Hammett correlation of nornicotine analogues in the aqueous aldol reaction: implications for green organocatalysis

[reaction: see text] A series of meta- and para-substituted 2-arylpyrrolidines were synthesized and examined for their ability to catalyze an aqueous aldol reaction under buffered conditions. Kinetic analysis of arylpyrrolidine-catalyzed reactions displayed a linear Hammett correlation with rho = 1.14 (R(2) = 0.996), indicating that the reaction is accelerated by electron-withdrawing aryl rings. These results show promise for the development of a synthetically viable aqueous organo-catalyst.     

Infrared emission spectroscopy of CO on Ni

We report the first observation of thermally emitted infrared radiation from vibrational modes of molecules adsorbed on clean, single crystal metal surfaces. The observation of emission from CO adsorbed on Ni demonstrates the surface sensitivity of a novel apparatus for infrared vibrational spectroscopy, with a resolution of 1 to 15 cm^?1 over the frequency range from 330 to 3000 cm^?1. A liquid helium cooled grating spectrometer measures the thermal radiation from a room temperature, single crystal sample, which is mounted in an ultrahigh vacuum system. Measurements of frequencies and linewidths of CO on a single crystal Ni sample, as a function of coverage, are discussed.     

Theory of phase transition kinetics with growth site impingement. I. Homogeneous nucleation

The nonlinear integral equations governing phase transition kinetics with homogeneous nucleation and growth site impingement are developed and solved to the first order for the two-dimensional case. It is shown that the fractional transformed area at time t is given approximately by a(t) = Kt³/(1 + Kt³). The iteration method used to get the solution is applicable to certain other nonlinear differential and integral equations. It is shown that the theory predicts the total number of growth sites formed, and that the nucleation rate and growth constants can be deduced from this and the gross kinetic data. The extension of the method of three-dimensional growth is indicated.     

A copper vapour laser operating at room temperature

Laser action on the 5106 and 5782 Å lines of neutral copper has been achieved at temperatures from 20 to 140°C in the vapour of copper acetylacetonate, and at temperatures between 150 and 215°C in the vapour of copper nitrate. The peak output powers are compared with those obtained in the vapours of the copper halides CuCl, CuBr and CuI using the same longitudinal discharge operated in a double-pulse mode in low pressure argon. The highest peak power from copper acetylacetonate obtained to date is 5 kW at a temperature of 40°C. The optimum temperature for the nitrate is 180°C at which the peak output power is 20 kW. The halides can give pulses of 50 kW although the temperatures required are much higher. For the acetylacetonate and the nitrate it is necessary to purge the gas mixture of dissociation products by flowing the argon through the discharge tube. It is probable that the resulting reduction in copper density is partly responsible for the poorer performance observed to date with these vapours. Optimum argon pressures and delay times between the two pulses of discharge current were approximately the same for all the copper compounds tested.     

Organolanthanide-catalyzed synthesis of phosphine-terminated polyethylenes

Organolanthanide-mediated hydrophosphination and ethylene polymerization are coupled in a catalytic cycle to produce diphenylphosphine-terminated polyethylenes. The resulting polymers were characterized by 1H, 13C, and 31P NMR, GPC, and DSC and compared spectroscopically to the model compound, 1-eicosyldiphenylphosphine oxide. High activities (107 g polymer/(mol Ln.atm ethylene.h)) and narrow polydispersities were observed in the polymerization/chain transfer process. Polyethylene molecular weights were found to be inversely proportional to diphenylphosphine concentration, supporting a chain transfer mechanism. The present discovery represents the first case in which an electron-rich phosphine functions efficiently as a chain transfer agent in a single-site fn/d0-mediated olefin polymerization process.     

D/H amide isotope effect in model alpha-helical peptides

The contribution of amide related hydrogen bonds to protein stability has recently been evaluated using the "Cm experiment", which measures the D/H amide isotope effect in proteins. We show here using isolated alpha-helical peptides that there is a significant effect of denaturant concentration on the measured D/H isotope effect, and that valid comparison of different proteins requires correcting for differences in denaturant (GdmHCl) concentration. Finally our results suggest that H-bonds in an isolated alpha-helix may contribute more to helix stability because of less strain compared to those in helical proteins and that the buried helical H-bonds in helical proteins are not necessarily energetically more favorable than solvent exposed H-bonds in isolated helices.     

High‐spatial‐resolution mapping of superhydrophobic cicada wing surface chemistry using infrared microspectroscopy and infrared imaging at two synchrotron beamlines

The wings of some insects, such as cicadae, have been reported to possess a number of interesting and unusual qualities such as superhydrophobicity, anisotropic wetting and antibacterial properties. Here, the chemical composition of the wings of the Clanger cicada (Psaltoda claripennis) were characterized using infrared (IR) microspectroscopy. In addition, the data generated from two separate synchrotron IR facilities, the Australian Synchrotron Infrared Microspectroscopy beamline (AS‐IRM) and the Synchrotron Radiation Center (SRC), University of Wisconsin‐Madison, IRENI beamline, were analysed and compared. Characteristic peaks in the IR spectra of the wings were assigned primarily to aliphatic hydrocarbon and amide functionalities, which were considered to be an indication of the presence of waxy and proteinaceous components, respectively, in good agreement with the literature. Chemical distribution maps showed that, while the protein component was homogeneously distributed, a significant degree of heterogeneity was observed in the distribution of the waxy component, which may contribute to the self‐cleaning and aerodynamic properties of the cicada wing. When comparing the data generated from the two beamlines, it was determined that the SRC IRENI beamline was capable of producing higher‐spatial‐resolution distribution images in a shorter time than was achievable at the AS‐IRM beamline, but that spectral noise levels per pixel were considerably lower on the AS‐IRM beamline, resulting in more favourable data where the detection of weak absorbances is required. The data generated by the two complementary synchrotron IR methods on the chemical composition of cicada wings will be immensely useful in understanding their unusual properties with a view to reproducing their characteristics in, for example, industry applications.