +/- 9, 87 +/- 7, and 95 +/- 6%, respectively. The method limits of detection for DNC in chicken, duck, goose, and snake eggs ranged from 0.015 to 0.035 microg/g. The reported method is much simpler than and equally efficient as previous methods developed for the determination of DNC residues in egg contents.     

Recoil spectrometry: Ion accelerator based elemental characterisation of surface layers

Recoil Spectrometry covers a group of techniques that are very similar to the well known Rutherford backscattering Spectrometry technique, but with the important difference that one measures the recoiling target atom rather than the projectile ion. This makes it possible to determine both the identity of the recoil and its depth of origin from its energy and velocity, using a suitable detector system. The incident ion is typically high-energy (30–100MeV)³⁵C1,⁸¹Br or¹²⁷I. Low concentrations of light elements such as C, O and N can be profiled in a heavy matrix such as Fe or GaAs. Here we present an overview of mass and energy dispersive recoil Spectrometry and illustrate its successful use in some typical applications.